Method for producing gravure printing ink composition

Abstract

To provide a method for producing an ink composition for gravure printing, which improves temporal stability as an ink composition and, at the same time, prevents residual odor of an ink composition itself and a printed part after printing.SOLUTION: A method for producing an ink composition for gravure printing includes the following steps A to E: step A of synthesizing an urethane prepolymer from an organic diisocyanate compound and a polymer diol compound; step B of mixing the urethane prepolymer with an organic solvent to obtain an urethane prepolymer solution; step C of adding thereto a compound obtained by ketiminating an amino group of a polyamine compound with a ketone compound, followed by mixing; step D of adding water thereto under the following condition, then subjecting the mixture to chain elongation and / or reaction termination to obtain a polyurethane polyurea resin solution for gravure printing; and step E of adding a coloring agent to the polyurethane polyurea resin solution for gravure printing. Condition: water is added to an extent such that the polyurethane polyurea resin for gravure printing obtained by the method for producing the polyurethane polyurea resin for gravure printing does not precipitate.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a gravure printing ink composition.

Background Art

[0002] As described in Patent Document 1, it is known that a urethane prepolymer is chain-extended and reaction-terminated, and then acetone is directly added to the solution of the obtained polyurethane resin to react a ketone compound with the amino group at the terminal of the polyurethane resin to perform ketimine formation. The ketimine-modified polyurethane resin obtained by such a method for synthesizing a ketimine-modified polyurethane resin is said to have reduced odor and excellent viscosity stability. The ketimine-modified polyurethane resin obtained by this synthesis method has a reduced pungent odor due to acetone, but the low molecular weight chain extender and reaction terminator present in the resin composition are also ketimine-modified. As a result, another odor is generated due to the ketimine-modified low molecular weight chain extender and reaction terminator, and ultimately, the odor of the entire resin composition could not be sufficiently suppressed. Furthermore, when the low molecular weight reduction of polyurethane during storage is suppressed, the viscosity stability is improved. However, there is a problem that the stability over time of these compositions decreases when used as an ink composition, paint, etc. due to the ketimine-modified low molecular weight chain extender and reaction terminator that remain without being completely removed. In addition, for the polyurethane resin obtained by a conventionally known production method, the smaller the molecular weight, the more uneven the reaction becomes, so an unreacted low molecular weight chain extender remains. As a result, the printing ink composition and printed matter using the polyurethane resin have an amine odor, and when such a polyurethane resin is used and a pigment is further dispersed, the dispersibility tends to decrease.

[0003] Also, as described in Patent Documents 2 and 3, it is known that a polyurethane polyurea resin powder for slush molding or the like can be obtained by reacting a ketimine compound obtained from a diamine and a ketone with a urethane prepolymer in an aqueous solvent. In particular, Patent Document 2 describes that a urethane prepolymer is chain-extended with a bimolecular condensate of a ketone in the presence of water and a dispersion stabilizer.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] The problem to be solved by the present invention is to provide a method for producing a gravure printing ink composition that improves the stability over time as an ink composition and simultaneously prevents the remaining odor of the ink composition itself and the printed portion after printing.

Means for Solving the Problems

[0006] The present inventors have found that the above problems can be solved by adopting a specific method for producing a gravure printing ink composition. That is, the present invention is 1. A method for producing a gravure printing ink composition having the following steps A to E. A. A step of synthesizing a urethane prepolymer from an organic diisocyanate compound and a high molecular diol compound, B. A step of mixing the urethane prepolymer and an organic solvent to obtain a urethane prepolymer solution, Step C: A step of adding and mixing a compound in which an amino group of a polyamine compound is ketiminated with a ketone compound. Step D: A step of adding water under the following conditions and then performing chain extension and / or reaction termination to obtain a polyurethane-polyurea resin solution for gravure printing. Condition: In the range where the polyurethane-polyurea resin for gravure printing obtained by the method for producing a polyurethane-polyurea resin for gravure printing does not precipitate. Step E: A step of adding a colorant to the polyurethane-polyurea resin solution for gravure printing. 2. Regarding the use ratio of the organic diisocyanate compound and the high molecular diol, the method for producing a gravure printing ink composition according to 1, wherein the equivalent ratio of isocyanate group to hydroxyl group (isocyanate index) is NCO group / OH group = 1.2 to 3.0. 3. The method for producing a gravure printing ink composition according to 1 or 2, wherein the organic solvent is a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent or an ester-based organic solvent. 4. The method for producing a gravure printing ink composition according to any one of 1 to 3, wherein the ketiminated compound is a compound in which an amino group of a polyamine compound is ketiminated with one or more ketone compounds selected from acetone, diethyl ketone, methyl ethyl ketone, and diacetone alcohol.

Effects of the Invention

[0007] According to the present invention, it is possible to obtain a gravure printing ink composition that is excellent in stability over time when used as an ink composition, does not generate odors peculiar to amines and ketimines, and the obtained printed matter does not have odors peculiar to amines and ketimines.

Modes for Carrying Out the Invention

[0008] Hereinafter, the method for producing a gravure printing ink composition of the present invention will be described. A method for producing a gravure printing ink composition having the following steps A to E. Step A: A step of synthesizing a urethane prepolymer from an organic diisocyanate compound and a high molecular diol compound. Step of mixing a urethane prepolymer and an organic solvent to obtain a urethane prepolymer solution, Step of mixing the urethane prepolymer solution and a compound in which an amino group of a polyamine compound is ketiminated with a ketone compound, Step of adding water under the following conditions and then performing chain extension and / or reaction termination to obtain a polyurethane-polyurea resin solution for gravure printing, Condition: Range in which the polyurethane-polyurea resin for gravure printing obtained by the production method of the polyurethane-polyurea resin for gravure printing does not precipitate Step of adding a colorant to the polyurethane-polyurea resin solution for gravure printing,

[0009] <Step of synthesizing a urethane prepolymer from an organic diisocyanate compound and a high molecular weight diol compound> The step of synthesizing the urethane prepolymer consists of the step of reacting the following organic diisocyanate compound and the high molecular weight diol compound. (Organic diisocyanate compound) Examples of the organic diisocyanate compound include aromatic diisocyanate compounds such as 1,3- and / or 1,4-phenylene diisocyanate, 4,4-diisocyanatobiphenyl, 3,3-dimethyl-4,4-diisocyanatobiphenyl, and tolylene diisocyanate; alicyclic diisocyanate compounds such as dicyclohexylmethane 4,4'-diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexylene diisocyanate, dicyclohexylmethane-4,4-diisocyanate (hydrogenated MDI), methylcyclohexylene diisocyanate (hydrogenated TDI), and isophorone diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate (HDI), ethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; and aromatic aliphatic diisocyanate compounds such as m- and / or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate. These organic diisocyanate compounds can be used alone or in admixture of two or more. Among them, alicyclic diisocyanate, aliphatic diisocyanate, and aromatic aliphatic diisocyanate are more preferred.

[0010] (Polymeric diol compound) Examples of the high molecular diol compounds include polyester diol compounds such as polyester diols obtained by subjecting one or more dibasic acids such as adipic acid, sebacic acid, and phthalic anhydride and one or more glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol to a condensation reaction, polycaprolactone diol compounds, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and polyether diol compounds such as alkylene oxide adducts of bisphenol A with ethylene oxide and propylene oxide. These high molecular diol compounds can be used alone or in combination of two or more. Among them, 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 1,000 to 8,000 obtained by subjecting adipic acid and 3-methyl-1,5-pentanediol to a condensation reaction is preferable, and 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 1,000 to 4,000 is more preferable.

[0011] (Biopolyester diol compound) When considering the environmental aspect, a biopolyester polyol is used as the high molecular diol compound. The biopolyester diol compound is preferably a biopolyester polyol compound obtained by reacting a short-chain diol component having 2 to 4 carbon atoms and a carboxylic acid 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 or both are derived from a plant.

[0012] The plant-derived short-chain diol component having 2 to 4 carbon atoms is not particularly limited. For example, the short-chain diol component may be 1,3-propanediol, 1,4-butanediol, ethylene glycol, etc. obtained from plant raw materials by the following method. These may be used in combination.

[0013] 1,3 - propanediol can be produced from glycerol via 3 - hydroxypropylaldehyde (HPA) by a fermentation method in which plant resources (such as corn, etc.) are decomposed to obtain glucose. The 1,3 - propanediol compound produced by a biological method such as the above - mentioned fermentation method can obtain useful by - products such as lactic acid in terms of safety compared with the 1,3 - propanediol compound in the EO production method, and moreover, the production cost can be kept low. 1,4 - butanediol can be produced by obtaining succinic acid obtained by producing and fermenting glycol from plant resources and then hydrogenating it. Also, ethylene glycol can be produced from bioethanol obtained by a conventional method via ethylene.

[0014] The carboxylic acid component derived from plants is not particularly limited. For example, the carboxylic acid component is sebacic acid, succinic acid, lactic acid, glutaric acid, dimer acid, etc. These may be used in combination. Among these, the carboxylic acid component preferably contains at least any one selected from the group consisting of sebacic acid, succinic acid, and dimer acid. Also, with respect to 100 parts by mass of sebacic acid, it may contain 0.05 - 0.5 parts by mass of malic acid.

[0015] The biomass polyurethane prepolymer obtained from these plant - derived components is preferably contained in an amount of 10% by mass or more, more preferably 40% by mass or more in terms of solid content in the total polyurethane prepolymer obtained from an environmental aspect.

[0016] (Other diol compounds) In addition to the above - mentioned high - molecular diol compound, alkanediols such as 1,4 - pentanediol, 2,5 - hexanediol, 3 - methyl - 1,5 - pentanediol, and low - molecular diol compounds such as ethylene glycol, propylene glycol, 1,4 - butanediol, 1,3 - butanediol can be used alone or in combination as a mixture of two or more.

[0017] When reacting the above-mentioned organic diisocyanate compound with the polymer diol compound, the respective usage ratios are preferably such that the equivalent ratio of isocyanate groups to hydroxyl groups (isocyanate index) is 1.2:1 to 3.0:1, more preferably 1.3:1 to 2.0:1. When the above-mentioned isocyanate index is less than 1.2, there is a tendency to form a flexible polyurethane-polyurea resin, and when printing the ink composition, the blocking resistance and the like may be low. In this case, it may be necessary to use it in combination with other hard resins.

[0018] (Reaction of organic diisocyanate compound and polymer diol compound) A catalyst can be used during the reaction of the organic diisocyanate compound and the polymer diol compound. Among them, it is preferable to use an organometallic compound. Such organometallic compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; tin compounds such as dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, tributyltin acetate, tributyltin chloride, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin trichloroacetate, and tin 2-ethylhexanoate; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; and further, iron 2-ethylhexanoate, iron acetylacetonate, cobalt benzoate, cobalt 2-ethylhexanoate, zinc naphthenate, zinc 2-ethylhexanoate, zirconium naphthenate, etc. Among these, titanium compounds such as tetrabutyl titanate are preferable. Also, a tertiary amine compound can be used. For example, triethylamine, triethylenediamine, 1,4-diazabicyclo(2,2,2)octane, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU) can be used.

[0019] <Step of stirring and mixing a urethane prepolymer and an organic solvent to obtain a urethane prepolymer solution> (Organic solvent) The organic solvent used in this step is not particularly limited, but from the perspective of environmental consideration, it is preferably free of aromatic hydrocarbon-based organic solvents. Such solvents include alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester-based organic solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; aliphatic hydrocarbon-based organic solvents such as n-hexane, n-heptane, and n-octane; and alicyclic hydrocarbon-based organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane. At least one of the above solvents may be used, and two or more of them can be used in combination considering the solubility and drying properties of the binder resin. However, from the perspective of further environmental consideration, it is preferable to suppress the use of ketone-based organic solvents among the above solvents. More preferably, a mixed solvent of an ester-based solvent and an alcohol-based solvent or an ester-based organic solvent is preferred. When using a mixed solvent of an ester-based solvent and an alcohol-based solvent, a mixed ester-based solvent formed by mixing ethyl acetate and propyl acetate at a mass ratio of ethyl acetate:propyl acetate = 1 to 4:1 and isopropyl alcohol at a mass ratio of mixed ester-based solvent:isopropyl alcohol = 1 to 5:1 is even more preferred.

[0020] (Mixing) Using a known stirring device, under any stirring conditions, add the above organic solvent to the above urethane prepolymer and mix to obtain a urethane prepolymer solution.

[0021] <Step of stirring and mixing the urethane prepolymer solution and a compound in which the amino group of the polyamine compound is ketiminated by a ketone compound> (Polyamine compound) As the polyamine compound, known polyamine compounds used in polyurethane-polyurea resins as binders for ink compositions can be used. For example, among polyamine compounds, aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, and hexamethylenediamine; alicyclic diamines such as isophoronediamine and 4,4'-dicyclohexylmethanediamine; aromatic diamines such as toluylenediamine; araliphatic diamines such as xylenediamine; diamines having a hydroxyl group such as N-(2-hydroxyethyl)ethylenediamine (aminoethylethanolamine), N-(2-hydroxyethyl)propylenediamine, and N,N'-di(2-hydroxyethyl)ethylenediamine can be mentioned. Furthermore, within the range where the polyurethane-polyurea resin does not gel, polyamine compounds such as diethylenetriamine and triethylenetetramine can be used in combination.

[0022] (Compound in which the amino group of the polyamine compound is ketiminated by a ketone compound) A polyamine compound previously ketiminated with an excessive amount of a ketone compound can be used as a chain extender and / or a reaction terminator. In particular, it is preferable to employ isophoronediamine and / or N-(2-hydroxyethyl)ethylenediamine as the polyamine compound. The polyamine compound ketiminated by a ketone compound has a structure in which the oxygen atom of the ketone compound is substituted by the nitrogen atom of the amino group of the polyamine compound. Moreover, as the ketone compound to be used, acetone, diethyl ketone, methyl ethyl ketone, and diacetone alcohol are preferable. In this ketimination reaction, it is preferable not to use a solvent other than the ketone compound. In addition, within the range that does not inhibit the subsequent chain extension and reaction termination reactions and the effect that the polyurethane-polyurea resin has no odor, a polar organic solvent may be blended instead of under solvent-free conditions.

[0023] (Mixing) A urethane prepolymer solution and a compound in which the amino groups of a polyamine compound are ketiminated by a ketone compound under solvent-free conditions are uniformly mixed.

[0024] In this step, a reaction terminator can be contained. Examples of the reaction terminator include alkanolamines such as monoethanolamine and diethanolamine, monoamine compounds such as n-propylamine and n-butylamine, dialkylamines such as di-n-butylamine, and monoalcohol compounds such as ethanol. However, it is preferable to add a reaction terminator to the urethane prepolymer solution in step B between step B and step C described below and react it with a part of the isocyanate of the urethane prepolymer.

[0025] <D. Step of adding water under the following conditions, followed by chain extension and / or reaction termination to obtain a polyurethane-polyurea resin solution for gravure printing> (Water) The amount of water added in the step of performing the following chain extension and / or reaction termination is preferably in the range such that the polyurethane-polyurea resin for gravure printing obtained by the production method of the polyurethane-polyurea resin solution for gravure printing does not precipitate. Specifically, it is preferably 0.2 to 5.0% by mass, more preferably 0.4 to 1.5% by mass, based on the solid content of the polyurethane-polyurea resin solution for gravure printing.

[0026] (Chain extension and / or reaction termination) Furthermore, after stirring and mixing the above urethane prepolymer and an organic solvent, water is added to a solution obtained by adding and uniformly stirring and mixing a compound in which the amino groups of a polyamine compound are ketiminated by a ketone compound under solvent-free conditions, and chain extension and / or reaction termination is performed to obtain a polyurethane-polyurea resin solution for gravure printing. The amine value of the polyurethane-polyurea resin for gravure printing obtained by this production method is preferably 1 to 10 mgKOH / g. When the amine value is less than 1 mgKOH / g, for example, when used as a gravure ink composition for lamination, the adhesiveness to the film decreases, and furthermore, the lamination suitability may decrease. When the amine value exceeds 10 mgKOH / g, the blocking resistance may decrease. In the present invention, the amine value means the amine value per 1 g of solid content, and after measuring by the potentiometric titration method (for example, COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATION K-900), manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1N hydrochloric acid aqueous solution, it refers to the value converted to the equivalent of potassium hydroxide.

[0027] Between the step B and the step C, a step of adding a reaction terminator to the urethane prepolymer solution in the step B and reacting it with a part of the isocyanate of the urethane prepolymer may be provided. (Reaction terminator) As the reaction terminator, known reaction terminators such as alkanolamines such as monoethanolamine and diethanolamine, monoamine compounds such as n-propylamine and n-butylamine, dialkylamines such as di-n-butylamine, and monoalcohol compounds such as ethanol can be used.

[0028] <Step of adding a colorant to the polyurethane-polyurea resin solution for gravure printing> In the present invention, a pigment and / or a dye can be used as the colorant. When the polyurethane-polyurea resin solution for gravure printing is made into a gravure printing ink, the content of the colorant in the ink composition is preferably about 1 to 50% by mass. (Pigment) The pigments that can be used in the present invention are, for example, various inorganic pigments, organic pigments, or extender pigments commonly used in printing inks. Examples of the inorganic pigments include colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, ultramarine blue, phthalocyanine blue, carbon black, graphite, etc., and examples of the extender pigments include silica particles, calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, talc, etc. Among them, it is preferable to use titanium oxide as the white pigment. Examples of the organic pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, etc.

[0029] (Dye) The dyes that can be used in the present invention are, for example, various dyes commonly used in gravure printing ink compositions. Such dyes include, for example, azo-based, phthalocyanine-based, anthraquinone-based, perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethine azo-based, diketopyrrolopyrrole-based, isoindoline-based, etc.

[0030] (Other compounds) In the step of incorporating a colorant into the polyurethane-polyurea resin solution for gravure printing, as the binder resin, vinyl chloride / vinyl acetate copolymer, vinyl chloride / acrylic copolymer, etc., as the adhesion improver, rosin and its derivatives, chlorinated polypropylene, dammar resin, as the anti-blocking agent, silica particles, polyethylene wax, fatty acid amide, cellulose acetate propionate resin, cellulose acetate butyrate resin, nitrocellulose, etc., a pigment dispersant and a dispersion aid, an organic solvent, water, an antistatic agent, and a silane coupling agent can be incorporated.

[0031] · Vinyl chloride / vinyl acetate copolymer as the binder resin As the vinyl chloride / vinyl acetate copolymer, conventionally, a copolymer containing vinyl chloride monomer and vinyl acetate monomer, which are essential components for use in gravure ink compositions and the like, and, if necessary, vinyl propionate, vinyl monochloroacetate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate and other fatty acid vinyl monomers, and monomers having functional groups such as hydroxyl groups, produced by known methods can be used. Among them, in the organic solvent system of the ink composition considering the environment, the vinyl chloride / vinyl acetate copolymer having a hydroxyl group, preferably a vinyl chloride / vinyl acetate copolymer having a hydroxyl group with a hydroxyl value of 50 to 200 mgKOH / g, is suitable. Such a vinyl chloride / vinyl acetate copolymer having a hydroxyl group can be obtained by saponifying a part of the acetate moiety or introducing a (meth)acrylic monomer having a hydroxyl group. In the case of a vinyl chloride / vinyl acetate copolymer having a hydroxyl group obtained by saponifying a part of the acetate moiety, the film physical properties and dissolution behavior of the resin are determined by the ratios of the structural units based on the reaction sites of vinyl chloride in the molecule (Formula 1 below), the structural units based on the reaction sites of vinyl acetate (Formula 2 below), and the structural units based on the saponification of the reaction sites of vinyl acetate (Formula 3 below). That is, the structural units based on the reaction sites of vinyl chloride impart toughness and hardness to the resin film, the structural units based on the reaction sites of vinyl acetate impart adhesiveness and flexibility, and the structural units based on the saponification of the reaction sites of vinyl acetate impart good solubility in the organic solvent system of the environmentally considerate ink composition. Formula 1 -CH2-CHCl- Formula 2 -CH2-CH(OCOCH3)- Formula 3 -CH2-CH(OH)- Such vinyl chloride / vinyl acetate copolymers may be commercially available products. For example, Solvaine A, AL, TA5R, TA2, TA3, TAO, TAOL, C, CH, CN, CNL manufactured by Nissin Chemical Industry Co., Ltd. can be mentioned. Furthermore, the vinyl chloride / vinyl acetate copolymer used in the ink composition containing the polyurethane-polyurea resin obtained by the present invention preferably has various functional groups in the molecule from the viewpoints of solubility in the organic solvents described below and printability. In addition, when a solvent considering the environment is used as the organic solvent, the vinyl chloride / vinyl acetate copolymer preferably has a hydroxyl group with a hydroxyl value of 50 to 200 mgKOH / g. As commercially available products of such vinyl chloride / vinyl acetate copolymers, for example, Solvaine A, AL, TA5R, TA2, TA3, TAO, TAOL, etc. manufactured by Nissin Chemical Industry Co., Ltd. are preferably used.

[0032] · Vinyl chloride / acrylic copolymer as a binder resin It is mainly composed of a copolymer of vinyl chloride 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 random manner, or may be graft copolymerized to the side chain of polyvinyl chloride. As the acrylic monomer, (meth)acrylic acid esters, acrylic monomers having a hydroxyl group, etc. can be used. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, and 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, octadecyl (meth)acrylate, etc. can be mentioned. Examples of acrylic monomers having a hydroxyl group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, caprolactone-modified (meth)acrylate, hydroxyethyl acrylamide, and the like. In addition, 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 a 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 weight average molecular weight of 10,000 to 70,000. Further, from the viewpoints of solubility in a solvent considering the environment and adhesion to a base material as the organic solvent, the vinyl chloride / acrylic copolymer preferably has a hydroxyl group having a hydroxyl value of 50 to 200 mgKOH / g.

[0033] The vinyl chloride / vinyl acetate copolymer and the vinyl chloride / acrylic copolymer as the binder resin can be included in the step of including a colorant in the gravure printing polyurethane polyurea resin solution in order to improve the adhesion according to the pigment to be blended. When containing a vinyl chloride / vinyl acetate copolymer or a vinyl chloride / acrylic copolymer as a binder resin, the polyurethane-polyurea resin for gravure printing and the (vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / acrylic copolymer) can be contained at a mass ratio of polyurethane-polyurea resin for gravure printing / (vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / acrylic copolymer) = 100 / 0 to 45 / 55. More preferably, the mass ratio can be 95 / 5 to 70 / 30. By containing the polyurethane-polyurea resin for gravure printing, the vinyl chloride / vinyl acetate copolymer, and / or the vinyl chloride / acrylic copolymer at such a ratio, the ink composition for gravure printing obtained according to the present invention will have even better printing suitability and adhesiveness to the film. Furthermore, when laminating is performed, it will have even better laminating suitability. When the above polyurethane-polyurea resin for gravure printing / (vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / acrylic copolymer) is less than 45 / 55, the proportion of the (vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / acrylic copolymer) increases, the printed matter formed using the ink composition for gravure printing obtained according to the present invention becomes hard, and there is a possibility that the adhesiveness to the above film will be insufficient.

[0034] · Rosin and its derivatives as adhesion improvers Examples of rosin include gum rosin, tall oil rosin, and wood rosin. Generally, rosin is an amber-colored, amorphous resin obtained from pine and is a mixture because it is obtained from nature. However, it may also be used after being isolated by each of the constituent components such as abietic acid, neoabietic acid, palustric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and dehydroabietic acid. In the present invention, these are also defined as rosin. Rosin derivatives are compounds obtained by modifying the above rosin, and are specifically listed below. (1) Hydrogenated rosin: Rosin in which hydrogen is added (hydrogenated) to the conjugated double bond to improve weather resistance. (2) disproportionated rosin: Disproportionation is a modification in which two molecules of rosin react to form two molecules of abietic acid with conjugated double bonds, one of which constitutes an aromatic group and the other is a molecule with an isolated double bond. Generally, it has inferior weather resistance compared to hydrogenated rosin but is improved compared to untreated rosin. (3) rosin-modified phenolic resin: Rosin-modified phenolic resin is often used as the main binder in the ink composition for offset printing. Rosin-modified phenolic resin can be obtained by known production methods. (4) rosin ester: It is an ester resin derived from rosin and has long been used as a tackifier for adhesives and adhesives. (5) rosin-modified maleic acid resin: It is obtained by adding maleic anhydride to rosin, and also includes those grafted by esterifying a hydroxyl group-containing compound such as glycerin with the anhydride group as required. (6) polymerized rosin: It is a derivative containing dimerized resin acid derived from 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. Furthermore, the acid value of the rosin and rosin derivative is preferably 120 mgKOH / g or more. When the acid value is 120 mgKOH / g or more, the laminate strength is improved. More preferably, the acid value is 160 mgKOH / g or more. Also, the total usage amount of the rosin and rosin derivative is preferably 3.0% by mass or less, more preferably 0.1 - 3.0% by mass, based on the solid content of the gravure printing ink composition obtained by the production method of the present invention.

[0035] · Chlorinated polypropylene as an adhesion improver As the chlorinated polypropylene, those with a chlorination degree of 20 to 50 can be used. Chlorinated polypropylene with a chlorination degree of less than 20 tends to have reduced compatibility with organic solvents. On the other hand, when the chlorination degree exceeds 50, the chlorinated polypropylene tends to have reduced adhesiveness to the film. The chlorination degree is defined as the mass percentage of chlorine atoms in the chlorinated polypropylene resin. Also, the chlorinated polypropylene is preferably a modified or unmodified chlorinated polypropylene with a weight average molecular weight of 5000 to 200000. When the weight average molecular weight is less than 5000, the chlorinated polypropylene tends to have reduced adhesiveness. On the other hand, when the weight average molecular weight exceeds 200000, the chlorinated polypropylene tends to have reduced solubility in organic solvents. Further, the usage amount of the chlorinated polypropylene is preferably 3.0 mass% or less, more preferably 0.1 to 3.0 mass% based on the solid content of the gravure printing ink obtained by the production method of the present invention.

[0036] · Damar resin as an adhesion improver Damar resin, also denoted as dammar, is a type of natural resin derived from plants. Specifically, it is a type of natural resin obtained from plants of the Burseraceae or Canarium family growing in Southeast Asia such as Malaysia and Indonesia. When used, it is dissolved in a suitable organic solvent to form a varnish. Since Damar resin does not contain chlorine, chlorine can be eliminated and reduced compared to the case where a chlorinated polyolefin resin is used in the ink composition. Also, the usage amount of Damar resin is preferably 3.0 mass% or less, more preferably 0.1 mass% to 3.0 mass% based on the solid content of the gravure printing ink composition obtained by the production method of the present invention.

[0037] · Silica particles as an anti-blocking agent Examples of silica include natural, synthetic, crystalline, amorphous, hydrophobic, hydrophilic, etc. Silica particles preferably have an average particle size in the range of 1 to 5 μm (note that the average particle size of silica particles means the particle size at the cumulative value of 50% (D50) in the particle size distribution and can be determined by the Coulter counter method). 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, but hydrophilic silica is preferred. The ink composition containing hydrophilic silica particles promotes the wetting and spreading of the ink composition during overprinting and also has the effect of improving the overprinting effect (hereinafter sometimes referred to as "trapping property"). The amount of silica particles used is preferably 3.0% by mass or less, more preferably 0.1 to 3.0% by mass, and even more preferably 0.2 to 1.5% by mass in the gravure printing ink composition obtained by the production method of the present invention. If it is more than 3.0% by mass, the gloss may decrease.

[0038] · Polyethylene wax as an anti-blocking agent As the polyethylene wax, those having an average particle size in the range of 1.0 to 20 μm (note that the average particle size means the particle size measured by Microtrac UPA manufactured by Honeywell) are used. If the particle size of the polyethylene wax is less than 1.0 μm, the slipperiness and blocking property during laminate formation decrease, and if the particle size is more than 20 μm, the trapping property decreases. Also, the content of the polyethylene wax is preferably 0.1 to 1.5% by mass in the gravure printing ink composition obtained by the production method of the present invention. If it is less than 0.1% by mass, the intended effect may not be obtained, and if it is more than 1.5% by mass, the gloss may decrease.

[0039] · Fatty acid amide as an anti-blocking agent The fatty acid amide is not particularly limited as long as it has a fatty acid residue and an amide group. Examples of fatty acid amides include monoamides, substituted amides, bisamides, methylol amides, and ester amides. To improve the antiblocking property, it is preferably at least one selected from the group consisting of monoamides, substituted amides, and bisamides. The amount of the fatty acid amide used is preferably 1.0% by mass or less, more preferably 0.01 to 1.0% by mass, in the gravure printing ink composition obtained by the production method of the present invention. · Monoamide: Monoamide is represented by the following general formula (1). General formula (1) R1-CONH2 (In the formula, R1 represents the residue obtained by removing COOH from a fatty acid.) Specific examples of monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid amide, erucic acid amide, and the like. · Substituted amide: Substituted amide is represented by the following general formula (2). General formula (2) R2-CONH-R3 (In the formula, R2 and R3 represent the residues obtained by removing COOH from fatty acids, and may be the same or different.) Specific examples of substituted amides include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid 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 the residues obtained by removing COOH from fatty acids, and may be the same or different. R5 and R8 represent an alkylene group or an arylene group 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 bisbehenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N,N'-distearyl adipic acid amide, N,N'-distearyl sebacic acid amide, N,N'-dioleyl adipic acid amide, N,N'-dioleyl sebacic acid amide, and the like. · Methylolamide: Methylolamide is represented by the following general formula (5). General formula (5) R10-CONHCH2OH (In the formula, R10 represents the residue obtained by removing COOH from a fatty acid.) Specific examples of methylolamide include methylol palmitic acid amide, methylol stearic acid amide, methylol behenic acid amide, methylol hydroxystearic acid amide, methylol oleic acid amide, methylol erucic acid amide, and the like. · Ester amide: 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 the residues obtained by removing COOH from a fatty acid, which 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 ester amide include stearamide ethyl stearate, oleylamide ethyl urearate, and the like. The melting point of the fatty acid amide is preferably 50°C to 150°C. In addition, as the fatty acid constituting the fatty acid amide, saturated fatty acids having 12 to 22 carbon atoms and / or unsaturated fatty acids having 16 to 25 carbon atoms are preferable, and saturated fatty acids having 16 to 18 carbon atoms and / or unsaturated fatty acids having 18 to 22 carbon atoms are more preferable. Particularly preferable saturated fatty acids are lauric acid, palmitic acid, stearic acid, behenic acid, and hydroxystearic acid, and particularly preferable unsaturated fatty acids are oleic acid and erucic acid.

[0040] · Cellulose acetate propionate resin as an anti-blocking agent As the cellulose acetate propionate resin, a cellulose acetate propionate resin conventionally used in gravure ink compositions and the like can be used. The cellulose acetate propionate resin is obtained by hydrolyzing cellulose after triesterifying it with acetic acid and propionic acid. Generally, commercially available resins have an acetyl group of 0.6 to 2.5% by weight, a propionate group of 42 to 46% by weight, and a hydroxyl group of 1.8 to 5% by weight. The amount of the cellulose acetate propionate resin used is preferably 3.0% by mass or less in the gravure printing ink composition obtained by the production method of the present invention.

[0041] · Cellulose acetate butyrate resin as an anti-blocking agent As the cellulose acetate butyrate resin, a cellulose acetate butyrate resin conventionally used in gravure ink compositions and the like can be used. The cellulose acetate butyrate resin is obtained by hydrolyzing after triesterifying with acetic acid and butyric acid. Generally, commercially available resins have an acetylation of 2 to 30% by weight, a butyrylation of 17 to 53% by weight, and a hydroxyl group of 1 to 5%. The amount of the cellulose acetate butyrate resin used is preferably 0.1 to 3.0% by mass in the gravure printing ink composition obtained by the production method of the present invention.

[0042] · Nitrocellulose as an anti-blocking agent As the nitrocellulose, the nitrocellulose conventionally used in gravure ink compositions and the like can be used. The nitrocellulose is obtained by reacting natural cellulose with nitric acid to substitute three hydroxyl groups in the six-membered ring of the anhydroglucopyranose group in natural cellulose with nitro groups as a nitrate ester. As the nitrocellulose used in the present invention, those having a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90 are preferably used. Specific examples include SS1 / 2, SS1 / 4, SS1 / 8, TR1 / 16, NC RS-2, (manufactured by KCNC, KOREA CNC LTD Co., Ltd.) and the like. The amount of nitrocellulose used is preferably 2.0% by mass or less in the gravure printing ink composition obtained by the production method of the present invention.

[0043] · Pigment dispersant As the pigment dispersant, a polyester-based pigment dispersant that can be generally used in ink compositions such as gravure ink compositions containing an organic solvent can be used. Specifically, Ajisper PB821, PB822, PB824, PB881 (manufactured by Ajinomoto Fine-Techno Co., Inc.), Solsperse 24000, 56000 (manufactured by Lubrizol Japan Ltd.) and the like can be mentioned. Among these, a basic group-containing polyester-based polymer dispersant can be preferably used. The content of the pigment dispersant is preferably 1 to 200 parts by mass, more preferably 1 to 60 parts by mass, based on 100 parts by mass of the total pigment.

[0044] · Organic solvent The organic solvent described in the step of stirring and mixing the urethane prepolymer, the organic solvent, and the chain extender and / or reaction terminator in which the amino group of the polyamine compound is ketiminated by the ketone compound under solvent-free conditions can be used. Furthermore, in order to improve the wet spreading property, 0.1 to 20% by weight of a glycol ether-based organic solvent can also be contained in 100% by weight of the organic solvent. Specific examples of the glycol ether-based organic solvent include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and the like.

[0045] · Water From the viewpoints of alleviating printing defects due to static electricity, preventing plate doubling, and improving cell reproducibility, it is preferable to contain water. However, it is necessary that the effects of the present invention are not impaired, such as the precipitation of resins or the like dissolved in the solvent not occurring. The amount of such water used is preferably 10.0% by mass or less, more preferably 0.1 to 5.0% by mass, in the gravure printing ink composition obtained by the production method of the present invention.

[0046] · Method for manufacturing a method for manufacturing a gravure printing ink composition As the method for manufacturing the gravure printing ink composition of the present invention, as described above, for example, a mixture of a polyurethane-polyurea resin solution for gravure printing, a pigment, a binder resin as required, an organic solvent, a pigment dispersant, etc. is kneaded using a high-speed mixer, a ball mill, a sand mill, an attritor, etc., and further, the remaining materials such as an adhesion improver, an anti-blocking agent, an organic solvent, and water are added and mixed to obtain it.

[0047] <Method for manufacturing a laminated printed matter using the gravure printing ink composition according to the present invention> A method for obtaining a laminated printed matter using the gravure printing ink composition obtained by the production method of the present invention will be described. The method for obtaining a laminated printed matter includes at least the following printing methods. For example, at least a gravure printing ink composition is printed one or more times by a gravure printing method on a resin film serving as a known substrate for lamination. Next, another gravure printing ink composition is printed by a gravure printing method at an arbitrary position on the surface side (the lower layer side when viewed from the surface layer after final lamination) of the gravure printing ink composition layer formed by these printings, and dried by a dryer. A resin film or the like can be laminated by various methods on the side of the layer formed by the gravure printing ink composition of the printed matter obtained by the above method to obtain a laminated printed matter for use in packaging bags or the like. As this lamination method, an extrusion lamination method in which an anchor coat agent is applied to the surface of the printed matter and then a molten polymer is laminated, or a dry lamination method in which an adhesive is applied to the surface of the printed matter and then a film-like polymer is bonded can be used.

[0048] The above extrusion lamination method is a method in which an anchor coat agent such as a titanium-based, urethane-based, imine-based, polybutadiene-based or the like is applied to the surface of a printed matter including a layer formed by a gravure printing ink composition as needed, and then a molten polymer is laminated by a known extrusion laminator. Furthermore, the molten resin can be laminated in a sandwich-like manner with other materials using the molten resin as an intermediate layer. As the molten polymer used in the above extrusion lamination method, resins that have been conventionally used, such as low-density polyethylene, ethylene-vinyl acetate copolymer, polypropylene, etc., can be used. Among them, the effect of the present invention is enhanced when low-density polyethylene, which is easily oxidized during melting to generate carbonyl groups, is adopted.

[0049] In addition, the dry lamination method is a method in which an adhesive such as a urethane-based or isocyanate-based adhesive is applied to the surface of a layer with a gravure printing ink composition, and then a film-shaped polymer is laminated by a known dry laminator. As the resin for the film used in the dry lamination method, polyethylene, unstretched polypropylene, etc. can be used. In particular, in order to obtain a packaging material used for retort applications, it is also possible to laminate with an aluminum foil sandwiched between the resin film to be laminated with the base material. Such a laminated product can also be used for boil-in-bag retort applications after being made into a bag and filled with contents. Examples of the resin film used at this time include stretched and unstretched polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, vinylon, etc. Furthermore, for these resin films, films obtained by processing the resin films such as pre-coating with an anti-fogging agent, kneading, surface coating with a matting agent, kneading, etc. can also be used.

Examples

[0050] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples only. Unless otherwise specified, “%” means “mass %” and “part” means “part by mass”. Also, the figures for the amounts of each material in the table are also “parts by mass”. The unit of acid value is mgKOH / g.

[0051] <Method for producing ketimine solution 1> 51 parts of isophoronediamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 174 parts of acetone were mixed and stirred at room temperature for 1 hour to obtain ketimine solution 1. <Method for producing ketimine solution 2> 51 parts of isophoronediamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 258 parts of diethyl ketone were mixed and stirred at room temperature for 1 hour to obtain ketimine solution 2. <Method for producing ketimine solution 3> 51 parts of isophoronediamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 210 parts of methyl ethyl ketone were mixed and stirred at room temperature for 1 hour to obtain ketimine solution 3. <Method for producing ketimine solution 4> 51 parts of isophoronediamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 348 parts of diacetone alcohol were mixed and stirred at room temperature for 1 hour to obtain ketimine solution 4.

[0052] <Method for producing PU-1 (ketiminization with acetone)> 400 parts of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged into a four-necked flask equipped with a stirrer, a cooling pipe, and a nitrogen gas inlet pipe, and reacted at 90 to 100 °C for 6 hours while introducing nitrogen gas. Next, 808 parts of propyl acetate and 201 parts of isopropyl alcohol were added, then cooled to near room temperature, 25.6 parts of ketimine solution 1 was added and stirred for 20 minutes, and further 3 parts by mass of water was added and stirred for 15 minutes to obtain PU-1 (solid content 30% by mass).

[0053] <Method for producing PU-2 (ketiminization with diethyl ketone)> 400 parts of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged into a four-necked flask equipped with a stirrer, a cooling pipe, and a nitrogen gas inlet pipe, and reacted at 90 to 100 °C for 6 hours while introducing nitrogen gas. Next, 801 parts of propyl acetate and 200 parts of isopropyl alcohol were added, then cooled to near room temperature, 34 parts of ketimine solution 2 was added and stirred for 20 minutes, and further 3 parts by mass of water was added and stirred to obtain PU-2 (solid content 30% by mass).

[0054] <Method for producing PU-3 (ketiminization with methyl ethyl ketone)> Into a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 400 parts of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged, and the reaction was carried out at 90 to 100 °C for 6 hours while introducing nitrogen gas. Next, 805 parts of propyl acetate and 201 parts of isopropyl alcohol were added, then it was cooled to near room temperature, 29.2 parts of ketimine solution 3 was added and stirred for 30 minutes, and further 3 parts by mass of water was added and stirred to obtain PU-3 (solid content 30% by mass).

[0055] <Production method of PU-4 (ketimine formation with diacetone alcohol)> Into a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 400 parts of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged, and the reaction was carried out at 90 to 100 °C for 6 hours while introducing nitrogen gas. Next, 795 parts of propyl acetate and 198 parts of isopropyl alcohol were added, then it was cooled to near room temperature, 43 parts of ketimine solution 4 was added and stirred for 30 minutes, and further 3 parts of water was added and stirred to obtain PU-4 (solid content 30% by mass).

[0056] <Production method of PU-5 (ketimine formation with biomass and acetone)> Into a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 400 parts of a polyester diol with an average molecular weight of 4000 obtained from sebacic acid (derived from castor oil) / succinic acid (derived from plants) = 70 / 30 (mass ratio) and 1,3-propanediol (derived from plants), 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged, and the reaction was carried out at 90 to 100 °C for 6 hours while introducing nitrogen gas. Next, 808 parts of propyl acetate and 201 parts of isopropyl alcohol were added, then it was cooled to near room temperature, 25.6 parts of ketimine solution 1 was added and stirred for 20 minutes, and further 3 parts by mass of water was added and stirred for 15 minutes to obtain PU-5 (solid content 30% by mass).

[0057] <Method for manufacturing PU-6 (ketimine formation with monoethanolamine and acetone)> Into a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 400 parts of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged, and the reaction was carried out at 90 to 100 °C for 6 hours while introducing nitrogen gas. After adding 810 parts of propyl acetate and 201 parts of isopropyl alcohol, it was cooled to near room temperature, 0.3 part of monoethanolamine was added, and after stirring for 15 minutes, 23.35 parts of ketimine solution 1 was further added and stirred for 20 minutes, and then 3 parts of water was added and stirred for 15 minutes to obtain PU-6 with a mass average molecular weight of 45,000 (solid content 30%).

[0058] <Method for manufacturing PU-7 (charging acetone after chain extension and end capping with diamine)> Into a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 400 parts of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged, and the reaction was carried out at 90 to 100 °C for 6 hours while introducing nitrogen gas. Next, after adding 810 parts of propyl acetate and 202 parts of isopropyl alcohol, it was cooled to near room temperature, 5.1 parts of isophorone diamine and 3.1 parts of N-(2-hydroxyethyl)ethylenediamine were added and stirred for 30 minutes, and then 17.4 parts of acetone was added and stirred for 60 minutes to obtain PU-7 (solid content 30% by mass).

[0059] <Method for manufacturing PU-8 (charging diethyl ketone after chain extension and end capping with diamine)> Into a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 400 parts of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged, and the reaction was carried out at 90 to 100 °C for 6 hours while introducing nitrogen gas. Next, 803 parts of propyl acetate and 201 parts of isopropyl alcohol were added, and then the mixture was cooled to near room temperature. After adding 5.1 parts of isophoronediamine and 3.1 parts of N-(2-hydroxyethyl)ethylenediamine and stirring for 30 minutes, 25.8 parts of diethyl ketone was added and stirred for 60 minutes to obtain PU-8 (solid content: 30% by mass).

[0060] <Production method of PU-9 (After chain extension and end capping with diamine, methyl ethyl ketone is charged)> Into a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 400 parts of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged, and the reaction was carried out at 90 to 100 °C for 6 hours while introducing nitrogen gas. Next, 807 parts of propyl acetate and 202 parts of isopropyl alcohol were added, and then the mixture was cooled to near room temperature. After adding 5.1 parts of isophoronediamine and 3.1 parts of N-(2-hydroxyethyl)ethylenediamine and stirring for 30 minutes, 21 parts of methyl ethyl ketone was added and stirred for 60 minutes to obtain PU-9 (solid content: 30% by mass).

[0061] <Production method of PU-10 (After chain extension and end capping with diamine, diacetone alcohol is charged)> Into a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 400 parts of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged, and the reaction was carried out at 90 to 100 °C for 6 hours while introducing nitrogen gas. Next, 796 parts of propyl acetate and 199 parts of isopropyl alcohol were added, and then the mixture was cooled to near room temperature. After adding 5.1 parts of isophoronediamine and 3.1 parts of N-(2-hydroxyethyl)ethylenediamine and stirring for 30 minutes, 34.8 parts of diacetone alcohol was added and stirred for 60 minutes to obtain PU-10 (solid content: 30% by mass).

[0062] <Manufacturing method of PU-11 (biomass, chain extension with diamine, terminal termination, and then charging acetone)> Into a four-necked flask equipped with a stirrer, a cooling pipe, and a nitrogen gas inlet pipe, 400 parts of a polyester diol with an average molecular weight of 4000 obtained from sebacic acid (derived from castor oil) / succinic acid (derived from plants) = 70 / 30 (mass ratio) and 1,3-propanediol (derived from plants), 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged, and the reaction was carried out at 90 to 100 °C for 6 hours while introducing nitrogen gas. Next, 810 parts of propyl acetate and 202 parts of isopropyl alcohol were added, then cooled to near room temperature, 5.1 parts of isophoronediamine and 3.1 parts of N-(2-hydroxyethyl)ethylenediamine were added and stirred for 30 minutes, and then 17.4 parts of acetone were added and stirred for 60 minutes to obtain PU-11 (solid content: 30% by mass).

[0063] <Manufacturing method of PU-12 (reaction termination with monoethanolamine, chain extension with diamine, terminal termination, and then charging acetone)> Into a four-necked flask equipped with a stirrer, a cooling pipe, and a nitrogen gas inlet pipe, 400 parts of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged, and the reaction was carried out at 90 to 100 °C for 6 hours while introducing nitrogen gas. After adding 810 parts of propyl acetate and 201 parts of isopropyl alcohol, it was cooled to near room temperature, 0.3 part of monoethanolamine was added and stirred for 15 minutes, then 4.65 parts of isophoronediamine and 2.84 parts of N-(2-hydroxyethyl)ethylenediamine were added and stirred for 30 minutes, and then 15.86 parts of acetone were added and stirred for 60 minutes to obtain PU-12 (solid content: 30% by mass).

[0064] <Manufacturing method of PU-13 (chain extension and terminal termination with diamine)> Into a four-necked flask equipped with a stirrer, a cooling pipe, and a nitrogen gas inlet pipe, 400 parts of 3-methyl-1,5-pentylene adipate diol with a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 part of tetrabutyl titanate were charged, and the reaction was carried out at 90 to 100 °C for 6 hours while introducing nitrogen gas. Next, 823.9 parts of propyl acetate and 205.5 parts of isopropyl alcohol were added, and then the mixture was cooled to near room temperature. 5.1 parts of isophoronediamine and 3.1 parts of N-(2-hydroxyethyl)ethylenediamine were added and stirred for 30 minutes to obtain PU-13 (solid content: 30% by mass).

[0065] (Pigment) Titanium oxide (R-960, manufactured by DuPont) Phthalocyanine blue (Pigment Blue 15:4) <Silica particles> Silica particles with an average particle diameter of 4.5 μm

[0066] <Production examples of each ink composition of Examples and Comparative Examples> Pigments, polyurethane resin varnishes (PU-1 to PU-13), silica, and solvents were kneaded using a paint conditioner manufactured by Red Devil to obtain the ink compositions of Examples and Comparative Examples shown in Table 1.

[0067] <Storage stability of ink composition> The ink compositions of Examples and Comparative Examples obtained above were collected in glass bottles, and the change in viscosity values before and after 14 days at 40 °C (the viscosity at a liquid temperature of 25 °C was measured using a No. 2 rotor of a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 30 rpm for ink viscosity measurement data) was used to evaluate the storage viscosity stability, and the evaluation was carried out according to the following evaluation criteria. The results are shown in Table 1. ○: The viscosity ratio after aging / before aging was less than 1.5. ×: The viscosity ratio after aging / before aging was 1.5 or more, and no sedimentation was observed.

[0068] <Manufacture of printed matter> 100 parts by mass of each of the ink compositions of the examples and comparative examples was diluted with a mixed solvent (ethyl acetate / propyl acetate / isopropyl alcohol = 50 / 25 / 25, mass ratio) to adjust the viscosity to 15 seconds using a Zahn cup No. 3 manufactured by a separate company, and an ink composition with adjusted concentration was obtained. Using each of the obtained ink compositions, printing and drying were performed on the treated surface of a polypropylene film (P-2161 manufactured by Toyobo Co., Ltd.) under the following conditions to obtain printed matter. Furthermore, the obtained printed matter was evaluated for amine odor and ketimine odor. The specific evaluation method is shown below.

[0069] (Printing method and printing conditions) Room environment during printing: Temperature 25°C, humidity 50% Coating machine: Gravure printing machine Coating speed: 150 m / min Printing plate: Direct 175 lines 28 μm solid plate Drying temperature: 55°C

[0070] (Evaluation method for amine odor and ketimine odor of printed matter) With the nose placed on the printed surface of each of the obtained printed matters, the odor was evaluated by a sensory test according to the following criteria. The results are shown in Table 1. ○: No amine odor or ketimine odor is recognized. △: A slight amine odor or ketimine odor is recognized. ×: An amine odor or ketimine odor is recognized.

[0071]

Table 1

[0072] The ink compositions of Examples 1 to 7 using the polyurethane-polyurea resin obtained by the method of the present invention were excellent in stability over time. In addition, there was no amine odor or ketimine odor in the printed part after making the printed matter. On the other hand, the ink compositions of Comparative Examples 1 to 7 using polyurethane-polyurea resins that were not ketiminated, regardless of the method of the present invention, were inferior in stability over time. In addition, there was a ketimine odor in the printed area after printing. Further, the ink compositions of Comparative Examples 8 and 9 using polyurethane-polyurea resins obtained only by the method of chain extension and end capping with diamine were slightly inferior in stability over time. In addition, there was an amine odor in the printed area after printing.

Claims

1. A method for producing an intaglio printing ink composition having the following steps A to E. A. A step of synthesizing a urethane prepolymer from an organic diisocyanate compound and a high molecular diol compound. B. A step of mixing the urethane prepolymer and an organic solvent to obtain a urethane prepolymer solution. C. A step of adding and mixing a compound in which the amino group of a polyamine compound is ketiminated by a ketone compound to the urethane prepolymer solution. D. A step of adding water under the following conditions to perform chain extension and / or reaction termination to obtain a polyurethane-polyurea resin solution for intaglio printing. Condition: In a range where the polyurethane-polyurea resin for intaglio printing obtained by the method for producing a polyurethane-polyurea resin for intaglio printing does not precipitate. E. A step of adding a colorant to the polyurethane-polyurea resin solution for intaglio printing.

2. Regarding the usage ratio of the organic diisocyanate compound and the high molecular diol, the method for producing an intaglio printing ink composition according to Claim 1, wherein the equivalent ratio of isocyanate group:hydroxyl group (isocyanate index) is NCO group / OH group = 1.2 to 3.

0.

3. The method for producing an intaglio printing ink composition according to Claim 1 or 2, wherein the organic solvent is a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent or an ester-based organic solvent.

4. The method for producing an intaglio printing ink composition according to any one of Claims 1 to 3, wherein the ketiminated compound is a compound in which the amino group of a polyamine compound is ketiminated by one or more ketone compounds selected from acetone, diethyl ketone, methyl ethyl ketone, and diacetone alcohol.

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