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Surfy nol Surfactants: Superior Substrate Wetting Agents in Water-Based Printing Inks

Introduction
The performance benefits of Surfy nol surfactants have been evaluated in water-based inks to assess their effectiveness in providing substrate wetting while reducing or eliminating the need for alcohols. The substrates evaluated were difficult-to-wet polypropylene and polyethylene films as well as flexible paper and coated stock. The results demonstrate that Surfy nol SE-F, Surfy nol 420, Surfy nol 440 and Surfy nol 104 surfactants provide important benefits, including: excellent substrate wetting and improved flow and leveling; VOC reduction through solvent reduction or elimination; antifoam/low foam; and broad FDA compliances (for specific information, call 800-345-3148). Additionally, the study results indicate that Surfy nol surfactants have no adverse effect on gloss, water sensitivity, blocking or flexographic plate swell. A summary of surfactant recommendations and use-levels for typical printing ink applications is provided in Table 1. Typical physical properties of Surfy nol SE-F, Surfy nol 420, Surfy nol 440 and Surfy nol 104 surfactants are presented in Table 2. Table 1 Surfy nol Surfactant Starting-Point Recommendations
Substrate Polypropylene Film Polyethylene Film Coated Stock Flexible Paper Other Selection Criteria VOC, wt% Foam Control Water Resistance Excellent
1

Surfy nol SE-F 1% + 35% alcohol 1% + 3% alcohol 1% 1%

Surfy nol 420 1% + 35% alcohol 1% + 3% alcohol 1% 1%

Surfy nol 440 1% + 35% alcohol 1% + 3% alcohol 1% 1%

Surfy nol 104 50% Blends1 1% + 35% alcohol 1% + 3% alcohol 1% 1%

IPA Comparison 10%

10%

2% 2%

40 Excellent Excellent Good

28 Excellent Excellent

4 Good Good

6087 Excellent Excellent

100% Excellent Excellent

Surfy nol 104 surfactant is available as a 50% solution in isopropanol, n-propanol, dipropylene glycol monomethyl ether (DPM), propylene glycol, ethylene glycol, 2-butoxy ethanol (EB) and 2-ethylhexanol.

Table 2 Typical Properties


Surfy nol SE-F Specific Gravity @ 25C Density, lb/gal Viscosity @ 20C, cps (Brookfield, Spindle #3) HLB (HydrophileLipophile Balance)
1

Surfy nol 420 0.943 7.9 <200 4

Surfy nol 440 0.982 8.2 <200 8

Surfy nol 104 50% Blends1 0.8390.999 7.08.3 <200 4

0.971 8.1 <200 45

Surfy nol 104 surfactant is available as a 50% solution in isopropanol, n-propanol, dipropylene glycol monomethyl ether (DPM), propylene glycol, ethylene glycol, 2-butoxy ethanol (EB) and 2-ethylhexanol.

Surface Tension and VOC Reduction


Water-based printing inks have inherently high surface tensions due to the surface tension of water (72 dynes/cm). To reduce surface tension and achieve good surface wetting with defect-free printing, solvents such as isopropanol (IPA) are often incorporated. Increasing concerns about Volatile Organic Compound (VOC) levels, however, require many formulators to reduce their use of solvents. Surfactants, as a result, have become an even more important component in water-based ink formulations.

The ink systems were evaluated for equilibrium and dynamic surface tension, ink printability, foam control, gloss, water sensitivity, blocking, film adhesion and flexographic photopolymer plate swell.

Performance Results
The data and results from the study are presented on the following pages. Experimental procedures for all systems tested are outlined in the Appendix of this brochure.
Flexible Polypropylene Film Inks Two model water-based flexographic ink formulations, suitable for printing polypropylene flexible packaging films, are provided in Figures 1 and 2. Figure 1 provides the equilibrium and dynamic surface tension results of ink formulation 1, with and without Surfy nol surfactants. A strong correlation can be seen between dynamic surface tension reduction and the printability of the inks on polypropylene. This is demonstrated both photographically and through a rating system. Here, Surfy nol surfactants (with Surfy nol SE-F and Surfy nol 420 the most noteworthy) provide equal or superior printability at a 70% reduced alcohol level compared to the isopropanol-containing control. Ink formulation 2 (Figure 2) was evaluated on an alternative polypropylene to demonstrate the broad-based performance of the Surfy nol surfactants. Surface tensions were again determined on the inks, both without surfactant and with combinations of surfactant and 50% reduced alcohol. Printability, as with the earlier system, improves as dynamic surface tension is reduced. Surfy nol SE-F and Surfy nol 420 surfactants, followed closely by Surfy nol 104 and Surfy nol 440, again demonstrate outstanding wetting properties. Figures 1 and 2 also demonstrate foam control performance for the ink systems. The 10% alcohol control acts as an antifoam, preventing foam formation, which results in higher ink foam densities. This performance is readily achieved with the Surfy nol surfactant systems without the use of defoamers required with typical surfactants. Surfy nol surfactants are unique in this balance of surface tension reduction and low foam, making them ideally suited for water-based printing inks. Other ink performance properties such as gloss, water sensitivity, blocking, adhesion and plate swell were evaluated with and without Surfy nol surfactants. The results, provided in Table 3, clearly demonstrate that the addition of Surfy nol additives does not adversely impact other ink properties.

Formulating Notes

Use-levels that include combinations of Surfy nol surfactants with reduced levels of alcohol were selected as starting point recommendations for the polymeric film applications. However, Surfy nol surfactants allow the formulating latitude required to balance the competing needs of performance, cost conTypical surface tension values, such as those tainment and VOC reduction. For instance, obtained with a DuNouy ring instrument, are nol surfactants can be utilized at less equilibrium measurements that characterize a Surfy than 1% use levels as a co-surfactant with the system at rest. These values, however, are not remaining alcohol. Alternatively, Surfy nol indicative of an inks ability to wet out a subsurfactants can be used as a total replacement strate under dynamic or high-speed printing for alcohol at 23% for polymeric film applicaconditions. Indications of high-speed printing performance can more accurately be predicted tions and 1% or less for paper substrates. by measuring dynamic surface tension with an A common problem with many surfactants is instrument such as a maximum bubble presthat they cause the ink viscosity to rise. If a sure tensiometer. rise in viscosity occurs with the use of a Surfy nol surfactant, introducing the surfactant Low dynamic surface tension occurs when a at an early stage of the letdown with good surfactant has the ability to migrate rapidly to mixing is recommended. the newly created ink/substrate interface. Typical surfactants, however, generally provide good equilibrium values, but poor Summary and Recommendations dynamic performance. Most commercial surSurfy nol surfactants demonstrate the ability to factants also tend to stabilize foam. Surfy nol provide excellent substrate wetting and overall surfactants, in contrast, provide high perforsystem VOC reduction in water-based ink mance under both equilibrium and dynamic formulations. These results are due to their conditions while minimizing foam. These unique combination of low dynamic surface properties make Surfy nol surfactants excellent tension and defoaming characteristics. In alternatives to solvents used in water-based addition, Surfy nol surfactants have no deleteriinks for substrate wetting and improved ous impact on the other ink properties tested. printability. The results reported in this study with isopropanol have been observed with other common Substrates solvents, such as n-propanol. Surfy nol surfactants were evaluated in the Please refer to Table 1 for assistance in selectfollowing flexographic and gravure printing ink ing Surfy nol surfactants. The starting point applications: recommendations in Table 1 are based on the printability results discussed in this brochure. Polymer film substrates for flexible In addition, various performance criteria are packaging listed in the table to further aid formulators in Polypropylene selecting appropriate Surfy nol surfactants for Polyethylene their particular ink systems. Paper substrates suitable for flexible packaging, folding cartons, food containers and preprint linerboard Flexible paper (C1S) Coated stock

Figure 1 Flexographic Ink for Polypropylene Flexible Film


Formulation 1 Model Formulation Acrylic Polymer Emulsion1 Acrylic Resin Solution
2

No Alcohol No Surfactant 44% 11 40 5 100%

With Isopropanol 40% 10 36 10 4 100%

With Surfy nol Surfactant 40% 10 36 3 1 10 100%

Flexiverse Phthalo Blue GS 15:3 Dispersion Isopropanol Surfy nol Surfactant (actives) Water

All inks adjusted to 25 seconds (#2 Zahn cup). Polypropylene Film: LBW 240 (ICI Americas Film Division); 3336 dynes/cm (critical surface tension estimate).

Excellent Wetting and VOC Reduction with Surfy nol Surfactants3

No IPA No Surfactant Printability Rating (1 = Poor; 10 = Excellent) Alcohol Replacement (wt %) 2

10% IPA Control 9 0%

3% IPA + 1% Surfy nol SE-F 10 70%

3% IPA + 1% Surfy nol 420 10 70%

3% IPA + 1% Surfy nol 440 9 70%

3% IPA + 1% Surfy nol 104 9 70%

Surface Tension
69.7

Equilibrium Dynamic
42.8 35.2 31.8 36.1 32.7 37.6 34.7 38.7 33.1 38.0

Dynes/cm

45 35 25

42.5

Excellent Foam Control with Surfy nol Surfactants


1.0 Unagitated Ink 0.84 0.72 0.52 0.75 0.71 0.83

Ink Density (g/ml)

0.9 0.8 0.7 0.6 0.5 0.4 No IPA No Surfactant

10% IPA Control

3% IPA + 1% - SE-F Surfynol

3% IPA + 1% - 420 Surfynol

3% IPA + 1% - 440 Surfynol

3% IPA + 1% - 104 Surfynol

1 2

Vancryl 954 (Air Products and Chemicals, Inc., Polymer Chemicals Division). Other choices include Joncryl 74 (S.C. Johnson Polymer) and Lucidene 603 (Morton International). Vancryl 68S. Other choices include Joncryl 61 and Morcryl 134 (Morton International). 3 Photos taken at 3.7x magnification.

Figure 2 Flexographic Ink for Polypropylene Flexible Film


Formulation 2 Model Formulation Acrylic Polymer Emulsion1 Flexiverse Diarylide AAOT Yellow 14 Dispersion PE Wax Emulsion2 Isopropanol Surfy nol Surfactant (actives) Water No Alcohol No Surfactant 47% 43 5 5 100%
All inks adjusted to 25 seconds (#2 Zahn cup). Polypropylene Film: Bicor BSR-ONE (Mobil); 3438 dynes/cm (critical surface tension estimate).

With Isopropanol 42% 39 5 10 4 100%

With Surfy nol Surfactant 42% 39 5 5 1 8 100%

Excellent Wetting and VOC Reduction with Surfy nol Surfactants3

No IPA No Surfactant Printability Rating (1 = Poor; 10 = Excellent) Alcohol Replacement (wt %) 2

10% IPA Control 9 0%

5% IPA + 1% Surfy nol SE-F 9 50%

5% IPA + 1% Surfy nol 420 9 50%

5% IPA + 1% Surfy nol 440 8 50%

5% IPA + 1% Surfy nol 104 8 50%

Surface Tension
70.9

Equilibrium Dynamic
43.4 36.3 35.5 31.7 32.0 35.9 37.6 34.3 33.2 36.1

Dynes/cm

45 35 25

44.7

Excellent Foam Control with Surfy nol Surfactants


1.0 Unagitated Ink 0.88 0.73 0.56

Ink Density (g/ml)

0.9 0.8 0.7 0.6 0.5 0.4 No IPA No Surfactant

0.89

0.87

0.87

10% IPA Control

5% IPA + 1% - SE-F Surfynol

5% IPA + 1% - 420 Surfynol

5% IPA + 1% - 440 Surfynol

5% IPA + 1% - 104 Surfynol

1 2

Joncryl 624. Other choices include Lucidene 605. Jonwax 26 (S.C. Johnson Polymers). 3 Photos taken at 3.7x magnification.

Flexible Polyethylene Film Inks A model flexographic ink suitable for printing polyethylene flexible packaging films is provided in Figure 3. The experimental results (Figure 3) again indicate a strong correlation between the dynamic surface tension of the ink and printability on the polyethylene substrate. In addition, the photographs and subjective printability ratings clearly demonstrate that a 70% reduction in alcohol in combination with 1% Surfy nol SE-F, Surfy nol 420 or Surfy nol 440 surfactant provides superior wetting performance compared to the 10% isopropanol-containing control. Foam control performance is also presented in Figure 3. Low foam is obtained with the control ink containing 10% alcohol. Yet, similar foam control performance is obtained in the formulation with a 70% alcohol reduction and the addition of 1% Surfy nol surfactant. Here again, Surfy nol surfactants demonstrate their defoaming and outstanding surface tension reducing capabilities, making them an excellent choice when formulating inks for polyethylene and other nonporous, difficult-to-wet surfaces. Other ink performance properties, such as gloss, water sensitivity, blocking, adhesion and plate swell, were investigated with and without Surfy nol surfactants. As seen with the polypropylene inks, the results provided in Table 3 clearly demonstrate that there are no deleterious effects with the addition of Surfy nol surfactants.

Table 3 No Detrimental Effects with Surfy nol Surfactants (Results for All Ink Formulations)
Gloss Water Sensitivity Blocking Substrate Adhesion Flexographic Plate Swell <1.5% variance with the IPA-containing control No difference from the IPA-containing control No difference from the IPA-containing control No difference from the IPA-containing control <1.5% weight gain over the IPA-containing control

Coated Stock and Flexible Paper Inks Inks formulated for porous substrates occasionally require wetting agents to assure wetout and defect-free coverage. Surface defects that may require wetting agents include mottling and snowflakes, both of which are related to poor flow and leveling. Surfy nol surfactants can solve these problems, while allowing the removal of alcohol and their VOCs. A model formulation suited for flexographic coated stock ink and gravure flexible paper ink applications is presented in Figure 4, along with test results. As with the flexographic film ink systems, a strong correlation can be seen between the dynamic surface tension values of the ink and printability on the substrates. The addition of 2% isopropanol reduces the dynamic surface tension enough to allow moderate printability. However, when the isopropanol is replaced by 1% Surfy nol surfactant, the surface tension reduction and printability improves significantly. Surfy nol 420 and Surfy nol 104 provide the best results on the coated stock, while Surfy nol SE-F, Surfy nol 420 and Surfy nol 104 perform best on the flexible paper substrate.

The foam control data in Figure 4 indicates that the Surfy nol surfactants provided similar or superior defoaming performance when compared to the isopropanol-containing control. As illustrated in the polymeric film application areas, the unique combination of dynamic surface tension reduction and defoaming capabilities also makes Surfy nol surfactants ideally suited for water-based inks for porous substrates. Gloss, water sensitivity, blocking, adhesion and plate swell were also evaluated with and without Surfy nol surfactants. The results in Table 3 indicate there are no adverse effects on ink performance with the addition of Surfy nol surfactants.

Figure 3 Flexographic Ink for Polyethylene Flexible Film


Model Formulation Acrylic Polymer Emulsion1 Flexiverse Diarylide AAOT Yellow 14 Dispersion PE Wax Emulsion Isopropanol Surfy nol Surfactant (actives) Water
2

No Alcohol No Surfactant 47% 43 5 5 100%

With Isopropanol 42% 39 5 10 4 100%

With Surfynol Surfactant 42% 39 5 3 1 10 100%

All inks adjusted to 25 seconds (#2 Zahn cup). Polyethylene Film: High Density, Corona Treated (Mobil); 3235 dynes/cm (critical surface tension estimate).

Excellent Wetting and VOC Reduction with Surfy nol Surfactants3

No IPA No Surfactant Printability Rating (1 = Poor; 10 = Excellent) Alcohol Replacement (wt %) 2

10% IPA Control 8 0%

3% IPA + 1% Surfy nol SE-F 9 70%

3% IPA + 1% Surfy nol 420 9 70%

3% IPA + 1% Surfy nol 440 9 70%

3% IPA + 1% Surfy nol 104 8 70%

Surface Tension
69.5 47.8

Equilibrium Dynamic
43.6 38.1 37.2 31.4 30.4 36.7 32.0 38.5 31.8 37.9

Dynes/cm

45 35 25

Excellent Foam Control with Surfy nol Surfactants


1.0 Unagitated Ink 0.89 0.79

Ink Density (g/ml)

0.9 0.8 0.7 0.6 0.5 0.4 No IPA No Surfactant 0.50

0.87

0.88

0.89

10% IPA Control

3% IPA + 1% - SE-F Surfynol

3% IPA + 1% - 420 Surfynol

3% IPA + 1% - 440 Surfynol

3% IPA + 1% - 104 Surfynol

1 2 3

Joncryl 624. Other choices include Lucidene 605. Jonwax 26. Photos taken at 3.7x magnification.

Figure 4 Ink for Coated Stock and Flexible Paper


Model Formulation Acrylic Polymer Emulsion1 Acrylic Resin Solution2 Flexiverse BFD-1121 Isopropanol Surfy nol Surfactant (actives) Water No Alcohol No Surfactant 45% 15 30 10 100% With Isopropanol 45% 15 30 2 8 100% With Surfy nol Surfactant 45% 15 30 1 9 100%

All inks adjusted to 25 seconds (#2 Zahn cup). Coated Stock: Clay-coated Linerboard (Riverwood), Flexographic Printed; Flexible Paper: Coated One-Side, C1S (James River Corp.), Gravure Printed.

Excellent Wetting and VOC Reduction with Surfy nol Surfactants3

No IPA No Surfactant Printability Rating (1 = Poor; 10 = Excellent) Coated Stock (shown above) Flexible Paper Alcohol Replacement (wt %) 4 6

2% IPA

1% Surfy nol SE-F

1% Surfy nol 420

1% Surfy nol 440

1% Surfy nol 104

7 7 0%

8 9 100%

9 9 100%

8 8 100%

9 9 100%

Surface Tension
68.7

Equilibrium Dynamic
44.7 38.3 35.5 30.5 29.5 34.1 35.9 31.7 32.6 28.2

Dynes/cm

45
38.8

35 25

Excellent Foam Control with Surfy nol Surfactants


1.0 Unagitated Ink 0.81 0.76 0.81 0.84 0.73 0.84

Ink Density (g/ml)

0.9 0.8 0.7 0.6 0.5 0.4 No IPA No Surfactant

2% IPA Control

1% - SE-F Surfynol

1% - 420 Surfynol

1% - 440 Surfynol

1% - 104 Surfynol

1 2

Joncryl 89. Other choices include Lucidene 370 and Vancryl 989. Joncryl 61. Other choices include Morcryl 134 and Vancryl 68S. 3 Photos taken at 3.7x magnification.

Appendix
Experimental Procedures Sample Preparation Ink bases for each formulation listed in Figures 14 were prepared both with and without alcohol or surfactant. For each flexible film ink, 90 parts of the base were mixed with 10 parts of a combination of surfactant, alcohol and water. For the paper substrate inks, 98 parts of the ink base were combined with 2 parts alcohol or surfactant and water. All formulations were adjusted to a viscosity of 25 seconds on a #2 Zahn cup. Surface Tension Measurements Surface tension values were determined on a SensaDyneTM 6000 Tensiometer (Chem-Dyne Research Corporation). Samples were diluted 50/50 with water to reduce viscosity to within the operating range of the instrument; therefore, the values are relative. Both equilibrium (1 bubble/second) and dynamic (5 bubbles/ second) surface tensions were evaluated. The critical surface tensions of the substrates were determined via surface tension fluids from Diversified Enterprises, Inc. Printability Flexographic printing (flexible films and coated stock) was performed using a Pamarco hand proofer equipped with a #165 anilox. A Geiger press was utilized for gravure printing (flexible paper). Printability was visually evaluated on a qualitative scale of 110, with 10 being an excellent film. Dewetting and pinholing were the major defects on the nonporous substrates, and mottling was the major defect on the porous substrates. Foam Test Ink samples (50 grams) were agitated at 12,000 rpm for 1 minute utilizing a Waring Blender. Densities were measured before and after agitation. Blocking Blocking was evaluated via ASTM D2793-69.

Adhesion Adhesion was evaluated via the 610 Scotch tape test. Water Resistance Water droplets were placed on the cured films and wiped off at the following intervals: 0.5, 1, 2 and 5 minutes. Gloss Gloss values were determined at 60 degrees with a Dr. Lange Reflectometer. Plate Swell One-inch squares of Letterflex Photopolymer flexographic printing plate on a steel backing (WR Grace) were cut and then pre-weighed on an analytical balance. The plates were placed in the formulated inks for 24 hours, then removed, cleaned and re-weighed to determine plate swelling via weight increase. These values were then compared with those of the control containing no surfactant.

Latin America Air Products and Chemicals, Inc. Latin American Region 7201 Hamilton Boulevard Allentown, PA 18195-1501 Telephone: 610-481-7290 Fax: 610-481-5817 Air Products and Chemicals de Mexico S.A. de C.V. Suite 26, Piso 12 World Trade Center Avenida de las Naciones No 1 Col. Napoles, Mxico D.F. 03810 Mexico Telephone: +52-5-488-0790 Fax: +52-5-488-0798 Air Products Gases Industriais Ltda. (APGIL) Praca Radialista Manoel de Nobrega, 65 Casa Verde 02517-160 So Paulo, SP Brazil Telephone: +55-11-856-1707 Fax: +55-11-856-1781 Europe Air Products Nederland B.V. Kanaalweg 15, Box 3193 3502 GD Utrecht Netherlands Telephone: +31-30-2857100 Fax: +31-30-2857111 Asia Air Products Japan, Inc. 3-18-19, Toranomon, Minato-Ku Tokyo 105 Japan Telephone: +81-3-3432-7031 Fax: +81-3-3432-7052

Raw Material Suppliers


Air Products and Chemicals, Inc.: Vancryl 954, Vancryl 68S; Sun Chemical Corporation: Flexiverse Phthalo Blue GS Dispersion, Flexiverse Diarylide AAOT Yellow Dispersion; S.C. Johnson Polymer: Joncryl 624, Joncryl 89, Joncryl 61, Jonwax 26 PE Wax Emulsion.

Air Products Asia, Inc. Rm 5507-10 Hopewell Centre 183 Queens Road East For More Information Wanchai If youd like additional information, write or call Hong Kong Air Products and Chemicals, Inc., at the follow- Telephone: +852-2527-0515 ing locations. Fax: +852-2527-1957 Air Products and Chemicals, Inc. Performance Chemicals 7201 Hamilton Boulevard Allentown, PA 18195-1501 Telephone: 800-345-3148 (Outside U.S./Canada 610-481-6799) Fax: 610-481-4381 http://www.airproducts.com

The information in this literature is offered without charge for use by technically qualified personnel at their discretion and risk. All statements, technical information and recommendations are based on tests and data which we believe to be reliable, but their accuracy or completeness is not guaranteed and no warranty of any kind is made.

Air Products and Chemicals, Inc., 1999 (20000)

Printed in USA 120-9937