JP2018002905A - Non-aqueous printing ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-aqueous printing ink composition having excellent leveling properties and excellent printability.SOLUTION: A non-aqueous printing ink composition contains a binder resin containing a polyvinyl chloride-acryl copolymer resin (A) and a polyurethane resin (B). In the polyvinyl chloride-acryl copolymer resin (A) 100 mass%, the content of a polyvinyl chloride-derived structure is 75-95 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a non-aqueous printing ink composition, and further relates to the printed matter and a laminate.

  When using film base materials such as OPP film, PET film, NY film, paper base materials such as coated cardboard, and aluminum base materials as packaging materials, printing ink is usually used to decorate the base material or protect the surface. The printing that was done is given. The substrate on which printing has been performed is then sent to a post-processing step such as laminating through a slitting process, and finally becomes a package for food packaging, cosmetic packaging, or any other application.

  In general, printing inks can be broadly classified into water-based inks and non-aqueous inks. 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. However, since 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.

  Further, in printing inks, further improvement in printability is desired from the viewpoint of color tone reproducibility of colors, characters, patterns and the like, mass productivity, and the like. One of the indexes of printability of non-aqueous inks is printability in gravure printing. For example, in many cases of printing on the film base and paper base, a gravure printing method is employed. The plate used for the gravure printing method is an intaglio plate with characters and patterns. Soak the ink in the plate to the extent that ink enters this cell, and rotate the plate while scraping off excess ink with a doctor blade. Then, the gravure ink is transferred to the base material and allowed to become thick. 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.

  Problems with printability of this gravure printing method include (I) plate fogging property and (II) plate clogging property. (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. (II) 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.

  Not only the gravure printing method but also other printing methods such as a flexographic printing method similarly have a problem of printability. For example, 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 inadequate printing defects and ink that is buried in the gaps between halftone dots (highlighted areas) of the plate and the halftone dots are crushed (plate squeezing properties).

  In order to solve the problem of printability, it is necessary to improve both printing conditions and ink. For example, improvement in plate fog is attempted by devising a device of a gravure printing machine (Patent Document 1). In addition, regarding the plate, that is, the use of aromatic organic solvents such as toluene under the Air Pollution Control Law has been recommended by the world, studies using ester / alcohol solvents have been made (patents) Reference 2).

  Further, the types of printing base materials are classified according to applications, such as for laminating (back printing), for surface printing, for paper, for aluminum, or for an aluminum evaporation base material. However, there are some common 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. In order to solve these problems, 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).

  As described in the above-mentioned patent documents, various contrivances have been made for printing inks, but none of the non-aqueous printing inks satisfy the printability and leveling properties at the same time.

JP-A-10-305555 Japanese Patent Laying-Open No. 2015-038177 JP2013-194081A JP 2005-298618 A

  An object of this invention is to provide the non-aqueous printing ink composition excellent in printability and leveling property.

  As a result of intensive studies on the above problems, the present inventor has found that the problem can be solved by using the following non-aqueous printing ink composition, and has reached the present invention.

[1] One aspect of the present invention contains a binder resin containing a vinyl chloride-acrylic copolymer resin (A) and a polyurethane resin (B),
It is related with the non-aqueous printing ink composition whose content rate of the structure derived from a vinyl chloride in 100 mass% of said vinyl chloride-acrylic copolymer resins (A) is 75-95 mass%.
[2] In a further aspect of the present invention, the solid content mass ratio between the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) is (A) :( B) = 5: 95-60. : It is related with the said non-aqueous printing ink composition which is the range of 40.
[3] In a further aspect of the present invention, the solid content mass ratio between the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) is (A) :( B) = 5: 95-50. : It is related with the said non-aqueous printing ink composition which is the range of 50.
[4] In a further embodiment of the present invention, the polyurethane resin (B) includes a structural unit derived from polyether polyol,
It is related with the said non-aqueous printing ink composition whose ratio of the structural unit derived from the said polyether polyol is the range of 5-80 mass% in 100 mass% of said polyurethane resins (B).
[5] In a further aspect of the present invention, the polyurethane resin (B) includes a structural unit derived from a polyester polyol,
It is related with the said non-aqueous printing ink composition whose ratio of the structural unit derived from the said polyester polyol is the range of 5-80 mass% in the said polyurethane resin (B) 100 mass%.
[6] In a further aspect of the present invention, the structural unit derived from a polyester polyol includes the structural unit derived from a polyester polyol obtained by reacting a diol having a branched structure with a dibasic acid. Related to things.
[7] 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.
[8] In a further embodiment of the present invention, the binder resin further contains at least one selected from the group consisting of vinyl chloride-vinyl acetate copolymer resin (b1) and cellulose resin (b2). The present invention relates to a printing ink composition.
[9] A further aspect of the present invention further comprises 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.
[10] A further aspect of the present invention relates to the above non-aqueous printing ink composition further containing an amino silane coupling agent (D).
[11] In a further aspect of the present invention, the amino silane coupling agent (D) has a primary amino group or a secondary amino group and four or more alkoxy groups. The present invention relates to an aqueous printing ink composition.
[12] A further aspect of the present invention relates to the above non-aqueous printing ink composition, wherein the amino silane coupling agent (D) has a primary amino group and a secondary amino group.
[13] A further aspect of the present invention relates to the non-aqueous printing ink composition, which is a gravure printing ink composition.
[14] A further aspect of the present invention relates to the above non-aqueous printing ink composition, which is a printing ink composition for laminating.
[15] 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 the vinyl chloride-derived structure in 100% by mass of the vinyl chloride-acrylic copolymer resin (A) is 75 to 95% by mass,
The solid content mass ratio between the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) is in the range of (A) :( B) = 5: 95 to 50:50,
The colorant (C) relates to a non-aqueous gravure ink composition for laminating containing a white inorganic pigment.
[16] Another aspect of the present invention relates to a printed matter having an ink layer formed on the printing substrate using the nonaqueous printing ink composition or the nonaqueous gravure ink composition for laminating.
[17] A further aspect of the present invention relates to the printed matter, wherein the printing substrate is a film.
[18] 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.

  ADVANTAGE OF THE INVENTION According to this invention, the non-aqueous printing ink composition excellent in printability and leveling property can be provided.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of constituent elements described below is an example of embodiments of the present invention, and the present invention is not limited to these contents unless it exceeds the gist. .

  This 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). It is related with the non-aqueous printing ink composition whose content rate of an origin structure is 75-95 mass%. Hereinafter, the non-aqueous printing ink composition of the present embodiment may be simply referred to as “ink composition”.

<Vinyl chloride-acrylic copolymer resin (A)>
The vinyl chloride-acrylic copolymer resin (A) is mainly composed of a copolymer of a vinyl chloride monomer and an acrylic monomer. The form of the copolymer is not particularly limited. For example, 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. .

In this embodiment, the ratio of the structure derived from the vinyl chloride monomer is 75 to 95% by mass in the solid content of 100% by mass of the vinyl chloride-acrylic copolymer resin (A). In this case, the solubility in an organic solvent is improved, and an effect of improving printability and leveling properties such as printing transferability and plate fogging property can be obtained. Furthermore, adhesion to a substrate, film (film) physical properties, laminate strength, etc. tend to be good. The ratio of the structure derived from the vinyl chloride monomer is more preferably from 80% by mass to 90% by mass in 100% by mass of the vinyl chloride-acrylic copolymer resin (A) solid content.
In addition, in this specification, 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 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. More preferably, it is 20-110 mgKOH / g, More preferably, it is 30-100 mgKOH / g.

  The glass transition temperature of the vinyl chloride-acrylic copolymer resin (A) is preferably 55 ° C to 85 ° C. Here, since the higher the glass transition temperature is, the harder the resin, the harder the binder resin is used in combination with the soft polyurethane resin (B) when the glass transition temperature is within the above range. The thickness / softness can be adjusted. The glass transition temperature of the vinyl chloride-acrylic copolymer resin (A) is more preferably 65 ° C 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 formula of FOX is represented by the following.
<FOX expression> 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... + Wn / Tgn
[In the FOX formula, the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n types of monomers is Tgi (K), the mass fraction of each monomer is Wi, and (W1 + W2 + ... + Wi +... Wn = 1). ]

  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.

  Although the example of the acrylic monomer which can be used for the vinyl chloride-acrylic copolymer resin (A) of this embodiment is demonstrated below, an acrylic monomer is not limited to these.

  In the following description, (meth) acryl or (meth) acrylate means methacryl and acryl, methacrylate and acrylate, respectively.

  As the acrylic monomer, a (meth) acrylic acid ester can be used. As an example of (meth) acrylic acid ester, (meth) acrylic acid alkyl ester is mentioned, 1-20 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, and 2-6 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, (meth) acrylic acid Examples include octadecyl. Furthermore, the alkyl group may further have a benzene ring structure. Examples of the benzene ring structure include monocyclic or condensed rings having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms. Among these, 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.

An acrylic monomer having a hydroxyl group can be used as the acrylic monomer. Examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) acrylic acid 3 -Hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, (meth) acrylic acid hydroxyalkyl esters such as 8-hydroxyoctyl, and polyethylene glycol mono (meta) ) Acrylate, polypropylene glycol mono (meth) acrylate, glycol mono (meth) acrylate such as 1,4-cyclohexanedimethanol mono (meth) acrylate, caprolactone modified (meth) acrylate, hydroxyethyl acrylamide, etc. It is below.
Among them, acrylic acid hydroxyalkyl ester is preferable, and the hydroxyalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 2 to 6 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group. Of these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate improve solubility in solvents and increase adhesion to substrates. More preferable. These can be used alone or in combination of two or more.

  Moreover, the acrylic monomer which has functional groups other than a hydroxyl group can also be used as an acrylic monomer. Examples of functional groups other than hydroxyl groups include carboxyl groups, amide bond groups, amino groups, alkylene oxide groups, and the like.

  Examples of carboxyl group-containing acrylic monomers 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, phthalic acid monohydroxypropyl (meth) acrylate, succinic acid monohydroxyethyl (meth) acrylate, β-carboxyethyl acrylate, 2-methacryloyloxyethyl hexahydrophthalic acid Etc. Further, esterified products of hydroxyalkyl (meth) acrylates with dicarboxylic acids such as maleic acid, monoethylmaleic acid, itaconic acid, citraconic acid, and fumaric acid can be used.

  Examples of acrylic monomers containing an amide bond 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. Although the repeating number of an alkylene oxide unit is not specifically limited, For example, it is 1-50, 1-30 are preferable and 1-20 are more preferable. Examples of 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). Examples include acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropyleneglycol (meth) acrylate, ethoxypolypropyleneglycol (meth) acrylate, phenoxypolyethyleneglycol (meth) acrylate, and phenoxypolypropyleneglycol (meth) acrylate.

  As an acrylic monomer, since the adhesiveness with respect to a base material and the solubility with respect to an organic solvent improve, the acrylic monomer which has an acrylic acid alkylester and a hydroxyl group is preferable, and the acrylic acid alkylester and the acrylic acid ester which has a hydroxyl group are more preferable. 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.

  Moreover, in one Embodiment, it is preferable that content of the acrylic acid ester containing a hydroxyl group is 5 mass% or more in an 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.

  An acrylic monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Further, the vinyl chloride-acrylic copolymer resin (A) of this embodiment may be further copolymerized with a double bond monomer other than the acrylic monomer. Examples of 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 bond 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) in this embodiment 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 in this embodiment. As a specific method, first, a vinyl chloride monomer and an acrylic monomer, which are liquefied by applying pressure, are placed in a reactor in which water and a suspending agent are placed in advance, and the monomer is very fine particles by stirring at high speed. To. Next, the polymerization reaction is started by putting an initiator for the polymerization reaction in a polymerization vessel and reacting under conditions of several atmospheric pressures and 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 μm, 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, production methods such as emulsion polymerization and bulk polymerization are 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. Examples of the peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, α, α′-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. Peroxyesters; 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; cumene hydro 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 peroxides such as peroxides; organic peroxides such as peroxydicarbonates such as bis (t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

  Examples of the azo compounds include 2,2′-azobisbutyronitriles 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), 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.

Further, 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 and a polymerization accelerator.

  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.

  By using the vinyl chloride-acrylic copolymer resin of this embodiment together with the polyurethane resin described later, the pigment dispersibility can be improved without increasing the viscosity. As a result, it is presumed that the effect of improving the leveling property and improving the printability is obtained. In addition, since the vinyl chloride-acrylic copolymer resin forms a high adhesion to the substrate and a strong film when the printed layer is formed, the effect of improving the friction resistance, oil resistance, and heat resistance is easily obtained. Further, when the laminate is further laminated, there is an advantage that the effect of improving the appearance of the laminate, the laminate strength and the retort suitability can be easily obtained by suppressing the penetration of the adhesive component into the ink layer. In addition, since it has a structure derived from an acrylic monomer such as an acrylic ester site, it has high compatibility with each component in the ink composition, so that a uniform ink layer can be formed to obtain a laminate having a better appearance. It is also advantageous in terms of ease. The above mechanism is inference and does not limit the present invention.

<Polyurethane resin (B)>
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, and the resulting ink composition From the standpoint of blocking resistance, the pigment can be appropriately dispersed by 15,000 or more, and more preferably 70,000 or less from the viewpoint of suppressing the increase in viscosity of the obtained ink composition. The weight average molecular weight of the polyurethane resin is more preferably 20,000 to 60,000.

  Further, the glass transition temperature is preferably −60 ° C. to 40 ° C., and further, the storage elastic modulus at 40 ° C. in the dynamic viscoelasticity measurement is preferably 1 to 100 MPa. In the polyurethane resin (B), the glass transition temperature is measured by a differential scanning calorimeter (DSC) according to JIS K 7121, and represents the middle point of the temperature range where the glass transition occurs.

  In addition, the polyurethane resin (B) preferably has an amine value or a 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 exist in the side chain and / or terminal of the polyurethane resin (B).

  In particular, when used for laminate printing described later, the hydroxyl value is preferably 1 to 15 mgKOH / g, more preferably 1 to 10 mgKOH / g. When the hydroxyl value is 1 mgKOH / g or more, 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. Further, when 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. In the polyurethane resin (B) of the present embodiment, hydroxyl groups can be added to the polyurethane resin (B) by any method, but hydroxyl groups are preferably 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. For example, 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.

  It does not specifically limit as a polyol, The polyol used for printing inks, such as a gravure ink and a flexo ink, can be used, and it can obtain by a polymerization reaction, a condensation reaction, a natural product, etc. For example, 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). It is 10-50 mass%.

Examples of the polyether polyol include polymer or copolymer polyether polyols such as methylene oxide, ethylene oxide, propylene oxide, and tetrahydrofuran. 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 base material is preferable. The number average molecular weight is preferably 500 to 10,000, and more preferably 1,000 to 5,000. The number average molecular weight is calculated from the hydroxyl value with the terminal being a hydroxyl group, and is obtained from (Equation 1).
(Formula 1) Number average molecular weight of polyol = 1000 × 56.1 × hydroxyl number of hydroxyl group / hydroxyl value

  The polyurethane resin (B) preferably contains a structural unit derived from polyester polyol, and the content thereof is preferably 5 to 90% by mass, and 5 to 80% by mass in 100% by mass of the solid content of the polyurethane resin (B). %, More preferably 20 to 75% by mass, and particularly preferably 30 to 70% by mass.

  Examples of the polyester polyol 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, polycarboxylic acids such as trimellitic acid and pyromellitic acid or anhydrides thereof, ethylene glycol, diethylene glycol, Triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 2methyl-1,3-propanediol, 2ethyl-2butyl-1,3propanediol, 1,4- Butanediol, 1,4-butynediol, 1 4-butylene diol, 1,3-butanediol, pentanediol, 3-methyl-1,5pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl-1,5-pentanediol, 1,12-octadecanediol Diols such as 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimer diol, hydrogenated dimer diol, or glycerin , Trimethylolpropane, trimethylolethane, 1 Condensates obtained by esterification reaction with saturated or unsaturated low molecular weight polyhydric alcohols such as 2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaesitol, etc .; polycaprolactone, And polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones such as polyvalerolactone and poly (β-methyl-γ-valerolactone). Among them, 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- A polyester polyol obtained from a diol having a branched structure such as pentanediol 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. Furthermore, a polyol having 3 or more hydroxyl groups and a polyvalent carboxylic acid having 3 or more carboxyl groups can be used in combination.

  The number average molecular weight of the polyester polyol is preferably 500 to 10,000. More preferably, it is 1,000-5,000. The number average molecular weight is determined by the above (Formula 1). The acid value of the polyester polyol used in this embodiment is preferably 1.0 mgKOH / g or less, and more preferably 0.5 mgKOH / g or less.

  Among the polyols, polyester polyols and polyether polyols are preferable 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.

  Examples of polyols other than the above-mentioned polyols 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 Or glycols obtained by adding propylene oxide; one or more hydroxyethyl, hydroxypropyl acrylate, acrylhydroxybutyl, etc., or their corresponding methacrylic acid derivatives in one molecule, for example, acrylic acid, methacryl Examples include acrylic polyols obtained by copolymerizing an acid or an ester thereof.

  Examples of the polyisocyanate include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. For example, 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, lysine diisocyanate, Cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate Nate, dimethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, bis Examples include -chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, dimerized isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group. These may be trimers to form an isocyanurate ring structure. These polyisocyanates can be used alone or in admixture of two or more. Of these, isocyanurate of tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate is preferable.

  Among the polyisocyanate compounds, isophorone diisocyanate, tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate are preferable, and isophorone diisocyanate is more preferable from the viewpoint of solubility.

  Examples of the amine chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, and a hydroxyl group on the side chain of the polyurethane urea resin. As chain extenders that can be added, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxy Water in the molecule such as ethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, di-2-hydroxypropylethylenediamine Amines having a group can also be used. These chain extenders can be used alone or in admixture of two or more. Moreover, if necessary, a polyfunctional amine chain extender can be used. Specifically, diethylenetriamine, iminobispropylamine: (IBPA, 3,3′-diaminodipropylamine), N- (3-aminopropyl) ) Butane-1,4-diamine: (spermidine), 6,6-iminodihexylamine, 3,7-diazanonan-1,9-diamine, N, N′-bis (3-aminopropyl) ethylenediamine. Of these, isophoronediamine, 2-hydroxyethylethylenediamine, hexamethylenediamine, and iminobispropylamine are preferable.

  Moreover, 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. Examples of such compounds include monoamine compounds, such as 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. Furthermore, when it is desired to introduce a carboxyl group into a polyurethane resin, amino acids such as glycine, L-alanine, glutamic acid, taurine, aspartic acid, aminobutyric acid, valine, aminocaproic acid, aminobenzoic acid, aminoisophthalic acid, sulfamic acid are polymerized. It can be used as a terminator. Alcohols such as ethanol and isopropyl alcohol can also be used. When using a polymerization terminator, the chain terminator and chain extender may be used together to carry out the chain extension reaction, and after the chain extension reaction has been performed to some extent with the chain extender, the end terminator is added alone. Thus, an end termination reaction may be performed. On the other hand, 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. For example, a polyol and polyisocyanate are optionally used in an inert solvent for the isocyanate group, and if necessary, a catalyst such as a urethanization catalyst is used at a temperature of 10 ° C. to 150 ° C., for example, 50 ° C. to 100 ° C. The prepolymer method of producing a polyurethane resin by producing a prepolymer having an isocyanate group at the terminal, and then reacting the prepolymer with an amine chain extender at, for example, 10 to 80 ° C. Is mentioned. The chain extension reaction between the urethane prepolymer and the amine chain extender can be carried out by gradually dropping the amine chain extender solution into the urethane prepolymer solution or by adding the urethane prepolymer to the amine chain extender solution. Although there is a method of dropping a polymer solution, etc., in this embodiment, the reaction can be performed by any method. Alternatively, it can be produced by a known method such as a one-shot method in which a polymer polyol, a polyisocyanate, an amine chain extender, and (and a polymerization terminator) are reacted in a single step to obtain a polyurethane resin (B). The amine chain extender can also be used in a urethanization reaction with polyisocyanate together with a polymer polyol.

  In producing the prepolymer, the amount of polyol and polyisocyanate is the ratio of the number of moles of isocyanate groups in 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.

  In addition, it is preferable in terms of reaction control to use 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.

  Furthermore, a catalyst can also be used for the synthesis reaction of this prepolymer. Examples of 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% with respect to the polyol compound.

  The above-obtained prepolymer having an isocyanate group at the terminal is reacted with diamine, triamine or the like which is an amine chain extender 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 of the present embodiment is, for example, 3/97 to 70/30, and 5/95 to 60/40 is preferred. 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.
In addition, in this specification, 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 sum of the content of the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) in 100 parts by mass of the non-aqueous printing ink composition of the present embodiment is preferably 3.0 to 25.0% by mass, 20 mass% is more preferable.

  In one embodiment, 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.

<Vinyl chloride-vinyl acetate copolymer resin (b1)>
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, and 10,000. More preferably, ˜70,000. The ratio 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%. Since vinyl acetate improves the solubility in organic solvents, a part of it is Ken. 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 ° C to 90 ° C.

<Cellulose-based resin (b2)>
Examples of the cellulose resin (b2) include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, carboxyalkyl cellulose and the like, and the alkyl group includes, for example, a methyl group, an ethyl group, a propyl group, An isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, and the like can be given. Further, the alkyl group may have a substituent. Among these, 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. Moreover, the thing whose glass transition temperature is 120 to 180 degreeC is preferable.

<Other combination resins>
The non-aqueous printing ink composition in this embodiment 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 acid 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, 0.5-10 mass% is more preferable.

<Colorant (C)>
A pigment is preferably used as the colorant in the present embodiment, and organic and inorganic pigments 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. These pigments are mentioned. Indigo ink is copper phthalocyanine, and transparent yellow ink is C.I. I. Pigment No Yellow 83 is preferably used. Further, although not limited to the following examples, for example, 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. 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.
Specifically, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 146, C.I. I. Pigment red 242, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 14, C.I. I. Pigment orange 38, C.I. I. Pigment orange 13, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 139, C.I. I. Pigment red 185, C.I. I. Pigment red 122, C.I. I. Pigment red 178, C.I. I. Pigment red 149, C.I. I. Pigment red 144, C.I. I. Pigment red 166, C.I. I. Pigment violet 23, C.I. I. Pigment violet 37, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. 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.

  Examples of 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. From the viewpoint of printing performance, the titanium oxide is subjected to silica and / or alumina treatment. Is preferred.

  Examples of inorganic pigments other than white 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 coloring power of the non-aqueous printing ink composition, that is, in a proportion of 1 to 50% by mass relative to the total mass of the ink composition. The mass% is more preferable. These pigments can be used alone or in combination of two or more.

  The hue of the non-aqueous printing ink composition of the present embodiment is an ink composition of another hue as required (a total of five colors of yellow, red, indigo, and black as the process basic color, outside of process gamut) The colors may be mixed with three colors of red (orange), grass (green), and purple, and transparent yellow, peony, vermilion, brown, and pearl.

(Printing ink composition for laminating)
The non-aqueous printing ink composition of the present embodiment can be used for various uses such as laminating (back printing), surface printing, paper, etc., but because of 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.

  When using a plastic substrate as a packaging material, printing using a printing ink is usually performed for decoration or surface protection of the plastic substrate. Among these, laminate (back printing) printing is a printing ink layer, an adhesive layer, and a base material (including sealant) in order on one side (hereinafter also referred to as back side and back side) of a transparent printing base material. It is the printing system which forms the laminated body which has. The sealant is a thermoplastic plastic base material that can be fused by heat, and an unstretched polyolefin base material is mainly used. In this printing method, 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.

  In recent years, in the field of packaging materials for foods, medical products, and cosmetics, composite films imparted with oxygen gas barrier properties and water vapor barrier properties may be used from the viewpoint of content protection. As 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. When a laminate is made through a laminating process, 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 water vapor barrier property are imparted to the laminate.

  In the use for laminating, after the ink is printed on the substrate, it is further bonded to the substrate 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 (Japanese Patent Laid-Open No. 2013-213109, etc.). Even when such a technique is applied, the laminate strength and printability are improved. It has been difficult to achieve both leveling properties and film properties.

  The dry laminate method and the solventless laminate method are methods for producing a laminate through urethane adhesives, but in order to reduce the production cost of packaging materials, the amount of adhesive applied can be reduced. It is required that a high-quality laminate can be obtained even when laminating is performed. However, when 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. In particular, the appearance defect in the ink part is promoted as the gas barrier property is imparted to the whole laminate by using a transparent vapor deposition film, metal foil or metal vapor deposition film, and in particular, the printed product is bonded to the metal foil or metal vapor deposition film. There is a tendency that poor appearance is more likely to occur in the laminated body. Moreover, since an adhesive layer having a sufficient thickness is not ensured particularly on the ink part by reducing the adhesive application amount, the laminate strength and retort suitability in the laminated body ink part are also problematic.

  For the above-described problems, for example, in an ink composition using a polyurethane resin as a main binder, a technique of using a curing agent having an alkoxysilyl group in addition to an isocyanate group for the purpose of improving the adhesion to a silica deposited film ( Japanese Patent Laid-Open No. 2002-030239) or a technique of adding a silane coupling agent having an amino group and an alkoxysilyl group and a curing agent having an isocyanate group to the ink (Japanese Patent Laid-Open No. 2001-00297) is known. However, even when such a technique is adopted, it is difficult to achieve both the laminate strength and retort suitability and the appearance defect in the laminate ink portion.

However, according to the printing ink composition for laminating of the present embodiment, the printability and leveling properties are good regardless of the type of base material to be printed, such as the type of plastic base material and metal vapor deposition film (base material), And the printed matter excellent in the lamination strength after a lamination process can be obtained.
Furthermore, in one embodiment, it is possible to obtain a printed matter having excellent appearance defects, laminate strength, retort suitability, and the like in laminate printing.
Furthermore, in one embodiment, even when the amount of adhesive is reduced as described later, good laminate appearance, laminate strength, and retort suitability can be achieved.

  In the printing ink composition for laminating of the present embodiment, the solid content mass ratio ((A) / (B)) of the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) is 5/95 to 40/60 is preferable, and a range of 5/95 to 50/50 is more preferable. When the mass ratio ((A) / (B)) of the vinyl chloride-acrylic copolymer resin is 5/95 or more, the adhesive easily suppresses the penetration into the ink layer, and the laminate appearance, laminate strength and retort suitability are improved. It is preferable from the viewpoint. When the mass ratio ((A) / (B)) of the vinyl chloride-acrylic copolymer resin is 50/50 or less, it is easy to maintain the adhesion between the ink composition and the printing substrate, and particularly the laminate strength and retort suitability. It is preferable from the viewpoint. 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.

  Moreover, in the printing ink composition for lamination of this embodiment, although a coloring agent is not specifically limited, When a white inorganic pigment is included, there can exist an outstanding effect at the point of the performance improvement of printed matter. In laminate printing, the ink layer generally consists of a multicolor ink layer and then a white ink layer that is laminated, but in white ink that is in direct contact with the adhesive layer, it is not possible to improve the laminate appearance, laminate strength and retort suitability. This is most effective for improving the performance of the entire 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 it can suppress the penetration of the adhesive into the white ink layer, and is suitable for obtaining a laminate having a good appearance from the viewpoint of coloring power and hiding power. In addition, titanium oxide is preferably surface-treated with an inorganic oxide from the viewpoint of dispersion stability and printability, and titanium oxide subjected to silica treatment, alumina treatment, or silica / alumina combined treatment is preferred.

  Moreover, in the printing ink composition for lamination of this embodiment, it is preferable to use together a white inorganic pigment and an amino-type silane coupling agent (D) as a pigment. Hereinafter, the amino-type silane coupling agent (D) in this embodiment is demonstrated.

  The amino-based silane coupling agent (D) in the present embodiment indicates a compound having any one of primary to tertiary amino groups and an alkoxysilyl group in one molecule. Preferably carbon number of an alkoxy group is 1-5, More preferably, it is 1-3. An alkoxysilyl group in the amino silane coupling agent molecule is a hydroxyl group that may be present on the surface of the white inorganic pigment in the ink composition, the vinyl chloride-acrylic copolymer resin (A) or the polyurethane resin (B). By forming the crosslink, 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 laminate appearance is improved. In addition, since 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. In addition, since 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 of this embodiment 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. When 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. In addition, it is more preferable that 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. 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. 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 inferior. On the other hand, when an excess amino-based silane coupling agent in the ink layer acts as a basic catalyst for the adhesive curing reaction, the viscosity of the adhesive layer during curing increases. As a result, the adhesive layer in the middle of curing cannot spread uniformly with respect to the ink layer, and the laminate appearance tends to be inferior. It is more preferable in terms of retort suitability and appearance when the content of the amino silane coupling agent (D) is within the above range. As for content of an amino type silane coupling agent (D), 0.3-5 mass% is more preferable.

  The amino-based silane coupling agent (D) in the present embodiment more preferably has a primary amino group. By having a primary amino group, the cross-linking reactivity of alkoxysilyl groups in the same molecule becomes superior, and the cross-linking structure is efficiently formed in the ink composition, so that the penetration of the adhesive composition into the ink layer is suppressed. And the laminate appearance, laminate strength and retort suitability are better. Examples of 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, and 3-aminopropylmethyldiethoxysilane.

  More preferably, the amino-based silane coupling agent having a primary amino group also has a secondary amino group. By having primary and secondary amino groups, 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.

  Moreover, it is preferable that the amino-type silane coupling agent in this embodiment 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. It is preferable that carbon number of an alkoxy group is 1-5. Examples of such compounds include bis (3-trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) amine, bis (3-methyldimethoxysilylpropyl) amine, bis (triethoxysilylmethyl) amine, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine and the like can be mentioned.

  As mentioned above, although preferable embodiment was described as a printing ink composition for lamination, 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.

<Organic solvent>
Examples of the organic solvent used in the non-aqueous printing ink composition of the present embodiment include aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, methyl acetate, ethyl acetate, and n-propyl acetate. Ester organic solvents such as 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 glycol monomethyl ether A known organic solvent such as an alcohol-based organic solvent such as ethylene glycol monopropyl ether can be used, or a mixture thereof may be used. Among these, from the viewpoint of the working environment, an organic solvent (non-toluene organic solvent) that does not contain 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.

  In addition, when the non-aqueous printing ink composition of this embodiment contains water, it is preferable that content of water is 10.0 mass% or less in the total mass of a non-aqueous printing ink composition. It is more preferably 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.

<Additives>
The non-aqueous printing ink composition of the present embodiment can appropriately include known additives as additives, and known additives such as pigment derivatives, dispersants, wetting agents, and the like can be 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, silanes other than the amino silane coupling agents (D) described above Coupling agents, chelating agents and the like can be used.

  In order to stably disperse the pigment in the organic solvent, it is possible to disperse only with the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B). However, in order to disperse the pigment stably, the dispersant is added. It can also be used together. As the dispersant, anionic, nonionic, cationic, amphoteric surfactants can be used. When using a dispersing agent, it is preferable that it is 0.01 mass% or more with respect to 100 mass% of total mass of ink from a viewpoint of the storage stability of ink, and it is contained in ink at 0.1-10.0 mass%. More preferably. Furthermore, it is more preferable that it is contained in the range of 0.1 to 5.0 mass%. In the above-mentioned laminate application, it is preferably contained in the ink composition 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. Furthermore, it is more preferable that it is contained in the range of 0.1 to 3 mass%.

<Manufacture of ink composition>
The non-aqueous printing ink composition of the present embodiment 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. Can do. Specifically, 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 further blending a polyurethane resin (B) and / or a vinyl chloride-acrylic copolymer resin (A), or other resins and additives as necessary, into the pigment dispersion obtained 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. As 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.

  In addition, although it is preferable to add a polyurethane resin (B) and / or a vinyl chloride-acrylic copolymer resin (A) in both a kneading process and a thinning process as mentioned above, either of a kneading process and a thinning process On the other hand, it may be added.

  In addition, when the amino silane coupling agent (D) is contained, 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. For example, (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, (3) Add to ink just before printing There are ways to do it. In particular, when the amino silane coupling agent (D) is added in the kneading process, the dispersion stability of the ink composition tends to be improved. Moreover, from the viewpoint of improving the laminate appearance, laminate strength, and retort suitability, a method of adding to the ink composition immediately before printing is preferable.

  In the case where bubbles or unexpectedly large particles are included 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 non-aqueous printing ink composition produced by the above method has a viscosity of 40 at 25 ° C. with a B-type viscometer in order 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 50-400 mPa * s. This viscosity range corresponds to a viscosity at Zahn Cup # 4 of about 9 to 40 seconds. 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. In addition, 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.

<Printed matter>
By printing the ink composition of the present embodiment on a substrate such as a film substrate and drying or curing, a printed matter in which an ink layer is formed on the printing substrate can be produced.

<Base material>
Examples of the substrate that can be used in the printed material of the present embodiment include a plastic substrate, a paper substrate, and an aluminum substrate.
Examples of 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. And a film-like or sheet-like substrate made of a composite material such as paper, aluminum, or a vapor-deposited substrate obtained by vapor-depositing an inorganic compound such as silica, alumina, or aluminum on polyethylene terephthalate or nylon film. Further, 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. GL-AE manufactured by Toppan Printing Co., Ltd., IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd., and the like. The base material may be further processed with an additive such as an antistatic agent, an ultraviolet light inhibitor, or a plasticizer as necessary, or may be subjected to a surface treatment such as a low temperature plasma treatment or a corona treatment. As 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 normal paper or cardboard, and the film thickness is not particularly specified. For example, 0.2 to 1.0 mm or 20 to 150 g / m ² can be used, and the printing surface is corona-treated. May be. 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>
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. As the cylinder used for gravure printing, known ones such as engraving type and corrosion type are used. The ink composition diluted with a diluent 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 temperature of the oven is usually 30 ° C. or higher, for example, 40 to 80 ° C., and the printing speed is usually 50 to 300 m / min. When 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.

<Laminated body>
The printed matter obtained by printing the ink composition of the present embodiment 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 matter.
The laminate of this embodiment is a normal extrusion in which a plastic substrate is laminated through 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. Laminating (extrusion laminating) method, applying adhesive such as urethane on the printed surface, and laminating plastic substrate on it, non-solvent laminating method, or directly bonding molten polypropylene to the printed surface It can be obtained by a known laminating process such as a direct laminating method.

More specifically, 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. As the adhesive used for adhering the sealant, a two-component type of polyol component / 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. Specific examples of the polyester adhesive include TM-250HV / CAT-RT86L-60 and TM-550 / CAT-RT37 manufactured by Toyo Morton Co., Ltd. Moreover, as said polyether adhesive, TM-314 / CAT-14B etc. are mentioned. The solid content application amount of the adhesive in the dry laminating method is generally 1.5 to 4 g / m ² , preferably 2.5 to 3.5 g / m ² in the polyester adhesive, and preferably 1.5 to 2. 5 g / m ² is defined as the low coating amount region. Meanwhile, the above polyether based adhesive generally range from 1 to 3 g / ^{m 2,} preferably ^{1.5~2.5g / m 2, 1.0~2.5g / m} 2 low coating weight region Is done. According to the non-aqueous printing ink composition of this embodiment, it is easy to obtain the effect of improving the appearance even in a low coating amount region. The coating amount of the low coating weight range, from the viewpoint of the compatibility of the production cost and appearance, preferably in the range of 1.4~2.4g / ^{m 2,} more in the range of 1.8~2.2g / ^{m 2} 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. As the adhesive, a two-component type of a polyol component / polyisocyanate component is the mainstream like the adhesive for dry laminate, and specific examples include EA-N373A / B manufactured by Toyo Morton Co., Ltd. The solid coating amount of common adhesives in solventless laminating method is preferably 1 to 5 g / ^{m 2} depending on the application, typically in the range of 1.5~3.5g / ^{m 2.} Moreover, according to the non-aqueous printing ink composition of this embodiment, the effect of improving the appearance is easily obtained even in a low coating amount region. The coating amount of the low coating weight range, from the viewpoint of the compatibility of the production cost and appearance, preferably in the range of 1.4~2.4g / ^{m 2,} more in the range of 1.8~2.2g / ^{m 2} 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. Specifically, there are TUX-FCD (LLDPE) manufactured by Mitsui Chemicals Tosero Co., Ltd., ZK93KM (CPP) manufactured by Toray Industries, Inc., and the like. 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 deposited 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. dialaster (aluminum vapor deposition PET), Toray Industries, Ltd. 2203 (aluminum vapor deposition CPP), etc. are mentioned. Note that PET represents a polyethylene terephthalate film, LLDPE represents a linear low density polyethylene film, and CPP represents an unstretched polypropylene film.

  By the above method, a laminate having an adhesive layer and a base material in order on the printed base material is obtained. When the laminate is further laminated to form a multilayer structure, the base material bonded last becomes the sealant layer. Then, 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. For example, 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, and cosmetics.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. In the present invention, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise noted.

(Hydroxyl value)
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 is a value performed according to JISK0070. In this example, the calculation was performed by the following method.
-Measuring method of hydroxyl value About 1 g of a sample was accurately weighed in a stoppered conical flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution was added and dissolved. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein test solution was added as an indicator and maintained for 30 seconds. Thereafter, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red. The hydroxyl value was determined by the following (Formula 2). The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
(Formula 1) Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Nonvolatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)

(Amine number)
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 acid value is the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of the resin, and the measurement method may be a known method, generally in accordance with JISK0070 (1996). Done. The amine value was measured by the following method.
-Measuring method of amine number 0.5-2g of samples are 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). The point at which the color of the solution changed from green to yellow was taken as the end point, and the amine value was determined by the following (Formula 2) using the titration amount (AmL) at this time.
(Formula 2) Amine number = (A × f × 0.2 × 56.108) / S

(Measurement method of weight average molecular weight (Mw) and number average molecular weight (Mn))
For the measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn), GPC (Gel Permeation Chromatography) “Shodex GPC System-21” manufactured by Showa Denko KK was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. Tetrohydrofuran is used as a solvent, and molecular weight is determined in terms of polystyrene.

Embodiment I
(Synthesis Example I-1) [Polyurethane resin PU1]
150 parts of 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. for 4 hours under a nitrogen stream to obtain a solvent solution 324 of a terminal isocyanate prepolymer. Got a part. Next, 26.3 parts of isophorone diamine (hereinafter “IPDA”), 2.0 parts of iminobispropylamine (hereinafter “IBPA”), 1.0 part of 2-ethanolamine (hereinafter “2EtAm”), ethyl acetate / isopropanol (hereinafter referred to as “below”) “IPA”) = 50/50 mixed solvent 607.4 parts was mixed, and the obtained terminal isocyanate prepolymer solution was gradually added at 40 ° C. and then reacted at 80 ° C. for 1 hour to obtain a solid content. A polyurethane resin solution PU1 having 30%, an amine value of 11.1 mgKOH / g, a hydroxyl value of 3.2 mgKOH / g, and a weight average molecular weight of 35,000 was obtained.

(Synthesis Examples I-2 to I-6) [Polyurethane resins PU2 to PU6]
Using the raw materials shown in Table 1, polyurethane resin solutions PU2 to PU6 were obtained in the same manner as in Synthesis Example 1. In Table 1, PPA, PEG and TDI are respectively
PPA: Polyester polyol which is a condensate of adipic acid and 1,2-propanediol PEG: Polyethylene glycol TDI: Tolylene diisocyanate (methyl-1,3-phenylene diisocyanate)
Represents.

(Synthesis Example I-7) [Vinyl chloride-acrylic copolymer resin A1]
In a 1.0 L autoclave, 1.0 g of potassium peroxodisulfate (K ₂ S ₂ O ₈ ) was dissolved in 500 g of ion-exchanged water and deaerated. After the temperature was raised to 60 ° C., 425 g of a mixture comprising 357 g of vinyl chloride, 63 g of 2-hydroxypropyl acrylate, and 5.0 g of sodium di-2-ethylhexylsulfosuccinate (aerosol OT) was placed in an autoclave at 60 ° C. Add and react at 6.5 atmospheres. The polymerization reaction was continued until the autoclave reached 2.5 atm. The resulting emulsion was precipitated with sodium chloride, filtered, washed and dried to obtain a vinyl chloride-acrylic copolymer resin (A1). Furthermore, vinyl chloride-acrylic copolymer resin (A1) was dissolved in ethyl acetate to obtain a varnish (AA1) having a solid content of 30%. In addition, the content rate of 2-hydroxypropyl acrylate in A1 was 15.0%, the weight average molecular weight 50000, and the glass transition temperature 69 degreeC.

(Synthesis Examples I-8 to I-13) [Vinyl chloride-acrylic copolymer resins A2 to A7]
The ratio of vinyl chloride monomer and acrylic monomer was changed to the ratio shown in Table 2, and vinyl chloride-acrylic copolymer resins A2 to A7 and their varnishes (AA2 to AA7) were obtained in the same manner as in Synthesis Example 7. In the synthesis of A4 and A5, 1.5 g of azobisisobutyronitrile (AIBN) was used instead of 1.0 g of potassium peroxodisulfate (K ₂ S ₂ O ₈ ).

(Synthesis Example I-14) [Synthesis of Acrylic Resin AP1]
In a reaction vessel, 85 parts of methyl methacrylate (hereinafter “MMA”), 10 parts of n-butyl acrylate (hereinafter “BA”), 5 parts of 2-hydroxyethyl acrylate (hereinafter “2HEA”), ethyl acetate: isopropyl alcohol = 1: 1 233 parts and 1.2 parts of azobisisobutyronitrile were added and mixed, and polymerized at 70 ° C. for 8 hours under a nitrogen gas atmosphere to obtain an acrylic resin AP1 having a hydroxyl group. The obtained resin solution had a solid content of 40% by mass, a weight average molecular weight of 25,000, a glass transition temperature of 89.4 ° C., and a hydroxyl value of 24.2 mgKOH / g.

(Example I-1) [Preparation of non-aqueous gravure ink S1]
42 parts of polyurethane resin solution PU1 (solid content 30%), 8 parts of vinyl chloride-acrylic copolymer resin solution A1 (solid content 30%), C.I. I. 11 parts of Pigment Blue 15: 3 and 39 parts of a solution of ethyl acetate / IPA = 50/50 were mixed and kneaded with an Eiger mill for 15 minutes to obtain a non-aqueous gravure ink S1.

(Examples I-2 to I-20) [Preparation of non-aqueous gravure inks S2 to S20]
Using the pigments shown in Table 3-1, the polyurethane resins (PU1 to PU6) in Table 1, the vinyl chloride-acrylic copolymer resin varnishes (AA1 to AA6) in Table 2, and the resins and additives listed in Table 3-1. In the same manner as in Example I-1, mixing was performed to obtain non-aqueous gravure inks S2 to S20. In addition, the abbreviation in Table 3-1 represents the following.
Solvain TAO: manufactured by Nissin Chemical Industry Co., Ltd. Hydroxyl-containing vinyl chloride-vinyl acetate copolymer Vinyl chloride: Vinyl acetate: Vinyl alcohol = 91: 2: 7 (solid content 30% ethyl acetate solution)
CAB38120BP: Eastman Chemical Cellulose Acetate Butyrate (Solid content 30% IPA solution)
Duranate P-301-75E: Hexamethylene diisocyanate trimethylolpropane adduct (trifunctional isocyanate) manufactured by Asahi Kasei Chemicals Corporation
N-phenyl-3-aminopropyltrimethoxysilane: silane compound In addition, Duranate P-301-75E and N-phenyl-3-aminopropyltrimethoxysilane were added immediately before printing and mixed well for printing. (The addition amount shown in the table is part by mass with respect to 100 parts by mass of the ink composition).

(Comparative Examples I-1 to I-18) [Preparation of non-aqueous gravure inks T1 to T18]
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. Abbreviations in Table 3-2 represent the following.
S-180: Polyester resin manufactured by Takamatsu Yushi Co., Ltd. Glass transition temperature 60 ° C. Weight average molecular weight 20000 (solid content 30% toluene / methyl ethyl ketone solution)

(Example I-21)
<Printing of non-aqueous gravure ink> (evaluation for laminating)
The non-aqueous gravure ink S1 (indigo) obtained above was mixed with a mixed solvent (methyl ethyl ketone “MEK”: N propyl acetate “NPAC”: isopropanol “IPA” = 40: 40: 20) for 16 seconds (25 ℃, Zaan Cup No. 3), helio 175 line gradation version (plate type Elon Gate, 100% to 10% up to 10% gradation, 10% to 5% or less up to 5% gradation, 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 μm and a corona discharge treatment and a corona discharge treatment polyester (PET) film having a thickness of 12 μm (Toyobo) E-5100) was printed on the corona discharge treated surface at a printing speed of 50 m / min to obtain printed materials G1 (OPP) and H1 (PET). 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.

  For the obtained printed matter G1 and H1, 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.) Extrusion was performed by melting and extruding at 315 ° C. and bonding with unstretched polypropylene (FCMN, film thickness 40 μm, manufactured by Tosero).

(Examples I-22 to I-40)
Prints G2-G20 (OPP) and H2-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.

(Comparative Examples I-19 to I-36)
Printed materials K1 to K18 (OPP) and L1 to L18 (PET) were obtained in the same manner as in Example I-21 except that the inks shown in Table 5-1 were used. Further, extrusion lamination was performed on each printed matter by the same method as described above.

<Base material transferability>
Substrate transferability evaluation was performed with the transfer area% of the gradation 3% portion in the obtained prints H1 to H20 (PET, Examples) and L1 to L18 (PET, comparative examples).
○: Ink transfer is 100%.
B: Ink transfer is 80% to 100%.
Δ: The ink transfer is 60 to 79%.
Δ ×: Ink transfer is 30 to 59%.
X: The ink transfer is less than 30%.
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

<Plate castability>
Plate fogging evaluation was performed for 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%.
Δ: The plate covering area is 11 to 30%.
Δ × The plate covering area is 31 to 50%.
X: The plate covering area is 50% or more.
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

<Leveling properties>
The printed matter of the obtained printed matter H1 to H20 (PET, Example) and L1 to L18 (PET, Comparative Example) was visually evaluated for the printing state of a 100% solid portion.
○: There is no unevenness in the printing section.
○ Δ: There is slight unevenness at the end of the printed part.
Δ: There is slight unevenness over the center of the printing section.
Δ ×: There is a large unevenness throughout the printing section.
× · · · There is a large unevenness in the entire printing section, and the striped pattern is clearly visible.
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

<Lamination strength>
The ink part of the extrusion laminate was cut at a width of 15 mm and peeled off between the ink surface and the substrate surface, and then the peel strength (laminate strength) was measured with an Intesco 2011 universal tensile tester. The practical level is 0.6 N / 15 mm or more.
The above results are shown in Tables 4-1 and 5-1.

(Example I-41)
<Color of non-aqueous gravure ink / white printing> (evaluation for laminating)
The non-aqueous gravure inks S1 (indigo) and S19 (white) obtained above were mixed with a mixed solvent (methyl ethyl ketone “MEK”: N propyl acetate “NPAC”: isopropanol “IPA” = 40: 40: 20). Is diluted to 16 seconds (25 ° C., Zaan Cup No. 3), and the thickness is measured by a gravure printing machine equipped with a helio 175 line solid plate and a helio 175 line 100% semi-solid plate (plate type compressed). On the corona discharge-treated surface of a 12 μm corona discharge-treated polyester (PET) film (E-5100 manufactured by Toyobo Co., Ltd.) at a printing speed of 50 m / min, in the order of film substrate / indigo (solid pattern) / white (semi-solid pattern). Printing was performed to obtain a printed material J1.

The obtained printed matter J1 was further coated and dried 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. Then, it was bonded to unstretched polypropylene (FCMN, film thickness 40 μm, manufactured by Tosero Co., Ltd.) and dry laminated.

(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. Furthermore, dry lamination was performed on each printed matter.

(Comparative Examples I-37 to I-48)
Prints N1 to N12 were obtained in the same manner as in Example I-41 except that the inks listed in Table 5-2 were used. Furthermore, dry lamination was performed on each printed matter. Evaluation was performed after the laminate was held at 50 ° C. for 48 hours.

<Color / white trapping properties>
The obtained printed materials J1 to J16 (Examples) and N1 to N12 (Comparative Examples) were observed from the printed surface, and the trapping properties of the substrate / color ink layer / white ink layer were confirmed and evaluated.
○: There is no unevenness in the printing section.
○ Δ: Unevenness is present in 1 to 10% of the printed portion.
Δ: There is unevenness in 11 to 30% of the printed portion.
Δ ×: 31 to 60% of the printed portion is uneven.
× ··· There is a large unevenness in the whole printing section.
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

<Lamination strength>
The ink part of the dry laminate laminate was cut at a width of 15 mm and peeled off between the ink surface and the substrate surface, and then 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.

<Appearance evaluation>
The obtained printed laminates J1 to J16 (Examples) and N1 to N12 (Comparative Examples) were observed from the film surface, and the appearance was confirmed and evaluated.
○: There is no delamination or unevenness in the printed part of the laminate.
B: There is slight delamination and unevenness in an area of 1 to 3% in the printed part of the laminate.
Δ: Delamination and unevenness in the printed portion of the laminate in an area of 4 to 20%.
Δx: Delamination and unevenness are observed in an area of 21 to 50% in the printed portion of the laminate.
× ··· Delamination and unevenness are observed in the entire printed portion of the laminate, and ◯ and Δ are ranges where there is no practical problem.
The above results are shown in Table 4-2 and Table 5-2.

(Example I-57)
<Color of non-aqueous gravure ink / white printing> (Evaluation for surface and paper gravure ink)
For 100 parts of each of the non-aqueous gravure inks S19 (white) and S1 (indigo) obtained above, 5 parts of fatty acid amide (product name: fatty acid amide S manufactured by Kao Corporation) and mixed solvent (methyl ethyl ketone “MEK”) ”: N-propyl acetate“ NPAC ”: Isopropanol“ IPA ”= 40: 40: 20), diluted to a viscosity of 16 seconds (25 ° C., Zaan Cup No. 3), and helio 175 line solid plate and helio A biaxially stretched polypropylene (OPP) film (FORP manufactured by Futamura Chemical Co., Ltd.) treated with a 25 μm corona discharge by a gravure printing machine equipped with a 175 line 100% semi-solid plate (plate type compressed) at a printing speed of 50 m / min. Printing was performed in the order of film base material / white (solid pattern) / indigo (semi-solid pattern) to obtain a printed material O1.

(Examples I-58 to I-77)
Printed materials O2 to O21 were obtained in the same manner as in Example I-57 except that the inks or paper base materials shown in Table 6-1 (product name: Ryuou coated paper 65 g / m ² manufactured by Daio Paper Co., Ltd.) were used.

(Comparative Examples I-51 to I-70)
Using the inks or base materials described in Table 6-2, printed materials Q1 to Q20 were obtained in the same manner as in Example I-57.

<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 from which the ink film is taken is less than 10% △ ・ ・ ・ ・ ・ The area from which the ink film is taken is 10% or more and less than 30% △ × ・ ・ ・ The area from which the ink film is taken is 30% More than less than 50% ×... Taken over the entire surface. O and Δ 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 overlapped with the printed surface with a soft PVC sheet or high-quality paper that has been cut into the same size. Evaluation of blocking resistance with a soft PVC sheet was applied with a load of 0.5 kg / cm ² , left for 15 hours in an atmosphere of 50 ° C.-80% RH, and then the printed surface and the PVC sheet were peeled off, and the printed film was removed. Was determined visually.
In addition, the high-quality paper and the blocking resistance were evaluated by applying a load of 5.0 kg / cm ² , leaving it in an atmosphere of 50 ° C.-80% RH for 15 hours, peeling off the printing surface and the high-quality paper, and removing the printed film. The condition was judged visually.
The determination criteria were as follows.
○ …… The ink on the printing surface does not peel off at all and is very good ○ △ ・ ・ ・ ・ Slightly peels off the ink film, but there is no problem △ …… Slight ink film Peeling, but no problem for practical use Δ × ···· The area where the ink film is taken is 50% or more, and there is a practical impediment × ··· the ink film is taken ○, Δ is a range where there is no practical problem.

<Adhesiveness>
About printed matter O1-O21 (Example) and Q1-Q20 (comparative example), after leaving at 25 degreeC for 1 day, the adhesive tape (Nichiban Co., Ltd. cellophane tape) of width 15mm was stuck on the printing surface, and this was peeled off rapidly. The appearance state of the printed film was visually judged. The determination criteria were as follows.
○ …… The ink on the printing surface does not peel off at all and is very good ○ △ ・ ・ ・ ・ Slightly peels off the ink film, but there is no problem △ …… Slight ink film Peeling, but no problem for practical use Δ × ···· The area where the ink film is taken is 50% or more, and there is a practical impediment × ··· the ink film is taken ○, Δ is a range where there is no practical problem.

<Heat resistance>
The printed materials O1 to O21 (Examples) and Q1 to Q20 (Comparative Examples) were cut into a size of 2 cm × 10 cm, and the aluminum foil cut into the same size and the printed surface were overlapped. Using a heat sealer manufactured by Sentinel, the aluminum foil was pressed at 120 ° C. for 1 second at a pressure of 2 × 9.8 N / cm ² , and the degree of removal of the printed film was visually determined. The determination criteria were as follows.
○ ・ ・ ・ The ink on the printing surface does not peel at all and is very good ○ △ ・ ・ Slightly peels off the ink film, but no problem △ ・ ・ ・ Slightly peels off the ink film, but practical No problem △ × ··· The area where the ink film is removed is 50% or more, and there is a practical impediment × ··· The ink film is removed ○, △ is a range where there is no practical problem .

<Oil resistance>
Printed products O1 to O21 (Examples) and Q1 to Q20 (Comparative Examples) were cut to a size of 2 cm × 20 cm, and a commercially available margarine (trade name: manufactured by Neosoft Snow Brand Milk Products Co., Ltd.) melted on the printing surface was applied to the entire 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 ink on the printing surface does not peel at all and is very good ○ △ ・ ・ Slightly peels off the ink film, but no problem △ ・ ・ ・ Slightly peels off the ink film, but practical No problem △ × ··· The area where the ink film is removed is 50% or more, and there is a practical impediment × ··· The ink film is removed ○, △ is a range where there is no practical problem .

  From the evaluation results, the non-aqueous gravure ink containing the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) as essential components as the 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. In addition, the gravure ink for lamination containing an amino group-containing silane compound has good leveling, gravure such as transferability to a substrate and plate fogging, printability, etc., and good physical properties of the ink film. It was found to be a gravure ink exhibiting excellent properties in lamination strength and appearance after lamination.

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 inlet 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 0.003 part tin 2-ethylhexanoate were charged, reacted at 90 ° C. for 5 hours under a nitrogen stream, cooled by adding 7.5 parts ethyl acetate, and a urethane prepolymer having an isocyanate group at the terminal. A solution was obtained. Next, 1.66 parts of isophoronediamine (hereinafter also abbreviated as IPDA), 0.18 part of 2-hydroxyethylethylenediamine, 0.07 part of monoethanolamine, 30.147 parts of ethyl acetate and 28 parts of isopropyl alcohol (hereinafter also abbreviated as IPA). 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.

[Synthesis Examples II-2 to II-5]
Polyurethane urea resin solutions <B2 to B5> were obtained in the same manner as in Synthesis Example 1 with the charging ratios shown in Table 7.

[Synthesis Example II-6]
After substituting the inside of a 35 L pressure vessel with N ₂ and sufficiently degassing, one-end acryloyl group polybutyl acrylate (number average molecular weight 12000) (2.0 kg) and vinyl chloride monomer (8.0 kg) are put in and spared for 60 min. Stir. Thereafter, α, α′-azobis-2,4-dimethylvaleronitrile (12.0 g) and t-butylperoxyneodecanoate (2.1 g) were added. An 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 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 A2 solution.

(Preparation of ink composition)
[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, ratio of structure derived from vinyl chloride monomer: 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 (mass ratio 75/25) after stirring and mixing , Diluted with a mixed solvent of methyl ethyl ketone, normal propyl acetate, and IPA (mass ratio 40:40:20), adjusted to 15 seconds with Zahn Cup # 3 (manufactured by Ransha Co., Ltd.) to obtain ink composition <i-1>. It was. The solid content mass ratio of the polyurethane urea resin (B) and the vinyl chloride-acrylate copolymer (A) in the ink composition is (B) / (A) = 75/25.

[Examples 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.
In addition to <C2>, the following were used as the pigment (C).
<C1>: Titanium oxide, TITON R45M, manufactured by Sakai Chemical In addition to <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
Further, as resins other than polyurethane urea resin and 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.
Nitrocellulose resin: DLX5-8, vinyl chloride-vinyl acetate copolymer manufactured by Nobel Enterprises: Solvain TA5R, manufactured by Nissin Chemical Industry Co., Ltd. Further, the following were used as additives.
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.

[Evaluation of laminate appearance]
The obtained ink composition was subjected to a corona discharge-treated PET film (E5100) having a thickness of 12 μm at a printing speed of 150 m / min and a drying temperature of 60 ° C. using a gravure printing machine equipped with a gravure printing plate having a gradation depth of 30 to 3 μm. , Manufactured by Toyobo Co., Ltd.) to obtain a printed matter. On the ink layer of this 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 , 1. Apply to 8 g / m ² and use a dry laminating machine at a line speed of 150 m / min to bond with aluminum foil (general aluminum foil AIN30H-0, Showa Aluminum Co.) PET film / ink layer / adhesion A laminate precursor having an agent 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.). The product which has PET film / ink layer / adhesive layer / aluminum foil / adhesive layer / CPP film in this order. To give the body. The laminate was aged at 40 ° C. for 3 days.
About the laminated body bonded together by each adhesive agent solid content application amount, the ink part was visually observed from the front side of the printing base film, and the following reference | standard evaluated. Evaluation was made at a plate depth of 30 μm.
5: Yuzu skin-like pattern and small spot-like pattern are not observed.
4: Small spot-like patterns are not observed, but some yuzu-skin patterns are observed. Level that is not problematic for use.
3: Small spot-like patterns are not observed, but many yuzu skin-like patterns are observed. Level that is not problematic for use.
2: Not only a yuzu skin-like pattern but also a small spot-like pattern is observed.
1: Many small spot-like patterns are observed in addition to the Yuzu skin-like pattern.

[Lamination strength]
The laminate was cut into a length of 300 mm and a width of 15 mm to obtain a test piece. Using an Instron type tensile tester, the sample was pulled at a peeling rate of 300 mm / min in an environment of 25 ° C., and the T-type peeling strength (N) between the PET film and the aluminum foil was measured at a width of 15 mm. This test was performed 5 times, the average value was calculated | required, and the following references | standards evaluated. Evaluation was made at a plate depth of 30 μm.
5: 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 0.4N * Adhesive strength of 0.8N or more is preferable for practical use.

[Retort aptitude]
The laminate is heat sealed with the CPP surface inside (temperature: 190 ° C., pressure: 2 kgf, time: 1 second) to make a bag body, and 1: 1: 1 soup (ketchup: vinegar: water = mass ratio) 1: 1: 1) was filled, and a retort treatment at 120 ° C. for 30 minutes was performed. 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 μm.
○: No change in appearance was observed.
(Triangle | delta): The laminate float was seen slightly in the external appearance.
X: Blister marks or laminate floating was observed in the appearance.
Practically, it is preferably in the range of ◯ or Δ.

[Print transfer]
In the above printed matter, the substrate transferability of the ink composition was evaluated at a transfer area% at a plate depth of 3 μm.
○: Ink transfer is 100%.
B: Ink transfer is 80% to 100%.
Δ: The ink transfer is 60 to 79%.
Δ ×: Ink transfer is 30 to 59%.
X: The ink transfer is less than 30%.
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

[Plate fog]
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%.
Δ: The plate covering area is 11 to 30%.
Δ × The plate covering area is 31 to 50%.
X: The plate covering area is 50% or more.
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

[Leveling properties]
In the printed matter, the printed state of the 100% solid portion was visually evaluated.
○: There is no unevenness in the printing section.
○ Δ: There is slight unevenness at the end of the printed part.
Δ: There is slight unevenness over the center of the printing section.
Δ ×: There is a large unevenness throughout the printing section.
× · · · There is a large unevenness in the entire printing section, and the striped pattern is clearly visible.
In addition, (circle) and (triangle | delta) are the ranges which do not have a problem practically.

  Tables 8 and 9 show the results. In the ink composition containing the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) of this embodiment, the leveling property and the printability were good. Among them, an ink containing a vinyl chloride-acrylic copolymer resin in a range of 95/5 to 50/50 in terms of a solid content mass ratio of the polyurethane urea resin (B) and the vinyl chloride-acrylic ester copolymer resin (A). In the composition, in addition to good leveling properties and printability, the laminate appearance, laminate strength, and retort suitability were improved. In an ink composition containing titanium oxide as a pigment and further containing an amino-based silane coupling agent in a range of 0.15 to 7% by mass in 100% by mass of the solid content of the ink composition, the laminate appearance is particularly good. became. Moreover, in the white ink composition containing an amino-type silane coupling agent, when the hydroxyl value of the polyurethane urea resin was in the range of 1 to 15 mgKOH / g, the laminate appearance and the laminate strength were particularly good. Furthermore, when 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.

Claims (18)

A binder resin containing a vinyl chloride-acrylic copolymer resin (A) and a polyurethane resin (B);
The non-aqueous printing ink composition whose content rate of the structure derived from a vinyl chloride in 100 mass% of said vinyl chloride-acrylic copolymer resins (A) is 75-95 mass%.   The solid content mass ratio of the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) is in the range of (A) :( B) = 5: 95 to 60:40. The non-aqueous printing ink composition as described.   The solid content mass ratio of the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) is in the range of (A) :( B) = 5: 95 to 50:50. The non-aqueous printing ink composition as described. The polyurethane resin (B) includes a structural unit derived from polyether polyol,
The ratio of the structural unit derived from the said polyether polyol is the range of 5-80 mass% in 100 mass% of said polyurethane resins (B), The non-aqueous printing ink of any one of Claims 1-3. Composition. The polyurethane resin (B) includes a structural unit derived from a polyester polyol,
The ratio of the structural unit derived from the said polyester polyol is the range of 5-80 mass% in 100 mass% of said polyurethane resins (B), The non-aqueous printing ink composition of any one of Claims 1-4. object.   The non-aqueous printing ink composition according to claim 5, wherein the structural unit derived from the polyester polyol includes a structural unit derived from a polyester polyol obtained by reacting a diol having a branched structure with a dibasic acid.   The non-aqueous printing ink composition of any one of Claims 1-6 whose hydroxyl value of the said polyurethane resin (B) is 1-20 mg / KOHg.   The non-binding composition according to any one of claims 1 to 7, 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). Water-based printing ink composition. Furthermore, a colorant (C) is contained,
The non-aqueous printing ink composition according to any one of claims 1 to 8, wherein the colorant (C) contains a white inorganic pigment.   The non-aqueous printing ink composition according to any one of claims 1 to 9, further comprising an amino silane coupling agent (D).   The non-aqueous printing ink composition according to claim 10, wherein the amino silane coupling agent (D) has a primary amino group, or has a secondary amino group and four or more alkoxy groups.   The non-aqueous printing ink composition according to claim 10, wherein the amino silane coupling agent (D) has a primary amino group and a secondary amino group.   The non-aqueous printing ink composition according to any one of claims 1 to 12, which is an ink composition for gravure printing.   The non-aqueous printing ink composition according to claim 1, which is a laminating printing ink composition. 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 the vinyl chloride-derived structure in 100% by mass of the vinyl chloride-acrylic copolymer resin (A) is 75 to 95% by mass,
The solid content mass ratio between the vinyl chloride-acrylic copolymer resin (A) and the polyurethane resin (B) is in the range of (A) :( B) = 5: 95 to 50:50,
A non-aqueous gravure ink composition for laminating, wherein the colorant (C) contains a white inorganic pigment.   It has the ink layer which uses the non-aqueous printing ink composition of any one of Claims 1-14 on the printing base material, or the non-aqueous gravure ink composition for lamination of Claim 15. , Printed matter.   The printed matter according to claim 16, wherein the printing substrate is a film.   The laminated body by which the adhesive bond layer and the base material were laminated | stacked in this order on the printing surface of the printed matter of Claim 16 or 17.