WATER-BASED INKS WITH RENEWABLE MATERIALS

Abstract

Described herein are water-based varnishes and inks that include a high renewable carbon content polyamide in an aqueous dispersion and a water-insoluble particulate material. The inks and varnishes exhibit stable viscosity, that is, they are varnishes and inks that exhibit little to no viscosity change over an extended period of time. Further, the inks and varnishes exhibit little to no settling of the insoluble particulate material over an extended period of time. The water-based varnishes include an aqueous polyamide resin dispersion and an additive selected from a water-insoluble particulate material, and the polyamide resin has a renewable carbon content of 50 wt %.

Claims

1. A water-based varnish comprising: an aqueous polyamide resin dispersion and an additive selected from a water-insoluble particulate material, wherein the polyamide resin has a renewable carbon content of 50% and the presence of the polyamide resin reduces settling of the water-insoluble particulate material.

2. The water-based varnish of claim 1, further comprising an acrylate polymer.

3. The water-based varnish of claim 1, wherein the polyamide resin is soluble in alcohol or a co-solvent blend of alcohol and a hydrocarbon.

4. The water-based varnish of claim 3, wherein the alcohol is a C.sub.2 to C.sub.6 alcohol.

5. The water-based varnish of claim 1, wherein the aqueous polyamide resin dispersion has a solids content of 30 wt % to 60 wt %, preferably 35 wt % to 55 wt %, more preferably 40 wt % to 50 wt %.

6. The water-based varnish of claim 1, wherein the aqueous polyamide resin dispersion has a pH at 25 C. of 6.5 to 9.5, preferably 7.0 to 9.0, more preferably 7.5 to 8.5.

7. The water-based varnish of claim 1, wherein the aqueous polyamide resin dispersion has a viscosity of 300 cps to 20,000 cps, preferably 375 cps to 575 cps, more preferably 425 cps to 525 cps.

8. The water-based varnish of claim 1, wherein the aqueous polyamide resin dispersion has an average particle size of 0.15 microns to 0.40 microns, preferably 0.20 microns to 0.40 microns, more preferably 0.25 microns to 0.35 microns.

9. The water-based varnish of claim 1, wherein the water-insoluble particulate material is selected from a polysaccharide, calcium carbonate, and mixtures thereof.

10. The water-based varnish of claim 9, wherein the polysaccharide is a starch.

11. The water-based varnish of claim 10, wherein the starch is an oxidized starch.

12. The water-based varnish of claim 1, wherein the polyamide resin has a renewable carbon content of 50 wt % to 99 wt %, preferably 60 wt % to 99 wt %, more preferably 70 wt % to 99 wt %, still more preferably 80 wt % to 99 wt %.

13. The water-based varnish of claim 1, wherein the renewable carbon content is based on the total carbon present in a sample of the aqueous polyamide resin dispersion, and the amount of renewable carbon is determined in accordance with ASTM D6866-18 Method B (AMS) using NIST Standard Reference Material (SRM) 4990C.

14. A water-based ink comprising the varnish of claim 1, and a colorant.

15. The water based ink of claim 14, wherein the colorant is a phosphorescent pigment.

16. The water-based ink of claim 14, wherein the ink maintains a reduced print viscosity of 18/seconds to 60/seconds for at least 70 days.

17. The water-based ink of claim 14, wherein the colorant is an acrylic pigment dispersion.

18. The water-based ink of claim 14, wherein the ink is a flexographic or gravure printing ink.

19. The water-based varnish or ink of claim 1, wherein the ink or varnish is substantially free of settling for at least 14 days, preferably for at least 50 days, more preferably for at least 70 days, and even more preferably for at least 90 days, and still even more preferably, one year.

20. A printed article comprising a substrate printed with the water-based varnish or ink of claim 1.

Description

EXAMPLES

[0049] The following examples illustrate specific aspects of the present invention. They are not intended to limit the scope thereof, and should not be construed as limiting.

[0050] Inventive Examples 1 and 4 and Comparative Examples 2, 3, and 5 are varnishes (also called vehicles). Inventive Examples 1 and 4 include the aqueous polyamide resin dispersion SNOWPACK 2362A. Comparative Examples 2 and 5 include all components of Inventive Examples 1 and 2 respectively, except they do not include SNOWPACK 2362A.

[0051] As can be seen in the data in Table 6, no settling occurs in Inventive Examples 1 and 4, whereas Comparative Examples 2 and 5 exhibit moderate settling after 2 days and severe settling after 90 days.

[0052] In Comparative Example 3, SNOWPACK 2362A is replaced with Urethane 940-1207, which provides the varnish with anti-settling properties. However, urethanes disadvantageously cause unacceptably large viscosity gains in finished inks.

TABLE-US-00001 TABLE 1 Inventive Example 1 - Varnish Containing SNOWPACK 2362A Material % Water 40.7 Ammonium Hydroxide 15% 3 Monoisopropanolamine 0.5 Tego 3062 -- a defoamer 0.3 Acticide LA -- microbiocide algicide and fungicide. 0.1 Filtrez 531 -- fumaric modified rosin ester, (Lawter) 4.9 Oxidized corn starch 11.4 Joncryl 662 6.4 Polestar 400 clay (kaolin) 0.5 Joncryl LMV 7031 11.5 Aquabead 425E -- anionic carnauba wax emulsion 14 SNOWPACK 2362A 5 Foam-A-Tac 2-255-37 1.7 Total 100.0 Joncryl 662 is an acrylic colloidal emulsion comprising 50% renewable raw materials on solids. Joncryl LMV 7031 is a film forming, low maintenance, pH stable acrylic emulsion.

TABLE-US-00002 TABLE 2 Comparative Example 2 - Inventive Example 1 without SNOWPACK 2362A Material % Water 43.0 Ammonium Hydroxide 15% 3.1 Monoisopropanolamine 0.5 Tego 3062 0.3 Acticide LA 0.1 Filtrez 531 5.2 Oxidized corn starch 12.0 Joncryl 662 6.7 Polestar 400 clay 0.5 Joncryl LMV 7031 12.1 Aquabead 425E 14.7 Foam-A-Tac 2-255-37 1.8 Total 100.0

TABLE-US-00003 TABLE 3 Comparative Example 3 - Inventive Example 1 (SNOWPACK 2362A Replaced by Urethane 940-1207) Material % Water 40.7 Ammonium Hydroxide 15% 3 Monoisopropanolamine 0.5 Tego 3062 0.3 Acticide LA 0.1 Filtrez 531 4.9 Oxidized corn starch 11.4 Joncryl 662 6.4 Polestar 400 clay 0.5 Joncryl LMV 7031 11.5 Aquabead 425E 14 Urethane 940-1207 5 Foam-A-Tac 2-255-37 1.7 Total 100.0

TABLE-US-00004 TABLE 4 Inventive Example 4 - Varnish Containing SNOWPACK 2362A Material % Water 24.6 Ammonium Hydroxide 15% 2.5 Monoisopropanolamine 0.5 Tego 3062 0.3 Reactol 5145 6.3 Oxidized corn starch 9.7 Joncryl LMV 7031 26.0 Joncryl 74-A 10.0 Aquabead 425E 8.0 Zinc Carbonate solution 3.0 SNOWPACK 2362A 8.0 Foam-A-Tac 2-255-37 1.0 Acticide LA 0.1 Total 100.0 Joncryl 74-A is a soft film forming, RC acrylic emulsion.

TABLE-US-00005 TABLE 5 Comparative Example 5 - Inventive Example 4 without SNOWPACK 2362A Material % Water 26.8 Ammonium Hydroxide 15% 2.7 Monoisopropanolamine 0.5 Tego 3062 0.3 Reactol 5145 6.8 Oxidized corn starch 10.5 Joncryl LMV 7031 28.3 Joncryl 74-A 10.9 Aquabead 425E 8.7 Zinc Carbonate solution 3.3 Foam-A-Tac 2-255-37 1.1 Acticide LA 0.1 Total 100.0

[0053] Settling, as the term is used herein, is determined by placing a sample of a liquid ink formulation in a sealed 4-ounce jar at room temperature (70 F.) and leaving the sample undisturbed for the time periods set forth in Tables 6, 10, and 12. The liquid ink passes the settling test if, without mixing or shaking of the jar, the sample pours out of the jar, leaving no solid materials on bottom of jar. The liquid ink fails the settling test if, under the same conditions, the solid material remains on the bottom of the container when the ink formulation is poured out.

TABLE-US-00006 TABLE 6 Settling Results Settling Example 2 Days 14 Days 90 Days Inv. Example 1 no settling no settling no settling Comp. Example 2 moderate severe severe settling settling settling Inv. Example 4 no settling no settling no settling Comp. Example 5 moderate severe severe settling settling settling Comp. Example 3 no settling no settling no settling

[0054] As shown in Table 6, inventive vehicles 1 and 4 containing SNOWPACK 2362A exhibited no settling, while the comparative examples 2 & 5, not containing SNOWPACK 2362A, exhibited severe settling by 14 days after formulation. Comparative Example 3, which contains urethane instead of SNOWPACK 2362A, is resistant to settling but exhibits a substantial increase in viscosity over time, as shown below.

[0055] Inventive Examples 6-15 were prepared by combining the Inventive Example 1 vehicle with the acrylic pigment dispersions identified in Table 7 to produce inventive inks, suited for example for flexo and gravure printing applications.

[0056] Comparative Examples 16-25 were prepared by combining the Comparative Example 3 vehicle (containing polyurethane) with the acrylic pigment dispersions identified in Table 8 below.

TABLE-US-00007 TABLE 7 Inventive Examples 6-15: Inventive Example 1 vehicle (w/SNOWPACK 2362A) Combined with Various Acrylic Dispersions Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 1 50 50 50 50 50 50 50 50 50 50 vehicle Yellow 14 50 YCD2004 Yellow 83 50 YGD8851 Orange 34 50 TPQ3034 Red 2 50 RCD9930 Red 22 50 RFD4241 Red 57:1 50 RFD9587 Blue 15:3 50 BFD8153 Green 7 50 GCD9957 Violet 23 50 VFD1157 Black 7 50 LAD7590 Total 100 100 100 100 100 100 100 100 100 100

TABLE-US-00008 TABLE 8 Comparative Examples 16-25: Comparative Example 3 Vehicle (Urethane 940-1207) Combined with the Acrylic Dispersions of Examples 6-15 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22 Ex. 23 Ex. 24 Ex. 25 Ex. 3 50 50 50 50 50 50 50 50 50 50 vehicle Yellow 14 50 YCD2004 Yellow 83 50 YGD8851 Orange 34 50 TPQ3034 Red 2 50 RCD9930 Red 22 50 RFD4241 Red 57:1 50 RFD9587 Blue 15:3 50 BFD8153 Green 7 50 GCD9957 Violet 23 50 VFD1157 Black 7 50 LAD7590 Total 100 100 100 100 100 100 100 100 100 100

[0057] The viscosity of the inks of the examples provided in Tables 7 and 8 was adjusted with water to a viscosity of 25 seconds, as determined with a #2 Signature Zahn cup in the manner described above.

[0058] The viscosity of inventive ink examples 6-15 of Table 7 was determined: (1) within 1 hour of formulation; (2) after 7 days; and (3) after 70 days in the manner described herein. Inventive ink examples 6-15 maintained a viscosity of 252 seconds for the entire 70 day testing period.

[0059] The viscosity of comparative ink examples 16-25 of Table 8 was determined within 1 hour of formulation and 24 hours after formulation in the manner described herein. Comparative ink examples 16-25 exhibited a viscosity gain from an initial 252/seconds to at least 32/seconds in 24 hours, which is unacceptable for most commercial printers, as it will lead to unacceptable color strength at print viscosity. In quantitative terms, a loss in strength corresponding to a DE>2.0 measured on an X-rite spectrometer or similar is not acceptable.

[0060] The acrylic emulsions available under the trade names Joncryl LMV 7031, Joncryl 74-A and Joncryl 662 are used in the inventive examples in combination with SNOWPACK 2362A. The examples further contain a polysaccharide and/or modified polysaccharide. The anti-settling influence of SNOWPACK 2362A upon the water-insoluble polysaccharide material is demonstrated in the above inventive examples. Aqueous polyamide resin dispersion would be expected to perform comparably in preventing settling of water insoluble particulates and in maintaining viscosity in combination with other water-based acrylics, such as, for example, the commercially available Joncryl 77, Joncryl 80, Joncryl 89, Lucidene 605, Joncryl 585, Joncryl 624, Vancryl 989, Lucidene 351, Vancryl K762, Joncryl 537, NeoCryl BT-101 and NeoCryl A-1127, among others.

[0061] The finished inks of the present application are suitable for application by printing methods such as flexographic, gravure, lithographic, screen, and digital.

Example 26 and Comparative Example 27

Water-Based Phosphorescent Printing Inks

[0062] Water-based inks were prepared from the following base composition that includes a phosphorescent pigment:

TABLE-US-00009 TABLE 9 Component Wt % BASF LMV 7040 acrylic emulsion 15.8 Silicone Defoamer 0.2 BASF JONCRYL LMV7050 acrylic emulsion 9.8 Defoamer 1.8 Tap Water 15.3 UVEDA GAF-2G Phosphorescent Pigment 50.0 Clay compound 0.6 Propylene Glycol 2.0 PE wax compound 3.0 Surfactant 1.5 TOTAL 100

[0063] Example 26 was prepared from the base composition by adding 10.0 wt % Snowpack 2362A to 90.0 wt % base composition. Viscosity=420 cps.

[0064] Comparative Example 27 was prepared from the base composition by adding 10.0 wt % Joncryl LMV 7040 to 90.0 wt % base composition. Viscosity=411 cps. Joncryl LMV 7040 is a pH stable acrylic emulsion.

[0065] Example 26 and Comparative Example 27 were mixed for 5 minutes, placed in sealed containers, and left undisturbed at 70 F. for 100 days.

[0066] After 100 days, the percentage of settled solid material and supernatant were measured. An ink knife was used to stir the settled solid material into a homogeneous ink.

TABLE-US-00010 TABLE 10 Qualitative Depth/Percent Depth/Percent description of settled Supernatant settled portion Example 26 11 mm 11 mm Soft settle, easily 50.0% 50.0% mixed with knife. Ink composition is easily re-homogenized Comparative 6 mm 14 mm Hard packed solid Example 27 30.0% 70.0% material, extremely difficult to mix with knife

Example 28 and Comparative Example 29

Water-Based Varnish Containing Calcium Carbonate

[0067] Water-based inks were prepared from the following base composition that includes calcium carbonate:

TABLE-US-00011 TABLE 11 % Component (Wt) JONCRYL 1698 acrylic emulsion 5.27 CALCIUM CARB 50% BASE in Solution Resin 71.93 Silicone defoamer 0.14 UREA Solution in water (50%) 6.42 Defoamer 0.55 WAX Emulsion 2.41 Solution FUMERIC VARNISH 9.28 Tap Water 4.00 TOTAL 100.00

[0068] Example 28 was prepared from the base composition by adding 7.0 wt % Snowpack 2362A to 93.0 wt % base composition. Viscosity 510 cps.

[0069] Comparative Example 29 was prepared from the base composition by adding 7.0 wt % Joncryl 1698 to 93.0 wt % base composition. Viscosity 548 cps.

[0070] Example 28 and Comparative Example 29 were mixed for 5 minutes, then placed on a shelf and maintained at 70 F. and left undisturbed for 100 days.

[0071] At the end of 100 days, the percentage of settlement and supernatant were measured. An ink knife was then used to stir the settlement into a homogeneous ink. Results are reported in Table 12.

TABLE-US-00012 TABLE 12 Qualitative Depth/Percent Depth/Percent description of settled Supernatant settled portion Example 28 32 mm 19 mm Soft settle, 62.70% 37.3% easily mixed with knife. Comparative 32 mm 25 mm Heavy settle, Example 29 56.1% 45.9% difficult to mix with knife

[0072] The present invention has been described in detail, including the preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/or improvements on this invention that fall within the scope and spirit of the invention.