JP2015537080A - Ink and coating composition having high lamination adhesive strength - Google Patents

Abstract

The following steps: (i) providing the composition (C) containing the emulsion polymer (a), and then (ii) adding the water-soluble polymer (b) containing an ether group to the composition (C). A composition obtained by adding a composition containing the water-soluble polymer (b) does not contain a carboxylate group, and the water-soluble polymer (b) has a solubility of at least 50 g / l in water. A composition having Methods for making such compositions and the use of such compositions for aqueous coatings or inks are described. (I) an emulsion polymer containing carboxylate groups (a), and (ii) a water-soluble random copolymer or water-soluble block copolymer of ethylene oxide and propylene oxide, at least 45 mass based on the amount of copolymer of ethylene oxide and propylene oxide. Also disclosed are compositions containing a water-soluble random copolymer or water-soluble block copolymer having a% ethylene oxide content and a weight average molecular weight of 300-4000 g / mol.

Description

  The present invention relates to a composition comprising an emulsion polymer and a water-soluble polymer having an ether group. In some cases, a supported resin having a carboxylate group may be included in the composition. The invention also relates to a method for producing such a composition and to the use of such a composition for aqueous coatings or inks. In particular, the invention relates to the use of such compositions for aqueous inks for printing on plastic substrates and for aqueous coatings such as overprint varnishes or paints, in particular as binders. In particular, the present invention relates to compositions useful for applications requiring high lamination adhesion strength.

BACKGROUND OF THE INVENTION Various plastic films are used in the packaging industry for goods storage and shipping. In many cases, text and images are printed on these plastic films. Printing inks used for this purpose need to meet certain end-use requirements for successful use in such applications. These requirements include good printability, good remeltability, good resistance properties and high lamination adhesion strength (LBS). Inks used in plastic packaging must also exhibit good wettability and good flow properties and fast drying times.

  Due to environmental and health concerns due to solvent-based inks, the use of water-based inks for printing on films used in packaging has become increasingly important in recent years. Therefore, a water-based ink having good printability, that is, good ink transferability and wettability, good adhesion to a substrate, and good image resolution is strongly desired.

  Similarly, water-based inks that have good resolubility, the ability of a dry ink to redisperse in the same ink in the wet state are also important. When the pressing is stopped, for example, the water-based ink starts to dry on the roller and may undergo physical and chemical changes due to film formation, pH change, etc., and the printability of these inks is problematic. To do.

  Finally, the durability of the printed or coated film to mechanical stress, water, solvents and other chemicals is also highly desirable. However, many water-based polymer coatings typically suffer from problems with adhesion, frictional resistance, and water and solvent resistance.

  Various polyvalent metal crosslinkers have been used as additives to aqueous coatings to improve the resistance properties of the coating.

  WO 2006/034229 A1 describes a stable aqueous polymer containing an aqueous polymer, a metal crosslinking agent, and a stabilizer having at least two functional groups selected from 2 to 10 carbon atoms and independently hydroxyl and carboxyl A composition is described.

  Good wettability, good drying speed, good flow behavior, good printability, good resistance when used for printing on plastic films and other substrates without the use of metal crosslinkers There is a need for water-based coatings, particularly inks, that exhibit properties, good resolubility and good lamination adhesion strength. Also, such coatings must be stable during storage and normal use conditions. The aqueous inks and coatings of the present invention exhibit these and other desirable properties when used on plastic films and other substrates.

  In the current market, solvent-based inks are often used. The types of binders used in these solvent-based inks range from nitrocellulose / plasticizer combinations to nitrocellulose / urethane combinations, including polyvinyl butyrate, polyvinyl chloride / urethane and polyurethane. Good printing in combinations with good LBS for applications such as laminating printed oriented polypropylene (OPP) to OPP or laminating printed polyethylene terephthalate (PET) to low density polyethylene (LDPE) The transition to water systems is slow due to the lack of water based alternatives that provide sex.

  Various aqueous printing ink compositions are known from the state of the art.

  WO95 / 28436 A1 includes a low-viscosity resin emulsion having an average particle size of less than about 0.5 microns and composed of a hydrophobic, moisture-resistant, adhesive resin-forming component, and a water-soluble polymer. A water-based printing ink composition suitable for use in gravure and flexographic printing on a hydrophobic substrate, manufactured by combining with a pigment paste is described.

  WO 97/19992 describes an aqueous polymer emulsion composition comprising a polymer. There are also described printing inks containing a colorant and a binder for said colorant comprising such an aqueous emulsion polymer.

  U.S. Pat. No. 5,284,894 describes printing inks for application on a variety of substrates and latexes for use in coatings. These latices are described as being suitable as vehicles for coating on polyolefin surfaces.

  U.S. Pat. No. 4,954,556 describes a water-based ink composition comprising an emulsion polymer and a rewet.

  A rheology controlled (RC) emulsion comprising an emulsion polymer stabilized by an alkali soluble resin containing a carboxylate group (support resin) is a binder for aqueous printing inks with good resolubility and good printability Known as. When such inks are applied to typical flexible packaging substrates such as polyethylene (PE), polypropylene (PP) or PET, some limitations of these compositions become apparent.

  A substrate with very specific and strict requirements is a laminated flexible packaging material, which is first printed on a transparent OPP or PET substrate, for example, followed by a second such as OPP or PE. It is a packaging material laminated using a flexible base material (coating film) and, for example, a 2K PU (two-component polyurethane) lamination adhesive that does not contain a solvent. This application requires high lamination bond strength, for example, bond strength typically greater than 2.0 N / 15 mm.

  In general, RC-emulsion based inks often exhibit excellent printability, but exhibit poor lamination adhesion strength (eg, typically less than 0.5 N / 15 mm).

  Therefore, it was an object of the present invention to provide an aqueous ink or coating that exhibits high lamination adhesion strength.

  Surprisingly, it has been found that an ink having good lamination adhesive strength can be obtained by combining a composition such as an RC-emulsion and a water-soluble polymer having an ether group.

SUMMARY OF THE INVENTION According to the present invention, the following steps are provided: (i) providing a composition (C) containing an emulsion polymer (a), preferably an emulsion polymer (a) containing carboxylate groups, and thereafter (Ii) A composition obtained by adding a composition containing a water-soluble polymer (b) containing an ether group to the composition (C), wherein the water-soluble polymer (b) is a carboxylate group. And the water-soluble polymer (b) has a solubility of at least 50 g / l in water.

  In a preferred embodiment of the composition according to the invention, the composition (C) further comprises a supported resin (s) containing carboxylate groups, and said supported resin (s) has an acid value in the range of 10-400. Have In this case, more preferably, the composition (C) corresponds to an RC-emulsion.

  Upon curing, these compositions provide excellent lamination adhesion properties that make them particularly suitable for use as binders in aqueous printing inks on plastic films and other substrates. The improved lamination adhesion strength of the compositions of the present invention allows their use in a wide range of applications including aqueous inks, overprint varnishes, paints, adhesives, sealing lacquers, molding materials, barrier coatings, electronic materials such as resists, etc. Enable.

  In other aspects, the present invention provides methods of making and using the compositions described herein. Thus, for example, the composition may be prepared by combining an emulsion polymer containing carboxylate groups and a water-soluble polymer containing ether groups, for example, by mixing aqueous solutions of these materials.

  The composition of the present invention may be applied as a film or coating to a substrate such as paper, wood, plastic or fabric. The composition may be applied using curtain coating, flow coating or roll coating. When prepared as an ink, the compositions of the present invention may be applied using gravure and flexographic printing processes including offset and screen printing processes.

Detailed Description of the Invention In one aspect, the present invention provides the following steps: (i) providing a composition (C) containing an emulsion polymer (a), preferably an emulsion polymer (a) comprising carboxylate groups; And (ii) a composition obtained by adding a composition containing a water-soluble polymer (b) containing an ether group to the composition (C),
Provided is a composition wherein the water-soluble polymer (b) contains no carboxylate groups and the water-soluble polymer (b) has a solubility of at least 50 g / l in water.

  In a preferred embodiment of the composition of the present invention, the composition (C) further contains a supported resin (s) containing a carboxylate group, and the supported resin (s) has an acid value in the range of 10 to 400. Have In this case, more preferably, the composition (C) corresponds to an RC-emulsion.

  The solubility in water is qualitatively determined by evaluating the substance solution in water at 25 ° C. so that the clear solution does not precipitate. Thus, the solubility is determined by increasing the concentration of the substance in water until the solution is no longer clear and / or no precipitate is present.

  In the constitution of the present invention, the term “water-soluble” characterizing the water-soluble polymer (b) is a water-soluble polymer having a solubility of at least 50 g / L in water at 25 ° C., preferably 100 g / L in water at 25 ° C. Understood as (b). Most preferably, the water soluble polymer (b) is sufficiently miscible with water.

  In other embodiments, the emulsion polymer (a) can preferably have an acid number in the range of 10-300, more preferably 15-200, most preferably 20-100. In a preferred embodiment, the emulsion polymer (a) has an acid number in the range of 40-100.

  The acid number is determined by potentiometric titration with 0.1 M KOH in water in a suitable solvent (acetone / water; 80/20) according to methods well known to those skilled in the art. Results are reported as “mg KOH / g product”.

  Supported resins (s) that can be used in the compositions of the present invention are typically acrylic, vinyl (including but not limited to styrene, polyvinyl alcohol and polyvinyl acetate), acrylic / vinyl, polyurethane, polyamide, polyester, A polymer selected from the group of polyethylene glycol, styrene-butadiene-rubber (SBR) polymer, nitrocellulose, hybrids thereof, or blends thereof.

  A hybrid polymer is a composition comprising two or more polymers and made by sequential polymerization of one polymer in the presence of the other polymer. The hybrid polymer may include a copolymer, and producing the second polymer in the presence of the first polymer leads to the formation of the copolymer. Hybrid polymers also include, but are not limited to, random copolymers, alternating copolymers or block copolymers.

  In a preferred embodiment of the composition, the support resin (s) includes a water-soluble resin.

  Preferably, the support resin (s) contains acrylic, acrylic / vinyl, polyester polymer, hybrids thereof or blends thereof.

  For example, the acrylic support resin (s) can be acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, acrylic anhydride, methacrylic anhydride, itaconic anhydride, maleic anhydride, fumaric. Acid anhydride, crotonic acid anhydride, ethyl methacrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, ethyl acrylate, vinyl acetate, methyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, methylol acrylamide, Glycidyl acrylate, glycidyl methacrylate, diacetone acrylamide, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, allyl acetoacetate, vinyl Selected from one or more of acetoacetate, acrolein, diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, hybrids thereof or blends thereof Including monomer polymers.

  In another preferred embodiment, the support resin (s) comprises an acrylic / styrene polymer and the support resin (s) is in addition to the acrylic group described above, styrene, methylstyrene, alpha-methylstyrene, ethylstyrene, Of a monomer selected from one or more of isopropyl styrene, t-butyl styrene, acyclic conjugated diene, vinyl ester, vinyl chloride, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, hybrids thereof or blends thereof Including polymers.

  Vinyl / acrylic supported polymers (s), such as styrene / acrylic polymers, are particularly suitable for use in the compositions of the present invention. Natural polymers are also contemplated for use in the present invention, and natural polymers include proteins, (hydroxyethyl) cellulose, cotton, starch and the like.

  In another embodiment, the support resin (s) further comprises vinyl, polyurethane, polyamide, styrene-butadiene-rubber polymer, nitrocellulose, hybrids thereof or blends thereof.

  Those skilled in the art will readily appreciate that the polymer can be adapted to the current specific application by modifying the mixture of monomers as needed. For example, the supporting resin (s) used in the composition of the present invention can have a wide range of acid values as described above.

  The combined dry weight of polymers (a), (s) and (b) may be adjusted depending on the application and may occupy anywhere from about 0.1 to about 95 weight percent (% by weight) of the composition. . In other embodiments, the weight of polymers (a) and (b) is from about 0.1 to about 70%, from about 0.1 to about 60%, from about 1 to about 50% by weight of the composition of the present invention. About 5 to about 50 mass%, or about 10 to about 50 mass%.

  The preparation of emulsion polymers (a) containing carboxylate groups is well known to those skilled in the art.

  For example, the production of emulsion polymers is described in Gilbert, R .; G. , Academic Press, N.A. Y. 1995, pages 1 to 23, "Emulsion polymerization". The production of styrenic / acrylic polymers is described in U.S. Pat. Nos. 4,546,160, 4,414,370, and 4,529,787.

  In general, such emulsion polymers are prepared using ethylenically unsaturated monomers and initiators, and optionally using surfactants, alkalis, and water or other reaction solvents. Examples of monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, acrylic anhydride, methacrylic anhydride, itaconic anhydride, maleic anhydride, fumaric anhydride, croton Acid anhydride, styrene, methyl styrene, alpha-methyl styrene, ethyl styrene, isopropyl styrene, tertiary butyl styrene, ethyl methacrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, ethyl acrylate, vinyl acetate, methyl Acrylate, acyclic conjugated diene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, vinyl ester Although vinyl chloride and the like, without limitation.

  Emulsion polymers suitable for use in the present invention are self-crosslinking polymers (eg, US Pat. Nos. 5,432,229, 5,605,722, 6,355,720, and 6, 538,062). Self-crosslinking polymers include self-crosslinking monomers such as diacetone acrylamide (DAAM), acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, allyl acetoacetate, vinyl acetoacetate, acrolein, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, Polymers such as vinyl butyl ketone, diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, and allyl methacrylate are included. Preferably, the emulsion polymer can be produced in the presence of a supported resin.

  In a preferred embodiment, the emulsion polymer (a) is acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, acrylic anhydride, methacrylic anhydride, itaconic anhydride, maleic anhydride. , Fumaric anhydride, crotonic anhydride, ethyl methacrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, ethyl acrylate, vinyl acetate, methyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, Methylolacrylamide, glycidyl acrylate, glycidyl methacrylate, diacetone acrylamide, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, allyl alcohol One or more of toacetate, vinyl acetoacetate, acrolein, diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, hybrids thereof or blends thereof A polymer of monomers selected from:

  Those skilled in the art will readily appreciate that the polymer can be adapted to the current specific application by modifying the mixture of monomers as needed. For example, the emulsion polymer (a) used in the composition of the present invention can have a wide range of acid values as described above.

  Compositions (C) useful in the compositions of the present invention can also have a wide range of glass transition temperatures (Tg). For example, polymers useful in the present invention can have a Tg value of -40 to 150 ° C, preferably -40 to 40 ° C. Tg values are determined by differential scanning microscopy (DSC).

  Water-soluble polymers (b) that can be used in the compositions of the present invention typically include polymers selected from the group of polyalkylene oxides, polyester polyols, hybrids thereof or blends thereof.

  The polyalkylene oxide is a polymer based on monomers selected from the group of epoxides, preferably ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, more preferably ethylene oxide and propylene oxide.

  In another embodiment, the water-soluble polymer (b) of the composition of the present invention is derived from alkylene oxide, preferably ethylene oxide (EO), propylene oxide (PO), butylene oxide, more preferably ethylene oxide and / or propylene oxide. Containing ether groups.

  In another embodiment, the water soluble polymer (b) of the composition of the present invention comprises a random alkylene oxide polymer or a block alkylene oxide polymer.

  Those skilled in the art will readily appreciate that the polymer can be adapted to the current specific application by modifying the mixture of monomers as needed.

  In yet another embodiment, the water-soluble polymer (b) of the composition of the present invention comprises groups derived from alcohols, natural alcohols such as castor oil, and alcohols derived from other natural materials, oxo alcohols, alkylphenols. Including.

  In another embodiment, the water-soluble polymer (b) of the composition of the present invention is 300-15000 g / mol, preferably 350-10000 g / mol, most preferably 400-8000 g / mol, and especially 400-6000 g / mol. Having a weight average molecular weight Mw in the range. Mw values are determined by gel permeation chromatography (GPC) using a Waters Alliance 2690 separation module equipped with a Waters 2414 refractive index detector at a concentration of about 10 mg / ml in THF solvent.

  In another embodiment, the water soluble polymer (b) of the composition of the present invention does not contain amine groups.

  In yet another embodiment, the water soluble polymer (b) of the composition of the present invention does not contain ester groups.

  In a preferred embodiment, the water-soluble polymer (b) of the composition of the present invention contains no ester groups or amine groups.

  The preparation of water-soluble polymers (b) containing ether groups is well known to those skilled in the art.

  In general, in the composition of the present invention, the amount of the emulsion polymer (a) is 70 to 99% by mass with respect to the total amount of the emulsion polymer (a) and the water-soluble polymer (b). The amount of b) is 1 to 30% by mass. Preferably, the amount of the emulsion polymer (a) is 80 to 99% by mass, and the amount of the water-soluble polymer (b) is 1 to 20% by mass, more preferably based on the total amount of the emulsion polymer and the water-soluble polymer. The amount of the emulsion polymer (a) is 85 to 99% by mass, the amount of the water-soluble polymer (b) is 1 to 15% by mass, most preferably the amount of the emulsion polymer (a) is 90 to 99% by mass. The amount of the water-soluble polymer (b) is 1 to 10% by mass.

  In a preferred embodiment, the total amount of the emulsion polymer (a) and the supporting resin (s) is 70 to 99% by mass with respect to the total amount of the emulsion polymer (a), the supporting resin (s) and the water-soluble polymer (b). The amount of the water-soluble polymer (b) is 1 to 30% by mass, preferably the total amount of the emulsion polymer (a) and the supporting resin (s) is 90 to 99% by mass, and the water-soluble polymer ( The amount of b) is 1 to 10% by mass.

  Generally, in the composition of the present invention, the amount of the emulsion polymer (a) is 50 to 95% by mass with respect to the total amount of the emulsion polymer (a) and the supporting resin (s), and the supporting resin (s ) Is 5 to 50% by mass.

In a preferred embodiment of the composition of the present invention, the emulsion polymer (a) comprises acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, acrylic anhydride, methacrylic anhydride, itaconic anhydride. , Maleic anhydride, fumaric anhydride, crotonic anhydride, ethyl methacrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, ethyl acrylate, vinyl acetate, methyl acrylate, 2-hydroxyethyl methacrylate, 2- Hydroxyethyl acrylate, methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, diacetone acrylamide, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate Allyl acetoacetate, vinyl acetoacetate, acrolein, diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, hybrids thereof or blends thereof A polymer of monomers selected from one or more, and the support resin (s) includes an acrylic polymer, an acrylic / vinyl polymer, a styrene polymer, an acrylic / styrene polymer, a polyester polymer,
And the water-soluble polymer (b) is a polymer of a monomer selected from the group of ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, preferably a monomer selected from the group of ethylene oxide and propylene oxide Of polymers.

Another aspect of the present invention provides:
(I) an emulsion polymer (a) containing carboxylate groups, and (ii) a water-soluble random copolymer or water-soluble block copolymer of ethylene oxide and propylene oxide, at least 45 relative to the amount of ethylene oxide and propylene oxide copolymer. A composition comprising a water-soluble random copolymer or a water-soluble block copolymer having an ethylene oxide content of mass% and a mass average molecular weight of 300 to 4000 g / mol, preferably 350 to 3000 g / mol.

  In one embodiment of the composition of the present invention, the composition further comprises a surfactant, a solvent, a leveling agent, a rheology modifier, a wax, a buffering agent, a dispersant, a defoaming agent, an antifoaming agent, a modified polymer, One or more additives (c) selected from rewetting agents, biocides, cross-linking agents or re-dissolving agents.

  Generally when one or more additives (c) are present, in the composition according to the invention, based on the total amount of emulsion polymer (a), water-soluble polymer (b) and one or more additives (c). The amount of the emulsion polymer (a) is 65 to 98.9% by mass, the amount of the water-soluble polymer (b) is 1 to 30%, and the amount of the one or more additives (c) is 0.00. 1 to 5% by mass.

  Generally, when one or more additives (c) and a supporting resin (s) are present, the emulsion polymer (a), the supporting resin (s), the water-soluble polymer (b) and the one in the composition of the present invention. The total amount of the emulsion polymer (a) and the supporting resin (s) is 65 to 98.9% by mass, and the amount of the water-soluble polymer (b) is 1 with respect to the total amount of the additive (c). -30 mass and the amount of one or more additives (c) is 0.1-5 mass%.

  A wide range of surfactants are suitable for applications including anionic, cationic and nonionic. Typically, alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfates, hydroxy alkanoate sulfates, alkyl disulfonates and alkyl aryl disulfonates, sulfonated fatty acids, polyethoxylated alkanols and alkyl phenol sulfates and sulfonates as anionic surfactants And esters of sulfosuccinic acid.

  Nonionic surfactants are particularly suitable for use with the compositions of the present invention, such as polyvinyl pyrrolidone, alkyl polysaccharides and the like.

  In another aspect of the present invention, a composition comprising an emulsion polymer (a), preferably having a supported resin (s), preferably in the amounts described herein, and a composition comprising a water-soluble polymer (b). A composition as described herein having a combining step, for example, a step of mixing a composition comprising an emulsion polymer (a), preferably having a support resin (s), and a composition comprising a water-soluble polymer (b). A manufacturing method is provided. Accordingly, the present invention also preferably comprises an emulsion polymer (a) having a support resin (s), a composition comprising a water-soluble polymer (b) or a water-soluble polymer (b) and optionally one or more additives (c And a method for producing the composition of the present invention.

  The step of combining the emulsion polymer (a) having a carboxylate group, preferably having a support resin (s), the water-soluble polymer (b) containing an ether group and optionally one or more additives (c) is preferably Is carried out by mixing aqueous solutions of these substances.

  In another embodiment, the water-soluble polymer (b) is preferably added to an aqueous solution of the emulsion polymer (a) having a support resin (s) and optionally one or more additives (c) in the resulting composition. Is added.

  In general, preferably an aqueous solution of the emulsion polymer (a) having a support resin (s) is first provided and the water-soluble polymer (b) and optionally one or more additives (c) are added later. The order of addition (b) and (c) is irrelevant. The water-soluble polymer (b) and optionally one or more additives (c) may be added as (dry) material or in aqueous solution.

  The term “aqueous solution” of a substance also includes dispersions and suspensions of the substance in water.

  In other embodiments, the composition of the present invention may further comprise a polyvalent metal crosslinker as disclosed in WO 2006/034229 A1. The amount of metal crosslinker used will vary depending on the amount of emulsion polymer (a) and the acid value of the polymer. Suitable polyvalent metals include zirconium, titanium, hafnium, chromium, zinc, aluminum, or a mixture of any two or more thereof. Zirconium is particularly suitable as a metal crosslinker. The metal crosslinker is typically an ammonia salt or complex, acetate, propionate, sulfate, carbonate, nitrate, phosphate, tartrate, acetylacetonate, oxide or any two of these It is a mixture of the above. Thus, exemplary metal crosslinking agents include ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, sodium zirconium phosphate, zirconium tartrate, zinc oxide and the above polyvalents. Other combinations of metals and counter ions are mentioned. Similarly, organic titanates such as titanium acetylacetonate and titanium lactate chelates can be used. The amount of any metal crosslinker used in the composition of the present invention will vary depending on the nature of the polymer and the polyvalent metal. Generally, the composition is about 10: 1 to about 1: 2, about 9: 1 to about 1: 2, about 8: 1 to about 1: 2, about 7: 1 to about 1: 2, about 6: 1 to about 1: 2, about 5: 1 to about 1: 2, about 4: 1 to about 1: 2, about 3: 1 to about 1: 2, about 10: 1 to about 1: 1, about 8: A molar ratio of carboxylate groups to metal crosslinker of 1 to about 1: 1, about 6: 1 to about 1: 1, about 4: 1 to about 1: 1, or about 3: 1 to about 1: 1. Have.

  In other embodiments, the compositions of the present invention may further comprise a wide variety of organic compounds as stabilizers, so long as the organic compound contains at least two hydroxyl groups or carboxyl groups or one respective group. Stabilizers are not limited to those having two functional groups, and additional hydroxyl and carboxy groups and other functional groups such as oxo, amino, thiol, cyano, It should be understood that nitro and the like may be included. If such compounds may contain 2 to 10 carbon atoms, these compounds usually have 2 to 8 or 2 to 6 carbon atoms. Accordingly, suitable stabilizers of the present invention include, but are not limited to, diols, hydroxy acids, dibasic acids, sugars, or mixtures of two or more thereof. For example, the stabilizer is tartaric acid, gluconic acid, mucic acid, sugar acid, oxalic acid, glycolic acid, lactic acid, malic acid, citric acid, mandelic acid, malonic acid, maleic acid, succinic acid, salts thereof or two of them It may be a mixture of the above. Stabilizers that are sugars include mannitol, fructose, glucose, and mixtures of two or more thereof or mixtures with diols, hydroxy acids or dibasic acids. The amount of stabilizer used in the composition of the present invention is 1.4 mol% or more of the amount of the crosslinking agent. In other embodiments, the amount of stabilizer may be 2.4 mol% or more, 3 mol% or more, 7 mol% or more, or 10 mol% or more of the amount of crosslinking agent. Alternatively, the mole ratio of stabilizer to metal crosslinker is at least 1.4 mol%, 2.4 mol%, 3 mol%, 7 mol%, 8 mol%, 9 mol% or 10 mol% up to about 40 mol%. Or at least 1.4 mol%, 2.4 mol%, 3 mol%, 7 mol%, 8 mol%, 9 mol% or 10 mol% up to about 30 mol%, or at least 1.4 mol% 2.4 mol%, 3 mol%, 7 mol%, 8 mol%, 9 mol% or 10 mol% up to about 20 mol%.

  When dried, the coating composition of the present invention exhibits excellent strength and hardness, such as top coating agents for plastics, overprint varnishes, printing inks, paints, adhesives, fillers, molding materials, electronic materials such as resists, etc. As particularly useful. Thus, each overprint varnish, paint or heat seal lacquer may independently comprise a composition as described herein. The ink may further contain a pigment.

  Furthermore, a composition containing an emulsion polymer (a) preferably containing a carboxylate group, a supported resin (s) containing a carboxylate group and a water-soluble polymer (b) containing an ether group is provided, and the supported resin (s ) Has an acid number in the range of 10 to 400, preferably 15 to 350, most preferably 50 to 300, the water soluble polymer (b) does not contain a carboxylate group, and the water soluble polymer (b) Has a solubility of at least 50 g / l in water and the amount of emulsion polymer (a), carrier resin (s) and water-soluble polymer (b) is sufficient for coatings containing the composition, such as inks, preferably carboxylate groups. A water-soluble polymer (b) is added to a composition containing an emulsion polymer (a) containing a carrier resin (s) containing a carboxylate group Without Rukoto is sufficient to assume that than the same coating represents a significant LBS. Some such compositions may further include a pigment.

  In yet another aspect of the present invention, there is provided a method for producing a film or coating comprising the step of applying a composition described herein as a film or coating to a substrate. Examples of the substrate include paper, wood, plastic, and woven fabric. In particular, the overprint varnish and ink of the present invention may be applied to paper and paper treated with polyethylene, polyvinyl chloride, polypropylene, polyester, polycarbonate and polyimide films or sheets, and any of these materials.

  Examples of the method for coating a substrate using the overprint varnish or ink of the present invention include well-known methods such as direct coating and printing. For direct coating of substrates with overprint varnish or ink, methods such as curtain coating, flow coating and roll coating can be used. If the viscosity of the composition is low, direct coating such as spray coating can also be used. Printing processes used for coating include offset printing processes, gravure offset printing processes, and gravure flexographic printing processes. The thickness of the coating film produced by these processes can be from about 0.25 to about 25 micrometers, typically from about 1 to about 10 micrometers.

  Furthermore, the present invention also relates to the use of the composition according to the invention for aqueous coatings or inks. Preferably, it relates to the use of water-based inks for printing on a substrate, preferably printing on a plastic film. It also preferably relates to the use of the composition according to the invention for aqueous coatings for overprint varnishes or paints.

  Furthermore, the invention also relates to the use of the composition according to the invention for water-based inks for laminating a printed (first) substrate to a (second) flexible film. These laminates provide high lamination adhesion strength, preferably above 1.5 N / 15 mm, and most preferably above 2 N / 15 mm, before and after heat sealing.

  Lamination is performed by techniques well known to those skilled in the art. In general, a laminate is obtained, for example, by applying a composition of the invention or an ink preparation of said composition to the surface of a plastic substrate. A substrate coated after drying is obtained. Subsequently, a lamination adhesive is used to secure the second plastic surface to the coated substrate.

Typical ink preparation:
A colored ink is prepared by mixing 30 parts of a pigment paste (for example, PB15.3) (resin-based or resin-free) and 70 parts of a test emulsion. The viscosity of the ink can be measured using a DIN 4 cup. The viscosity of the ink can be reduced to DIN 4 of 20 seconds using a 30/70 part blend of pigment paste / water.

  A white ink is prepared by mixing 40 parts of a pigment paste (for example, PW6) containing no resin and 60 parts of a test emulsion. The viscosity of the ink can be measured using a DIN 4 cup. The viscosity of the ink can be reduced to DIN 4 of 20 seconds using a 40/60 part blend of pigment paste / water.

Typical ink application:
Using wire bar 0 on the treated side of co-extruded OPP (30MB400-stretched polypropylene film available from Exxon Mobile Chemical) and chemically treated polyester (Mylar® 813 available from DuPont Teijin Films) The ink was applied (4 μm wet ink). The ink was applied as 100% color (1 layer), 200% color (2 layers), 100% color and 100% white (2 layers). The resulting print was dried in an oven at 60 ° C. for 60 seconds followed by a further drying period of about 16 hours (overnight) at room temperature prior to laminate manufacture.

Typical lamination procedure:
To test the lamination adhesion strength, the prints on coextruded OPP and chemically treated polyester were laminated to coextruded OPP and standard LDPE (low density polyethylene), respectively, OPP // OPP and PET //, respectively. An LDPE laminate was obtained.

1. Preparation of two-component polyurethane lamination adhesive Liofol Hardener UR6080: 8.0 (obtained from Henkel Industrial Adhesives)
Liofol UR7780: 20.0 (obtained from Henkel Industrial Adhesives)
Ethyl acetate: 20.0 (solvent for easy application)
2. Laminate preparation The freshly prepared adhesive is applied to a second (unprinted) film at a coating weight of 2.5 g / m ² (dry), followed by drying in an oven at 60 ° C. for 10 seconds. The solvent was evaporated. The printed film is then carefully applied to the adhesive print on the printed side, thereby preventing air bubbles from occurring in the laminate. The resulting laminate is stored under pressure for 3 days to cure the adhesive.

3. Adhesive strength measurement:
A 15 mm wide strip is cut from the cured laminate and the lamination bond strength is measured using a Lloyd Instruments tensile tester (available from AMETEK, Inc.). The measurement is performed at a speed of 150 mm / min. During the measurement, the laminated strip should be kept at an angle of 90 ° to the film clamp.

  To simulate heat seal adhesion strength, the test is repeated after the laminated strip is heat sealed at 140 ° C./400 N / 1 sec using a Brugger heat seal machine (available from Brugger Feinchanik GmbH).

  Lamination bond strength is reported at N / 15 mm.

  All ranges disclosed herein are also intended to cover any and all possible subranges and their ranges, as will be understood by those skilled in the art for any and all purposes, particularly when providing the specification. Includes combinations of subranges. The arbitrarily described ranges can be easily recognized as being fully described and divided into at least equal half, third, quarter, fifth, tenth, etc. of the same range. As a non-limiting example, each range described herein can be easily divided into a smaller third, a middle third, a larger third, and so forth. As will be understood by those skilled in the art, all terms such as “to”, “at least”, “larger”, “smaller”, etc. include the stated number, followed by subranges as described above. Refer to the range that can be divided into

  All patent publications and publications mentioned in this specification are incorporated by reference in their entirety for all purposes.

EXAMPLES The following non-limiting examples serve to further illustrate the advantages of the disclosed invention, but are not limiting.

Example 1 Provision of Supported Resin (s) Using a continuous polymerization process described in US Pat. Nos. 4,546,160, 4,414,370, and 4,529,787, The supported resin compositions shown in the table were prepared.

  The amount of each component is shown in mass% with respect to the total amount of the components.

Example 2 Emulsion Polymerization to Obtain Emulsion Polymer (a) in the Presence of Supported Resin (s) Emulsion polymers shown in Table 2 were prepared from the supported resins shown in Table 1. A solution of supported resin, ammonia (25%) and deionized (DI) water was brought to 85 ° C. in a four neck round bottom flask under a gentle stream of nitrogen. A mixture of monomers was prepared and charged to the reactor. The reactor was then charged with ammonium persulfate (APS) dissolved in DI water. After 15 minutes, the remaining monomer mixture was charged to the reactor over 45-60 minutes. The temperature remained at 85 ° C. during the process. After this, the reactor contents were maintained under these conditions for 60 minutes to reduce residual monomer content. After this holding period, the emulsion was cooled. The emulsion was mixed for an additional 15 minutes and subsequently filtered.

Example 3-Preparation of polymer mixture The emulsion polymer (E-1, E-2, E-3) described in Table 2 and the water-soluble polymer (P-1, P-2, P-) described in Table 3 3, P-4, P-5) were prepared by physical mixing at room temperature. Selected preparations are shown in Table 4.

  The amount of EO (ethylene oxide) is given in% by weight relative to the total amount of copolymer. PO represents propylene oxide.

  The amount of each component is shown in mass% with respect to the total amount of the components.

Example 4-Preparation of Lamination Ink To study the effect on lamination adhesion strength, together with the selected polymer mixture (B-1 to B-11) listed in Table 4, both BASF S. E. Pigment concentrate containing PB15.3 (Heliogen® Blue D 7088) and Joncryl® HPD96-E (high molecular weight, high acid styrene acrylic resin) obtained from Ink preparations were prepared by mixing in ratio. By adding a mixture of pigment concentrate and water (30/70), the viscosity of the resulting ink was adjusted to the required printing viscosity (20 ″ DIN 4 / ˜150 mPa.s).

  The amount of each component is shown in mass% with respect to the total amount of the components.

Example 5-Preparation of laminate and measurement of adhesive strength Using wire bar 0, the resulting ink was applied on the treated side of co-extruded OPP (30MB400) and on the chemically treated polyester (Mylar 813). Applied (4 μm wet ink). The print was dried in an oven at 60 ° C. for 60 seconds and left overnight (16 hours).

A freshly prepared two-component polyurethane adhesive (8.0 g Liofol UR6080, 20.0 g Liofol UR7780, 20.0 g ethyl acetate) is applied to the second (unprinted) film and dried at 2.5 g / cm ² And then dried in an oven at 60 ° C. for 10 seconds to prepare a laminate. Apply the printed side of the printed film (coextruded OPP and chemically treated PET) to the adhesive side of the second film (for each of the coextruded OPP and LDPE) to obtain OPP // OPP And a PET // LDPE laminate structure. The laminate structure was stored under pressure (approximately 0.25 kg / cm ² ) for 3 days to fully cure the adhesive.

  To measure the lamination bond strength, a 15 mm wide strip is cut from the cured laminate and the bond strength is measured using a Lloyd Instruments tensile tester (available from AMETEK, Inc.). The measurement is performed at a speed of 150 mm / min. During the measurement, the laminated strip should be kept at a 90 ° angle to the film clamp.

  To simulate heat seal adhesion strength, the test is repeated after heat sealing the laminated strip at 140 ° C./400 N / 1 sec using a Brugger heat seal machine (available from Brugger Feinchanik GmbH).

  Lamination bond strength is reported at N / 15 mm.

  The composition of the present invention comprising a water soluble polymer exhibits improved results in lamination adhesion strength compared to the composition without water soluble polymer (I-8).

Claims (15)

The following steps:
(I) a step of providing a composition (C) containing an emulsion polymer (a), and then (ii) a composition containing a water-soluble polymer (b) containing an ether group to the composition (C) A composition obtained by adding
A composition wherein the water-soluble polymer (b) contains no carboxylate groups and the water-soluble polymer (b) has a solubility of at least 50 g / l in water.   The composition according to claim 1, wherein the composition (C) further comprises a supported resin (s) containing a carboxylate group, and the supported resin (s) has an acid value in the range of 10 to 400. .   The composition according to claim 1 or 2, wherein the water-soluble polymer (b) comprises an ether group derived from an alkylene oxide.   The composition according to any one of claims 1 to 3, wherein the water-soluble polymer (b) contains a random alkylene oxide polymer or a block alkylene oxide polymer.   The emulsion polymer (a) is acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, acrylic anhydride, methacrylic anhydride, itaconic anhydride, maleic anhydride, fumaric anhydride. , Crotonic anhydride, ethyl methacrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, ethyl acrylate, vinyl acetate, methyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, methylol acrylamide, glycidyl acrylate , Glycidyl methacrylate, diacetone acrylamide, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, allyl acetoacetate, vinyl Comprising a polymer of monomers selected from one or more of acetoacetate, acrolein, diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate. Item 5. The composition according to any one of Items 1 to 4.   The composition according to any one of claims 2 to 5, wherein the supporting resin (s) contains a water-soluble resin.   The composition according to any one of claims 2 to 6, wherein the supporting resin (s) contains an acrylic polymer, an acrylic / vinyl polymer, and a polyester polymer.   The composition according to any one of claims 2 to 7, wherein the carrier resin (s) contains an acrylic / styrene copolymer.   Furthermore, surfactants, solvents, leveling agents, rheology modifiers, waxes, buffering agents, dispersants, defoamers, antifoaming agents, modified polymers, rewetting agents, biocides, cross-linking agents or re-dissolving agents The composition according to any one of claims 1 to 8, comprising one or more additives (c) selected from:   Combining the composition comprising the emulsion polymer (a) and, if present, the support resin (s) with the composition comprising the water-soluble polymer (b) and optionally one or more additives (c). The method for producing a composition according to any one of claims 1 to 9.   Use of a composition according to any one of claims 1 to 9 for an aqueous coating or ink.   Use of a composition according to any one of claims 1 to 9 for water-based inks for printing on a substrate, preferably printing on a plastic film.   Use of a composition according to any one of claims 1 to 9 for aqueous coatings for overprint varnishes or paints.   Use of a composition according to any one of claims 1 to 9 for water-based inks for laminating a printed substrate to a second flexible film. (I) an emulsion polymer containing carboxylate groups (a), and (ii) a water-soluble random copolymer or water-soluble block copolymer of ethylene oxide and propylene oxide, at least 45 mass based on the amount of copolymer of ethylene oxide and propylene oxide. Water-soluble random copolymer or water-soluble block copolymer having an ethylene oxide content of 100% and a weight average molecular weight of 300 to 4000 g / mol,
A composition containing