EP2917294A1 - Composition pour des encres et des revêtements à haute résistance d'adhérence de stratification - Google Patents

Composition pour des encres et des revêtements à haute résistance d'adhérence de stratification

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Publication number
EP2917294A1
EP2917294A1 EP13786269.4A EP13786269A EP2917294A1 EP 2917294 A1 EP2917294 A1 EP 2917294A1 EP 13786269 A EP13786269 A EP 13786269A EP 2917294 A1 EP2917294 A1 EP 2917294A1
Authority
EP
European Patent Office
Prior art keywords
water
composition
acrylate
polymer
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13786269.4A
Other languages
German (de)
English (en)
Inventor
Cedric Du Fresne Von Hohenesche
Bernd Reck
Achim LÖFFLER
Steven ZIJLSTRA
Arjan Thomas Termaten
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP13786269.4A priority Critical patent/EP2917294A1/fr
Publication of EP2917294A1 publication Critical patent/EP2917294A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides

Definitions

  • the invention relates to a composition comprising emulsion polymers and water-soluble poly- mers with ether groups.
  • support resins with carboxylate groups may be comprised in the composition.
  • the invention relates to a method of making such composition and to the use of such composition for water based coatings or inks.
  • the invention relates to the use of such composition for water based inks for printing on plastic substrates and for water based coatings such as overprint varnishes or paints, especially as binders.
  • the invention relates to compositions useful for applications that require high lamination bond strength.
  • plastic films are used in the packaging industry for storage and shipping of goods. In many cases these plastic films are printed with text and images. Printing inks used for this purpose must meet certain end-use requirements for successful use in this application. These requirements include good printability, resolubility, resistance properties, and high lamination bond strength (LBS). Inks used with plastic packaging must also exhibit good wetting and flow properties and fast drying times.
  • LBS lamination bond strength
  • water-based inks which have good resolubility, the ability of dry ink to redisperse in the same ink when in a wet state, are also important. If a press is stopped, for example, water- based inks begin to dry on the rollers and can undergo physical and chemical changes due to film formation, change in pH, and the like which render the printability of these inks problematic.
  • WO 2006/034229 A1 describes stable water-borne polymer compositions which comprise a water-borne polymer, a metal cross-linking agent and a stabilizing agent comprising from 2 to 10 carbon atoms and at least two functional groups independently selected from hydroxy and carboxy.
  • solvent-based inks are often used.
  • the binder types used in these solvent- based inks range from nitrocellulose/plasticizer to nitrocellulose/urethane combinations, and include polyvinylbutyrate, polyvinylchloride/urethane and polyurethanes.
  • the transition to water based systems is slow due to a lack of water-based alternatives that offer good printability in combination with good LBS for applications such as printed oriented polypropylene (OPP) laminated to OPP or printed polyethyleneterephthalate (PET) laminated to low density polyethylene (LDPE).
  • OPP printed oriented polypropylene
  • PET printed polyethyleneterephthalate
  • WO 95/28436 A1 describes aqueous-based printing ink compositions adapted for use in gra- vure and flexographic printing on hydrophobic substrates which are prepared by combining a low-viscosity resin emulsion having an average particle diameter of less than about 0.5 microns and comprised of hydrophobic, moisture resistant, adherent resin forming components with a pigment paste containing a water-soluble polymer.
  • WO 97/19992 describes aqueous polymer emulsion compositions comprising a polymer. Also described therein are printing inks comprising a colorant and a binder for said colorant comprising such an aqueous emulsion polymer.
  • Substrates with very specific and stringent requirements are laminated flexible packing materials, which are first printed e.g. on a transparent OPP or PET substrate and subsequently lami- nated with a second flexible substrate (film) such as OPP or PE, e.g. with a solvent free 2K PU (two component polyurethane) lamination adhesive.
  • a second flexible substrate such as OPP or PE
  • a solvent free 2K PU two component polyurethane lamination adhesive.
  • This application requires high lamination bond strengths, e.g. typically higher than 2.0 N/15 mm.
  • RC-emulsion based inks often show excellent printability but insufficient lamination bond strength (e.g. typically below 0.5 N/15mm).
  • compositions such as RC-emulsions with certain water-soluble polymers comprising ether groups, inks with good lamination bond strength can be obtained.
  • compositions obtained by the following steps: (i) furnishing a composition (C) comprising an emulsion polymer (a), preferably comprising carboxylate groups, and thereafter (ii) adding to said composition (C) a composition comprising a water-soluble polymer (b) comprising ether groups, wherein said water-soluble polymer (b) does not comprise carboxylate groups and, said water-soluble polymer (b) has a solubility in water of at least 50 g/l.
  • composition (C) further comprises a support resin (s) comprising carboxylate groups and said support resin (s) has an acid number in the range of from 10 to 400.
  • composition (C) corresponds to a RC-emulsion.
  • compositions Upon curing, these compositions provide excellent lamination binding properties making them particularly suitable for use as binders in water-based inks for printing on plastic films and other substrates.
  • the improved lamination binding strength of inventive compositions permit their use in a wide variety of applications including water-based inks, overprint varnishes, paints, adhe- sives, sealing lacquers, molding materials, barrier coatings, electronic materials such as resists, and the like.
  • compositions may be prepared by combining an emulsion polymer comprising carboxylate groups with a water-soluble polymer comprising ether groups, for example by mixing aqueous solutions of these substances.
  • compositions of the invention may be applied as a film or coating to a substrate such as paper, wood, plastic, or textiles.
  • the compositions may be applied using curtain coating, flow coating or roll coating.
  • inventive compositions may be applied using gravure and flexographic printing processes including offset and screen printing processes.
  • the present invention provides compositions obtained by the following steps
  • composition (i) furnishing a composition (C) comprising an emulsion polymer (a), preferably comprising carboxylate groups, and thereafter
  • said water-soluble polymer (b) does not comprise carboxylate groups and,
  • said water-soluble polymer (b) has a solubility in water of at least 50 g/l.
  • composition (C) further comprises a support resin (s) comprising carboxylate groups and said support resin (s) has an acid number in the range of from 10 to 400.
  • composition (C) corresponds to a RC-emulsion.
  • Solubility in water is determined qualitatively by assessing a solution of a substance in water at 25°C which should render a clear solution free of sediment. Solubility is thus determined by increasing the concentration of said substance in water until the solution is no longer clear and/or free of sediment.
  • water-soluble characterizing said water- soluble polymer (b) is understood as a water-soluble polymer (b) that has a solubility of at least 50 g/L in water at 25°C, preferably 100 g/L in water at 25°C. Most preferably the water-soluble polymer (b) is fully miscible with water.
  • the emulsion polymer (a) can have an acid number preferably in the range from 10 to 300, more preferably from 15 to 200 and most preferably from 20 to 100. In a preferable embodiment, the emulsion polymer (a) has an acid number in the range from 40 to 100.
  • Acid numbers are determined according to methods well-known to a person skilled in the art by a potentiometric titration with 0.1 M KOH in water in a suitable solvent (aceton/water; 80/20). The results are reported as "mg KOH /g product".
  • Support resins (s) that can be used in inventive compositions typically include polymers selected from the group of acrylics, vinyls (including but not limited to styrenics, polyvinyl alcohols, and polyvinyl acetates), acrylic/vinyls, polyurethanes, polyamides, polyesters, polyethylene glycols, styrene-butadiene-rubber (SBR) polymers, nitrocelluloses, hybrids thereof, or blends thereof.
  • Hybrid polymers are compositions containing more than one type of polymer and are made by sequential polymerization of one polymer in the presence of another.
  • Hybrid polymers can include copolymers wherein the preparation of the second polymer in the presence of the first polymer results in the formation of copolymer.
  • Hybrid polymers also include, but are not limited to random, alternating or block-copolymers.
  • the support resin (s) comprises a water-soluble resin.
  • the support resin (s) comprises an acrylic, acrylic/vinyl, polyester polymer, a hybrid thereof, or a blend thereof.
  • the acrylic support resin (s) comprises polymerized monomers selected from one or more of 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 methac- rylate, 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 aceto-
  • the support resin (s) comprises an acrylic/styrenic polymer
  • the support resin (s) in addition to the acrylic groups listed above, comprises polymerized monomers selected from one or more of styrene, methyl styrene, alpha-methyl styrene, ethyl styrene, isopropyl styrene, tertiary-butyl styrene, acyclic conjugated dienes, vinyl esters, vinyl chloride, formyl styrol, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, a hybrid thereof, or a blend thereof.
  • Vinyl/acrylic support polymers (s) such as styrene/acrylic polymers are particularly suitable for use in inventive compositions. Natural polymers are also contemplated for use in the present invention and include proteins, (hydroxyethyl)cellulose, cotton, starch and the like.
  • the support resin (s) further comprises a vinyl, polyurethane, polyamide, styrene-butadiene-rubber polymer, nitrocellulose, a hydrid thereof, or a blend thereof.
  • support resins (s) used in inventive compositions can have a wide range of acid numbers as described above.
  • the dry weight of the polymers (a), (s) and (b) together may be adjusted according to the application and can make up anywhere from about 0.1 to about 95 weight percent (weight-%) of the composition.
  • the weight of the polymers (a) and (b) constitutes from about 0.1 to about 70 weight-%, about 0.1 to about 60 weight-%, about 1 to about 50 weight-%, about 5 to about 50 weight-%, or about 10 to about 50 weight-% of the composition according to the invention.
  • emulsion polymers For example, the preparation of emulsion polymers is described in Emulsion Polymerization by Gilbert, R.G., Academic Press, N.Y., 1995, pp 1 -23. The preparation of styrene/acrylic polymers is described in U.S. patents 4,546,160, 4,414,370, 4,529,787. Generally such emulsion polymers are prepared with ethylenically unsaturated monomers, and initiators, and optionally with surfactants, alkali, and water or another reaction solvent.
  • Exemplary monomers include but are not limited to acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, acrylic anhydride, methacrylic anhydride, itaconic anhydride, maleic anhydride, fumaric anhydride, crotonic anhydride, styrene, methyl styrene, alpha-methyl styrene, ethyl styrene, isopropyl styrene, tertiarybutyl styrene, ethyl methacrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, ethyl acrylate, vinyl acetate, methyl acrylate, acyclic conjugated dienes, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, methylol acrylamide, gly
  • Emulsion polymers suitable for use with the present invention include self-crosslinkable polymers (see, e.g., U.S. Patent Nos. 5,432,229, 5,605,722, 6,355,720, and 6,538,062).
  • Self- crosslinkable polymers comprise polymerized self-crosslinkable monomers such as diacetone acrylamide (DAAM), acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, allyl aceto- acetate, vinyl acetoacetate, acrolein, formyl-styrol, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate acetylacetate, butanediol-1 ,4-acrylate acetylacetate, allyl methacrylate, and the like.
  • the emulsion polymer (a) comprises polymerized monomers selected from one or more of 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 methacrylamide, glycidyl acrylate, glycidyl methacrylate, di
  • emulsion polymers (a) used in inventive compositions can have a wide range of acid numbers as described above.
  • compositions (C) useful in the inventive compositions can also have a wide range of glass transition temperatures (Tg).
  • Tg glass transition temperatures
  • polymers useful in this invention can have Tg values from -40 to 150°C, preferably from -40 to 40°C. Tg values are determined by Differential Scanning Microscopy (DSC).
  • Water-soluble polymers (b) that can be used in inventive compositions typically include poly- mers selected from the group of polyalkylene oxides, polyesterpolyols, hybrids thereof, or blends thereof.
  • Polyalkylene oxides are polymers based on monomers selected from the group of epoxides, preferably ethylene oxide, propylene oxide, 1 ,2-butylen oxide and 2,3-butylen oxide, more pref- erably ethylene oxide and propylene oxide.
  • the water-soluble polymer (b) of the inventive composition comprises ether groups derived from alkylene oxides, preferably ethylene oxide (EO), propylene oxide (PO), butylen oxide, more preferably ethylene oxide and/or propylene oxide.
  • alkylene oxides preferably ethylene oxide (EO), propylene oxide (PO), butylen oxide, more preferably ethylene oxide and/or propylene oxide.
  • the water-soluble polymer (b) of the inventive composition comprises a random or block alkylene oxide polymer.
  • the water-soluble polymer (b) of the inventive composition comprises groups derived from alcohols, such as alcohols derived from natural oils like castor oil and other natural materials, oxoalcohols, alkylphenols.
  • the water-soluble polymer (b) of the inventive composition has a weight average molecular weight Mw in the range from 300 to 15000 g/mol, preferably from 350 to 10000 g/mol, most preferably from 400 to 8000 g/mol and particularly from 400 to 6000 g/mol. Mw values are determined by Gel Permeation Chromatography (GPC) using a Waters Alliance 2690 Separations Module equipped with a Waters 2414 Refractive Index detector at a concentration of around 10 mg/ml in THF solvent.
  • the water-soluble polymer (b) of the inventive composition does not comprise amine groups.
  • water-soluble polymer (b) of the inventive composition does not comprise ester groups.
  • the water-soluble polymer (b) of the inventive composition does comprise neither ester nor amine groups.
  • the preparation of water-soluble polymers (b) comprising ether groups is well known to those skilled in the art.
  • the amount of emulsion polymer (a) is from 70 to 99 weight-% and the amount of water-soluble polymer (b) is from 1 to 30 weight-%, based on the total amount of emulsion polymer (a) and water-soluble polymer (b).
  • the amount of emulsion polymer (a) is from 80 to 99 weight-% and the amount of water-soluble polymer (b) is from 1 to 20 weight-%, more preferably the amount of emulsion polymer (a) is from 85 to 99 weight-% and the amount of water-soluble polymer (b) is from 1 to 15 weight-%, and most preferably the amount of emulsion polymer (a) is from 90 to 99 weight-% and the amount of water- soluble polymer (b) is from 1 to 10 weight-%, based on the total amount of emulsion polymer and water-soluble polymer.
  • the amount of emulsion polymer (a) and support resin (s) together is from 70 to 99 weight-% and the amount of water-soluble polymer (b) is from 1 to 30 weight-%, preferably the amount of emulsion polymer (a) and support resin (s) together is from 90 to 99 weight-% and the amount of water-soluble polymer (b) is from 1 to 10 weight-%, based on the total amount of emulsion polymer (a), support resin (s) and water-soluble polymer (b).
  • the amount of emulsion polymer (a) is from 50 to 95 weight-% and the amount of support resin (s) is from 5 to 50 weight-%, based on the total amount of emulsion polymer(a) and support resin (s).
  • the emulsion polymer (a) comprises polymerized monomers selected from one or more of 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, acetoacetoxyethy
  • Another ascpect of the invention is a composition comprising
  • the composition further comprises one or more additives (c) selected from surfactants, solvents, leveling agents, rheology agents, waxes, buffering agents, dispersing agents, defoaming agents, antifoaming agents, modifying polymers, rewetting agents, biocides, crosslinking agents or resolubility agents.
  • additives selected from surfactants, solvents, leveling agents, rheology agents, waxes, buffering agents, dispersing agents, defoaming agents, antifoaming agents, modifying polymers, rewetting agents, biocides, crosslinking agents or resolubility agents.
  • the amount of emulsion polymer (a) is from 65 to 98.9 weight-% and the amount of water- soluble polymer (b) is from 1 to 30 weight-% and the amount of one or more additive (c) is from 0,1 to 5 weight-% based on the total amount of emulsion polymer (a), water-soluble polymer (b) and one or more additives (c).
  • the amount of emulsion polymer (a) together with support resin (s) is from 65 to 98.9 weight-% and the amount of water-soluble polymer (b) is from 1 to 30 weight-% and the amount of one or more additive (c) is from 0,1 to 5 weight-% based on the total amount of emulsion polymer (a), support resin (s) water-soluble polymer (b) and one or more additives (c).
  • anionic surfactants include alkyl sulfonates, alkylaryl sulfonates, alkyl sulfates, sulfates of hydroxyalkanols, alkyl and alkylaryl disulfonates, sulfonated fatty acids, sulfates and sulfonates of polyethoxylated alkanols and alkylphenols as well as esters of sulfosuccinic acid.
  • Nonionic surfactants are particularly suitable for use with inventive compositions and include, e.g., polyvinylpyrrolidone, alkyl polysaccharides, and the like.
  • compositions as described herein comprising combining, e.g. mixing, the composition comprising emulsion polymer (a), preferably with the support resin (s), with the composition comprising the water-soluble polymer (b), preferably in the amounts described herein.
  • the invention therefore also relates to a method of making the inventive composition comprising combining the emulsion polymer (a), preferably with the support resin (s), with the composition comprising the water-soluble polymer (b), the water-soluble polymer (b) and optionally one or more additives (c).
  • emulsion polymer (a) comprising carboxylate groups, preferably with the support resin (s), with a water-soluble polymer (b) comprising ether groups and optionally one or more additives (c) is carried out by mixing aqueous solutions of these substances.
  • water-soluble polymer (b) is added to an aqueous solution of emulsion polymer (a), preferably with the support resin (s), and optionally one or more additives (c) are added to the resulting composition.
  • aqueous solution of emulsion polymer (a) preferably with the support resin (s)
  • water-soluble polymer (b) and optionally one or more additives (c) may be added as (dry) substances or in aqueous solution.
  • aqueous solution of a substance also comprises dispersions and suspensions of the substance in water.
  • the inventive compositions can additionally comprise polyvalent metal cross-linking agents as disclosed in WO 2006/034229 A1.
  • the amount of metal crosslinking agents employed will vary depending upon the amount of emulsion polymer (a) and the acid number of the polymer.
  • Suitable polyvalent metals include zirconium, titanium, hafnium, chromium, zinc, aluminum, or a mixture of any two or more thereof. Zirconium is especially well suited as a metal cross-linking agent.
  • the metalcrosslinking agent is typically a salt or complex of am- monia, acetate, propionate, sulfate, carbonate, nitrate, phosphate, tartrate, acetylacetonate, oxide, or a mixture of any two or more thereof.
  • exemplary metal crosslinking agents include ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate, zirconium tartrate, zinc oxide, and other combinations of the above polyva- lent metals and counter ions.
  • inventive compositions will vary with the nature of the polymer and polyvalent metal.
  • the composition generally has a molar ratio of carboxylate groups to metal cross-linking agent of from about 10:1 to about 1 :2, from about 9:1 to about 1 :2, from about 8:1 to about 1 :2, from about 7:1 to about 1 :2, from about 6:1 to about 1 :2, from about 5:1 to about 1 :2, from about 4: 1 to about 1 :2, from about 3:1 to about 1 :2, from about 10:1 to about 1 : 1 , from about 8:1 to about 1 : 1 , from about 6: 1 to about 1 : 1 , from about 4:1 to about 1 : 1 , or from about 3:1 to about 1 : 1.
  • the inventive compositions can additionally comprise a wide variety of organic compounds as stabilizing agents so long as they contain at least two hydroxy or car- boxy groups or one of each. It is to be understood that the stabilizing agents are not to be limited to two functional groups and may include additional hydroxy and carboxy groups as well as other functional groups such as oxo, amino, thiol, cyano, nitro, and the like if such groups do not interfere with the stabilizing ability of
  • Suitable stabilizing agents of the invention therefore include but are not limited to diols, hydroxy acids, diacids, sugars, or mixtures of two or more thereof.
  • a stabilizing agent can be tartaric acid, gluconic acid, mu- cic acid, saccharic acid, oxalic acid, glycolic acid, lactic acid, malic acid, citric acid, mandelic acid, malonic acid, maleic acid, succinic acid, a salt thereof, or a mixture of two or more thereof.
  • Stabilizing agents which are sugars include mannitol, fructose, glucose, and mixtures of two or more thereof or mixtures with diols, hydroxy acids or diacids.
  • the amount of stabilizing agent used in compositions of the invention is 1.4 mole percent or more of the amount of the cross- linking agent. In other embodiments, the amount of stabilizing agent can be 2.4 mole percent or more, 3 mole percent or more, or 7 or 10 mole percent or more of the amount of the cross- linking agent. Alternatively, the molar percentage of the stabilizing
  • agent ofmetal cross-linking agent is at least 1 .4, 2.4, 3, 7, 8, 9, or 10 to about 40 mole percent or at least 1 .4, 2.4, 3, 7, 8, 9, or I0 to about 30 mole percent or is at least 1 .4, 2.4, 3, 7, 8, 9, or 10 to about 20 mole percent.
  • coating compositions of the invention display excellent strength and hardness and are especially useful as top coating agents for plastics, overprint varnishes, printing inks, paints, adhesives, fillers, molding materials, electronic materials such as resists, or the like.
  • an overprint varnish, a paint or a heat seal lacquer may each independently include a composition as described herein.
  • An ink may further include a pigment.
  • compositions which include emulsion polymer (a), preferably comprising carboxylate groups, support resin (s) comprising carboxylate groups and a water-soluble polymer (b) comprising ether groups, wherein said support resin (s) has an acid number in the range from 10 to 400, preferably from 15 to 350, most preferably from 50 to 300, said water- soluble polymer (b) does not comprise carboxylate groups and, said water-soluble polymer (b) has a solubility in water of at least 50 g/l, wherein the amounts of emulsion-polymer (a), support resin (s) and water-soluble polymer (b) are sufficient to cause a coating, such as an ink, comprising the composition to display a larger LBS than the same coating without the water-soluble polymer (b) being added to a composition comprising an emulsion polymer (a), preferably comprising carboxylate groups and support resin (s) comprising carboxylate groups.
  • Some such compositions can further include a pigment.
  • a composition as described herein as a film or coating comprising applying a composition as described herein as a film or coating to a substrate.
  • Sub- strates may include paper, wood, plastic, or textiles.
  • overprint varnishes and inks of the invention may be applied to paper and films or sheets of polyethylene, polyvinyl chloride, polypropylene, polyester, polycarbonate, and polyimide, and paper treated with any of these materials.
  • Methods for coating the substrate with the overprint varnish or ink of the invention include well- known methods such as direct coating and printing.
  • direct coating such as spray coating can also be em- ployed.
  • Printing processes used for coating include offset printing, gravure offset printing, and gravure and flexographic printing processes.
  • the thickness of the coating film produced by these processes can be about 0.25 to about 25 micrometers, typically, about 1 to about 10 micrometers.
  • the invention also relates to the use of the inventive compositions for water based coatings or inks.
  • compositions according to the invention for water based inks for printing on substrates, preferably for printing on plastic films.
  • compositions according to the invention for water based coatings for overprint varnishes or paints are also relates to the use of compositions according to the invention for water based inks for laminating printed (primary) substrates to (secondary) flexible films. These laminates render high lamination bondstrengths of preferably >1 .5 N/15mm and most preferably >2 N/15mm before and after heatseal. Lamination is carried out by procedures well known to a person skilled in the art.
  • Laminates in general are obtained for example by applying the composition according to the invention or an ink-formulation of said composition to the surface of a plastic substrate. After drying a coated substrate is obtained. Subsequently a lamination adhesive is used to fix a second plastic surface to the coated substrate.
  • Coloured ink is prepared by blending 30 parts of a (resin-based or resin-free) pigment paste (e.g. PB15.3) and 70 parts of a test emulsion.
  • the viscosity of the ink can be measured employing a DIN4 cup.
  • the viscosity of the ink can be reduced to 20 s DIN4 using a 30/70 blend of pigment paste/water.
  • White ink is prepared by blending 40 parts of a resin-free pigment paste (e.g. PW6) and 60 parts of a test emulsion.
  • the viscosity of the ink can be measured employing a DIN4 cup.
  • the viscosity of the ink can be reduced to 20 s DIN4 using a 40/60 blend of pigment paste/water.
  • Ink was applied on the treated side of coex-OPP (30MB400 - Oriented Polypropylene Film which can be obtained from ExxonMobil Chemical) and on chemically treated polyester (Mylar® 813 which can be obtained from DuPont Teijin Films), using a wire-bar 0 (4 ⁇ wet ink). Inks were applied as 100% colour (1 layer), 200% colour (2 layers) and 100% colour plus 100% white (2 layers). The resulting prints were dried in an oven for 60 s at 60°C followed by a further drying period of about 16 hours (overnight) at room temperature, before making a laminate
  • Liofol Hardener UR6080 8.0 (obtained from Henkel Industrial Adhesives)
  • Liofol UR7780 20.0 obtained from Henkel Industrial Adhesives
  • the freshly prepared adhesive is applied to the secondary (unprinted) film at a coating weight of 2.5 g/m 2 (dry), and subsequently dried in the oven for 10 s at 60°C to evaporate the solvent.
  • the printed film is next carefully applied with the printed side to the adhesive print, thereby avoiding creation of air bubbles in the laminate.
  • the resulting laminates are stored for 3 days under pressure, in order to allow the adhesive to cure.
  • a strip of 15mm width is cut from the cured laminate and lamination bond strength is measured using a Lloyd Instruments tensile tester (which can be purchased from AMETEK, Inc.). Measurement is done at a speed of 150mm/min. During the measurement, the laminated strip should be kept under a 90° angle against the film clamps.
  • the support resin compositions given in Table 1 were prepared using a continuous polymerization process described in U.S. Pat. Nos. 4,546,160, 4,414,370, 4,529,787.
  • Amounts of Components are given in weight-% relative to the total amount of Components.
  • Emulsion polymers given in Table 2 were prepared from the support resins given in Table 1 .
  • a solution of support resin, ammonia (25%) and de-ionized (Dl) water was brought to 85°C in a 4- neck round bottom flask under a mild flow of nitrogen.
  • a mixture of monomers was prepared and charged to the reactor.
  • ammonium persulfate (APS) dissolved in Dl water was charged to the reactor. After 15 minutes, the remaining monomer mixture was charged to the reactor over 45-60 minutes. During the process, temperature remained at 85°C. After this, the reactor content was kept under these conditions for 60 minutes to reduce residual monomer content. After this hold-period, the emulsion was cooled. The emulsion was mixed for an additional 15 minutes and subsequently filtered.
  • Trigonox AW70 2-hydroperoxy-2-methylpropane
  • Blends of the described emulsion polymers (E-1 , E-2, E-3) described in table 2 and water soluble polymers (P-1 , P-2, P-3, P-4, P-5) described in table 3 were prepared by physical blending at room temperature.
  • the selected formulations are given in Table 4.
  • P-5 EO-PO-EO block copolymer 50 1900 The amount of EO (ethylene oxide) is given in weight-% relative to the total amount of the copolymer. PO stands for propylene oxide.
  • Amounts of Components are given in weight-% relative to the total amount of Components.
  • Example 4 Preparation of lamination inks
  • ink formulations were prepared by blending of the selected polymer blends (B-1 - B-1 1 ) described in Table 4 with a pigment concentrate comprising PB15.3 (Heliogen® Blue D 7088) and Joncryl® HPD96-E (high molecular weight, high acid value styrene acrylic resin), both obtained from BASF S.E., in a 4:1 ratio.
  • the viscosity of the resulting ink was adjusted to required print viscosity (20" DIN4 / -150 mPa.s) by addition of a mixture of pigment concentrate and water (30/70).
  • Viscosity 250 290 140 450 150 2900 300 205 155 125 115
  • Example 5 Preparation of laminates and bond strength measurement
  • the resulting inks were applied on the treated side of coex-OPP (30MB400) and on chemically treated polyester (Mylar 813) using a wire-bar 0 (4 ⁇ wet ink).
  • the prints were dried in an oven for 60 s at 60°C and left overnight (16 hours).
  • Laminates were prepared by application of freshly prepared 2 component Polyurethane adhe- sive (8.0 g Liofol UR6080, 20.0 g Liofol UR7780, 20.0 g Ethylacetate) to a secondary (unpriced) film rendering a coating weight of 2.5 g/m 2 dry, followed by drying in the oven for 10 s at 60°C.
  • the printed films (coex-OPP and chemically treated PET) are applied with the printed side to the adhesive side of the secondary films (coex-OPP and LDPE, respectively) to give OPP//OPP and PET//LDPE laminate structures.
  • the laminate structures were stored for 3 days under pressure (ca 0.25 kg/cm 2 ) to allow full cure of the adhesive.
  • a strip of 15mm width is cut from the cured laminate and bond strength is measured using a Lloyd Instruments tensile tester (which can be purchased from AMETEK, Inc.). Measurement is done at a speed of 150mm/min. During the measurement, the laminated strip should be kept under a 90° angle against the film clamps.
  • compositions according to the invention including a water soluble polymer show improved results of lamination bond strength compared to compositions without water soluble polymers (I- 8).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention porte sur une composition obtenue par les étapes suivantes : (i) l'utilisation d'une composition (C) comprenant un polymère en émulsion (a) et après cela (ii) l'ajout à ladite composition (C) d'une composition comprenant un polymère hydrosoluble (b) comprenant des groupes éther, ledit polymère hydrosoluble (b) ne comprenant pas de groupes carboxylate et ledit polymère hydrosoluble (b) ayant une solubilité dans l'eau d'au moins 50 g/l. L'invention porte également sur un procédé de fabrication d'une telle composition et sur l'utilisation de celle-ci pour des revêtements ou encres à base d'eau. L'invention porte également sur une composition comprenant (i) un polymère en émulsion (a) comprenant des groupes carboxylate et (ii) un copolymère statistique ou séquencé hydrosoluble d'oxyde d'éthylène et d'oxyde de propylène ayant une teneur en oxyde d'éthylène d'au moins 45 % en poids par rapport à la quantité totale du copolymère d'oxyde d'éthylène et d'oxyde d'éthylène et ayant une masse moléculaire moyenne en poids de 300 à 4000 g/mole.
EP13786269.4A 2012-11-09 2013-11-06 Composition pour des encres et des revêtements à haute résistance d'adhérence de stratification Withdrawn EP2917294A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13786269.4A EP2917294A1 (fr) 2012-11-09 2013-11-06 Composition pour des encres et des revêtements à haute résistance d'adhérence de stratification

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12191990 2012-11-09
EP13786269.4A EP2917294A1 (fr) 2012-11-09 2013-11-06 Composition pour des encres et des revêtements à haute résistance d'adhérence de stratification
PCT/EP2013/073088 WO2014072302A1 (fr) 2012-11-09 2013-11-06 Composition pour des encres et des revêtements à haute résistance d'adhérence de stratification

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EP2917294A1 true EP2917294A1 (fr) 2015-09-16

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JP (1) JP6324397B2 (fr)
KR (1) KR20150084883A (fr)
CN (1) CN104769052B (fr)
BR (1) BR112015009926A2 (fr)
WO (1) WO2014072302A1 (fr)

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CN107743511A (zh) 2015-06-18 2018-02-27 巴斯夫欧洲公司 包含水分散的聚氨酯粘合剂和水分散的聚(甲基)丙烯酸酯粘合剂的水基印刷油墨
WO2018102331A1 (fr) * 2016-11-30 2018-06-07 Basf Se Émulsions polymères aqueuses pour des applications d'amortissement sonore
US11352522B2 (en) * 2017-08-17 2022-06-07 Sun Chemical Corporation Water-based inks with high renewable content
EP3941751B1 (fr) 2019-03-18 2023-10-11 Hewlett-Packard Development Company, L.P. Ensemble support de formation d'image comportant de la résine

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US5284894A (en) * 1990-02-22 1994-02-08 Basf Corporation Low-foaming latexes for use in printing ink formulations
US6120638A (en) * 1996-01-25 2000-09-19 Rohm And Haas Company Dispersible, high speed book casing-in vinyl ester/(meth)acrylate adhesive
US5874498A (en) * 1996-03-11 1999-02-23 Air Products And Chemicals, Inc. Vinyl acetate emulsions for high scrub paints
JP3803171B2 (ja) * 1997-06-27 2006-08-02 旭化成ケミカルズ株式会社 複合塗膜およびそれを有する物品
DE69825289T3 (de) * 1997-08-15 2012-07-05 Eastman Chemical Co. Verwendung von tensiden als weichmacher zur verminderung der flüchtigen organischen verbindungen in wässrigen polymeren überzugszusammensetzungen
JP2000212490A (ja) * 1999-01-19 2000-08-02 Shachihata Inc インキ組成物
DE102004016645A1 (de) * 2004-03-31 2005-10-27 Basf Ag Wässrige Dispersionen mit verbesserter Ionenverträglichkeit und ihre Verwendung in Papierstreichmassen
JP2008063472A (ja) * 2006-09-08 2008-03-21 Nisshin Chem Ind Co Ltd 金属用塗料及び該金属用塗料の塗膜が形成された金属材料

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Also Published As

Publication number Publication date
JP6324397B2 (ja) 2018-05-16
CN104769052B (zh) 2017-07-18
CN104769052A (zh) 2015-07-08
KR20150084883A (ko) 2015-07-22
BR112015009926A2 (pt) 2017-07-11
JP2015537080A (ja) 2015-12-24
WO2014072302A1 (fr) 2014-05-15

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