WO2022209932A1 - Stratifié ayant une couche d'impression d'encre liquide à base d'eau - Google Patents

Stratifié ayant une couche d'impression d'encre liquide à base d'eau Download PDF

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Publication number
WO2022209932A1
WO2022209932A1 PCT/JP2022/012142 JP2022012142W WO2022209932A1 WO 2022209932 A1 WO2022209932 A1 WO 2022209932A1 JP 2022012142 W JP2022012142 W JP 2022012142W WO 2022209932 A1 WO2022209932 A1 WO 2022209932A1
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WIPO (PCT)
Prior art keywords
pigment
ink
pigment red
printed layer
meth
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PCT/JP2022/012142
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English (en)
Japanese (ja)
Inventor
拓哉 大坪
友香 佐藤
康敬 小代
Original Assignee
Ｄｉｃグラフィックス株式会社
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Priority to JP2022563973A priority Critical patent/JP7195494B1/ja
Publication of WO2022209932A1 publication Critical patent/WO2022209932A1/fr

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    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C09D11/023—Emulsion 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the present invention relates to a laminate having a printed layer formed by water-based gravure printing or water-based flexographic printing on a plastic film.
  • Gravure inks and flexographic inks are widely used for the purpose of imparting aesthetics and functionality to printed materials for flexible packaging films.
  • a gravure or flexographic printed material is used as a flexible packaging material for food products or sanitary goods among other packaging materials, it is generally subjected to lamination.
  • various printing materials and lamination processes are used depending on the type of contents and purpose of use.
  • laminating printed matter and various films with an adhesive it is possible to maintain film surface strength, storage stability, boiling and retort suitability, etc., which cannot be obtained with printed matter alone.
  • the printed matter When laminating printed matter, it is often the case that the printed matter itself is intended to protect the contents. In this case, since the printed material consisting of the base plastic and the printing ink layer is laminated with the sealant film using an adhesive, the printing ink layer does not directly touch the contents, but lamination aptitude is required. . In order to maintain the suitability for lamination, it is common practice to provide an anchor coat layer under the printed ink layer to improve the adhesion between the plastic film as the substrate and the printed ink layer.
  • the printing ink layer itself is required to have high coating film properties such as film adhesion, abrasion resistance, water resistance, and blocking resistance.
  • the superiority or inferiority of the printed design of flexible packaging film packaging material has a great impact on the quality of the contents, and high image reproducibility that can correspond to advanced designs that are conscious of aesthetics is required. .
  • Patent Document 1 discloses an invention of a printing ink laminate using a water-based liquid ink containing an acrylic resin or a polyurethane resin as the printing ink adjacent to a polyethylene terephthalate (PET) film.
  • Patent Document 1 uses a polyethylene terephthalate (PET) film as the plastic film.
  • PET polyethylene terephthalate
  • Plastic films used for flexible packaging film packaging include film substrates used for beverage labels, such as biaxially oriented polypropylene (OPP) film, shrink PET, shrink biaxially oriented polystyrene (OPS), and shrink PET/OPS.
  • OPP biaxially oriented polypropylene
  • OPS shrink PET
  • OPS shrink biaxially oriented polystyrene
  • shrink PET/OPS shrink PET/OPS.
  • hybrids etc.
  • film substrates from the viewpoint of recent diversification of packaging materials and recyclability. Conventionally, it has been done to design the optimum ink for these various film substrates, but there is a problem that it is time-consuming because it is necessary to switch the printing ink at the same time as the film substrate is switched. .
  • the problem to be solved by the present invention is to provide a laminate having an aqueous liquid ink printed layer that has excellent adhesion to various plastic substrates and also has excellent water resistance and abrasion resistance. to provide.
  • the present invention provides a laminate having at least a first printed layer and a second printed layer in this order on a plastic film
  • the first printing layer is an aqueous varnish or aqueous liquid ink printing layer containing at least a urethane resin that is a reaction product of a polyol (ia) containing a polyether polyol (ia-1) and a polyisocyanate (ib).
  • the laminate is such that the second printed layer is a printed layer of aqueous varnish or aqueous liquid ink containing a (meth)acrylic resin and an alcohol alkoxylate leveling agent.
  • the present invention it is possible to provide a laminate in which the plastic substrate and the printed layer have excellent adhesion, and the printed layer has excellent water resistance and abrasion resistance.
  • ink used in the following description all means “aqueous liquid ink”. All “parts” indicate “parts by mass”, and all “%” indicate “% by mass”.
  • the laminate of the present invention has at least a first printed layer and a second printed layer in this order on a plastic film, and the first printed layer is a polyol (ia) containing a polyether polyol (ia-1) and polyisocyanate (ib), and the second printed layer contains a (meth)acrylic resin and an alcohol alkoxylate leveling agent.
  • the first printed layer is a polyol (ia) containing a polyether polyol (ia-1) and polyisocyanate (ib)
  • the second printed layer contains a (meth)acrylic resin and an alcohol alkoxylate leveling agent.
  • the first printing layer is printed with aqueous liquid ink or aqueous varnish containing at least urethane resin (I) which is a reaction product of polyol (ia) containing polyether polyol (ia-1) and polyisocyanate (ib). It is formed by The laminate of the present invention has improved adhesion by having the first printed layer as a layer in direct contact with the plastic film.
  • the water-based liquid ink or water-based varnish forming the first printed layer is a composition containing at least the urethane resin (I) (hereinafter referred to as "first composition").
  • first composition a composition containing at least the urethane resin (I) (hereinafter referred to as "first composition").
  • Polyol (ia) constituting urethane resin (I) contains at least polyether polyol (ia-1).
  • the polyether polyol (ia-1) for example, one or more compounds having two or more groups having active hydrogen atoms (—NH— or —OH) are used as an initiator, and an alkylene oxide is subjected to addition polymerization.
  • the initiator examples include hydroxyl groups such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and bisphenol A. and compounds having three hydroxyl groups such as glycerin, trimethylolethane, and trimethylolpropane.
  • alkylene oxide examples include epoxide compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide and epichlorohydrin; Cyclic ethers having 4) carbon atoms and the like can be mentioned.
  • the number average molecular weight of the polyether polyol is preferably 500 or more, more preferably 1,000 or more, and preferably 4,000 or less, more preferably 3,000 or less, from the viewpoint of compatibility with pigments and the like. be.
  • the number average molecular weight shall represent the value obtained by measuring by gel permeation chromatography (GPC) method.
  • Polyol (ia) preferably contains a polyol other than polyether polyol (ia-1).
  • Other polyols preferably include a polyol (ia-2) having an acid group.
  • the acid group of the acid group-containing polyol (ia-2) includes, for example, a carboxy group or a sulfonic acid group
  • the acid group-containing polyol (ia-2) includes, for example, a carboxy group-containing polyol, Examples thereof include polyols having sulfonic acid groups.
  • polyol having a carboxyl group one or two or more can be used, and examples thereof include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, hydroxy acid; polyester polyol having a carboxy group; The polyester polyol having the carboxy group can be obtained by reacting the hydroxy acid with various polycarboxylic acids.
  • the polyol having a sulfonic acid group one or more kinds can be used.
  • a polyester polyol or the like, which is a reactant, may be mentioned.
  • the dicarboxylic acid having a sulfonic acid group include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5-(4-sulfophenoxy)isophthalic acid and the like.
  • Examples of the low-molecular-weight polyol include alkanediols having 1 to 10 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; carbon atoms such as diethylene glycol; Examples include polyether polyols having a number of 2 to 10.
  • the number average molecular weight of the acid group-containing polyol (ia-2) is preferably 100 or more, preferably 2000 or less, more preferably 1000 or less.
  • the number-average molecular weight and weight-average molecular weight represent polystyrene-equivalent values obtained by measuring by gel permeation chromatography (GPC).
  • the polyol (ia) is preferably composed of a polyether polyol (ia-1) and a polyol (ia-2) having an acid group from the viewpoint of further improving adhesion, and the polyether polyol (ia-1) and a polyol (ia-2) having a carboxy group.
  • the total content of the polyether polyol (ia-1) and the polyol (ia-2) having an acid group is preferably 60% by mass or more, more preferably 75% by mass or more, more preferably 75% by mass or more in the polyol (ia). is 80% by mass or more, more preferably 90% by mass or more, and may be 95% by mass or less.
  • the polyol (ia) may further contain a polyol (ia-3) having an alicyclic structure.
  • a polyol (ia-3) having an alicyclic structure one or two or more can be used.
  • Saturated diols having an alicyclic structure such as diols, butylcyclohexanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, dicyclohexanediol, hydrogenated bisphenol A, 1,3-adamantanediol; 1,1′-bicyclohexane
  • Unsaturated diols having an alicyclic structure such as silidenediol; saturated triols having an alicyclic structure such as cyclohexanetriol;
  • the polyol (ia-3) having an alicyclic structure preferably has a number average molecular weight of 100 or more and 500 or less.
  • the content is preferably 0% by mass or more, more preferably 5% by mass, based on the total amount of polyol (ia) from the viewpoint of suppressing blocking of printed matter. or more, preferably 40% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
  • the total content of the polyether polyol (ia-1), the polyol (ia-2) having an acid group, and the polyol (ia-3) having an alicyclic structure is preferably 70 mass in the polyol (ia) % or more, more preferably 80 mass % or more, and still more preferably 90 mass % or more.
  • the polyol (ia) may further contain another polyol (ia-4).
  • the other polyols include polyester polyols, low-molecular-weight polyols (for example, molecular weights of 50 to 300), polycarbonate polyols, and polyolefin polyols.
  • the polyester polyols include polyester polyols obtained by esterifying a low-molecular-weight polyol (e.g., a polyol having a molecular weight of 50 to 300) and a polycarboxylic acid; ring-opening polymerization of a cyclic ester compound such as ⁇ -caprolactone; polyester polyols obtained by reaction; and copolymerized polyester polyols thereof.
  • low molecular weight polyol examples include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol and 1,4-butanediol. , 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol, etc. ) and the like.
  • polycarboxylic acid examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; and anhydride- or ester-forming derivatives of polycarboxylic acids and aromatic polycarboxylic acids.
  • aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid
  • aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid
  • anhydride- or ester-forming derivatives of polycarboxylic acids and aromatic polycarboxylic acids examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dode
  • Examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. , 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol and other aliphatic polyols having 2 to 6 carbon atoms; 1,4-cyclohexanediol, cyclohexane alicyclic structure-containing polyols such as dimethanol; bisphenol compounds such as bisphenol A and bisphenol F; and aromatic structure-containing polyols such as alkylene oxide adducts thereof.
  • polycarbonate polyol examples include a reaction product of carbonate ester and polyol; a reaction product of phosgene and bisphenol A and the like.
  • Examples of the carbonate include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.
  • Examples of the polyol that can react with the carbonate ester include, for example, the polyols exemplified as the low-molecular-weight polyols; high-molecular-weight polyols (weight average molecular weight of 500 or more and 5,000 or less).
  • polystyrene polyol examples include polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, and hydrogenated (hydrogenated) polyisoprene polyol.
  • the content of the other polyol (ia-4) in the polyol (ia) is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and even more preferably 20% by mass. Below, particularly preferably, it is 10% by mass or less.
  • the polyester polyol content in the polyol (ia) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less.
  • polyisocyanate (ib) one or two or more can be used.
  • Aromatic polyisocyanates such as tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane Examples include polyisocyanates having an alicyclic structure such as diisocyanates.
  • the polyisocyanate (ib) preferably contains a polyisocyanate having an alicyclic structure.
  • the content of the polyisocyanate having an alicyclic structure is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass in the polyisocyanate (ib). % or less.
  • the equivalent ratio [isocyanate group/hydroxyl group] of the isocyanate group of the polyisocyanate (ib) to the hydroxyl group contained in the polyol (ia) is preferably 0.8 or more, more preferably 0.9 or more on a molar basis. , preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.5 or less.
  • a chain extender may be used as necessary when producing the urethane resin (I).
  • chain extender one or more can be used, and examples thereof include polyamines, hydrazine compounds, and other compounds having active hydrogen atoms.
  • polyamines examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, N-ethylaminoethylamine, N-methylaminopropylamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N- diamines having a hydroxyl group such as hydroxypropylaminopropylamine; triamines such as diethylenetriamine and dipropylenetriamine; and tetramines such as triethylenetetramine.
  • ethylenediamine is preferred.
  • hydrazine compound examples include hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, and ⁇ -semicarbazide.
  • Examples of other compounds having active hydrogen include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and saccharose. , methylene glycol, glycerin, glycols such as sorbitol; etc.
  • the equivalent ratio [amino group/isocyanate group] between the amino group and the isocyanate group in the polyamine is preferably 1.2 or less, and is preferably in the range of 0.3 to 1. more preferred.
  • the weight average molecular weight of the urethane resin (I) is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and preferably 500,000, from the viewpoint of improving the durability of the printed matter. Below, more preferably 200,000 or less, still more preferably 100,000 or less. By increasing the weight average molecular weight, it is possible not only to improve the durability of the printed matter, but also to suppress blocking due to poor drying. etc. can be suppressed.
  • the acid value of the urethane resin (I) is preferably 3 mgKOH/g or more, more preferably 5 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 25 mgKOH/g or less.
  • the acid value means a theoretical value calculated based on the amount of the acid group-containing compound such as polyol (i) used in the production of the urethane resin (I).
  • the urethane resin (I) can be produced by reacting the polyol (ia) and the polyisocyanate (ib) and, if necessary, further reacting with a chain extender.
  • An organic solvent may coexist when the polyol (ia) and the polyisocyanate (ib) are reacted.
  • the reaction temperature for reacting the polyol (ia) and the polyisocyanate (ib) is preferably 50° C. or higher and 150° C. or lower.
  • organic solvent one or two or more can be used.
  • examples include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; ester solvents such as ethyl acetate and butyl acetate; and nitriles such as acetonitrile.
  • Solvent amide solvents such as dimethylformamide and N-methylpyrrolidone.
  • the organic solvent may be partially or wholly removed, for example, by distillation under reduced pressure during or after the production of the urethane resin (I), in order to reduce the load on the environment and safety.
  • the content of the urethane resin (I) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and particularly preferably 100% by mass, based on the total amount of the binder in the first composition. %.
  • the urethane resin (I) may be dispersed in advance in an aqueous medium to be described later.
  • urethane resin (I) As a method for dispersing urethane resin (I) in an aqueous medium (aqueous method), urethane resin (I) is prepared (urethane resin (I) preparation step), the obtained urethane resin (I) and a base described later (neutralization step), and mixing the resulting mixture with the aqueous medium to prepare a dispersion (dispersion step).
  • a chain extender the chain extender may be added in the urethane resin (I) preparation step, or may be added after the dispersion step.
  • the content of the urethane resin (I) is preferably 10% by mass or more in the dispersion, from the viewpoints of resolubility of the aqueous ink, inhibition of blocking of printed matter, improvement of printing density, and adhesion to the substrate. It is more preferably 20% by mass or more, preferably 50% by mass or less, and more preferably 40% by mass or less.
  • An emulsifier may be used as necessary in the aqueous method.
  • a machine such as a homogenizer may be used as necessary.
  • the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene/polyoxypropylene copolymers.
  • Fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, alkyldiphenyl ether sulfonate sodium salts, etc.
  • cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts and alkyldimethylbenzylammonium salts. Among them, anionic or nonionic emulsifiers are preferable from the viewpoint of storage stability.
  • the basic compound preferably contains a basic metal compound and an organic amine.
  • the basic metal compound include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and magnesium hydroxide; metal chlorides such as sodium chloride and potassium chloride; metals such as copper sulfate. Sulfate and the like can be mentioned.
  • organic amines examples include ammonia; primary amines such as monoethanolamine; tertiary amines such as triethylamine and diethylethanolamine; and cyclic amines such as morpholine.
  • the basic metal compound and the organic amine may form a salt with the acid group of the urethane resin (I) in the first composition. Since the basic compound and the organic amine neutralize the acid group of the binder having the acid group, the water dispersibility can be easily improved.
  • the content of the basic compound is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the urethane resin (I). Yes, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 4 parts by mass or less.
  • solvents contained in the first composition include water; hydrophilic organic solvents; water and hydrophilic water; hydrophilic organic solvents; mixtures of water and hydrophilic organic solvents; from the viewpoint of water or a mixture of water and a hydrophilic organic solvent.
  • hydrophilic organic solvent one or more kinds can be used, and it is preferable to use one that is miscible with water.
  • alcohol solvents such as methanol, ethanol, n-propanol and 2-propanol; acetone , methyl ethyl ketone and other ketone solvents; ethylene glycol, diethylene glycol, propylene glycol, polyalkylene glycol, glycerin and other polyhydric alcohol solvents; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, ethyl carbitol and ether solvents such as N-methyl-2-pyrrolidone; and amide solvents such as N-methyl-2-pyrrolidone.
  • the content of water is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more in the entire solvent. % by mass or less, or even 95% by mass or less is allowed.
  • the first composition may be used as a water-based anchor coat varnish without containing a coloring material, or may contain a coloring material and may be used as so-called ink for white, black, or color printing.
  • colorants include inorganic pigments and organic pigments used in general inks, paints, and recording agents.
  • organic pigments include soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthanthrone, dianthraquinonyl, anthrapyrimidine, perylene, perinone, quinacridone, Examples include thioindigo, dioxazine, isoindolinone, quinophthalone, azomethineazo, flavanthrone, diketopyrrolopyrrole, isoindoline, indanthrone, and carbon black pigments.
  • black pigment for example, C.I. I. Pigment Black 1, C.I. I. Pigment Black 6, C.I. I. Pigment Black 7, C.I. I. Pigment Black 9, C.I. I. Pigment Black 20 and the like.
  • Pigment Blue 62 C.I. I. Pigment Blue 63, C.I. I. Pigment Blue 64, C.I. I. Pigment Blue 75, C.I. I. Pigment Blue 79, C.I. I. Pigment Blue 80 and the like.
  • a green pigment for example, C.I. I. Pigment Green 1, C.I. I. Pigment Green 4, C.I. I. Pigment Green 7, C.I. I. Pigment Green 8, C.I. I. Pigment Green 10, C.I. I. Pigment Green 36 and the like.
  • red pigments examples include C.I. I. Pigment Red 1, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 4, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 8, C.I. I. Pigment Red 9, C.I. I. Pigment Red 10, C.I. I. Pigment Red 11, C.I. I. Pigment Red 12, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 17, C.I. I. Pigment Red 18, C.I. I. Pigment Red 19, C.I. I. Pigment Red 20, C.I. I.
  • Pigment Red 112 C.I. I. Pigment Red 114, C.I. I. Pigment Red 119, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 136, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 147, C.I. I. Pigment Red 149, C.I. I. Pigment Red 150, C.I. I. Pigment Red 164, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I. Pigment Red 169, C.I. I. Pigment Red 170, C.I. I.
  • Pigment Red 220 C.I. I. Pigment Red 221, C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I. I. Pigment Red 226, C.I. I. Pigment Red 237, C.I. I. Pigment Red 238, C.I. I. Pigment Red 239, C.I. I. Pigment Red 240, C.I. I. Pigment Red 242, C.I. I. Pigment Red 245, C.I. I. Pigment Red 247, C.I. I. Pigment Red 248, C.I. I. Pigment Red 251, C.I. I. Pigment Red 253, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I.
  • C.I. I. Pigment Yellow 1 C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, Pigment Yellow 17, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 42, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 65, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I.
  • Pigment Yellow 95 C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 120, Pigment Yellow 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 137, C.I. I. Pigment, Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I.
  • orange pigment for example, C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 16, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 37, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment Range 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 71, or C.I. I. Pigment Orange 74 and the like.
  • brown pigment for example, C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, or C.I. I. Pigment Brown 26 and the like.
  • Inorganic pigments include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, litbon, antimony white, and gypsum.
  • white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, litbon, antimony white, and gypsum.
  • titanium oxide exhibits a white color and is preferable from the viewpoints of coloring power, hiding power, chemical resistance and weather resistance. From the viewpoint of printing performance, the titanium oxide is preferably treated with silica and/or alumina.
  • non-white inorganic pigments examples include aluminum particles, mica (mica), bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, Prussian blue, red iron oxide, yellow iron oxide, iron black, and zircon.
  • the aluminum is in the form of powder or paste, it is preferable to use it in the form of paste from the viewpoints of handling and safety, and whether to use leafing or non-leafing is appropriately selected from the viewpoint of brightness and density.
  • the average particle size of the pigment is preferably in the range of 1 to 300 nm, more preferably about 50 to 150 nm.
  • the amount of the pigment is sufficient to ensure the concentration and coloring strength of the aqueous liquid printing ink, that is, 1 to 60% by weight relative to the total weight of the ink composition, and the solid content weight ratio in the ink composition is 10 to 10%. It is preferably contained in a proportion of 90% by weight.
  • these pigments can be used individually or in combination of 2 or more types.
  • the first composition may further contain general-purpose resins and auxiliaries other than the urethane resin (I), if necessary.
  • auxiliary agent include waxes such as paraffin waxes, polyethylene waxes, and carnauba waxes for imparting abrasion resistance and slipperiness; fatty acid amide compounds such as oleic acid amide, stearic acid amide, and erucic acid amide; printing; A silicone-based or non-silicon-based antifoaming agent, dispersant, extender, or the like can be used as appropriate to suppress foaming at the time.
  • the dispersant a nonionic dispersant is preferable.
  • the acid value of the dispersant is preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, still more preferably 20 mgKOH/g or less, and may be, for example, 1 mgKOH/g or more, or even 3 mgKOH/g or more. .
  • the acid value of the dispersant is preferably smaller than the acid value of the urethane resin (I).
  • the difference between the acid value of the urethane resin (I) and the dispersant is, for example, 1 mgKOH/g or more, more preferably 3 mgKOH/g or more, preferably 30 mgKOH/g or less, more preferably 20 mgKOH/g. It is below.
  • the content of the dispersant is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, and preferably 100 parts by mass or less, with respect to 100 parts by mass of the coloring agent. It is more preferably 80 parts by mass or less, still more preferably 75 parts by mass or less.
  • the content of the dispersant is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 100 parts by mass with respect to 100 parts by mass of the urethane resin (I). parts or less, more preferably 80 parts by mass or less, and even more preferably 60 parts by mass or less.
  • the second printed layer is formed by printing a water-based liquid ink or water-based varnish containing at least (meth)acrylic resin (II) and an alcohol alkoxylate leveling agent.
  • the laminate of the present invention has improved water resistance by having the second printed layer.
  • the second printed layer is excellent in coating film strength, particularly abrasion resistance and scratch resistance, and is therefore suitable for a configuration in which the printed layer is the outermost layer.
  • a laminate having the second printed layer of the present invention on the outermost layer during distribution is preferable because the effect of the present invention can be maximized.
  • the water-based liquid ink or water-based varnish that forms the second printed layer is a composition containing at least a (meth)acrylic resin (II) and an alcohol alkoxylate-based leveling agent (hereinafter referred to as a "second composition").
  • a (meth)acrylic resin (II) can be a (meth)acrylate homopolymer or copolymer.
  • polymers are not particularly limited, but for example, polymers or copolymers of one or two or more (meth)acrylate monomers, one or two or more (meth)acrylate monomers and vinyl monomers It is preferable to use a copolymer with Further, it is preferably a copolymer having an acid value for the purpose of imparting water dispersibility and water solubility.
  • (meth)acrylate refers to either or both of acrylate and methacrylate
  • (meth)acryl refers to either or both of acrylic and methacrylic.
  • the (meth)acrylate monomer is not particularly limited, and examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2 - ethylhexyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, di cyclopentanyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-pentafluoropropyl (meth)acryl
  • vinyl monomer examples include vinyl acetate, vinyl propionate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, (meth)acrylonitrile, styrene, ⁇ -methylstyrene, divinylstyrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone and the like.
  • styrene-based monomers such as styrene, ⁇ -methylstyrene and divinylstyrene are preferably used. Each of these may be used alone, or two or more of them may be used in combination.
  • (Meth)acrylic acid, crotonic acid, itaconic acid It can be obtained by copolymerizing a (meth)acrylic monomer having a carboxyl group such as maleic acid, fumaric acid, ⁇ -(meth)acryloyloxyethyl hydrogen succinate, ⁇ -(meth)acryloyloxyethyl hydrogen phthalate.
  • a (meth)acrylic monomer having a carboxyl group such as maleic acid, fumaric acid, ⁇ -(meth)acryloyloxyethyl hydrogen succinate, ⁇ -(meth)acryloyloxyethyl hydrogen phthalate.
  • an acidic group it is preferable to appropriately adjust the amount of the monomer so that the acid value is within the desired range, which will be described later in detail.
  • the (meth)acrylic resin (II) is a copolymer of two or more (meth)acrylate monomers, or a copolymer of one or more (meth)acrylate monomers and a vinyl monomer. preferable.
  • Acrylic copolymer (2) A copolymer of two or more (meth)acrylate monomers having no carboxyl group, a styrenic monomer, and a (meth)acrylate monomer having a carboxyl group such as (meth)acrylic acid, Styrene (meth)acrylic copolymers with acid numbers are preferred.
  • the (meth)acrylic monomer having no carboxyl group used in (1) or (2) is methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl Aliphatic chain (meth)acrylates such as (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and hexyl (meth)acrylate are preferred.
  • the (meth)acrylic resin (II) can be produced, for example, by polymerizing various monomers in the presence of a polymerization initiator in a temperature range of 50°C to 180°C. A region is more preferable.
  • Polymerization methods include, for example, bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
  • the polymerization mode includes, for example, random copolymers, block copolymers, graft copolymers, and the like.
  • the (meth)acrylic resin (II) used in the present invention may be an emulsion forming a core-shell type.
  • the core-shell emulsion refers to a state in which the polymer (a2) is dispersed by the polymer (a1) in an aqueous medium. portion, and part or all of the polymer (a2) often forms the core portion.
  • the resin forming the shell portion is referred to as polymer (a1)
  • polymer (a2) the resin forming the core portion is referred to as polymer (a2).
  • the core-shell type emulsion used in the present invention has one or more hydrophilic groups selected from the group consisting of carboxyl groups and carboxylate groups formed by neutralizing carboxyl groups for the polymer (iia) constituting the shell portion. It is preferably composed of an acrylic copolymer having At that time, the acid value of the shell portion is preferably in the range of 40 mgKOH/g or more and 250 mgKOH/g or less, more preferably 120 mgKOH/g or less.
  • the carboxyl groups of the polymer (iia) constituting the shell portion are preferably neutralized with a basic compound to form carboxylate groups.
  • Examples of the basic compound that can be used for neutralization include ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine, etc.
  • Use of ammonia and triethylamine improves the hot water resistance of the coating film. , is preferable for further improving corrosion resistance and chemical resistance.
  • the monomers having polymerizable unsaturated double bonds it is preferable to use those obtained by polymerizing (meth)acrylic monomers including (meth)acrylic monomers having a carboxyl group.
  • the polymer (iia) methyl (meth)acrylate, butyl (meth)acrylate
  • Polymer (iib) constituting core portion As the polymer (iib) constituting the core portion, a copolymer such as an acrylic monomer similar to the acrylic resin described above can be used. At this time, the weight average molecular weight of the core portion is preferably in the range of 200,000 to 3,000,000, more preferably 800,000 or more. Tg is preferably in the range of -30°C to 30°C.
  • the polymer (iib) that constitutes the core portion may be a copolymer of acrylic monomers similar to the acrylic resin described above, but is preferably produced using an aqueous medium. Specifically, it can be produced by supplying the above-mentioned monomers, a polymerization initiator, etc. to a reaction vessel containing an aqueous medium all at once or successively for polymerization. At that time, a pre-emulsion is produced by mixing the monomer, an aqueous medium, and, if necessary, a reactive surfactant or the like in advance, and the polymerization initiator or the like is supplied to a reaction vessel containing the aqueous medium. may be polymerized.
  • polymerization initiators examples include radical polymerization initiators such as persulfates, organic peroxides and hydrogen peroxide, 4,4′-azobis(4-cyano valeric acid), 2,2'-azobis(2-amidinopropane) dihydrochloride and the like can be used.
  • radical polymerization initiator such as persulfates, organic peroxides and hydrogen peroxide, 4,4′-azobis(4-cyano valeric acid), 2,2'-azobis(2-amidinopropane) dihydrochloride and the like can be used.
  • the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent to be described later.
  • persulfate for example, potassium persulfate, sodium persulfate, ammonium persulfate, etc.
  • organic peroxide examples include benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxylaurate, and t-butyl peroxybenzoate.
  • cumene hydroperoxide, paramenthane hydroperoxide, t-butyl hydroperoxide and the like can be used.
  • reducing agent examples include ascorbic acid and its salts, erythorbic acid and its salts (sodium salts, etc.), tartaric acid and its salts, citric acid and its salts, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, Sodium bisulfite, ferric chloride and the like can be used.
  • the amount of the polymerization initiator to be used should be an amount that allows the polymerization to proceed smoothly. It is preferably 0.01% by mass to 0.5% by mass with respect to the total amount of monomers used. Moreover, when the polymerization initiator is used in combination with the reducing agent, the total amount used is preferably within the above range.
  • reactive surfactants anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, etc. are used. good too.
  • the acid value of the (meth)acrylic resin (I) is preferably 20 mgKOH/g or more and 120 mgKOH/g or less, more preferably 25 mgKOH or more. If the acid value is 20 mgKOH/g or more, the abrasion resistance, water abrasion resistance, and scratch resistance of the laminate can be improved when the curing agent is added.
  • the term "acid value” as used herein refers to the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of resin.
  • the (meth)acrylic resin (I) preferably has a weight average molecular weight in the range of 5,000 to 100,000.
  • the weight-average molecular weight is 5,000 or more, the heat resistance of the resin film does not deteriorate, and the laminate tends to retain its abrasion resistance and water abrasion resistance. If it is 100,000 or less, there is a tendency that the laminate can have both adhesion to the substrate and scratch resistance.
  • the glass transition temperature (sometimes referred to as Tg) of the (meth)acrylic resin (I) is preferably in the range of 0°C to 55°C. When the Tg of the copolymer (A) is 0° C. or higher, the film strength is maintained and the water abrasion resistance of the laminate does not decrease. There is a tendency that the abrasion resistance, water abrasion resistance, and scratch resistance of the laminate can be maintained satisfactorily without deterioration.
  • the glass transition temperature (Tg) refers to a so-called calculated glass transition temperature, which is a value calculated by the following method.
  • Tg (°C) Tg (K) - 273 W1, W2, . It represents the glass transition temperature (K).
  • the values of T1, T2, . . . Tn are those described in Polymer Handbook (Fourth Edition, J. Brandrup, EH Immergut, EA Grulke).
  • the glass transition temperature of the homopolymer of each monomer is not described in the Polymer Hand Book, the glass transition temperature is measured using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument) and conforms to JIS K7121. It was measured by the method. Specifically, the polymer, from which the solvent has been completely removed by vacuum suction, is measured for changes in calorific value in the range of ⁇ 100° C. to +200° C. at a heating rate of 20° C./min. The point at which a straight line equidistant from the vertical axis and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.
  • DSC Q-100 manufactured by TA Instrument
  • the (meth)acrylic resin (I) is preferably contained in the water-based liquid ink of the present invention in an amount of 5 to 50% by mass in terms of solid content.
  • the content of the (meth)acrylic resin (I) is 5% by mass or more, the strength of the ink coating film does not decrease, and the adhesiveness to the substrate and the resistance to water rubbing are well maintained.
  • the amount is 50% by mass or less, it is possible to suppress a decrease in coloring power, avoid high viscosity, and prevent a decrease in workability.
  • the second composition contains an alcohol alkoxylate leveling agent as a leveling agent.
  • alcohol alkoxylate-based surfactants include alcohol ethoxylates and alcohol polyethoxylates.
  • the alcohol alkoxylate leveling agents may be used alone or in combination of two or more. Moreover, other leveling agents than the alcohol alkoxylate-based leveling agent may be used in combination.
  • the total amount of the alcohol alkoxylate-based leveling agent added is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, more preferably 0.1 to 1% by mass, of the total amount of the ink. is most preferred.
  • the total amount of the alcohol alkoxylate leveling agent added is 0.1 mass % or more of the total amount of the ink, the wettability with the substrate is improved and the adhesion with the substrate can be maintained. If the total amount of the alcohol alkoxylate-based leveling agent added is 5% by mass or less of the total amount of the ink, abrasion resistance, water abrasion resistance and scratch resistance do not deteriorate.
  • leveling agents such as acetylene-based leveling agents, acrylic polymer-based leveling agents (eg Polyflow WS-314 manufactured by Kyoeisha Chemical Co., Ltd.) and modified silicone-based leveling agents (eg Polyflow KL-401 Kyoeisha) (manufactured by Kagaku Co., Ltd.) may also be used.
  • the total amount of the leveling agent used is preferably 0.1 to 5 mass % of the total amount of the ink for the reasons described above.
  • the second composition preferably contains wax.
  • a hydrocarbon wax is preferable as the wax. Specific examples include liquid paraffin, natural paraffin, synthetic paraffin, microcrystalline wax, polyethylene wax, fluorocarbon wax, ethylene-propylene copolymer wax, tetrafluoroethylene resin wax, and Fischer-Tropsch wax. Among them, polyethylene wax is preferred.
  • waxes may be used alone or in combination of two or more, and the total amount of these waxes added is preferably 0.5 to 5% by mass of the total amount of the ink. If the total amount of wax added is 0.5% by mass or more based on the total amount of the ink, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained. If the total amount of wax added is 5% by mass or less of the total amount of the ink, adhesion to the substrate, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained.
  • a curing agent capable of reacting with acid may be used in combination.
  • the curing agent that can react with an acid is not particularly limited, and known curing agents that can be used in an aqueous medium can be used. Examples thereof include epoxy-based curing agents, carbodiimide-based curing agents, and oxazoline-based curing agents.
  • a curing agent is further added to the liquid ink, it is possible to achieve excellent viscosity stability, substrate adhesion of the cured coating film, and various coating film strengths.
  • the epoxy-based curing agent is not particularly limited as long as it is a compound having at least one epoxy group.
  • epoxy-based curing agents include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.
  • a polycarbodiimide compound having at least two carbodiimide groups is preferred.
  • the oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton.
  • Specific examples of oxazoline-based curing agents include Epocross series manufactured by Nippon Shokubai Co., Ltd., and the like.
  • epoxy compound examples include diglycidyl ether of bisphenol A and its oligomers, diglycidyl ether of hydrogenated bisphenol A and its oligomers, diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl terephthalate, and p-oxybenzoic acid.
  • diglycidyl ester diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, Examples include diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol te
  • the addition amount of the curing agent used in the present invention is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 9.0% by mass in terms of solid content of the total amount of the composition. If the amount added is 0.1% by mass or more, the effect as a curing agent is obtained, while if it is 10.0% by mass or less, substrate adhesion, abrasion resistance, and water abrasion resistance tend to be maintained. Become.
  • solvent As the solvent used for the second composition, the same solvent as the liquid ink for forming the first printing layer can be used.
  • the second composition may be used as a water-based varnish without containing a coloring material, or may be used as a so-called ink for white, black, or color printing with a coloring material. If it does not contain a coloring material, it becomes a transparent film after printing and is a colorless transparent ink (in this technical field, it is used for the purpose of solid printing on the outermost layer of the color printing layer and protecting the color printing layer, so it is commonly called overcoat varnish, OP In the present invention, it may be referred to as OP varnish). Of course, they can also be used as inks for so-called white, black and color printing containing coloring materials.
  • the same liquid ink as used for forming the first printing layer can be used.
  • the second composition may optionally contain a general-purpose resin other than the acrylic resin (I), an extender pigment, a pigment dispersant, a leveling agent, an antifoaming agent, a plasticizer, an infrared absorber, and an ultraviolet absorber. , fragrances, flame retardants, and the like.
  • a general-purpose resin other than the acrylic resin (I) an extender pigment, a pigment dispersant, a leveling agent, an antifoaming agent, a plasticizer, an infrared absorber, and an ultraviolet absorber.
  • fragrances, flame retardants, and the like Among them, fatty acid amides such as oleic acid amide, stearic acid amide, and erucic acid amide for imparting friction resistance, slipperiness, etc., silicon-based and non-silicon-based defoaming agents for suppressing foaming during printing,
  • Various pigment dispersants and the like are often contained to improve the wettability of the pigment.
  • the first composition or the second composition is obtained by dispersing a pigment, water alone, or a mixture containing water and an organic solvent that is miscible with water, a pigment dispersant, an antifoaming agent, etc., using a dispersing machine, to obtain a pigment dispersion.
  • a resin, water, or an organic solvent miscible with water, and if necessary, additives such as a leveling agent are added to the obtained pigment dispersion, and mixed with stirring to form the first composition or the second composition. can get.
  • a dispersing machine a bead mill, eiger mill, sand mill, gamma mill, attritor, etc., which are generally used for the production of gravure and flexographic printing inks, are used.
  • the viscosity is preferably 7 to 25 seconds at 25° C. using Zahn Cup #4 manufactured by Rigosha, more preferably 10 to 25 seconds. 20 seconds.
  • the surface tension of the obtained flexographic ink at 25° C. is preferably 25-50 mN/m, more preferably 33-43 mN/m.
  • the lower the surface tension of the ink the better the wettability of the ink to the substrate such as a film. tends to be easily connected, and tends to cause stains on the printing surface called dot bridges.
  • the surface tension exceeds 50 mN/m, the wettability of the ink to the base material such as a film is lowered, which tends to cause repelling.
  • the viscosity is preferably 7 to 25 seconds at 25° C. using Zahn Cup #3 manufactured by Rigosha. 10-20 seconds.
  • the surface tension of the obtained gravure ink at 25° C. is preferably 25 to 50 mN/m, more preferably 33 to 43 mN/m, like the flexo ink.
  • the lower the surface tension of the ink the better the wettability of the ink to the substrate such as a film. tends to be easily connected, and tends to cause stains on the printing surface called dot bridges.
  • the surface tension exceeds 50 mN/m, the wettability of the ink to the base material such as a film is lowered, which tends to cause repelling.
  • the first printed layer or the second printed layer is obtained by printing the first composition or the second composition on the substrate to provide the printed layer.
  • a printing layer is obtained by applying ink to a base material using a printing method such as gravure or flexography, drying the ink in an oven, and fixing the ink.
  • the drying temperature is usually about 40-60°C.
  • Flexographic printing is a type of letterpress printing, and mainly uses a rubber plate as a printing plate (letterpress), and uses a fine-mesh engraving roll called an anilox roll for the part that supplies ink to the printing plate.
  • the anilox roll receives ink from the chamber-type doctor and applies ink to the printing plate, and there is an advantage that the ink can be uniformly transferred to the printing plate through the anilox roll.
  • ink is applied to the surface of an anilox roll having partition walls and many openings surrounded by the partition walls, and a doctor is pressed against the surface of the anilox roll to scrape off the ink present on the top surface of the partition walls of the anilox roll. , to fill the recesses, which are openings, with ink.
  • the flexographic plate is pressed against the anilox roll to transfer the ink present in the concave portions of the anilox roll to the convex portions (patterned portions) of the printing plate, and then the plate is brought into contact with the base material to transfer the ink present in the patterned portions of the plate.
  • the ink is transferred to the substrate to obtain a print.
  • the rotary printing method may be combined.
  • a method for producing a thermoplastic resin film rotary print rotary printing is performed on the surface of a wound thermoplastic resin film using an aqueous liquid ink. After printing, processes such as lamination, slitting (cutting unnecessary width portions), and bag making (cutting and heat-sealing to form bags) can be performed. High-speed printing is possible by rolling the liquid printing ink onto a thermoplastic resin film, and productivity is excellent.
  • Rotary printing includes gravure rotary printing and flexographic rotary printing, and either method may be used. Rotary printing will be described in detail. In this specification, rotary printing means rotary gravure printing and flexographic rotary printing, and does not include other printing methods such as ink jet printing and silk screen printing.
  • ink is supplied directly from a container for storing liquid printing ink or via an ink supply pump or the like to an anilox roller having an uneven surface. It is transferred to the plate surface by contact with the projections, and finally transferred to the thermoplastic resin film by contact between the plate surface and the thermoplastic resin film to form a pattern and/or characters.
  • the ink drying property is slightly inferior to solvent-based flexographic printing ink, so it is preferable that the thickness of the ink be as thin as possible. From this point of view, it is preferable that the amount of ink supplied to the Aronix roller is as small as possible.
  • the pigment density of the water-based flexographic printing ink to be used may be appropriately controlled. Specifically, when the pigment concentration of the water-based flexographic printing ink is 1 to 5% by weight higher than the concentration of the solvent-based flexographic printing ink, a suitable printing density can be obtained.
  • Rolled thermoplastic resin film is a roll of thermoplastic resin film with a specified width, and is different from sheet paper in which each sheet is cut in advance, and is used for rotary printing. is.
  • the width of the film is appropriately selected based on the plate width of the rotary printing press to be used and the width of the image (pattern) portion of the gravure plate.
  • the order of printing is not particularly limited.
  • the substrate is white
  • a paper substrate and a thermoplastic resin film into which a white pigment is kneaded printing with only color inks is possible as required.
  • reverse printing it is common to first print color ink and then white ink on the wound thermoplastic resin film.
  • printing can be performed in the order of black, cyan, magenta, and yellow, but there is no particular limitation.
  • special colors and the like can be used in addition to the basic colors. That is, a large-sized printing press has a plurality of printing units corresponding to 5 to 10 colors, one printing unit is provided with ink of one color, and 5 to 10 colors of overprinting can be performed at one time.
  • the printed matter obtained by reverse printing may be used as it is, or the printed surface of the rotary printed matter obtained by the above method may be coated with an anchor coating agent, an adhesive, etc., dried as necessary, and then coated with a film, etc. It can also be laminated to form a laminate.
  • the laminate of the present invention may be a laminate having at least a laminate structure in which a first printed layer and a second printed layer are laminated in this order on a plastic film by a printing method using a plate.
  • thermoplastic resin film is not particularly limited, for example, a thermoplastic resin film is preferable.
  • the thermoplastic resin film is not particularly limited, and examples thereof include polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene phthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, and polybutylene.
  • Biodegradable resins typified by polyester resins such as terephthalate and polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, and aliphatic polyester resins such as poly(ethylene succinate) and poly(butylene succinate), Polyolefin resins such as polypropylene (PP) and polyethylene, films made of thermoplastic resins such as polyimide resins, polyarylate resins, or mixtures thereof, and laminates thereof include polyester, polyamide, polyethylene, and polypropylene. A film can be preferably used.
  • These films may be either unstretched films or stretched films, and the manufacturing method thereof is not limited.
  • the thickness of the base film is not particularly limited, but it is usually in the range of 1 to 500 ⁇ m.
  • the adhesiveness to the substrate can be further improved, which is preferable.
  • silica, alumina, or the like may be vapor-deposited, and a gas barrier coating layer such as an oxygen gas barrier layer may be laminated.
  • it may be a base material in which another base material is laminated on the surface of the plastic film different from the first printed layer.
  • substrates include paper, synthetic paper, thermoplastic resin films, steel plates, aluminum foil, wood, woven fabrics, knitted fabrics, non-woven fabrics, gypsum boards, wood boards, and the like. It is possible to use a base material in which a plurality of types of base materials are combined. Specifically, for example, a base material in which paper and a plastic film are laminated, a base material in which a plastic film and an aluminum foil are laminated, and the like can be mentioned.
  • the lamination method is also not particularly limited, and a general-purpose one-liquid adhesive, two-liquid adhesive, etc. may be used for adhesion, or if a plurality of thermoplastic resin films are laminated together by extrusion molding. may be
  • a first printed layer and a second printed layer of the present invention are provided on the substrate.
  • the number of printed layers is not particularly limited, and the laminate may have a third printed layer.
  • the third printed layer may be provided between the first printed layer and the second printed layer, or may be provided on the second printed layer.
  • the third printed layer can be formed of a printed layer formed with a general-purpose ink. For example, liquid ink containing at least the same acrylic resin as the second printed layer, or It is preferably composed of an ink containing at least a urethane resin similar to the above.
  • the laminate of the present invention may further have one or more other printed layers in addition to the first printed layer, the second printed layer, and the third printed layer.
  • the structure of the other layers is not particularly limited, and a known ink layer or overcoat varnish layer can be provided.
  • a printed layer containing a known urethane resin is provided on the first printed layer, or a printed layer containing a known urethane resin is provided between the third printed layer and the second printed layer. preferable.
  • the present invention is not limited to this configuration, and it is possible to obtain a printed matter and a laminate expressed by a plurality of printed layers according to a desired design.
  • the overcoat varnish is expressed as "OP”
  • the anchor coat varnish as "AC”
  • the layer printed with a general-purpose water-based liquid ink as a "general-purpose printed layer”.
  • “/” means adjacent, for example, in the case of "substrate/first printing layer (color)/second printing layer OP", the first printing ink is adjacent to the substrate.
  • a layer is provided and adjacent to the printed ink layer an overcoat varnish with a second printed layer is provided. It means.
  • the second printed layer of the present invention is excellent in coating film strength, particularly abrasion resistance and scratch resistance
  • the outermost layer of the laminate that is, the uppermost layer farthest from the thermoplastic resin film that is the base material
  • the strength of the laminate becomes more sufficient, and the basic coating film strength such as substrate adhesion, abrasion resistance, water abrasion resistance, and scratch resistance is better maintained.
  • the printed layer at this time may be applied as a colored ink containing a suitable coloring material or as an overcoat varnish containing no coloring material.
  • a white ink containing a white pigment is most often applied as a color ink containing a coloring material.
  • the second printed layer can be printed in the same color (for example, white ink again on top of white ink). It may be made into a layered printing layer.
  • a printing layer may be formed by stacking a plurality of overcoat varnishes containing no colorant on a color ink (for example, white ink).
  • the laminate of the present invention has excellent adhesion regardless of the type of plastic film substrate, and the second printed layer has excellent coating strength, especially abrasion resistance and scratch resistance. , is suitable for a form in which the printed layer is the outermost layer.
  • a printed matter having a printed layer of the water-based liquid ink (A) according to the present invention on the outermost surface during distribution is preferable because the effect of the present invention can be maximized. It can be used in a variety of applications, such as plastic labels for beverage and food bottles (such as shrink labels and body wrap labels), integrated packages, and exterior packages.
  • Parts in the following examples represent “parts by mass”, and “%” represents “% by mass”.
  • the measurement of the weight average molecular weight (in terms of polystyrene) by GPC (gel permeation chromatography) in the present invention was carried out under the following conditions using an HLC8220 system manufactured by Tosoh Corporation. Separation column: 4 TSKgelGMHHR-N manufactured by Tosoh Corporation are used. Column temperature: 40°C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml/min. Sample concentration: 1.0% by mass. Sample injection volume: 100 microliters. Detector: differential refractometer.
  • the acid value indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin. ⁇ Calculated from potentiometric titration with ethanol solution.
  • T1, T2, . . . Tn are those described in Polymer Handbook (Fourth Edition, J. Brandrup, EH Immergut, EA Grulke).
  • the glass transition temperature of the homopolymer of each monomer is not described in the above Polymer Hand Book, the glass transition temperature is measured using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument) and conforms to JIS K7121. It was measured by the method. Specifically, the polymer, from which the solvent has been completely removed by vacuum suction, is measured for changes in calorific value in the range of ⁇ 100° C. to +200° C. at a heating rate of 20° C./min. The glass transition temperature was defined as the intersection of a straight line equidistant from the vertical axis and the curve of the stepwise change portion of the glass transition.
  • This polyurethane resin U1 had a glass transition point Tg of 25°C and an acid value of 17 mgKOH/g.
  • This polyurethane resin U2 had a glass transition point Tg of -50°C and an acid value of 40 mgKOH/g.
  • THF tetrahydrofuran
  • the temperature was raised to 90° C. while stirring in a nitrogen atmosphere.
  • aqueous acrylic resin solution having a solid content of 30%.
  • the acid value was 250 mgKOH/g, the Tg was 61°C, and the weight average molecular weight was 10,200.
  • the acid value was 105 mgKOH/g, the Tg was 65°C, and the weight average molecular weight was 16,000.
  • Titanium (IV) oxide JR-800 (manufactured by Tayka) Copolymer (A1): Core-shell styrene-acrylic emulsion (A1) having the copolymer prepared in Synthesis Example 4
  • Epoxy curing agent Denacol EX-612 (manufactured by sorbitol polyglycidyl ether Nagase ChemteX Co., Ltd.)
  • Preparation of printing ink laminate> Examples 1 to 27, Comparative Examples 1
  • the OP varnish or water-based liquid ink was printed according to Tables 7 to 14 in the order of the first printed layer, the second printed layer, the third printed layer, the fourth printed layer, and the fifth printed layer.
  • the first printed layer described in Tables 7 to 14 corresponds to the "first printed layer”
  • the outermost layer of the second printed layer to the fifth printed layer is the "second It corresponds to the "printing layer”.
  • the adhesiveness to the substrate, abrasion resistance, water abrasion resistance, and scratch resistance were evaluated as follows, and the viscosity stability of the prepared acrylic resin ink and varnish was also evaluated. gone.
  • ⁇ Substrate adhesion> A cellophane tape (12 mm width, manufactured by Nichiban Co., Ltd.) was applied to the ink-coated surface of the resulting printed ink laminate, and then rapidly peeled off to visually determine the degree of ink peeling. The practical level is ⁇ or higher.
  • the printed ink laminate thus obtained was rubbed with high-quality paper using a Gakushin rub resistance tester, and the degree of peeling of the ink layer was visually determined. (500 reciprocations at a load of 500g) The practical level is ⁇ or higher.
  • ⁇ PET Corona-treated PET film (E5100, thickness 12 ⁇ m, manufactured by Toyobo Co., Ltd.)
  • OPP Corona-treated polypropylene biaxially stretched film (Pylen P2161 manufactured by Toyobo Co., Ltd., thickness 20 ⁇ m)
  • OPP Corona-treated polystyrene biaxially stretched film (thickness 50 ⁇ m)

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne un stratifié comportant au moins une première couche d'impression et une deuxième couche d'impression dans l'ordre indiqué sur un film plastique, la première couche d'impression étant une couche d'impression d'un vernis à base d'eau ou d'une encre liquide à base d'eau contenant au moins une résine d'uréthane qui est un produit de réaction d'un polyol (ia), contenant un polyol de polyéther (ia-1), et d'un polyisocyanate (ib) ; et la deuxième couche d'impression étant une couche d'impression d'un vernis à base d'eau ou d'une encre liquide à base d'eau contenant une résine (méth)acrylique et un agent de nivellement à base d'alcoxylate d'alcool.
PCT/JP2022/012142 2021-03-30 2022-03-17 Stratifié ayant une couche d'impression d'encre liquide à base d'eau WO2022209932A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015029878A1 (fr) * 2013-08-30 2015-03-05 Ｄｉｃグラフィックス株式会社 Composition aqueuse de vernis de surimpression durcissable par rayonnement uv
WO2019069736A1 (fr) * 2017-10-02 2019-04-11 Ｄｉｃグラフィックス株式会社 Encre flexographique à base d'eau durcissable par faisceau d'électrons pour impression de surface, et sachet stérilisable en autoclave l'utilisant
JP2019094423A (ja) * 2017-11-22 2019-06-20 Ｄｉｃグラフィックス株式会社 水性リキッドインキ、及び該水性リキッドインキを用いた積層体
WO2019235048A1 (fr) * 2018-06-08 2019-12-12 花王株式会社 Encre d'héliogravure aqueuse
WO2020213413A1 (fr) * 2019-04-17 2020-10-22 Ｄｉｃグラフィックス株式会社 Encre liquide à base d'eau et stratifié
JP2020193321A (ja) * 2019-05-27 2020-12-03 花王株式会社 版印刷用水性インキ
JP2021046522A (ja) * 2019-09-20 2021-03-25 Ｄｉｃグラフィックス株式会社 水性ニス組成物及び塗工物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015029878A1 (fr) * 2013-08-30 2015-03-05 Ｄｉｃグラフィックス株式会社 Composition aqueuse de vernis de surimpression durcissable par rayonnement uv
WO2019069736A1 (fr) * 2017-10-02 2019-04-11 Ｄｉｃグラフィックス株式会社 Encre flexographique à base d'eau durcissable par faisceau d'électrons pour impression de surface, et sachet stérilisable en autoclave l'utilisant
JP2019094423A (ja) * 2017-11-22 2019-06-20 Ｄｉｃグラフィックス株式会社 水性リキッドインキ、及び該水性リキッドインキを用いた積層体
WO2019235048A1 (fr) * 2018-06-08 2019-12-12 花王株式会社 Encre d'héliogravure aqueuse
WO2020213413A1 (fr) * 2019-04-17 2020-10-22 Ｄｉｃグラフィックス株式会社 Encre liquide à base d'eau et stratifié
JP2020193321A (ja) * 2019-05-27 2020-12-03 花王株式会社 版印刷用水性インキ
JP2021046522A (ja) * 2019-09-20 2021-03-25 Ｄｉｃグラフィックス株式会社 水性ニス組成物及び塗工物

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