Flexible Solutions for Coatings

Trademark of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Trademark of The Dow Chemical Company (Dow) or an affiliated company of Dow.

UCAR Solution Vinyl Resins

Contents
UCAR Solution Vinyl Resins for Coatings Typical Properties Table Applications Table General Characteristics Table FDA Status Vinyl Chloride/Vinyl Acetate Copolymers Carboxyl-Modified Vinyl Chloride/Vinyl Acetate Copolymers Epoxy-Modified Vinyl Chloride/Vinyl Acetate Copolymers Hydroxyl-Modified Vinyl Chloride/Vinyl Acetate Copolymers Hydrolyzed Resins Directly Polymerized Resins Carboxyl Modified/Hydroxyl Modified Vinyl Chloride/Vinyl Acetate Copolymer Sulfonate Modified Copolymer Solution Vinyl Resins for VOC-Compliant CoatingsWater-based Resin Solutions Viscosity Behavior Application Methods Solution Preparation Formulation of Clear Coatings Plasticizers Heat Stabilizers Light Stabilizers Formulation of Pigmented Coatings Modification with Other Polymers Compatibility Reactive (Crosslinking) Systems Adhesion Where Not to Use Vinyl Coatings Product Stewardship 3 4 6 6 7 8

10 10 10

11 11

12 12 22 23 23 25 25 25 26 27 30 30 30 32 32 34

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

UCAR Solution Vinyl Resins for Coatings

Through advanced solution vinyl resin technology, Dow has successfully extended the 50 years of proven performance of the vinyl chloride backbone.
When properly pigmented, coatings based on vinyl chloride/acetate copolymers have excellent outdoor durability. Hydroxyl-modification improves compatibility and adhesion, and provides a site for crosslinking. Carboxyl modification permits formulation of coatings that will adhere to clean metal surfaces on airdry. Epoxy modification provides the ability to crosslink with carboxyl-modified vinyl resins to give an all-vinyl reactive system that yields thermoset-like characteristics, most notably improved toughness, enhanced physical properties, and superior chemical resistance. UCAR Solution Vinyl Resins, produced by a proprietary solution polymerization process, offer several advantages:

UCAR Solution Vinyl Resins are available in four general copolymer types: Vinyl Chloride/Vinyl Acetate Carboxyl-Modified Vinyl Chloride/Vinyl Acetate Epoxy-Modified Vinyl Chloride/Vinyl Acetate Hydroxyl-Modified Vinyl Chloride/Vinyl Acetate These copolymers are available as powders and solutions in a range of molecular weights and compositions. Coatings based on these resins are nonoxidizing and permanently flexible, and are characterized by the absence of color, odor, and taste. They are not attacked at normal temperatures by dilute alkalies or mineral acids, alcohols, greases, oils, or aliphatic hydrocarbons. They have a low moisture-vapor transmission rate, low order of water absorption, and are tough and durable. The molecular weight and the ratio of vinyl chloride to vinyl acetate affect the solubility and other physical properties of the resin. As the molecular weight (degree of polymerization) is increased, the solution viscosity increases and the strength of the film increases. Vinyl chloride contributes film strength and toughness, as well as water and chemical resistance. Vinyl acetate improves solubility and film flexibility.

High Purity
No water-soluble suspending agents or surfactants are used in the manufacture; therefore, water resistance is outstanding. Additionally, the as-received vinyl chloride monomer (VCM) content of dry vinyl powders is nondetectable.

Uniform Polymer Composition and Narrow Molecular Weight Distribution

Provide predictable solution viscosities and batch-to-batch production uniformity.

Low in Gels
Easily dissolved and low in gels and insoluble materials.

Compatibility
All UCAR Solution Vinyl Resins are completely compatible with each other and many different types of resins.

Recoatable
Typically dry by evaporation. Hydroxyl-modified vinyls can be cured by crosslinking.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Table 1A-Typical Properties of UCAR Solution Vinyl Resins

UCAR Solution Vinyl Resins VYNS-3 Polymer Composition % by Wt VCl VAc Other Reactive Functionality Type % by Wt Acid No. Hydroxyl Value Epoxy Equivalent Wt Inherent Viscosity ASTM-D1243 Specific Gravity ASTM-D792 Glass Transition Temp. (Tg), C Average Molecular Wt, Mnb Solution Viscosityc at 25C, cP Typical Solution Properties Solids, % by Wt MEK/Toluene Viscosity at 25C, cP
(a) (b) (c) (d) Maleic acid Referenced to polystyrene standard. 30% resin in MEK 20% resin in MEK

VYHH 86 14

VYHD 86 14

VMCH 86 13 1a

VMCC 83 16 1a

VMCA 81 17 2a

90 10

0.74 1.36 79 44,000 1300d

0.50 1.35 72 27,000 600

0.40 1.35 72 22,000 200

carboxyl 1.0 10 0.50 1.35 74 27,000 650

carboxyl 1.0 10 0.38 1.34 72 19,000 100

carboxyl 2.0 19 0.32 1.34 70 15,000 55

15 67/33 250

20 50/50 200

25 33/67 175

20 50/50 150

25 25/75 250

30 25/75 370

The

physical property data listed here are considered to be typical properties, not specifications.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Table 1BTypical Properties of UCAR Solution Vinyl Resins

UCAR Solution Vinyl Resins VAGH Polymer Composition % by Wt VCl VAc Other Reactive Functionality Type % by Wt Acid No. Hydroxyl Value Epoxy Equivalent Wt Inherent Viscosity ASTM-D1243 Specific Gravity ASTM-D792 Glass Transition Temp. (Tg), C Average Molecular Wt, Mnj Solution Viscosityk at 25C, cP Typical Solution Properties Solids, % by Wt MEK/Toluene Viscosity at 25C, cP 90 4 6d VAGD 90 4 6d VAGF 81 4 15e VAGC 81 4 15e VROH 81 4 15e UCARMAG Binder 527 569 82 4 14a,e 85 13 2f

hydroxyl hydroxyl 2.3 76 0.53 1.39 79 27,000 1,000 2.3 76 0.44 1.39 77 22,000 400

hydroxyl hydroxyl hydroxyl hydroxyl/ sulfonate carboxyl 1.8 1.9 2.0 2.0 1.0 59 0.56 1.37 70 33,000 930 63 0.44 1.36 65 24,000 275 66 0.30 1.37 65 15,000 70 59 0.56 1.37 72 35,000 720 0.33 1.35 72 17,000 850

20 50/50 350

25 50/50 400

20 50/50 171

30 50/50 184

30 25/75 340

20 50/50 170

20 50/50 500

(a) (d) (e) (f) (j) (k)

Maleic acid Vinyl alcohol Hydroxyalkyl acrylate Sulfonate-containing monomer Referenced to polystyrene standard. 30% resin in MEK

The

physical property data listed here are considered to be typical properties, not specifications.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Applications and Characteristics

Table 2Applications
UCAR Solution Packaging Vinyl Resin Food Non-Food VYNS-3 VYHH VYHD VMCH VMCC VMCA VAGH VAGD VAGF VAGC VROH UCARMAG Binder 527 569 General Metals Marine and Maintenance Magnetic Media Inks Adhesives Strippable Wood Coatings Finishes

Table 3General Characteristics of UCAR Solution Vinyl Resins

Appearance Particle Size % by wt, min, through 20 mesh Bulk Density, lb/ft3 Heat Loss, % by wt, max Water Content, % by wt, max Melting Point, C White powder 98 24 to 34 3.0 0.5 93 to 135

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

FDA Status
The UCAR Solution Vinyl Resins listed below are cited in the following regulations1 of the United States Food and Drug Administration (FDA) for use in food-contact applications, such as can, paper, film, and foil coatings, and coatings for closures. FDA Regulation 21CFR 175.105 Use Components of adhesives used in articles intended for packaging, transporting, or holding food. Components of resinous and polymeric coatings to be applied as continuous films to food-contact surfaces of articles intended for use in processing, manufacturing, packing, producing, heating, packaging, holding, or transporting food. Components of a coating that is applied as a continuous film over one or both sides of a base film produced from one or more of the basic olefin polymers complying with 177.1520. Components of the food-contact surface of paper and paperboard used to package aqueous and fatty foods. Components of paper and paperboard in contact with dry food. Components of closures with sealing gaskets for food containers. UCAR Solution Vinyl Resin VYHD, VYHH, VYNS-3, VMCA, VMCC, VMCH, VAGD, VAGH VYHD, VYHH, VYNS-3, VMCA, VMCC, VMCH, VAGD, VAGH

21CFR 175.300 (b)(3)(XV)

21CFR 175.320

VYHD, VYHH, VYNS-3, VMCA, VMCC, VMCH, VAGD, VAGH VYHD, VYHH, VYNS-3, VMCA, VMCC, VMCH, VAGD, VAGH VYHD, VYHH, VYNS-3, VMCA, VMCC, VMCH, VAGD, VAGH VYHD, VYHH, VYNS-3, VMCA, VMCC, VMCH, VAGD, VAGH

21CFR 176.170 (b)

21CFR 176.180

21CFR 177.1210

(1) Since government regulations are subject to revision, it is the users responsibility to refer to the Code of Federal Regulations or the Federal Register to determine current regulatory status.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Vinyl Chloride/Vinyl Acetate Copolymers

UCAR VYNS-3 Solution Vinyl Resin
The highest molecular weight Solution Vinyl Resin, having a composition of approximately 90 percent vinyl chloride and 10 percent vinyl acetate, UCAR VYNS-3 Solution Vinyl Resin is usually dissolved in relatively strong ketone systems to provide resin solutions of 13 to 17 percent solids. It is used where the ultimate toughness, durability, and chemical resistance are required. Because of its excellent tensile tear properties, UCAR VYNS-3 Solution Vinyl Resin is ideally suited for strippable coatings applications. UCAR VYHH Solution Vinyl Resin is often blended with UCAR VYNS-3 Solution Vinyl Resin to increase sprayable solids. diluent (50/50 percent by weight). With this system, a solids content of 20 to 22 percent can be achieved. Marine and maintenance coatings, ink and overlacquers for vinyl substrates, strippable coatings, and masonry and metal coatings are among the principal appli-cations for UCAR VYHH Solution Vinyl Resin.

UCAR VYHD Solution Vinyl Resin

A medium molecular weight resin having a composition of approximately 86 percent vinyl chloride and 14 percent vinyl acetate; UCAR VYHD Solution Vinyl Resin is more soluble in ketones and other solvents than UCAR VYHH Solution Vinyl Resin and, therefore, has a greater tolerance for aromatic hydrocarbon diluents. Resin solutions of 25 percent solids can be achieved by dissolving UCAR VYHD Solution Vinyl Resin in a system consisting of ketone solvent/aromatic diluent (35/65 percent by weight). UCAR VYHD Solution Vinyl Resin can be substituted for UCAR VYHH Solution Vinyl Resin in most applications where higher solids are needed.

UCAR VYHH Solution Vinyl Resin

A high molecular weight resin having a composition of approximately 86 percent vinyl chloride and 14 percent vinyl acetate, UCAR VYHH Solution Vinyl Resin offers a desirable balance of chemical resistance, solubility, film strength, and thermoplasticity. It is usually dissolved in a relatively strong solvent/diluent combination, such as ketone solvent/aromatic

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Carboxyl-Modified Vinyl Chloride/Vinyl Acetate Copolymers

The carboxyl-modified vinyl chloride/vinyl acetate copolymers are made specifically for the formulation of coatings having excellent adhesion to various substrates, especially metals, cellulosics, and certain plastics. UCAR VMCC Solution Vinyl Resin also has a higher tolerance for aromatic hydrocarbon diluents. When dissolved in a suitable solvent system, such as a 50 percent ketone/50 percent aromatic hydrocarbon, resin solutions of 23 to 25 percent solids can be achieved. UCAR VMCC Solution Vinyl Resin is often used in the same applications as UCAR VMCH Solution Vinyl Resin. However, because of its better solubility, it is also used as an adhesion promoter for vinyl organosols in can coatings.

UCAR VMCH Solution Vinyl Resin

A high molecular weight resin containing approx-imately 86 percent vinyl chloride, 13 percent vinyl acetate, and 1 percent maleic acid; UCAR VMCH Solution Vinyl Resin is usually dissolved in relatively strong solvent/diluent combinations, such as 50 percent ketone/50 percent aromatic hydrocarbon, to produce solutions of 20 to 22 percent solids. UCAR VMCH Solution Vinyl Resin is used primarily for air-dry finishes, such as maintenance, marine, and metal coatings, and is often used to make heat-sealable packaging coatings.

UCAR VMCA Solution Vinyl Resin

A low molecular weight resin containing approximately 81 percent vinyl chloride, 17 percent vinyl acetate, and 2 percent maleic acid; UCAR VMCA Solution Vinyl Resin is characterized by a high degree of solubility in solvent systems having a high aromatic hydrocarbon content. When dissolved in a suitable solvent/diluent combination, such as 25 percent ketone/75 percent aromatic hydrocarbon, resin solutions of 30 percent solids can be achieved. UCAR VMCA Solution Vinyl Resin yields the good balance of solubility and viscosity properties needed for high-build, air-dry maintenance finishes. It can also be used in coatings and adhesives applications where higher solids are desirable.

UCAR VMCC Solution Vinyl Resin

A medium molecular weight resin containing approximately 83 percent vinyl chloride, 16 percent vinyl acetate, and 1 percent maleic acid; UCAR VMCC Solution Vinyl Resin is more soluble than UCAR VMCH Solution Vinyl Resin in ketones, esters, and other solvents used to dissolve vinyl resins.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Hydroxyl-Modified Vinyl Chloride/Vinyl Acetate Copolymers

Hydroxyl-modified vinyl chloride/vinyl acetate copolymers are manufactured using two different processes. UCAR VAGH and VAGD Solution Vinyl Resins are polymers made in a two-step process that yields vinyl alcohol in the backbone. The other hydroxyl-modified resins are produced by a one-step polymerization process similar to that used to make the copolymer and carboxy-functional solution polymerized resins described above. Hydroxyl-modified vinyl chloride/vinyl acetate copolymers are noted particularly for compatibility with other film-forming resins, such as alkyds, urethane elastomers, isocyanate resins, epoxy polymers, and urea and melamine resins. Hydroxyl-modified vinyls are, therefore, often formulated with these and other filmforming materials to improve coating properties, such as adhesion, flexibility, toughness, hardness, and chemical resistance. Hydroxyl-modified resins are often used to impart snap-dry properties to a coating. The hydroxyl functionality permits crosslinking reactions for thermoset coating systems that exhibit outstanding chemical and water resistance. Coatings based on these resins also have good adhesion to wash primers, metals, wood, and many plastic substrates.

UCAR VAGD Solution Vinyl Resin

A medium molecular weight, partially hydrolyzed vinyl chloride/vinyl acetate resin having a composition of approximately 90 percent vinyl chloride, 4 percent vinyl acetate, with a hydroxyl content of approximately 2.3 percent. The lower molecular weight provides improved solubility and permits the formulation of solutions containing higher solids.

Directly Polymerized Resins

UCAR VAGF Solution Vinyl Resin
A high molecular weight copolymer comprised of vinyl chloride, vinyl acetate, and a hydroxyalkyl acrylate. The vinyl chloride portion is about 81 percent with the hydroxyl content at 1.8 percent. The solution viscosity and other properties of UCAR VAGF Solution Vinyl Resin strongly resemble those of UCAR VAGH Solution Vinyl Resin. UCAR VAGF Solution Vinyl Resin can be used for a wide range of coatings applications, including industrial maintenance and marine finishes, paper coatings, general metal finishes, and as a binder in magnetic tape.

UCAR VAGC Solution Vinyl Resin

A medium molecular weight copolymer comprised of vinyl chloride, vinyl acetate, and a hydroxyalkyl acrylate. The vinyl chloride portion is about 81 percent with the hydroxyl content at 1.9 percent. The solution viscosity and other properties of UCAR VAGC Solution Vinyl Resin are very similar to those of UCAR VAGD Solution Vinyl Resin. UCAR VAGC Solution Vinyl Resin finds commercial application in clear and pigmented coatings for metal, wood, paper, concrete, masonry, films, foils, fabrics, and leather.

Hydrolyzed Resins
UCAR VAGH Solution Vinyl Resin
A high molecular weight, partially hydrolyzed vinyl chloride/vinyl acetate resin having a composition of approximately 90 percent vinyl chloride, 4 percent vinyl acetate, with a hydroxyl content of approximately 2.3 percent; UCAR VAGH Solution Vinyl Resin can be dissolved in relatively strong solvent/diluent combinations, such as 50 percent ketone/50 percent aromatic hydrocarbon, to produce resin solutions of 20 percent solids. UCAR VAGH Solution Vinyl Resin can be used for a wide range of coatings applications, including industrial maintenance and marine finishes, wood finishes, paper coatings, metal decorative and container coatings, and as a binder in magnetic tape.

10

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Sulfonate Modified Copolymer

UCAR VROH Solution Vinyl Resin
A low molecular weight copolymer comprised of vinyl chloride, vinyl acetate, and a hydroxyalkyl acrylate. The vinyl chloride portion is approximately 81 percent, and the hydroxyl content is approximately 2 percent. High tolerance for alcohols and aliphatic diluents broadens the usefulness of UCAR VROH Solution Vinyl Resin. UCAR VROH Solution Vinyl Resin can be dissolved in solvent/diluent combinations, such as 25 percent ketone/75 percent aromatic hydrocarbon, to produce resin solutions of 30 percent solids. Also, 35 percent resin solutions can be prepared with UCAR VROH Solution Vinyl Resin using Rule 66-type exempt solvent systems (for the wood coatings industry) containing as much as 30 percent by volume butanol. UCAR VROH Solution Vinyl Resin can be used in a wide variety of clear and pigmented coatings for metal, wood, paper, film, foil, and fabric.

UCARMAG 569 Binder Resin

A medium molecular weight copolymer containing vinyl chloride, vinyl acetate, and a monomer with metal sulfonate functionality. The vinyl chloride of the copolymer is about 85 percent by weight. The sulfonate functional monomer provides the copolymer with exceptional wetting characteristics which make it an excellent dispersing medium for high surface area pigments used in magnetic media applications. Since the copolymer has excellent heat stability, it can be used in applications requiring high shear milling operations to disperse high surface area or highly porous pigments. UCARMAG 569 Binder Resin, because of its sulfonate functionality, may also be useful in other nonmagnetic media applications where good dispersing capabilities are needed. For example, UCARMAG 569 Binder Resin is an efficient grinding vehicle for hard-to-disperse organic colors such as lithol rubine red. Color concentrates impart high gloss and tinting strength in inks and coatings.

Carboxyl Modified/ Hydroxyl Modified Vinyl Chloride/Vinyl Acetate Copolymer

UCARMAG 527 Binder Resin
A high molecular weight copolymer comprised of vinyl chloride, vinyl acetate, a hydroxy-alkyl acrylate, and a carboxylated monomer. The vinyl chloride content is about 80 percent by weight and the hydroxyl content is about 1.8 percent. The molecular weight and physical properties of UCARMAG 527 Binder Resin are similar to those of UCAR VAGF Solution Vinyl Resin. A carboxyl monomer in the UCARMAG 527 Binder Resin gives the copolymer excellent wetting and pigment dispersion properties and has made the resin especially useful in magnetic tape coatings containing neutral or basic pigments. Because of its unique functionality, UCARMAG 527 Binder Resin might also be considered as a binder for printing inks, paper coatings, and general metal finishes.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

11

Solution Vinyl Resins for VOC-Compliant Coatings Water-based Resin

UCAR AW-875 Waterborne Vinyl Resin Dispersion
Since their commercialization about 50 years ago, UCAR Solution-Polymerized Vinyl Resins have become the standards for a wide range of coatings applications. UCAR AW-875 Waterborne Vinyl Resin dispersion has been developed for compliant waterborne coatings, adhesives, and inks. This waterborne resin dispersion utilizes a solution-polymerized vinyl resin backbone that has been chemically modified to allow dispersion in water.

Solutions
Several criteria must be weighed in choosing solvents and diluents for UCAR Solution Vinyl Resins: Solvent Strength Volatility Toxicity Odor Cost Flammability Type of Application UCAR Solution Vinyl Resins are readily dissolved into clear solutions at room temperature by ketones, nitroparaffins, esters, and chlorinated hydrocarbons. In general, ketones are the most suitable solvents for vinyl resins. Compared to other solvents, ketones yield higher resin concentrations without gelling and lower solution viscosities at equivalent solids content. Because of their solvency, they tolerate greater dilution with economical hydrocarbon diluents and exhibit better storage stability. Figure 1 compares the solvent strength of different ketones for UCAR VYHD Solution Vinyl Resin. Esters are useful in applications where minimal attack on the substrate is desirable (as with coatings on plastics). Because of their low solvency for vinyls, they should be used in combination with other active solvents. Urethane-grade esters are preferred for minimum viscosity and optimum viscosity stability. Figure 2 compares the solvent strength of different esters for UCAR VYHD Solution Vinyl Resin.

12

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Figure 1Viscosity vs. Concentration of UCAR VYHD Solution Vinyl Resin in Ketones
10,000 8,000 6,000 5,000 4,000 3,000 Methyl Isobutyl Ketone 2,000 Methyl Ethyl Ketone Acetone Isophorone Cyclohexanone

1,000 800

Viscosity at 25 C, cP

600 500 400 300 200

100 80 60 50 40 30 20

10

10

20

30

40

50

Solids, percentage by weight

NOTE: Viscosity was determined using a Brookfield viscometer model RVT, running at 50 or 100 rpm with spindles #2 through #5, selected as appropriate for the solution being tested.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

13

Figure 2Viscosity vs. Concentration of UCAR VYHD Solution Vinyl Resin in Esters
10,000 8,000 6,000 5,000 4,000 3,000 Butyl Acetate 2,000 Ethyl Acetat e 1,000 800 Methyl PROPASOL Acetate

Isopropyl Acetat e

Viscosity at 25 C, cP

600 500 400 300 200

100 80 60 50 40 30 20

10

10

15

20

25

30

35

Solids, percentage by weight

NOTE: Viscosity was determined using a Brookfield viscometer model RVT, running at 50 or 100 rpm with spindles #2 through #5, selected as appropriate for the solution being tested.

14

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Table 4Solution Viscosity of UCAR VYHH Solution Vinyl Resin in Ketones and Ketone/Aromatic Blends
Ketone Solvent Acetone Methyl Ethyl Ketone Methyl Propyl Ketone Methyl Isobutyl Ketone Methyl Isoamyl Ketone Methyl n-Amyl Ketone Cyclohexanone Isophorone Formulation UCAR VYHH Solution Vinyl Resin Ketone Solvent Xylene Toluene Parts by Weight Solution Viscosity at 25C, cP Formula A Formula B 84 88 86 130 124 212 230 360 304 504 316 684 672 360 930 484 Formula A 20 80 100 Formula B 20 40 20 20 100

NOTE: Viscosity was determined using a Brookfield viscometer model RVT, running at 50 or 100 rpm with spindles #2 through #5, selected as appropriate for the solution being tested.

Diluents lower coating costs, alter the evaporation rates, and provide other important coating characteristics. Typical diluents for use with UCAR Solution Vinyl Resins include aromatic hydrocarbons, such as toluene and xylene. Aliphatic hydrocarbons, such as mineral spirits, VM&P naphtha, and heptane can also be used. These aliphatic hydrocarbons are less effective than aromatic hydrocarbons and should be used at levels not exceeding 10 percent of the solvent blend. Ketones tolerate greater amounts of aromatic diluents than do the ester solvents. Table 4 compares the viscosity of UCAR VYHH Solution Vinyl Resin in ketones with the viscosity in ketone/diluent mixtures.

Optimum formulation stability and the lowest solution viscosities are obtained when the solvent system contains only active solvents. As the proportion of diluent increases, the stability declines. Figures 3 to 5 compare the solution viscosity of UCAR Solution Vinyl Resins versus solids content in methyl ethyl ketone and in a methyl isobutyl ketone/toluene (50/50) blend. Formulating at excessively high solids or with weak solvent mixtures can result in solutions having unstable viscosities and can even lead to the formation of gel structures. As the molecular weight of the vinyl resin decreases, however, the diluent level can be increased while maintaining the same level of viscosity.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

15

Figure 3Viscosity vs. Concentration of Vinyl Chloride/Vinyl Acetate Copolymers in Methyl Ethyl Ketone
10,000 8,000 6,000 5,000 4,000 3,000 2,000 VYHH VYHD 1,000 800 VYNS-3

Viscosity at 25 C, cP

600 500 400 300 200

100 80 60 50 40 30 20

10

10

20

30

40

50

Solids, percentage by weight

NOTE: Viscosity was determined using a Brookfield viscometer model RVT, running at 50 or 100 rpm with spindles #2 through #5, selected as appropriate for the solution being tested.

16

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Figure 3AViscosity vs. Concentration of Vinyl Chloride/Vinyl Acetate Copolymers in Methyl Isobutyl Ketone/Toluene (50/50)
10,000 8,000 6,000 5,000 4,000 3,000 2,000 VYHH VYHD 1,000 800 VYNS-3

Viscosity at 25 C, cP

600 500 400 300 200

100 80 60 50 40 30 20

10

10

20

30

40

50

Solids, percentage by weight

NOTE: Viscosity was determined using a Brookfield viscometer model RVT, running at 50 or 100 rpm with spindles #2 through #5, selected as appropriate for the solution being tested.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

17

Figure 4Viscosity vs. Concentration of Hydroxyl-Modified Copolymers in Methyl Ethyl Ketone

10,000 8,000 6,000 5,000 4,000 3,000 VAGD 2,000 VAGC 1,000 800 VROH VAGH VAGF

Viscosity at 25 C, cP

600 500 400 300 200

100 80 60 50 40 30 20

10

10

20

30

40

50

Solids, percentage by weight

NOTE: Viscosity was determined using a Brookfield viscometer model RVT, running at 50 or 100 rpm with spindles #2 through #5, selected as appropriate for the solution being tested.

18

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Figure 4AViscosity vs. Concentration of Hydroxyl-Modified Copolymers in Methyl Isobutyl Ketone/Toluene (50/50)
10,000 8,000 6,000 5,000 4,000 3,000 VAGD 2,000 VAGC 1,000 800 VROH VAGH VAGF

Viscosity at 25 C, cP

600 500 400 300 200

100 80 60 50 40 30 20

10

10

20

30

40

50

Solids, percentage by weight

NOTE: Viscosity was determined using a Brookfield viscometer model RVT, running at 50 or 100 rpm with spindles #2 through #5, selected as appropriate for the solution being tested.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

19

Figure 5Viscosity vs. Concentration of Carboxyl-Modified Copolymers in Methyl Ethyl Ketone

10,000 8,000 6,000 5,000 4,000 3,000 VMCH 2,000 VMCC 1,000 800 VMCA

Viscosity at 25 C, cP

600 500 400 300 200

100 80 60 50 40 30 20

10

10

20

30

40

50

Solids, percentage by weight

NOTE: Viscosity was determined using a Brookfield viscometer model RVT, running at 50 or 100 rpm with spindles #2 through #5, selected as appropriate for the solution being tested.

20

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Figure 5AViscosity vs. Concentration of Carboxyl-Modified Copolymers in Methyl Isobutyl Ketone/Toluene (50/50)
10,000 8,000 6,000 5,000 4,000 3,000 VMCH 2,000 VMCC VMCA

1,000 800

Viscosity at 25 C, cP

600 500 400 300 200

100 80 60 50 40 30 20

10

10

20

30

40

50

Solids, percentage by weight

NOTE: Viscosity was determined using a Brookfield viscometer model RVT, running at 50 or 100 rpm with spindles #2 through #5, selected as appropriate for the solution being tested.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

21

Figure 6Memory Effect of Vinyl Resin Solutions

Cooled

Viscosity

Room T emperatur e Heated

Time (weeks)

Viscosity Behavior
Viscosity behavior of vinyl solutions is influenced by resin concentration, active solvent used, ratio of solvent to diluent, and solution temperature. Viscosity changes in vinyl solutions are the result of different equilibrium effects that occur during the preparation and storage of resin solutions. The formation of a slight degree of microcrystallinity among adjacent polymer molecules in solution is responsible for the observed viscosity increase. The time required to reach equilibrium viscosity for vinyl resin solutions is influenced by resin molecular weight, solids content, solvent strength, processing time, and temperature. Vinyl resin solutions usually increase in viscosity with time. The extent of the total increase can range from a minor viscosity drift to a major change, such as gelation. Vinyl solutions that have gelled because of excessive solids content or a solvent mix that is too weak can be restored to fluidity by proper thinning and mixing. Another equilibrium condition that affects solution viscosity is the memory effect. It is noted in vinyl solutions that have been subjected to increases or decreases in temperature and is characterized by a significant lag in the rate at which a vinyl solution returns to equilibrium viscosity after a temperature change. For example, a vinyl solution that has been heated will maintain an abnormally low viscosity for extended periods after it has returned to its initial temperature. This viscosity change is caused by differences in the degree of microcrystallinity of the solution at various temperatures. As the temperature increases, the degree of microcrystalline regions that exist in the solution decreases and the viscosity decreases. The memory effect is illustrated in Figure 6. Formulators must be aware of both these effects and the time required to reach equilibrium conditions, so that viscosity stability problems, resulting from the preparation of solutions at incorrect solids levels or solvent blends, are avoided.

22

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Application Methods
Coatings based on UCAR Solution Vinyl Resins may be readily applied by commonly used application methods, such as brushing, spraying, dipping, and roller coating. Of major considertion for all applications is the correct consistency of the coating and proper evaporation rate of the solvent used in a particularapplication method. Table 5 shows the properties of solvents useful with UCAR Solution Vinyl Resins. Paper and cloth coatings may be formulated with highly volatile solvents, such as acetone and methyl ethyl ketone. Application by roller coaters requires solvents and diluents with a slow evaporation rate. Isophorone is used for roller coating because it is an excellent solvent for vinyls and has a slow evaporation rate. Methyl PROPASOL Acetate and Cyclohexanone Solvents are used for brush applications because they are slow-evaporating solvents that promote ease of application and good flow-out.

Solution Preparation
Use a high-shear mixer to prepare solutions of UCAR Solution Vinyl Resins. Slow-speed, paddle-type agitators are not as effective as highshear mixers. Equip the mixers with tight-fitting covers. Add the solvent/diluent mixtures to the highshear mixer. As the solvent mixture is agitated, add the resin slowly. The resin must be added slowly or lumping may occur. UCAR Solution Vinyl Resins should not be charged into equipment containing flammable liquid or vapor unless precautions are taken to eliminate static electrical discharge (see Storage and Handling guide for UCAR Solution Vinyl Resin.) As an alternate procedure, slurry the vinyl resin in a solvent/diluent blend containing about 20 percent of active solvent. Add the resin slowly. When all the resin is thoroughly wetted, vigorously agitate the slurry and slowly add the remaining portion of the active solvent. Do not slurry the vinyl resin in the diluent alone; slurrying with diluents may produce a static electrical discharge and cause a flash fire. Follow all precautions for the safe handling of organic solvents and diluents. High-shear mixing will heat solutions, especially viscous solutions. Maintain the solution temperature as low as possible. If solutions are held at elevated temperatures for long periods of time, discoloration may result. The addition of about 1.0 to 2.0 percent ERL-4221 cycloaliphatic epoxide on resin will help control discoloration without affecting coating performance. For maximum stability, vinyl resin solutions should be stored in baked phenolic-lined containers.

Note: ERL-4221 cycloaliphatic epoxide does not have FDA clearances for use in food-contact applications.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

23

Table 5Solvents for UCAR Solution Vinyl Resins

Relative Evaporation Rate (BuAc=100) 1160 615 570 500 275 Weight per gallon at 20C, lb 6.59 7.51 6.71 7.26 7.39 Flash Point, Closed Cup, F 0 30 24 42 58

Solvents Fast Evaporating Acetone Ethyl Acetate, 99% Methyl Ethyl Ketone Isopropyl Acetate, 99% Propyl Acetate Medium Evaporating Methyl Isobutyl Ketone Isobutyl Acetate, Urethane Grade Butyl Acetate, Urethane Grade Slow Evaporating Amyl Acetate, Primary Cyclohexanone Methyl PROPASOL Acetate Solvent Diisobutyl Ketone Diacetone Alcohol Isophorone
(a) 0.5g VYHH to 4.5ml solvent (b) S = Soluble S-G = Soluble, tendency to gel

Solubility with VYHHa,b S S S S-G S

Distillation Range, C 56-57 76-78 78-81 86-90 99-103

165 145 100

S S S

6.67 7.25 7.34

114-117 112-117 124-129

61 62 84

42 23 34 18 14 3

S S S S-G S S

7.29 7.89 8.09 6.72 7.82 7.67

140-150 156 146 163-173 145-172 210-218

101 111 114 120 133 179

24

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Formulation of Clear Coatings

Clear vinyl coatings can be modified with plasticizers, heat and light stabilizers, and other materials for specific performance properties. Before incorporating any modifier in the formulation, understand clearly how the modifier meets the demands of the application. Do not use clear vinyl coatings for applications that involve long-term exposure to ultraviolet light. The optimum level of plasticizer for a formulation will depend upon the specific resin used and the performance property required by the application. To obtain equivalent degrees of flexibility, higher molecular weight resins require more plasticizer than lower molecular weight resins. Proportions of 10 to 25 parts plasticizer per 100 parts of resin are typically used. Table 6 provides a list of plasticizers having good compatibility with UCAR Solution Vinyl Resins.

Plasticizers
The addition of a plasticizer in the coating formulation will enhance flexibility and help to minimize solvent retention in the film. The typical phthalate, adipate, citrate, epoxy, and phosphate plasticizers are compatible with UCAR Solution Vinyl Resins. In general, compatibility decreases as the hydrocarbon nature of the plasticizer increases. Polymeric plasticizers are less efficient than monomeric plasticizers. Other factors to consider in selecting plasticizers include solubility, volatility, the effect on outdoor durability, the need for low-temperature flexibility, and suitability for contact with food. Certain citrates, epoxies, and phthalates are permitted under FDA regulations. Monomeric plasticizers are most commonly used, although the polymeric plasticizers are used to provide special film characteristics, such as low extractability or migration. Phosphate plasticizers are generally not recommended for outdoor exposure because of poor light stability. When a bake cycle is required, the volatility of the plasticizer is particularly important. The plasticizer may volatilize sufficiently to lower the concentration below what was originally intended for the dried or cured formulation.

Heat Stabilizers
As with all vinyl resins, UCAR Solution Vinyl Resins are degraded upon prolonged exposure to heat. The degradation products include hydrogen chloride, which accelerates further resin degradation and leads to the development of unsaturated polymer structures that can be easily oxidized. The result is embrittlement, loss of flexibility, and discoloration of the vinyl film. To minimize the degradation of vinyl films, add suitable heat stabilizers. Baking at temperatures above 248F (120C) for more than five minutes will usually require a thermal stabilizer to avoid degradation of the film. The use of a tin mercaptide stabilizer (1 percent) in combination with a liquid epoxy resin, such as ERL-4221 cycloaliphatic epoxy resin, or diglycidyl ether of bisphenol A resin (3 to 5 percent) gives the best results. Do not use barium, cadmium, or zinc stabilizers with the carboxyl-modified vinyl resins; they tend to react with the carboxyl groups. Zinc stabilizers also tend to develop color quickly, especially in low plasticizer systems. Iron and zinc surfaces can accelerate decomposition and discoloration.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

25

on weight of vinyl resin

Light Stabilizers
An adequate quantity of a hiding pigment will screen out incident radiation and prove the best light stabilizer for pigmented vinyl coatings. Do not use unpigmented vinyl coatings outdoors. Where only limited ultraviolet light exposure will be encountered, clear films should be formulated with a light stabilizer system to prevent discoloration. The best light stabilizer system includes an ultraviolet light absorber (substituted benzophenones), a hindered amine light stabilizer (HALS), and ERL-4221 cycloaliphatic epoxy resin. A typical system would be comprised of the following: Ingredients UV Absorber1 HALS 2 ERL-4221 cycloaliphatic epoxy resin

Table 6Typical Plasticizers for UCAR Solution Vinyl Resins

Type Phthalate Product Diisooctyl Phthalate Diisodecyl Phthalate Butyl Benzyl Phthalate Butyl 2-Ethylhexyl Phthalate 2-Ethylhexyl Isodecyl Phthalate Acetyl Tributyl Citrate Acetyl Triethyl Citrate Tributyl Citrate Tri(2-ethylhexyl) Phosphate Triphenyl Phosphate Tributyl Phosphate FLEXOL EPO Plasticizer (Epoxidized soybean oil) FLEXOL EP-8 Plasticizer (2-Ethylhexyl epoxy tallate) FLEXOL LOE Plasticizer (Epoxidized linseed oil) Adipic Acid Polyester Azelaic Acid Polyester Sebacic Acid Polyester Blown Castor Oil Blown Soybean Oil Blown Linseed Oil Dibutyl Sebacate Di(2-ethylhexyl) Sebacate Di(2-ethylhexyl) Azelate

Citrate

Phosphate

Epoxy

% 1 2 3

Polymeric

on weight of vinyl resin (1) UV AbsorberUvinul D-5O (BASF), Tinuvin 327 or 328 (Ciba Geigy) or equivalent. (2) HALSTinuvin 292 (Ciba Geigy) or equivalent.

In all cases, choose stabilizers carefully and test them under actual use conditions. Consult suppliers of stabilizers for specific recommendations.

Miscellaneous

26

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Formulation of Pigmented Coatings

Pigments are selected for hiding power, ultraviolet protection, purity, and ease of wetting. Although most commercially available pigments are suitable for use with UCAR Solution Vinyl Resins, there are some general constraints. Additionally, there are specific constraints that apply to UCAR Carboxyl-Modified Solution Vinyl Resins. Do not use natural iron oxide pigments with any UCAR Solution Vinyl Resin. These pigments contain trace impurities that can gel the coating or cause discoloration or excessive chalking of the film. Do not use iron-containing pigments, such as Prussian blue or the so-called chrome greens (blends of Prussian blue and lead chromate). Chromium oxide green, however, performs well with UCAR Solution Vinyl Resins. When an iron oxide pigment is desired, use synthetic iron oxides; they perform well with UCAR Solution Vinyl Resins. With coatings containing synthetic iron oxides, use a heat stabilizer, particularly when bake temperatures may reach 248F (120C). Gold bronze metallic pigments are powdered alloys of copper and zinc. They tend to react with vinyl, causing color development and gellation. When used to make gold inks, the powder is stirred into the ink vehicle shortly before use, and quantities sufficient for the job at hand are prepared. There is a minimum amount of pigment that must be used to impart opacity to ultraviolet light. For example, about 65 parts of titanium dioxide (TiO2) per 100 parts of vinyl resin is the minimum amount that should be used. To obtain maximum hiding power in thin films, about 125 parts TiO2 per 100 parts of vinyl resin is a practical maximum concentration. Exceeding this level can cause excessive chalking. If color pigments are desired, they can generally be substituted for TiO2 at an equal volume replacement. There are exceptionsultra-fine particle size pigments, for example, are used at much lower concentrations. The use of extender pigments or fillers will help improve the economics of the formulation. They will also help prevent sagging of thick wet films on vertical surfaces, will help control gloss (flatting) at low levels, and will permit greater film thickness per coat. Talcs, clays, barytes, and silicas may be used as extender pigments. If they are used, they will contribute little to ultraviolet absorption. A sufficient quantity of ultravioletlight-absorbing prime pigment must be included in the formulation. Table 7 provides a listing of pigment types and loadings typically recommended for UCAR Vinyl Copolymer and Hydroxyl-Modified Vinyl Resins. Formulation with UCAR VMCH, VMCC, and VMCA Carboxyl-Modified Solution Vinyl Resins involves special considerations. The carboxyl groups of these products are randomly spaced along the polymer chain and will react with basic materials to form irreversible gels or increased consistency of pigment-vinyl combinations. Do not use basic pigments, extenders, or fillers with UCAR Carboxyl-Modified Solution Vinyl Resins. Particularly, avoid lead-containing pigments (red lead, chrome yellow, chrome orange), zinc dust or zinc oxide, strontium-containing pigments, and calcium carbonate. Do not even use small amounts of these basic materials in pigment blends. With minor proportions of basic pigments, viscosity aberrations may not be predictable; some batches may have a normal viscosity and others will gel. Table 8 lists pigments typically used with UCAR Carboxyl-Modified Solution Vinyl Resins.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

27

Table 7Typical Pigments for UCAR Vinyl Copolymer and Hydroxyl-Modified Solution Vinyl Resins
Pigment Red Pigment Scarlet Permanent Red 2B (Non-Resinated Calcium, Barium, or Strontium Lakes of 2-B Acid BON Reds Pyrazolone Reds Indanthrene Reds Quinacridone Reds Perylene Scarlet Pyranthrone Scarlet Perylene Vermillion Iron Oxide, Synthetic Types Yellow Nickel-Titanium Yellow Indanthrene Types Benzidines Nickel Azo Types Flavanthrone Anthrapyrimidine Pyratex Yellows Iron Oxide, Synthetic Types Orange Vat Orange Dianisidine Orange Benzidine Orange Anthanthrone Green Phthalocyanine Green

Parts per 100 Parts Resin

Pigment Maroon Thioindigo Types Alizarine Types BON Types Perylene Maroon Brown Iron Oxide, Synthetic Types Black Carbon Black Furnace Black Lampblack Iron Oxide, Synthetic Types White Antimony Oxide Titanium Dioxide Zinc Oxide Violet Carbazole Carbozole Dioxane Metallic Aluminum Pastes (65%) Leafing or Non-Leafing Blue Phthalocyanine Blue

Parts per 100 Parts Resin

55 to 100

55 to 100

5 to 7 5 to 7 5 to 7 55 to 100

55 to 100

75 to 125

60 to 85

15 to 25

indicates that the minimum level of pigment to prevent ultraviolet light degradation has not been established.

28

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Table 8Typical Pigments for UCAR Carboxyl-Modified Solution Vinyl Resins

Pigment Aluminum Powder Titanium Dioxide Phthalocyanine Green (Non-Resinated) Phthalocyanine Blue (Non-Resinated) Carbon Black Iron Blue a Iron Oxide Yellow, Synthetic a Iron Oxide Red, Synthetic a Iron Oxide Black, Synthetic a Iron Oxide Brown, Synthetic Ultramarine Blue Zinc Phosphate Talc Clay Barytes Parts per 100 Parts Resin 35 to 50 75 to 125 15 to 30 15 to 30 7 Chalks badly 60 to 125 60 to 125 60 to 125 60 to 125 Chalks and fades 75 Use as filler or extender pigments

If water is present in a pigmented coating containing a carboxyl-modified vinyl, the water molecule may form a bridge between the polymers carboxyl group and the pigment surface. Silica and alumina hydrate are prone to bridging or hydrogen bonding. Since most chloride-process TiO2 pigments have silica, zinc oxide, or alumina treatments, they can develop hydrogen bonding. Hydrogen bonding manifests itself as viscosity instability. The viscosity may increase slowly over a period of several months or it may increase rapidly in a few days or weeks. If the water content reaches two percent based on the weight of carboxyl-modified vinyl, the paint may even gel. Commercial-grade materials typically limit water content adequately and should introduce no serious viscosity instability. If water does contaminate the formulation, it may come from the solvents or be introduced through poor storage practices. Organic acids, mineral acids, and certain acid-esters will reverse bridging from excessive moisture. Organic acids (such as citric, maleic, or malonic) or mineral acids (such as phosphoric) are all effective at concentrations of one-fourth to one percent, based on the weight of the carboxyl-modified vinyl resin. To restore a gelled paint to fluidity, first prepare a solution of the acid or acid-ester in acetone or other compatible solvent. Then, slowly add the solution to the gelled paint with agitation. Acid treatment of the coating may, however, affect adhesion and reduce gloss.

(a) Natural oxides are not satisfactory. Synthetic oxides are satisfactory in either air-dried or baked coatings.

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

29

A small amount of acid or acid-ester can also prevent or minimize viscosity excursions during paint manufacture. As with the restoration of gelled paints, this treatment may also affect adhesion and reduce gloss. The best way to control viscosity aberrations from water content is to prevent water from entering the formulation. Pigments can be easily dispersed into vinyl coatings with conventional equipment, such as a pebble mill, sand grinder, and high-speed stirrers. To prevent iron contamination, do not use steel ball mills for pigment dispersion. The most common technique is to dissolve the vinyl resin in the appropriate solvents. The vinyl solution is

then blended with the plasticizers, stabilizers, grinding aid, and pigments. For higher gloss coatings, predisperse the pigment in plasticizer, thinner, and grinding aid before adding to the vinyl resin solution. Where maximum gloss is desired, add pigments in either vinyl pigment chip or vinyl pigment paste form. For faster dispersion, incorporate wetting agents in the formulation. Soya lecithin or Nuosperse 657 (Creanova, Inc.) have been extensively tested and are effective wetting agents, when used in concentrations of one to five percent, based on pigment weight. Other suppliers such as Byk Chemie offer additives useful for pigment dispersion.

Modification with Other Polymers

Compatibility
The vinyl chloride/vinyl acetate copolymers are compatible with each other and with most acrylic resins. They have, however, a low order of compatibility with most other resin types. UCAR Carboxyl-Modified Solution Vinyl Resins will improve the general adhesion characteristics of other UCAR Solution Vinyl Resins. They will also improve air-dry adhesion of many acrylic coatings. UCAR HydroxylModified Solution Vinyl Resins (notably VAGF, VAGC, VAGH, VAGD, VROH) are compatible with a broad range of other film formers, such as alkyds, melamines, ureas, epoxies, and urethane prepolymers. Table 9 lists typical modifiers and shows their relative compatibility with UCAR Hydroxyl-Modified Solution Vinyl Resins.

Reactive (Crosslinking) Systems

UCAR Hydroxyl-Modified Solution Vinyl Resins can be cured with amino resins or isocyanate prepolymers to increase film hardness and resistance to solvents, chemicals, and moisture. Vinyl wood sealers cured with urea formaldehyde resins and acid catalysts cure rapidly at ambient temperature or short, low-temperature bake cycles. Vinyl coatings for metal containers cured with phenolic or melamine resins require higher bake temperatures, but the resulting coatings have excellent resistance to water immersion, pasteurization, and steam sterilization. Hydroxyl-modified resins cured with urethane prepolymers cure at ambient temperature or low bakes. Films can range from hard to elastomeric depending on the choice of urethane prepolymer.

30

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Table 9Compatibility a of UCAR Hydroxyl-Modified Solution Vinyl Resins with Other Resins
Vinyl/Modifier Ratiob VAGH VAGD VROH 4:1 1:4 4:1 1:4 4:1 1:4
c

Modifier Resin Alkyds (non-drying) Beckosol 12-021, coconut, short oil, PA content - 47% Alkyds (drying) Beckosol 11-035, soya, medium oil, PA content - 35% Beckosol 12-005, soya, short oil, PA content - 42% Beckosol 11-070, linseed/soya, medium oil, PA content - 31% Beckosol 12-054, tall oil fatty acids, short oil, PA content - 41% Urea-Formaldehyde Resins Beetle 55 (methylated resin) Beetle 60 (methylated resin) Beetle 65 (methylated resin) Beetle 80 (butylated resin) Hexamethoxymethylmelamine Cymel 303
d d c

C C C C

I C I C

C C C C

I C I C

H C H C

I C I C

I I I C

I I I C

I I I C

I I I C

I I I C

I I I C

C
d

Melamine-Formaldehyde Resins Cymel 350 Cymel 370 (methylated resin) Cymel 225-10 (rapid-cure resin) Urethane Prepolymers Mondur CB-60, aromatic polyisocyanate Desmondur N-75, aliphatic polyisocyanate Mondur HC, polyisocyanate copolymer
Key: C= H= I= PA = Compatible Haze in film, but coating uniform Incompatible Phthalic Anhydride e

C C H

C C I

C C H

C C I

C C H

C C I

C C C

C C C

C C C

C C C

C C C

C C C

(a) 5-mil (125 microns) wet drawdowns on glass; coatings dried 20 min at 140F (60C) prior to rating (b) Solids basis (c) Supplier: Reichhold (d) Supplier: Cytec Industries (e) Supplier: Bayer

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

31

Adhesion
For good adhesion, surfaces must be free of rust, grease, oil, dirt, and other contamination. Common techniques for cleaning surfaces include solvent wash, vapor degreasing, chemical treatment, and brush cleaning. For maximum adhesion, use a phosphate treatment or a vinyl butyral wash primer before applying the vinyl coating. Where vinyl butyral primers are used, the next coat must be based predominantly on hydroxyl-modified resins (VAGF, VAGC, VAGH, or VAGD). Maximum adhesion of vinyl coatings is usually obtained at bake temperatures high enough to drive out traces of residual solvents. Over porous surfaces, such as concrete and cloth, mechanical adhesion should be sufficient for good performance; baking is not generally needed. Baking finishes can be cured with heated air, infrared radiation, or by heating the metal surface on which the coating is applied. Control temperature carefully to avoid overbaking the coating. Maintain proper ventilation and uniform temperature distribution. UCAR Hydroxyl-Modified Solution Vinyl Resins adhere well to many types of finishes and are quite useful in applications where coatings based on the unmodified vinyl resins will not adhere. UCAR Carboxyl-Modified Solution Vinyl Resins adhere to clean metal and to air-dry or baked topcoats or primers. Table 10 compares the air-dry adhesion of coatings based on the three basic types of UCAR Solution Vinyl Resins.

Where Not to Use Vinyl Coatings

Vinyl coatings should not be used in applications where the continuous service temperature exceeds 140F (60C). No specific recommendations can be made for applications where the service temperature of the coating exceeds 140F (60C) intermittently or repeatedly. The recommendations for the use of heat stabilizers in UCAR Solution Vinyl Resins, given elsewhere in this booklet, are specific to a single-bake operation. The formulator is cautioned not to directly apply information about heat stabilizers to applications where service temperature exceeds 140F (60C) intermittently. Heat stabilizers that are effective at high bakesin excess of 350F (176C)may have an adverse effect on coating adhesion if used at lower service temperatures.

32

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

Table 10Air-Dry Adhesion of Coatings Based on UCAR Solution Vinyl Resins

Substrate Acrylic and Methacrylic Ester Resins Alkyd Resin Cloth Concrete (somewhat dependent on type) Glass Metal (clean and smooth) Metal, Phosphatized Nitrocellulose Oleoresinous (varies widely) Paper Phenolic Resins Plaster (somewhat dependent on type) Rubber, Chlorinated Shellac Urea Resins Vinyl Butyral Resin Vinyl Chloride Resins Wood VYHH Excellent Poor Poor Good Poor Poor Poor Poor Poor Poor Poor Good Fair Poor Poor Poor Excellent Poor VAGH Excellent Excellent Good Good Fair Poor Fair Poor Fair to Excellent Good Good Good Fair Good Good Excellent Excellent Fair VMCH Excellent Fair Fair to Excellent Excellent Fair Excellent Excellent Fair Poor Good Fair Excellent Fair Poor Fair Fair Excellent Fair

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

33

Product Stewardship
The Dow Chemical Company has a fundamental concern for all who make, distribute, and use its products, and for the environment in which we live. This concern is the basis of our Product Stewardship philosophy by which we assess the health and environmental information on our products and then take appropriate steps to protect employee and public health and the environment. Our Product Stewardship program rests with every individual involved with Dow products from the initial concept and research to the manufacture, sale, distribution, and disposal of each product. When considering the use of any Dow products in a particular application, you should review our latest Material Safety Data Sheets and ensure that the use you intend can be accomplished safely. For Material Safety Data Sheets and other product safety information, contact Dow at the numbers of the back cover of this brochure. Before handling any other products mentioned in the text, you should obtain available product safety information and take necessary steps to ensure safety of use.

34

Trademark

of The Dow Chemical Company (Dow) or an affiliated company of Dow.

35

The Dow Chemical Company Midland, Michigan 48674 U.S.A.

In the United States and Canada: call 1-800-447-4369 fax 1-989-832-1465 In Europe: call toll-free +800 3 694 6367 call +32 3 450 2240 fax +32 3 450 2815 In the Pacific: call toll-free +800 7776-7776 fax toll-free +800 7779-7779 call +60 3-7958-3392 fax +60 3-7958-5598 In Latin America: call (+55) 11-5188-9222 fax (+55)-11-5188-9749 Or visit us at www.dow.com

NOTICE: No freedom from any patent owned by Seller or others is to be inferred. Because use conditions and applicable laws may differ from one location to another and may change with time, Customer is responsible for determining whether products and the information in this document are appropriate for Customers use and for ensuring that Customers workplace and disposal practices are in compliance with applicable laws and other governmental enactments. Seller assumes no obligation or liability for the information in this document. NO WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCLUDED. Published December 2006.

Trademark of The Dow Chemical Company

Form No. 322-00051-1206 AMS