WO2012173032A1 - Encre aqueuse pour l'impression par jet d'encre pour stratification et procédé pour la production d'un stratifié - Google Patents

Encre aqueuse pour l'impression par jet d'encre pour stratification et procédé pour la production d'un stratifié Download PDF

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Publication number
WO2012173032A1
WO2012173032A1 PCT/JP2012/064643 JP2012064643W WO2012173032A1 WO 2012173032 A1 WO2012173032 A1 WO 2012173032A1 JP 2012064643 W JP2012064643 W JP 2012064643W WO 2012173032 A1 WO2012173032 A1 WO 2012173032A1
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resin
aqueous
inkjet recording
ink
water
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PCT/JP2012/064643
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English (en)
Japanese (ja)
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能高 木内
悠 片山
佐藤　義浩
伊藤　弘行
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Dic株式会社
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Publication of WO2012173032A1 publication Critical patent/WO2012173032A1/fr

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    • 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
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules

Definitions

  • the present invention relates to an aqueous inkjet recording ink, and more particularly to an aqueous inkjet recording ink for laminating that can be used as laminating ink for packaging materials such as food.
  • Printing with an inkjet printer recording device is a method that ejects ink from nozzles and attaches it to the recording material. Unlike conventional printing, it is a printing method that does not use a plate, so it has become a small variety of products that have been in increasing demand in recent years. Demand is expanding as an on-demand printing method that can be supported.
  • the packaging material uses a plastic film that is a non-absorbing substrate.
  • the packaging material is printed directly on the surface of the plastic film, and printed on the back surface of the plastic film that is an outer layer with product protection and various functions.
  • the latter packaging material is excellent in aesthetics such as making use of the glossiness of the plastic film and preventing the scratch resistance of the ink, as well as strength to protect the contents from distribution, refrigeration, storage, heat sterilization, etc. Functions such as resistance to cracking, resistance to retort, and heat resistance can be imparted by combining a plurality of films, and this is the current mainstream.
  • laminating is usually performed by a roll-to-roll method.
  • the film after printing is wound up once after drying and then unwound again in the adhesive coating process.
  • a so-called blocking phenomenon may occur in which the printing surface sticks to the back surface.
  • the laminating ability is particularly important for laminated packaging materials. If the laminate strength is insufficient, there is a possibility that the package is peeled off after being filled with food or the bag is broken from the heat seal portion.
  • gravure ink has been used as printing ink for food packaging materials.
  • gravure ink for the blocking property, there is a formulation that prevents the blocking phenomenon by the effect of particles floating on the surface of the ink film by adding polyethylene wax or inorganic fine particles having a particle size of about several ⁇ m. Be taken.
  • the nozzle diameter for ejecting ink is small and a sufficient effect cannot be obtained.
  • an aqueous gravure printing ink for laminating using a polyurethane resin having a hydrazine residue in the molecule and not having a functional group that reacts with the hydrazine residue as a binder is known.
  • the present invention provides a water-based inkjet recording ink for laminating that has good ejection properties, can form an image as an ink for packaging materials for foods, is less susceptible to blocking during the winding process, and has excellent laminating properties. There is to do.
  • an aqueous polyurethane resin (b-1) produced through a step of reacting a chain extender comprising a hydrazine derivative with a carbonyl group or
  • an aqueous resin containing an amide group-containing acrylic copolymer (b-2) By using an aqueous resin containing an amide group-containing acrylic copolymer (b-2), it is possible to form an image as an ink for packaging materials for foods with excellent ink ejection properties, and to give sufficient laminate strength. It has been found that a water-based inkjet recording ink for laminating can be obtained.
  • the present invention is an aqueous inkjet recording ink for laminating processing comprising (a) a pigment and (b) an aqueous resin
  • the aqueous resin (b) includes an aqueous polyurethane resin (b-1) produced through a step of reacting a chain extender comprising a hydrazine derivative, and a carbonyl group or amide group-containing acrylic copolymer (b-2).
  • An aqueous inkjet recording ink for laminating which is an aqueous resin containing
  • the present invention also includes a step of forming a printing layer on a non-absorbent substrate by an inkjet recording method using the water-based inkjet recording ink described above, and a step of forming an adhesive layer on the printing layer. And a method for producing a laminate comprising a step of laminating a sealant film layer on the adhesive layer surface.
  • INDUSTRIAL APPLICABILITY it is possible to form an image as an ink for packaging materials for foods with good ejection properties, and a blocking phenomenon is hardly generated in the winding process, and it can be applied as a food packaging material having excellent laminating properties.
  • a water-based inkjet recording ink for laminating that can give a laminate can be obtained.
  • the laminate of the present invention is excellent in laminate suitability and is suitable as a food packaging material.
  • the pigment used in the present invention is not particularly limited, and those usually used as pigments for water-based inkjet recording inks can be used. Specifically, it can be dispersed in water or a water-soluble organic solvent, and a known inorganic pigment or organic pigment can be used. Examples of the inorganic pigment include carbon black produced by a known method such as titanium oxide, iron oxide, a contact method, a furnace method, and a thermal method.
  • Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye chelates, acidic dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like.
  • azo pigments including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments
  • polycyclic pigments for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines.
  • pigments include carbon black, No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 2200B, no. 900, no. 980, no. 33, no. 40, No, 45, No. 45L, no. 52, HCF88, MA7, MA8, MA100, etc. are Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc. manufactured by Columbia, Regal 400R, Regal 330R, Regal 660R, Mull 660R, Mull 660R Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc.
  • pigments used in magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, etc. It is done.
  • pigments used for cyan ink include C.I. I. Pigment blue 1, 2, 3, 15, 15: 3, 15: 4, 16, 22, 60, 63, 66, and the like.
  • a so-called self-dispersing pigment (surface-treated pigment) having a water dispersibility-imparting group on the pigment surface and capable of stably maintaining the dispersion state without a dispersant may be used.
  • capsule pigments water-dispersible polymer-containing pigments
  • pigments dispersed with a dispersant may be used.
  • the pigment may be preferably dispersed in (b) an aqueous resin or a water-soluble solvent described later as a pigment dispersion dispersed by various pigment dispersants or surfactants.
  • the pigment dispersant is preferably an aqueous resin, and preferable examples include polyvinyl alcohols, polyvinylpyrrolidones, acrylic resins such as acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid.
  • Styrenes such as acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene- ⁇ -methylstyrene-acrylic acid copolymers, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymers, etc.
  • examples thereof include acrylic resins, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, and salts of the aqueous resins.
  • the compounds for forming the copolymer salt include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, Examples include propylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol, and morpholine.
  • the amount of the compound used to form these salts is preferably equal to or greater than the neutralization equivalent of the copolymer.
  • Commercially available products include Ajinomoto Fine Techno Co., Ltd. product Ajisper PB series, Big Chemie Japan Co., Ltd. Disperbyk series, BYK-series, and EFKA series manufactured by Ciba Specialty Chemicals.
  • the aqueous resin (b) used in the present invention comprises an aqueous polyurethane resin (b-1) produced through a step of reacting a chain extender composed of a hydrazine derivative, and a carbonyl group or amide group-containing acrylic copolymer ( b-2) and an aqueous resin.
  • the aqueous resin (b) includes an —NHNH 2 group at the molecular end of the aqueous polyurethane resin (b-1) generated by reacting a chain extender composed of a hydrazine derivative, and an acrylic copolymer (b-2). Reacts with the carbonyl group or amide group possessed by the resin, so that the resin has a crosslinking point at least after printing and drying. This is presumed to be the cause of the blocking phenomenon hardly occurring.
  • the aqueous polyurethane resin (b-1) and the acrylic copolymer (b-2) may be mixed in an aqueous medium. In this case, a resin having a crosslinking point after printing is dried. It becomes. Further, by copolymerizing various acrylic monomers as raw materials of the acrylic copolymer (b-2) in the presence of the aqueous polyurethane resin (b-1), the aqueous polyurethane resin (b- An aqueous dispersion of resin particles obtained by crosslinking 1) and the acrylic copolymer (b-2) can also be obtained. In the present invention, either system may be used, but an aqueous dispersion of resin particles obtained by the latter method is more preferable because of excellent storage stability because the reaction site has already reacted.
  • the aqueous polyurethane resin (b-1) produced through the step of reacting the chain extender comprising the hydrazine derivative is produced as follows.
  • a urethane prepolymer is obtained by urethanizing diisocyanate with glycol and glycol having a carboxylic acid group.
  • diisocyanates used at this time include aliphatic, alicyclic or aromatic diisocyanates. Examples of these are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4-diphenylmethane.
  • diisocyanate m- phenylene diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, lysine diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4 '- dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4-biphenylene diisocyanate, 3 , 3'-Dimethoxy-4,4-biphenylene diisocyanate, 3,3'-dichloro-4,4-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphtha Down diisocyanate, and isophorone diisocyanate.
  • low molecular weight glycols As the glycols for preparing the urethane prepolymer, low molecular weight glycols, high molecular weight glycols, polyester diols, polycarbonate diols, etc. may be used alone or as well known in urethane technology. In addition, low molecular weight glycols may be used in combination with polyester diols and high molecular weight glycols.
  • Examples of the low molecular weight glycols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, tetramethylene glycol, mexamethylene glycol, decamethylene glycol, octanediol, tricyclodehydride. There are candimethylol, hydrogenated bisphenol A, cyclohexane dimethal, and the like, and two or more of these may be mixed.
  • Examples of the high molecular weight glycols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • the glycols and dicarboxylic acids for example, linear aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferable. Specific examples thereof include succinic acid, adipic acid, azelaic acid, sebacic acid.
  • Aliphatic dicarboxylic acids such as decanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl
  • dicarboxylic acid such as dicarboxylic acid, diphenic acid, and aromatic dicarboxylic acids, such as its anhydride, and it manufactures by a well-known method.
  • polyester polyols can also be produced by transesterification using lower alkyl esters of glycols and dicarboxylic acids.
  • the polycarbonate polyol may be any of those obtained by reacting the glycols with carbonates such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate and the like. It is manufactured by the method.
  • glycols having a carboxylic acid group examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, and the like.
  • the urethanization reaction is desirably performed in an organic solvent that is inert to isocyanate groups and has a high affinity for water, such as dioxane, acetone, methyl ethyl ketone, N-methylpyrrolidone, and tetrahydrofuran.
  • organic solvent that is inert to isocyanate groups and has a high affinity for water, such as dioxane, acetone, methyl ethyl ketone, N-methylpyrrolidone, and tetrahydrofuran.
  • the prepolymer is neutralized and chain-extended, and distilled water is added to obtain an aqueous polyurethane resin.
  • the neutralizing agent used for neutralization include amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine; sodium hydroxide, potassium hydroxide, ammonia and the like.
  • hydrazine or derivatives thereof used for chain extension include hydrazine, ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-hydrazine, and hydrates thereof. Etc.
  • Polyols such as ethylene glycol and propylene glycol, which are widely used as chain extenders for urethane prepolymers; ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminocyclohexylmethane, piperazine, Aliphatic, alicyclic and aromatic diamines such as 2-methylpiperazine and isophorone diamine tend to be inferior in laminate suitability, which is an effect of the present invention.
  • the acid value of the polyurethane resin is preferably 10 to 200 mgKOH / g per resin solid content.
  • the acid value is less than 10 mgKOH / g, when the urethane prepolymer reacted in an organic solvent is made aqueous by using a neutralizer, a chain extender, or distilled water, aggregates are likely to be formed, or the obtained aqueous polyurethane There is a possibility that the storage stability of the resin is poor.
  • the acid value exceeds 200 mgKOH / g, physical properties such as preferable durability and water resistance may not be obtained.
  • the glass transition temperature (hereinafter abbreviated as Tg) of the polyurethane resin is preferably set as appropriate depending on the desired application.
  • Tg glass transition temperature of the polyurethane resin
  • the Tg of the polyurethane resin used is preferably in the range of ⁇ 80 ° C. to 30 ° C., more preferably in the range of ⁇ 50 ° C. to 20 ° C.
  • the acrylic monomer that is a raw material of the carbonyl group or amide group-containing acrylic copolymer (b-2) has a carbonyl group-containing monomer or an amide group-containing monomer as an essential component.
  • the blending amount is preferably at least 0.5 parts by weight with respect to 100 parts by weight of the total polymerizable monomer.
  • conventionally known surfactants, protective colloids, and polymerization initiators used for emulsion polymerization can be used.
  • the carbonyl group-containing monomer is a monomer containing an aldo group or a keto group, and does not include a compound having only an ester bond or a carboxyl group.
  • Examples of the carbonyl group-containing monomer used in the present invention include acrolein, diacetone acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, diacetone acrylate, acetonitrile acrylate and the like.
  • amide group-containing monomers include monoolefinic unsaturated carboxylic acid amides, N-alkyl derivatives of monoolefinic unsaturated carboxylic acid amides, and N-alkylol derivatives of monoolefinic unsaturated carboxylic acid amides.
  • Such monomers are amides of acrylic acid, methacrylic acid, itaconic acid or maleic acid; N-methylacrylamide, N-isobutylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylic Examples thereof include amide, N-ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isopropoxymethacrylamide and the like.
  • carbonyl group-containing monomers or amide group-containing monomers may be used alone or in combination, but at least 0.5 parts by weight with respect to 100 parts by weight of the total polymerizable monomers. It is preferable to use it, and a particularly preferable region is 1.0 to 10.0 parts by weight.
  • acrylic monomers other than the above used for emulsion polymerization in the present invention include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, methacrylic acid Methacrylic acid esters such as ethyl acid, and other polymerizable unsaturated monomers that can be copolymerized with the acrylic monomers, such as maleic acid, fumaric acid, itaconic acid esters; vinyl acetate , Vinyl esters such as vinyl propionate and vinyl tertiary carboxylate; aromatic vinyl esters such as styrene and vinyl toluene; heterocyclic vinyl compounds such as vinyl pyrrolidone; vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, vinyl amide Etc .; Halogens such as vinylidene chloride and vinylidene fluoride Fluoride compounds, ethylene, alpha-
  • Examples of the polymerizable unsaturated monomer having a reactive polar group include glycidyl compounds such as glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether: vinyltrichlorosilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, Silane compounds such as ⁇ -methacryloxypropyltrimethoxysilane; Acrylic acid, methacrylic acid, maleic acid or half-ester thereof, fumaric acid or half-ester thereof, itaconic acid or half-ester thereof, carboxyl compounds such as crotonic acid; ⁇ -Hydroxyl compounds such as hydroxyethyl acrylate and ⁇ -hydroxyethyl methacrylate; and amine compounds such as alkylamino acrylate and alkylamino methacrylate.
  • glycidyl compounds such as glycidyl acryl
  • the acrylic copolymer (b-2) when using a system in which the aqueous polyurethane resin (b-1) and the acrylic copolymer (b-2) are mixed in an aqueous medium, the acrylic copolymer (b- After obtaining 2), each may be blended in a desired ratio.
  • a method for obtaining the acrylic copolymer (b-2) include known emulsion polymerization methods. Specifically, a radical polymerization initiator, the monomer, etc. are sequentially added to a mixture of water and an emulsifier (surfactant) while stirring with heating as necessary, and then polymerized. Can be obtained.
  • conventionally known surfactants (emulsifiers) used for emulsion polymerization can be used.
  • Anionic emulsifiers such as sodium dodecylbenzene sulfate, sodium dodecylbenzene sulfonate, alkylaryl polyether sulfate, etc .; polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene-polyoxypropylene block copolymer Nonionic emulsifiers such as coalescents; and cationic emulsifiers such as cetyltrimethylammonium bromide and laurylpyridinium chloride can be appropriately selected and used.
  • a water-soluble oligomer as a dispersant in place of the above-mentioned emulsifier or in combination with an emulsifier.
  • a water-soluble polymer substance such as polyvinyl alcohol or hydroxyethyl cellulose in combination with the above-mentioned emulsifier, or add it to the emulsion after polymerization.
  • the total amount of the emulsifier, the water-soluble oligomer and the water-soluble polymer substance is preferably used in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the acrylic monomer. If it exceeds this, the water resistance of the printed matter may be inferior, and if the amount used is less than this, the stability during emulsion polymerization and the stability of the resulting emulsion polymer may be reduced.
  • radical polymerization initiator used in the emulsion polymerization of the acrylic copolymer (b-2) those used in usual emulsion polymerization can be used, and examples thereof include potassium persulfate, Examples thereof include ammonium persulfate, azobisisobutyronitrile, and hydrochloride thereof, and organic peroxides such as cumene hydroperoxide and tert-butyl hydroperoxide can also be used as necessary.
  • known redox initiators using these persulfates or peroxides in combination with metal ions such as iron ions, and reducing agents such as sodium sulfooxylate formaldehyde, sodium pyrosulfite, and L-ascorbic acid Can also be used.
  • the concentration during emulsion polymerization should be such that the final composition has a solid content of 25 to 65% by weight from a practical viewpoint, and the ethylenically unsaturated monomer and radical polymerization in the reaction system.
  • the initiator can be carried out by any known method such as batch charging, continuous dropping, or divided addition.
  • the temperature at the time of emulsion polymerization may be within the range that is used in known emulsion polymerization, and the emulsion polymerization is performed under normal pressure or under pressure when a gaseous ethylenically unsaturated monomer is used.
  • the aqueous polyurethane resin (b-1) is increased by increasing the ratio of the aqueous polyurethane resin (b-1).
  • Characteristics are emphasized and the laminate strength tends to be improved.
  • by increasing the ratio of the acrylic copolymer (b-2) the characteristics of the acrylic copolymer (b-2) are emphasized.
  • blocking properties tend to be improved. From this, it is preferable to determine the blending ratio as appropriate according to the desired physical properties.
  • the water-based polyurethane resin (b-1) / the acrylic copolymer (b-2) is preferably blended so as to be 95/5 to 5/95. More preferably, 80/20 to 40/60 is particularly preferable.
  • the aqueous polyurethane resin (b-2) By copolymerizing various acrylic monomers as raw materials of the acrylic copolymer (b-2) in the presence of the aqueous polyurethane resin (b-1), the aqueous polyurethane resin (b- An aqueous dispersion of resin particles obtained by crosslinking 1) and the acrylic copolymer (b-2) can also be obtained.
  • a radical polymerization initiator, the monomer and the like are sequentially added to the mixture of the water, the emulsifier (surfactant) and the aqueous polyurethane resin (b-1) by a method such as dropwise addition, and polymerized. Can be obtained at
  • the water-based resin (b) used in the present invention emphasizes the resin properties of the water-based polyurethane resin (b-1) and the acrylic copolymer (b-2), and is effective in laminate strength and blocking properties.
  • the resin solid content in the total amount of the ink is preferably 1.0 to 10.0% by weight, and particularly preferably 3.0 to 5.0%.
  • the average particle diameter of the polyurethane resin particles is as small as possible because the influence on ejection failure is small. Specifically, it is preferably in the range of 10 nm to 500 nm, and particularly preferably in the range of 10 to 100 nm.
  • the particle diameter can be measured by a known and common centrifugal sedimentation method, laser diffraction method (light scattering method), ESA method, capillary method, electron microscope method, or the like. Preferable is measurement by Microtrac UPA using a dynamic light scattering method.
  • the (a) pigment and the (b) aqueous resin are blended to obtain the water-based inkjet recording ink for laminating of the present invention.
  • the resin solid content (%) of the (b) aqueous resin is preferably 1.0 to 10.0% by weight based on the total amount of ink. By setting it within this range, an ink having an excellent balance between laminate suitability and blocking resistance can be obtained.
  • the blending method of the ink is not particularly limited, and can be performed by a generally used method.
  • a pigment if necessary, (a) a pigment dispersion in which a pigment is dispersed with a pigment dispersant may be used), (b) an aqueous resin (various solvents after being adjusted by the above method) May be included), an aqueous solvent such as water or a water-soluble organic solvent, and, if necessary, a surfactant, a pigment dispersant, a viscosity modifier, an antifoaming agent, an antiseptic, etc.
  • Examples of the dispersing and mixing method include a bead mill, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, an ultrahigh pressure homogenizer, and a pearl mill. If necessary, various additives may be further added thereafter.
  • the water-soluble organic solvent used in the present invention is not particularly limited, but those that are miscible with water and can prevent clogging of the head of an inkjet printer are preferred.
  • glycerin ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less
  • Examples include diol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, mesoerythritol, pentaerythritol, and the like.
  • the inclusion of propylene glycol and 1,3-butyl glycol has safety and excellent effects in ink drying properties and ejection performance.
  • examples of the surfactant used in the present invention include acetylene surfactants.
  • acetylene surfactants 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3-
  • commercially available products such as Surfinol 104, 82, 440, 465, 485, or TG (available from Air Products and Chemicals. Inc.), Olfin STG, Olfin E1010 (trade names manufactured by Nisshin Chemical Co., Ltd.) ) And the like.
  • the water-based inkjet recording ink for laminating according to the present invention is used as a printing ink for laminates such as laminate films used for food packaging materials and the like.
  • the plastic film which is a non-absorbing substrate used in the present invention is not particularly limited as long as it is used for food packaging materials, and a known plastic film can be used.
  • Specific examples include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polyamide films such as nylon, polystyrene films, polyvinyl alcohol films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, Examples include biodegradable films such as polylactic acid films.
  • a polyester film, a polyolefin film, and a polyamide film are preferable, and polyethylene terephthalate, polypropylene, and nylon are more preferable.
  • the above-mentioned film coated with polyvinylidene chloride or the like for imparting a barrier property may be used, and if necessary, a film in which a deposited layer of a metal oxide such as aluminum or a metal oxide such as silica or alumina is used in combination. May be.
  • the plastic film may be an unstretched film, but is preferably stretched uniaxially or biaxially. Further, the surface of the film may be untreated, but those subjected to various treatments for improving adhesive properties such as corona discharge treatment, ozone treatment, low temperature plasma treatment, flame treatment, glow discharge treatment and the like are preferable.
  • the film thickness of the plastic film is appropriately changed according to the application. For example, in the case of a flexible packaging application, the film thickness is 10 ⁇ m to 100 ⁇ m assuming that it has flexibility, durability, and curl resistance. Preferably there is. More preferably, it is 10 ⁇ m to 30 ⁇ m.
  • a printing layer is formed on the plastic film with the water-based inkjet recording ink for laminating according to the present invention.
  • Any conventionally known method can be used as the ink jet recording method.
  • a method of ejecting droplets using vibration of a piezoelectric element a recording method using an ink jet head that forms ink droplets by mechanical deformation of an electrostrictive element
  • a method of using thermal energy can be given.
  • an adhesive layer for laminating is formed on the printed layer.
  • the adhesive used for the adhesive layer is not particularly limited as long as it is generally used for laminating, and a known adhesive can be used. Specific examples include acrylic resin, urethane resin, urethane-modified polyester resin, polyester resin, epoxy resin, ethylene-vinyl acetate copolymer resin (EVA), vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, natural rubber, SBR.
  • Adhesives such as synthetic rubber such as NBR, silicone rubber, etc., but preferably as one- or two-component curable polyether polyurethane adhesive, polyester polyurethane adhesive, polyester adhesive as an adhesive for dry lamination Good adhesive.
  • polyethyleneimine, alkyl titanate, polyurethane resin, urethane adhesive, and the like are preferable.
  • a sealant film layer is formed by laminating.
  • a laminating method known lamination such as dry lamination, non-solvent lamination, extrusion lamination, etc. can be used.
  • the adhesive is applied to one of the base films by the gravure roll method, and the other base film is stacked and bonded by dry lamination (dry lamination method).
  • Non-solvent lamination is a new film material on the surface immediately after applying the above-mentioned adhesive heated to room temperature to about 120 ° C on a base film with a roll such as a roll coater heated to room temperature to about 120 ° C.
  • a laminated film can be obtained by laminating.
  • an organic solvent solution of the adhesive is applied to the base film as an adhesion auxiliary agent (anchor coating agent) by a roll such as a gravure roll, and the solvent is dried and cured at room temperature to 140 ° C.
  • an adhesion auxiliary agent an adhesion auxiliary agent
  • a laminate film can be obtained by laminating the polymer material melted by the extruder.
  • the polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.
  • the thickness of the plastic film, the thickness of the ink layer, and the thickness of the adhesive layer is controlled so that the thickness is 300 ⁇ m or less. It is preferable.
  • a pre-emulsion comprising 75 parts of ion-exchanged water, 41.7 parts of New Coal 707SF, 12.5 parts of 80% methacrylic acid, 300 parts of methyl methacrylate and 190 parts of n-butyl methacrylate was prepared in the dropping funnel. 31.0 parts corresponding to 5% of the above was added. Next, after adding 10.2 parts of a 1.5% aqueous potassium persulfate solution and holding at that temperature for 15 minutes, the remaining 95% of the pre-emulsion and 65.4 parts of a 0.5% aqueous potassium persulfate solution were added. , And dropped from another dropping port over 3 hours. The reaction temperature at this time was kept at 80 ⁇ 3 ° C.
  • Pre-emulsion consisting of 22.5 parts, Newcol 707SF 31.5 parts, sodium styrenesulfonate 6.3 parts, diacetone acrylamide 1.6 parts, methyl methacrylate 44 parts, n-butyl methacrylate 22 parts and 5% 47.3 parts of an ammonium persulfate aqueous solution was added dropwise from another dropping port over 1 hour, and the reaction temperature was maintained at 80 ⁇ 3 ° C. After the completion of dropping. While maintaining the temperature range for 2 hours, the reaction is continued with stirring, then cooled and adjusted to pH 8.0 to 9.0 with 14% aqueous ammonia, the non-volatile content is 35.4%, and the viscosity is 17 mPa ⁇ s. An aqueous resin (b-X1) having a pH of 8.7 and an average particle diameter of 60 nm was obtained.
  • a nonvolatile resin was produced in the same manner as in Production Example 4 except that the aqueous polyurethane resin used was changed to the aqueous polyurethane resin (b-1-2) of Production Example 2.
  • an aqueous resin (b-X3) having a non-volatile content of 35.5%, a viscosity of 30 mPa ⁇ s, a pH of 8.5, and an average particle diameter of 50 nm was obtained.
  • Pigment dispersion (a-4) Black pigment dispersion 20 parts of black pigment “Carbon Black # 960” manufactured by Mitsubishi Chemical Corporation, 30 parts of “Disperbyk-190” manufactured by Big Chemie Japan Co., Ltd., 5 parts of isopropyl alcohol, and 45 parts of pure water as a pigment dispersant Mixed.
  • black pigment dispersion (a-4) adjusted to a pigment concentration of 15%.
  • Pigment dispersion (a-5) White pigment dispersion 40 parts of white pigment “JR-804” manufactured by Teika Co., Ltd., 10 parts of “Disperbyk-190” manufactured by Big Chemie Japan Co., Ltd. as a pigment dispersant, 5 parts of isopropyl alcohol, and 45 parts of pure water are mixed with stirring.
  • a white pigment dispersion (a-5) was prepared by dispersing the kneaded meat using a bead mill and then adding pure water to adjust the pigment concentration to 38%.
  • Solid content measurement method The weight of the evaporating dish (A), the total weight of the pigment dispersion dropped onto the evaporating dish (B), and the evaporating dish on which the pigment dispersion was dropped was allowed to stand in a dryer heated to 100 ° C. for 2 hours to evaporate water. The total amount (C) of the pigment dispersion and the evaporating dish that had been solidified was measured, and the solid content was determined by the following formula.
  • Example 1 to Example 12 Ink adjustment According to the formulation shown in Tables 1 and 2, a mixed solution obtained by stirring and mixing was prepared. The mixture was filtered through a 0.5 ⁇ m filter to obtain water-based inkjet recording inks (1) to (12) for laminating.
  • Aqueous gravure ink (manufactured by DIC Graphics, Inc., Marine Plus G R507 primary color indigo (C1)) 100 parts, ethanol 21 parts, and pure water 9 parts were mixed and stirred to obtain an aqueous inkjet recording ink (H7) for laminating.
  • Example 4 Laminate production method A PET film (Ester E-5100 manufactured by Toyobo Co., Ltd.) and an OPP film (FOR30 manufactured by Futamura Chemical Co., Ltd.) used for food packaging materials are coated with a bar coater No.
  • Example 4 the inks of Examples 1 to 12 and Comparative Examples 1 to 5 were applied and allowed to stand for 3 minutes in a dryer heated to 100 ° C. to dry the ink. After the ink dries, the bar coater no.
  • Tables 1 to 3 show ink formulations, and Tables 4 to 6 show physical property evaluation results.
  • Comparative Examples 1 to 4 are examples in which (b) an aqueous resin is not used, but it was impossible to achieve both laminate strength and blocking resistance.
  • Comparative Example 5 is an example in which gravure ink is applied to inkjet ink, but ejection was not possible.
  • PET film used as a packaging material for food in an ink jet printer having a piezo head having the maximum driving frequency of 7.6 KHz and resolution of 360 DPI (360 dots per 25.4 mm).
  • Ester E-5100), OPP film (FOR30, FORMURA CHEMICAL CO., LTD.) was discharged onto the dryer and allowed to stand in a dryer heated to 100 ° C. for 1 minute to dry the ink.
  • the ink of Example 7 was ejected and dried in the same manner as in Example 1, and the same operation was performed for the inks of Examples 8, 9, and 10 for each color ink.
  • a multicolored print was produced.
  • a bar coater no After the adhesive was applied and cured using No. 10, the laminate strength was measured. As a result, the evaluation was good.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention porte sur une encre aqueuse pour l'impression par jet d'encre pour stratification, qui contient (a) un pigment et (b) une résine aqueuse et qui est caractérisée en ce que la résine aqueuse (b) contient une résine aqueuse de polyuréthane (b-1) qui est produite par un procédé dans lequel un allongeur de chaîne constitué d'un dérivé d'hydrazine est amené à réagir avec un copolymère acrylique (b-2) qui contient un groupe carbonyle ou un groupe amide. L'invention porte également sur un procédé pour la production d'un stratifié utilisant l'encre aqueuse pour l'impression par jet d'encre pour stratification.
PCT/JP2012/064643 2011-06-15 2012-06-07 Encre aqueuse pour l'impression par jet d'encre pour stratification et procédé pour la production d'un stratifié WO2012173032A1 (fr)

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JP2011133169A JP2013001775A (ja) 2011-06-15 2011-06-15 ラミネート加工用水性インクジェット記録用インク及び積層体の製造方法

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Cited By (4)

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WO2017158015A1 (fr) 2016-03-15 2017-09-21 Dsm Ip Assets B.V. Composition de revêtement aqueuse
WO2020183139A1 (fr) 2019-03-12 2020-09-17 Sun Chemical Corporation Fluides aqueux composites pour jet d'encre
WO2021075272A1 (fr) * 2019-10-17 2021-04-22 Dic株式会社 Encre
EP3842499A4 (fr) * 2018-08-20 2022-05-18 Sakata INX Corp. Composition d'encre pour jet d'encre à base aqueuse pour stratification, matière imprimée utilisant celle-ci, produit stratifié et procédé de stratification

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JP6822331B2 (ja) * 2017-06-28 2021-01-27 三菱ケミカル株式会社 複合樹脂水分散液の製造方法
JP2021031169A (ja) 2019-08-29 2021-03-01 サカタインクス株式会社 包材
KR102338075B1 (ko) * 2019-10-08 2021-12-13 (주)성보잉크 수성 타입 라미네이트용 잉크 및 이를 제조하는 방법
JP2023005740A (ja) 2021-06-29 2023-01-18 サカタインクス株式会社 インクジェット用インクセット、及びラミネートフィルム

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JPH10139839A (ja) * 1996-11-14 1998-05-26 Taisei Kako Kk 水性アクリル−ウレタン複合体である常温硬化性水性樹脂組成物及びこれを用いたコーティング剤又はインキ
JP2000290553A (ja) * 1999-04-06 2000-10-17 Seiko Epson Corp 安定性に優れたインク組成物
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Publication number Priority date Publication date Assignee Title
WO2017158015A1 (fr) 2016-03-15 2017-09-21 Dsm Ip Assets B.V. Composition de revêtement aqueuse
CN108779200A (zh) * 2016-03-15 2018-11-09 帝斯曼知识产权资产管理有限公司 水性涂料组合物
EP3842499A4 (fr) * 2018-08-20 2022-05-18 Sakata INX Corp. Composition d'encre pour jet d'encre à base aqueuse pour stratification, matière imprimée utilisant celle-ci, produit stratifié et procédé de stratification
WO2020183139A1 (fr) 2019-03-12 2020-09-17 Sun Chemical Corporation Fluides aqueux composites pour jet d'encre
US11485868B2 (en) 2019-03-12 2022-11-01 Sun Chemical Corporation Composite aqueous inkjet fluids
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JPWO2021075272A1 (ja) * 2019-10-17 2021-11-25 Dic株式会社 インク
JP7147992B2 (ja) 2019-10-17 2022-10-05 Dic株式会社 インク

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