EP4677035A1

EP4677035A1 - Bio-renewable binders for inks and overprint varnishes

Info

Publication number: EP4677035A1
Application number: EP24717045.9A
Authority: EP
Inventors: Titus David DR. LEMAN; Gary Deeter; David TAPPA; Brandon Mark CHANCE; Saumya DR. DABRAL
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2023-03-09
Filing date: 2024-03-08
Publication date: 2026-01-14
Also published as: CN120752315A; WO2024187103A1

Abstract

Disclosed herein are bio-renewable binders for inks and varnishes, and methods of synthesizing and using the binder compositions.

Description

BIO-RENEWABLE BINDERS FOR INKS AND OVERPRINT VARNISHES

FIELD OF THE DISCLOSURE

[001] This disclosure relates generally to water-based inks and overprint varnishes, and more particularly to high bio-renewable containing aqueous emulsion binders for these inks and varnishes, and to methods of synthesizing and using the emulsion compositions.

BACKGROUND OF THE DISCLOSURE

[002] Water-based inks often contain materials that are water-insoluble, such as particulate materials. Over time, water-insoluble materials may settle out of the ink and form sediment at the bottom of the container. This settling may take place between the time of manufacture and printing. In order to limit the amount of settling of such particulate components, water-based polyurethanes and polyamides have been included in ink compositions.

[003] A disadvantage that arises from the inclusion of polyurethanes and other acrylic polymeric materials used as ink ingredients in the state of the art is that they are produced from fossil fuels. The manufacture and usage of such components depletes the earth’s natural resources and pollute the environment. In recent years, ink and varnish formulators have been moving towards environmentally friendly approaches to contending with greenhouse gas emissions and when possible, avoiding populating landfills with singleuse carbon products. Because many of the components used in ink and varnish products are carbon-based, a more environmentally friendly approach in which organic components produced from renewable carbon sources is desired.

SUMMARY OF THE DISCLOSURE

[004] Disclosed herein is a method for preparing a high bio-renewable containing polymer emulsion. The present disclosure further provides water-based inks and varnishes that include a high renewable content rosin ester in an aqueous dispersion and a waterinsoluble particulate material.

[005] In one form thereof, the present disclosure provides a high bio-renewable containing emulsion composition suitable for use as a binder, the emulsion composition comprising: (i) a rosin ester; (ii) co-polymerizable monomers and (iii) water.

[006] In a second form thereof, the present disclosure provides a process for preparing the high bio-renewable containing polymer emulsion comprising: (i) providing a resin dispersion comprising at least one resin in aqueous solution; (ii) adding at least one initiator and a polymerization mixture to the resin dispersion, the polymerization mixture comprising at least one co-polymerizable monomer; and (iii) preparing a polymer emulsion in water by radical emulsion polymerization of the polymerization mixture, the resin dispersion, and the initiator.

BRIEF DESCRIPTION OF THE DRAWINGS

[007] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the disclosure and together with the description, serve to explain the principles of the disclosure.

[008] Fig. 1 is an image showing the drawdown of an ink formulation containing the binder of Example 1 with bio-renewable content (left and right) vs. Standard Joncryl ECO 2189 (Center) on the Leneta card 3NT-31 using pigment Flexiverse BFD-1121 dispersion in a standard ink formulation.

[009] Fig. 2 is an image showing the drawdown of ink formulation containing the binder of Example 2 containing bio-renewable content (left) vs. standard Joncryl ECO 2177 (right) on the Leneta card 3NT-31 using pigment Flexiverse BFD-1121 dispersion in a standard ink formulation.

DETAILED DESCRIPTION

I. Definitions

[0010] As used herein, the term “bio-renewable” refers to anything originating from renewable feedstocks. The presence and amount of “bio-renewable” matter is measured, for example, under the procedure described in ASTM D6866-18. A composition may be deemed “bio-renewable,” for example, if it comprises at least 20 wt.% “bio-renewable” components, in particular 20 to 60% by weight “bio-renewable” components, in particular 30 to 50% by weight “bio-renewable” components.

[0011] The term “comprising”, and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of” and “consisting of’ can be used in place of “comprising” and “including” to provide for more specific embodiments and are also disclosed. As used in this disclosure and in the appended claims, the singular forms a”, “an”, “the”, include plural referents unless the context clearly dictates otherwise. The disclosure of percentage ranges and other ranges herein includes the disclosure of the endpoints of the range and any integers provided in the range.

II. High Bio-Renewable Containing Emulsion Binders

[0012] The present disclosure provides a high bio-renewable containing emulsion binder for inks and overprint varnishes.

[0013] The emulsion binder may comprise a resin, co-polymerizable monomers, and water.

[0014] An aspect of the presently claimed invention relates to a process for preparing the high bio-renewable containing polymer emulsion comprising at least the steps of:

(i) providing a resin dispersion comprising at least one resin in aqueous solution;

(ii) adding at least one initiator and a polymerization mixture to the resin dispersion, the polymerization mixture comprising at least one co-polymerizable monomer; and

(iii) preparing a polymer emulsion in water by radical emulsion polymerization of the polymerization mixture, the resin dispersion, and the initiator.

[0015] The resin may be a support resin. The resin may be derived, in whole or in part, from a bio-renewable source. Suitable sources may include plants, trees, and byproducts of wood pulping processes, for example.

[0016] The bio-renewable resins may include rosin esters. Suitable rosin esters may include fumarate esters. For example, Filtrez 531 is a fumaric rosin ester obtained from Lawter. In addition, XR2780 from Lawter may be used.

[0017] The rosin ester may have an acid value of about 125 mg KOH/g or greater, 150 mg KOH/g or greater, about 155 mg KOH/g or greater, about 160 mg KOH/g or greater, about 165 mg KOH/g or greater, about 170 mg KOH/g or greater, about 175 mg KOH/g or less, about 180 mg KOH/g or less, about 185 mg KOH/g or less, about 190 mg KOH/g or less, about 195 mg KOH/g or less, about 200 mg KOH/g or less, or any value encompassed by these endpoints. [0018] The number average molecular weight (Mn) of the rosin ester may be about 600 g/mol or greater, about 620 g/mol or greater, about 640 g/mol or greater, about 660 g/mol or greater, about 680 g/mol or greater, about 700 g/mol or less, about 720 g/mol or less, about 740 g/mol or less, about 760 g/mol or less, about 780 g/mol or less, about 800 g/mol or less, or any value encompassed by these endpoints. [0019] The weight average molecular weight (Mw) of the rosin ester may be about 1500 g/mol or greater, about 2000 g/mol or greater, about 2500 g/mol or greater, about 3000 g/mol or greater, about 3500 g/mol or greater, about 4000 g/mol or greater, about 4500 g/mol or less, about 5000 g/mol or less, about 5500 g/mol or less, about 6000 g/mol or less about 6500 g/mol or less, about 7000 g/mol or less, about 10,000 g/mol or less, about 15,000 g/mol or less, or any value encompassed by these endpoints.

[0020] The rosin ester may be present in the polymer emulsion in an amount of 40 wt.% or greater, 45 wt.% or greater, 50 wt.% or greater, 55 wt.% or greater, 60 wt.% or greater, 65 wt.% or greater, 70 wt.% or greater, 75 wt.% or greater, 80 wt.% or greater, 85 wt.% or greater, 90 wt.% or greater, or 95 wt.% or greater based on the total weight of the polymer emulsion composition.

[0021] When preparing the polymer, the rosin ester may be dispersed in an aqueous solution. Suitable aqueous solutions may include aqueous ammonia, for example. The concentration of the rosin ester in the aqueous ammonia may be about 15% or greater, about 20% or greater, about 25% or greater, about 30% or less, about 35% or less, about 40% or less, as determined either by oven (150°C, 30 min) or microwave solid analyzer.

[0022] A surfactant may then be added to the dispersion of the rosin ester in the aqueous phase. Suitable surfactants may include Poly Step A16-22 (Sodium Dodecyl benzene sulfonate from Stephan Company), Disponil AFX 1080 or Calfax DB45, for example. The surfactant may be present in the reaction mixture in an amount of about 0.1 wt.% or greater, about 0.2 wt.% or greater, about 0.3 wt.% or greater, about 0.4 wt.% or greater, about 0.5 wt.% or greater, about 0.6 wt.% or less, about 0.7 wt.% or less, about 0.8 wt.% or less, about 0.9 wt.% or less, about 1 wt.% or less, or any value encompassed by these endpoints.

[0023] The emulsion may then be initiated by adding a redox initiator. Suitable redox initiators may include redox initiators, such as isoascorbic acid (IAA), /-butyl hydroperoxide (TBHP), sodium erythobate, sodium metabisulfate, or combinations thereof, for example.

[0024] The initiator may be fed to the reaction mixture over a period of about 60 minutes or greater, about 70 minutes or greater, about 80 minutes of greater, about 90 minutes or less, about 100 minutes or less, about 110 minutes or less, about 120 minutes or less, or any value encompassed by these endpoints. [0025] The initiator may be fed to the reaction mixture at a temperature of about 60°C or greater, about 65°C or greater, about 70°C or less, about 75°C or less, about 80°C or less, or any value encompassed by these endpoints.

[0026] A catalyst may also be added. Suitable catalysts may include copper(II) sulfate (C11SO4) and iron(II) sulfate, for example.

[0027] In some embodiments, the emulsion polymerization monomers may include a styrene acrylic based copolymer and also an acrylic-based copolymer. Acrylic-based copolymers include copolymers derived from one or more (meth) acrylate monomers. The aery lie -based copolymer can be a pure acrylic polymer (i.e., a copolymer derived primarily from (meth)acrylate monomers), a styrene-acrylic polymer (i.e., a copolymer derived from styrene and one or more (meth)acrylate monomers), or a vinyl-acrylic polymer (i.e., a copolymer derived from one or more vinyl ester monomers and one or more (meth) acrylate monomers).

[0028] Exemplary acrylate and methacrylate monomers include, but are not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, 2-methylheptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, alkyl crotonates, vinyl acetate, di-n-butyl maleate, di-octylmaleate, hydroxyethyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxy (meth)acrylate, 2-(2- ethoxyethoxy)ethyl (meth)acrylate, 2-propylheptyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, caprolactone (meth) acrylate, polypropyleneglycol mono(meth)acrylate, polyethyleneglycol (meth)acrylate, benzyl (meth)acrylate, hydroxypropyl (meth)acrylate, methylpolyglycol (meth)acrylate, 3,4- epoxycyclohexylmethyl (meth)acrylate, 1,6 hexanediol di(meth)acrylate, 1,4 butanediol di(meth)acrylate, and combinations thereof.

[0029] The emulsion polymerization mixture may also comprise one or more soft ethylenically-unsaturated monomers, as well as one or more hard ethylenically-unsaturated monomers. As used herein, the term “soft ethylenically-unsaturated monomer” refers to an ethylenically-unsaturated monomer that, when homopolymerized, forms a polymer having a glass transition temperature, as measured using differential scanning calorimetry (DSC), of

0° C. or less. Soft ethylenically-unsaturated monomers are known in the art, and include, for example, ethyl acrylate (T_g=-24° C.), butyl acrylate (n-butyl acrylate, T_g=-54° C.), secbutyl acrylate (T_g=-26° C.), sec -butyl acrylate (T_g=-26° C.), isobutyl acrylate (T_g=-24° C.), n-hexyl acrylate (T_g=-45° C.), n-hexyl methacrylate (T_g=-5° C.), 2-ethylhexyl acrylate (T_g=-85° C.), 2-ethylhexyl methacrylate (T_g=-10° C.), octyl methacrylate (T_g=-20° C.), n- decyl methacrylate (T_g=-30° C.), isodecyl acrylate (T_g=-55° C.), dodecyl acrylate (T_g=-3° C.), dodecyl methacrylate (T_g=-65° C.), 2-ethoxyethyl acrylate (T_g=-50° C.), 2-methoxy acrylate (T_g=-50° C.), and 2-(2-ethoxyethoxy)ethyl acrylate (T_g=-70° C.).

[0030] In some embodiments, the emulsion polymerization mixture may comprise soft ethylenically-unsaturated monomer that, when homopolymerized, forms a polymer having a low glass transition temperature, as measured using DSC, of about -30°C or greater, about -25°C or greater, about -24°C or greater, about -23°C or greater, about -22°C or greater, about -21 °C or greater, about -20°C or greater, about -19°C or less, about -18°C or less, about -17°C or less, about -16°C or less, about -15°C or less, about -10°C or less, or any value encompassed by these endpoints, as measured by ASTM D3418-15. For example, the first theoretical T_g may be about -25°C to about -15°C, about -18°C to about - 10°C, about -22°C to about -15°C, among others. In some embodiments, the emulsion polymerization mixture may comprise soft ethylenically-unsaturated monomer that, when homopolymerized, forms a polymer having a medium glass transition temperature, as measured using DSC of 10°C or greater, 12°C or greater, 15°C or greater, 17°C or greater, 20°C or greater, 22°C or greater, 25°C or less, 27°C or less, 30°C or less, 32°C or less, 35°C or less, or any value encompassed by these endpoints, as measured by ASTM D3418-15. For example, the first theoretical T_g may be about 10°C to about 35°C, about 15°C to about 25°C, or about 17°C to about 22°C, among others. In some embodiments, the emulsion polymerization mixture may comprise soft ethylenically-unsaturated monomer that, when homopolymerized, forms a polymer having a high glass transition temperature, as measured using DSC of 80°C or greater, 82°C or greater, 85°C or greater, 87°C or greater, 90°C or greater, 92°C or greater, 95°C or less, 97°C or less, 100°C or less, 102°C or less, 105°C or less, or any value encompassed by these endpoints, as measured by ASTM D3418-15. For example, the first theoretical T_g may be about 80°C to about 105°C, about 85°C to about 95°C, or about 87°C to about 92°C, among others. [0031] The emulsion polymerization mixture may also comprise a hard ethylenically unsaturated monomer. Suitable hard ethylenically unsaturated monomers may include styrene with T_g = 100°C or methyl methacrylate, T_g = 125°C.

[0032] The styrene or methyl methacrylate may be present in the composition in an amount of about 30 wt.% or greater, about 35 wt.% or greater, about 40 wt.% or less, about 45 wt.% or less, about 50 wt.% or less, or any value or range encompassed by these endpoints, based on the total weight of monomers used, for example from 30 to 50 wt.%, or from 35 to 45 wt.%.

[0033] The emulsion polymerization mixture may also comprise one or more carboxylic acid-containing monomers based on the total weight of monomers. Suitable carboxylic acid-containing monomers are known in the art, and include a, [3- monoethylenically unsaturated mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, dimethacrylic acid, ethylacrylic acid, allylacetic acid, vinylacetic acid, mesaconic acid, methylenemalonic acid, citraconic acid, and combinations thereof.

[0034] In some embodiments, the emulsion polymerization mixture may be substantially free of styrene. In other words, the amount of styrene in the mixture may be 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, or 0 wt.% based on the total weight of the mixture.

[0035] In certain embodiments, the emulsion polymerization mixture may be substantially free of solid grade oligomer (SGO) resins. In other words, the amount of SGOs in the mixture may be 5 wt.% or less, 3 wt.% or less, 1 wt.% or less, 0.1 wt.% or less, or 0 wt.% based on the total weight of the mixture.

[0036] In certain embodiments, the emulsion polymerization monomers may comprise a mixture of styrene or methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and additional functional monomers, such as acrylic acid, methyl acrylic acid, and/or itaconic acid.

[0037] In certain embodiments, the amount of styrene monomers present in the emulsion polymerization mixture may be about 30 wt.% or greater, about 35 wt.% or greater, about 40 wt.% or greater, about 45 wt.% or greater, about 50 wt.% or greater, about 55 wt.% or greater about 60 wt.% or less, about 65 wt.% or less, about 70 wt.% or less, about 75 wt.% or less, about 80 wt.% or less, about 85 wt.% or less, about 90 wt.% or less, about 95 wt.% or less, about 100 wt.% or less, or any value or range encompassed by these endpoints, as a percentage of the total emulsion polymerization mixture.

[0038] In certain embodiments, the amount of methyl methacrylate monomers present in the emulsion polymerization mixture may be about 40 wt.% or greater, about 41 wt.% or greater, about 42 wt.% or greater, about 43 wt.% or greater, about 44 wt.% or greater, about 45 wt.% or greater, about 46 wt.% or less, about 47 wt.% or less, about 48 wt.% or less, about 49 wt.% or less, about 50 wt.% or less, or any value encompassed by these endpoints, as a percentage of the total emulsion polymerization mixture.

[0039] In certain embodiments, the amount of butyl acrylate monomers present in the emulsion polymerization mixture may be about 30 wt.% or greater, about 31 wt.% or greater, about 32 wt.% or greater, about 33 wt.% or greater, about 34 wt.% or greater, about 35 wt.% or greater, about 36 wt.% or less, about 37 wt.% or less, about 38 wt.% or less, about 39 wt.% or less, about 40 wt.% or less, or any value encompassed by these endpoints, as a percentage of the total emulsion polymerization mixture.

[0040] In certain embodiments, the amount of 2-ethylhexyl acrylate monomers present in the emulsion polymerization mixture may be about 10 wt.% or greater, 15 wt.% or greater, 20 wt.% or greater, 25 wt.% or greater, 30 wt.% or greater, about 35 wt.% or greater, about 40 wt.% or greater, about 45 wt.% or greater, about 50 wt.% or greater, about 55 wt.% or greater about 60 wt.% or less, about 65 wt.% or less, about 70 wt.% or less, about 75 wt.% or less, about 80 wt.% or less, about 85 wt.% or less, about 90 wt.% or less, about 95 wt.% or less, about 100 wt.% or less, or any value or range encompassed by these endpoints, as a percentage of the total emulsion polymerization mixture.

[0041] In certain embodiments, the emulsion polymerization mixture may include one or more functional monomers. The functional monomers may include one or more of acrylic acid monomers, methyl acrylic acid monomers, and itaconic acid monomers. The functional monomers may be present in the emulsion polymerization mixture in an amount of 0 wt.% or greater, about 0.1 wt.% or greater, about 0.2 wt.% or greater, about 0.3 wt.% or greater, about 0.4 wt.% or greater, about 0.5 wt.% or greater, about 0.6 wt.% or greater, about 0.7 wt.% or greater, about 0.8 wt.% or greater, about 0.9 wt.% or greater, about 1.0 wt.% or less, about 1.1 wt.% or less, about 1.2 wt.% or less, about 1.3 wt.% or less, about 1.4 wt.% or less, about 1.5 wt.% or less, about 1.6 wt.% or less, about 1.7 wt.% or less, about 1.8 wt.% or less, about 1.9 wt.% or less, about 2.0 wt.% or less, or any value encompassed by these endpoints, as a percentage of the total emulsion polymerization mixture.

[0042] In certain embodiments, the emulsion polymerization mixture may also have a modified starch added as a post addition. After the high bio-renewable containing polymer dispersions are prepared, approximately 5-20 wt.% modified or degraded starch solution (DE: 15-40%) may be added as a post add to the dispersion. Adding the modified starch enhances the bio-renewable content of the emulsion polymerization mixture.

[0043] In some embodiments, the emulsion polymerization mixture may also comprise co-stabilizers such as polysaccharides, lignin sulfonates, and glycoside surfactants.

III. Ink and Overprint Varnish Compositions

[0044] Also provided are aqueous ink or overprint varnish compositions comprising one or more of the polymer emulsions described above. The aqueous compositions can further include one or more additives, including pigments, fillers, dispersants, coalescents, defoamers, surfactants, thickeners, biocides, and combinations thereof. The choice of additives in the composition will be influenced by a number of factors, including the nature of the polymers dispersed in the aqueous composition, as well as the intended use of the composition. Although the present compositions are particularly well-suited for use as binders in ink and overprint varnish formulations, they may also be employed in other applications, including top coating agents for plastics, paints, adhesives, fillers, molding materials, electronic materials such as resists, or the like. In some cases, the composition can be, for example, a coating composition, including a food-safety compliant coating composition. In some embodiments, the composition comprises less than or equal to 50 grams per liter of volatile organic compounds.

[0045] The aqueous composition may comprise greater than 30% solids, such as about 30% or greater, 40% or greater, about 50% or greater, about 55% or greater, about 60% or greater, about 65% or greater, or about 70% or greater.

[0046] In some embodiments, the aqueous composition can further comprise one or more surfactants. Suitable surfactants may include Poly Step A16-22 (Sodium Dodecyl benzene sulfonate from Stephan Company), Disonil A 1080, Calfax DB45, Aeorosol OT 75 (sodium dioctyl sulfosuccinate), Tergitol 15-S-9 (Secondary alcohol ethoxylate from from Dow chemical company) and combinations thereof, for example. [0047] The composition can include 0% by weight or greater of one or more surfactants, based on the total weight of all components of the aqueous composition (e.g., 0% by weight, at least 0.5% by weight, at least 1% by weight, at least 1.5% by weight, at least 2% by weight, at least 2.5% by weight, at least 3% by weight, at least 3.5% by weight, at least 4% by weight, at least 4.5% by weight, at least 5% by weight, at least 5.5% by weight, at least 6% by weight, at least 6.5% by weight, at least 7% by weight, at least 7.5% by weight, at least 8% by weight, at least 8.5% by weight, at least 9% by weight, or at least 9.5% by weight). The composition can include 10% or less of one or more surfactants, based on the total weight of all components of the aqueous composition (e.g., from 9.5% or less by weight, from 8% or less by weight, from 8.5% or less by weight, from 8% or less by weight, from 7.5% or less by weight, from 7% or less by weight, from 6.5% or less by weight, from 6% or less by weight, from 5.5% or less by weight, from 5% or less by weight, from 4.5% or less by weight, from 4% or less by weight, from 3.5% or less by weight, from 3% or less by weight, from 2.5% or less by weight, from 2% or less by weight, from 1.5% or less by weight, from 1% or less by weight, or from 0.5% or less by weight).

[0048] The composition can include one or more surfactants in an amount ranging from any of the minimum percentages described above to any of the maximum percentages described above. For example, the composition can include from 0% by weight to 10% by weight of one or more surfactants, based on the total weight of all components of the aqueous composition (e.g., from 0% by weight to 3% by weight of one or more surfactants, from 0% by weight to 2.5% by weight of one or more surfactants, from 0% by weight to 1.5% by weight of one or more surfactants, or 0% by weight to 1% by weight of one or more surfactants). In some embodiments, the composition is substantially free (i.e., the composition includes 0.1% or less by weight) of surfactants.

[0049] Examples of suitable pigments include metal oxides, such as titanium dioxide, zinc oxide, iron oxide, or combinations thereof. The composition may also contain organic pigments such as phthalocyanine, available from Sun Chemical as Sunfast® Blue 15:3, 249-1283. Other examples include phthalocyanine dispersions Flexiverse® BFD- 1121, BFD-8153, and BFD-3153 available from Sun Chemical Corp. In certain embodiments, the composition includes a titanium dioxide pigment. Examples of commercially titanium dioxide pigments are KRONOS® 2101, KRONOS® 2310, available from Kronos Worldwide, Inc. (Cranbury, N.J.), TI-PURE® R-900, available from DuPont (Wilmington, Del.), or TIONA® ATI commercially available from Millenium Inorganic Chemicals. Titanium dioxide is also available in concentrated dispersion form. An example of a titanium dioxide dispersion is KRONOS® 4311, also available from Kronos Worldwide, Inc.

[0050] Examples of suitable fillers include calcium carbonate, nepheline syenite, (25% nepheline, 55% sodium feldspar, and 20% potassium feldspar), feldspar (an aluminosilicate), diatomaceous earth, calcined diatomaceous earth, talc (hydrated magnesium silicate), aluminosilicates, silica (silicon dioxide), alumina (aluminum oxide), clay, (hydrated aluminum silicate), kaolin (kaolinite, hydrated aluminum silicate), mica (hydrous aluminum potassium silicate), pyrophyllite (aluminum silicate hydroxide), perlite, baryte (barium sulfate), Wollastonite (calcium metasilicate), and combinations thereof. In certain embodiments, the composition comprises a calcium carbonate filler.

[0051] Examples of suitable dispersants are polyacid dispersants and hydrophobic copolymer dispersants. Polyacid dispersants are typically polycarboxylic acids, such as polyacrylic acid or polymethacrylic acid, which are partially or completely in the form of their ammonium, alkali metal, alkaline earth metal, ammonium, or lower alkyl quaternary ammonium salts. Hydrophobic copolymer dispersants include copolymers of acrylic acid, methacrylic acid, or maleic acid with hydrophobic monomers. In certain embodiments, the composition includes a polyacrylic acid-type dispersing agent, such as Pigment Disperser N, commercially available from BASF SE.

[0052] Suitable coalescents, which aid in film formation during drying, include ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, 2, 2, 4-trimethyl- 1,3 -pentanediol monoisobutyrate, and combinations thereof.

[0053] Examples of suitable thickening agents include hydrophobically modified ethylene oxide urethane (HEUR) polymers, hydrophobically modified alkali soluble emulsion (HASE) polymers, hydrophobically modified hydroxyethyl celluloses (HMHECs), hydrophobically modified polyacrylamide, and combinations thereof. HEUR polymers are linear reaction products of diisocyanates with polyethylene oxide end-capped with hydrophobic hydrocarbon groups. HASE polymers are homopolymers of (meth)acrylic acid, or copolymers of (meth)acrylic acid, (meth)acrylate esters, or maleic acid modified with hydrophobic vinyl monomers. HMHECs include hydroxy ethyl cellulose modified with hydrophobic alkyl chains. Hydrophobically modified polyacrylamides include copolymers of acrylamide with acrylamide modified with hydrophobic alkyl chains (N-alkyl acrylamide). In certain embodiments, the coating composition includes a hydrophobically modified hydroxyethyl cellulose thickener.

[0054] Defoamers serve to minimize frothing during mixing and/or application of the coating composition. Suitable defoamers include silicone oil defoamers, such as poly siloxanes, polydimethylsiloxanes, polyether modified polysiloxanes, and combinations thereof. Exemplary silicone-based defoamers include BYKO-035, available from BYK USA Inc. (Wallingford, Conn.), the TEGO® series of defoamers, available from Evonik Industries (Hopewell, Va.), and the DREWPLUS® series of defoamers, available from Ashland Inc. (Covington, Ky.).

[0055] Suitable surfactants include nonionic surfactants and anionic surfactants. Examples of nonionic surfactants are alkylphenoxy polyethoxyethanols having alkyl groups of about 7 to about 18 carbon atoms, and having from about 6 to about 60 oxyethylene units; ethylene oxide derivatives of long chain carboxylic acids; analogous ethylene oxide condensates of long chain alcohols, and combinations thereof. Exemplary anionic surfactants include ammonium, alkali metal, alkaline earth metal, and lower alkyl quaternary ammonium salts of sulfosuccinates, higher fatty alcohol sulfates, aryl sulfonates, alkyl sulfonates, alkylaryl sulfonates, and combinations thereof. In certain embodiments, the composition comprises a nonionic alkylpolyethylene glycol surfactant, such as LUTENSOL® TDA 8 or LUTENSOL® AT-18, commercially available from BASF SE. In certain embodiments, the composition comprises an anionic alkyl ether sulfate surfactant. In certain embodiments, the composition comprises an anionic diphenyl oxide disulfonate surfactant, such as CALF AX® DB-45, commercially available from Pilot Chemical. In some embodiments, the composition comprises an anionic surfactant, such as Aeorosol OT75. In some embodiments, the composition is substantially free (i.e., the composition includes 0.1% or less by weight) of sulfate surfactants. In some embodiments, the composition is substantially free (i.e., the composition includes 0.1% or less by weight) of sulfonate surfactants. In some embodiments, the composition is substantially free (i.e., the composition includes 0.1 % or less by weight) of sulfate surfactants and sulfonate surfactants.

[0056] Suitable biocides can be incorporated to inhibit the growth of bacteria and other microbes in the coating composition during storage. Exemplary biocides include 2- [(hydroxymethyl)amino]ethanol, 2- [(hydroxymethyl) amino]2-methyl-l -propanol, o- phenylphenol, sodium salt, l,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro2-methyland-4-isothiazolin-3-one (CIT), 2-octyl-4-isothiazolin-3-one (OTT), 4,5-dichloro-2-n-octyl-3-isothiazolone, as well as acceptable salts and combinations thereof. Suitable biocides also include mildewcides that inhibit the growth mildew or its spores in the coating. Examples of mildewcides include 2- (thiocyanomethylthio)benzothiazole, 3-iodo-2-propynyl butyl carbamate, 2, 4,5,6- tetrachloroisophthalonitrile, 2-(4-thiazolyl)benzimidazole, 2-N-octyl4-isothiazolin-3-one, diiodomethyl p-tolyl sulfone, as well as acceptable salts and combinations thereof. In certain embodiments, the coating composition contains l,2-benzisothiazolin-3-one or a salt thereof. Biocides of this type include PROXEL® BD20, commercially available from Arch Chemicals, Inc (Atlanta, Ga.).

[0057] Other suitable additives that can optionally be incorporated into the composition include rheology modifiers, wetting and spreading agents, leveling agents, conductivity additives, adhesion promoters, anti-blocking agents, anti-cratering agents and anti-crawling agents, anti-freezing agents, corrosion inhibitors, anti-static agents, flame retardants and intumescent additives, dyes, optical brighteners and fluorescent additives, UV absorbers and light stabilizers, chelating agents, cleanability additives, crosslinking agents, flatting agents, flocculants, humectants, insecticides, lubricants, odorants, oils, waxes and slip aids, soil repellants, stain resisting agents, and combinations thereof.

[0058] The examples below are intended to further illustrate certain aspects of the methods and compositions described herein and are not intended to limit the scope of the claims.

EXAMPLES

[0059] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compositions and/or methods claimed herein are made and evaluated and are intended to be purely exemplary and are not intended to limit the scope of the disclosure. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric.

Procedure 1: Synthesis of Polymeric Resin Dispersion [0060] To a reaction vessel equipped with a condenser, thermometer, nitrogen inlet, and an overhead stirrer, deionized water, the rosin ester solution, defoamer (Dow P1200) and surfactant (Poly step A16-22) were added and heated to a temperature of 75-76°C under a stream of nitrogen. At 75°C, the initiator (reductant) and catalyst were added. The monomers and surfactant (secondary alcohol ethoxylate or sodium dioctyl sulfosuccinate) and initiator (tert-butylhydroperoxide) were fed in two separate feeds over 65 minutes, followed by a hold for 30 minutes hold with agitation during post polymerization. Then, a two-chemical strips were started simultaneously for 60 minutes. After the chemical strip 1 and 2 were completed, the post polymerization mixture was added for 30 minutes. The reaction was cooled to room temperature. At 25 °C, Acticide MV was added and then the reaction was filtered. The desired aqueous polymeric resin dispersion was obtained and its properties including solids content, pH, Brookfield viscosity, % coagulum, mictrotrac particle size, GC, and Tg, were measured.

[0061] The solid content of the dispersions was measured gravimetrically by drying about 0.5 g to about 2 g sample of dispersions in a 140°C oven for 1 hour.

[0062] The viscosity was measured by a Brookfield LV at 20 °C to 25°C.

[0063] The particle size and volume average particle size was measured using a nano-flex particle sizer from Microtrac.

[0064] The coagulum was measured by filtering 1 kilogram of dispersion with a 150-mesh filter then measuring.

[0065] The glass transition temperature was measured by differential scanning calorimetry (DSC) according to ASTM D3418-15.

[0066] Polymeric resin dispersions obtainable by Procedure 1 outlined above were formulated into hard film forming binders and non-film forming binders. The physical properties and application test data of these binders are provided in the Examples below.

Non-Film Forming Bio-Renewable Containing Binders

[0067] The physical properties of non-film forming bio-renewable containing binders are presented in Table 1 below. In Table 1, SM= Styrene, AA - acrylic acid, MMA = Methyl Methacrylate, nBA = n-butylacrylate, EA: Ethyl Acrylate, IBA: IsoButhyl acrylate; BRC = Bio-Renewable Content.

TABLE 1

[0068] The binder emulsions above were formulated into inks using the components listed below in Table 2.

TABLE 2

[0069] The inks prepared according to Table 2 above were then tested to determine their optical and physical properties. The results of these tests are outlined in the tables below.

[0070] Tables 3 and 4 summarize the optical testing of the Examples using a glossmeter.

TABLE 4

[0071] The inks were also subjected to dry rub testing with a 4-pound sled weight. A total of 100 rubs were conducted and each example was evaluated at 50 rub intervals using a 1-10 point rub rating system described in Table 5 below. In Table 5, SBS refers to a solid bleached sulfate board. CIS is a coated SBS paper board

TABLE 5

TABLE 6

TABLE 7 [0072] The inks were subjected to water spot testing using de-ionized water. The water testing was conducted at the following intervals: 30 seconds, 1 minute, and 2 minutes. Each example was evaluated using a 1-10 point rub rating system described in Table 8 below.

TABLE 8

TABLE 9

TABLE 10

[0073] The inks were also subjected to block testing using a B01 spring at 36.7mm and 60 pounds of force. Subsequently, the samples were aged for 24 hours at 50°C. Each example was evaluated using a 0-5 point block rating system described in Table 11 below and the results of the block testing are presented in Tables 12 and 13.

TABLE 11

TABLE 12

TABLE 13

[0074] The inks were subjected to resolubility testing in a Geiger Press using 5” rolls with 30 seconds free run time and 15 minutes dry time according to the following procedure. [0075] Inks were placed in each side of the split pan of a Geiger proofer. The proofer was turned on, and a print was made to determine a baseline appearance of the inks. The proofer was then shut off. After being turned off, the proofer was turned back on and a proof was made immediately, and at 30s or 1 minute intervals thereafter, up to 5 minutes while the anilox roll continues to rotate through the ink.

[0076] The rolls were 200Q split rolls and the testing was done on speed level 3. The results are summarized in Table 14 below.

TABLE 14

TABLE 15

Hard-Film Forming Bio-Renewable Containing Binders

[0077] The physical properties of hard-film forming bio-renewable containing binders are presented in Table 16 below.

TABLE 16

[0078] The binder emulsions above were formulated into inks using the components listed below in Table 17.

TABLE 17 [0079] The inks prepared according to Table 17 above were then tested to determine their optical and physical properties. The results of these tests are outlined in the tables below.

Table 18 summarizes the optical testing of the Examples using a glossmeter.

TABLE 18

[0080] The inks were also subjected to dry rub testing with a 4-pound sled weight at speed 2. A total of 100 rubs were conducted and each example was evaluated at 50 rub intervals using the 1-10 point rub rating system previously described in Table 5. The results of the dry rub testing are summarized below in Table 19.

TABLE 19

[0081] The inks were also subjected to water spot testing using de-ionized water. The water testing was conducted at the following intervals: 30 seconds, 1 minute, and 2 minutes. Each example was evaluated using the 1-10 point rub rating system previously described in Table 8. The results of the water spot testing are shown below in Table 20.

TABLE 20

[0082] The inks were also subjected to block testing using a B01 spring at 36.7mm and 60 pounds of force. Subsequently, the samples were aged for 24 hours at 50°C. Each example was evaluated using the 0-5 point block rating system previously described in Table 11. The results of the block testing are summarized below in Table 21.

TABLE 21 [0083] The inks were subjected to resolubility testing in a Geiger Press using 5” rolls with 30 seconds free run time and 5 minutes dry time. The rolls were 200Q split rolls and the testing was done on speed level 3. The results are summarized in Table 22 below.

TABLE 22

Soft-Film Forming Bio-Renewable Containing Binders

[0084] The formulation of soft- film forming binders 1 S and 2S containing biorenewable monomers is presented below in Table 23. In Table 23, DW = Deionized water;

2-EHA = 2-Ethylhexylacrylate; IBOMA = Isobornyl methacrylate; Na-Ery = sodium erythrobate

TABLE 23

[0085] A comparison of soft film forming binders IS and 2S with Joncryl 8052 is provided in Table 24 below.

TABLE 24

[0086] The soft- film forming binders IS and 2S containing bio-renewable monomers were further formulated with rosin ester XR2780 in two ratios (w/w): 50/50 and 70/30. Details of the rosin ester (XR2780 from Lawter B.V.) formulations for IS and 2S are provided below in Table 25

TABLE 25

[0087] In Table 25 above, a 100% neutralized solution of rosin resin XR2780 from Lawter B. V. (30% non-volatile content) has been used.

[0088] The binders were formulated into a flexo/gravure ink for testing. The ink formulation is provided below in Table 26.

TABLE 26

[0089] A series of tests were conducted on the ink formulations. These tests are detailed below.

[0090] A draw down test was made on 50pm (treated) white low-density polyethylene (LDPE) and/or treated biaxially-oriented polypropylene (BOPP). A blue ink (viscosity-!-/- 20 sec. DIN4) was applied using an 4pm wire bar, speed 10. The substrate was dried in an oven at 60°C for 20 seconds. For blocking test and re-solubility an 6pm wire bar was used.

[0091] A heatseal release test was conducted. The drawdown was stacked with the coated site facing the mat side of aluminum foil. Next, the aluminum foil was folded with the non-printed site facing each other. The sample was sealed on the heat seal machine using two-sided heating for 1.0s with a pressure of 450N. The samples were observed for damage and release. The seal conditions with flat seal 10 mm are as follows. Jaws: flat seal 10x15 mm. Seal temperature: 140 - 160 - 180°C.

[0092] A draw down test was also completed on corona treated foil(s). Tape adhesion, (H/FF 03-01) after 20 seconds at 60°C. Pressure-sensitive adhesive tape was applied to an area of the coating. Adhesion is considered to be adequate if no coating is pulled off by the tape when it is removed. Scratch/Scuff resistance after 1 minute at 60°C. Explanation scratch: scratch 5x with the top of a fingernail over the foil. Explanation scuff: scuff 5x with a flat fingernail over the foil. Wrinkle (wet). (H/FF 03-02) Wrinkle 10 times the foil between two hands and observe on damage. Blocking. (H/FC 03-02) Place on top of the dried draw-down another foil with the non-treated side on the ink side. Place the drawdown in the blocking machine for 24hours at 30°C and 5T pressure. Wet satra. (See H/FF 04-01). Leave the substrate for 2 hours in tap water. Satra cotton is immerged in tap water. Draw-down is rubbed with cotton 200 times. Observe on damage. 200 / 100 mean 200 rubs where 0% ink is coming of the substrate.

[0093] Ink testing was done on both with both color and white. Color: Dilute (if needed) the ink to 19 - 20” DIN4 using a blend of PC HPD396 / water in the ration of 35 : 65. Check viscosity stability after 1 day, 1 week and after 4 weeks. White: Dilute (if needed) the ink to 19 - 20” DIN4 using a blend of a blend of PC T750W I water in the ratio of 40 : 60. Check viscosity stability after 1 day, 1 week and after 4 weeks.

[0094] Fingertip re-solubility was conducted according to test method H/FF 06-02. For the neat binder, a drawdown and gloss test were conducted. A draw-down is made on Leneta 2A gloss card using a 12pm wire-bar, or on a Leneta N2A-2 card using a 6pm wirebar. The substrate is dried in an oven at 60°C for 1 minute. The gloss test was done by measuring for gloss using he BYK-Gardner micro-gloss 60°. This BYK Gardner microgloss is a single angle instrument for specific applications. A specific 600 Gloss Meter is designed for determining the gloss of paint coatings, plastics, paper or similar materials. Light is directed onto the surface of the test specimen at a defined angle and the reflected light is measured photo electrically.

[0095] A summary of the results from the foregoing tests is described in Tables 27 and 28 below.

TABLE 27

The film clarity in Table 27 was rated based on a visual test scale of 1-5 with 1 = very opaque and 5 = very clear. Note that Example 2S was not diluted to 150 mPa.s due to the very small amount of product.

TABLE 28

Claims

1. A high bio-renewable containing emulsion composition suitable for use as a binder, the emulsion composition comprising:

(i) a rosin ester;

(ii) co-polymerizable monomers and

(iii) water.

2. The emulsion composition of claim 1, wherein the rosin ester is present in an amount of 60 wt.% or greater based on the total weight of the composition.

3. The emulsion composition of claim 1 , wherein the co-polymerizable monomers comprise isobutyl acrylate.

4. The emulsion composition of claim 1 , wherein the co-polymerizable monomers comprise ethyl acrylate.

5. The emulsion composition of claim 1, wherein the co-polymerizable monomers comprise 2-octyl acrylate

6. The emulsion composition of claim 1 , wherein the co-polymerizable monomers comprise lauryl methacrylate.

7. The emulsion composition of claim 1, wherein the composition further comprises a costabilizer selected from the group consisting of polysaccharides, lignin sulfonates, and glycoside surfactants.

8. The emulsion composition of claim 1, wherein the emulsion composition comprises less than 1 wt.% of styrene based on the total weight of the composition

9. The emulsion composition of claim 1, wherein the emulsion composition comprises less than 1 wt.% of solid grade oligomer resins based on the total weight of the composition

10. A process for preparing the high bio-renewable containing polymer emulsion comprising:

(i) providing a resin dispersion comprising at least one resin in aqueous solution; (ii) adding at least one initiator and a polymerization mixture to the resin dispersion, the polymerization mixture comprising at least one co-polymerizable monomer; and

11. The process of claim 10, wherein the co-polymerizable monomers comprise isobutyl acrylate.

12. The process of claim 10, wherein the co-polymerizable monomers comprise ethyl acrylate.

13. The process of claim 10, wherein the co-polymerizable monomers comprise 2-octyl acrylate

14. The process of claim 10, wherein the co-polymerizable monomers comprise lauryl methacrylate.

15. The process of claim 8, wherein a modified starch is post-added to the polymer emulsion.

16. A printing ink comprising the emulsion composition of claim 1.

17. An overprint varnish comprising the emulsion composition of claim 1.