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WO2018008639A1 - Composition d'encre d'impression non aqueuse - Google Patents

Composition d'encre d'impression non aqueuse Download PDF

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Publication number
WO2018008639A1
WO2018008639A1 PCT/JP2017/024507 JP2017024507W WO2018008639A1 WO 2018008639 A1 WO2018008639 A1 WO 2018008639A1 JP 2017024507 W JP2017024507 W JP 2017024507W WO 2018008639 A1 WO2018008639 A1 WO 2018008639A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink composition
vinyl chloride
mass
printing ink
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/024507
Other languages
English (en)
Japanese (ja)
Inventor
結科 早坂
通久 小藤
賢吾 飛田
比呂 木林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Ink Co Ltd
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
Toyo Ink Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Ink SC Holdings Co Ltd, Toyo Ink Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Priority to CN201780042582.1A priority Critical patent/CN109476942B/zh
Publication of WO2018008639A1 publication Critical patent/WO2018008639A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/10—Intaglio printing ; Gravure printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
    • 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
    • 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

Definitions

  • Embodiments of the present invention relate to a non-aqueous printing ink composition, and further to a printed material and a laminate.
  • a film substrate such as OPP film, PET film, NY film, paper substrate such as coated cardboard, or aluminum substrate
  • printing ink is usually used to decorate the substrate or protect the surface.
  • the printing used is applied.
  • the printed substrate is then passed through a slitting process and optionally sent to a post-processing step such as laminating, and finally becomes a package for food packaging, cosmetic packaging, and all other applications.
  • Non-aqueous inks are superior to water-based inks in terms of film (film) physical properties, laminate physical properties, and the like, and are also suitable as printing inks for the packaging materials described above.
  • non-water-based inks have a fast solvent volatilization during the drying process in printing, improvement of leveling property (smoothness) of the ink film is a problem.
  • printability in gravure printing is printability in gravure printing.
  • a gravure printing method is employed.
  • the plate used in the gravure printing method is a concave indentation (cell) where characters and patterns are indented, so that the ink is immersed in the plate to the extent that ink enters this cell, and the surface is rotated by a doctor blade while rotating the plate.
  • the ink is scraped off, and the gravure ink is transferred to the base material and allowed to settle. Since this printing method can express fine shades, it is optimal for reproducing rich gradations such as photographs and is suitable for mass production because high-speed printing is possible.
  • the problems of printability of this gravure printing method include (I) plate fog and (II) plate clogging.
  • (I) Plate fogging is a phenomenon in which ink cannot be scraped off by the above-mentioned doctor blade and the ink is removed. As a result, the plain portion of the base material is colored (stained), The pattern appears unintentionally.
  • the plate that is, the property, means a poor ink transfer, and appears on the printed surface in the form of a blur.
  • the plate that is, the phenomenon is likely to occur particularly in a portion having a shallow plate depth, that is, a portion having a shallow cell depth (highlight portion). Such print defects are handled as defective lots by the print converter, causing production loss.
  • a flexographic printing plate has a letterpress shape, but if the above problem is improved by printing suitability in gravure printing, the flexographic printing also lacks the balance of transferability between the solid part and the halftone part (highlight part). This is considered to improve printing defects such as printing defects, or ink that fills the gaps between halftone dots (highlighted areas) of the plate and the halftone dots are crushed (plate blurring property).
  • Patent Document 1 improvement in plate fog is attempted by devising a device of a gravure printing machine.
  • Patent Document 2 the ability to use aromatic organic solvents such as toluene is publicly recommended by the Air Pollution Control Law, studies have been made on esters and alcohol solvents (patents).
  • Patent Document 2 the ability to use aromatic organic solvents such as toluene is publicly recommended by the Air Pollution Control Law, studies have been made on esters and alcohol solvents (patents).
  • the types of printing base materials are classified into laminate (back printing), surface printing, paper, aluminum or aluminum vapor deposition base, etc., depending on applications.
  • film properties required for each application such as adhesion to the substrate, blocking resistance at the time of printing winding, film strength, water resistance, heat resistance and the like.
  • a contrivance has been made such as using a polyurethane-based resin as a binder resin or using a polyurethane resin and a vinyl chloride-vinyl acetate copolymer (Patent Documents 3 and 4).
  • JP-A-10-305555 Japanese Patent Laying-Open No. 2015-038177 JP2013-194081A JP 2005-298618 A
  • Embodiment of this invention aims at providing the non-aqueous printing ink composition excellent in printability and leveling property.
  • One aspect of the present invention contains a binder resin containing a vinyl chloride-acrylic copolymer resin (A) and a polyurethane resin (B),
  • the present invention relates to a non-aqueous printing ink composition in which the content of vinyl chloride-derived structure in 100% by mass of the vinyl chloride-acrylic copolymer resin (A) is 75 to 95% by mass.
  • the polyurethane resin (B) includes a structural unit derived from polyether polyol, The present invention relates to the above non-aqueous printing ink composition, wherein the proportion of the structural unit derived from the polyether polyol is in the range of 5 to 80% by mass in 100% by mass of the polyurethane resin (B).
  • the polyurethane resin (B) includes a structural unit derived from a polyester polyol
  • the present invention relates to the above non-aqueous printing ink composition, wherein the proportion of structural units derived from the polyester polyol is in the range of 5 to 80% by mass in 100% by mass of the polyurethane resin (B).
  • mode of this invention is related with the said non-aqueous printing ink composition in which the structural unit derived from the said polyester polyol contains the structural unit derived from the polyester polyol formed by making the diol which has a branched structure, and a dibasic acid react.
  • a further aspect of the present invention relates to the above non-aqueous printing ink composition, wherein the polyurethane resin (B) has a hydroxyl value of 1 to 20 mg / KOHg.
  • the non-aqueous printing ink composition described above, wherein the binder resin further contains at least one selected from the group consisting of a vinyl chloride-vinyl acetate copolymer resin (b1) and a cellulose resin (b2).
  • a further aspect of the present invention further contains a colorant (C), It is related with the said non-aqueous printing ink composition in which the said colorant (C) contains a white inorganic pigment.
  • mode of this invention is related with the said non-aqueous printing ink composition which further contains an amino-type silane coupling agent (D).
  • the amino-based silane coupling agent (D) has a primary amino group or a secondary amino group and four or more alkoxy groups. Relates to the composition.
  • mode of this invention is related with the said non-aqueous printing ink composition in which the said amino-type silane coupling agent (D) has a primary amino group and a secondary amino group.
  • mode of this invention is related with the said non-aqueous printing ink composition which is an ink composition for gravure printing.
  • mode of this invention is related with the said non-aqueous printing ink composition which is a printing ink composition for lamination.
  • Another aspect of the present invention is a binder resin containing a vinyl chloride-acrylic copolymer resin (A) and a polyurethane resin (B), Colorant (C), and amino-based silane coupling agent (D) Containing
  • the content of vinyl chloride-derived structure in 100% by mass of the vinyl chloride-acrylic copolymer resin (A) is 75 to 95% by mass
  • the colorant (C) relates to a non-aqueous gravure ink composition for laminating containing a white inorganic pigment.
  • Another aspect of the present invention includes a printing substrate and an ink layer formed on the printing substrate using the non-aqueous printing ink composition or the non-aqueous gravure ink composition for lamination. It relates to printed matter.
  • mode of this invention is related with the said printed matter whose said printing base material is a film.
  • Another aspect of the present invention relates to a laminate in which an adhesive layer and a substrate are laminated in this order on the printed surface of the printed matter.
  • the present invention relates to the subject matter described in Japanese Patent Application No. 2016-132597 filed on July 4, 2016, the disclosure of which is incorporated herein by reference.
  • One embodiment contains vinyl chloride-acrylic copolymer resin (A) and polyurethane resin (B) as essential components as a binder resin, and vinyl chloride in 100% by mass of the vinyl chloride-acrylic copolymer resin (A).
  • the present invention relates to a non-aqueous printing ink composition having a content of the derived structure of 75 to 95% by mass.
  • the non-aqueous printing ink composition may be simply referred to as “ink composition” or “ink”.
  • the vinyl chloride-acrylic copolymer resin (A) is a copolymer mainly composed of a vinyl chloride monomer and an acrylic monomer.
  • the form of the copolymer is not particularly limited.
  • the acrylic monomer may be incorporated into the main chain of polyvinyl chloride in a block or randomly, or may be graft copolymerized with the side chain of polyvinyl chloride. .
  • the ratio of the structure derived from the vinyl chloride monomer in the solid content of 100% by mass of the vinyl chloride-acrylic copolymer resin (A) is 75 to 95% by mass.
  • the ratio of the structure derived from the vinyl chloride monomer is more preferably 80% by mass or more and 90% by mass or less in the solid content of 100% by mass of the vinyl chloride-acrylic copolymer resin (A).
  • the ratio (mass%) of the structure derived from each monomer in a copolymer is computable from the ratio (mass%) of the preparation amount of each monomer at the time of manufacture of a copolymer.
  • the ratio of the structure derived from the acrylic monomer is preferably 5 to 25% by mass, and more preferably 10 to 20% by mass.
  • the vinyl chloride-acrylic copolymer resin (A) preferably contains a hydroxyl group from the viewpoint of improving solubility in an organic solvent and adhesion to a substrate, and preferably has a hydroxyl value of 10 to 120 mgKOH / g. 20 to 110 mgKOH / g is more preferable, and 30 to 100 mgKOH / g is still more preferable.
  • the glass transition temperature of the vinyl chloride-acrylic copolymer resin (A) is preferably 55 to 85 ° C.
  • the glass transition temperature of the vinyl chloride-acrylic copolymer resin (A) is more preferably 65 to 80 ° C.
  • the glass transition temperature (hereinafter sometimes referred to as “Tg”) for the vinyl chloride-acrylic copolymer resin (A) is a value obtained by calculation from the following FOX equation.
  • the vinyl chloride-acrylic copolymer resin (A) preferably has a weight average molecular weight in the range of 10,000 to 100,000. When it is 10,000 or more, it is preferable from the viewpoint of securing blocking resistance and solvent resistance in the printed matter, and when it is 100,000 or less, it is easy to maintain solubility in a solvent, and it is preferable from the viewpoint of printability.
  • the weight average molecular weight is more preferably 30,000 to 70,000, still more preferably 40,000 to 60,000.
  • acrylic monomers that can be used in the vinyl chloride-acrylic copolymer resin (A) will be described below, but the acrylic monomers are not limited to these.
  • (meth) acryl or (meth) acrylate means methacryl and acryl, or methacrylate and acrylate, respectively.
  • (Meth) acrylic acid ester can be used as the acrylic monomer.
  • (meth) acrylic acid esters include (meth) acrylic acid alkyl esters, and the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 2 to 6 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group.
  • examples include octadecyl.
  • the alkyl group may further have a benzene ring structure.
  • the benzene ring structure include monocyclic or condensed rings having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms.
  • butyl (meth) acrylate is preferable from the viewpoint that good adhesion is easily obtained. These can be used alone or in combination of two or more.
  • the acrylic monomer which has a hydroxyl group as an acrylic monomer.
  • examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) acrylic acid 3 -(Meth) acrylic acid hydroxyalkyl esters such as hydroxybutyl, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate; polyethylene glycol mono (meth) Glycol mono (meth) acrylates such as acrylate, polypropylene glycol mono (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate; caprolactone modified (meth) acrylate; hydroxyethyl acrylamide, etc.
  • hydroxyalkyl esters of acrylic acid are preferred, and the number of carbon atoms of the hydroxyalkyl group is preferably 1-20, more preferably 1-10, and even more preferably 2-6.
  • the alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group.
  • 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate improve solubility in solvents and improve adhesion to substrates. Therefore, it is more preferable. These can be used alone or in combination of two or more.
  • an acrylic monomer having a functional group other than a hydroxyl group can be used as the acrylic monomer.
  • functional groups other than hydroxyl groups include carboxyl groups, amide bond groups, amino groups, alkylene oxide groups, and the like.
  • carboxyl group-containing acrylic monomers examples include (meth) acrylic acid and carboxyl group-containing acrylic esters such as monohydroxyethyl (meth) acrylate, p-carboxybenzyl (meth) acrylate, ethylene oxide modified (addition moles). Number: 2 to 18) phthalic acid (meth) acrylate, monohydroxypropyl (meth) acrylate phthalate, monohydroxyethyl (meth) acrylate succinate, ⁇ -carboxyethyl acrylate, 2-methacryloyloxyethyl hexahydrophthalic acid Etc. Further, esterified products of hydroxyalkyl (meth) acrylates with maleic acid, monoethylmaleic acid, itaconic acid, citraconic acid, and fumaric acid are also included.
  • carboxyl group-containing acrylic esters such as monohydroxyethyl (meth) acrylate, p-carboxybenzyl (meth) acryl
  • acrylic monomers containing an amide bond examples include (meth) acrylamide, N-methylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminopropyl (meth).
  • examples include (meth) acrylamide compounds such as acrylamide, diacetone acrylamide, N- (hydroxymethyl) acrylamide, and N- (butoxymethyl) acrylamide.
  • Amino group-containing acrylic monomers include amino acid-containing acrylic esters such as monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, (meth) And (meth) acrylic acid monoalkylamino esters such as monoethylaminopropyl acrylate.
  • the acrylic monomer may have an alkylene oxide unit. Although it does not specifically limit as an alkylene oxide unit, An ethylene oxide unit, a propylene oxide unit, etc. are illustrated.
  • the number of repeating alkylene oxide units is not particularly limited, but is, for example, 1 to 50, preferably 1 to 30, and more preferably 1 to 20.
  • acrylic monomers having alkylene oxide units include acrylic acid esters having alkylene oxide units, such as 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-phenoxyethyl acrylate, methoxypolyethylene glycol (meth)
  • acrylic acid esters having alkylene oxide units such as 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-phenoxyethyl acrylate, methoxypolyethylene glycol (meth)
  • examples include acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropyleneglycol (meth) acrylate, ethoxypolypropyleneglycol (meth) acrylate, phenoxypolyethyleneglycol (meth) acrylate, and phenoxypolypropyleneglycol (meth) acrylate.
  • the acrylic monomer is preferably an acrylic acid alkyl ester and an acrylic monomer having a hydroxyl group, more preferably an acrylic acid alkyl ester and an acrylic acid ester having a hydroxyl group, because adhesion to a substrate and solubility in an organic solvent are improved.
  • One or more of these monomers are preferably contained in an acrylic monomer in an amount of 50% by mass or more, and more preferably 70% by mass or more. The upper limit is 100% by mass.
  • the content of the acrylic acid ester containing a hydroxyl group is preferably 5% by mass or more in the acrylic monomer. Within the above range, it is also preferable from the viewpoint of improving printability when an ink is produced only with a non-toluene solvent. The upper limit is 100% by mass.
  • acrylic monomer one kind may be used alone, or two or more kinds may be mixed and used.
  • the vinyl chloride-acrylic copolymer resin (A) may be further copolymerized with a double bond monomer other than the acrylic monomer.
  • double bond monomers other than acrylic monomers include vinyl alcohol, styrene, maleic anhydride and the like. Vinyl alcohol is preferred for the purpose of increasing the solubility in a solvent or the compatibility between resins.
  • the proportion of structural units derived from double bondable monomers other than these acrylic monomers is preferably 5% by mass or less in the vinyl chloride-acrylic copolymer resin (A).
  • the vinyl chloride-acrylic copolymer resin (A) can be obtained, for example, by radical polymerization of a monomer mixture using a radical polymerization initiator.
  • the radical polymerization may be a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc., but suspension polymerization is preferred.
  • a vinyl chloride monomer and an acrylic monomer which are liquefied by applying pressure, are placed in a reactor containing water and a suspending agent in advance, and the monomer is extremely fine by stirring at high speed. Make particles.
  • the polymerization reaction is initiated by placing the polymerization reaction initiator in a polymerization vessel and reacting under several atmospheres at 40 ° C. to 80 ° C. Since the vinyl chloride-acrylic copolymer resin obtained by the suspension polymerization method is usually suspended in water (slurry state) as particles having a diameter of 80 to 200 ⁇ m, it is dehydrated and dried after being extracted from the reaction vessel. To a white powder. The unreacted monomer such as vinyl chloride monomer which has not been reacted at the time of the polymerization reaction is recovered through a stripping step and can be used again as a raw material after purification. In addition to suspension polymerization, a production method called emulsion polymerization or bulk polymerization is also preferably used.
  • the radical polymerization initiator is not particularly limited as long as it is a compound capable of generating radicals at the polymerization temperature, and known compounds such as peroxides and azo compounds can be used.
  • the peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, ⁇ , ⁇ ′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5- Dialkyl peroxides such as di (t-butylperoxy) hexyne-3; t-butylperoxybenzoate, t-butylperoxyacetate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, etc.
  • ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide; 2,2-bis (4,4-di-t-butylperoxycyclohexyl) ) Propane, 1,1-bis (t-butylperoxy) Peroxyketals such as 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valate; cumenehydro Hydroperoxides such as peroxide, diisopropylbenzene hydroperoxide, 2,5-dimethylcyclohexane-2,5-dihydroperoxide; benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl Examples thereof include diacyl
  • Examples of the azo compound include 2,2′-azobisbutyronitrile such as 2,2′-azobisisobutyronitrile (abbreviation: AIBN) and 2,2′-azobis (2-methylbutyronitrile).
  • 2,2′-azobisvaleronitriles such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile);
  • 2 2,2′-azobispropionitriles such as 1,2′-azobis (2-hydroxymethylpropionitrile); 1,1′-azobis such as 1,1′-azobis (cyclohexane-1-carbonitrile) -1-Alkanenitriles can be used.
  • the radical polymerization initiators can be used alone or in combination of two or more.
  • potassium peroxodisulfate is preferably used as an initiator.
  • Potassium peroxodisulfate is a persulfate of potassium represented by the chemical formula K 2 S 2 O 8 . It is obtained by anodizing an aqueous solution of potassium sulfate or potassium hydrogen sulfate, and is used as an oxidizing agent, a polymerization accelerator or the like.
  • the radical polymerization initiator is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the mixture of the vinyl chloride monomer and the acrylic monomer.
  • the pigment dispersibility can be improved without increasing the viscosity. As a result, it is presumed that the effects of improving the leveling property and improving the printability are exhibited.
  • vinyl chloride-acrylic copolymer resin forms high adhesion to the substrate and a strong coating when the printed layer is formed, it is easy to obtain the effect of improving friction resistance, oil resistance, and heat resistance. .
  • a laminated laminate there is also an advantage that the effect of improving the appearance of the laminated body, the laminate strength, and the retort suitability can be easily obtained by suppressing the penetration of the adhesive component into the ink layer.
  • the polyurethane resin (B) is not particularly limited as long as it can be used in a non-aqueous printing ink composition, but the weight average molecular weight is preferably 10,000 to 100,000. From the viewpoint of blocking resistance of the obtained ink composition, it is more preferably 15,000 or more, and from the viewpoint of suppressing the increase in viscosity of the obtained ink composition while being able to disperse the pigment appropriately. More preferably, it is 000 or less.
  • the weight average molecular weight of the polyurethane resin is more preferably 20,000 to 60,000.
  • the glass transition temperature is preferably ⁇ 60 to 40 ° C.
  • the storage elastic modulus at 40 ° C. in the dynamic viscoelasticity measurement is preferably 1 to 100 MPa.
  • the glass transition temperature is measured with a differential scanning calorimeter (DSC) in accordance with JIS K 7121 and represents the middle point of the temperature range where the glass transition occurs.
  • the polyurethane resin (B) preferably has an appropriate amine value and / or hydroxyl value because adhesion to a substrate and solubility in an organic solvent are improved.
  • the amine value is preferably 1.0 to 20.0 mgKOH / g, and more preferably 2 to 15 mgKOH / g.
  • the hydroxyl value is preferably 1.0 to 20.0 mgKOH / g, more preferably 1 to 15 mgKOH / g, and still more preferably 1 to 10 mgKOH / g.
  • the hydroxyl group may be present in the side chain and / or terminal of the polyurethane resin (B).
  • the hydroxyl value is preferably 1 to 15 mgKOH / g, more preferably 1 to 10 mgKOH / g.
  • the solubility in an organic solvent is further improved, and when the hydroxyl value is 15 mgKOH / g or less, the cohesive force of the polyurethane resin (B) is increased and the substrate adhesion is improved.
  • the coating strength is further improved. Therefore, the components in the adhesive composition are less likely to penetrate into the ink layer, so that the laminate appearance and physical properties are further improved.
  • an amino-based silane coupling agent (D) described later is used, it is easy to obtain a tougher ink layer by crosslinking with a hydroxyl group or the like of the resin. Since the components in the adhesive composition described later are less likely to penetrate into the tough ink layer, the appearance of the laminate, the laminate strength, and the retort suitability are further improved.
  • Examples of the method of adding a hydroxyl group to the side chain of the polyurethane resin (B) include using amines having a hydroxyl group as a chain extender described later. Moreover, the method of adding a hydroxyl group to the terminal of a polyurethane resin (B) includes using the monoamine which has a hydroxyl group as a terminal blocker mentioned later. According to one embodiment, in the polyurethane resin (B), a hydroxyl group can be added to the polyurethane resin (B) by an arbitrary method, but it is preferable that a hydroxyl group is added to both the side chain and the terminal.
  • the polyurethane resin (B) is not particularly limited and can be appropriately produced by a known method.
  • a polyurethane resin (polyurethane urea resin) (B) obtained by reacting a urethane prepolymer of terminal isocyanate composed of polyol and polyisocyanate with an amine chain extender is preferable.
  • polyol used for printing inks for gravure ink, a flexo ink, etc.
  • combination by a polymerization reaction, a condensation reaction, etc., a natural product, etc. can be used.
  • polyester polyol, polyether polyol, polycaprolactone diol, polycarbonate polyol, polyolefin polyol, castor oil polyol, hydrogenated castor oil polyol, dimer diol, hydrogenated dimer diol and the like can be mentioned. In general, those having a number average molecular weight of 400 to 10,000 are preferred.
  • a polyol may be used individually by 1 type and may be used in combination of 2 or more type.
  • the polyurethane resin (B) preferably contains a structural unit derived from polyether polyol, and the content thereof is preferably 5 to 80% by mass, more preferably 100% by mass of the solid content of the polyurethane resin (B). 10 to 50% by mass.
  • polyether polyol examples include polyether polyols that are polymers or copolymers of methylene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, and the like. Among these, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol are preferable, and a propylene oxide polymer having moderate flexibility in terms of adhesion to the substrate is preferable.
  • the polyurethane resin (B) preferably contains a structural unit derived from a polyester polyol, and its content is preferably 5 to 90% by mass in 100% by mass of the solid content of the polyurethane resin (B), and preferably 5 to 80% by mass. %, More preferably 20 to 75% by mass, and particularly preferably 30 to 70% by mass.
  • polyester polyol examples include adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, and suberic acid.
  • Dibasic acids such as glutaric acid, 1,4-cyclohexyl dicarboxylic acid, dimer acid and hydrogenated dimer acid; polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; or anhydrides thereof and ethylene glycol, diethylene glycol , Triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propane Diol, 1,4-butanediol, 1,4-butyne All, 1,4-butylenediol, 1,3-butanediol, pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol Neopent
  • dibasic acids such as adipic acid or sebacic acid, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,4-diethyl-1,5-pentane
  • a polyester polyol obtained from a diol having a branched structure such as a diol is particularly preferred because it improves the dispersion stability of the pigment, the solubility of the ink, and the blocking resistance.
  • the diol having a branched structure means a diol having an alkyl side chain having a structure in which at least one hydrogen atom of an alkylene group contained in the diol is substituted with an alkyl group.
  • These polyester polyols can be used alone or in admixture of two or more.
  • a polyol having 3 or more hydroxyl groups, a polyvalent carboxylic acid having 3 or more carboxyl groups, and the like can be used in combination.
  • the number average molecular weight of the polyester polyol is preferably 500 to 10,000. More preferably, it is 1,000 to 5,000.
  • the number average molecular weight is determined by the above (Formula 1).
  • the acid value of the polyester polyol is preferably 1.0 mgKOH / g or less, and more preferably 0.5 mgKOH / g or less.
  • polyester polyols and polyether polyols are preferred from the viewpoint of adhesion of the ink layer to the printing substrate and solubility in the solvent of the ink composition, and a polyester polyol having a branched structure and a polyether polyol are used in combination. More preferably.
  • polyols other than the above-mentioned polyols examples include polycarbonate polyols obtained by reaction of the low molecular weight polyhydric alcohols with, for example, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc .; polybutadiene glycols; bisphenol A and ethylene oxide Alternatively, glycols obtained by adding propylene oxide; acrylic polyols having a hydroxyl group derived from hydroxyethyl acrylate, hydroxypropacrylate, and the like can be used.
  • polyisocyanate examples include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins.
  • 1,5-naphthylene diisocyanate 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1 , 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate
  • trimers to form an isocyanurate ring structure.
  • These polyisocyanates can be used alone or in admixture of two or more. Of these, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isocyanurate of hexamethylene diisocyanate are preferable.
  • isophorone diisocyanate isophorone diisocyanate, tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate are preferable, and isophorone diisocyanate is more preferable from the viewpoint of solubility.
  • amine chain extender examples include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine and the like.
  • chain extender capable of adding a hydroxyl group to the side chain of the polyurethane resin
  • amines having a hydroxyl group in the molecule such as 2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, di-2-hydroxypropylethylenediamine. it can.
  • These chain extenders can be used alone or in admixture of two or more.
  • polyfunctional amine chain extenders can also be used.
  • IBPA iminobispropylamine
  • N- (3-aminopropyl) Examples include butane-1,4-diamine (spermidine), 6,6-iminodihexylamine, 3,7-diazanonane-1,9-diamine, and N, N′-bis (3-aminopropyl) ethylenediamine.
  • isophoronediamine, 2-hydroxyethylethylenediamine, hexamethylenediamine, and iminobispropylamine are preferable.
  • a monovalent active hydrogen compound can also be used as a polymerization terminator (also referred to as a terminal terminator or a terminal blocking agent) for the purpose of terminating the excessive reaction.
  • a polymerization terminator also referred to as a terminal terminator or a terminal blocking agent
  • examples of such compounds are monoamine compounds, dialkylamines such as di-n-butylamine; 2-ethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2 -Amino alcohols such as amino-2-ethyl-1,3-propanediol and the like.
  • amino acids such as glycine, L-alanine, glutamic acid, taurine, aspartic acid, aminobutyric acid, valine, aminocaproic acid, aminobenzoic acid, aminoisophthalic acid, and sulfamic acid are polymerized. It can be used as a terminator. Alcohols such as ethanol and isopropyl alcohol can also be used.
  • the chain terminator may be used together with a chain extender to carry out a chain extension reaction. It may be added to perform a terminal termination reaction.
  • the molecular weight can be controlled without using a terminal terminator, but in this case, a method of adding a prepolymer to a solution containing a chain extender is preferable in terms of reaction control.
  • the polyurethane resin (B) is preferably synthesized by reacting a polyol with a polyisocyanate and then reacting with an amine chain extender and, if necessary, a polymerization terminator to form a polyurethane resin.
  • polyol and polyisocyanate may be used at a temperature of 10 ° C. to 150 ° C., for example, 50 ° C. to 100 ° C., if necessary using a solvent inert to the isocyanate group, and if necessary, using a catalyst such as a urethanization catalyst.
  • a catalyst such as a urethanization catalyst.
  • a prepolymer method in which an amine chain extender is reacted with this prepolymer at, for example, 10 to 80 ° C. to obtain a polyurethane resin.
  • the chain extension reaction between the urethane prepolymer and the amine chain extender is performed by gradually dropping the amine chain extender solution into the urethane prepolymer solution.
  • the urethane prepolymer is added to the amine chain extender solution.
  • any method can be used.
  • amine chain extender can also be used in a urethanization reaction with polyisocyanate together with a polymer polyol.
  • the amount of polyol and polyisocyanate is the ratio of the number of moles of isocyanate groups of the polyisocyanate to the number of moles of hydroxyl groups in the total of the polymer polyol.
  • NCO / OH ratio 1.1-3 It is preferable to be in the range of 0.0. More preferably, the NCO / OH ratio is 1.3 to 2.5.
  • an organic solvent for the synthesis of the prepolymer.
  • the organic solvent that can be used is preferably an organic solvent that is inactive with an isocyanate group, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dioxane and tetrahydrofuran; aromatic hydrocarbons such as toluene and xylene. And the like; esters such as ethyl acetate and butyl acetate; and halogenated hydrocarbons such as chlorobenzene and perchlene. These may be used alone or in combination as a mixed solvent.
  • a catalyst can be used for the synthesis reaction of the prepolymer.
  • catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts are usually used in the range of 0.001 to 1 mol% based on the polyol.
  • the prepolymer having an isocyanate group at the terminal obtained above and the amine chain extender diamine, triamine or the like are reacted at 10 to 60 ° C., and a high molecular weight polyurethane resin containing an active hydrogen group at the terminal (B ) Is obtained.
  • the ratio of the total number of moles of amino groups of the amine chain extender to the number of moles of isocyanate groups in the prepolymer is 1.01 to 2.00, preferably 1.03 to 1.06. It is preferable to make it react.
  • the solid content mass ratio of the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) in the non-aqueous printing ink composition Is, for example, 3/97 to 70/30, and preferably 5/95 to 60/40. Within this range, leveling properties, printability, substrate adhesion, coating film properties and laminate strength tend to be good.
  • the solid content mass ratio between the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) is more preferably 5/95 to 50/50, further preferably 10/90 to 40/60, and 10/90 to 30. Particularly preferred is a range of / 70.
  • solid content mass means the mass of the residual component which removed the volatile component by heating a composition for 30 minutes at 120 degreeC on normal-pressure conditions.
  • the total content of the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) in 100% by mass of the non-aqueous printing ink composition is preferably 3.0 to 25.0% by mass, 5 to 20% by mass is more preferable.
  • the non-aqueous printing ink composition preferably further contains at least one selected from the group consisting of vinyl chloride-vinyl acetate copolymer resin (b1) and cellulose resin (b2) as a binder resin.
  • the vinyl chloride-vinyl acetate copolymer resin (b1) is a copolymer of vinyl chloride and vinyl acetate, and the molecular weight is preferably 5,000 to 100,000 in terms of weight average molecular weight. 10,000 More preferred is 70.000.
  • the proportion of vinyl chloride in the solid content of 100% by mass of the vinyl chloride-vinyl acetate copolymer resin (b1) is preferably 70 to 95% by mass. Since vinyl acetate improves the solubility in organic solvents, a part of More preferable is vinyl alcohol obtained by the oxidization reaction, and the hydroxyl value is preferably 20 to 200 mgKOH / g.
  • the glass transition temperature is preferably 50 to 90 ° C.
  • the cellulose resin (b2) include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, carboxyalkyl cellulose, and the like.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group, and the alkyl group may have a substituent.
  • cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferable.
  • the molecular weight is preferably 5,000 to 1,000,000 in terms of weight average molecular weight, more preferably 10,000 to 200,000. Further, those having a glass transition temperature of 120 to 180 ° C. are preferable.
  • the non-aqueous printing ink composition may contain other polymer materials, such as chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, acrylic resin, Polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin modified maleic resin, terpene resin, phenol modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, and modified resins thereof Can be mentioned. These resins can be used alone or in admixture of two or more, and the content thereof is preferably 0.1 to 10% by mass in 100% by mass of the solid content of the non-aqueous printing ink composition, 0.5 to 10% by mass is more preferable.
  • other polymer materials such as chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, acrylic resin, Polyester resin, alkyd resin, polyvinyl chloride resin,
  • a pigment used in general inks, paints, and recording agents can be used alone or in combination.
  • Organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, isoindoline, etc.
  • Indigo ink is copper phthalocyanine
  • transparent yellow ink is C.I. from the viewpoint of cost and light resistance.
  • I. Pigment No Yellow 83 is preferably used.
  • carmine 6B lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, chromophthal yellow, chromophthal red, phthalocyanine blue, phthalocyanine green, dioxazine violet , Quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo Bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, carbon black, daylight fluorescence And pigments.
  • C.I. As the organic pigment, among the colorants described in Color Index International (abbreviation C.I.), C.I. which is an organic compound or an organometallic complex.
  • I. Pigment black, C.I. I. Pigment blue, C.I. I. Pigment Green, C.I. I. Pigment Red, C.I. I. Pigment violet, C.I. I. Pigment yellow, C.I. I. Pigment orange, C.I. I. Pigment brown is preferred.
  • Pigment blue 15: 2 C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 7, C.I. I. Pigment orange 34, C.I. I. Pigment orange 64, C.I. I. Pigment black 7 and the like.
  • white inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, and silica. It is preferable to use titanium oxide for the pigment of the white ink from the viewpoint of coloring power, hiding power, chemical resistance, and weather resistance, and from the viewpoint of printing performance, the titanium oxide is subjected to silica and / or alumina treatment. Those are preferred.
  • inorganic pigments other than white examples include aluminum powder, mica (mica), bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, aluminum hydroxide, ultramarine blue, bitumen, bengara, yellow iron oxide, iron black , Titanium oxide, zinc oxide, etc., and aluminum is in the form of a powder or paste, but is preferably used in the form of a paste from the viewpoint of handling and safety, and whether to use leafing or non-leafing is a brightness feeling and It is appropriately selected from the point of concentration.
  • the pigment is preferably contained in an amount sufficient to ensure the concentration and tinting strength of the non-aqueous printing ink composition, that is, 1 to 50% by mass relative to the total mass of the ink composition.
  • the mass% is more preferable.
  • the non-aqueous printing ink composition may be used in other hues as necessary (in addition to white as a process basic color, a total of five colors of yellow, red, indigo, and black; red (orange as a color outside the process gamut) ), Grass (green), and purple; ink compositions such as transparent yellow, peony, vermilion, brown, and pearl) may also be used.
  • the non-aqueous printing ink composition can be used for various uses such as laminating (back printing), surface printing, and paper, but has excellent laminating strength after laminating. It can be suitably used as a printing ink composition for laminating. Embodiments suitable for laminating printing and laminating printing will be described below.
  • printing using a printing ink is usually performed for decoration or surface protection of the plastic substrate.
  • laminate (back printing) printing is sometimes referred to as a printing ink layer (“printing layer” or “ink layer”) on one side (hereinafter, also referred to as back side or back side) of a transparent printing substrate. ), An adhesive layer, and a substrate (including a sealant) in order.
  • the sealant is a thermoplastic plastic base material that can be fused by heat, and an unstretched polyolefin base material is mainly used.
  • the pattern of the printing layer is seen from the non-printing surface (hereinafter also referred to as the front surface or the front side) of the transparent substrate.
  • the printing ink layer may be provided so as to cover the entire surface, or may be provided partially.
  • the printing ink layer may be a single layer or a plurality of layers may be stacked.
  • the portion where the printing ink layer is provided is also called an ink portion, and the portion where the printing ink layer is not provided is also called a plain portion.
  • composite films imparted with oxygen gas barrier properties and / or water vapor barrier properties may be used from the viewpoint of content protection.
  • a composite film the metal vapor deposition film which vapor-deposited the metal on the plastic film, the transparent vapor deposition film which vapor-deposited the inorganic oxide on the plastic base material, etc. are mentioned, for example.
  • a transparent vapor deposition film is used as a printing substrate and laminated with another substrate to form a laminate, or a plastic film is used as a printing substrate, a metal foil or a metal vapor deposition film And a high gas barrier property and a water vapor barrier property are imparted to the laminate.
  • ink is printed on the base material, and then it is further bonded to the base material with an adhesive.
  • the methods are roughly classified into three types: an extrusion laminating method, a dry laminating method, and a non-solvent laminating method.
  • Various devices have been devised to increase the laminate strength regardless of the type of substrate and the laminate configuration (JP 2013-213109, etc.), but even when such a technique is applied, the laminate strength and printability It has been difficult to achieve both leveling properties and film properties.
  • the dry laminating method and the solventless laminating method are methods for producing a laminate through an adhesive such as a urethane adhesive.
  • an adhesive such as a urethane adhesive.
  • the amount of adhesive applied it is required that a high-quality laminate can be obtained even when laminating is performed.
  • the application amount of the adhesive is reduced, there is a problem that it is liable to cause a skin-like appearance defect on the ink part of the laminate.
  • the use of a transparent vapor deposition film, a metal foil, or a metal vapor deposition film gives a higher gas barrier property to the entire laminate, and the appearance defect in the ink part is promoted.
  • the printed material is adhered to the metal foil or the metal vapor deposition film.
  • the printing ink composition for laminating is used, and the printability and leveling properties are good regardless of the type of substrate to be printed, such as the type of plastic substrate and the metal vapor-deposited film (substrate).
  • a printed matter having excellent lamination strength after the lamination step can be obtained.
  • even when the amount of the adhesive is reduced as will be described later, good laminate appearance, laminate strength, and retort suitability can be achieved.
  • the above-mentioned vinyl chloride-acrylic copolymer resin (A) and polyurethane resin (B) have a solid content mass ratio ((A) / (B)) of 5/95. -40/60 is preferable, and a range of 5 / 95-50 / 50 is more preferable.
  • the mass ratio ((A) / (B)) between the vinyl chloride-acrylic copolymer resin and the polyurethane resin is 5/95 or more, the adhesive easily suppresses the penetration into the ink layer, and the appearance of the laminate, the laminate strength, It is preferable from the viewpoint of retort suitability.
  • the mass ratio ((A) / (B)) between the vinyl chloride-acrylic copolymer resin and the polyurethane resin is 50/50 or less, it is easy to maintain the adhesion between the ink composition and the printing substrate. It is preferable from the viewpoint of retort suitability. Moreover, since it is easy to maintain the leveling property of an ink composition, a more uniform ink layer is easy to be obtained and a favorable laminate appearance is easy to be obtained.
  • the colorant in the printing ink composition for laminating, is not particularly limited, but in particular, when a white inorganic pigment is included, an excellent effect can be achieved in terms of improving the performance of the printed matter.
  • the ink layer is composed of, for example, a multi-color ink layer and then a white ink layer to be laminated.
  • the white ink that is in direct contact with the adhesive layer, the laminate appearance, laminate strength and retort suitability are improved. Is most effective for improving the performance of the overall packaging material obtained. Therefore, the pigment is a white inorganic pigment, and it is particularly preferable that the white inorganic pigment is titanium oxide.
  • Titanium oxide is excellent in chemical resistance, so that the penetration of the adhesive into the white ink layer can be suppressed, and is suitable for obtaining a laminate having a good appearance from the viewpoint of coloring power and hiding power.
  • titanium oxide is preferably surface-treated with an inorganic oxide from the viewpoint of dispersion stability and printability, and is preferably silica-treated, alumina-treated, or titanium oxide treated with silica and alumina in combination. .
  • the printing ink composition for laminating it is preferable to use a white inorganic pigment and an amino silane coupling agent (D) as a pigment.
  • an amino silane coupling agent (D) will be described.
  • the amino-based silane coupling agent (D) represents a compound having any one of primary to tertiary amino groups and an alkoxysilyl group in one molecule.
  • the alkoxy group preferably has 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.
  • the alkoxysilyl group in the amino silane coupling agent molecule is cross-linked with a hydroxyl group that may also be present on the surface of the white inorganic pigment, the vinyl chloride-acrylic copolymer resin (A), or the polyurethane resin (B) in the ink composition.
  • a tough ink layer capable of suppressing the penetration of the laminated adhesive is formed, and the leveling property of the adhesive is improved, so that the appearance of the laminated body is improved.
  • the polyisocyanate component in the adhesive is difficult to penetrate into the ink layer, it is possible to achieve good laminate properties without inhibiting the curing of the adhesive layer.
  • the alkoxysilyl group of the amino silane coupling agent (D) can form a crosslink with the hydroxyl group on the corona-treated printing substrate surface, the viewpoint of improving the adhesion between the ink layer and the printing substrate. Also, good laminate strength can be obtained.
  • the ink composition preferably contains the amino silane coupling agent (D) in an amount of 0.15 to 7% by mass in 100% by mass of the solid content of the ink composition.
  • the content of the amino silane coupling agent (D) is 0.15% by mass or more, the ink layer can be sufficiently crosslinked, and the laminate appearance and laminate strength can be further improved.
  • the content of the amino silane coupling agent (D) is 7% by mass or less from the viewpoint of improving the appearance of the laminate, the laminate strength, and the retort suitability. The reason for this is considered as follows.
  • the amino silane coupling agent (D) When an excessive amount of the amino silane coupling agent (D) is contained in the ink layer, a part of the amino silane coupling agent (D) moves into the adhesive layer.
  • the amino group of the amino silane coupling agent (D) can also react with the polyisocyanate component in the adhesive. It can also act as a basic catalyst during the curing reaction of the adhesive. Since the amino group is more reactive with the isocyanate group than the hydroxyl group, when the excess amino silane coupling agent (D) in the ink layer moves into the adhesive layer, the polyisocyanate of the adhesive The component reacts preferentially with the amino group of the amino silane coupling agent (D) over the polyol component of the adhesive.
  • the physical properties of the laminate By inhibiting the curing of the adhesive component not only in the vicinity of the interface between the ink layer and the adhesive layer but also in the adhesive layer, the physical properties of the laminate, particularly the retort suitability, tend to be reduced.
  • an excess amino-based silane coupling agent in the ink layer acts as a basic catalyst for the curing reaction of the adhesive, the viscosity of the adhesive layer during curing increases. As a result, the adhesive layer in the middle of curing cannot spread evenly with respect to the ink layer, and the appearance of the laminate tends to deteriorate. It is more preferable in terms of retort suitability and appearance when the content of the amino-based silane coupling agent (D) is within the above range.
  • the content of the amino silane coupling agent (D) is more preferably 0.3 to 5% by mass.
  • the amino silane coupling agent (D) has a primary amino group.
  • the primary amino group include an amino group and an aminoalkyl group having 1 to 8 carbon atoms, preferably 2 to 6 carbon atoms.
  • Examples of such compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and the like.
  • the amino-based silane coupling agent having a primary amino group also has a secondary amino group.
  • the cross-linking reactivity of alkoxysilyl groups in the same molecule is particularly excellent, and the laminate appearance, laminate strength, and retort suitability are particularly good.
  • examples of such compounds include N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and the like.
  • the amino silane coupling agent preferably has a secondary amino group and four or more alkoxy groups.
  • Secondary amino groups tend to have poorer crosslinking reactivity of alkoxysilyl groups than primary amino groups, but the presence of four or more alkoxy groups increases the crosslink density, so primary amino groups
  • the appearance of the laminate is as good as the amino-based silane coupling agent having a group.
  • the upper limit of the number of alkoxy groups is not particularly limited, but is, for example, 9 or less, preferably 6 or less.
  • the alkoxy group preferably has 1 to 5 carbon atoms.
  • Examples of such compounds include bis (3-trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) amine, bis (3-methyldimethoxysilylpropyl) amine, bis (triethoxysilylmethyl) amine, N, And N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine.
  • the above-mentioned embodiment improves the adhesiveness of a base material and an ink layer, the strength improvement of an ink layer, friction resistance, other than a lamination use, Effects such as heat resistance can be achieved. Therefore, naturally, the above-described embodiment can be suitably used for applications other than the laminate application.
  • the organic solvent used in the non-aqueous printing ink composition includes aromatic organic solvents such as toluene and xylene; ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone; methyl acetate, ethyl acetate, acetic acid Ester organic solvents such as n-propyl, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; methanol, ethanol, n-propanol, isopropanol, n-butanol, propylene glycol monoethyl ether, propylene Known organic solvents such as alcohol-based organic solvents such as glycol monomethyl ether and ethylene glycol monopropyl ether can be used, and they may be used in combination.
  • aromatic organic solvents such as toluene and xylene
  • an organic solvent not containing an aromatic organic solvent such as toluene and xylene is more preferable. More preferably, an organic solvent containing no ketone organic solvent such as methyl ethyl ketone (hereinafter referred to as “MEK”) is more preferable.
  • MEK methyl ethyl ketone
  • the content of water is preferably 10.0% by mass or less in the total mass of the non-aqueous printing ink composition. It is more preferably 0.0% by mass or less, and it may be particularly preferable that no water is contained except for the water content inevitably contained in each component of the non-aqueous printing ink composition.
  • the non-aqueous printing ink composition can appropriately contain known additives as additives, and known additives such as pigment derivatives, dispersants, wetting agents are used as necessary in the production of the ink composition.
  • Adhesion aids, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, wax components, silica particles, plasticizers, isocyanate curing agents, and amino-based silane coupling agents (D) other than those described above Silane coupling agents, chelating agents, and the like can be used.
  • the dispersant is added. It can also be used together.
  • the dispersant anionic, nonionic, cationic, amphoteric surfactants can be used.
  • a dispersant it is preferably 0.01% by mass or more with respect to 100% by mass of the total mass of the ink from the viewpoint of the storage stability of the ink, and is contained in the ink at 0.1 to 10.0% by mass. More preferably.
  • the ink composition is preferably contained at 0.01% by mass or more with respect to the total mass of the ink and 5% by mass or less from the viewpoint of suitability for lamination. Further, it is more preferably contained in the range of 0.1 to 3% by mass.
  • the non-aqueous printing ink composition is produced by dissolving and / or dispersing a colorant such as vinyl chloride-acrylic copolymer resin (A), polyurethane resin (B), or pigment in an organic solvent.
  • a colorant such as vinyl chloride-acrylic copolymer resin (A), polyurethane resin (B), or pigment in an organic solvent.
  • a pigment dispersion in which a pigment is mixed with a polyurethane resin (B), a vinyl chloride-acrylic copolymer resin (A), and, if necessary, the dispersant is dispersed in an organic solvent is obtained.
  • a non-aqueous printing ink composition by blending the obtained pigment dispersion with a polyurethane resin (B) and / or a vinyl chloride-acrylic copolymer resin (A), or other resins and additives as necessary. Can be manufactured.
  • the particle size distribution of the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion processing time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to.
  • the disperser generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.
  • the step of obtaining the pigment dispersion is also referred to as a kneading step, and the step of blending the obtained pigment dispersion with a polyurethane resin, other resins, organic solvents, and other compounds as necessary is also referred to as a thinning step.
  • the polyurethane resin (B) and / or the vinyl chloride-acrylic copolymer resin (A) is preferably added in both the milling process and the thinning process as described above. On the other hand, it may be added.
  • the ink composition contains the additive as a general method for containing the amino silane coupling agent (D) in the ink composition.
  • the method is not particularly limited.
  • (1) Amino silane coupling agent is added all at once in the kneading process
  • (2) Amino silane coupling agent is added in the thinning process after kneading
  • the amino silane coupling agent (D) is added in the kneading process
  • the dispersion stability of the ink composition tends to be improved.
  • a method of adding to the ink composition immediately before printing is preferable.
  • the ink When air bubbles or unexpectedly coarse particles are contained in the ink, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter.
  • a conventionally well-known filter can be used.
  • the viscosity of the non-aqueous printing ink composition produced by the above method is such that the viscosity at 25 ° C. with a B-type viscometer is 40 to correspond to high-speed printing (50 to 300 m / min) in gravure printing, flexographic printing, and the like.
  • a viscosity range of ⁇ 500 mPa ⁇ s is preferred. More preferably, it is 50 to 400 mPa ⁇ s.
  • This viscosity range corresponds to a viscosity of 9 to 40 seconds in Zahn cup # 4.
  • the viscosity of the gravure ink composition can be adjusted by adjusting the type and amount of raw materials used and the particle size and particle size distribution of the organic pigment in the ink.
  • the said viscosity is a viscosity measured at 25 degreeC with the Tokimec B-type viscometer.
  • the viscosity of the non-aqueous printing ink composition can be adjusted by appropriately selecting the type and amount of raw materials used, for example, the amount of binder resin, colorant, organic solvent and the like.
  • the viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink.
  • a printed matter in which an ink layer is formed on a printing substrate can be produced by printing the ink composition on a substrate such as a film substrate and drying or curing the ink composition.
  • examples of the substrate that can be used for the printed material include a plastic substrate, a paper substrate, and an aluminum substrate.
  • plastic substrates include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate and polylactic acid, polystyrene resins such as polystyrene, AS resin and ABS resin, nylon, polyamide, polyvinyl chloride, polyvinylidene chloride and cellophane.
  • a film-like or sheet-like base material made of paper, aluminum, or a composite material thereof; and a vapor-deposited base material obtained by vapor-depositing an inorganic compound such as silica, alumina, or aluminum on polyethylene terephthalate or nylon film.
  • the vapor deposition base material may be subjected to a coating treatment with a primer such as polyvinyl alcohol after being subjected to a vapor deposition treatment on a surface of a metal oxide such as silica or alumina.
  • the substrate may be a substrate treated with an additive such as an antistatic agent, an ultraviolet ray inhibitor, or a plasticizer, or a substrate that has been subjected to a surface treatment such as low-temperature plasma treatment or corona treatment, if necessary. good.
  • an additive such as an antistatic agent, an ultraviolet ray inhibitor, or a plasticizer
  • a substrate that has been subjected to a surface treatment such as low-temperature plasma treatment or corona treatment, if necessary. good.
  • a plastic base material which does not have a vapor deposition layer, what the printing surface is corona-treated among the said base materials is preferable.
  • the paper base material is ordinary paper or cardboard, and the film thickness is not particularly specified. For example, 0.2 to 1.0 mm and 20 to 150 g / m 2 can be used, and the printing surface is corona. It may be processed.
  • the surface of the paper substrate may be vapor-deposited with a metal such as aluminum for the purpose of imparting design properties, and surface coating with an acrylic resin, urethane resin, polyester resin, polyolefin resin, or other resin. Further, surface treatment such as corona treatment may be applied. Examples thereof include coated cardboard and marie coated paper.
  • Printing on the printing substrate can be performed by a known printing method such as gravure printing or flexographic printing, but printing by a gravure printing method is particularly preferable.
  • a gravure printing method such as engraving type and corrosion type are used.
  • An ink composition diluted with a diluting solvent to a viscosity and concentration suitable for gravure printing is supplied to each printing unit alone or mixed, passed through an oven after printing, dried or cured, and an ink layer is formed. It is formed.
  • the oven temperature is usually 30 ° C. or higher, for example 40 to 80 ° C., and the printing speed is usually 50 to 300 m / min.
  • the ink composition contains an amino silane coupling agent (D), particularly in the winter when the printing environment is low, the crosslinking reaction by the amino silane coupling agent is surely advanced to cure the ink composition. It is preferable to perform laminating after 12 hours or more have elapsed since printing.
  • D amino silane coupling agent
  • the printed matter obtained by printing the ink composition can be laminated to form a laminate by further laminating the film through an adhesive layer.
  • the laminate can be obtained by applying at least one layer of lamination to the printed material.
  • the laminate is a normal extract in which a plastic substrate is laminated via a molten polyethylene resin after applying various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium on the printed surface of the printed matter.
  • the adhesive lamination method (extrusion laminating), urethane-based adhesives, etc. are applied to the printed surface, and the plastic substrate is laminated on top of it.
  • the non-solvent laminating method is used. Can be obtained by a known laminating process such as a direct laminating method.
  • the dry laminating method is a method in which an adhesive is diluted to an appropriate viscosity with an organic solvent, applied to the printed surface of the obtained printed matter, dried and then pressure bonded to a sealant for lamination.
  • an adhesive used for adhering the sealant, a two-component type of a polyol component and a polyisocyanate component is mainly used.
  • Dry laminate adhesives are broadly classified into polyester adhesives in which the polyol component is a polyester polyol resin, and polyether adhesives in which the polyol component is a polyether polyol resin.
  • polyester adhesive examples include TM-250HV / CAT-RT86L-60 and TM-550 / CAT-RT37 manufactured by Toyo Morton Co., Ltd.
  • polyether adhesive examples include TM-314 / CAT-14B.
  • the solid coating amount of adhesive in the dry lamination method said polyester-based adhesive generally is 1.5 ⁇ 4g / m 2, preferably 2.5 ⁇ 3.5g / m 2, 1.5 ⁇ 2. 5 g / m 2 is defined as the low coating amount region.
  • the above polyether-based adhesive is generally in the range of 1 ⁇ 3g / m 2, preferably 1.5 ⁇ 2.5g / m 2, 1.0 ⁇ 2.5g / m 2 low coating weight region Is done.
  • the effect of improving the appearance is easily obtained even in a low coating amount region.
  • the coating amount in the low coating amount region is preferably in the range of 1.4 to 2.4 g / m 2 and more preferably in the range of 1.8 to 2.2 g / m 2 from the viewpoint of achieving both production cost and appearance. preferable.
  • the solventless laminating method is a method in which an adhesive having a solid content of 100% is applied to the printing surface of a printed material, and is laminated by pressing with a sealant.
  • the adhesive a two-component type of a polyol component and a polyisocyanate component is mainly used as in the case of the dry laminate adhesive, and specifically, EA-N373A / B manufactured by Toyo Morton Co., Ltd. can be mentioned.
  • the solid content coating amount of a general adhesive in the solventless laminating method is preferably 1 to 5 g / m 2 depending on the application, and is generally in the range of 1.5 to 3.5 g / m 2 .
  • the non-aqueous printing ink composition an effect of improving the appearance is easily obtained even in a low coating amount region.
  • the coating amount in the low coating amount region is preferably in the range of 1.4 to 2.4 g / m 2 and more preferably in the range of 1.8 to 2.2 g / m 2 from the viewpoint of achieving both production cost and appearance. preferable.
  • Examples of the film to be bonded to the printed material by laminating include the above-mentioned various films used for the printing substrate film, and transparent substrates such as cellophane. Specific examples include TUX-FCD (LLDPE) manufactured by Mitsui Chemicals Tosero Co., Ltd. and ZK93KM (CPP) manufactured by Toray Industries, Inc. Further, for the purpose of improving the gas barrier property, water vapor barrier property and the like of the laminate as a packaging material, a metal foil or a metal vapor deposition film may be used, and the aluminum foil is preferable as the metal foil. As a metal vapor deposition film, an aluminum vapor deposition film is preferable, for example, Reiko Co., Ltd.
  • PET represents a polyethylene terephthalate film
  • LLDPE represents a linear low density polyethylene film
  • CPP represents an unstretched polypropylene film.
  • a laminate having an adhesive layer and a base material in order on the printed base material is obtained.
  • the substrate to be bonded last becomes the sealant layer.
  • the sealant surfaces are heat-sealed (heat-sealed) and formed into a packaging bag. Therefore, a film for imparting heat sealability is used for the sealant that hits the innermost side in the packaging bag.
  • polyolefin base materials such as an unstretched polyethylene base material or a polypropylene base material, etc. are mentioned.
  • the packaging bag is filled with contents and used as a packaging material for food, medical products, cosmetics, and the like.
  • the hydroxyl value is a value obtained by converting the amount of hydroxyl group in 1 g of resin calculated by esterifying or acetylating the hydroxyl group in the resin with an excess of anhydrous acid and back titrating the remaining acid with alkali to the number of mg of potassium hydroxide. Thus, it was determined according to JIS K 0070 (1992).
  • the amine value is the number of mg of potassium hydroxide equivalent to the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of resin.
  • the amine value was measured by the following method. -Measuring method of amine value 0.5-2g of sample is precisely weighed (sample amount: Sg). 30 mL of neutral ethanol (BDG neutral) is added to the accurately weighed sample and dissolved. The resulting solution is titrated with a 0.2 mol / l ethanolic hydrochloric acid solution (titer: f).
  • GPC gel permeation chromatography
  • Embodiment I (Synthesis Example I-1) [Polyurethane resin PU1] 150 parts of a polyester diol (hereinafter “PMPA”) obtained from adipic acid having a number average molecular weight of 2000 and 3-methyl-1,5-pentanediol, 20 parts of polypropylene glycol (hereinafter “PPG”) having a number average molecular weight of 2000 30 parts of PPG having an average molecular weight of 1000, 58.8 parts of isophorone diisocyanate (hereinafter “IPDI”), and 64.7 parts of ethyl acetate were reacted at 80 ° C.
  • PMPA polyester diol
  • PPG polypropylene glycol
  • IPDI isophorone diisocyanate
  • IPDA isophorone diamine
  • IBPA iminobispropylamine
  • 2EtAm 2-ethanolamine
  • IPA ethyl acetate / isopropanol
  • the resulting emulsion was precipitated with sodium chloride, filtered, washed, and dried to obtain a vinyl chloride-acrylic copolymer resin (A1). Further, vinyl chloride-acrylic copolymer resin (A1) was dissolved in ethyl acetate to obtain a varnish (AA1) having a solid content of 30%.
  • the content of 2-hydroxypropyl acrylate in A1 was 15.0%, the weight average molecular weight was 50000, and the glass transition temperature was 69 ° C.
  • Examples I-2 to I-20 Preparation of non-aqueous gravure inks S2 to S20
  • Pigments shown in Table 3-1 Polyurethane resins (PU1 to PU6) in Table 1, vinyl chloride-acrylic copolymer varnishes (AA1 to AA6) in Table 2, and resins and additives listed in Table 3-1. And mixing in the same manner as in Example I-1 to obtain non-aqueous gravure inks S2 to S20.
  • Abbreviations in Table 3-1 represent the following.
  • Solvain TAO hydroxyl group-containing vinyl chloride-vinyl acetate copolymer manufactured by Nissin Chemical Industry Co., Ltd.
  • N-phenyl-3-aminopropyltrimethoxysilane silane compound Note that N-phenyl-3-aminopropyltrimethoxysilane was added immediately before printing and mixed well for printing (addition amount shown in the table) Is a part by mass with respect to 100 parts by mass of the ink composition).
  • Non-aqueous gravure inks T1 to T18 were obtained in the same manner as in Examples I-1 to I-20 except that the raw materials shown in Table 3-2 were used. In addition to the above, the abbreviations in Table 3-2 represent the following.
  • S-180 Polyester resin manufactured by Takamatsu Yushi Co., Ltd. Glass transition temperature 60 ° C.
  • Duranate P-301-75E Hexamethylene diisocyanate trimethylolpropane adduct (trifunctional isocyanate) manufactured by Asahi Kasei Chemicals Corporation Duranate P-301-75E was added immediately before printing and mixed well for printing (addition amounts shown in the table are parts by mass with respect to 100 parts by mass of the ink composition).
  • helio 175 line gradation version plate type Elon Gate, 10% gradation from 100% to 10%, 10% to 5% gradation at 5%, 5% or less is 1% gradation, and a biaxially oriented polypropylene (OPP) film (FORP manufactured by Futamura Chemical Co., Ltd.) having a thickness of 20 ⁇ m and a corona discharge treatment and a corona discharge treatment polyester (PET) film having a thickness of 12 ⁇ m (Toyobo) E-5100), a corona discharge-treated surface, was printed at a printing speed of 50 m / min to obtain printed materials G1 (OPP) and H1 (PET).
  • OPP biaxially oriented polypropylene
  • PET corona discharge treatment polyester
  • the printing conditions are as follows: printing is performed at a high temperature and high humidity of 4000 m, temperature of 28 ° C., humidity of 65%, and the substrate transferability is confirmed at the 3% gradation portion, and the plate covering property is confirmed by idling for 60 minutes after printing. did.
  • a polyethyleneimine-based anchor coating agent (EL420 manufactured by Toyo Morton Co., Ltd.) was further coated with a 1% by mass methanol solution, and low density polyethylene (Novatech LC600, manufactured by Nippon Polychem Co., Ltd.) was applied. Extrusion was performed by melting and extruding at 315 ° C. and bonding with unstretched polypropylene (FCMN, film thickness 40 ⁇ m, manufactured by Tosero).
  • Example I-22 to I-40 Printed materials G2 to G20 (OPP) and H2 to H20 (PET) were obtained in the same manner as in Example I-21 except that the inks shown in Table 4-1 were used. Further, extrusion lamination was performed on each printed matter by the same method as described above.
  • Plate fogging evaluation was performed for the non-aqueous gravure inks S1 to S20 (Examples) and T1 to T18 (Comparative Examples). The evaluation was performed based on the colored area on the plate after 60 minutes of idling. ⁇ The plate covering area is 0 to 5%. B: The plate covering area is 6 to 10%. ⁇ : The plate covering area is 11 to 30%. ⁇ ⁇ : The plate covering area is 31 to 50%. X: The plate covering area is more than 50%. In addition, (circle) and (triangle
  • Example I-41 ⁇ Color of non-aqueous gravure ink / white printing> (Evaluation for laminating)
  • MEK methyl ethyl ketone
  • NPAC isopropanol
  • IPA isopropanol
  • the obtained printed matter J1 was further coated with a polyether urethane laminate adhesive (TM320 / CAT13B manufactured by Toyo Morton Co., Ltd.) as an ethyl acetate solution having a solid content of 25% by mass to 1.5 g / m 2 and dried. Then, it was bonded to unstretched polypropylene (FCMN, film thickness 40 ⁇ m, manufactured by Tosero Co., Ltd.) and dry laminated.
  • TM320 / CAT13B manufactured by Toyo Morton Co., Ltd.
  • Examples I-42 to I-56 Printed materials J2 to J16 were obtained in the same manner as in Example I-41 except that the inks listed in Table 4-2 were used. Further, each printed material was dry laminated.
  • ⁇ Lamination strength> The ink part of the dry laminate laminate was cut at a width of 15 mm, peeled off at the ink surface and the substrate surface, and the peel strength (laminate strength) was measured with an Intesco 2010 universal tensile tester. The practical level is 0.7 N / 15 mm or more.
  • a biaxially stretched polypropylene (OPP) film (FORP manufactured by Futamura Chemical Co., Ltd.) treated with a corona discharge of 25 ⁇ m by a gravure printing machine equipped with a semi-solid plate (plate type compressed) of 100% Helio 175 line at a printing speed of 50 m / min.
  • the printed material O1 was obtained by printing in the order of film base material / white (solid pattern) / indigo (semi-solid pattern).
  • Example I-58 to I-77 Printed materials O2 to O21 were obtained in the same manner as in Example I-57 except that the ink or paper substrate shown in Table 6-1 (product name: Ryuou coated paper 65 g / m 2 manufactured by Daio Paper Co., Ltd.) was used.
  • ⁇ Abrasion resistance> For the printed materials O1 to O21 (Examples) and Q1 to Q20 (Comparative Examples), the film strength was measured using a Gakushoku type friction fastness tester manufactured by Tester Sangyo Co., Ltd., and evaluated according to the following evaluation criteria. The results are shown in Table 6-1 and Table 6-2. The measurement conditions were a test piece width of 20 mm, a load of 0.2 gf, 20 reciprocations, and Kanakin No. 3. ⁇ : No ink film is removed. ⁇ ⁇ : The area where the ink film is taken is less than 10%. ⁇ ... The area where the ink film is taken is 10% or more and less than 30%. ⁇ ⁇ ... The area where the ink film is taken is 30% or more and 50%. Less than x ⁇ The entire surface is taken. Note that ⁇ and ⁇ are ranges where there is no practical problem.
  • ⁇ Blocking resistance> The printed materials O1 to O21 (Examples) and Q1 to Q20 (Comparative Examples) are cut into a size of 4 cm ⁇ 4 cm, and a soft PVC sheet or high-quality paper cut into the same size is overlapped with the printing surface.
  • the blocking resistance evaluation with a soft PVC sheet was applied with a load of 0.5 kg / cm 2 and left for 15 hours in an atmosphere of 50 ° C.-80% RH. Was determined visually.
  • the evaluation of blocking resistance with fine paper was applied with a load of 5.0 kg / cm 2 and left for 15 hours in an atmosphere of 50 ° C.-80% RH, and then the printed surface and fine paper were peeled off to remove the printed film. The condition was judged visually.
  • the determination criteria were as follows. ⁇ ⁇ Slightly peels off the ink film No problem in practical use ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ The area where the ink film is taken is 50% or more, and there are practical problems. ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ The ink film is taken in. There is no range.
  • Printed products O1 to O21 (Examples) and Q1 to Q20 (Comparative Examples) were cut to a size of 2 cm ⁇ 20 cm, and commercially available margarine (trade name: manufactured by Neosoft Snow Brand Milk Products Co., Ltd.) melted on the printing surface After coating and allowing to stand at 25 ° C. for 6 hours, the test piece was rubbed 10 times with a Gakushin type friction fastness tester manufactured by Tester Sangyo Co., Ltd., and the degree of ink peeling was visually determined.
  • the determination criteria were as follows.
  • the non-aqueous gravure ink containing vinyl chloride-acrylic copolymer resin (A) and polyurethane resin (B) as essential components as a binder resin is leveling, transferability to the substrate, and plate fogging. It was found that the printability such as was good. Furthermore, a laminate having a high laminate strength could be obtained.
  • the gravure ink for laminating containing an amino group-containing silane compound has good leveling properties, gravure printing suitability such as transferability to a substrate and plate fogging property, and the physical properties of the ink film are also good. Moreover, it turned out that it is a gravure ink which shows the property excellent in the lamination strength and external appearance after a lamination process.
  • Embodiment II (Synthesis of polyurethane urea resin) [Synthesis Example II-1] To a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, PMPA2000 (Kuraray polyol P-2010, 3-methyl-1,5-pentanediol and adipic acid copolymer, number average molecular weight) 2000, manufactured by Kuraray Co., Ltd.) 11.49 parts, PPG 2000 (EXCENOL 2020, polymer of propylene oxide, number average molecular weight 2000, manufactured by Asahi Glass Co., Ltd.) 11.49 parts, isophorone diisocyanate (hereinafter also abbreviated as IPDI) 5.11 parts, ethyl acetate 11 .86 parts and tin 2-ethylhexanoate 0.003 part were allowed to react at 90 ° C.
  • IPDI isophorone diisocyanate
  • a urethane prepolymer having an isocyanate group at the terminal Solution was obtained.
  • IPDA isophoronediamine
  • IPA isopropyl alcohol
  • the resulting urethane prepolymer solution is gradually added to the mixture at room temperature, and then reacted at 50 ° C. for 1 hour to give a polyurethane having a solid content of 30%, a weight average molecular weight of 50000, and a hydroxyl value of 5.4 mgKOH / g.
  • a urea resin solution ⁇ B1> was obtained.
  • aqueous emulsifier solution (20.0 kg) in which stearyl alcohol (31.7 g), cetyl alcohol (43.0 g), and sodium lauryl sulfate (66.4 g) were dissolved in advance was added to the vessel, and homogenized for 30 min. A monomer dispersion was obtained. The temperature inside the container was kept at 50 ° C. and the polymerization was started. After 8 hours, the pressure in the container began to drop. After the unreacted vinyl chloride monomer in the polymerization machine was recovered and the container was cooled, the latex Paid out. (The conversion of the vinyl chloride monomer was about 90%).
  • the latex was dried with a two-fluid nozzle spray dryer (inlet 110 ° C./outlet 50 ° C.) to obtain a powdered vinyl chloride / polybutyl acrylate graft copolymer resin. This was diluted with ethyl acetate to a solid content of 30% to obtain a butyl acrylate grafted vinyl chloride copolymer solution ⁇ A2>.
  • Example II-1 5 parts of polyurethane urea resin solution ⁇ B1>, 10 parts of pigment ⁇ C2> (Lionol Blue FG-7400G, CI Pigment Blue 15, manufactured by Toyocolor Co., Ltd.), vinyl chloride-acrylate copolymer solution ⁇ A1 > 5 parts of (VINNOL E15 / 40A, hydroxyl group-containing vinyl chloride-acrylic acid ester copolymer, manufactured by Wacker, solid content 30% by mass ethyl acetate solution, vinyl chloride monomer-derived structure ratio: 84% by mass), acetic acid After stirring and mixing 20 parts of ethyl / IPA mixed solvent (mass ratio 75/25) and grinding with a sand mill, 32.5 parts of polyurethane urea resin solution ⁇ B1>, vinyl chloride-acrylate copolymer solution ⁇ A1 > 7.5 parts and 20 parts of ethyl acetate / IPA mixed solution (
  • Example II-2 to II-19 Reference Examples II-1 to II-2, Comparative Examples II-1 to II-6
  • Ink compositions ⁇ i-2 to i-27> were obtained in the same manner as in Example II-1 with the charging ratios shown in Tables 8 and 9.
  • the following were used as the pigment (C).
  • ⁇ C1> Titanium oxide, TITON R45M, manufactured by Sakai Chemical
  • ⁇ A1> the following were used as the vinyl chloride-vinyl acetate copolymer solution.
  • ⁇ A2> butyl acrylate grafted vinyl chloride copolymer, solid content 30% by mass ethyl acetate solution, ratio of structure derived from vinyl chloride monomer: 80% by mass
  • resins other than the polyurethane urea resin and the vinyl chloride-acrylic ester copolymer the following resins were used as resin solutions diluted with ethyl acetate to a solid content of 30% by mass.
  • Si-1 N-phenyl-3-aminopropyltrimethoxysilane
  • Si-2 3-aminopropyltrimethoxysilane
  • Si-3 bis (3-trimethoxysilylpropyl) amine
  • Si-4 N-2- (amino Ethyl) -3-aminopropyltrimethoxysilane isocyanic curing agent (SP curing agent, manufactured by Toyo Ink Co., Ltd.)
  • the obtained ink composition was subjected to a corona discharge-treated PET film (E5100) having a thickness of 12 ⁇ m at a printing speed of 150 m / min and a drying temperature of 60 ° C. using a gravure printing machine equipped with a gradation pattern gravure plate having a plate depth of 30 to 3 ⁇ m. , Manufactured by Toyobo Co., Ltd.) to obtain a printed matter.
  • an adhesive for dry lamination (TM-250HV / CAT-RT86L-60 manufactured by Toyo Morton Co., Ltd.) was applied in a solid content of 2.2 g / m 2 , 2.0 g / m 2 , and 1 .8 g / m 2 and coated with an aluminum foil (general aluminum foil AIN30H-0, manufactured by Showa Aluminum) using a dry laminator at a line speed of 150 m / min.
  • a laminate precursor having an adhesive layer / aluminum foil in this order is obtained, and an adhesive is applied to the aluminum foil surface of the laminate precursor in the same manner as described above to obtain a CPP film (ZK93KM, Toray Industries, Inc.).
  • Adhesive force 1.8N or more 4 Adhesive force 1.2N or more, less than 1.8N 3: Adhesive force 0.8N or more, less than 1.2N 2: Adhesive force 0.4N or more, less than 0.8N 1: Adhesion Force Less than 0.4 N
  • Adhesion Force 0.8 N or more is preferable.
  • the laminate appearance after the retort treatment was visually observed and evaluated according to the following criteria. Evaluation was made at a plate depth of 30 ⁇ m. ⁇ : No change in appearance was observed. (Triangle
  • the above-mentioned ink composition was evaluated for plate fogging. The evaluation was performed based on the colored area on the plate after 60 minutes of idling. ⁇ The plate covering area is 0 to 5%. B: The plate covering area is 6 to 10%. ⁇ : The plate covering area is 11 to 30%. ⁇ ⁇ : The plate covering area is 31 to 50%. X: The plate covering area is more than 50%. In addition, (circle) and (triangle
  • the ink composition containing the vinyl chloride-acrylic copolymer resin (A) and the polyurethane urea resin (B) has good leveling properties and printability.
  • the laminate appearance, laminate strength, and retort suitability were improved.
  • the laminate appearance is particularly good. became.
  • the appearance of the laminate and the laminate strength were particularly good because the hydroxyl value of the polyurethane urea resin was in the range of 1 to 15 mgKOH / g.
  • the amino-type silane coupling agent to be used has a primary amino group, or a secondary amino group and 4 or more alkoxy groups, the further improvement of the laminated body external appearance was confirmed. Since the amino-based silane coupling agent has a primary amino group and a secondary amino group, the appearance of the laminate is the best.

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  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Printing Methods (AREA)
  • Laminated Bodies (AREA)

Abstract

Un mode de réalisation de la présente invention concerne une composition d'encre d'impression non aqueuse contenant une résine liante comprenant : une résine copolymère chlorure de vinyle - acrylique (A) ; et une résine de polyuréthane (B), la teneur en structure issue du chlorure de vinyle étant de 75 à 95% en masse dans 100% en masse de la résine copolymère chlorure de vinyle - acrylique (A).
PCT/JP2017/024507 2016-07-04 2017-07-04 Composition d'encre d'impression non aqueuse Ceased WO2018008639A1 (fr)

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JP7110508B1 (ja) 2022-03-31 2022-08-01 サカタインクス株式会社 裏刷り用活性エネルギー線硬化型インキ組成物

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WO2021053424A1 (fr) * 2019-09-20 2021-03-25 3M Innovative Properties Company Film de filtre optique d'erreur à front d'onde faible
JP7608690B2 (ja) * 2021-11-30 2025-01-07 サカタインクス株式会社 脱離用プライマー組成物層を有する積層体
JP2025132586A (ja) * 2024-02-29 2025-09-10 ａｒｔｉｅｎｃｅ株式会社 グラビア又はフレキソインキ

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