WO2022004082A1 - Laminate printing ink composition for flexible packaging - Google Patents

Abstract

A laminate printing ink composition for flexible packaging that includes a pigment, a polyurethane-polyurea resin, an ester-based solvent, and 0.1-10 mass% of water, the polyurethane-polyurea resin including 30 mass% or more of a polyester polyol component as a polyol component that constitutes the polyurethane-polyurea resin and having an amine value of 1.0-10.0 mg KOH/g, and the composition being substantially free of solvents other than ester-based solvents.

Description

Laminate printing ink composition for flexible packaging

The present invention relates to a laminated printing ink composition for flexible packaging.

In recent years, in the gravure printing industry, which uses a large amount of organic solvents, there is increasing interest in solvent recovery due to the need to comply with hydrocarbon emission regulations and regulations such as the Fire Service Law and the Industrial Safety and Health Law. .. As such a solvent recovery type ink composition, the easy solvent recovery printing ink composition described in Patent Document 1 has been developed.

Japanese Unexamined Patent Publication No. 6-40767

However, the ink composition described in Patent Document 1 has a problem of insufficient dispersion stability, adhesiveness, and laminating suitability.

The present invention has been made in view of such conventional problems, and provides a laminated printing ink composition for flexible packaging, which is excellent in dispersion stability over time, adhesiveness and laminating suitability, and can easily recover a solvent. With the goal.

The laminated printing ink composition for flexible packaging of the present invention, which solves the above problems, contains a pigment, a polyurethane polyurea resin, an ester solvent, and 0.1 to 10% by mass of water, and the polyurethane polyurea resin. Contains 30% by mass or more of a polyester polyol component as a polyol component constituting the polyurethane polyurea resin, has an amine value of 1.0 to 10.0 mgKOH / g, and substantially contains a solvent other than an ester solvent. No, it is a laminating printing ink composition for flexible packaging.

Further, the printed matter of the present invention that solves the above-mentioned problems is a printed matter on which the above-mentioned laminated printing ink composition for flexible packaging is printed.

<Laminate printing ink composition for flexible packaging>
The laminated printing ink composition for flexible packaging (hereinafter, also referred to as an ink composition) according to an embodiment of the present invention comprises a pigment, a polyurethane polyurea resin, an ester solvent, and 0.1 to 10% by mass of water. including. The polyurethane polyurea resin contains a polyester polyol component in an amount of 30% by mass or more as a polyol component constituting the polyurethane polyurea resin, and has an amine value of 1.0 to 10.0 mgKOH / g. Further, the ink composition does not substantially contain a solvent other than the ester solvent. Each will be described below.

(Pigment)
The pigment is not particularly limited. As an example, the pigment is various inorganic pigments and organic pigments. Specifically, the inorganic pigments include colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, ultramarine, dark blue, carbon black, and graphite (including achromatic pigments such as white and black). And, it is an extender pigment such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc. The organic pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments and the like. Pigments may be used in combination.

The titanium oxide used as the white pigment is preferably silica alumina and / or titanium oxide having an organic surface treatment for the reason of stability over time. The titanium oxide used as the white pigment is preferably titanium oxide having an average particle size of 0.2 to 0.3 μm and an oil absorption of 17 to 35 ml / 100 g.

The content of the pigment is not particularly limited. As an example, the pigment may be contained in the ink composition in an amount of 0.5 to 60% by mass. When the content of the pigment is within the above range, the ink composition is easy to obtain sufficient color development and has excellent printability.

(Polyurethane polyurea resin)
As the constituent polyol component of the polyurethane polyurea resin, a polyester polyol component and, if necessary, a polyether polyol component can be used. The polyurethane polyurea resin contains a polyester polyol component in an amount of 30% by mass or more in the polyol component because it is excellent in printability such as production with an ester solvent and anti-fog property and laminating suitability.

When the pigment is an organic pigment, it is preferable that the polyester polyol component and the polyether polyol component are used in combination as the polyol component. In this case, the content of the polyester polyol component is preferably 30% by mass or more in the polyol component from the viewpoint of blocking resistance and adhesiveness. Further, from the viewpoint of stability over time, adhesiveness and laminating suitability, a polyurethane polyurea resin having an amine value of 1.0 to 10.0 mgKOH / g is used.

The polyurethane polyurea resin is preferably a polyurethane polyurea resin having an amino group from the viewpoint of the stability over time, adhesiveness and laminating suitability of the ink, and the primary amino group and the secondary are secondary at the terminal of the molecule. A polyurethane polyurea resin having at least one selected from amino groups is more preferable.

The polyurethane polyurea resin is more preferably a polyurethane polyurea resin having a hydroxyl group and having at least one selected from a primary amino group and a secondary amino group at the terminal of the molecule.

The above-mentioned polyol component is, for example, a polyether such as a polyalkylene glycol such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol, a high content polyether diol compound such as an ethylene oxide of bisphenol A or an alkylene oxide adduct such as propylene oxide. One or more dibasic acids such as polyol component, adipic acid, sebacic acid, phthalic anhydride, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5 -Examples include high-polymer polyesterdiols obtained by subjecting one or more of glycols such as pentanediol to a condensation reaction, and polyester polyol components such as polyesterdiol compounds such as polycaprolactone diols. These high molecular weight polyol compounds may be used in combination. When used in combination, it is preferable that the polyester polyol component is contained in an amount of 30% by mass or more in the polyol component from the viewpoint of excellent printability such as production with an ester solvent and anti-fog property and laminating suitability.

Further, in addition to the above, the polyol component includes alkanediol such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, and ethylene glycol as long as the performance does not deteriorate. , Propylene glycol, 1,4-butanediol, 1,3-butanediol and other low molecular weight diol compounds may be used in combination.

When an ester solvent is used as the organic solvent described later in the synthesis of the polyurethane polyurea resin, the polyester polyol component contains glycol and glycol in terms of printability, low temperature stability, blocking resistance and laminating suitability. It is preferably a polyester polyol composed of adipic acid. The glycol contains neopentyl glycol and butanediol and / or ethylene glycol, and the total amount of butanediol and ethylene glycol is preferably 40 to 80 mass with respect to the total amount of glycol. Further, as the polyether polyol component, one selected from polyethylene glycol, polypropylene glycol and polytetramethylene glycol is preferable from the viewpoint of production with an ester solvent and printability. Above all, when polypropylene glycol is used, the solubility of the obtained polyurethane polyurea resin tends to be high, and the printability such as gradation reproducibility and fog prevention property tends to be good, and the required performance is required. It is preferable in that it is possible to design a wide range of inks according to the above.

Such a polyurethane polyurea resin is a polyurethane polyurea resin obtained by synthesizing a urethane prepolymer by reacting an organic diisocyanate compound with a polyol component and, if necessary, reacting it with a chain extender and a reaction terminator. Suitable.

The organic diisocyanate compounds include, for example, aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate, aliphatic diisocyanate compounds such as hexamethylene diisocyanate, and α and α. , Α', α'-Aromatic aliphatic diisocyanate compounds such as tetramethylxylylene diisocyanate. These organic diisocyanate compounds may be used in combination. The organic diisocyanate compound is more preferably an alicyclic diisocyanate, an aliphatic diisocyanate and an aromatic aliphatic diisocyanate. More preferably, it is an aliphatic diisocyanate.

The ratio of the organic diisocyanate compound to the polyol component is preferably 1.3: 1.0 to 3.0: 1.0, more preferably 1. Isocyanate group: hydroxyl group equivalent ratio (isocyanate index). It is 5: 1.0 to 2.5: 1.0. When the isocyanate index is within the above range, the hardness of the polyurethane polyurea resin becomes appropriate, and the blocking resistance does not easily decrease when the ink composition of the present embodiment is printed. Therefore, it is not essential for the ink composition to be used in combination with other hard resins. In addition, the ink composition is excellent in adhesiveness and laminating suitability.

As the chain extender, a known chain extender used in polyurethane polyurea resin as a binder for ink can be used, and for example, an aliphatic diamine such as ethylenediamine, propylenediamine, tetramethylenediamine, and hexamethylenediamine can be used. , Isophorone diamine, alicyclic diamines such as 4,4'-dicyclohexylmethanediamine, aromatic diamines such as toluylene diamine, aromatic aliphatic diamines such as xylenediamine, N- (2-hydroxyethyl) ethylenediamine. , N- (2-Hydroxyethyl) propylene diamine, N, N'-di (2-hydroxyethyl) diamines having hydroxyl groups such as ethylenediamine, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, Examples thereof include diol compounds such as diamine glycol and triethylene glycol. Further, polyamines such as diethylenetriamine and triethylenetetramine may be used in combination as long as the polyurethane polyurea resin does not gel.

Examples of the reaction terminator for introducing a primary amino group and a secondary amino group into the terminal of the polyurethane polyurea resin include aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, and hexamethylenediamine, isophoronediamine, and 4 , 4'-Alicyclic diamines such as dicyclohexylmethanediamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylene diamine, aromatic aliphatic diamines such as xylenediamine, N- (2). Examples of diamines having a hydroxyl group such as -hydroxyethyl) ethylene diamine and N- (2-hydroxyethyl) propylene diamine can be exemplified. Among these, alicyclic diamines such as isophorone diamine and 4,4'-dicyclohexylmethane diamine, and diamines having hydroxyl groups such as N- (2-hydroxyethyl) ethylenediamine and N- (2-hydroxyethyl) propylenediamine are included. preferable.

As the reaction terminator for introducing a hydroxyl group into the polyurethane polyurea resin, alkanolamines such as monoethanolamine and diethanolamine, and hydroxyl groups such as N- (2-hydroxyethyl) ethylenediamine and N- (2-hydroxyethyl) propylenediamine are used. Examples thereof include diamines having. Further, monoamine compounds and monoalcohol compounds which are known reaction terminators can be used, specifically, monoalkylamines such as n-propylamine and n-butylamine, and dialkylamines such as di-n-butylamine. Kind, monoalcohols such as ethanol can be exemplified.

Since the above-mentioned preferable polyurethane polyurea resin has a specific functional group, the ink composition of the present embodiment has excellent printability and adhesiveness to a film.

The amine value of the polyurethane polyurea resin is preferably 0.1 to 10.0 mgKOH / g, and more preferably 0.2 to 8.0 mgKOH / g. If the amine value is less than 0.1 mgKOH / g, the adhesiveness of the ink composition of the present embodiment to the film may be lowered, and the laminating suitability may be further lowered, so that the amine value is 10.0 mgKOH / g. If it exceeds g, the blocking resistance may decrease. In this embodiment, the amine value means the amine value per 1 g of solid content, and a potentiometric titration method (for example, COMTITE (AUTOTITTOR COM-900, BURET B-900,) using a 0.1 N hydrochloric acid aqueous solution is used. TISTATIONK-900), manufactured by Hiranuma Sangyo Co., Ltd.), and then converted to the equivalent of potassium hydroxide.

The number average molecular weight of the polyurethane polyurea resin of the present embodiment is preferably 10,000 or more. The number average molecular weight of the polyurethane resin is preferably 150,000 or less.

Further, a biomass polyester polyol component can be used as the polyester polyol component of the polyurethane polyurea resin, and an organic diisocyanate compound derived from vegetable oil can be used as the organic diisocyanate compound. By using these, it is possible to contribute to prevention of global warming and reduction of environmental load as compared with the case of using other depleting resources.

The biomass polyester polyol component is preferably a biopolyester polyol obtained by reacting a short-chain diol component having 2 to 4 carbon atoms with a carboxylic acid component. As for the biomass polyol component, it is more preferable that at least one of the short chain diol component and the carboxylic acid component is derived from a plant, and it is further preferable that both are derived from a plant.

The plant-derived short chain diol component having 2 to 4 carbon atoms is not particularly limited. As an example, the short chain diol component is 1,3-propanediol, 1,4-butanediol, ethylene glycol or the like obtained from a plant raw material by the following method. These may be used together.

1,3-Propanediol can be produced from glycerol via 3-hydroxypropylaldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant resources (for example, corn). The 1,3-propanediol compound produced by a bio method such as the above fermentation method has a useful by-product such as lactic acid in terms of safety as compared with the 1,3-propanediol compound produced by the EO production method. It can be obtained and the manufacturing cost can be kept low.

1,4-Butanediol can be produced by hydrogenating succinic acid obtained by producing glycol from plant resources and fermenting it. Further, ethylene glycol can be produced from bioethanol obtained by a conventional method via ethylene.

The plant-derived carboxylic acid component is not particularly limited. As an example, the carboxylic acid component is sebacic acid, succinic acid, lactic acid, glutaric acid, dimer acid and the like. These may be used together. Among these, the carboxylic acid component preferably contains at least two kinds selected from the group consisting of sebacic acid, succinic acid and dimer acid.

The biomass polyol component can be produced as a 100% plant-derived biopolyester polyol by appropriately condensing a plant-derived short-chain diol component and a plant-derived carboxylic acid component. When an ester solvent is used as the organic solvent described later, the polyester polyol component is 1,3-propane as a plant-derived short-chain diol component from the viewpoints of printability, low temperature stability, blocking resistance and laminating suitability. A biopolyester polyol obtained by subjecting a diol to a condensation reaction with at least two selected from the group consisting of sebacic acid, succinic acid and dimer acid as a carboxylic acid component derived from vegetable oil is preferable.

The organic diisocyanate compound derived from vegetable oil is obtained by converting a dihydric carboxylic acid derived from a plant into a terminal amino group by acid amidation and reduction, and further reacting with phosgene to convert the amino group into an isocyanate group. can get. Examples of the plant-derived biopolyisocyanate include dimerate diisocyanate (DDI), pentane-1,5-diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate. Further, a plant-derived isocyanate compound can also be obtained by using a plant-derived amino acid as a raw material and converting the amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by methyl esterifying the carboxyl group of lysine and then converting the amino group to an isocyanate group. Further, 1,5-pentamethylene diisocyanate is obtained by decarboxylating the carboxyl group of lysine and then converting the amino group into an isocyanate group.

As a method for producing the polyurethane polyurea resin of the present embodiment, for example, a urethane prepolymer is synthesized by reacting an organic diisocyanate compound with a polyol component in an ester-based solvent, then water and an ester-based solvent are added, and the mixture is stirred and mixed. , The polyurethane polyurea resin can be produced by reacting the chain extender and, if necessary, the reaction terminator.

(Ester solvent)
The ester solvent is not particularly limited. As an example, the ester solvent is ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like. Among these, the ester solvent is preferably ethyl acetate, n-propyl acetate, or isopropyl acetate because of its excellent drying property and residual solvent, and ethyl acetate because of its excellent drying property, residual solvent, and cost. It is more preferable to have.

The content of the ester solvent is not particularly limited. As an example, the content of the ester solvent is preferably 15% by mass or more in the ink composition from the viewpoint of excellent printability of the obtained ink composition. The content of the ester solvent is preferably 90% by mass or less in the ink composition. When the content of the organic solvent is within the above range, the ink composition has excellent printability, and it is easy to obtain sufficient color development in the obtained printed matter.

The ink composition of the present embodiment substantially does not contain a solvent other than the ester solvent. As a result, the ink composition has an advantage that the solvent can be easily recovered and it is easy to reuse because the solvent is only the ester solvent. In addition, in this embodiment, "substantially free of solvent other than ester solvent" is substantially 0%, but includes the case where a small amount of solvent is contained in the additive.

(water)
Water is blended in the ink composition in an amount of 0.1 to 10% by mass in order to impart the fluidity of the ink composition.

The water content may be 0.1% by mass or more in the ink composition, and preferably 1% by mass or more. The water content is preferably 9% by mass or less in the ink composition. When the water content is less than 0.1% by weight, the ink composition tends to have a high viscosity. On the other hand, when the water content exceeds 10% by mass, the ink composition tends to be out of balance.

Further, the ink composition of the present embodiment preferably contains at least one selected from the group consisting of rosin and its derivatives, cellulose ester resins, and vinyl chloride / vinyl acetate copolymers.

(Cellulose ester resin)
The ink composition of the present embodiment preferably contains a cellulose ester resin for blocking resistance and viscosity adjustment. Examples of the cellulose ester resin include cellulose acetate propionate resin and cellulose acetate butyrate resin.

As the cellulose acetate propionate resin, the resin conventionally used in the gravure printing ink composition can be used. Cellulose acetate propionate resin is obtained by hydrolyzing cellulose after triesterification with acetic acid and propionic acid. Generally, a cellulose acetate propionate resin having an acetylation of 0.6 to 2.5% by mass, a propionylation of 42 to 46% by mass, and a hydroxyl group of 1.8 to 5% by mass is commercially available. The cellulose acetate propionate resin is preferably used in the range of 0.1 to 3.0% by mass in the composition of the gravure printing ink for film, depending on the type of pigment.

As the cellulose acetate butyrate resin, the resin conventionally used in the gravure printing ink composition can be used. Cellulose acetate butyrate resin is obtained by hydrolyzing cellulose after triesterification with acetic acid and butyric acid. Generally, cellulose acetate butyrate resins having 2 to 30% by mass of acetylation, 17 to 53% by mass of butyrylation, and 1 to 5% by mass of hydroxyl groups are commercially available. The cellulose acetate butyrate resin is preferably used in the range of 0.1 to 3.0% by mass in the gravure printing ink composition for film, depending on the type of pigment.

(Rosin and its derivatives)
Further, it is preferable that the present embodiment contains rosin and a derivative thereof for the purpose of adhesion and stability over time.

Examples of rosin include gum rosin, tall oil rosin, wood rosin and the like. Generally, rosin is an amber, amorphous resin obtained from pine and is a mixture because it is obtained from nature. Rosin may be isolated and used for each component of abietic acid, neo-avietic acid, palastolic acid, pimalic acid, isopimalic acid, sandaracopimaric acid, and dehydroabietic acid, and these are also defined as rosin in the present embodiment. ..

The rosin derivative is a compound obtained by modifying the above rosin, and is specifically listed below.
(1) Hydrogenated rosin: A rosin having improved weather resistance by adding (hydrogenating) hydrogen to a conjugated double bond.
(2) Disproportionation rosin: Disproportionation is a reaction of two molecules of rosin, two molecules of abietic acid having a conjugated double bond, one to aromatic and the other to a single double bond. It is a modification that becomes a molecule. Disproportionated rosins are generally less weather resistant than hydrogenated rosins, but have better weather resistance than untreated rosins.
(3) Rosin-modified phenolic resin: A rosin-modified phenolic resin is often used as a main binder in offset printing inks. The rosin-modified phenolic resin can be obtained by a known production method.
(4) Rosin ester: An ester resin derived from rosin, which has been used as a tackifier (tack fire) for adhesives and adhesives for a long time.
(5) Rosin-modified maleic acid resin: A rosin to which maleic anhydride is added and reacted, and if necessary, a hydroxyl group-containing compound such as glycerin is esterified with no hydroxyl group and grafted.
(6) Polymerized rosin: A derivative containing a dimerized resin acid derived from a natural resin rosin.
In addition, known rosins and rosin derivatives can also be used, and these can be used not only alone but also in combination.

Further, the acid value of rosin and its rosin derivative is preferably 120 mgKOH / g or more. When the acid value is 120 mgKOH / g or more, the ink composition has improved lamination strength. More preferably, the acid value is 160 mgKOH / g or more. The total amount of rosin and its derivatives used when blended is preferably 0.1% by mass to 3.0% by mass in terms of the solid content mass% of the ink composition.

(Vinyl chloride / vinyl acetate copolymer)
Further, in this embodiment, a vinyl chloride / vinyl acetate-based copolymer is contained from the viewpoint of adhesiveness.

The vinyl chloride / vinyl acetate-based copolymer contains vinyl chloride monomer and vinyl acetate monomer, which have been conventionally used in gravure printing ink compositions, as essential components, and vinyl propionate, monochloroacetate, and versatic as needed. A vinyl acetate, a fatty acid vinyl monomer such as vinyl laurate, vinyl stearate, vinyl benzoate and a monomer having a functional group such as a hydroxyl group can be used as a copolymerization component, which is produced by a known method.

Among them, the vinyl chloride / vinyl acetate-based copolymer is preferably a vinyl chloride / vinyl acetate-based copolymer having 50 to 200 hydroxyl groups in the organic solvent-based polymer of the present embodiment. Such a vinyl chloride / vinyl acetate-based copolymer having a hydroxyl group can be obtained by saponifying a part of the acetate ester moiety and introducing a (meth) acrylic monomer having a hydroxyl group.

In the case of a vinyl chloride / vinyl acetate-based copolymer having a hydroxyl group obtained by saponifying a part of the acetic acid ester moiety, the structural unit based on the reaction site of vinyl chloride in the molecule (formula 1 below), acetic acid. The film properties and dissolution behavior of the resin are determined by the ratio of the structural unit based on the reaction site of vinyl (formula 2 below) and the structural unit based on the saponification of the reaction site of vinyl acetate (formula 3 below). That is, the structural unit based on the reaction site of vinyl chloride imparts the toughness and hardness of the resin film, and the structural unit based on the reaction site of vinyl acetate imparts adhesiveness and flexibility, and the reaction site of vinyl acetate is saponified. The structural unit based on the above imparts good solubility in the organic solvent system of the present embodiment.
Equation 1-CH _2- CHCl-
Equation 2-CH _2- CH (OCOCH ₃ )-
Equation 3-CH _2- CH (OH)-

Such a vinyl chloride / vinyl acetate copolymer may be commercially available, for example, Solvine A, AL, TA5R, TA2, TA3, TAO, TAOL, C, CH, manufactured by Nissin Chemical Industry Co., Ltd. CN, CNL, etc. can be mentioned.

The vinyl chloride / vinyl acetate copolymer may have various functional groups in the molecule from the viewpoint of solubility in the organic solvent used in the ink composition of the present embodiment and printability. It preferably has ~ 200 hydroxyl groups. As a commercially available product of such a vinyl chloride / vinyl acetate copolymer, for example, it is preferable to use solvene A, AL, TA5R, TA2, TA3, TAO, TAOL and the like.

The amount of the vinyl chloride / vinyl acetate-based copolymer used is preferably in the range of polyurethane resin / vinyl chloride / vinyl acetate-based copolymer = 95/5 to 45/55 (mass ratio).

(Optional ingredient)
The ink composition of the present embodiment contains the above-mentioned pigment, polyurethane polyurea resin, ester solvent, water, cellulosic resin, rosin and its derivatives, vinyl chloride / vinyl acetate copolymer, and any other components as appropriate. May be blended. The optional component is not particularly limited. As an example, the optional component may be adhered to a polyurethane polyurea resin, a binder resin other than a vinyl chloride / vinyl acetate copolymer, a pigment dispersant, a cross-linking agent, a lubricant, a surfactant, a chlorinated polypropylene, a dammar resin, or the like. It is a property improver, silica particles, polyethylene wax, fatty acid amide, vitrified cotton, a blocking inhibitor such as a polyamide resin, and the like.

(Polyurethane polyurea resin, which is an optional component, binder resin other than vinyl chloride / vinyl acetate copolymer)
A vinyl chloride / acrylic polymer can be used in the ink composition of the present embodiment from the viewpoint of adhesiveness. The amount of the vinyl chloride / acrylic polymer used is polyurethane resin / (vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / acrylic copolymer) = 95/5 to 45/55 (mass ratio). It may be used up to the range.

<Vinyl chloride / acrylic copolymer>
The vinyl chloride / acrylic copolymer contains a copolymer of vinyl chloride and an acrylic monomer as a main component. The form of the copolymer is not particularly limited, and for example, the acrylic monomer may be blocked or randomly incorporated in the main chain of polyvinyl chloride, or may be graft-copolymerized in the side chain of polyvinyl chloride. ..

As the acrylic monomer, a (meth) acrylic acid ester, an acrylic monomer having a hydroxyl group, or the like can be used. Examples of the (meth) acrylic acid ester include a (meth) acrylic acid alkyl ester, and the alkyl group may be linear, branched or cyclic, and is preferably a linear alkyl group.

The (meth) acrylic acid ester is, for example, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, butyl (meth) acrylic acid, pentyl (meth) acrylic acid, (meth) acrylic acid. Hexil, (meth) cyclohexyl acrylate, (meth) 2-ethylhexyl acrylate, (meth) isooctyl acrylate, (meth) decyl acrylate, (meth) dodecyl acrylate, (meth) tetradecyl acrylate, (meth) acrylic Examples thereof include hexadecyl acid acid and octadecyl (meth) acrylate.

Examples of acrylic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (Meta) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, (meth) acrylic acid 8-hydroxyoctyl, etc. , Polyethylene glycol mono (meth) 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. Can be mentioned.

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

The vinyl chloride / acrylic copolymer resin preferably has a mass average molecular weight of 10,000 to 70,000.

Further, from the viewpoint of the solubility in the organic solvent and the adhesiveness to the substrate of the present embodiment, the vinyl chloride / acrylic copolymer preferably has 50 to 200 hydroxyl groups.

(Adhesion improver, which is an optional ingredient)
<Chlorinated polypropylene>
As the chlorinated polypropylene, those having a chlorination degree of 20 to 50% are preferably used. When the degree of chlorination is within the above range, the chlorinated polypropylene has excellent compatibility with an organic solvent and excellent adhesiveness to a film. In this embodiment, the degree of chlorination is defined by the mass% of chlorine atoms in the chlorinated polypropylene resin. Further, the chlorinated polypropylene is preferably a modified or unmodified chlorinated polypropylene having a mass average molecular weight of 5000 to 200,000. When the mass average molecular weight is within the above range, the chlorinated polypropylene has excellent adhesiveness and excellent solubility in an organic solvent. When chlorinated polypropylene is used, the solid content of the ink composition is preferably 3.0% by mass or less.

<Dammar resin>
Dammar resin, also referred to as dammar or dammar, is a type of plant-derived natural resin. Specifically, it is a kind of natural resin obtained from plants of the family Dipterocarpaceae or Torchwoodaceae that grow in Southeast Asia such as Malaysia and Indonesia. When using the dammar resin, dissolve it in a suitable organic solvent to make a varnish. Since the dammar resin does not contain chlorine, chlorine can be eliminated or reduced as compared with the case where a chlorinated polyolefin resin is used in the printing ink composition. When a dammar resin is used, the solid content of the ink composition is preferably 3.0% by mass or less.

(Anti-blocking agent that is an optional ingredient)
<Silica particles>
Examples of the silica particles include natural products, synthetic products, crystalline, amorphous, hydrophobic, and hydrophilic particles. The silica particles preferably have an average particle size of 1.0 to 5.0 μm (the average particle size of the silica particles means a particle size at an integrated value of 50% (D50) in the particle size distribution, and is a Coulter counter method. Can be obtained by). The silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or hydrophobic silica obtained by modifying the hydrophilic functional group with an alkylsilane or the like to make it hydrophobic. Among these, the silica particles are preferably hydrophilic. The ink composition containing hydrophilic silica particles also has an effect of promoting wetting and spreading of the ink during overprinting and improving the overprinting effect (hereinafter, may be referred to as “trapping property”). When silica particles are used, they are used in an ink composition in an amount of 3.0% by mass or less, preferably 1.0% by mass or less.

<Polyethylene wax>
As the polyethylene wax, one having an average particle size in the range of 1.0 to 3.0 μm (the average particle size means the particle size measured by Microtrac UPA manufactured by Honeywell Co., Ltd.) is used. When the particle size of the polyethylene wax is within the above range, the ink composition is excellent in slipperiness, blocking property, and trapping property. When polyethylene wax is used, the content in the ink composition is preferably 1.5% by mass or less.

<Nitrified cotton>
As the nitrified cotton, nitrified cotton conventionally used in a gravure printing ink composition can be used. The vitrified cotton is obtained as a nitrate ester in which the three hydroxyl groups in the 6-membered ring of the anhydrous glucopyranose group in the natural cellulose are replaced with the nitric acid group by reacting the natural cellulose with nitric acid. As the nitricized cotton used in this embodiment, one having a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90 is preferably used. Specific examples of the nitrified cotton include SS1 / 2, SS1 / 4, SS1 / 8, TR1 / 16, NCRS-2, (manufactured by KOREA CNC LTD) and the like. When nitrified cotton is used, it is preferable to use it in an ink composition so as to have a content of 2.0% by mass or less, depending on the type of pigment.

<Fatty acid amide>
The fatty acid amide is not particularly limited as long as it has a residue obtained by removing an acid group from the fatty acid and an amide group. Examples of the fatty acid amide include monoamide, substituted amide, bisamide, methylolamide, and ester amide, and are at least one selected from the group consisting of monoamide, substituted amide, and bisamide because the blocking resistance is improved. Is preferable. The amount of the fatty acid amide used is preferably in the range of 1% by mass or less in the ink composition.

-Monoamide: Monoamide is represented by the following general formula (1).
General formula (1) R1-CONH ₂
(In the formula, R1 represents a residue obtained by removing COOH from fatty acid.)

Specific examples of monoamides include lauric acid amides, palmitic acid amides, stearic acid amides, behenic acid amides, hydroxystearic acid amides, oleic acid amides, and erucic acid amides.

Substituted amide: The substituted amide is represented by the following general formula (2).
General formula (2) R2-CONH-R3
(In the formula, R2 and R3 represent residues obtained by removing COOH from fatty acids, and may be the same or different.)

Specific examples of the substituted amide include N-oleyl palmitate amide, N-stearyl stearyl amide, N-stearyl oleate amide, N-oleyl stealic acid amide, N-stearyl erucate amide and the like.

Bisamide: Bisamide is represented by the following general formula (3) or general formula (4).
General formula (3) R4-CONH-R5-HNCO-R6
General formula (4) R7-NHCO-R8-CONH-R9
(In the formula, R4, R6, R7, and R9 represent residues obtained by removing COOH from fatty acids, and may be the same or different, and R5 and R8 represent alkylene groups or arylene groups having 1 to 10 carbon atoms. )

Specific examples of the bisamide include methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbechenic acid amide, and hexamethylene bisstearic acid amide. , Hexamethylene bisbechenic acid amide, hexamethylene hydroxystearic acid amide, ethylene bisoleic acid amide, ethylene biserukaic acid amide, hexamethylene bisoleic acid amide, N, N'-distealyl adipic acid amide, N, N'- Examples thereof include distearyl sevacinic acid amide, N, N'-diorail adipic acid amide, N, N'-diorail sevacinic acid amide and the like.

-Methylolamide: Methylolamide is represented by the following general formula (5).
General formula (5) R10-CONHCH ₂ OH
(In the formula, R10 represents a residue obtained by removing COOH from fatty acid.)

Specific examples of the methylol amide include methylol palmitate amide, methylol stearate amide, methylol behenic acid amide, methylol hydroxystearic acid amide, methylol oleic acid amide, and methylol erucic acid amide.

-Ester amide: The ester amide is represented by the following general formula (6).
General formula (6) R11-CONH-R12-OCO-R13
(In the formula, R11 and R13 represent residues obtained by removing COOH from fatty acids, and may be the same or different, and R12 represents an alkylene group or an arylene group having 1 to 10 carbon atoms.)

Specific examples of the ester amide include stearylamide ethyl stearate and oleylamide ethyl stearate.

The melting point of the fatty acid amide is preferably 50 ° C to 150 ° C.

The fatty acid constituting the fatty acid amide is preferably a saturated fatty acid having 12 to 22 carbon atoms and / or an unsaturated fatty acid having 16 to 25 carbon atoms, and a saturated fatty acid having 16 to 18 carbon atoms and / or 18 to 22 carbon atoms. Unsaturated fatty acids are more preferred. Saturated fatty acids are more preferably lauric acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid, and unsaturated fatty acids are more preferably oleic acid and erucic acid.

(Antistatic agent that is an optional component)
As the antistatic agent, a known one that can be used as a gravure printing ink can be used. Specific examples include coconut alkylbis (hydroxyethyl) methyl nitrate and coconut alkylbis (hydroxyethyl) methyl chloride, quaternary ammonium salt compounds (sulfate), monoalkyltrimethylammonium chloride, monoalkylbenzyldimethylammonium chloride, and the like. Examples thereof include quaternary ammonium salts (hydrochloride) such as dialkyldimethylammonium chloride, thiocyanate, alkylimidazolin, and alkylimidazolium. When an antistatic agent is used, it is preferable to use the antistatic agent so that the content of the antistatic agent is 3.0% by mass or less in the ink composition.

The method for producing the ink composition of the present embodiment is not particularly limited. As an example, the ink composition is prepared by kneading a pigment, a polyurethane polyurea resin, and an ester solvent using various kneading machines such as a bead mill, a ball mill, a sand mill, an attritor, a roll mill, and a pearl mill. , Water and various optional components may be added and mixed by stirring.

The obtained ink composition has a viscosity of 10 to 1000 mPa · s. When used during gravure printing, the ink composition has a specific viscosity of 12 to 23 seconds for the Zahn Cup No. 3 so that the ink composition has an appropriate viscosity according to the printing conditions at the atmospheric temperature at the time of printing. For high-speed printing at / 25 ° C, it is preferable to dilute with an ester solvent until the temperature reaches about 14 to 16 seconds / 25 ° C.

(Method of obtaining a laminated product using a printing ink composition for laminating for flexible packaging)
Next, a method of obtaining a laminated product using the ink composition of the present embodiment will be described.

In the laminated product of the present embodiment, for example, an ink composition other than white is first printed on a resin film at least once by a gravure printing method. Next, a white ink composition is optionally printed on the surface side (after the final laminating, the lower layer side when viewed from the surface layer) of the colored ink layer formed by these printing by a gravure printing method, and dried by a dryer.

A resin film or the like can be laminated by various laminating methods on the side of the layer of the obtained printed matter made of the white ink composition to obtain a laminated product for a packaging bag or the like.

As a method for obtaining this laminated product, an anchor coating agent is applied to the surface of the printed material, and then an extruded laminating method in which a molten polymer is laminated, and an adhesive diluted with an organic solvent to an appropriate viscosity is applied to the surface of the printed material. After that, a dry laminating method in which the film-shaped polymer is bonded, and a non-sol laminating method in which the film-shaped polymer is bonded after applying a solvent-free adhesive to the surface of the printed matter can be used. The above-mentioned extrusion laminating method is a method in which an anchor coating agent such as titanium-based, urethane-based, imine-based, or polybutadiene is applied to the surface of a printed matter as needed, and then the molten polymer is laminated by a known extrusion laminating machine. Further, the molten resin can be used as an intermediate layer and laminated with other materials in a sandwich shape.

As the molten polymer used in the extruded laminating method, conventionally used resins such as low-density polyethylene, ethylene-vinyl acetate copolymer, and polypropylene can be used. Among them, the effect of the present invention is enhanced in the configuration with low-density polyethylene which is oxidized at the time of melting and easily generates a carbonyl group.

Further, in the above dry laminating method, an adhesive such as urethane or isocyanate diluted with an organic solvent to an appropriate viscosity is applied to the surface of the printed matter, and after drying, a film-like polymer is attached by a known dry laminating machine. It is a method of matching. Further, the non-sol laminating method is a method in which a urethane-based or isocyanate-based adhesive is applied to the surface of a printed matter, and then a film-like polymer is bonded by a known dry laminating machine. As the resin for the film used in the dry laminating method and the non-sol laminating method, polyethylene, unstretched polypropylene and the like can be used. Especially for packaging materials used for retort pouches, aluminum foil can be sandwiched between the resin film to be bonded to the base material and laminated. Such a laminated product can also be used for boiled retort after making a bag and filling the contents.

The resin film used at this time is not particularly limited. Resin films include, for example, polyester films such as polyethylene terephthalate (PET), polylactic acid, and polycaprolactone, various printing plastic films such as nylon and vinylon, and barriers obtained by coating these various printing plastic films with metal vapor deposition or barrier resin. A film or the like in which layers are laminated can be used.

The embodiment of the present invention has been described above. The present invention is not particularly limited to the above embodiment. The above-described embodiment mainly describes an invention having the following configuration.

(1) The polyurethane polyurea resin contains a pigment, a polyurethane polyurea resin, an ester solvent, and 0.1 to 10% by mass of water, and the polyurethane polyurea resin is a polyester polyol component as a polyol component constituting the polyurethane polyurea resin. A laminated printing ink composition for flexible packaging, which contains 30% by mass or more, has an amine value of 1.0 to 10.0 mgKOH / g, and substantially does not contain a solvent other than an ester solvent.

(2) The laminated printing ink composition for flexible packaging according to (1), wherein the pigment contains at least one of an organic pigment and titanium oxide.

(3) The laminated printing ink composition for flexible packaging according to (2), wherein the titanium oxide is titanium oxide surface-treated with silica alumina.

(4) The laminated printing ink for flexible packaging according to (2) or (3), wherein the titanium oxide has an average particle size of 0.2 to 0.3 μm and an oil absorption of 17 to 35 ml / 100 g. Composition.

(5) The polyurethane polyurea resin is a polyurethane polyurea resin containing at least one of a primary amino group and a secondary amino group at the end, according to any one of (1) to (4). Laminate printing ink composition for flexible packaging.

(6) The laminated printing ink composition for flexible packaging according to any one of (1) to (5), wherein the polyester polyol component is a plant-derived biopolyester polyol.

(7) The laminate printing ink composition for flexible packaging according to any one of (1) to (6), which contains a polyether polyol component as a polyol component constituting the polyurethane polyurea resin.

(8) The laminate printing ink composition for flexible packaging according to (7), wherein the polyether polyol component is a polymer or copolymer of methylene oxide, ethylene oxide, propylene oxide, or tetrahydrofuran.

(9) The flexible packaging according to any one of (1) to (8), further comprising at least one selected from the group consisting of rosin and its derivatives, cellulose ester resins, and vinyl chloride / vinyl acetate-based copolymers. For laminate printing ink composition.

(10) The laminate printing ink composition for flexible packaging according to any one of (1) to (9), wherein the ester solvent is ethyl acetate.

(11) A printed matter on which the laminated printing ink composition for flexible packaging according to any one of (1) to (10) is printed.

Hereinafter, the present invention will be described more specifically by way of examples. The present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "part" means "part by mass".

The raw materials used are shown below.
(Pigment)
Pigment 1: Titanium oxide (particle size 0.23 μm, oil supply amount 24 g / 100 g, silica alumina treatment, PH 6.5-8.5)
Pigment 2: Titanium oxide (particle size 0.25 μm, oil supply amount 18-23 g / 100 g, silica alumina organic zinc treatment, PH 6.5-8.5)
Pigment 3: PY14

(Production Example 1: Polyurethane Polyurea Resin Varnish 1)
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 100 parts by mass of a polyester polyol containing ethylene glycol / neopentyl glycol = 7/3 having an average molecular weight of 2000 and adipic acid and 100 parts by mass of a polypropylene glycol having an average molecular weight of 2000. A part by mass and 42.0 parts by mass of isophorone diisocyanate were charged and reacted at 85 to 90 ° C. for 3 hours while introducing nitrogen gas. Allow to cool to near room temperature, add 16.9 parts by mass of water and 754.1 parts by mass of ethyl acetate, then add 0.4 parts by mass of monoethanolamine to react, and further add 14.3 parts by mass of isophorone diamine. A polyurethane polyurea resin varnish 1 (solid content 25% by mass) was obtained by adding 0.3 parts by mass of diaminetriamine, chain extension and reaction termination.

(Production Example 2: Polyurethane Polyurea Resin Varnish 2)
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 80 parts by mass of a polyester polyol containing ethylene glycol / neopentyl glycol = 7/3 having an average molecular weight of 2000 and adipic acid and a polypropylene glycol 120 having an average molecular weight of 2000. A part by mass and 42.0 parts by mass of isophorone diisocyanate were charged and reacted at 85 to 90 ° C. for 3 hours while introducing nitrogen gas. Allow to cool to near room temperature, add 16.9 parts by mass of water and 754.1 parts by mass of ethyl acetate, then add 0.4 parts by mass of monoethanolamine to react, and further add 14.3 parts by mass of isophorone diamine. A polyurethane polyurea resin varnish 2 (solid content 25% by mass) was obtained by adding 0.3 parts by mass of diaminetriamine, chain extension and reaction termination.

(Production Example 3: Polyurethane Polyurea Resin Varnish 3)
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 120 parts by mass of a polyester polyol having an average molecular weight of 2000 ethylene glycol / neopentyl glycol = 7/3 and adipic acid and an average molecular weight of 2000 polypropylene glycol 80 A part by mass and 42.0 parts by mass of isophorone diisocyanate were charged and reacted at 85 to 90 ° C. for 3 hours while introducing nitrogen gas. Allow to cool to near room temperature, add 16.9 parts by mass of water and 754.1 parts by mass of ethyl acetate, then add 0.4 parts by mass of monoethanolamine to react, and further add 14.3 parts by mass of isophorone diamine. A polyurethane polyurea resin varnish 3 (solid content 25% by mass) was obtained by adding 0.3 parts by mass of diaminetriamine, chain extension and reaction termination.

(Production Example 4: Polyurethane Polyurea Resin Varnish 4)
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 100 parts by mass of a polyester polyol containing ethylene glycol / neopentyl glycol = 5/5 having an average molecular weight of 2000 and adipic acid and 100 parts by mass of a polypropylene glycol having an average molecular weight of 2000. A part by mass and 42.0 parts by mass of isophorone diisocyanate were charged and reacted at 85 to 90 ° C. for 3 hours while introducing nitrogen gas. Allow to cool to near room temperature, add 16.9 parts by mass of water and 754.1 parts by mass of ethyl acetate, then add 0.4 parts by mass of monoethanolamine to react, and further add 14.3 parts by mass of isophorone diamine. A polyurethane polyurea resin varnish 4 (solid content 25% by mass) was obtained by adding 0.3 parts by mass of diaminetriamine, chain extension and reaction termination.

(Production Example 5: Polyurethane Polyurea Resin Varnish 5)
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 100 parts by mass of a polyester polyol containing ethylene glycol / neopentyl glycol = 7/3 having an average molecular weight of 2000 and adipic acid and 100 parts by mass of a polypropylene glycol having an average molecular weight of 2000. A part by mass and 42.0 parts by mass of isophorone diisocyanate were charged and reacted at 85 to 90 ° C. for 3 hours while introducing nitrogen gas. Allow to cool to near room temperature, add 16.9 parts by mass of water and 754.1 parts by mass of ethyl acetate, then add 0.4 parts by mass of monoethanolamine to react, and further add 14.6 parts by mass of isophorone diamine. A polyurethane polyurea resin varnish 5 (solid content: 25% by mass) was obtained by adding a portion, extending the chain, and terminating the reaction.

(Production Example 6: Polyurethane Polyurea Resin Varnish 6)
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 100 parts by mass of a polyester polyol containing ethylene glycol / neopentyl glycol = 7/3 with an average molecular weight of 2000 and adipic acid and a polyether polyol having an average molecular weight of 2000. 100 parts by mass of polypropylene glycol and 42.0 parts by mass of isophorone diisocyanate as organic diisocyanate were charged and reacted at 85 to 90 ° C. for 3 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 16.9 parts by mass of water and 754.7 parts by mass of ethyl acetate were added, and then 0.4 parts by mass of monoethanolamine was added as a reaction terminator to react, and the reaction was further terminated. 15.0 parts by mass of isophorone diamine was added as a chain extender, and the chain was extended and the reaction was stopped to obtain a polyurethane polyurea resin varnish 6 (solid content 25% by mass).

(Production Examples 7 to 28: Polyurethane Polyurea Resin Varnish 7 to 28)
Polyurethane polyurea resin The polyester polyol, polyether polyol, organic diisocyanate, reaction terminator, reaction terminator / chain extender, and solvent of the varnish 6 are arranged in the types and amounts shown in Tables 1 and 2 so that the polyurethane polyurea resin is blended. Polyurethane polyurea resin varnishes 7 to 28 having a mass average molecular weight and an amine value shown in Tables 1 and 2 were obtained by the same synthesis method as the varnish 6.

(Cellulose Acetate Propionate (CAP) Solution)
20 parts by mass of cellulose acetate propionate (manufactured by Kanto Chemical Co., Ltd., number average molecular weight 25000, propionyl 43-47%) was dissolved in a mixed solvent mixed with 80% by mass of ethyl acetate, and cellulose acetate pro with a solid content of 20% was dissolved. A pionate (CAP) solution was obtained.

(Rosin and its derivatives)
Polymerized rosin: Acid value 160 mgKOH / g
(Chlorinated polypropylene)
40 parts by mass of chlorinated polypropylene (solid content 50%) having a degree of chlorination of 40% and a mass average molecular weight of 100,000 and 60 parts by mass of ethyl acetate were mixed and stirred to obtain a chlorinated polypropylene varnish having a solid content of 20%.
(Vinyl chloride / vinyl acetate resin)
Vinyl chloride / vinyl acetate copolymer (Solvine TA-3, manufactured by Nisshin Kagaku Kogyo Co., Ltd.)
(Polyethylene wax)
Average particle size: 2.11 μm
(Ester solvent)
Ethyl acetate

(Examples 1 to 36, Comparative Examples 1 to 2)
According to the formulations shown in Tables 3 to 6 and the following production examples, ink compositions for laminate printing for flexible packaging of Examples 1 to 36 and Comparative Examples 1 and 2 were obtained.

<Manufacturing example of ink composition for laminating for flexible packaging>
The pigment, the polyurethane polyurea resin varnish, and ethyl acetate are kneaded using a paint conditioner manufactured by Red Devil, and water, polymerized rosin, cellulose acetate propionate CAP, and ethyl acetate are added and stirred, and Tables 3 to 3 are shown. The ink compositions for laminate printing for flexible packaging of Examples and Comparative Examples shown in 6 were obtained.

(Ink storage stability)
The printing ink composition for laminating for flexible packaging obtained above was collected in a glass bottle, and the storage stability of the ink was evaluated from the presence or absence of pigment settling when stored at an atmospheric temperature of 60 ° C. for 14 days. The results are shown in Tables 3 to 6.
(Evaluation criteria)
A: No sedimentation was observed, and the storage stability of the ink was good.
B: Sedimentation was observed, and the storage stability of the ink was poor.

<Manufacturing of laminated body>
100 parts by mass of each of the printing white ink compositions for laminating for flexible packaging was diluted with a mixed solvent according to the formulations shown in Tables 1 and 2, and the viscosity was adjusted to 15 seconds with Zahn Cup No. 3 manufactured by Rigosha. A printed matter for laminating for flexible packaging was printed on the treated surface of various films using a gravure printing machine and dried under the following conditions to obtain a printed matter for laminating. In addition, the obtained laminated printed matter was used to evaluate blocking resistance, adhesiveness, and retort resistance. The results are shown in Tables 3 to 6. The specific evaluation method is shown below.
(Printing method / printing conditions)
Room environment at the time of printing: temperature 25 ° C, humidity 50%
Coating machine: Gravure proofing machine Coating speed: 150 m / min Printing plate: Direct 175-line solid plate Drying temperature: 100 ° C (air volume 80%)

<About film>
PET: Polyethylene terephthalate film with corona discharge treatment on one side, manufactured by Toyobo Co., Ltd., E-5101, thickness 12 μm
OPP: Corona discharged biaxially stretched polypropylene film, P-2161 manufactured by Toyobo Co., Ltd., thickness 25 μm
NY: Nylon film, manufactured by Toyobo Co., Ltd., N-1102, thickness 15 μm
Fine barrier: PET film with alumina vapor deposition treatment on one side (trade name: Fine Barrier AT-R, manufactured by Reiko Co., Ltd.)
Tech Barrier: PET film with silica vapor deposition treatment on one side (Product name: Tech Barrier TXR, manufactured by Mitsubishi Plastics Co., Ltd.)
A-OP: Stretched polypropylene film coated with polyvinyl alcohol on one side (trade name: A-OPBH, manufactured by Mitsui Chemicals Tocello Co., Ltd.)
Emblem: Stretched nylon film coated with polyvinylidene chloride on one side (trade name: Emblem-DC DCR, manufactured by Unitika Ltd.)
Besera: PET film coated with acrylic polymer on one side (trade name: Besera ET140R, manufactured by Toppan Printing Co., Ltd.)
GL: PET film with alumina vapor deposition on one side (trade name: GL-ARH, manufactured by Toppan Printing Co., Ltd.)

(Blocking resistance)
The printed surface of each film printed matter one day after printing of each test ink was combined with the untreated surface of each film, and ^{a load of 400 g / cm 2} was applied and the film was left at 40 ° C. for 12 hours, and then each film was peeled off. The blocking resistance was evaluated from the state of time.
(Evaluation criteria)
A: There was no resistance when the film was peeled off, and the ink did not peel off from the printed surface.
B: There was resistance when the film was peeled off, but the ink did not peel off from the printed surface.
C: There was resistance when the film was peeled off, and the ink peeled off from the printed surface.

(Adhesiveness)
After rubbing twice with the abdomen of the thumb on the printed surface immediately after printing of each obtained printed matter, a cellophane tape is attached, and the adhesiveness is evaluated from the ratio of the area where the ink film is peeled off from the adherend when peeled off. did.
(Evaluation criteria)
A: The film did not peel off at all.
B: The area where the film was peeled off was less than 20%.
C: The area where the film was peeled off was 20% or more.

(Retort resistance)
After applying a urethane adhesive (Takelac A-626 / Takenate A-50, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) in an amount of ^{solid content of 3.0 g / m 2} to each printed matter one day after printing. A non-stretched polypropylene film (RXC-3, thickness 60 μm, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) was bonded with a dry laminating machine and left at 40 ° C. for 3 days to obtain a dry laminated matter. Whether or not the laminate film floats when this dry laminate is made into a bag, filled with a mixture of 90% by weight of water and 10% by weight of salad oil, sealed, and then immersed in hot water at 120 ° C. for 30 minutes. The retort resistance was evaluated from. The evaluation criteria were the same as the boil suitability.
(Evaluation criteria)
A: No Lami float was seen at all.
B: A pinhole-like or partly thin and short Lami float was observed.
C: Long streaky lami floats were seen on the entire surface.
-: The film itself used for printing did not have retort suitability, so the retort suitability test was not performed.

Claims (11)

It contains a pigment, a polyurethane polyurea resin, an ester solvent, and 0.1 to 10% by mass of water.
The polyurethane polyurea resin contains a polyester polyol component in an amount of 30% by mass or more as a polyol component constituting the polyurethane polyurea resin, and has an amine value of 1.0 to 10.0 mgKOH / g.
A laminated printing ink composition for flexible packaging that contains substantially no solvent other than an ester solvent. The laminated printing ink composition for flexible packaging according to claim 1, wherein the pigment contains at least one of an organic pigment and titanium oxide. The laminated printing ink composition for flexible packaging according to claim 2, wherein the titanium oxide is titanium oxide surface-treated with silica alumina. The laminated printing ink composition for flexible packaging according to claim 2 or 3, wherein the titanium oxide has an average particle size of 0.2 to 0.3 μm and an oil absorption of 17 to 35 ml / 100 g. The flexible packaging according to any one of claims 1 to 4, wherein the polyurethane polyurea resin is a polyurethane polyurea resin containing at least one of a primary amino group and a secondary amino group at the end. Laminate printing ink composition. The laminate printing ink composition for flexible packaging according to any one of claims 1 to 5, wherein the polyester polyol component is a plant-derived biopolyester polyol. The laminated printing ink composition for flexible packaging according to any one of claims 1 to 6, which contains a polyether polyol component as a polyol component constituting the polyurethane polyurea resin. The laminated printing ink composition for flexible packaging according to claim 7, wherein the polyether polyol component is a polymer or copolymer of methylene oxide, ethylene oxide, propylene oxide, or tetrahydrofuran. The flexible packaging laminate printing according to any one of claims 1 to 8, further comprising at least one selected from the group consisting of rosin and its derivatives, cellulose ester resins, and vinyl chloride / vinyl acetate copolymers. Ink composition. The laminate printing ink composition for flexible packaging according to any one of claims 1 to 9, wherein the ester solvent is ethyl acetate. A printed matter on which the laminate printing ink composition for flexible packaging according to any one of claims 1 to 10 is printed.