Developments in Colour Protection For Detergents 2008

Developments in Colour Protection
for Detergents
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Contents
List of tables vii Sodium hypochlorite bleach 18

List of figures viii Oxygen bleach (or all-fabric bleach) 18
Executive summary ix Colour removers 19
1
Towards colour protection use of oxygen
bleaches 19
Chelating agents 20
Powdered oxygen bleach products 21
Introduction and methodology 1 Introduction 21
Scope, objective and methodology 1 What are oxygen bleaches? 21
Abbreviations 1 Advantages of powdered oxygen
2
bleach 22
Disadvantages 22
Liquid oxygen bleaches 22
Differences in oxygen bleaching
A general overview of detergent products 23
components 3 Sodium perborate 24
Detergency mechanism and colour The chemistry of sodium perborate
protection 3 bleaching 24
How do surfactants work? 6 Activating sodium perborate for low-
Properties of surfactants 7 temperature performance 25
Adsorption 8 Pre-soak practices 26
Self-assembly 8 Beyond activators: metal catalysis 26
Dispersing polymers 9 The parameters of peroxygen
Builders and chelants 11 bleaching 27
Detergent boosters 12 New physical forms of perborate 27
Laundry cleaning additives 13 Storage stability 28
Properties 13 Non-oxidative bleaching 28
Detergent fillers 13 Liquid formulations for fabric
Materials 14 laundering 29
Bleaches and compounds 14 Fabric care: chlorine scavenging 29
Types of bleaches 14 Gentler hydrophobics 30
Performance-enhancing minor Bleach-free detergents 30
ingredients 14 Bleach-free detergent tablets 31
Physical forms of detergents 15 Summary of the invention 31
Colour protection 16 Detergent tablet 31
3 4
N-heterocyclic polymers 32
Colour care 17
What is dye bleeding? 17 Colour protection agents 33
Causes of dye bleeding 17 Chemicals used for colour protection 33
Laundry bleaches 18 Fabric evaluation methods 34
Page Copyright Pira International Ltd 2008

Developments in Colour Protection for Detergents
Contents
5
PVP K-30 20% Solution 42
PVP K-30 30% Solution 42
PVP K-30 30% Solution-P 42
PVP K-30 CI 42
Dye transfer inhibitors 37 PVP K-30 Fines 42
How do DTIs work and how are they PVP K-30 G PreStep 42
used? 37 PVP K-30 MB 42
Bleeding: what can be done? 37 PVP K-30 Solution-A 42
Conclusion 37 An alternative method of colour protection:
N-heterocyclic polymers 37 colour catcher sheet 43
6
Other DTI agents 38
Water soluble dye complexing
polymers as dye transfer inhibitors in
laundry detergent and fabric softener
compositions 38 Environmental acceptability of colour
DTI compositions with specifically selected
7
care agents 45
metallo catalysts 39
An analysis of commercially available
DTIs 40
DTI products by International Specialty
Products 41 Patents 47
ChromaBond S-100 41 Commentary on patents 59
8
ChromaBond S-400 41
ChromaBond S-403E 41
Polyquart FDI 41
PVP K-120 41
PVP K-120 Solution 41 Technology trends 61
PVP K-120 Solution A 42 Colour and fabric care ingredients: the
PVP K-15 42 future 62
PVP K-15 Solution 42 Cellulase enzymes 63
PVP K-15 Solution A 42 Focus change: from DTI to dye fixation 63
PVP K-15 Solution Intermediate 42
PVP K-30 42
Page vi Copyright Pira International Ltd 2008

List of tables
2.1 Detergent compositions 3 3.1Avox content and bulk density of PBS1,

2.2 Detergent bleaches 14 PBS4, PCS and densified PBS 28
7.1 US patents 47
Page vii Copyright Pira International Ltd 2008

List of figures
2.1 Structure of surfactant 4 2.6Formation of micelles 9

2.2Structures of common surfactants 2.7Homopolymers of acrylic acid and
used in the industry 6 maleic acids 10
2.3Representation of the surfactant 2.8Hybrid anionic dispersing
molecule 7 polymers 10
2.4Adsorption mechanism of surfactant 2.9Sulphonated monomer groups 11
molecules 8 2.10Citric acid and sodium
2.5Self-assembly of surfactant nitrilotriacetate 12
molecules 8
Page viii Copyright Pira International Ltd 2008

Executive summary
Detergents are a complex cocktail of chemicals, or more accurately, a cocktail of

complex chemicals. A modern detergent contains more than 20 ingredients, each
delivering a specific benefit.
While the core ingredients form the bulk of the detergent, and cleaning remains
its primary purpose, a number of speciality ingredients are added to provide various
associated benefits, including fragrance, extra whiteness, tough stain removal, cleaning
ability in cold water and less usage of water. One core ingredient present in small
quantities, but integral to the performance of a good detergent is the colour care agent.
Clothes pass through a violent phase while being washed. The wash water is
generally at a high temperature, and the chemicals in the detergent not only attack
stains, but also the desirable components of the fabric with the same vigour. This
environment is physically grueling, with high-speed rotation (in the case of machine
washing) and repeated rinsing and wringing (in the case of hand washing).
All these factors take their toll on the fabric, and in particular its dyes, which are
firmly held by the fabric a hold that is reduced by repeated washing. The dye may then
break free and leach out in the wash water, fading the cloth and leaving the dye free to
deposit itself on any other part of the cloth, or another fabric being washed in the same
water known as dye transfer.
As a result, the key to colour care is twofold:
Preventing dyes from leaching out (dye fixation); and
Backing this up by preventing the leached dye from re-depositing itself on other
surfaces (dye transfer inhibition).
One of the ingredients added to the detergent to give it the power to remove stains is the
bleaching agent. This works effectively, but also has the undesirable effect of attacking
the dyes. Just like the drugs used in chemotherapy, which do not distinguish well between
cancerous and healthy cells, the bleach also has an adverse impact on the fabrics colour.
Hence why detergent manufacturers constantly strive to make the bleach more gentle on
the clothes.
This report discusses the bleaching technology extensively. This, along with a
lengthy discussion on dye transfer inhibition, forms the bulk of the report. It discusses
the chemical agents used in colour protection (or dye fixing agents) and dye transfer
inhibitors. A chapter is dedicated to the discussion of the environmental aspects of using
these chemical compounds. The report concludes with a chapter on patents in this field
and from this, technology trends are identified.
Page ix Copyright Pira International Ltd 2008

Introduction and methodology
1
Scope, objective and The primary purpose of a laundry detergent is to remove soil and stains from fabrics.
methodology However, it is expected to provide a host of other benefits, too fabric softening, low-
temperature activation of active components, removal of tough stains, post-wash
fragrance, UV protection and colour protection, etc.
These benefits are delivered by a host of chemical complexes, which are incorporated
in the detergent formulation. In fact, a modern day detergent typically consists of more
than 20 ingredients, each meant to deliver a specific benefit. Once the primary purpose is
achieved, detergent marketers rely on the ability of their product to deliver these specific
advantage(s) to give them a competitive edge.
The scope of this report is limited to the analysis of colour protection technologies
and colour care agents used in detergents. It broadly defines colour protection and looks
at technologies that fall in one of two categories: dye fixation and dye transfer inhibition.
The report explores recent developments in colour care technologies and explains
how colour care agents function. It takes a detailed look at bleaches, the chemicals used
for colour protection, advances in dye transfer inhibitor technologies and the commercial
products in these categories. Environmental regulations pertaining to these chemicals are
also discussed.
The report examines the advances in colour protection in detergents, provides an
overview of current technology and identifies likely technological developments. Although
it discusses the technical advances in this field, it is presented in a manner that can be
easily understood by any person not involved in the science or industry of detergency.
The objective of the report is to bring the reader up to date on the current state of the art
of colour care technologies and explore what the future advances will look like. A section
also discusses the patents granted in this field.
The report is based on secondary research (technical papers and journals, World
Conference on Detergents papers and manufacturers literature, etc). Inputs from this
secondary research have been validated by interviews with industry experts.
Abbreviations DTI: Dye transfer inhibitor

PVP: Polyvinylpyrrolidone
PVP NO: Polyvinylpyrrolidone N-oxide
O/W: Oil in water
W/O: Water in oil
STPP: Sodium tri poly phosphate
TAED: Tetra acetyl ethylene diamine
NOBS: N-oxydienthylene-2-benzothiazole sulphenamid
HEDP: 1-hydroxy ethylidene-1,1-diphosphonic acid
DTPA: Diethylene triamine pentaacetic acid
CMC: Carboxy methyl cellulose
AHPS: Sodium 3-allyloxy-2-hydroxypropanesulphonate

Introduction and methodology
SPMS: Sulphopropylomethacrylate
AMPS: (Meth)acrylamido methyl propane sulphonic acid
CMC: Carboxymethyl cellulose
PCS: Sodium percarbonate
RH: Relative humidity
FWA: Fluorescent whitening agents
ISP: International Speciality Products
UV: Ultraviolet
SDS: Sodium dodecyl sulphate
SLES: Sodium laureth sulphate, also known as sodium lauryl ether sulphate
CTAB: Cetyl trimethylammonium bromide, also known as hexadecyl trimethyl ammonium
CPC: Cetylpyridinium chloride
POEA: Polyethoxylated tallow amine
BAC: Benzalkonium chloride
BZT: Benzethonium chloride
MEA: Cocamide

A general overview of
detergent components
2
A modern laundry detergent comprises 20 or more ingredients, each delivering different
benefits. A few representative granular laundry detergent formulations for three detergent
samples, identified as A, B and C are given in the table below.
TABLE 2.1 Detergent compositions

Ingredient Weight %
A B C
C11 C13 linear alkyl benzene sulphonate 8 10
C12 C16 alkyl ethoxy sulphate 5.3
C14 C16 secondary alkyl sulphate 2
C14 C15 alkyl sulphate 7
C16 C18 alkyl sulphate 2
C14 C15 alkyl ethoxy sulphate 1
C12 C15 alcohol ethoxylate E7 3.4
C14 C15 alcohol ethoxylate E7 1 3.3
STPP 10.7
Zeolite A 18 22 10.7
Carbonate 13 19 6
Silicate 1.4 1 7
Sodium sulphate 26 10 40
Na perborate tetrahydrate 9 5
Na perborate monohydrate 1
TAED 1.5 0.5
NOBS 4
HEDP 0.3
DTPA 0.4
Protease 0.8 0.3 0.3
Amylase 0.8 0.1 0.1
Lipase 0.2 0.2
Cellulase 0.15 0.3
Acrylic/maleic copolymer 0.3 1 0.8
CMC 0.2 0.2
Polyester-based soil release polymer 0.2 0.4
Minors Balance Balance Balance
Source: Handbook of Detergents: Part D: Formulations, CRC Press, 2005
As seen in Table 2.1, detergents are a cocktail of complex chemicals. It is not within
the scope of this report to provide an extensive review of the myriad ingredients used.
Instead, the report focuses on the aspect of colour protection of fabrics and the
methods used to achieve this. In this chapter, a general overview of the more common
elements surfactants, dispersing polymers, builders and chelants, bleaching systems,
solvents and performance-enhancing minors, is provided.
Detergency A detergents main performance objective is to remove soil and other contaminants from
mechanism and the fabric and ensure materials that belong there are not removed in the laundering
colour protection process. One such material is the dye.

A general overview of detergent components
The chemical and physical processes involved in the cleaning mechanism are complex
and the detergent ingredients, if not optimised with care agents, will attack the dyes with
as much vigour as they attack the stains and contaminants.
The two most important ingredients are the surfactants and the builders. Surfactants
significantly aid the solubilisation, dispersion and emulsification of soil from the fabrics
surface. Unfortunately, surfactants are also very good at removing dyes, leading to colour
loss and fading over time. These fugitive dyes can also re-deposit on other fabrics, or
other places on the same fabric, leading to hue changes and loss of whiteness. Another
key ingredient in detergents is bleach; the effect of this on fabric dyes will be discussed in
detail later.
A surfactant is briefly defined as a material that can greatly reduce the surface
tension of water when used in very low concentrations. They have amphiphilic
qualities the combination of hydrophobic (water insoluble) and hydrophilic
(water soluble) components, as shown in Figure 2.1.
FIGURE 2.1 Structure of surfactant
)ZESPQIPCF
)ZESPQIJMF
Source: Pira International Ltd
The hydrophobe is usually the equivalent of an eight to 18 carbon hydrocarbon, and can
be aliphatic, aromatic, or a mixture of the two. The sources of hydrophobes are normally
natural fats and oils, petroleum fractions, relatively short synthetic polymers, or relatively
high molecular weight synthetic alcohols.
The hydrophilic groups give the primary classification to surfactants. A surfactant
can be classified by the presence of formally charged groups in its head. A non-ionic
surfactant has no charge groups in its head. The head of an ionic surfactant carries a net
charge. If the charge is negative, the surfactant is more specifically called anionic; if the
charge is positive, it is called cationic. If a surfactant contains a head with two oppositely
charged groups, it is termed zwitterionic.
Some commonly encountered surfactants of each type include:
Ionic;
Anionic (based on sulphate, sulphonate or carboxylate anions);
Sodium dodecyl sulphate (SDS), ammonium lauryl sulphate, and other alkyl
sulphate salts;
Sodium laureth sulphate, also known as sodium lauryl ether sulphate (SLES);
Alkyl benzene sulphonate;

2
Soaps, or fatty acid salts;

Cationic (based on quaternary ammonium cations);
Cetyl trimethylammonium bromide (CTAB), also known as hexadecyl trimethyl
ammonium bromide, and other alkyltrimethylammonium salts;
Cetylpyridinium chloride (CPC);
Polyethoxylated tallow amine (POEA);
Benzalkonium chloride (BAC);
Benzethonium chloride (BZT);
Zwitterionic (amphoteric);
Dodecyl betaine;
Dodecyl dimethylamine oxide;
Cocamidopropyl betaine;
Coco ampho glycinate;
Nonionic;
Alkyl poly(ethylene oxide);
Copolymers of poly(ethylene oxide) and poly(propylene oxide) commercially called
Poloxamers or Poloxamines; and
Alkyl polyglucosides, including:
Octyl glucoside
Decyl maltoside
Fatty alcohols
Cetyl alcohol
Oleyl alcohol
Cocamide MEA, cocamide DEA
Polysorbates: Tween 20, Tween 80.

FIGURE 2.2 Structures of common surfactants used in the industry
$) $)
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Source: Handbook of Detergents: Part D: Formulations, CRC Press, 2005
Most brands of laundry detergent have anionic or nonionic surfactants, or a mixture of

the two, although cationic surfactants have been used. The use of cationic and anionic
surfactants together is incompatible in the same detergent. Foaming agents, emulsifiers
and dispersants are surfactants that suspend, respectively, a gas, an immiscible liquid,
or a solid in water or some other liquid.
Although there is similarity in these functions, in practice the surfactants required
to perform these functions differ widely. In emulsification, for example, the selection
of surfactant or surfactant system will depend on the materials to be used and the
properties desired in the end product. An emulsion can be either oil droplets suspended
in water, an oil in water (O/W) emulsion, water suspended in a continuous oil phase,
water in oil (W/O) emulsion, or a mixed emulsion. Selection of surfactants, orders of
addition and relative amounts of the two phases determine the class of emulsion.
How do surfactants The surfactants (or surface-active agents) are basic cleaning agents in soaps and
work? detergents. When added to water they lower its surface tension, increasing the wetting
and spreading properties.
Dirt, grease and stains are organic in nature, and can logically be removed by
washing them in an organic solution that will dissolve and thereby remove them. However,

2
use of an organic solvent is not possible in home laundry solutions (dry cleaning uses
organic compounds).
Surfactants are usually organic compounds that are amphiphilic, meaning they are
soluble in both organic solvents and water. Surface-active agents have two parts, one is
hydrophilic (water loving) and another is hydrophobic (water repelling). Surface-active
molecules concentrate at the areas of contact, or interfaces, between oil and water. One
end of the molecule seeks oil, while the other end seeks water. At the interface of water
and oil they emulsify oil and mix it into the liquid in the same way fat is mixed in milk.
At the interface of water, these agents trap air molecules to produce foam.
FIGURE 2.3Representation of the surfactant molecule
UBJM IFBE
IZESPQIPCJD IZESPQIJMJD
XBUFSIBUJOH
XBUFSMPWJOH
Source: http://discovery.kcpc.usyd.edu.au/9.5.5/9.5.5_introsurfactants.html
By reducing the surface tension of water, surfactants improve the cleaning performance
by enabling the solution to wet a surface (for example, dishes, clothes and counter tops)
quickly and effectively, and hence any dirt can be readily loosened and removed.
Surface-active agents also emulsify oily soils and keep them suspended and dispersed
so they do not settle back on the surface. To achieve superior cleaning performance,
most cleaning products contain two or more surfactants.
Properties of The molecular structure of surface-active agents means they have unusual characteristics,
surfactants leading to their use in widespread and highly specialised applications. Their properties
can be categorised into two types:
Adsorption; and
Self-assembly.

Adsorption Adsorption is the tendency of the molecule of a surfactant to collect as an interface.

It is the taking up of a liquid or gas at the surface of a substance, generally a solid
(for example, activated charcoal adsorbs gases). The process involves molecular attraction
at the surface.
FIGURE 2.4 Adsorption mechanism of surfactant molecules
8BUFS IZESPQIJMJDIFBET
0JM IZESPQIPCJDUBJMT
Surfactants adsorption property means their molecules are generally found at the
interface between a water phase and an oil phase; an air phase and a water phase.
This results in the macroscopic properties of wetting, detergency, foaming and emulsion
formation. The molecules of a surface-active agent tend to adsorb to the surface of oil
droplets. While the hydrophilic heads stick out into the water phase, the hydrophobic tails
stick into the oil phase.
Self-assembly Self-assembly is the inclination of surfactant molecules to organise and coordinate

themselves into extended structures in water. The process includes the formation
of micelles, liquid crystals and bilayers, formed when the hydrophobic tails of surfactant
molecules cluster together to produce small aggregates, like micelles, or large layer
structures like bilayers (similar to a cell wall). These characteristics of surfactants make
them an interesting study and an area of research.
FIGURE 2.5 Self-assembly of surfactant molecules

2
Surfactants can also form micelles. This allows the hydrophobic tails to get out of the
water, while allowing the hydrophilic heads to stay in the water. There is typically between
a few dozen to a couple of hundred surfactant molecules in a micelle.
FIGURE 2.6 Formation of micelles
Surfactants also aggregate to develop and produce extended structures in water, similar to
that of surfactant bilayers. The concentration at which surfactants start forming micelles is
known as the critical micelle concentration, or CMC. When micelles are formed in water their
tails form a core, which can encapsulate an oil droplet, and their (ionic/polar) heads produce
an outer shell, which maintains a favourable contact with water. When the surfactants
assemble in oil, their aggregate is referred to as reverse micelle. In a reverse micelle, the
heads remain in the core and the tails maintain a favourable contact with the oil.
Thermodynamics of surface-active agents is of great importance theoretically, as well
as practically. This is due to the fact that these agents represent systems between the
ordered and disordered states of matter.
Dispersing polymers Suspension of soil after its removal from a surface is important in cleaning applications to
avoid re-deposition of the soil back onto the cleaned surface. Generally speaking, the particles
to be suspended are sufficiently large that definite surfaces of separation exist between the
dispersed phase and the dispersion medium. In order to keep the dispersed phase stable it is
important to adsorb functional actives at these surfaces to prevent aggregation. This is one of
the critical functions of the surfactants. However, another class of detergent actives has been
developed to assist in particle suspension the polymeric dispersant.
In general, two types of polymeric dispersants are used in detergent formulations
polymers comprising ionically charged groups and nonionic polymers. Typical of the ionic
dispersing polymers are the homopolymers of acrylic acid and maleic acids, which are
widely used in laundry detergent formulations (Figure 2.7).

FIGURE 2.7 Homopolymers of acrylic acid and maleic acids
) )
$ $
; $00) O
Where Z is either hydrogen, in the case of homopolymers of acrylic acid, or a carboxyl

group, in the case where the monomer unit is maleic acid. Polymers of this type are
generally found in powdered laundry detergent formulations where they act as a dispersant
for soils and inorganic salts, provide alkalinity control and serve as crystal growth inhibitors.
Anionic dispersing polymers, comprising carboxyl and sulphonate groups in the same
backbone, have been developed for use in water treatment, where they act to prevent
formation of inorganic scale. The polymers are generally of the hybrid type shown in
Figure 2.8.
FIGURE 2.8 Hybrid anionic dispersing polymers
" # $ %
0QUJPOBM 0QUJPOBM
4VMQIPOBUFE $BSCPYZMBUF OFVUSBM DIBSHFE
NPOPNFS T
NPOPNFS T
NPOPNFS T
NPOPNFS T
The key features are A and B. A, the sulphonated monomers, include the groups shown in
Figure 2.9.
Page 10 Copyright Pira International Ltd 2008

2
FIGURE 2.9 Sulphonated monomer groups
) 3
/ 3 40) 0 40)
40) 3 O
0 0
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O40) $)
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R40) / 40) 40)
R
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444
40)
0)
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0
0)
")14 3
41.4
B usually comprises maleic acid, acrylic acid or methacrylic acid. C and D are optional
but can include acrylamide, vinyl acetate, acrylate esters, cationics or phosphonates.
Nonionic polymers include polyethylene glycol, polyvinyl alcohol, and random and
block ethoxy propoxy copolymers. Graft copolymers of polyalkylene oxide and vinyl
acetate are reported to be effective anti-reposition agents for hydrophobic surfaces like
polyester fabric.
Considerable attention has been paid over the years to the preparation of
biodegradable dispersants. Examples include poly amino acid polymers, such as
polyaspartate, prepared from the catalytic condensation of polyaspartic acid, and
functionalised polysaccharides, such as oxidised starches. Cationic dispersants are less
commonly used, although some amphiphilic structures have been described as effective
in high salt content media.
Builders and Metal ion control is a common need in many detergent formulations. For example,
chelants in aqueous cleaning applications the presence of Ca2+ in the water can lead to the
precipitation of anionic surfactant, reducing the effective concentration available for
cleaning. Fatty acids can precipitate as calcium soaps, resulting in the formation of soap
scum on hard surfaces, and many soils, especially inorganic clays, will precipitate with
calcium, leading to deposition of the soil onto the surface being cleaned.
Builders a generic term used to refer to any number of materials whose primary
function is to remove Ca2+ and Mg2+ ions from aqueous solutions and chelants are
widely used in the formulations of various detergents.

Sodium tripolyphosphate (STTP) is among the best known and widely used detergent
builders. In laundry detergent formulations it serves not only as an extremely effective
calcium control agent, but also provides dispersion, suspension and anti-encrustation
benefits. However, environmental concerns associated with large-scale release of
phosphates into the environment led to the development of a number of substitutes.
Citric acid and sodium nitrilotriacetate are representative of soluble detergent builders
(Figure 2.10).
FIGURE 2.10 Citric acid and sodium nitrilotriacetate
$)$00) $)$00/B
)0 $ $00) / $)$00/B
$)$00) $)$00/B
$JUSJDBDJE 4PEJVNOJUSJMPUSJBDFUBUF
Sodium carbonates and non-crystalline sodium silicate form sparingly soluble precipitates
with calcium, and are frequently used in powdered detergent formulations where they also
provide a source of alkalinity. However, to avoid encrustation of the calcium carbonate/
silicate onto surfaces, these building agents are generally co-formulated with a dispersing
polymer, such as the polyacrylate/maleic acid copolymers described above, and crystal
growth inhibitors, for example HEDP (1-hydroxyethane diphosphonic acid).
Insoluble builders include the zeolites and layered silicates, which bind calcium via an
ion exchange mechanism. Zeolite A, Na12(AlO2)12(SiO2)12.27H2O, is the principal alternative
to the phosphate as a detergent builder. The Na+ ions are exchangeable for Ca2+ while
the larger hydration shell around Mg2+ tends to impede exchange.
Citric acid is also an excellent chelant for metal ions other than calcium and can
be employed where the removal of transition metals such as copper, zinc and iron is
important. Other commonly used detergent chelants include ethylenediaminetetraacetate
(EDTA).
Detergent boosters Detergent boosters are fabric-care products designed to reinforce specific characteristics
required in laundering and improve the cleaning performance. They should be used
in the wash along with the recommended amount of detergent to improve soil and
stain removal, as well as the buffering, brightening and water softening performance
ofdetergents.
The prime function of detergent boosters is to condition the water to optimise the
cleaning action of detergents. They are formulated for effective cleaning in hard water

2
and can be used to enhance and improve the cleaning power of detergent. These products
should be used as per the recommended amount of detergent for a particular size of wash
load, and come in two forms powder and liquid. Liquid detergent boosters can be used
to pre-treat stains, and are formulated using optical brighteners and nonionic surfactants
to deliver excellent wash performance across a comprehensive range of soil classifications
and fabric types.
Common ingredients include surfactants, builders, enzymes, borax, corrosion inhibitors
and fluorescent brighteners. These are integrated in various divergent ratios that depend
on the objectives and requirement of the given product. Based on a concentrated, super-
potent blend of synthetic detergent complex with neutral pH additives, detergent boosters
are formulated to enhance and improve the cleaning power of cleaning agents without
the risks of over wetting or browning.
Laundry cleaning Along with sodium hypochlorite bleach and soil and stain removers, detergent boosters
additives are laundry cleaning additives. However, these additives do not include laundry
conditioners, such as ironing aids and fabric softeners.
Detergent boosters and soil and stain removers are more expensive and thus less
widely used than sodium hypochlorite bleach. They include different types of products,
some of which can be defined and classified in more than one way. Bleach-free boosters
ensure additional safety for colours.
Properties Formulated as a powder or liquid concentrate;

Emulsifying, with high oil absorption;
Superior in lowering the surface tension and dissolving pigments;
Improves the effectiveness of detergent on whites and colours;
Minimises rust stains;
Reduces hard water deposits;
Helps prevent greying soap residue;
Helps remove mineral soap and detergent deposits, which build up in your
laundry; and
Can be used as a detergent booster in addition to a builder for all materials.
Detergent fillers Detergent fillers are the materials added to detergents to alter their physical
characteristics and properties. Their objective is to make detergents fluid or turn fluid
detergents into powder form. Generally, the fillers are bulk components, with their primary
role to modify and alter the physical properties of the material.
We can also define detergent fillers as additives to detergents (along with bleaches,
bleach activators, anti-static agents, fabric softners, optical brighteners and anti-
redeposition agents) to improve the cleansing performance.

Materials Materials that can be used as fillers in detergents include:

Sodium sulphate
Sodium chloride
Borax
Alcohols
Anti-foaming agents.
Borax can be used in solid detergents to make the detergent powder free-flowing.
Alcohols can be added to liquid detergents to increase the solubility of compounds and
reduce the freezing point of the mixture. Anti-foaming agents help to lower the production
of foam, thereby making the presence of detergents in waste water less obvious.
Sodium chloride, or sodium sulphate, can also be used. Sodium sulphate comes at
an economical price and has some cleansing effect, especially when it is mixed with a
cleansing agent. Corrosion inhibitors, such as sodium silicate, can be added to increase
the lifetime of washing machines. Generally, the usual content of fillers in detergents is
about 545%.
Bleaches and Bleaches are compounds used to clean, whiten and brighten fabrics and help remove
compounds stubborn stains. They have proved to be highly effective and useful in converting the soils
into colourless, soluble particles, which can be removed and carried away by detergents
in the wash water. Bleaches can be used for different cleansing applications, including
laundry, dishwasher cleaning and household cleaning products.
Types of bleaches Bleaches can be broadly categorised into two types:

Chlorine bleach
Oxygen bleach.
TABLE 2.2 Detergent bleaches

Bleaches Used for whitening, brightening and removing stains in clothes and fabrics, dishes
and household products
Types Primary function Example
Chlorine bleach Along with whitening, brightening and removing Sodium hypochlorite
stains, it also works as a disinfectant
Oxygen bleach Oxygen bleach can be combined with bleach Sodium perborate, sodium
activators in some products for improved percarbonate
performance at lower temperatures
Source: http://www.detergentsandsoaps.com/bleaches-compounds.html
Performance- Detergent marketers often emphasise one particular benefit of the detergent they are
enhancing minor marketing. These benefits are delivered by adding specialty chemicals, which enhance
ingredients a particular action of detergency. These include:
Enzymes: breakdown of soil components can be achieved using enzymes, which
catalyse the process of breakdown. Protein degrading enzymes (proteases) are the

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most commonly used enzymes, but lipid degrading (lipases) and cellulose degrading
(cellulases) are also used.
Fabric whitening agents: the benefit of extra white is delivered by using fabric
whitening agents, or brighteners. They function by absorbing ultraviolet radiation
and emitting via fluorescence in the visible portion of the spectrum, enhancing the
visual appearance of white surfaces. Typical whitening agents are built from direct
linkage or ethylenic bridging of aromatic or heteraromatic moieties. Derivatives of
4,4-diaminostilbene-2,2disulphonic acid are the most commonly used brighteners.
Anti-foaming agents: modern washing machines require the use of a detergent
that does not generate too much foam, as it can interfere with the working of the
machine. Hence anti-foaming agents are added to detergent formulations. These
reduce or eliminate foam by either preventing its formation or accelerating its
collapse. Alkyl ethoxylate non-ionic surfactants are commonly used as foam control
agents.
Soil-release polymers: these can alter surface polarity, thereby decreasing the
adherence of soil to the fabrics surface. They provide significant changes in the
surface energy, which in turn can lead to dramatic improvements in the removal of
soil. Carboxymethyl cellulose (CMC) is a typical soil release polymer. CMC absorbs
onto cotton fabric owing to the similarity in structure between the cellulose backbone
of CMC and the cellulose polymer of the cotton fibres. Once absorbed, the carboxyl
moiety creates a high net negative charge on the fabric surface, effectively repelling
negatively charged soils, especially clays. Other soil release polymers used are
derivatives of polyesterpolyether block copolymers.
Colour protection and dye transfer inhibition agents: these are discussed in details in
the following chapters.
Physical forms All detergent forms powder, liquid, tablets and liquitabs are primarily composed of
of detergents surfactants and builders (except non-built liquid detergents, which contain primarily
surfactants). They also contain processing or delivery aids for product stability, and can
contain many optional ingredients to give performance or aesthetic benefits, as already
described.
A key difference between powder and liquid laundry detergents is their builder
system. Typically, powder detergents are better built than liquid laundry detergents and
have a carbonate-builder system, often containing aluminosilicates (zeolites) for added
builder capacity.
For the past ten years, liquid laundry detergents have made up at least 50% of the
US detergent market and now make up nearly 60%. Laundry tablets have evoked a
lukewarm response from the US consumer, and their market share remains in single digits.
However, tablets have found a greater acceptance in European markets, and in some
countries tablets command a market share of 25%.

Colour protection Although powder and liquid detergents are designed to provide cleaning and stain
removal, they achieve these objectives in different ways. A key difference is the pH regime
in which the two product forms operate.
Powder detergents perform optimally at higher pHs (pH=~10). This higher pH is a
relatively hostile environment for stains, making powder detergents effective at stain
removal; however, the higher pH also tends to negatively impact fibres and dyes. Over the
years, technologies have been developed to deliver benefits under high pH conditions,
and powder detergents have been able to overcome many of their initial disadvantages.
Heavy-duty liquid laundry detergents are typically citrate-built and perform optimally
at lower pHs (pH=~8.5). Because this pH is closer to neutrality, liquid laundry detergents
tend to be less harsh on fabrics and dyes. Over the years, technologies have been
developed to help liquid laundry detergents deliver stronger cleaning benefits, while
maintaining the less harsh fabric and dye profiles.
Colour care additives (colour protection agents and dye transfer inhibitors) are essentially
the same in all detergent forms, and the findings of this report are applicable to all.

Colour care
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When consumers do their laundry, they want not only excellent cleaning from their
detergent, but superior fabric-care benefits too, including: wrinkle reduction, removal or
prevention; fabric softness; improved feel; garment shape retention and shape recovery;
elasticity; ease of ironing; perfume and colour care benefits; anti-abrasion and anti-pilling
benefits; or any combination thereof. Compositions that provide both cleaning and fabric
care benefits, for example fabric softening, are known as two-in-one.
In laundering, unique and significant challenges exist for securing fabric care. In spite
of the advances in the art, there remains a need for compositions that provide improved
cleaning and fabric-care benefits in a single application. In particular, important unsolved
problems remain with respect to selecting compatible fabric-care and cleaning ingredients
so the combination of both provides uncompromising levels of fabric care. Furthermore,
it remains particularly difficult to combine anionic surfactants and beneficial cationic
fabric care agents in such a way as to achieve superior fabric care, at the same time as
outstanding cleaning and formulation stability or flexibility.
As well as attacking undesirable stains on the fabrics surface, surfactants and other
detergent components also act to dull the dye. While washing, dye molecules leach out,
or bleed, and the extent to which this happens depends on the newness of the garment,
type of fabric, type of dye and wash conditions.
The surfactants in the wash often contribute to this bleeding phenomenon, and the
dye, once leached, is then free to deposit on any other surface of the fabric known as
dye transfer. Abrasion is the physical duress that a fabric undergoes while being washed.
What is dye Dye bleeding occurs when an unstable dye transfers from the fibre in the presence of
bleeding? water. This is often confused with the phenomenon of crocking, which is essentially dye
bleeding, but when the fabric is dry. Dye bleeding is the transfer of a coloured substance
to another, and it is most visible in areas of high contrast light-coloured or un-dyed
fabrics can readily accept the mobile dye and absorb it. Because of this absorption/
adsorption process, the colour balance of the fabric changes. For example, in an area of
fabric where white fibre resides next to an unstable red dye, bleeding will cause the white
area to turn pink.
Causes of dye bleeding There are three main causes of dye bleeding, and the first of these is a poor cleaning
method and chemical choice. The introduction of a dyed textile to a highly alkaline
cleaning environment in detergent washes can cause the weakening of the fibredye
bond and initiate dye bleeding. Some fabrics are particularly poor at accepting dyes
(for example, linen) and an experienced cleaner will spot this.
The second cause is a defective dye or dying process during the fabric manufacture.
In cases such as these, the fabric dye is either poorly selected or misused during the
manufacturing process and not properly set onto the surface of the fibre. Either of these

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conditions will lead to an excess of weakly bonded, unstable dye. During cleaning, this
can become mobile and begin the dye bleeding process.
The final cause is chemical changes in the dye during use. In some cases, the dye
was initially 100% stable, but over time the chemical bond between the dye and fibre has
been weakened and become unstable. For example, a dye might be weakened if a fabric
is subjected to high levels of sunlight, fumes, chemicals or pet residues over a long period
of time.
This chapter discusses the action of bleaches on fabric. Chapter 4 focuses on dye
transfer inhibition.
Laundry bleaches Bleach is a popular laundry aid and helps detergents remove soils and stains. Through
oxidisation, laundry bleaches convert soil into more soluble, colourless or dispersible
particles that can be removed by the detergent and carried away in the wash water.
Generally speaking, the two oxidising types are sodium hypochlorite (also called
chlorine or liquid household bleach) and oxygen, though these should not be used
together, as the benefits of both are lost when combined. Colour removers, considered
reducing bleaches, are also bleach products.
Sodium hypochlorite Liquid sodium hypochlorite bleach is the most widely used, although a dry form is also
bleach available. It is made by combining chlorine with a solution of sodium hydroxide to
produce sodium hypochlorite, sodium chloride and water. The sodium chloride is a
by-product of the chemical reaction and remains in the solution as an inactive ingredient.
When liquid sodium hypochlorite bleach is added to the wash, sodium hypochlorite reacts
with the soil and organic matter. As a result, liquid household bleach:
1. Oxidises soil and aids in its removal.
2. Acts as a disinfectant on both bacteria and viruses likely to be encountered in
the home.
3. Generally whitens fabrics.
The bleaching action of sodium hypochlorite is essentially completed in around five
minutes, even less in hot water, but slightly longer in cold. The dry version performs like
liquid sodium hypochlorite bleach when dissolved in water. Sodium hypochlorite bleach
can be used on all washable colourfast natural fibres (cotton or linen) except protein
fibres like wool, silk and mohair. It is also safe on all washable synthetic and permanent
press fabrics, except Spandex.
Oxygen bleach Oxygen bleaches are available in both a dry and liquid form. All dry oxygen bleaches
(or all-fabric bleach) contain inorganic peroxygen compounds, such as sodium perborate tetrahydrate and
sodium percarbonate. When dissolved, the inorganic peroxygen compounds release
hydrogen peroxide (the oxidising agent) and the residue of the compound, for example,
sodium borate or carbonate. Liquid oxygen bleaches contain hydrogen peroxide, which
supplies the oxidising agent directly. This reacts with the soil and organic materials in the

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wash to either de-colourise or break them up. Hydrogen peroxide provides a more gentle
bleaching action than the sodium hypochlorite used in chlorine bleaches.
Water temperature affects the bleaching rate of oxygen bleaches, and hot water
accelerates the bleaching action. As water temperature decreases below 130F, exposure
time must be increased substantially. Powdered oxygen bleaches also contain a builder,
usually sodium carbonate, which provides additional alkalinity and allows the perborate
to function more effectively as a bleach.
Other ingredients, such as surfactants, brighteners, bluing agents and fragrance,
can be incorporated into both liquid and powdered formulations. Enzymes are used in
powdered bleaches.
Colour removers Colour removers, available as a packaged product, contain sodium hydrosulphite, sodium
carbonate and sodium metasilicate. They can remove most colours, but some dyes,
especially prints, cannot be removed. In most cases, colour will be reduced or removed
enough to permit re-dyeing to another colour. Colour removers also help to whiten dingy
colours and remove brown (rust) stains from clothes washed in water that contains iron
and manganese. They can also help to remove transferred dye stains from whites washed
with coloured items.
Towards colour Liquid hydrogen peroxide bleaches offer the key advantages over hypochlorite of being
protection use of safer on coloured items and less aggressive towards the fabric in general. While this
oxygen bleaches is true without a doubt, it is essential for the formulator to recognise that the risk of
damage still exists with these milder products, particularly when peroxide bleach is used
to pre-treat a stain prior to a machine or hand wash. In this situation there are two key
factors that may play a role in colour or fabric damage:
The presence of transition metal ion impurities, such as copper, chromium, iron and
manganese, on the fabric surface. These may come from dyes present on the fabric,
for instance metal-azo dyes, or from stains and soil.
The time interval between product application on fabrics and the main wash.
The longer this time interval, the higher the likelihood of damage due to water
evaporation, which causes an increase in the concentration of hydrogen peroxide
in contact with the fabric.
A combination of the above factors may lead to the start of a radical decomposition
process on the fabrics surface, which can result in colour fading or even fabric damage.
Starting from the assumption that the damage risk is essentially related to the
formation of free radicals on the fabrics surface, some formulators have proposed the use
of radical scavengers to decrease it. In model experiments they found that white cotton
swatches artificially contaminated with 50ppm (parts per million) of copper ions, had
a significant tensile strength loss when pre-treated for 24 hours by a hydrogen peroxide
bleach without radical scavengers. However, tensile strength loss was as low as 2%,

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i.e. within experimental error, when pre-treatment was done by formulations containing
combinations of radical scavengers such as di-tert-butyl hydroxy toluene (BHT) and
2-tert-butylhydroquinone (MTBHQ). Benefits were also observed in terms of reduced
colour fading on cotton swatches dyed with Direct Blue 1 and Reactive Purple. (Reference:
Handbook of Detergents: Part D: Formulations, CRC Press, 2005, Page 201.)
In order to control the first factor described above, namely transition metals, other
formulators found specific chelants and radical trapsand and their combinations to be
particularly effective in reducing the damage risk. Examples of these are polyamines such
as 1,4-butyl diamine, propylene diamine, and ethylene diamine.
An important criterion for the selection of chelants, or radical scavengers, to control
damage, is their ability to migrate through the fabric fibres as the product is applied
and progressively spread, wetting different fabric areas. During this wetting process,
partitioning equilibria are established for each ingredient between the solution and the
fibres, similar to what happens in chromatography. Thus ingredients with a high mobility
on cellulose (in the case of cotton fabrics) will move together with the hydrogen peroxide
fluid, while ingredients with a high affinity for cellulose, and therefore low mobility, will
tend to separate from the fluid.
Chelants and radical scavengers with a high mobility on cellulose deliver the best
protection against colour and fabric damage, because they are able to be present in every
point of the fabric reached by hydrogen peroxide. Mobility can be measured by running
a thin-layer chromatography of a solution containing the ingredients of interest on a
chromatographic plate made of cellulose (or other materials depending on the fabric
of interest). Examples of fabric protection agents with a high mobility on cellulose are
glycine, salicylic acid, aspartic acid, glutamic acid and malonic acid.
In order to specifically mitigate the effects of water evaporation and the subsequent
concentration of hydrogen peroxide in contact with the fabric, one can also try to
decrease the evaporation rate. This can be achieved by introducing suitable polymers into
the formulation, typically cross-linked polyacrylates or copolymers of acrylic acid and other
co-monomers. By retaining at least part of the water originally present in the formulation,
these polymers can prevent or delay complete product drying, decreasing the risk of
damage.
Chelating agents Colour safe detergents contain one or more of a transition-metal selective sequestrant
(the chelating agent) for example, iron and/or copper and/or manganese chelating
agents provided that such materials are compatible or suitably formulated. Chelating
agents suitable for use can be selected from the group consisting of:
Aminocarboxylates;
Iminodisuccinates;
Hydroxycarboxylates (especially citrates);
Phosphonates (especially the aminophosphonates);

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Polyfunctionally substituted aromatic chelating agents, phosphates and mixtures

thereof.
Without intending to be bound by theory, it is believed that the benefit of these materials
is due in part to their exceptional ability to remove iron, copper and manganese ions from
washing solutions by the formation of soluble chelates.
Commercial chelating agents include Iminodisuccinate TP from Bayer and the
Dequest series and chelants from Monsanto, DuPont and Nalco, Inc. If utilised,
chelating agents or transition-metal-selective sequestrants will preferably comprise from
about 0.001% to about 10%, more preferably from about 0.05% to about 1%, by weight
of the compositions herein.
Powdered oxygen Types of oxygen bleach products include:

bleach products Oxiclean
Oxy-Boost
Clorox Oxy Magic
Stain Solver
White Wave
Ajax
Deck And Siding Brightener.
Introduction Many of us are familiar with powdered oxygen bleaching products seen in stores
or advertised on television. They range from Tide with Bleach and OxiClean,
to Ajax Oxygen Bleach Powder Cleanser, Wolmans Deck and Siding Brightener.
While these unique cleaners and stain removers have been around for years, it is only
recently that they have come to prominence in the consumer market. This section looks
at these products and provides an overview of what they are, how they work and how they
are used.
What are oxygen Oxygen bleaches release oxygen for cleaning and bleaching stains and dirt upon
bleaches? addition to water. There are three types sold in the consumer market: hydrogen peroxide,
sodium percarbonate and sodium perborate. While hydrogen peroxide is a liquid, sodium
percarbonate and sodium perborate are powders. Sodium percarbonate is used in deck,
carpet, household and laundry cleaning products. Sodium perborate is used mostly in
automatic dishwashing and laundry products as a hot water bleaching agent. While
sodium percarbonate has the highest solubility in water, sodium perborate is more storage
stable in detergent formulations.
Powdered bleaches are made by treating natural soda ash or natural borax with
hydrogen peroxide. Upon dissolving in water, they release hydrogen peroxide and function
by transferring an oxygen atom to the substrate. (One popular infomercial seen on
television claims that their oxygen bleach takes the oxygen right out of the air, which

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is totally false.) Pure sodium percarbonate contains about 1314% oxygen, and sodium
perborate contains about 1015% oxygen.
They are currently manufactured in the US, Korea and China. While Asian bleaches
are generally lower in cost, US-produced bleaches are the most consistent
in terms of composition and performance.
Advantages of Probably the biggest advantage of an oxygen bleach is that stubborn dirt and organic
powdered oxygen stains can be removed without having to use toxic and hazardous materials, like chlorine
bleach bleach. Oxygen bleaches are also colour-safe and will not bleach dyed fabrics, like chlorine
bleach will. They can be used on carpet, upholstery and even the most delicate linens
(except for some types of wool and silk) without harming the fabric. Unlike many products
that are sold as environment-friendly cleaners that are not particularly effective, oxygen
bleaches really do work and for some stains do a better job than traditional bleaches or
cleaners.
Other advantages include:
Better long-term shelf stability than liquid hydrogen peroxide products;
Act as a disinfectant on both bacteria and viruses likely to be encountered in the
home;
Brightens fabrics;
Oxygen bleaches can be mixed or used with other household cleaners;
Non-toxic to animals, plants and humans;
Environment-friendly as they break down into natural soda ash and/or borax after
the oxygen is released.
Disadvantages Powdered oxygen bleaches do have some drawbacks:

Oxygen bleaching products can cost more to use than standard cleaning products
They take time to dissolve in water
While effective, oxygen bleaches can take longer to work
They are not suited to some finer grades of silk or wool.
Liquid oxygen As mentioned previously, another way to buy oxygen bleach is as a water solution
bleaches of hydrogen peroxide. It functions by transferring an oxygen atom to the substrate, which
does the cleaning and bleaching, leaving only water as the byproduct.
Hydrogen peroxide can be bought in many dilutions. Some consumers use 3%
hydrogen peroxide for general household purposes; other popular dilutions are 30% and
35% food grade quality, which do not contain chemical stabilisers, as the 3% solution
does. However, these products have shorter shelf life stabilities of only a few months.
Also, care must be taken as they are extreme oxidisers and can be dangerous if not
handled properly.
With the recent explosion of oxygen bleaches available to consumers, new liquid
peroxide-based products have appeared. Woolite OxyDeep Spot and Stain Carpet Cleaners

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(Platex Products, Inc.) and Formula 409 Oxi Magic Multi-Surface Stain Cleaner (The Clorox
Company) are examples of US brands.
Citrus oil/hydrogen peroxide-based household cleaners are another category in this
area that try to capitalise on the grease and oil removal properties of citrus oil, along
with the advantages of hydrogen peroxide. However, there is typically only a few per cent
citrus oil present, which is not enough to do more than light to medium duty cleaning.
HPCitrus (Coastwise Laboratories) and Bio-Ox Citrus Concentrate (Bio-Ox International)
are examples of this type of product.
While the purchase price of hydrogen peroxide products is cheaper than the
powdered versions, it must be considered that much of the product is water. Typically,
consumer products will be only 37% hydrogen peroxide (by law these products cannot
contain more than 8% hydrogen peroxide without special warning labels). On an oxygen
equivalency basis the costs are similar to powdered products. While hydrogen peroxide
solutions have the advantage over powdered products of being sold ready to use,
powdered bleaches are easier to handle, have better storage stability and do not need any
added chemicals to enhance stability.
Differences in oxygen There are four categories of powdered oxygen bleach products sold in the consumer
bleaching products market. These are:
Ultra-concentrated oxygen bleaches
Ultra-concentrated bleaches generally contain between 80100% oxygen bleach
(usually sodium percarbonate). While the most expensive to buy, they are also the
most effective for bleaching and cleaning. Ultra-concentrated products are more
versatile in the type and severity of jobs they can tackle. Put simply, the more oxygen
available for cleaning the better.
Concentrated oxygen bleaches
Products sold in this classification generally contain 4070% sodium percarbonate.
Oxygen bleaches that used to be sold as ultra-concentrated are now sold under this
classification. While now more reasonably priced, they do not work as well on really
tough cleaning jobs, where a more concentrated product is needed.
Oxygen bleaches with additives and other cleaning agents
One approach that some manufacturers have taken is to add surfactants, additives,
fillers, detergent builders and other cleaning agents. These additives are used to
maintain and assist the oxygen bleachs cleaning ability but lower the overall cost of
use. This is especially the case for products intended for laundry use. Generally, these
products contain 2040% bleach.
Cleaning products that contain oxygen bleach
The vast majority of oxygen bleaching products fall into this category. They include
laundry and dishwashing detergents, toilet bowl cleaners, cleansers, concrete cleaners
and carpet cleaners. Generally, these products contain 25% or less oxygen bleach.

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Sodium perborate Laundry bleaching the whitening, lightening and brightening of fabrics and other
articles by chemical means is a combination of oxidative and non-oxidative processes.
Sodium perborate is recognised as an outstanding oxidative bleaching agent and
has been widely used as such for almost a century. What is less well appreciated is
that perborates and other borates also provide significant non-oxidative bleaching
properties. This section concentrates on powders for fabric washing, but notes on liquids,
formulations and household cleaners are appended.
Different machine washing practices around the world, derived either from the
wash temperature, detergent concentration, wash time, or user willingness to add bleach
separately from the detergent, have in the main determined the bleaching agent used.
As oxidative bleaches, hydrogen peroxide and sodium hypochlorite are very effective,
albeit over different temperature ranges, but cannot be incorporated directly into
washing powders. Sodium perborate (PBS, NaBO3.nH2O where n=1 or 4) can readily be
incorporated. It has been described as a stable, solid form of hydrogen peroxide allowing
its introduction into the wash at the same time as the detergent. Sodium perborate is a
gentler bleach than sodium hypochlorite, causing less damage to fabrics and dyes, but by
itself it is only effective at high (>60C) temperatures. Although solid chlorine bleaches
exist, they are rarely used in laundry detergents.
In practice today, the effectiveness of sodium perborate as a source of available
oxygen at more moderate temperatures (4060C) is regained by the use of activators.
Activators such as TAED (tetraacetylethylenediamine) are precursors for peracid bleaches
formed in situ during the washing process. In general, peracids, which are more powerful
bleach species, cannot be formulated directly into detergent powders for stability reasons
and have to be formed in situ.
However, at the even lower wash temperatures found outside, and increasingly in,
Europe, encouraged by energy considerations, the performance of activated perborate
declines. It is expected that new technologies, based on bleach activators or catalysts, will
promote successful perborate bleaching at these lower temperatures in future.
The chemistry of Sodium perborate, formed by the reaction of borax pentahydrate, sodium hydroxide and
sodium perborate hydrogen peroxide, is commercially available as the tetrahydrate (NaBO3.4H2O, or PBS4)
bleaching or the monohydrate (NaBO3.H2O, or PBS1, formed by heating PBS4), which dissolves faster
than PBS4 at lower temperatures. They contain true peroxygen bonds, unlike, for instance,
sodium percarbonate or sodium perphosphate. In the case of percarbonate, for example,
the lack of a peroxocarbonate bond results in a product which is inherently less stable.
To enable this material to be safely handled in bulk, and to be used in certain super
compact heavy-duty laundry powders, requires the use of various stabilising coatings.
Without these, thermal run-away reactions and rapid loss of available oxygen would occur.
In the crystalline form, PBS exists as a dimeric cyclic peroxodiborate salt, which in
aqueous media, rapidly hydrolyses to form an equilibrium solution of hydrogen peroxide,

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tetrahydroxy borate anions, and one or more peroxoborate species. The equilibrium
constants determining the hydrolysis imply that, in practice, sodium perborate can indeed
be regarded as a solid, stable source of hydrogen peroxide bleach.
Peroxoborate species, such as (HO)3BOOH-, that is those in which the peroxo group
remains co-ordinated to boron, are stable in solution. Calculations show that under
European laundry conditions, with 0.01M borate and 0.01M available oxygen, about one
sixth of the available oxygen and borate is contained in peroxoborate species, principally
(HO)3BOOH-. (Reference: Technical literature released by Rio Tinto Borax.)
Peroxoborates may be better bleaching agents than hydrogen peroxide itself. The
electrophilic nature of the peroxygen groups is increased by the coordination to the boron
centre. As a result, sodium perborate can be a superior bleaching agent to hydrogen
peroxide at equivalent, high temperatures.
The exact mechanism of bleaching by available oxygen is subject to conjecture. Stains
susceptible to oxidative bleaching comprise chemicals with a degree of unsaturation.
The conjugated double bonds in such compounds can give rise to the colour of such
components: these double bonds may be disrupted by epoxidation leading to their
decolourisation. The epoxides may be hydrolysed to 1,2-diols, with a consequent increase
in water solubility, hence facilitating the removal of the bleached substance from the
stained surface.
Another effect may be the removal of chemical bonds that bind the stain to the
fabric, without necessarily disrupting the bonds in the chromophore, especially in the
case of aged stains.
The perhydroxyl anion (HOO-) is believed to be an important, perhaps the most
important, bleaching species. However others, including peroxoborates and singlet oxygen,
may also be involved. Recent work has indicated that the superoxide radical, O2-, might act
as the active oxygen species in some circumstances. However, the extent of the contribution
of the superoxide radical is currently thought to be insignificant compared to the
perhydroxyl anion, and further research is warranted to determine the exact contribution.
Hydrogen peroxide can react with both nucleophiles and electrophiles, and a given
chromophore may well contain sites susceptible to either kind of attack. The available
oxygen also has an important microbiocidal function.
Activating sodium Many bleach activators have been described that react with hydrogen peroxide to
perborate for low- generate peracid, with its more reactive form of available oxygen, in situ. Most are acyl
temperature donors, generally attached to a phenol or secondary/tertiary nitrogen source, since the
performance resultant compounds are less stable in alkaline solution than simple alcohol esters.
Activators acylate the perhydroxyl anion to form peracids and peracyl anions the
perhydrolysis reaction. An essential feature of activators is the presence of a good leaving
group (pKa~810). Two widely used activators are tetraacetylethylenediamine (TAED) and
sodium nonanoyloxybenzenesulphonate (NOBS).

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TAED is favoured in Europe, while in the US, where washes are typically at lower
temperatures with shorter wash times and more dilute detergent, NOBS is favoured. This
has been attributed to the surfactancy of the pernonanoic acid generated by NOBS, which
is interfacially active and more effective on stains, particularly so for lipophilic types.
Peracetic acid (PAA) from TAED is less interfacially active, or more hydrophilic, and better
suited to European conditions. However, TAED is more weight-effective than NOBS, so
increased bleach level can compensate for lack of surface activity.
The activator should not act on the perborate until they are both present in the
wash liquor, and so TAED and NOBS are encapsulated as prills or granules for powder
formulations. The usual package composition is 26wt.% TAED with 1225wt.% perborate
(Europe), or 12wt.% NOBS (US) with 25wt.% PBS1.
The ratio of perborate to activator is important. The rate of peracid generation is
enhanced by a higher peroxide: activator ratio, higher pH and higher temperature; however,
peracid bleaching is more effective at a lower pH. Conveniently, the pH profile during the
wash changes, falling from 10 to 10.5 at the outset to approximately 9 after perhydrolysis.
The bleaching mechanism responsible, where a reaction between nucleophilic stains
and peroxide is involved, is the heterolysis of the peroxidic bond. Electrophilic activation
of hydrogen peroxide can be achieved by the replacement of the existing leaving group
OH- by a weaker base (RO-), for example CH3CO2-. The result is a much faster bleaching
reaction, activating the otherwise slow kinetics of hydrogen peroxide.
This is exactly what is achieved by converting hydrogen peroxide into peracetic acid
in TAED-activated perborate bleaching. Much of the effort in developing improved low
temperature peroxygen bleaching technologies is focused on maximising the rate of this
reaction, although other mechanisms may be in play. The reaction of the peracid with its
anion, promoted at a pH equal to the pKa of the peracid, may lead to the formation of
active oxygen species.
Pre-soak practices In some markets, notably the Peoples Republic of China and South America, it is usual to
soak laundry before washing at ambient temperatures in a detergent that typically does
not contain a bleach. Although a perborate/activator combination, for example PBS1/
TAED, will not produce effective bleaching by washing at these temperatures, Borax has
shown that after soaking overnight using a detergent containing PBS and TAED, followed
by a machine wash, a variety of stains are effectively bleached, especially tea stains.
These results demonstrate that the performance of PBS/TAED is not only dependent on
temperature, but also upon the contact time between stained fabric and bleach solution.
Activated perborate is slow to react at low temperatures, but given long enough, it is able
to deliver excellent results.
Beyond activators: Activators effectively increase the reactivity of available oxygen from PBS. It is
metal catalysis undeniable that commercially available bleach activators do not perform well

3
Colour care
below 40C. New activators are under development, but other approaches are being
considered. For example, ions of the transition metals (manganese has attracted much
attention) can also catalyse peroxy reactions to promote the formation of reactive peroxy
or oxy derivatives at low temperatures.
The attractions of a catalytic route to expose the stain to available oxygen are
obvious it is as effective as activators, but with less bulk, at less cost and with greater
economy of chemical usage.
The invention of a transition metal-based bleach catalyst was first commercialised in
the early 1990s, but resulted in unacceptable dye and fabric damage under some washing
conditions. Despite the setback, transition metal catalyst systems are under active scrutiny.
An effective catalyst-based formulation, apart from being kind to fabrics and dyes, must:
Be hydrolytically and oxidatively stable, for example not form coloured insoluble
metal oxides or hydroxides;
Promote useful rather than wasteful release of the available oxygen;
Be safe in use and as an effluent;
Be economical to produce.
The parameters of Of the many forms of sodium perborate known, the two most familiar in detergents are
peroxygen bleaching the mono- and tetrahydrates. Their dissolving rates vary with temperature, and because
of this, and their different available oxygen content, tailored intermediate perborate
mixtures enable attainment of the optimum available oxygen (concentration versus time)
profiles.
Other means of altering solution rates exist. Polyhydroxycarboxylates capable of
forming complexes with perborate increase the perborate dissolution rate (see Builders
section). Specific bleach activity is measured by the available oxygen content. The
theoretical limit of PBS4 is 10.4 wt.% available oxygen, and PBS1 up to 16 wt.%.
New physical forms A recognised benefit of sodium percarbonate (PCS) is its higher available oxygen density
of perborate (mass of available oxygen in a given volume) compared with either of the perborates
(mono- or tetrahydrate). This has tended to favour sodium percarbonate usage in premium
super compact heavy-duty laundry powders and tablets, where low-volume dosing is an
important feature.
Studies carried out by Borax and other groups have, however, led to the development
of forms of perborate on a laboratory scale, which have improved Avox densities, while
maintaining other vital properties such as dissolution rate, bleaching performance,
moisture uptake and stability. The physical properties of the densified perborate, and
those of the existing commercial persalts, are shown in Table 3.1.

Colour care
TABLE 3.1 Avox content and bulk density of PBS1, PBS4, PCS and densified PBS
Sample % Avox by weight Bulk density (g/m3) % Avox by volume
PBS1 15.1 0.58 8.8
PBS4 10.2 0.81 8.3
PCS (uncoated) 14.4 1.00 14.4
Densified PBS 16.2 0.77 12.5
Source: Rio Tinto Borax
Stain removal remains the consumers key requirement in laundering, and peroxygen
bleaches (perborate and percarbonate) are employed for this purpose in heavy-duty
laundry powders. When compared on an equivalent available oxygen basis, reference
detergents containing perborate/TAED and percarbonate/TAED deliver very similar
bleaching performances under controlled test conditions. Only at temperatures below
40C is there some evidence of a minor performance benefit from percarbonate.
Studies conducted by Borax reveal that under TAED-activated, unbuffered conditions
where pH might vary, sodium percarbonate performance against the tea stain falls short
of both PBS4 and PBS1. This is due to the higher pH of PCS wash liquors (pH 10 for PCS
versus pH 9.5 for PBS). Stain removal with peracids falls at high pH for many stains,
and this explains the poorer performance of PCS under these conditions. Percarbonate
is not able to match the versatility of perborate activity either (as builders, stabilisers,
solubilisers and pH buffers).
Storage stability It is important for a detergent to maintain its available oxygen while being stored. In tests
under stressed conditions, perborate demonstrates the superiority of its true peroxygen
bonding over percarbonate, whose H2O is held in the crystal lattice. Here, 50:50 (wt.%)
mixtures of commercial persalts with zeolite A builder were stored at 30C and 70%
relative humidity (RH). Measurement of percentage decomposition (residual available
oxygen) over time reveals that although coated percarbonate is more stable than
uncoated samples, it fails to match the performances of both sodium perborate mono-
and tetrahydrate. Better results are reported with phosphate builders, but these are not
currently used in detergents Europe wide.
Non-oxidative In conjunction with peroxide/peracid bleaching activity, borates other than sodium
bleaching perborate can act as important non-oxidative bleaches, due to the ability of borate
to solubilise stains by forming negatively charged complexes. These are more water
soluble, and as the fabric surface is also negatively charged in the high-pH wash liquor,
electrostatic repulsion helps remove the stain from the fabric. Additionally, borates have
the ability to inhibit the adsorption of stain back onto the fabric surface.
Many stains are of vegetable origin and comprise, in the main, polyphenolic
components with polyhydroxy functionality. These are known to interact with the
tetrahydroxy borate anion in solution to form borate ester complexes. As these are

3
Colour care
negatively charged, they will be electrostatically repelled from the similarly charged fabric
surface. This is particularly evident in red wine stain removal.
In conjunction with oxidative bleaches, such as sodium perborate and hydrogen
peroxide, borate addition has been shown to enhance the total bleaching performance.
Data indicates that this is probably due to the enhancement of the non-oxidative
pathway, or process, rather than the increased levels of peroxoborate anions caused by
added borate, but it is also likely that peroxoborate is more reactive toward some stain
components than hydrogen peroxide, giving it a broadband efficacy.
Liquid formulations Many advances in the incorporation of peroxygen bleach, including perborate, into main
for fabric laundering wash liquor detergents have been described, but not proved fully viable. In aqueous
formulations, perborate bleach suffers from loss of available oxygen and low solubility.
The catalytic breakdown of available oxygen by trace metal ions, particularly
of copper, iron and manganese, is considered to be the reason for this loss. Many
effective stabilisers, essentially powerful sequestrants or cocktails of sequestrants, with
a specific ability to form very strong complexes with the various metal ions, have been
described that slow the loss to practical levels. From Borax studies, it is clear that the
most effective in water-based liquors appear to be sodium phosphate and sodium
diphenylaminesulponate (DPAS). Significant stabilisation is achieved at 10ppm and
practical stabilisation (<5% loss of Avox in one month at 30C) occurs with 1wt.% DPAS.
Several other stabilising agents have been described that extend the shelf life with
respect to available oxygen, but thus far its loss over time is considered too great.
Bleach-containing non-aqueous detergent formulations, based upon one or
more glycol-based compounds or non-ionic surfactants, an activator such as TAED
and appropriate stabilisers, show promise. In bleach-containing aqueous detergent
formulations, the solubility of components such as perborate is clearly critical, as are their
stabilities in storage. Sodium perborate solubilisation can be increased tenfold by the
addition of borate or other co-solutes. Liquids based on hydrogen peroxide are currently
only used as separate bleaches or stain pre-treatments because of their lack of stability
at the higher pH of detergents. However, the discovery of the so-called borate-polyol pH
jump phenomenon in conjunction with a source of available oxygen including perborate,
may result in complete liquid detergents containing bleach.
Fabric care: chlorine The hypochlorite anion (OCl-) can contribute to fabric and dye damage during washing.
scavenging Even the low concentrations of chlorine bleach encountered in domestic water supplies
can, over many washes, cause significant fading. However, the inclusion of about 1wt.%
sodium perborate in laundry detergent powders results in the destruction of the chlorine
bleach. Additionally, cotton and some synthetic fabrics like polyamide-elasthanes have
free hydroxyl groups.
It is thought that damage may also occur from the oxidation of these groups when
hypochlorite is used as the bleaching agent. The hypochlorite decomposes to form

Colour care
hypochlorous acid and free radicals, especially in the presence of metal ions (species
having an unpaired electron), which are reactive with, and oxidise, the fabrics hydroxyl
groups.
At lower pH the hydroxyl groups can oxidise to aldehyde groups, which are
responsible for yellowing. In order to prevent this, a borate system has been developed
which, in the presence of a catalyst, forms an ester with the fabric, so protecting the
hydroxyl groups from oxidation. Borates that yield boric acid, or the tetrahydroxy
borate anion, will be effective in this application. The catalyst can be any Lewis acid,
but particularly suitable are organic and inorganic salts of zinc, aluminium, titanium,
magnesium, tin, antimony and bismuth.
One compound embodies both esterification and catalytic actions zinc borate.
The borate also helps buffer the solution, so the equilibrium between hypochlorite and
hypochlorous acid is shifted in favour of hypochlorite.
Gentler hydrophobics Hydrophobic oxygen bleaches, for example PBS/NOBS, have the advantage that they
have a tendency to migrate to the fabrics surface and work there, rather than exerting
their activity within the wash liquor. In certain usage conditions these bleaches have been
found to have an adverse effect on some synthetic fabrics that have unsaturated moieties
or a high degree of polymer cross-linking, perhaps because of a side reaction to the
bleaching process involving a single-electron, free radical mechanism.
A polymer-kind hydrophobic bleach has been described that does not have this
effect a peroxyacid bleach precursor combined with an antioxidant and a binder/
agglomerating agent. The antioxidant can be a phenolic ester of, for example, boric acid,
and the combination appears to scavenge free radicals, hence preventing fabric damage.
Bleach-free Enzymes make up an important class of naturally occuring proteins, and each class
detergents catalyses a different kind of chemical reaction. One class, known as proteases, are known
for their ability to hydrolyse other proteins (where a compound is broken down into two or
more smaller compounds, with the uptake of the H and OH parts of a water molecule on
either side of the chemical bond cleaved).
This ability to hydrolyse proteins has been taken advantage of by incorporating
naturally occurring and protein engineered proteases as an additive to laundry detergent
preparations. Many stains and soils on clothes are proteinaceous and water-insoluble.
Wide-specificity proteases can substantially improve the removal of such stains by
hydrolysing the water-insoluble proteins into smaller water-soluble fragments.
Unfortunately, the efficacy level of these proteins in their natural environment often
does not translate when applied to the relatively unnatural wash environment. Specifically,
protease characteristics such as thermal stability, pH stability, oxidative stability and
substrate specificity are not necessarily optimised for utilisation outside the natural
environment of the enzyme. Also, cleaning/stain removal performance and fabric care,
specifically wool/silk compatibility, are not necessarily optimised.

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Colour care
Considering a specific type of protease, for example subtilisins of B.amyloliquefaciens,

B. lentus and B. licheniformis, the amino acid sequence of the protease enzyme
determines the characteristics of the protease. Changing the sequence may alter the
properties of the enzyme to varying degrees, or even inactivate it, depending on the
location, nature and/or magnitude of the change in the sequence.
Several approaches have been taken to alter the amino acid sequence of proteases
in an attempt to improve their properties, with the goal of increasing the efficacy of the
protease for cleaning uses. These include altering the amino acid sequence to enhance
thermal stability, proteolytic activity and oxidation stability under diverse conditions.
Despite the variety of approaches described, there is a continuing need for new,
effective variants of proteases useful for cleaning a variety of fabrics, without damaging
the textile properties. US Patent 6291414 (Assignee The Procter and Gamble Company,
issue date September 2001) describes such detergent compositions as substantially free of
bleach and dye transfer inhibitors, containing high alkaline protease enzymes combining
excellent cleaning/stain removal performance to good wool and/or silk compatibility.
Bleach-free (Patented by The Procter and Gamble Company, issue date August 2007): The invention
detergent tablets relates to detergent tablets having improved bleachable-soil removal from coloured
garments without the use of bleaching agents. The object of the invention is to develop
a detergent composition in tablet form that does not comprise bleach, but that does
effectively remove bleachable, highly coloured soils, without detrimentally affecting the
colour of the garment.
Summary of the According to the invention, a bleach-free detergent tablet comprising a composition
invention providing a pH through the wash of less than 9 is provided, comprising at least one
surfactant and having an average normalised soil removal index of greater than minus 2.
According to another aspect of the invention, a bleach-free detergent tablet kit is
provided, comprising one or more tablets, wherein the composition of the tablet provides
a pH through the wash of less than 9, comprises at least one surfactant and where the
dosage weight of the kit is less than 75g.
Detergent tablet The tablets of the invention are characterised by a low pH. They provide a pH through
the wash of less than 9; more preferably a pH of between 7 and 8.9, and most preferably
between 8.3 and 8.7.
One benefit of successfully formulating a detergent at low pH is that other
ingredients that are either efficient at high pH, or added to stabilise a high pH formula,
can be removed. In order to maintain the same weight of tablet, these ingredients can
be replaced by sulphate. Although not providing any cleaning efficacy, sulphate is an
economical ingredient, allowing the manufacturer to decrease the cost of the formula.

Colour care
(It may be important to maintain the tablet weight, as costly tablet making equipment
does not have to be replaced.)
Thus, in one embodiment of the present invention, the detergent tablet composition
comprises greater than 10% alkaline or alkaline earth metal sulphate, more preferably
greater than 15% alkaline or alkaline earth metal sulphate.
Alternatively, the elimination of bleach and ingredients that are efficient only at
high pH, or are used to stabilise a high pH formula in tablets according to the present
invention, means that the tablet dosage weight can be reduced. While requiring initial
capital outlay in new or modified equipment, the eventual cost saving is greater as there
is less need for fillers, such as sulphate. Thus, in an alternative embodiment of the present
invention the dosage weight of the detergent tablet kit is less than 75g, more preferably
less than 70g, and most preferably less than 65g.
N-heterocyclic A second component of the present invention is an N-heterocyclic polymeric dye transfer
polymers inhibiting agent. Such agents are normally incorporated into detergent compositions to
inhibit the transfer of dyes from coloured fabrics onto fabrics washed therewith. These
polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed
fabrics before they have the opportunity to become attached to other articles in the wash.
Not included within this definition are components that are fabric softeners.
Especially suitable polymeric dye transfer inhibiting agents are PVP N-oxide polymers,
copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers,
polyvinyloxazolidones and polyvinylimidazoles, 4-vinyl pyridine polymers, 2-vinyl pyridine
polymers or mixtures thereof, and the like. Such polymers may or may not be quaternised.
Useful polymeric dye transfer inhibiting agents are described in US Pat.
No.5,849,684; issued on December 15, 1998 to Donoghue, et al., which is here
incorporated by reference: Preferably an alkali metal or ammonium salt of Poly
(N-carboxymethyl-4-vinylpyridinium) chloride such as the sodium salt, obtainable as
Chromabond S-100 from ISP Chemical Corp.; or PVP homopolymer obtainable from
BASF Chemical Corp. may be used.

Colour protection agents
4
Chemicals used for The appearance of coloured fabrics, for example clothing, bedding and household fabrics
colour protection like table linens, is one of the areas of concern to consumers. Indeed, upon wearing,
washing, rinsing and/or tumble drying, a loss in appearance, which is at least partly due
to loss of colour shade intensity, fidelity and colour definition, is observed. Colour loss is
even more acute in laundry treatment after multi-wash cycles, especially for dark colors,
such as blacks, reds, blues and greens.
Several mechanisms have been speculated upon for colour loss and various means
have been proposed to prevent or reduce the extent of the loss or transfer of colour.
For example, colour fixatives have been proposed, as have agents such as PVP to hold
colour materials in solution to prevent re-deposition or abrasion between fibres. Adding
bleaching agents to wash liquor has also been suggested, to bleach any dye that enters
the solution.
One cause of colour loss is the use of an inappropriate detergent composition. As
a result, many manufacturers produce colour care formulations that do not contain
bleaches. Despite this, colour damage remains a significant problem in the eyes of
consumers.
WO 00/15746 (P&G), filed September 15, 1998, and published March 23, 2000,
discloses fabric care compositions, which comprise low molecular weight polyamines
for colour care. It is believed that the polyamines intercept peroxygen bleaching. A dye
fixative may also be present in the compositions disclosed, as may an abrasion reducing
polymer, such as the N-heterocyclic polymer PVP.
A combination of a dye fixing agent, an N-heterocyclic polymer, and a nonionic
surfactant can be used as an additive in conjunction with a laundry detergent, or in
a pre-soak step to solve the problem of dark colour preservation. Dye fixing agents,
or fixatives, are well-known, commercially available materials designed to improve the
appearance of dyed fabrics by minimising the loss of dye from fabrics due to washing.
Many dye fixing agents are cationic, and are based on various quaternised or otherwise
cationically charged organic nitrogen compounds.
Cationic fixatives are available under various trade names from several suppliers,
including:
Tinofix CL, ECO, RTM, and RTM.FRD from Ciba-Geigy;
Burcofix NF and Burcoterg from Burlington Chemical;
Mirapol A-15 from Rhodia;
CROSCOLOR PMF (July 1981, code no. 7894) from Crosfield;
CROSCOLOR NOFF (January 1988, code no. 8544) from Crosfield;
INDOSOL E-50 (February 27, 1984, ref. no. 6008.35.84; polyethyleneamine-based)
from Sandoz, such as SANDOFIX TPS, and SANDOFIX SWE (cationic resinous
compound), REWIN SRF, REWIN SRF-O and REWIN DWR from CHT-Beitlich GMBH.
Other compounds that can effectively be used as dye fixing agents are ammonium
compounds, such as fatty acid-diamine condensates. Examples include the

hydrochloride, acetate, metasulphate and benzyl hydrochloride of oleyldiethyl

aminoethylamide, oleylmethyldiethylenediaminemethosulphate, monostearyl-ethylene
diaminotrimethylammonium methosulphate and oxidised products of tertiary amines;
derivatives of polymeric alkyldiamines, polyaminecyanuric chloride condensates and
aminated glycerol dichlorohydrins.
A typical amount of dye fixing agent to be employed in the composition of the
invention is preferably up to 90% by weight, more preferably up to 50% by weight, even
more preferably from 0.1% to 20% by weight, and most preferably from 1% to 10% active
by weight of the composition.
Detergents offering colour protection are in their third or fourth generation, with the
current emphasis on the consumers desire to protect and maintain dark clothing. Henkels
Black Magic and the new Woolite Dark Laundry from Reckitt Benckiser are examples of
specialty detergents that meet this need.
P&Gs Cheer with Colorguard contains a sophisticated colour-protection system. It
uses peroxide to scavenge chlorine, hydrophobically modified carboxymethylcellulose
to reduce abrasion of cotton surfaces, a cationic polymer based on imidazole and
epichlorohydrin to lock or fix dyes, and the vinylimidazole variant of polyvinylpyrrolidone
to inhibit dye transfer. The latter two technologies are also part of Tide Wear Care powder.
Ciba has marketed the Tinofix brand of dye fixatives to detergent makers for
approximately four years. In October 2002, at the 5th World Conference on Detergents in
Montreux, Switzerland, the firm announced the forthcoming launch of a new bleaching
technology, Tinocat, based on oxidation catalysis. Ciba calls Tinocat a selective catalytic
chemistry: it destroys stains by bleaching them and inhibits dye transfer by oxidising
fugitive dyes in the wash.
The manganese-based catalyst works by effectively activating sodium percarbonate
and perborate bleaches, particularly at low wash temperatures. Initial applications
will likely be in powdered laundry additives that contain these persalts, but Ciba says
researchers are working to adapt the technology for liquid detergents as well, possibly
by using it to capture and harness ambient oxygen.
Fabric evaluation The colour care benefit, with regard to shade stability and colour shifting, may be
methods assessed visually by a trained panel, by determination of the so-called delta-E values,
or by other recognised techniques.
When visual assessment is used, a panel of expert graders visually compare fabrics
treated with and without the colour care composition. Each panellist assigns five points
for the least faded example, four points for the next best, and so on when five samples
are being compared. The rank scores for all the panellists are then summed and compared
to each other. The maximum points to be assigned is set to equal the number of samples
to be compared.

4
Another useful assessment method is the determination of delta-E values.

Delta-Es are defined, for instance, in ASTM D2244, where delta-E is the computed
colour difference as defined, namely the magnitude and direction of the difference
between two psychophysical colour stimuli. This is defined by tristimulus values, or by
chromaticity coordinates and the luminance factor, as computed by means of a specified
set of colour-difference equations, defined in the CIE 1976 CIELAB opponent-colour space,
the Hunter opponent-colour space, the Friele-Mac Adam-Chickering colour space or any
equivalent colour space.

Dye transfer inhibitors
5
A dye transfer inhibitor (DTI) is pretty much as the name suggests: a substance that
prevents the transfer of dyes from one garment to another in the wash. Todays multi-
coloured (often brightly coloured) fabric loads put high demands on the laundry
detergent. In the wash, dye molecules leach out of the garments, also called bleeding,
and the extent to which this happens depends on the newness of the garment, type of
fabric, type of dye and wash conditions. The surfactants in the wash often contribute to
this bleeding phenomenon.
If such free dye molecules were to re-deposit themselves randomly on other garments,
pretty soon our brights would no longer be so bright. Bleach cannot offer a solution
in this case, because it would attack the dye molecules in solution as well as the dye
molecules on the fabric, causing bleach stains. This is where DTIs come in: they act as
dye scavengers.
How do DTIs work DTIs bind irreversibly to free dye molecules in the wash water and form water-soluble
and how are macromolecules. This way, the dyes are prevented from re-depositing onto garments
they used? and are removed with the spent wash water. DTIs may be added up to 0.5% (w/w) to
specialty powdered detergents for delicate and coloured fabrics. Such products are usually
marketed as colour care detergents, and typically these do not contain bleach or optical
brighteners (fluorescent whitening agents or FWAs). They were first introduced in Europe
in 1991.
Not all DTIs work for all dyes. Certain combinations work better than others,
depending on the chemical structures of the dye and the DTI. The most commonly used
DTIs in laundry detergents are PVP and PVP-NO.
Bleeding: In most cases, it is difficult to reverse the dye bleeding process. Most people have
what can be done? experienced this while washing clothes and forgetting the red sock in the white wash.
In the minority of cases where the bleeding is localised on the fabric, bleaching agents
can be used to remove the mobile dye. However, this rarely meets with success and a
much better approach is to avoid it.
Conclusion Dye bleeding changes the appearance of fabrics and is difficult to resolve. By far the
best approach is to avoid it completely by selecting a professional cleaning company
with trained operators. Professionals avoid dye bleeding by carrying out thorough tests
on each dye to determine the choice of cleaning agents and techniques. If you are going
to tackle a stain on your fabrics, we recommend you test your products thoroughly on an
inconspicuous area of fabric before proceeding.
N-heterocyclic The most commonly used DTI agents belong to the N-heterocyclic polymeric family.
polymers Such agents are normally incorporated to inhibit the transfer of dyes from coloured fabrics
onto fabrics washed with them. These polymers have the ability to complex or adsorb

the fugitive dyes washed out of dyed fabrics before they have the opportunity to become
attached to other articles in the wash.
Especially suitable agents are PVP N-oxide polymers, copolymers of N-vinylpyrrolidone
and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and
polyvinylimidazoles, 4-vinyl pyridine polymers, 2-vinyl pyridine polymers or mixtures
thereof, and the like.
The combination of a dye fixing agent, an N-heterocyclic polymer (as described above),
and a nonionic surfactant in conjunction with a laundry detergent, or in a pre-soak step,
effectively solves the problem of dark colour preservation. Preferably a chelating compound
is added to reduce colour shifting, especially to reduce bluing of direct red dyes when tap
water containing dissolved metals such as iron and copper is used.
Other DTI agents WO 00/15746 (P&G), filed 15 September, 1998, published 23 March, 2000, discloses fabric
care compositions, which comprise low molecular weight polyamines for colour care. It is
believed that the polyamines intercept peroxygen bleaching. A dye fixative may also be
present in the compositions disclosed, as may an abrasion reducing polymer such as the
N-heterocyclic polymer PVP. A detailed description of this patent is given below.
Water soluble dye This invention relates to dye complexing polymers, and, more particularly, to water soluble
complexing polymers poly (vinylpyridine betaines) containing a quaternary nitrogen and a carboxylate salt. The
as dye transfer polymers herein have effective dye transfer inhibitor (DTI) properties for use, for example,
inhibitors in laundry in laundry detergent and fabric softener compositions.
detergent and fabric Dye complexing polymers have been used in laundry detergent and fabric softener
softener compositions compositions. In such application, during washing a mixture of colored and white fabrics,
some of the dyes may bleed out of a colored fabric under washing conditions. The degree
of bleeding is influenced by the structure of the dye, the type of cloth and the pH,
temperature and mechanical efficiency of the agitation process.
The bled dye in the wash liquor can be totally innocuous and get washed off in the
wash liquor. However, in reality, this fugitive dye has a tendency to redeposit either onto
the same fabric or onto another fabric leading to patches and an ugly appearance of the
washed material. This redeposition of the bled dye can be inhibited in several ways. One
method is to introduce a DTI compound which can complex with the fugitive dye and get
washed off thus preventing redeposition.
Polyvinylpyrrolidone (PVP), by virtue of its dye complexation ability, has been used
to inhibit dye deposition during washing of colored fabrics under laundry conditions.
The performance of PVP as a DTI, however, is adversely affected by the presence of
anionic surfactants in the washing process. Other polymers which have been used as
DTIs in laundry detergent compositions include polyvinylpyridine N-oxide (PVPNO);
polyvinylimidazole (PVI) and copolymers of polyvinylpyridine and polyvinylimidazole
(PVP-PVI).

5
A feature of the invention is the provision of a water soluble poly (vinylpyridine

betaine) compound containing a quaternary nitrogen and a carboxylate salt in laundry
detergent and fabric softener compositions which compounds exhibit particularly effective
dye transfer inhibition properties during the washing process even in the presence
of anionic surfactants. The water soluble poly (vinylpyridine betaine) polymer of the
invention contains a quaternary nitrogen and a carboxylate salt.
A preferred polymer has a weight average molecular weight of about 5,000 to
1,000,000; preferably 20,000 to 200,000, where m is about 305,000, preferably
1001,000. Water soluble copolymers of the defined polymer above with polymerizable
monomers, such as vinyl pyrrolidone, vinyl imidazole, acrylamide and vinyl caprolactam
also are useful herein.
A preferred use of the polymer and copolymers herein are laundry detergent and
fabric softener compositions including in a dye transfer inhibiting amount. Generally, this
amount is about 21,000ppm of the polymer or copolymer. In a preferred embodiment
of the invention, the water soluble polymers of the invention are made by polymerizing
a vinylpyridine under suitable polymerization conditions to form a poly (vinylpyridine)
intermediate, and then reacting the intermediate polymer with sodium chloroacetate
in an aqueous medium. The reaction product is a poly (vinylpyridine betaine) polymer
containing a quaternary nitrogen and a carboxylate salt. In the polymerization step,
which may be solution, precipitation or emulsion polymerization, any suitable solvent
may be used, for example, an alcohol, such as methanol, ethanol or isopropanol; water;
or mixtures of water and alcohol. The reaction temperature is about 40C to 150C,
preferably 50C to 90C, and most preferably about60C to 85C.The polymerization
initiator is a free radical initiator, such as perester, peroxide, percarbonate, or VazoO type
initiators may be used. The polymerization is carried out at a solids level of about 5% to
80%, preferably 20% to 50%.
Anionic surfactants may be used in the compositions of the invention without being
affected by the presence of the DTI polymer therein.
DTI compositions Suspended or solubilised dyes can, to some degree, be oxidised in solution by employing
with specifically known bleaching agents. However, it is important at the same time not to bleach the dyes
selected metallo actually remaining on the fabrics and damage the colour. US Patent 4,077,768 describes
catalysts a process for inhibiting dye transfer by the use of an oxidising bleaching agent, together
with a catalytic compound such as iron porphins. It has now been found that specifically
selected metallo catalysts in the presence of an efficient amount of a quick releasing
bleaching agent are very efficient in preventing dye transfer.
Such dye transfer inhibition compositions comprise:
i) One or more of a specific metallo catalyst, selected from the group of porphyrins and/
or phthalocyanines; and
ii) an efficient amount of bleaching agent.

The term specific metallo catalysts encompasses one or more of a specific metallo
catalyst selected from the groups of porphyrins and/or phthalocyanines. An efficient
amount of bleach is by definition the necessary amount, which when combined with
a bleach catalyst, leads to a level of dye oxidation which is between 40% to 100%,
preferably 40% to 60%, more preferably 60% to 80%, and most preferably 80% to
100% of the maximum (Z) per cent of dye oxidation that can be achieved under the most
optimal conditions determined by those skilled in the art.
The bleaches suitable for the present invention can be activated or non-activated.
Preferably, these include peroxygen bleaches. However, DTIs based on metal catalysts are
not yet being used commercially.
An analysis of ISP has long been a player in DTI through its workhorse product, polyvinylpyrrolidone
commercially (PVP), which was commercialised in the early 1990s. In 1999, following briefings from
available DTIs several European customers, the company developed a next-generation inhibitor called
ChromaBond S-100, a patented poly(4-vinylpyridinium betaine) based on pyridine
chemistry. The new polymer is already in extensive use in Europe, and its debut by a
US laundry detergent maker was delayed due to restructuring at the company.
In October 2000, ISP added yet another DTI compound, Reillys poly-4-vinylpyridine-
N-oxide (PVNO), to its line-up. DTI application for PVNO was patented by P&G in the early
1990s and commercialised in several products around the globe. It was later licensed to
Reilly, a leader in pyridine chemistry, as part of a P&G plan to generate additional revenue
from royalties. Reilly, in turn, approached ISP, partly because of ISPs strong position in DTI
and partly because Reilly was already contract manufacturing some of ISPs ChromaBond
S-100 needs.
Each of ISPs three dye-transfer products has its own detergent formula niche: PVP is
a lower cost product for basic brands, whereas the two pyridine compounds are targeted
at different premium applications. S-100, for example, is not compatible with bleach-
containing products, whereas PVNO, now called ChromaBond S-400, is.
ISP claims leadership in dye-transfer inhibition a market it says is worth $50 million
(32 million) per year but other specialty chemical makers are pursuing DTI and the
related dye-fixation segment with equal enthusiasm.
Ciba Specialty is another firm active in colour protection, in its case largely through
dye fixative technology. One result of Cibas home care effort is its Tinofix dye fixative. In
the early part of this decade, there were reports of Ciba trying to expand beyond fixatives
into the DTI arena. Under development in Ciba research labs was an oxidative additive
that selectively destroys fugitive dyes, rather than merely complexing them as current
products do. However, there is no commercially available DTI in Cibas portfolio, and
TinoFix remains its only offering in the colour protection space.
Ciba is already finding success in the auxiliaries market with its Tinosorb UV
absorbers, designed to be added to the wash to increase the sun protection of lightweight

5
garments during the summer months. The company has marketed this product to the
detergent industry for several years, and in 1999 it launched a version targeted at fabric
softeners.
P&G is extending the colour protection concept to dryer-added fabric softener sheets
with Bounce ColorSmart, which it calls the first sheet with specific colour-protection
technology. The sheets are based primarily on a water-soluble diamine chelant that
prevents or repairs damage caused by heavy metals to coloured fabrics.
Metals such as copper, iron and manganese from water and dirt can accumulate
on fabrics during washing. The chelant in Bounce ColorSmart which patent literature
indicates may be tetrakis(2-hydroxypropyl) ethylenediamine removes the metals and
restores the dyes to their original colour.
DTI products by ISP (International Specialty Products) EU ChromaBond S-100 is a dye transfer inhibitor
International for colour-safe laundry detergents. ChromaBond S-100 is a polybetaine of aromatic
Specialty Products pyridine units, which are solubilised through conversion to a zwitterionic form. The unique
polybetaine structure plays an important role in dye binding, exhibits a higher level of
ChromaBond S-100 tolerance to the presence of anionic surfactants in the wash liquor, and performs more
effectively in the presence of non-ionic surfactants than existing DTI agents.
Chroma-Bond S-400 ISP (International Specialty Products) EU ChromaBond S-400, an oxidation product of
poly (vinyl pyridine), is a water-soluble linear polymer used as a dye transfer inhibitor. The
structural motifs of this polymer permit efficient dye binding across a diverse set of dye
structures and a wide spectrum of washing conditions.
Chroma-Bond S-403E ISP (International Specialty Products) EU ChromaBond S-403E, an oxidation product of
poly (vinyl pyridine), is a water-soluble linear polymer used as a dye transfer inhibitor.
The structural motifs of this polymer permit efficient dye binding across a diverse set of
dye structures and a wide spectrum of washing conditions.
Polyquart FDI Cognis Europe DTI for liquid laundry detergents.
The following polyvinylpyrrolidones are considered to be physiologically inert and can be

plasticised with water and most common organic plasticisers:
PVP K-120 ISP (International Specialty Products) EU applications include use as a metal quenchant
bath.
PVP K-120 Solution ISP (International Specialty Products) EU can be used as a viscosity modifier, detergent
component, media component in solution chemistry, and for the control of dyes and inks.

PVP K-120 Solution A ISP (International Specialty Products) EU can be used as a viscosity modifier, detergent
PVP K-15 ISP (International Specialty Products) EU applications include dye transfer inhibition in
detergents and on lithographic plates using hydrophobic inks.
PVP K-15 Solution A ISP (International Specialty Products) EU can be used as a viscosity modifier, detergent
Intermediate component, media component in solution chemistry, and for the control of dyes and inks.
PVP K-30 ISP (International Specialty Products) EU a versatile product with many applications.
20% Solution
PVP K-30 ISP (International Specialty Products) EU can be used as a viscosity modifier, detergent
30% Solution component, media component in solution chemistry, and for the control of dyes and inks.
30% Solution-A component, media component in solution chemistry, and for the control of dyes and inks.
PVP K-30 CI ISP (International Specialty Products) EU can be used as a viscosity modifier, detergent
PVP K-30 Fines ISP (International Specialty Products) EU can be used as a viscosity modifier, detergent
PVP K-30 G PreStep ISP (International Specialty Products) EU can be used as a viscosity modifier, detergent
PVP K-30 MB ISP (International Specialty Products) EU can be used as a viscosity modifier, detergent
PVP K-30 Solution-A ISP (International Specialty Products) EU can be used as a viscosity modifier, detergent

5
An alternative Colour catcher sheets are dye-trapping cloths that are thrown in with laundry loads
method of colour to absorb and trap the loose dyes that can stain clothes. The sheets allow mixing of
protection: colour more colours in a single laundry load, while helping to whiten the whites and keep other
catcher sheet colours vivid.
The sheets measure just over 7in by just under 7in and are a bit thicker than the
average dryer sheet, with a pleasant scent. Out of the box they are white, but after a wash
they soak up the dye so they usually end up pink or a dingy blue-grey, depending on the
colours of the clothes washed.
To use, one sheet is thrown (or two if the load is large) into the washing machine
with the laundry. The usual detergents and other laundry products are used as normal.
After the wash is complete the sheet is thrown away.
According to the manufacturer SC Johnson, it works equally well on all fabrics, at all
temperatures, and with all laundry products. SC Johnson also states that the effectiveness
cannot be guaranteed if there are large amounts of dye bleed from non-colourfast
garments, and that reasonable care should be taken when washing whites with colours or
washing new garments for the first time. It will not repair clothes that have already been
stained; it just keeps new dye stains from happening, or being as bad as they would be
without the colour catcher sheet.
SC Johnson & Son, Inc. holds the patent for this technology: A multifunctional
laundry sheet that comprises, and combines the benefits of, a color catcher, a fabric
softener, and a fragrance is disclosed. The color catcher absorbs or traps loose dye
in wash liquor during a typical wash cycle of a washing machine, thereby preventing
the re-deposition of the dye to fabrics being washed therein, while the fabric softener
enhances the appearance of fabrics during a typical drying cycle of an automatic dryer
bydecreasing static cling, increasing softness and fluffiness, or decreasing wrinkles, of
the fabrics.
Preferably, at least a portion of the catcher remains associated with the laundry
sheet during the washing and imparts visual color change to the laundry sheet after the
color catcher is affiliated with loose colorants in the laundry bath. It is also preferable
that at least a portion of the fabric softener remains associated with the laundry sheet
during the washing process so that the laundry sheet can be further used in a drying
process to impart fabric conditioning benefits to the fabrics.
A potential drawback of using the colour catcher sheet is that it also traps key
anionic detergent ingredients, thus reducing detergency.

Environmental acceptability
of colour care agents
6
The environmental impact of detergents is a well researched, legislated and regulated
issue. There are several legislations guiding the use of surfactants and other detergent
components on both sides of the Atlantic. However, these legislations are outside the
scope of this report.
The environmental impact of colour care agents is apparently a non-issue. For
example, European Commission regulation no. 648/2004 of the European Parliament
and of the Council on Detergents (which updates and consolidates existing directives
on detergents) contains no regulatory clauses on any colour care agent or dye transfer
inhibition agent used in detergents. No researched colour care agent is mentioned
in the list of 29 allergenic substances (published by the EC) found in detergents.
Polyvinylpyrrolidone, the most commonly used DTI finds mention in the EPA published
List of chemicals considered in the draft CCL3 (Contaminant Candidate List 3) Universe,
but has not been included in the final CCL3.
A report entitled Non-surfactant organic ingredients and zeolite-based detergents,
prepared in 2006 by Risk & Policy Analysts Limited for the European Commission
groups the non-surfactant detergent ingredients in 11 groups and assesses the potential
environmental concern of these groups, one of which is dye transfer inhibitors with
particular reference to polyvinylpyrrolidone. The report concludes that polyvinylpyrrolidone
is: Safe for human use and there appears to be a general consensus that PVP is of limited
environmental concern. Nevertheless, further data would be desirable to demonstrate that
PVP presents no significant environmental risks.
In the summary of risk assessment of PVP, the report states: PVP was patented
in 1939 and used, initially, in blood plasma during the Second World War before being
used more widely in the pharmaceutical industry (Schmidt, 1999). It has been used in
personal care products since 1950 and for many years has been used as a food additive.
The safety of the use of PVP as a food additive was assessed in 1966, 1973 and
1980 by a WHO/FAO committee, which established an ADI (Allowable Daily Intake) of up
to 50mg/kg bodyweight in 1987 (JECFA, 1980; SCF, 2002). In 2005, PVP was approved for
use as a (European) food additive (E1201) (BASF, 2004). In summary, PVP has been used
in consumer products for over 50 years and there is a general consensus that it is of no
concern from a human/mammalian toxicology point of view.
In relation to the environment, no specific assessments have been identified.
However, 1-vinyl-2-pydrrolodine has been the subject of an ESR RAR. Although of
limited relevance to the environmental risks of PVP, the CSTEE (2001) indicates that the
EU consumption of PVP is about 20,000 t/year. It is of note that this is substantially
greater than the figure of 3,500 t/year estimated by the SCF (2002) as discussed in S3.7.
However, it appears its use in detergents is a very minor use of PVP. There appears to be
a general consensus that PVP is of limited environmental concern due to its solubility,
low toxicity and low bioaccumulation potential. As a consequence, it is permitted in
eco-labeled detergents.

Environmental acceptability of colour care agents
The Environmental Protection Agency (EPA) has, under its Design for The Environment
Program, started a program called the Safer Detergents Stewardship Initiative(SDSI).
Through this, EPAs Design for the Environment (DfE) programme will recognise
environmental leaders who voluntarily commit to the use of safer surfactants. These
are surfactants that break down quickly to non-polluting compounds and help protect
aquatic life in both fresh and salt water. Nonylphenol ethoxylates, commonly referred to
as NPEs, are an example of a surfactant class that does not meet the definition of a safer
surfactant.
Please note: the aforementioned documents in this section are included in Chapter 7
for further reference.

Patents
7
TABLE 7.1 US patents
Title Assignee Patent date Key highlights
Liquid detergent Cognis IP 20 May 2008 Liquid compositions containing one or more anionic
comprising anionic and Management GmbH surfactants in combination with one or more polydiallyl
nonionic surfactant (Dsseldorf, Germany) dialkyl ammonium compounds or derivatives or
mixtures copolymers thereof, these compositions being suitable for
the production of liquid laundry detergents, preferably for
dye transfer inhibiting liquid color-protecting detergents.
Liquid detergent Cognis IP 20 May 2008 Liquid compositions containing one or more anionic
comprising anionic Management GmbH surfactants in combination with one or more polydiallyl
and nonionic (Dsseldorf, Germany) dialkyl ammonium compounds or derivatives or
surfactant mixtures copolymers thereof, these compositions being suitable for
the production of liquid laundry detergents, preferably for
dye transfer inhibiting liquid color-protecting detergents.
Liquid laundry The Procter & 26 February 2008 The invention is directed to aqueous liquid laundry
detergent Gamble Company detergent compositions for cleaning and imparting
compositions with (Cincinnati, OH) fabric care benefits to fabrics laundered therewith.
silicone blends as Such compositions comprise (A) at least one detersive
fabric care agents surfactant; (B) droplets of a silicone blend comprising
a nitrogen-containing amino or ammonium functionalized
polysiloxane and a nitrogen-free non-functionalized
polysiloxane; and (C) at least one additional non-silicone
laundry adjunct selected from detersive enzymes, dye
transfer inhibiting agents, optical brighteners, suds
suppressors, and combinations thereof.
Liquid laundry The Procter & 5 February 2008 The invention is directed to liquid laundry detergent
detergent Gamble Company compositions for treating non-keratinous substrates
compositions (Cincinnati, OH) under domestic wash conditions, such composition
comprising a comprise (A) at least one surfactant selected from the
silicone blend of group consisting of anionic surfactants, nonionic
non-functionalized and surfactants, zwitterionic surfactants, amphoteric
amino-functionalized surfactants, and combinations thereof; (B) a silicone
silicone polymers blend comprising a non-functionalized silicone and a
functionalized silicone; and (C) at least one additional
non-silicone laundry adjunct selected from the group
consisting of detergent builders, detersive enzymes, dye
transfer inhibiting agents, and combinations thereof.
The claimed compositions are further essentially free of
any coacervate phase-forming polymer and essentially
free of any cationic deposition aid.
Liquid laundry The Procter & 5 February 2008 The invention is directed to aqueous liquid laundry
detergent Gamble Company detergent compositions for cleaning and imparting
compositions (Cincinnati, OH) fabric care benefits to fabrics laundered therewith.
with silicone Such compositions comprise (A) at least one detersive
fabric care agents surfactant; (B) droplets of a silicone blend comprising
a nitrogen-containing amino or ammonium functionalized
polysiloxane and a nitrogen-free non-functionalized
polysiloxane; and (C) at least one additional non-silicone
laundry adjunct selected from detersive enzymes, dye
transfer inhibiting agents, optical brighteners, suds
suppressors, and combinations thereof.

Patents
TABLE 7.1 (Continued)

Compositions The Procter & 22 January 2008 The invention relates to compositions comprising
comprising complexes Gamble Company (A) a complex of cyclodextrin and at least one laundry
of cyclodextrin and at (Cincinnati, OH) treatment active wherein the complex is prepared by the
least one laundry steps of: (a) combining cyclodextrin and at least one
treatment active laundry treatment active wherein the cyclodextrin and
the laundry treatment active is dissolved, dispersed,
suspended, or emulsified in at least one solvent; and
(b) removing at least partially the solvent; (B) further
comprising at least one laundry adjunct material selected
from the group consisting of surfactants; stabilizers;
builders; perfumes; enzymes; chelating agents; suds
suppressors; colors; opacifiers; anti-oxidants; bactericides;
neutralizing agents; buffering agents; phase regulants,
dye transfer inhibitors, hydrotropes, thickeners, and
mixtures thereof.
Liquid laundry Conopco, Inc., d/b/a 6 November 2007 An aqueous liquid laundry detergent composition
detergent with an Unilever (Englewood comprising an alkoxylated carboxylic acid surfactant and
alkoxylated ester Cliffs, NJ) a free radical scavenger in the mole ratio of from about
surfactant 500:1 to about 20:1. The composition substantially
prevents the degradation of the alkoxylated ester
surfactant upon storage and is also color-stable.
Laundry detergents Clariant GmbH 15 August 2006 The following dye transfer inhibiting dye fixatives are
and laundry (Frankfurt, Germany) used in laundry detergents which comprise nonionic
treatment surfactants: reaction products of a) amines with
compositions epichlorohydrin or b) cyanamide with amines and
comprising dye aldehydes.
transfer inhibiting
dye fixatives
Laundry detergents Clariant GmbH 22 February 2005 The following dye transfer inhibiting dye fixatives are
and laundry (Frankfurt, Germany) used in laundry detergents: reaction products of
treatment a) polyamines with cyanamides and amidosulfuric acid, or
compositions b) cyanamides with aldehydes and ammonium salts, or
comprising one or c) amines with epichlorohydrin.
more dye transfer
inhibiting dye
fixatives
Color safe laundry The Procter & 30 November 2004 The invention relates to cationic organic catalyst
methods employing Gamble Company compound bleach systems and methods using such
cationic formulation (Cincinnati, OH) bleach systems to increase color safety during laundering
components fabrics, especially colored fabrics. More particularly,
this invention relates to bleach systems comprising
cationic, quaternary imine bleach boosting compounds,
cationic, quarternary oxaziridinium bleaching species and
mixtures thereof, and methods employing such bleach
systems in the laundering of fabrics, especially colored
fabrics.

7
Patents

Color safe laundry The Procter & 23 November 2004 The invention relates to zwitterionic organic catalyst
methods employing Gamble Company compound bleach systems and methods for using such
zwitterionic formulation (Cincinnati, OH) bleach systems to increase color safety during laundering
components of fabrics, especially colored fabrics.
Laundry detergent The Procter & 12 October 2004 Detergent compositions are formulated with a mixture
compositions with Gamble Company of hydrophobically modified cellulose polymers or
fabric enhancing (Cincinnati, OH) oligomers and cyclic amine based polymers or oligomers.
component The cellulose/amine mixture maintains the integrity and
appearance of fabrics laundered in the compositions.
Dye maintenance and anti-pilling benefits are provided.
The compositions are provided in containers, which alert
the user of the benefits provided by the compositions.
Detergent The Proctor & 14 September 2004 The invention relates to a laundry detergent composition
compositions Gamble Company comprising an anionically modified cellulose (AMC);
having an (Cincinnati, OH) and a cationic metal ion. The molar ratio of the
anionically modified anionically modified group of the AMC to the cationic
cellulose polymer metal ion is preferably from about 50:1 to about 1:50.
The laundry detergent composition containing such
materials maintain a good fabric appearance, such as
better pill/fuzz prevention and color maintenance.
Laundry detergent The Procter & 22 June 2004 A detergent composition comprising from about 4% to
compositions with Gamble Company about 70% of a surfactant, and from about 0.05% to
a cationically (Cincinnati, OH) about 10% of a dye maintenance polymer or oligomer
charged dye having at least three net positive charges per molecule.
maintenance polymer The dye maintenance polymer should have a Dye
Maintenance Parameter, as determined by the Dye
Maintenance Parameter Test defined herein, of greater
than about 0.23. Further, the dye maintenance polymer
is not a polyethyleneimine or alkoxylated derivative
thereof.
Laundry detergent The Procter & 11 May 2004 The invention relates to laundry detergent compositions
compositions with Gamble Company providing dye protection benefits to fabric comprising:
certain cationically (Cincinnati, OH) a) from about 4% to about 70% by weight, of a
charged dye surfactant; b) from about 0.01% by weight, of a dye
maintenance polymers maintenance polymer or oligomer, said polymer or
copolymer comprising one or more linearly polymerizing
monomers, cyclically polymerizing monomers, and
mixtures thereof; and c) the balance carriers and adjunct
ingredients.

Patents

Laundry compositions Reckitt Benckiser NV 25 November 2003 A laundry composition, preferably to be used in addition
(Hoofddorp, Netherlands) to a laundry detergent, comprising an acidic peroxidic
liquid, and particles suspended in the liquid. The
particles comprise a protective coating around a core
which includes at least one active ingredient selected
from a chelating agent, a dye transfer inhibitor, an
anti-fading agent, an anti-bacterial agent, a fabric
softener, a transition metal compound and an optical
brightener. The particles are stable in the acidic peroxidic
liquid but dissolve or disperse under alkaline washing
conditions. Surprisingly incorporation of active
ingredient(s) into particles appears to give better washing
results than the dissolution of such active ingredients in
such a liquid.
Laundry Reckitt Benckiser NV 17 June 2003 A laundry composition, preferably to be used in addition
compositions (Hoofddorp, Netherlands) to a laundry detergent, comprising an acidic peroxidic
liquid, and particles suspended in the liquid.
The particles comprise a protective coating around a core
which includes at least one active ingredient selected
from a chelating agent, a dye transfer inhibitor, an
anti-fading agent, an anti-bacterial agent, a fabric
softener, a transition metal compound and an optical
brightener. The particles are stable in the acidic peroxidic
liquid but dissolve or disperse under alkaline washing
conditions. Surprisingly incorporation of active
ingredient(s) into particles appears to give better washing
results than the dissolution of such active ingredients in
such a liquid.
Method of The Procter & 19 February 2002 Disclosed is a method of laundering soiled fabrics
laundering soiled Gamble Company comprising the steps of contacting said fabric in an
fabrics by (Cincinnati, OH) aqueous laundering solution with a non-aqueous
non-aqueous detergent liquid detergent composition containing from about
formulated to control 40% to about 99% by weight of the composition of
dye transfer and sudsing a surfactant-containing non-aqueous liquid phase and
in high efficiency from about 1% to about 50% by weight of the
washing machines composition of particulate material which is substantially
insoluble in said liquid phase and which is selected from
peroxygen bleaching agents, bleach activators, organic
detergent builders, inorganic alkalinity sources and
combinations thereof. A dye transfer inhibitor and suds
suppressors are essential components in one aspect of
the present invention. The detergent composition is added
to the aqueous solution in a washing machine at a
concentration in the aqueous solution of from 2,000ppm
to about 10,000ppm, wherein from about 3 gallons to
about 8 gallons of water is used to form the aqueous
solution, said fabric to water weight ratio is from about
1:1 to about 1:10 and said fabrics undergo a wash time
of from about 6 minutes to about 34 minutes.

7
Patents

Bleaching and dye Unilever Home & 22 January 2002 A bleaching composition for laundry fabrics is provided,
transfer inhibiting Personal Care USA, comprising: a bleach catalyst comprising a ligand which
composition and division of Conopco, forms a complex with a transition metal, the complex
method for laundry Inc. (Greenwich, CT) catalysing bleaching of stains in the absence of
fabrics peroxygen bleach or a peroxy-based or -generating
bleach system; and a dye transfer inhibition agent,
and wherein the composition is substantially devoid of
peroxygen bleach or a peroxy-based or -generating
bleach system. The bleaching composition provides
effective bleaching performance on fabric stains without
unacceptable transfer of dyes between fabrics.
Detergent The Procter & 18 September 2001 The invention relates to a detergent composition having
composition Gamble Company a wool compatible high alkaline protease with at least
containing wool (Cincinnati, OH) one mutation in each of the regions 96110 and
compatible high 123135 according to the BPN-numbering. The
alkaline proteases detergent composition is preferably substantially free of
bleach and does contain so-called dye transfer inhibition
technology.
Dye-transfer-inhibiting Unilever Home & 14 August 2001 A free-flowing granular polymer composition suitable for
compositions and Personal Care USA, incorporation into a particulate detergent composition
particulate detergent division of Conopco, comprises a defined dye transfer inhibiting polymer,
compositions containing Inc. (Greenwich, CT) preferably poly(4-vinylpyridine) sodium carboxymethyl
them betaine chloride, and a silica-based carrier material.
A preferred carrier material is an acidic silica. The
silica-based carrier material may optionally comprise a
solid acid, for example, polyacrylic acid or phthalic acid.
Detergent The Procter & 14 August 2001 A cleaning composition comprising: a) about 0.1% to
compositions Gamble Company about 99.9% by weight of said composition of an
containing mixtures (Cincinnati, OH) alkylarylsulfonate surfactant system comprising from
of crystallinity-disrupted about 10% to about 100% by weight of said surfactant
surfactants system of two or more crystallinity-disrupted
alkylarylsulfonate surfactants of formula; b) from about
0.00001% to about 99.9% by weight of said
composition of cleaning composition adjunct ingredients,
at least one of which is selected from the group
consisting of: i) detersive enzymes; ii) organic detergent
builders; iii) oxygen bleaching agent; iv) bleach activators;
v) transition metal bleach catalysts; vi) oxygen transfer
agents and precursors; vii) polymeric soil release agents;
viii) water-soluble ethoxylated amines having clay
soil removal and anti-redeposition properties; ix)
polymeric dispersing agents; x) polymeric dye transfer
inhibiting agents; xi) alkoxylated polycarboxylates; and
xii) mixtures thereof.

Patents

Use of quaternized BASF Aktiengesellschaft 26 December 2000 The use of polymers which comprise at least 5 mol %
polymerizates (Ludwigshafen, Germany) of quaternized 1-vinylimidazole as color-fixing and color
containing units of transfer-inhibiting additive to laundry after-treatment
vinyl imidazol as a color aids and to detergents
fixing and color transfer
inhibiting additive to
detergent post-treatment
agents and detergents .
Detergent Genencor 19 December 2000 Detergent with cellulase compositions containing one or
compositions International, Inc. more endoglucanase components and less than about
containing cellulase (Palo Alto, CA) 5 weight percent of CBH I type components. When
compositions incorporated into detergent compositions and used
deficient in CBH I in acidic, neutral, or alkaline washing media, such
type components cellulase compositions impart color retention/restoration
properties as well as improved softening properties to
cotton-containing fabrics. Additionally, such compositions
impart reduced strength loss to cotton-containing fabrics
as compared to cellulase compositions containing greater
amounts of CBH I type components.
Detergent having The Dial 19 December 2000 A carbonate-based detergent having improved properties
improved color Corporation is provided. Preferably, a base detergent includes an
retention properties (Scottsdale, AZ) alkali metal carbonate builder, an anionic surfactant,
an inert diluent, a copolymer, and a chlorine scavenger.
The base detergent is mixed with an agglomerate,
including nonionic surfactants and a builder such as an
alkali metal carbonate. The detergent has improved color
retention properties. A method of preparing the improved
detergent composition is also provided.
Process for The Procter & 17 October 2000 Process for making a free-flowing, particulate dye transfer
making a Gamble Company inhibiting detergent admix for inclusion in a granular
free-flowing (Cincinnati, OH) laundry detergent composition consisting essentially of
particulate dye the steps of: charging from 50% to 95%, by weight of
transfer inhibiting the dye transfer inhibiting detergent admix, of a
detergent admix detergent builder into a mixer/granulator; adding to
the detergent builder from 5% to 50%, by weight of the
dye transfer inhibiting detergent admix, of a dye transfer
inhibitor solution to thereby form a mixture; and
agglomerating the mixture of the dye transfer inhibitor
solution and the detergent builder so as to form the dye
transfer inhibiting detergent admix.
Detergent Lever Brothers 19 September 2000 Overcomes a persistent problem that in a detergent
composition Company, division composition it is difficult to formulate a composition that
comprising dye of Conopco, Inc. mitigates both photo-fading and dye transfer of fabrics
transfer inhibiting (New York, NY) and yet increases the UV barrier of fabrics due to the
polymer and incompatibility of the active agents used.
water soluble
sunscreen

7
Patents

Detergent Lever Brothers 19 September 2000 A detergent composition having excellent color care
composition Company, division properties when used to launder colored fabrics.
comprising dye of Conopco, Inc. The composition comprises a dye transfer inhibiting
transfer inhibiting (New York, NY) polymer comprising one or more monomeric units
polymer and water containing at least one .dbd.NC(.dbd.O) with the proviso
soluble sunscreen that the dye transfer inhibiting agent does not comprise
an oxide group and a water soluble sunscreen.
Dye-transfer-inhibiting Unilever Home 12 September 2000 A free-flowing granular polymer composition suitable
compositions and & Personal Care for incorporation into a particulate detergent composition
particulate detergent USA (Greenwich, CT) comprises a defined dye transfer inhibiting polymer,
compositions preferably poly(4-vinylpyridine) sodium carboxymethyl
containing them betaine chloride, and a carrier material comprising zeolite
and a solid acid, for example, polyacrylic acid.
Use of polycationic BASF Aktiengesellschaft 15 February 2000 Polycationic condensates obtainable by condensing
condensation (Ludwigshafen, Germany) piperazine used as color transfer inhibiting and color
products as release reducing additive, and fabric conditioners which
an additive for comprise a fabric softener, a nonionic surfactant
detergents or and 0.12.5% by weight of said polycationic
detergent after condensates.
treatment agents
in order to inhibit
running of colors
and to reduce color
loss
Rinse added The Procter & 7 December 1999 The invention relates to rinse-added laundry additive
laundry additive Gamble Company compounds having a color care agent and to methods for
compositions (Cincinnati, OH) using the compositions. The laundry additive composition
having color comprises from about 0.1% to about 50% of by
care agents weight of the composition of a color care agent.
Detergent Lever Brothers 2 November 1999 A detergent composition suitable for washing colored
composition Company, division fabrics. The composition comprises: a) a N-vinylimidazole
of Conopco, Inc. N-vinylpyrrolidone copolymer (PVP/PVI) in an amount
(New York, NY) effective to inhibit dye transfer between fabrics during
the wash; and b) an organic surfactant system comprising
(i) alkylbenzene sulphonate, (ii) a nonionic surfactant in
which the ratio of (i) to (ii) is from 7:3 to 99:1.
Detergent having The Dial 5 October 1999 A carbonate-based detergent having improved
improved color Corporation properties is provided. Preferably, a base detergent
retention properties (Phoenix, AZ) includes an alkali metal carbonate builder, an
anionic surfactant, an inert diluent, a copolymer, and
a chlorine scavenger. The base detergent may be mixed
with an agglomerate including nonionic surfactants
and a builder such as an alkali metal carbonate.
The detergent has improved color retention properties.
A method of preparing the improved detergent
composition is also provided.

Patents

Dryer-activated The Procter & 24 August 1999 The invention relates to dryer-activated laundry additive
laundry additive Gamble Company compositions and products having a color care agent and
compositions (Cincinnati, OH) to methods for using the compositions and products.
with color care The dryer-activated laundry additive composition
agents comprises from about 0.1% to about 50% of by weight
of the composition of a color care agent having the
formula: wherein X, R.sub.1, R.sub.2, R.sub.3 and R.sub.4
are as defined within. Optional ingredients include a
quaternary ammonium fabric softening compound, a
cyclodextrin, or a perfume. Products according to the
invention involved the color care composition described
above disposed on a substrate such as a sheet.
Detergent The Procter & 13 July 1999 The invention relates to a detergent composition
composition Gamble Company having a wool compatible high alkaline protease with
containing wool (Cincinnati, OH) at least one mutation in each of the regions 96110 and
compatible 123135 according to the BPN-numbering. The
detergent composition is preferably substantially free of bleach
high alkaline and does contain so-called dye transfer inhibition
proteases technology.
Detergent The Procter & 6 July 1999 The invention relates to a detergent composition
composition Gamble Company which comprises a nonionic polysaccharide ether, a
comprising (Cincinnati, OH) surfactant, a dye transfer inhibition agent, a cellulase
cellulase enzyme enzyme and a chelating agents. In addition the invention
and nonionic further relates to a method of treating fabrics with
cellulose ether the detergent composition.
Laundry detergent The Procter & 15 June 1999 The invention relates to laundry detergent compositions
composition Gamble Company which are suitable for use in inhibiting the re-deposition
comprising (Cincinnati, OH) of fugitive dyes onto fabric during the course of the
substantially laundry process, said compositions comprising:
water-insoluble a) 0.01% to 3% by weight, of a substantially
polymeric dye water-insoluble polymeric dye transfer inhibiting agent,
transfer said agent consisting of a substantially water-insoluble
inhibiting agent cross linked polymer selected from the group consisting
of polyamine N-oxide polymers; copolymers of
N-vinylpyrrolidone and N-vinylimidazole;
polyvinylpyrrolidones; polyvinyloxazolidones;
polyvinylimidazoles; and mixtures thereof; wherein said
agents have a particle size less than 50 microns; b) from
0.2% to 25% by weight of a surfactant system, said
surfactant system comprising one or more detersive
surfactants selected from the group consisting of anionic,
nonionic, cationic, zwitterionic, ampholytic surfactants,
and mixtures thereof; and c) the balance carriers and
adjunct ingredients. The compositions of the present
invention are also compatible with peroxygen, as well as,
hypochlorite bleaching systems.

7
Patents

Rinse added The Procter & 23 February 1999 The invention relates to rinse-added laundry additive
laundry additive Gamble Company compositions having a color care agent and to methods
compositions (Cincinnati, OH) for using the compositions. The laundry additive
having color care composition comprises from about 0.1% to about 50%
agents of by weight of the composition of a color care agent.
Detergent Lever Brothers 16 February 1999 The main drawback of traditional compositions* in
compostion Company, division preventing dye transfer is that they exert a rather
of Conopco, Inc. strong direct fabric bleaching effect, tending to cause
(New York, NY) fading of the coloured fabrics. The present invention
is based on the discovery that dye transfer can be further
prevented by the use of certain macromolecular
compounds not previously used in detergent compositions.
Laundry detergent ISP Investments Inc. 26 January 1999 A laundry detergent composition suitable for washing
compositions (Wilmington, Germany) colored fabrics includes a water soluble
containing poly(4-vinylpyridine betaine) polymer containing a
water soluble dye quaternary nitrogen and a carboxylate salt as a dye
complexing polymers transfer inhibitor therein.
Detergent The Procter & 15 December 1998 Free-flowing powder detergent additives particularly
additives Gamble Company useful as agglomerates to be added during the
comprising dye (Cincinnati, OH) manufacture of detergents suitable for washing colored
transfer inhibitors, fabric and which contain certain detergent builders, dye
and process for transfer inhibiting polymers and optionally a detersive
making them surfactant. Also disclosed are methods for preparing
a premix of specific hygroscopic dye transfer inhibitors for
use in a spray-drying powder formation process.
The compositions utilized for such premixes include
a powder builder such as zeolite and the dye transfer
inhibition polymers polyamine N-oxide, and copolymers
of N-vinylpyrrolidone and N-vinylimidazole.
Use of BASF Aktiengesellschaft 8 December 1998 There are described the use of copolymers obtainable by
vinylpyrrolidone and (Ludwigshafen, Germany) free-radically initiated copolymerization of monomer
vinylimidazole mixtures comprising (a) 6099% by weight of
copolymers as 1-vinylpyrrolidone, 1-vinyl-imidazole or mixtures thereof,
detergent additives, (b) 140% by weight of nitrogen-containing, basic
novel polymers of ethylenically unsaturated monomers in the form of the
vinylpyrrolidone free bases, in the form of salts or in quaternized form,
and of vinylimidazole, and optionally (c) up to 20% by weight of other
and preparation thereof monoethylenically unsaturated monomers, as detergent
additives for inhibiting dye transfer during the wash,
detergents which contain such polymers, and polymers
which are obtainable by free-radically initiated
polymerization of (a) 1-vinylpyrrolidone, 1-vinylimidazole,
1-vinylimidazolium compounds, or mixtures thereof.
Detergent The Procter & 27 October 1998 Detergent compositions having color care agents are
compositions Gamble Company provided. The detergent compositions comprise from
having color (Cincinnati, OH) about 0.1% to about 50% by weight of the composition
care agents of a color care agent having the formula wherein X is
selected from the group consisting of hydrogen, linear or
branched; substituted or unsubstituted alkyl having from
110 carbons atoms.

Patents

Color-safe The Procter & 6 October 1998 Bleach boosters comprising quaternary imine
bleach boosters, Gamble Company zwitterions are disclosed. The bleach boosters increase
compositions and (Cincinnati, OH) bleaching effectiveness in lower temperature solutions
laundry methods and demonstrate superior color safety profiles. The bleach
employing same boosters are ideally suited for inclusion into bleaching
compositions including those with detersive surfactants
and enzymes. Also provided is a laundry additive product
including quaternary imine zwitterions. A method for
laundering a fabric employing the bleach boosters of the
present invention is also disclosed.
Detergent The Procter & 8 September 1998 Disclosed are detergent compositions and methods
compositions Gamble Company suitable for washing colored fabrics in aqueous washing
with optimized (Cincinnati, OH) solution with little or no transfer of dye between fabrics.
surfactant The compositions utilized comprise certain nil-LAS
systems to provide detersive surfactants, detergent builder and certain
dye transfer selected polymeric dye transfer inhibiting agents.
inhibition benefits The detersive surfactants used must comprise alkyl ether
sulfates and certain types of nonionic surfactants
(polyhydroxy fatty acid amides and/or alcohol
ethoxylates). The polymeric dye transfer inhibiting agents
are polyamine N-oxides such as poly(4-vinylpyridine-N-
oxide), i.e., PVNO and/or copolymers of
N-vinylpyrrolidone and N-vinylimidazole, i.e., PVPVI.
Dryer-activated The Procter & 8 September 1998 The invention relates to dryer-activated laundry additive
laundry additive Gamble Company compositions and products having a color care agent,
compositions (Cincinnati, OH) and to methods for using the compositions and products.
with color The dryer-activated laundry additive composition
care agents comprises from about 0.1% to about 50% by weight
of the composition of a color care agent. Optional
ingredients include a quaternary ammonium fabric
softening compound, a cyclodextrin, or a perfume.
Products according to the invention involved in the color
care composition described above are disposed on a
substrate such as a sheet.
Laundry additive 4 August 1998 Laundry additive compositions and methods for their use
compositions are provided. The compositions include a dispersible
including dispersible polyolefin, preferably polyethylene, and at least one
polyolefin compound selected from the group consisting of dye
fixative agents, chelating agents, dye transfer inhibiting
agents, chlorine scavenging agents, free radical
scavenging agents, cellulase enzymes, and mixtures
thereof. Preferably, the composition is a liquid
composition added to the rinse cycle of a consumer
laundry process or to a pre-treatment cycle before a
wash cycle of a consumer laundry process.
Stable liquid The Procter & 21 July 1998 The present invention relates to inhibiting dye transfer
detergent Gamble Company compositions comprising: (A) from 0.01% to 5% of a
compositions (Cincinnati, OH) polyamine N-oxide polymer, (B) from 0.01% to 1% of a
inhibiting dye brightener, and (C) from 5% to 30% of a non-aromatic
transfer anionic surfactant.

7
Patents

Color-safe The Procter & 20 January 1998 Bleach boosters comprising zwitterionic imines and
bleach boosters, Gamble Company anionic imine polyions having a net negative charge are
compositions and (Cincinnati, OH) disclosed. The bleach boosters increase bleaching
laundry methods effectiveness in lower temperature solutions and
employing same demonstrate superior color safety profiles. The bleach
boosters are ideally suited for inclusion into bleaching
including zwitterionic imines and anionic imine polyions
with a net negative charge as bleach boosters. A method
for laundering a fabric employing the bleach boosters of
the present invention is also disclosed.
Laundry composition The Procter & 13 January 1998 Laundry compositions, specifically fabric-conditioning
containing dye Gamble Company compositions, to be used in the rinse cycle of laundry
fixatives and (Cincinnati, OH) washing processes, are disclosed in order to improve color
cellulase depth maintenance of colored fabrics upon single or
multiple washing cycles. To achieve this, specific levels of
cellulase and dye-fixing agents of the cationic type as
well are used in the laundry compositions.
Laundry article for The Clorox Company 16 December 1997 A system for removing extraneous, random free-flowing
preventing dye (Oakland, CA) dyes from laundry washing applications, which comprises
carry-over and a novel unitary dosing laundry article that can freely
indicator therefore circulate among items being laundered. The laundry
article further comprises a dye absorber and a dye
transfer inhibitor, which are introduced into a wash
liquor via a support matrix. The dye absorber maintains
a relational association with the support matrix in
the wash liquor, whereas the dye transfer inhibitor is
delivered up from the support matrix to the wash liquor
and may be evenly distributed throughout the wash
liquor. The laundry article of the present invention
provides a method for preventing the redeposition of
extraneous dyes onto other wash items, while
simultaneously providing an indicator system for the
manifestation of such scavenging process.
Grafted BASF Aktiengesellschaft 14 October 1997 Grafted polyamidoamines and grafted polyethyleneimines
polyamidoamines (Ludwigshafen, Germany) obtainable by free-radically initiated polymerization of
and grafted (a) 1-vinylpyrrolidone, 1-vinyltriazole, 1-vinylimidazoles,
polyethyleneimines, mixtures of said monomers, or mixtures of at least one of
preparation thereof, said monomers, with up to 20% by weight of other
and use thereof as monoethylenically unsaturated monomers in the
detergent additives presence of (b) water-soluble or -dispersible
polyamidoamines, polyethyleneimines or mixtures there
of in a weight ratio of (a):(b) from 5:95 to 95:5. These
are useful as dye transfer inhibitors in surfactant-based
detergents when included therein in an amount from
0.05 to 10% by weight.

Patents

Detergent The Procter & 27 May 1997 The invention relates to a dye transfer inhibiting
compositions Gamble Company detergent composition comprising a) 0.0001% to 10%
inhibiting dye (Cincinnati, OH) by weight of a dye transfer inhibitor having a ratio of
transfer amine to amine N-oxide of from about 2:3 to about
1:1,000,000, selected from the group consisting of
poly(2-vinylpyridine-N-oxide), poly-2-(dimethylamino)-
ethylmethacrylate-N-oxide and poly-1-vinylimidazole-N-
oxide; and b) a detersive effective amount of a
surfactant; and c) a detersive effective amount of a
builder.
Use of BASF Aktiengesellschaft 6 May 1997 There are, described, the use of copolymers obtainable by
vinylpyrrolidone (Ludwigshafen, Germany) free-radically initiated copolymerization of monomer
copolymers as mixtures comprising (a) 6099% by weight of
detergent additives, 1-vinylpyrrolidone, 1-vinylimidazole, or mixtures thereof;
novel polymers of (b) 140% by weight of nitrogen-containing, basic
vinylpyrrolidone, ethylenically unsaturated monomers in the form of the
and preparation free bases, in the form of salts or in quaternized form;
thereof and optionally (c) up to 20% by weight of other
monoethylenically unsaturated monomers, as detergent
additives for inhibiting dye transfer during the wash.
Detergent The Procter & 28 January 1997 The present invention relates to an inhibiting dye transfer
compositions Gamble Company composition comprising Polyamine N-oxide containing
inhibiting dye (Cincinnati, OH) polymers and terephthalate polymers.
transfer
Color-safe The Procter & 19 November 1996 Bleach boosters comprising zwitterionic imines and
bleach boosters, Gamble Company anionic imine polyions having a net negative charge are
compositions and (Cincinnati, OH) disclosed. The bleach boosters increase bleaching
laundry methods effectiveness in lower temperature solutions and
employing same demonstrate superior color safety profiles. The bleach
boosters are ideally suited for inclusion into bleaching
including zwitterionic imines and anionic imine polyions
with a net negative charge as bleach boosters. A method
for laundering a fabric employing the bleach boosters of
the present invention is also disclosed.
Detergent The Procter & 12 November 1996 Dye transfer inhibiting compositions are disclosed,
compositions Gamble Company comprising: (A) an iron catalyst selected from a) iron
inhibiting dye (Cincinnati, OH) porphin and water-soluble or water-dispersable
transfer in derivatives thereof; b) iron porphyrin and water-soluble
washing or water-dispersable derivatives thereof; c) iron
phthalocyanine and water-soluble or water-dispersable
derivatives thereof; (B) an enzymatic system capable of
generating hydrogen peroxide.

7
Patents

Process and Rohm and Haas 9 July 1996 This invention provides a process for preventing dye from
laundry Company (Phila., PA) transferring from one fabric to the same or different
formulations for fabric in a laundry process. This invention also provides
preventing the dye transfer inhibiting agents formulated into laundry
transfer of dye in detergent and fabric softening formulations. More
laundry processes specifically, a process is provided where 1) an aqueous
bath is formed comprising a) water, b) dyed fabric, and
c) a dye transfer inhibiting agent, 2) the dyed fabric
is laundered in the aqueous bath and the fabric releases
a portion of the dye from the dyed fabric into the bath,
and 3) the dye transfer inhibiting agent is maintained
in contact with the dyed fabric for the duration of the
laundering step. The laundry detergent and fabric
softening formulations are comprised of 0.1% to 15%
by weight of one or more dye transfer inhibiting agents.
Source: http://patft.uspto.gov/netahtml/PTO/search-adv.htm
Commentary on The US Patent database was searched with the following representative search strings:
patents TTL/detergent and ABST/colour
TTL/colour and (detergent or laundry)
TTL/(detergent or laundry) and ABST/dye and (transfer or maintenance).
Patents granted in the past 12 years in the field of colour protection and dye transfer
inhibition were analysed. A total of 59 patents have been granted during this period,
with The Procter & Gamble Company having an overwhelmingly large share of the patents
granted.
PVP and its derivatives continue to be the preferred agents for inhibiting dye transfer,
though some attempts were made by manufacturers to introduce substitutes, e.g.
acrylamide-containing polymers acting as DTIs. However, a significant disadvantage of
the DTIs commercially available hitherto is that they not only bind the dye detached from
the textiles and present in the wash liquor, but can also remove dyes from the textiles
and promote fading of the washed coloured fabric. Hence, in the past five years, we have
witnessed activity in the area of DTI technology that takes care of this adverse effect of
traditional agents.
US Patent number 6858570 describes reaction products of a) polyamines with
cyanamides and amidosulfuric acid, or b) cyanamides with aldehydes and ammonium
salts, or c) amines with epichlorohydrin, used as effective DTIs.
Mitigation of colour loss or dye damage is a key element of fabric care. Historically,
leaching of dyes from fabric produced an inexorable fading problem, which has been
largely overcome by the use of modern fabric substantive dyes inter alia azo dyes.
One drawback of azo dyes relates to the interaction of these dye molecules with
heavy metals found in water. Dissolved metals interact with fabric dye molecules, thereby

Patents
shifting the fabric dye emission spectra and producing a diffuse, rather than a sharp,
narrow emission band hue. Although the dye molecule itself is still present on the fabric,
the result of this heavy metal/dye interaction is colour loss or fabric fading.
Polyamine chelants inter alia polyethyleneimines have been used as chelants
to suppress the activity of unwanted heavy metals. However, one drawback to the use
of polyamines is their capacity to also chelate metal atoms, which are a part of the dye
molecule itself, e.g. phthalocyanine dyes. This chelation of dye-based metals also results in
the attenuation of fabric colour. One solution is to strictly limit the amount of polyamine
chelant used in detergent formulation to an amount that is sufficient only to chelate and
remove unwanted heavy metals in the laundry liquor.
Polyamines that serve as chelating agents are also effective scavengers of fugitive
bleaches. Bleaches are damaging to dyed fabric because they can chemically alter dye
molecules, thereby producing non-coloured molecules. The polyamines scavenge bleaches
by reacting with them to form N-oxides or N-chloro polyamines, depending upon the
type of fugitive bleach. The reaction of polyamines with bleaches produces a modified
polyamine, thereby reducing or otherwise nullifying the usefulness of the polyamine as a
chelant. Therefore, the formulator is left with the problem of deciding the proper amount
of chelant to use.
Not every consumer will be faced with the same level of fugitive bleach, therefore,
a formulation which anticipates heavy bleach scavenging will provide excess polyamine
in a non-bleach context, and an excess of polyamine, which can react pejoratively with the
fabric dye molecules. On the other hand, a composition comprising an insufficient amount
of polyamine chelant will not have a sufficient amount present to insure chelation of
unwanted heavy metals, and thereby ameliorate any colour loss due to heavy metal/
fabric dye association.
There has been a long-felt need for a laundry detergent composition or fabric care
additive composition that will effectively mitigate the fabric dye damage caused by
fugitive bleaches, while allowing the formulation of polyamine chelants in an amount
necessary to remove unwanted heavy metal ions.
Patent action in this direction has been in the field of certain sulphur-containing
compounds, which are effective bleach scavenging agents, e.g. P&Gs patent 7074752,
and also in the area of cationically charged dye maintenance polymers, e.g. P&Gs
patent 6753307.
Overall, patenting activity has been lethargic in this field. Barring a few instances of
an innovative new agent being patented, most of the patented detergent compositions
have dye transfer inhibitors and colour care agents as the standard agents used.

Technology trends
8
The bulk of the detergent composition is made up of some core ingredients surfactant,
builders, etc. However, the core ingredients are generally not the ones that differentiate
one specific detergent from another. Hence, if detergent manufacturers do not innovate,
detergents run the risk of being commoditised. Hence, a key challenge for the detergent
industry is to innovate constantly in order to avoid the commoditisation, and to build
consumer preferences.
Detergent compositions can be represented in the form of a pyramid wherein,
the base of the pyramid represents the core ingredients, and the higher levels represent
the speciality ingredients. These ingredients can be broadly classified into a number of
categories:
Cleanliness: the very basic value of detergents is getting clothes clean. Hence,
cleanliness is the very foundation of the hierarchy;
Whiteness: this is an important detergent deliverable in the minds of consumers;
Stain removal: the third basic category. Common claims that express this functionality
include removes fatty stains or effective stain removal at low temperatures; and
Care: as some of the more sophisticated ingredients, colour care and fabric care are
at the top of the pyramid.
The core ingredients do not differentiate one specific detergent from another at the
consumer level. In contrast, the specialty ingredients are usually the ones which support
detergent product innovation and brand differentiation. Even though they actually
represent a smaller fraction of the total detergent costs, the power ingredients are usually
the most valuable from a brand building point of view.
Detergent manufacturers have differentiated their products based on these power
ingredients. When white clothing was all the rage, manufacturers launched detergents
with bleach; when environment-friendly products were in demand, detergents with
ingredients capable of delivering benefits in cold water were on the shelves; when
researchers discovered that the consumer had sensitive skin, they created detergents
without dyes or perfumes. Now, manufacturers are taking on dry cleaning, testing
eco-friendly retail options and launching pocketbook-friendly at-home solutions for
taking care of delicate apparel.
The power ingredients, of which colour care agents are a part, give the brand the
competitive edge. However, innovations in this category have been painfully slow. More
often than not, a detergent manufacturer claiming to have cracked the code of making
a dye-friendly detergent is merely removing the bleaching agent from the detergent
composition and not adding a path-breaking new agent which will act as a dye fixative.
(As is the case with Ariel Excel Gel, Color and Style, which is essentially a bleach-free
detergent, hence with the ability to wash in cold water.) Furthermore, in the dye transfer
inhibiting agents space, PVP continues to be the preferred agent and not much innovation
has happened here.

Technology trends
The following section discusses various colour safe detergent offerings by some of the
leading detergent manufacturers:
Henkel
Persil Color launched in 1991, this continues to be Henkels offering in the colour care
detergent space. The formula was changed in 2003, when it was reintroduced as a gel,
with cleaning ability at 30C, and then again in 2005, when a special long-term colour
protection additive was added to the formula.
Procter & Gamble
Cheer with Colorguard contains chlorine scavengers, a dye fixative agent (a cationic
polymer based on imidazole and epichlorohydrin), and PVP as a dye transfer inhibitor.
Tide ColorClean a chlorine bleach-free detergent.
Unilever
No product positioned specifically as a colour care offering.
Colour and fabric One of the key areas of research that holds the promise of revolutionising fabric care
care ingredients: technology is enzyme technology. Modern heavy-duty detergents and bleaching washing
the future aids normally contain an oxygen-based oxidising agent, more particularly a peracid, a
peracid salt, hydrogen peroxide or a substance which yields hydrogen peroxide under
aqueous in-use conditions.
Since the bleaching effect of hydrogen peroxide on its own is often found to be
inadequate, bleaching systems of a per compound which yields hydrogen peroxide in
water, and a bleach activator which generates a peracid under perhydrolysis conditions
are generally used. The most prominent example of such a bleaching system is the widely
used combination of alkali metal perborate and N-tetraacetyl ethylenediamine.
There has been no shortage of attempts to improve this bleaching system by
modification. For example, it is proposed in international patent application WO
89/09813 to use a peroxidase enzyme, i.e. an enzyme which catalyses the reaction
of hydrogen peroxide with organic or inorganic substances as a bleach activator.
Besides inorganic hydrogen peroxide precursors such as, for example, perborate,
percarbonate, perphosphate and persilicate, it has also occasionally been proposed to use
enzymatic systems capable of producing hydrogen peroxide from oxygen, for example from
atmospheric oxygen. Enzymes such as these are normally referred to as oxidases and are
classified according to their substrate.
Oxidases are redox enzymes with the classification EC1 (classification of the Enzyme
Commission) which are generally flavine-dependent, and of which the oxidised form is
capable of oxidising a substrate. The resulting reduced form of the enzyme is reoxidised
by molecular oxygen in aqueous systems; hydrogen peroxide being formed as another
product. Examples of such enzymes and their substrates that follow the name of the
enzyme are phenol oxidase, amino acid oxidase, xanthine oxidase, urate oxidase, alcohol
oxidase, cholesterol oxidase and glucose oxidase.

8
Technology trends
It has been found that the bleaching effect of hydrogen peroxide produced
enzymatically in typical washing, bleaching and cleaning liquors can be significantly
increased, even in the absence of typical activators, if the hydrogen peroxide is produced
in situ through the use of amino alcohol oxidase or D-amino acid oxidase. These also
reduce dye transfer from dyed fabrics to undyed or differently coloured fabrics.
Peroxidase enzymes are bleaching enzymes that have been proposed for dye transfer
inhibition. It has been determined that to achieve good dye bleaching, particularly at
high pH levels, e.g. levels above about eight or nine, an accelerator is required for the
peroxidase enzyme. It has been found that the efficiency of peroxidases in terms of dye
transfer inhibition, particularly at pH above about 9, is considerably enhanced by using
an accelerator, preferably a phenothiazine or phenoxazine accelerator together with the
peroxidase. Detergent compositions are being developed to provide DTI systems by using
said peroxidase in conjunction with a phenothiazine accelerator.
Cellulase enzymes A recent development in detergent enzymes has been the introduction of a cellulase
preparation for use in washing cotton fabrics. During washing, small fibres are raised
from the surface of cotton thread, resulting in a change in the feel of the fabric and,
particularly, in the lowering of the brightness of colours. Treatment with cellulase removes
the small fibres without apparently damaging the major fibres, and restores the fabric
to its as new condition. The cellulase also aids the removal of soil particles from the
wash by hydrolysing associated cellulose fibres. An example of a commercially available
cellulase enzyme is SEBrite Color by the Specialty Enzymes and Biochemicals Company.
Focus change: from After a peak of patent activity in the area of DTI, the focus now seems to have shifted to
DTI to dye fixation stop the dye from bleeding altogether, or dye fixation. Woolite Dark Laundry, Tide Wear
Care, and Cheer with Liquifiber all contain technologies to provide improved dye loss
protection.
Consumers spend a lot of their disposable income on expensive clothing and there
is a growing desire to keep them looking new for as long as possible. Hence there is
an increased focus on the development of colour care agents that will not attack the
dye of the fibre. One of the disappointing facts in this field is that there have been no
technological breakthroughs in bleaching technology for several years. Party as a result of
the disaster of the unsuccessful market introduction of a manganese catalyst in 1994, the
patent activity in bleach technology has been low over the past few years.

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List of tables vii Sodium hypochlorite bleach 18

Page  Copyright Pira International Ltd 2008

Page vi Copyright Pira International Ltd 2008

2.1 Detergent compositions 3 3.1Avox content and bulk density of PBS1,

Page vii Copyright Pira International Ltd 2008

2.1 Structure of surfactant 4 2.6Formation of micelles 9

Page viii Copyright Pira International Ltd 2008

Detergents are a complex cocktail of chemicals, or more accurately, a cocktail of

Page ix Copyright Pira International Ltd 2008

Abbreviations DTI: Dye transfer inhibitor

Page  Copyright Pira International Ltd 2008

Page  Copyright Pira International Ltd 2008

TABLE 2.1 Detergent compositions

Page  Copyright Pira International Ltd 2008

FIGURE 2.1 Structure of surfactant

Source: Pira International Ltd

Page  Copyright Pira International Ltd 2008

Soaps, or fatty acid salts;

Page  Copyright Pira International Ltd 2008

FIGURE 2.2 Structures of common surfactants used in the industry

Source: Handbook of Detergents: Part D: Formulations, CRC Press, 2005

Most brands of laundry detergent have anionic or nonionic surfactants, or a mixture of

Page  Copyright Pira International Ltd 2008

FIGURE 2.3Representation of the surfactant molecule

Page  Copyright Pira International Ltd 2008

Adsorption Adsorption is the tendency of the molecule of a surfactant to collect as an interface.

FIGURE 2.4 Adsorption mechanism of surfactant molecules

Self-assembly Self-assembly is the inclination of surfactant molecules to organise and coordinate

FIGURE 2.5 Self-assembly of surfactant molecules

Page  Copyright Pira International Ltd 2008

FIGURE 2.6 Formation of micelles

Page  Copyright Pira International Ltd 2008

FIGURE 2.7 Homopolymers of acrylic acid and maleic acids

Where Z is either hydrogen, in the case of homopolymers of acrylic acid, or a carboxyl

FIGURE 2.8 Hybrid anionic dispersing polymers

Page 10 Copyright Pira International Ltd 2008

FIGURE 2.9 Sulphonated monomer groups

Page 11 Copyright Pira International Ltd 2008

FIGURE 2.10 Citric acid and sodium nitrilotriacetate

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Properties Formulated as a powder or liquid concentrate;

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Materials Materials that can be used as fillers in detergents include:

Types of bleaches Bleaches can be broadly categorised into two types:

TABLE 2.2 Detergent bleaches

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Polyfunctionally substituted aromatic chelating agents, phosphates and mixtures

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2.1 Detergent compositions 3 3.1Avox content and bulk density of PBS1,

2.1 Structure of surfactant 4 2.6Formation of micelles 9

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Polyfunctionally substituted aromatic chelating agents, phosphates and mixtures