JP2020189903A - Flexible packaging laminate printing ink composition - Google Patents

Abstract

To provide a flexible packaging laminate printing ink composition that has excellent long-term stability, allows an increased content of a plant-derived material to be used, and can improve adhesiveness to films including various films and various high-function barrier films.SOLUTION: Provided is a packaging laminate printing ink composition, which is a printing ink composition for a laminate, containing a pigment, a binder resin, and an organic solvent, wherein the binder resin contains a polyurethane resin (A) having a urethane group concentration of 0.3 to 2.4 mmol/g and containing, at each terminus, a urea bond having an amino group, and a polyurethane resin (B) having a urethane group concentration of 2.0 to 6.0 mmol/g, containing no urea bond, and having a mass average molecular weight of 1000-6000, a polyvinyl chloride-vinyl acetate copolymer resin having a hydroxy group and/or a polyvinyl chloride-acryl copolymer resin having a hydroxy group, the mass ratio between the polyurethane resin (A) and the polyurethane resin (B) being 95:5 to 50:50.SELECTED DRAWING: None

Description

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

Packaging materials using various plastic films are used for foods, confectionery, household goods, pet foods, etc. from the viewpoints of design, economy, content protection, transportability, and the like. In addition, many packaging materials are subjected to gravure printing or flexographic printing with the intention of giving a design, message, etc. that appeals to consumers.
Then, in order to obtain a packaging material, front printing is performed by printing on the surface of the base film of the packaging material, or an adhesive or anchoring agent is applied to the printed surface of the back surface of the base film of the packaging material as necessary, and the film is coated. Backprint printing is performed with lamination processing.
In back printing, color ink and white ink are sequentially printed on various films such as various general-purpose films (polyester, nylon), aluminum foil, and various high-performance films (films coated with inorganic or organic barrier materials). A polyethylene film, a polypropylene film, or the like is laminated on the printing layer of the white ink for the purpose of heat sealing by a dry laminating process using an adhesive, an extrusion laminating process using an anchor coating agent, or the like.

The printing ink composition for flexible packaging laminates used in backprint printing includes polypropylene glycol-containing polyurethane resin as a binder resin and vinyl chloride acetate having a hydroxyl group used to improve pigment dispersibility and adhesion. A printing ink composition for laminating for flexible packaging containing a vinyl copolymer resin as an essential component has been proposed (see, for example, Patent Document 1).
The proposed printing ink composition for laminating for flexible packaging may have insufficient adhesion to films such as polypropylene films and various high-performance barrier films, and inks having higher adhesion are required. It is becoming more like.
In order to solve these problems, as a binder resin, a polyurethane resin having a urea bond and having a weight average molecular weight in the range of 10,000 to 100,000 and a polyurethane resin having no urea bond having a weight average molecular weight of 10,000 to 100 are used. A liquid ink composition containing a polyurethane resin in the range of 000 and a vinyl chloride vinyl acetate copolymer having a hydroxyl group has been proposed (see, for example, Patent Document 2).
However, in recent years, higher performance has been required, and there is room for improvement.

Japanese Unexamined Patent Publication No. 2005-298618 Japanese Unexamined Patent Publication No. 2017-019991

INDUSTRIAL APPLICABILITY The present invention is a laminate for flexible packaging which is excellent in stability over time, can be adopted so that a plant-derived material has a higher content, and can improve adhesion to various films and films such as various high-performance barrier films. An object of the present invention is to provide a printing ink composition.

As a result of diligent studies to solve the above problems, the present inventors have made a vinyl chloride / vinyl acetate copolymer resin having a specific combination of polyurethane resin and a hydroxyl group in the laminated printing ink composition for flexible packaging and / or We have found that the above problems can be solved by containing a vinyl chloride / acrylic copolymer resin having a hydroxyl group, and have completed the following invention.
That is, the present invention is as follows.
1. 1. A printing ink composition for lamination containing a pigment, a binder resin, and an organic solvent. The binder resin is a polyurethane resin having a urethane group concentration of 0.3 to 2.4 mmol / g and a urea bond having an amino group at the terminal. (A), a polyurethane resin (B) having a urethane group concentration of 2.0 to 6.0 mmol / g and a mass average molecular weight of 1000 to 6000 without a urea bond, a vinyl chloride / vinyl acetate copolymer resin having a hydroxyl group, and / Or a laminated printing ink composition for packaging containing a vinyl chloride / acrylic copolymer resin having a hydroxyl group and having a mass ratio of polyurethane resin (A) to polyurethane resin (B) of 95: 5 to 50:50.
2. 2. The soft according to 1, wherein the polyurethane resin (A) has a urethane group concentration of 0.5 to 1.3 mmol / g, and the polyurethane resin (B) has a urethane group concentration of 3.5 to 5.5 mmol / g. Laminate printing ink composition for packaging.
3. 3. The laminate printing ink composition for flexible packaging according to 1 or 2, wherein the polyurethane resin (A) has an amine value of 1.0 to 15.0 mgKOH / g.
4. The total mass content of the polyurethane resin (A) and the polyurethane resin (B), the vinyl chloride / vinyl acetate copolymer resin having a hydroxyl group, and the vinyl chloride / acrylic copolymer resin having a hydroxyl group is 100/0 to 0. The laminate printing ink composition for flexible packaging according to any one of 1 to 3 which is 45/55.
5. The laminate printing ink composition for flexible packaging according to any one of 1 to 4, wherein the polyurethane resin (A) and / or the polyurethane resin (B) is a biomass polyurethane resin.
6. The laminate printing ink composition for flexible packaging according to any one of 1 to 5, wherein the pigment is a neutral carbon, a phthalocyanine pigment, or PR146.
7. The laminate printing ink composition for flexible packaging according to any one of 1 to 6, which contains at least one selected from an adhesion improver and an antiblocking agent.
8. 7. The laminated printing ink composition for flexible packaging according to 7, which contains an adhesion improver and an antiblocking agent.
9. The adhesion improver is at least one selected from rosin and its derivatives, chlorinated polypropylene, and dammar resin, and the blocking inhibitor is silica particles, polyethylene wax, fatty acid amide, cellulose acetate propionate resin, and cellulose acetate butyrate resin. The laminate printing ink composition for flexible packaging according to 7 or 8, which is at least one selected from nitrocellulose.
10. The laminate printing ink composition for flexible packaging according to any one of 1 to 9, wherein the organic solvent is a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent.
11. The laminated printing ink composition for flexible packaging according to any one of 1 to 10 containing water.
12. The laminated printing ink composition for flexible packaging according to any one of 1 to 11, further comprising a glycol ether-based organic solvent.

The laminated printing ink composition for flexible packaging of the present invention has excellent stability over time, can be used so that a plant-derived material has a higher content, and adheres to various films and films such as various high-performance barrier films. It is possible to obtain a laminated printing ink composition for flexible packaging, a printing method, a printed matter, and a laminate capable of improving the properties.

The present invention is a laminate printing ink composition for flexible packaging containing a pigment, a binder resin, and an organic solvent, wherein the binder resin has a urethane group concentration of 0.3 to 2.4 mmol / g, preferably 0.5 to. A polyurethane resin (A) having a urea bond having an amino group at the terminal, which is 1.3 mmol / g, and a urethane group concentration of 3.0 to 6.0 mmol / g, preferably 3.5 to 5.5 mmol / g. Contains a polyurethane resin (B) having a mass average molecular weight of 1000 to 6000 without a urea bond, which is g, a vinyl chloride / vinyl acetate copolymer resin having a hydroxyl group, and / or a vinyl chloride / acrylic copolymer resin having a hydroxyl group. A laminate printing ink composition for flexible packaging.
Hereinafter, the laminated printing ink composition for flexible packaging of the present invention will be specifically described.

(Pigment)
As the pigment, for example, various inorganic pigments, organic pigments or extender pigments generally used in printing inks can be used.
Examples of the inorganic pigments include colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, navy blue, ultramarine, carbon black and graphite, and examples of extender pigments include silica particles, calcium carbonate, kaolin and clay. Examples thereof include barium sulfate, aluminum hydroxide, and talc. Of these, it is preferable to use titanium oxide as the white pigment.
Examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, phthalocyanine pigments such as copper, condensed polycyclic pigments and the like.
Since the present invention uses a vinyl chloride / vinyl acetate copolymer resin having a hydroxyl group and / or a vinyl chloride / acrylic copolymer resin having a hydroxyl group as the binder resin, it is difficult to disperse the pigment, and neutral carbon and phthalocyanine are difficult to disperse. The pigment, PR146, and the like also have good pigment dispersibility, and the stability over time of the printing ink composition for laminating for flexible packaging is also good.
The content of these pigments in the ink composition is usually about 1 to 50% by mass.

(Binder resin)
The binder resin is the following polyurethane, which is a polyurethane resin having a urethane group concentration of 0.3 to 2.4 mmol / g, preferably a urethane group concentration of 0.5 to 1.3 mmol / g and having an amino group at the terminal. The resin (A) and a polyurethane resin having a urethane group concentration of 3.0 to 6.0 mmol / g, preferably a urethane group concentration of 3.5 to 5.5 mmol / g and having no urea bond. Further, it contains the following polyurethane resin (B) and a vinyl chloride / vinyl acetate copolymer resin having a hydroxyl group and / or a vinyl chloride / acrylic copolymer resin having a hydroxyl group.
From an environmental point of view, the polyurethane resin (A) and / or the polyurethane resin (B) is preferably a biomass polyurethane resin.
Further, the mass content ratio of the polyurethane resin (A) and the polyurethane resin (B) is preferably in the range of 95: 5 to 50:50, more preferably 90:10 to 70:30, and 92: 8 to 65: 35 is more preferable. If the ratio of the polyurethane resin (B) is out of the range, the adhesiveness tends to decrease.
The urethane group concentration and the urea group concentration can be calculated by the following formulas.
(Urethane group concentration)
Urethane group concentration = {(W1 x OH1 + W2 x OH2 + ... + Wi x OHi) x 1000} / (56100 x S)
In the formula, they are as follows.
When a plurality of types of polyols are used, they are calculated as polyol 1, polyol 2 to polyol i, respectively.
W1: Mass of polyol 1 OH1: Hydroxyl value of polyol 1 W2: Mass of polyol 2 OH2: Mass of polyol 2 Wi: Mass of polyol i OHi: Hydroxyl value of polyol i S: Mass of urethane resin solid content (urea group) concentration)
Urea group concentration = {(X1 / M1 + X2 / M2 + ... + Xi / Mi) x 2- (W1 x OH1 + W2 x OH2 + ... + Wi x OHi) / 56100} x 1000 / S
In the formula, the symbols are as follows.
X1: Weight of diisocyanate compound 1 M1: Molecular weight of diisocyanate compound X2: Weight of diisocyanate compound 2 M2: Molecular weight of diisocyanate compound 2 Xi: Weight of diisocyanate compound i Mi: Molecular weight of diisocyanate compound i W1: Weight of polyol 1 OH1: The hydroxyl value of the polyol 1 W2: the weight of the polyol 2 OH2: the hydroxyl value of the polyol 2 Wi: the weight of the polyol i OHi: the hydroxyl value of the polyol i S: the weight of the urethane resin solid content

<Polyurethane resin (A)>
The polyurethane resin (A) is a polyurethane having a urethane group concentration of 0.3 to 2.4 mmol / g, preferably a urethane group concentration of 0.5 to 1.3 mmol / g, and having a urea bond having an amino group at the terminal. It is a resin. If the urethane group concentration is less than 0.3 mmol / g, synthesis becomes difficult, and if it exceeds 2.4 mmol / g, the adhesion tends to decrease.
Further, the urea group concentration is preferably 0.30 to 2.00 mmol / g, more preferably 0.30 to 1.50 mmol / g, and further preferably 0.30 to 1.20 mmol / g. is there.
The mass average molecular weight of the polyurethane resin (A) is preferably 10,000 to 100,000, more preferably 15,000 to 80,000, and even more preferably 20,000 to 50,000.
Further, the polyurethane resin (A) has one or more selected from a primary amino group, a secondary amino group and a tertiary amino group at the end of the molecule, particularly a primary amino group and a second amino group at the end of the molecule. It is desirable to have one or more selected from the secondary amino groups, and it is preferable to have a hydroxyl group.
The amine value of the polyurethane resin (A) is preferably 1.0 to 15.0 mgKOH / g, more preferably 2.0 to 10.0 mgKOH / g, and 2.5 to 7.0 mgKOH / g. Is more preferable. If the amine value is less than 1.0 mgKOH / g, the stability over time of the laminated printing ink composition for flexible packaging of the present invention may decrease, the adhesiveness to the film may decrease, and the laminating suitability may decrease. It may decrease, and if the amine value exceeds 15.0 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 a potential difference titration method (for example, COMITE (AUTO TITTOROR COM-900, BURET B-900, TITSTATIONK) is used using a 0.1 N hydrochloric acid aqueous solution. -900), the value converted to the equivalent of potassium hydroxide after measurement by Hiranuma Sangyo Co., Ltd.).

As the polyurethane resin (A), a polyurethane resin obtained by synthesizing a urethane prepolymer by reacting an organic diisocyanate compound with a high molecular weight diol compound and reacting the urethane prepolymer with a chain extender and a reaction terminator as necessary is preferable. Can be used for.
Examples of the organic diisocyanate compound include aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as 1,4-cyclohexanediisocyanate and isophorone diisocyanate, aliphatic diisocyanate compounds such as hexamethylene diisocyanate, and α, Examples thereof include aromatic aliphatic diisocyanate compounds such as α, α', α'-tetramethylxylylene diisocyanate. These organic diisocyanate compounds can be used alone or in admixture of two or more. Of these, alicyclic diisocyanates, aliphatic diisocyanates and aromatic aliphatic diisocyanates are more preferable.

Examples of the polymer diol compound include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyether diol compounds such as ethylene oxide of bisphenol A and alkylene oxide adduct such as propylene oxide, adipic acid, sebacic acid, and anhydrous. One or more dibasic acids such as phthalic acid and one of glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol Alternatively, polyesterdiol compounds obtained by subjecting two or more kinds to a condensation reaction, polyesterdiol compounds such as polycaprolactone diols, and the like can be mentioned. These polymer diol compounds can be used alone or in admixture of two or more.

Further, in addition to the above high molecular weight diol compound, alkanediols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4- One or a mixture of two or more low molecular weight diol compounds such as butanediol and 1,3-butanediol can also be used in combination.
When synthesizing the polyurethane resin, when a mixed solvent system of an ester solvent and an alcohol solvent is used as the organic solvent described later, a polyether diol compound, preferably polypropylene glycol, is used as the polymer diol compound. , The obtained polyurethane resin tends to have high solubility, and printability such as gradation reproducibility and anti-fog property tends to be good, so that a wide range of inks can be designed according to the required performance. It is preferable in that it becomes.
Further, the organic diisocyanate compound and the high molecular weight diol compound are reacted so that the equivalent ratio of isocyanate group: hydroxyl group (isocyanate index) is in a range larger than 1.

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

As the reaction terminator to be introduced having a primary amino group, a secondary amino group and a tertiary amino group at the end of the polyurethane resin, aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine and hexamethylenediamine , Isophorone diamine, alicyclic diamines such as 4,4'-dicyclohexylmethanediamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylenediamine, aromatic aliphatic diamines such as xylenediamine. , N- (2-Hydroxyethyl) ethylene diamine, N- (2-hydroxyethyl) propylene diamine and other diamines having a hydroxyl group can be exemplified. Among these, polyamines having a primary amino group such as diethylenetriamine and triethylenetetratriamine are preferable.

Examples of the reaction terminator for introducing a hydroxyl group into the polyurethane resin include alkanolamines such as monoethanolamine and diethanolamine, and diamines having hydroxyl groups such as N- (2-hydroxyethyl) ethylenediamine and N- (2-hydroxyethyl) propylenediamine. Can be exemplified. Further, known reaction terminators such as monoamine compounds and monoalcohol compounds 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.
In order to obtain the polyurethane resin (A) used in the laminate printing ink composition for flexible packaging of the present invention using the above synthetic components, the urethane group concentration is 0.3 to 2.4 mmol / g, preferably urea. The diisocyanate compound and the diol compound are reacted so that the group concentration is 0.3 to 2.0 mmol / g to obtain a urethane prepolymer containing a terminal isocyanate group, and then a chain extender and / or a reaction terminator is reacted. Can be obtained by

Further, the polyurethane resin (A) may have a biomass polyurethane resin in consideration of the environment. The biomass polyurethane resin will be described. In the description of the biomass polyurethane resin, the description common to the above-mentioned polyurethane resin will be omitted as appropriate.
The biomass polyurethane resin is a polyurethane resin containing components derived from biomass (derived from plants). Since biomass polyurethane resin can contribute to prevention of global warming and reduction of environmental load compared to the case of using other depleting resources, it is necessary to synthesize urethane prepolymer by reaction with the biopolypoly component isocyanate component. It is preferably a biomass polyurethane resin obtained by reacting a chain extender and a reaction terminator according to the above, and more preferably the isocyanate component is a plant-derived bioisocyanate.

The biopolyol 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 the biopolyol 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 may be 1,3-propanediol, 1,4-butanediol, ethylene glycol or the like obtained from a plant material by the following method, or may be used in combination thereof. Good.
1,3-Propanediol can be produced from glycerol via 3-hydroxypropyl aldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant resources (such as corn). Compared with the 1,3-propanediol compound produced by the EO production method, 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. 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. In addition, 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 one selected from the group consisting of sebacic acid, succinic acid and dimer acid.
The biopolyol 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. Specifically, a polytrimethylene sebacate polyol can be obtained by directly dehydrating and condensing plant-derived sebacic acid and plant-derived 1,3-propanediol. Further, a polybutylene succinate polyol can be obtained by directly dehydrating and condensing plant-derived succinic acid and plant-derived 1,4-butanediol, and these may be used in combination.
In order to obtain the biomass polyurethane resin (A) used in the laminate printing ink composition for flexible packaging of the present invention using the above synthetic components, the urethane group concentration is 0.3 to 2.4 mmol / g, and the urea group. The diisocyanate compound and the diol compound are reacted to obtain a urethane prepolymer containing a terminal isocyanate group so that the concentration is 0.3 to 0.7 mmol / g, and then a chain extender and / or a reaction terminator is reacted. Can be obtained by

<Polyurethane resin (B)>
The polyurethane resin (B) has a urethane group concentration of 2.0 to 6.0 mmol / g, preferably a urethane group concentration of 3.5 to 5.5 mmol / g. Further, it does not have to have an amine value. The mass average molecular weight is preferably 1,000 to 6,000, more preferably 2,000 to 5,000, and even more preferably 1,500 to 4,000. If the range of the mass average molecular weight is out of the range, the adhesion tends to decrease. In addition, a polyurethane resin that does not have a urea bond can be selected and used, and is an essential component for enhancing adhesion.
If the urethane group concentration of the polyurethane resin (B) is less than 2.0 mmol / g, production becomes difficult, and if it exceeds 6.0 mmol / g, the adhesiveness tends to decrease.

The polyurethane resin (B) is, for example, a polyurethane resin having a hydroxyl group at the terminal, which can be obtained by reacting a diisocyanate compound, a low molecular weight polyol compound having an average mass molecular weight of 1000 or less, and a low molecular weight compound having two or more hydroxyl groups. is there.
Here, examples of the diisocyanate compounds that can be used include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and 4,4-cyclohexylmethane diisocyanate. Examples thereof include aromatic aliphatic diisocyanate compounds such as alicyclic diisocyanate compounds, xylylene diisocyanate, α, α, α', α'-tetramethylxylylene diisocyanate, and aromatic diisocyanate compounds such as toluylene diisocyanate and diphenylmethane diisocyanate. ..

Low molecular weight polyol compounds having an average mass molecular weight of 1,000 or less include, for example, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyetherdiol compounds such as ethylene oxide of bisphenol A and alkylene oxide adducts such as propylene oxide, and adipine. One or more dibasic acids such as acid, sebacic acid, phthalic anhydride, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, etc. Diol compounds such as polyester diols obtained by condensing one or more of the glycols of the above and polyester diol compounds such as polycaprolactone diols can be obtained by mixing one or more of the above.

Examples of the low molecular weight compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and hexamethylene glycol. , Saccharose, methylene glycol, glycerin, sorbitol and other aliphatic polyols; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, etc. One or more of the aromatic polyols of the above can be exemplified.

In order to obtain the polyurethane resin (B) having no urea bond used in the laminate printing ink composition for flexible packaging of the present invention using the above synthetic components, the urethane group concentration is 2.0 to 6.0 mmol /. g, preferably, a diisocyanate compound, a low molecular weight polyol compound having an average mass molecular weight of 1000 or less, and two or more hydroxyl groups so that the urethane group concentration is 3.5 to 5.5 mmol / g and the mass average molecular weight is 1000 to 6000. It can be obtained by reacting the compound having a low molecular weight with the compound so that the terminal becomes a hydroxyl group.

Further, as the polyurethane resin (B), a biomass polyurethane resin may be used in consideration of the environment. The biomass polyurethane resin will be described. In the description of the biomass polyurethane resin, the description common to the above-mentioned polyurethane resin will be omitted as appropriate.
The biomass polyurethane resin is a polyurethane resin containing components derived from biomass (derived from plants). The biomass polyurethane resin can contribute to the prevention of global warming and the reduction of the environmental load as compared with the case of using other depleting resources. Therefore, for example, a diisocyanate compound (diisocyanate compound which is a biomass is more preferable from the environmental point of view), average A low molecular weight polyol compound containing a biomass low molecular weight polyol compound having a mass molecular weight of 1000 or less and a low molecular weight compound having two or more hydroxyl groups (a low molecular weight compound having two or more hydroxyl groups, which is biomass, are more preferable from the environmental point of view. ) Is a biomass polyurethane resin that can be obtained by reacting.

In order to obtain a low molecular weight polyol compound containing a biomass low molecular weight polyol compound having an average mass molecular weight of 1,000 or less, biomass polyester polyol alone, polyethylene glycol other than biomass polyester polyol, polyalkylene glycols such as polypropylene glycol, and bisphenol A Ethylene oxide, polyetherdiol compounds such as alkylene oxide adducts such as propylene oxide, one or more dibasic acids such as adipic acid, sebacic acid, and phthalic anhydride, and ethylene glycol, propylene glycol, 1, Polyesterdiol compounds such as polyesterdiols and polycaprolactone diols obtained by condensing one or more glycols such as 4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol and the like. It can also be used by using one kind or two or more kinds of diol compounds such as
The biomass polyester polyol includes polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyetherdiol compounds such as ethylene oxide of bisphenol A and alkylene oxide adducts such as propylene oxide, and adipic acid, sebacic acid, phthalic anhydride and the like. Polycaprolactone diols, polyester diols obtained by condensing a basic acid with glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol. Various high molecular weight diol compounds such as polyester diol compounds. And one or more of these compounds are plant-derived compounds.
The above 1,3-propanediol, 1,4-butanediol, ethylene glycol and the like may be plant-derived short-chain diol components obtained from plant raw materials by the following methods. These may be used together.

1,3-Propanediol can be produced from glycerol via 3-hydroxypropyl aldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant resources (such as corn). Compared with the 1,3-propanediol compound produced by the EO production method, 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. It can be obtained and the manufacturing cost can be kept low. 1,4-Butanediol can be produced by obtaining succinic acid obtained by producing glycol from plant resources and fermenting it, and hydrogenating it.
In addition, ethylene glycol can be produced from bioethanol obtained by a conventional method via ethylene.

The plant-derived dicarboxylic acid component is not particularly limited. As an example, the dicarboxylic acid component is sebacic acid, succinic acid, lactic acid, glutaric acid, malic acid, dimer acid and the like. These may be used together. Among these, the dicarboxylic acid components are sebacic acid, succinic acid, and malic acid from the viewpoint of further excellent blocking resistance and laminating suitability of the printed matter when the obtained adhesive composition is printed or applied to the flexible packaging. And at least one selected from the group consisting of dimeric acid is preferably included.
The biomass polyester polyol may contain an organic acid having a molecular weight of 300 or less and having three or more active hydrogen groups in one molecule. The organic acid component is not particularly limited. As an example, the organic acid component having three or more active hydrogen groups in one molecule and having a molecular weight of 300 or less is malic acid, succinic acid, tartaric acid and the like. These may be used together. The amount of the organic acid component having a molecular weight of 300 or less and having three or more active hydrogen groups in one molecule is preferably 3000 ppm or less, more preferably 1000 to 3000 ppm with respect to the dicarboxylic acid. When a higher resistance is required by using an organic acid component having three or more active hydrogen groups and a molecular weight of 300 or less with respect to a dicarboxylic acid of 1000 ppm or more, blocking property and retort property are obtained. Easy to express well.

The biomass polyester polyol has conventionally known short-chain diol components derived from plants, carboxylic acid components derived from plants, and organic acid components having a molecular weight of 300 or less having three or more active hydrogen groups in one molecule, if necessary. It can be obtained by appropriately conducting a condensation reaction by the method.
Examples of the compound having two or more low molecular weight hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and hexamethylene glycol. , Saccharose, methylene glycol, glycerin, sorbitol and other aliphatic polyols; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, etc. One or more of the aromatic polyols of the above can be exemplified. From the environmental point of view, 1,3-propanediol, 1,4-butanediol, ethylene glycol and the like obtained from plant raw materials are preferable.

In order to obtain the biomass polyurethane resin (B) used in the laminate printing ink composition for flexible packaging of the present invention using the above synthetic components, the urethane group concentration is 3.0 to 6.0 mmol / g, preferably. , Urethane group concentration 3.5-5.5 mmol / g, diisocyanate compound (diisocyanate compound which is a biomass is more preferable from the environmental point of view) so that the mass average molecular weight is 1000 to 6000, biomass low with an average mass molecular weight of 1000 or less. A low molecular weight polyol compound containing a molecular weight polyol compound and a low molecular weight compound having two or more hydroxyl groups (a low molecular weight compound having two or more hydroxyl groups, which is a biomass, is more preferable from an environmental point of view) with an isocyanate group at the end. It can be obtained by reacting so as to become.

<Vinyl chloride / vinyl acetate copolymer>
A vinyl chloride / vinyl acetate copolymer can be blended in the laminated printing ink composition for flexible packaging of the present invention. The content thereof is preferably 0 to 20 parts by mass, more preferably 0 to 15 parts by mass, based on 100 parts by mass of the total solid content of the polyurethane resins (A) and (B) in consideration of pigment dispersibility and adhesiveness. preferable.
The vinyl chloride / vinyl acetate 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, if necessary. A vinyl acetate monomer such as vinyl acetate, vinyl laurate, vinyl stearate, vinyl benzoate, or 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 copolymer is preferably a vinyl chloride / vinyl acetate copolymer having 50 to 200 hydroxyl groups in an organic solvent system of an environmentally friendly ink. Such a vinyl chloride / vinyl acetate-based copolymer having a hydroxyl group can be obtained by saponifying a part of the acetic acid ester portion 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, a structural unit based on the reaction site of vinyl chloride in the molecule (formula 1 below), acetic acid. The physical properties and dissolution behavior of the resin film 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 provides good solubility of environmentally friendly inks in organic solvent systems.
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, and for example, Solvine A, AL, TA5R, TA2, TA3, TAO, TAOL, C, CH, CN, manufactured by Nissin Chemical Industries, Ltd. CNL and the like can be mentioned.
From the viewpoint of solubility in organic solvents and printability described later, which are used in the laminated printing ink composition for flexible packaging of the present invention, the above-mentioned vinyl chloride / vinyl acetate copolymer has various functional groups in the molecule. You may have.
When an environment-friendly solvent is used as the organic solvent, the vinyl chloride / vinyl acetate copolymer preferably has a hydroxyl group of 50 to 200 mgKOH / g. As a commercially available product of such a vinyl chloride / vinyl acetate copolymer, for example, it is preferable to use solvers A, AL, TA5R, TA2, TA3, TAO, TAOL and the like.

<Vinyl chloride / acrylic copolymer>
A vinyl chloride / acrylic copolymer can be blended in the gravure printing ink composition for lamination of the present invention. The content thereof is preferably 0 to 20 parts by mass, more preferably 0 to 15 parts by mass, based on 100 parts by mass of the total solid content of the polyurethane resins (A) and (B) in consideration of adhesiveness. The vinyl chloride / acrylic copolymer is mainly composed of a copolymer of vinyl chloride and an acrylic monomer, and the form of the copolymer is not particularly limited. 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, but a linear alkyl group is preferable.
For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate. , (Meta) 2-ethylhexyl acrylate, (meth) isooctyl acrylate, (meth) decyl acrylate, (meth) dodecyl acrylate, (meth) tetradecyl acrylate, (meth) hexadecyl acrylate, (meth) acrylate Octadecil and the like can be mentioned.

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) acrylate hydroxyalkyl esters such as (meth) acrylate 3-hydroxybutyl, (meth) acrylate 4-hydroxybutyl, (meth) acrylate 6-hydroxyhexyl, (meth) acrylate 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 functional groups other than hydroxyl groups include carboxyl groups, amide bond groups, amino groups, alkylene oxide groups and the like.
The vinyl chloride / acrylic copolymer resin preferably has a mass average molecular weight of 10,000 to 70,000, and more preferably 20,000 to 50,000.
Further, the vinyl chloride / acrylic copolymer may have a hydroxyl group of 50 to 200 mgKOH / g from the viewpoint of solubility in an environmentally friendly solvent as the organic solvent and adhesiveness to a substrate. preferable.

The vinyl chloride / vinyl acetate copolymer and / or the vinyl chloride / acrylic copolymer contained in the laminated printing ink composition for flexible packaging of the present invention is a polyurethane resin (A) and a polyurethane resin (B). (Hereinafter referred to as the total amount of polyurethane resin) and (vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / acrylic copolymer) are the total amount of polyurethane resin / (chloride). The total amount of the vinyl / vinyl acetate copolymer and the vinyl chloride / acrylic copolymer) = 100/0 to 45/55 (mass ratio), preferably 95/5 to 70/30. is there.
The total amount of polyurethane resin / (vinyl chloride / vinyl acetate copolymer) may be in the range of 90/10 to 75/25, and the total amount of polyurethane resin / (vinyl chloride / acrylic copolymer) is 95/5. It may be in the range of ~ 85/15.

Then, the polyurethane resin (A) and the polyurethane resin (B) are contained in a vinyl chloride / vinyl acetate copolymer and / or a vinyl chloride / acrylic copolymer in a ratio of 100/0 to 45/55. As a result, the laminated printing ink composition of the present invention has excellent pigment dispersibility, and further excellent printability and adhesiveness to the film. Further, when the laminating process is performed, it will have better laminating suitability.
When the total amount of the polyurethane resin / (vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / acrylic copolymer) is less than 45/55, (vinyl chloride / vinyl acetate copolymer and / or The proportion of vinyl chloride / acrylic copolymer) may increase, the printed matter formed by using the ink composition of the present invention may become hard, and the adhesiveness to the film may be insufficient.

Therefore, in the present invention, when (vinyl chloride / vinyl acetate-based copolymer and / or vinyl chloride / acrylic-based copolymer) is contained, the total amount of the above polyurethane resin / (vinyl chloride / vinyl acetate-based copolymer). And / or a vinyl chloride / acrylic copolymer) is preferably 100/0 to 45/55 (mass ratio).
The total amount of the polyurethane resin and the total content of the vinyl chloride / vinyl acetate copolymer and / or the vinyl chloride / acrylic copolymer in the ink composition of the present invention is 5 to 30% by mass. Is preferable.
Further, in the present invention, one kind selected from the adhesion improver and the blocking inhibitor, preferably the adhesion improver and the blocking inhibitor, may be used as long as the performance intended by the present invention is not deteriorated. preferable.

(Adhesion improver)
Examples of the adhesion improver include rosin and its derivatives, chlorinated polypropylene, dammar resin and the like, and at least one selected from rosin and its derivatives, more preferably two or more, are contained.

<Rosin and its derivatives>
Examples of the 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. Dehydroabietic acid may be isolated and used for each component, and these are also defined as rosins in the present invention.
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) Disproportionated rosin: Disproportionation is the reaction of two molecules of rosin to two molecules of abietic acid having a conjugated double bond, one to an aromatic and the other to a single double bond. It is a modification that becomes a molecule. It is generally inferior in weather resistance to hydrogenated rosin, but has better weather resistance than untreated rosin.
(3) Rosin-modified phenolic resin: Rosin-modified phenolic resin is often used as the main binder for 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 long been used as a tackifier (tack fire) for adhesives and adhesives.
(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 laminate strength is improved. 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 solid content mass% of the laminated printing ink composition for flexible packaging.

<Chlorinated polypropylene>
As the chlorinated polypropylene, polypropylene having a degree of chlorination of 20 to 50 can be used. Chlorinated polypropylene having a degree of chlorination of less than 20 tends to have low compatibility with an organic solvent. On the other hand, when the degree of chlorination exceeds 50, the chlorinated polypropylene tends to have a reduced adhesiveness to the film. In the present invention, 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 20000. When the mass average molecular weight is less than 5000, the chlorinated polypropylene tends to have low adhesiveness. On the other hand, when the mass average molecular weight exceeds 200,000, the chlorinated polypropylene tends to have a reduced solubility in an organic solvent. The amount used when blending the chlorinated polypropylene is preferably 0.1% by mass to 3.0% by mass in terms of the solid content mass% of the laminated printing ink composition for flexible packaging.

<Dammal resin>
Dammar resin, also referred to as damar or dammer, 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 growing in Southeast Asia such as Malaysia and Indonesia. When using, dissolve 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. The amount of the dammar resin used when blending is preferably 3.0% by mass or less in terms of the solid content mass% of the laminating printing ink composition for flexible packaging.

(Anti-blocking agent)
Examples of the blocking inhibitor include silica particles, polyethylene wax, fatty acid amide, cellulose acetate butyrate, cellulose acetate propionate, nitrocellulose cotton, and one or more, preferably two types of silica particles, polyethylene wax, and fatty acid amide. It is preferable to contain the above, and depending on the type of pigment, it is preferable to further contain cellulose acetate butyrate, cellulose acetate propionate, and nitrocellulose cotton.

<Silica particles>
Examples of the silica particles include natural products, synthetic products, crystalline, non-crystalline, 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 alkylsilane or the like to make it hydrophobic, but hydrophilic ones are preferable and hydrophilic. The ink containing silica particles also has the effect of promoting the wetting and spreading of the ink during overlay printing and improving the overlay printing effect (hereinafter, may be referred to as "trapping property"). The amount of silica particles used is preferably 0.0 to 3.0% by mass, more preferably 0.1 to 1.0% by mass in the laminated printing ink composition for flexible packaging.

<Polyethylene wax>
As the polyethylene wax, one having an average particle size in the range of 1.0 to 20 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 smaller than 1.0 μm, the slipperiness and blocking property are lowered, and when the particle size is larger than 20 μm, the trapping property is lowered. The content of polyethylene wax in the flexible packaging laminate printing ink composition is preferably in the range of 0.1 to 1.5% by mass. If the content is less than 0.1% by mass, the desired effect cannot be obtained, and if the content is more than 1.5% by mass, the gloss tends to decrease.

<Nitrocellulose>
As the nitric acid cotton, nitric acid cotton conventionally used in a gravure printing ink composition can be used. The vitrified cotton is obtained as a nitrate ester in which three hydroxyl groups in the 6-membered ring of the anhydrous glucopyranose group in the natural cellulose are replaced with a nitric acid group by reacting natural cellulose with nitric acid. As the nitricized cotton used in the present invention, one having a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90 is preferably used. Specific examples include SS1 / 2, SS1 / 4, SS1 / 8, TR1 / 16, NCRS-2, (manufactured by KOREA CNC LTD) and the like. The amount of nitrocellulose used is preferably in the range of 0.1 to 2.0% by mass in the laminate printing ink composition for flexible packaging, depending on the type of pigment.

<Cellulose Acetate Propionate Resin>
As the cellulose acetate propionate resin, a resin conventionally used in a 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, resins having acetylation of 0.6 to 2.5% by weight, propionylation of 42 to 46% by weight, and hydroxyl groups of 1.8 to 5% by weight are commercially available. Depending on the type of pigment, the cellulose acetate propionate resin is preferably used in the range of 0.1 to 3.0% by mass during the formation of the laminate printing ink composition for flexible packaging.

<Cellulose acetate butyrate resin>
As the cellulose acetate butyrate resin, a resin conventionally used in a gravure printing ink composition can be used.
Cellulose acetate butyrate resin is obtained by triesterifying cellulose with acetic acid and butyric acid and then hydrolyzing it. Generally, resins having 2 to 30% by weight of acetylation, 17 to 53% by weight of butyrylation, and 1 to 5% of hydroxyl groups are commercially available. The amount of the cellulose acetate butyrate resin used is preferably in the range of 0.1 to 3.0% by mass in the laminated printing ink composition for flexible packaging, 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 in order to improve blocking resistance. Is preferable. The amount of the fatty acid amide used is preferably in the range of 0.01 to 1% by mass in the laminated printing ink composition for flexible packaging.
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 the monoamide include lauric acid amide, palmitate amide, stearic acid amide, bechenic acid amide, hydroxystearic acid amide, oleic acid amide, erucic acid amide and the like.
-Substitution amide: The substitution 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 palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic 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 bisamides 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 biserucate amide, Hexamethylene bisoleic acid amide, N, N'-Distearyl adipate amide, N, N'- Examples thereof include distearyl sebacic acid amide, N, N'-diorail adipic acid amide, N, N'-diorail sebacic 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 acids.)
Specific examples of the methylol amide include methylol palmitate amide, methylol stearic acid amide, methylol bechenic 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 oleyl amide 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. Lauric acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid are particularly preferable as saturated fatty acids, and oleic acid and erucic acid are particularly preferable as unsaturated fatty acids.

(Organic solvent)
Examples of the organic solvent include ketone organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester organic solvents such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate and isobutyl acetate, methanol and ethanol. Alcohol-based organic solvents such as n-propanol, isopropanol and butanol, and hydrocarbon solvents such as toluene and methylcyclohexane can be used.
From the aspect of environmental issues, we use a mixed solvent of ester-based organic solvent, alcohol-based organic solvent and ketone-based organic solvent, or a mixed solvent of ester-based organic solvent and alcohol-based organic solvent that are more compatible with environmental problems. It is preferable to do so.

<Water>
The laminated printing ink composition for flexible packaging of the present invention preferably contains water from the viewpoints of alleviating printing defects due to static electricity, preventing plate fog, and cell reproducibility. The amount of water used is preferably 10% by mass or less, more preferably 0.1 to 5.0% by mass in the flexible packaging laminate printing ink composition.

<Glycol ether-based organic solvent>
The laminated printing ink composition for flexible packaging of the present invention contains 0.1 to 20% by weight of a glycol ether-based organic solvent in 100% by weight of the glycol ether-based organic solvent in order to improve the wettability. It is preferable to let it. 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, and ethylene glycol. Examples thereof include monoisobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monon-propyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether.

<Other materials>
Various additives such as pigment dispersants, antistatic agents, and plasticizers can be further added to the laminated printing ink composition for flexible packaging of the present invention. A silane coupling agent may or may not be contained.

As a method for producing a laminated printing ink composition for flexible packaging using the above constituent materials, a known method can be used. Specifically, for example, a mixture of a pigment, a binder resin, an organic solvent and, if necessary, a pigment dispersant is kneaded using a high-speed mixer, a ball mill, a sand mill, an attritor or the like, and further, a predetermined additive or the like is used. It can be obtained by adding and mixing the rest of the materials of.

(Printing method using a laminated printing ink composition for flexible packaging, and a laminate obtained thereby)
Next, a method of performing printing using the printing ink composition for flexible packaging lamination of the present invention to obtain a laminate will be described.
As the laminate, for example, a laminate printing ink composition for flexible packaging other than white is first printed on a film such as various resin films and various high-performance barrier films at least once by a gravure printing method. Next, a laminated white printing ink composition for flexible packaging is optionally printed on the surface side of the colored ink layer formed by these printing (after the final laminating, the lower layer side when viewed from the surface layer) by a gravure printing method, and a dryer is used. It can be obtained by drying with.
A laminated body for a packaging bag or the like can be obtained by laminating a resin film or the like by various laminating processing methods on the side of the layer of the obtained printed matter made of the white ink composition.

The laminating method includes an extrusion laminating method in which an anchor coating agent is applied to the surface of a printed matter and then a molten polymer is laminated, and a dry laminating method in which an adhesive is applied to the surface of the printed matter and then a film-like polymer is bonded. The law is available. 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-based is applied to the surface of a printed matter as necessary, and then the molten polymer is laminated by a known extrusion laminating machine. Further, the molten resin can be laminated as an intermediate layer 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.

The dry laminating method is a method in which a urethane-based or isocyanate-based adhesive is applied to the surface of a layer made of a white ink composition, 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, polyethylene, unstretched polypropylene, etc. can be used, and especially in the packaging material used for retort pouching, an aluminum foil is placed between the base material and the resin film to be bonded. You can also laminate with. Such a laminated product can also be used for boiled retort after bag making and filling the contents. It is also excellent in boil resistance, electrical suitability (whiskers, misting), cell reproducibility, and plate fog prevention.
The resin film used at this time is not particularly limited, and may be used for polyester films such as polyethylene terephthalate (PET), polylactic acid and polycaprolactone, various printing plastic films such as nylon and vinylon, and various printing plastic films. A film in which a barrier layer coated with a metal vapor deposition or a barrier resin is laminated can be used.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples. Unless otherwise specified, "%" means "% by mass" and "part" means "part by mass".

<Polyurethane resin (A)>
The properties of the polyurethane resin (A) are shown in Table 1.
(Urethane resin A-1)
A four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a nitrogen gas introduction tube is charged with 100 parts by mass of 3-methyl-1,5-pentylene adipatediol and 8.9 parts by mass of isophorone diisocyanate having an average molecular weight of 5000, and nitrogen. The reaction was carried out at 95 to 105 ° C. for 5 hours while introducing gas. After cooling, 196 parts by mass of propyl acetate was added to uniformly dissolve the mixture, 65 parts of isopropyl alcohol and 2.0 parts of isophorone diamine were added to extend the chain, and 0.35 parts of monoethanolamine was added, and then isophorone diamine 0. 51 parts were added to terminate the reaction to obtain a polyurethane resin varnish A-1 (solid content: 30%, theoretical mass molecular weight: 37,000, urethane group concentration: 0.36 mmol / g).

(Urethane resin A-2)
A four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a nitrogen gas introduction tube is charged with 100 parts by mass of 3-methyl-1,5-pentylene adipatediol and 13 parts by mass of isophorone diisocyanate having an average molecular weight of 3000, and nitrogen gas is charged. The reaction was carried out at 95 to 105 ° C. for 5 hours while introducing. After cooling, 206 parts by mass of propyl acetate was added to uniformly dissolve the mixture, 69 parts of isopropyl alcohol and 3.2 parts of isophorone diamine were added to extend the chain, and 0.35 parts of monoethanolamine was added, and then isophorone diamine 0. Five parts were added to terminate the reaction to obtain a polyurethane resin varnish A-2 (solid content 30%, theoretical mass molecular weight 38,000, urethane group concentration 0.57 mmol / g).

(Polyurethane resin A-3)
A four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a nitrogen gas introduction tube is charged with 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 1000 and 42 parts by mass of isophorone diisocyanate, and nitrogen gas is charged. Is allowed to react at 95-105 ° C. for 5 hours while introducing. After cooling, 274 parts by mass of propyl acetate was added to uniformly dissolve the mixture, 91.4 parts of isopropyl alcohol and 13.3 parts of isophorone diamine were added to extend the chain, and 0.5 part of monoethanolamine was added and then isophorone diamine. 0.74 parts were added to terminate the reaction to obtain a polyurethane resin varnish A-3 (solid content 30%, theoretical mass molecular weight 35,000, urethane group concentration 1.28 mmol / g).

(Urethane resin A-4)
Sebacic acid (derived from castor oil) / succinic acid (derived from plant) = 70/30 (mass ratio) and 1,3-propanediol (derived from plant) in a four-necked flask equipped with a stirrer, thermometer, Dimroth condenser and nitrogen gas introduction tube. ), 100 parts by mass of an average molecular weight of 1000 and 42 parts by mass of isophorone diisocyanate are charged and reacted at 95 to 105 ° C. for 5 hours while introducing nitrogen gas. After cooling, 274 parts by mass of propyl acetate was added to uniformly dissolve the mixture, 91.4 parts of isopropyl alcohol and 13.3 parts of isophorone diamine were added to extend the chain, and 0.5 part of monoethanolamine was added and then isophorone diamine. 0.74 parts were added to terminate the reaction to obtain a polyurethane resin varnish A-4 (solid content 30%, theoretical mass molecular weight 35,000, urethane group concentration 1.28 mmol / g).

(Polyurethane resin A-5)
A four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a nitrogen gas introduction tube is charged with 100 parts by mass of 3-methyl-1,5-pentylene adipatediol and 80 parts by mass of isophorone diisocyanate having an average molecular weight of 500, and nitrogen gas is charged. The reaction was carried out at 95 to 105 ° C. for 5 hours while introducing. After cooling, 360 parts by mass of propyl acetate was added to uniformly dissolve the mixture, 120 parts of isopropyl alcohol and 24.5 parts of isophorone diamine were added to extend the chain, and 0.69 parts of monoethanolamine was added, and then isophorone diamine 1. The reaction was stopped by adding 0 parts to obtain a polyurethane resin varnish A-5 (solid content: 30%, theoretical mass molecular weight: 34,000, urethane group concentration: 1.94 mmol / g).

(Polyurethane resin A-6)
A four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a nitrogen gas introduction tube is charged with 100 parts by mass of 3-methyl-1,5-pentylene adipatediol and 53.3 parts by mass of isophorone diisocyanate having an average molecular weight of 500, and nitrogen. The reaction is carried out at 95 to 105 ° C. for 5 hours while introducing gas. After cooling, 278 parts by mass of propyl acetate was added to uniformly dissolve the mixture, 93 parts of isopropyl alcohol and 4.77 parts of isophorone diamine were added to extend the chain, and 0.52 parts of monoethanolamine was added, and then isophorone diamine 0. 76 parts were added to terminate the reaction to obtain a polyurethane resin varnish A-6 (solid content 30%, theoretical mass molecular weight 35,000, urethane group concentration 2.51 mmol / g).

<Polyurethane resin B>
The properties of the polyurethane resin (B) are shown in Table 1.
(Polyurethane resin B-1)
20 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 1000 and 13.5 parts by mass of polypropylene glycol having an average molecular weight of 400 in a four-necked flask equipped with a stirrer, a thermometer, a gym funnel and a nitrogen gas introduction tube. , 25 parts by mass of monoethylene glycol, 41.5 parts by mass of propylene glycol, and 156 parts by mass of isophorone diisocyanate were charged and reacted at 95 to 105 ° C. for 3 hours while introducing nitrogen gas. After cooling, add 447 parts by mass of propyl acetate to uniformly dissolve, add 149 parts by mass of isopropyl alcohol, and add polyurethane resin varnish B-1 (solid content 30%, theoretical mass molecular weight 850, urethane group concentration 7.84 mmol / g). Obtained.

(Polyurethane resin B-2)
60 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 1000 and 13.5 parts by mass of polypropylene glycol having an average molecular weight of 400 in a four-necked flask equipped with a stirrer, a thermometer, a gym funnel and a nitrogen gas introduction tube. , 20 parts by mass of monoethylene glycol, 6.5 parts by mass of propylene glycol, and 89 parts by mass of isophorone diisocyanate were charged and reacted at 95 to 105 ° C. for 3 hours while introducing nitrogen gas. After cooling, add 330 parts by mass of propyl acetate to uniformly dissolve, add 110 parts by mass of isopropyl alcohol, and add polyurethane resin varnish B-2 (solid content 30%, theoretical mass molecular weight 1,885, urethane group concentration 5.30 mmol / g). ) Was obtained.

(Polyurethane resin B-3)
Sebacic acid (derived from castor oil) / succinic acid (derived from plant) = 70/30 (mass ratio) and 1,3-propanediol (derived from plant) in a four-necked flask equipped with a stirrer, thermometer, gym funnel and nitrogen gas introduction tube. ), 60 parts by mass of an average molecular weight of 1000, 13.5 parts by mass of polypropylene glycol having an average molecular weight of 400, 20 parts by mass of monoethylene glycol, 6.5 parts by mass of propylene glycol, and 89 parts by mass of isophorone diisocyanate are charged with nitrogen gas. The reaction was carried out at 95 to 105 ° C. for 3 hours while introducing. After cooling, add 330 parts by mass of propyl acetate to uniformly dissolve, add 110 parts by mass of isopropyl alcohol, and add polyurethane resin varnish B-3 (solid content 30%, theoretical mass molecular weight 1,885, urethane group concentration 5.30 mmol / g). ) Was obtained.

(Polyurethane resin B-4)
75 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 1000, 10 parts by mass of polypropylene glycol having an average molecular weight of 400, in a four-necked flask equipped with a stirrer, a thermometer, a gym funnel and a nitrogen gas introduction tube. 5 parts by mass of ethylene glycol, 5 parts by mass of propylene glycol, and 42 parts by mass of isophorone diisocyanate were charged and reacted at 95 to 105 ° C. for 3 hours while introducing nitrogen gas. After cooling, add 248 parts by mass of propyl acetate to uniformly dissolve, add 83 parts by mass of isopropyl alcohol, and add polyurethane resin varnish B-4 (solid content 30%, theoretical mass molecular weight 2,260, urethane group concentration 3.54 mmol / g). ) Was obtained.

(Vinyl chloride / vinyl acetate resin)
Vinyl chloride / vinyl acetate copolymer (Solvine TA-3, manufactured by Nissin Chemical Industry Co., Ltd.)
(Vinyl chloride / acrylic copolymer)
A vinyl chloride / acrylic copolymer (vinyl chloride / 2-hydroxypropyl acrylate = 84/16, weight average molecular weight 45,000) was dissolved in propyl acetate to prepare a varnish having a solid content of 30% by mass.
(Pigment)
-Neutral carbon black (particle diameter 56 nm, DBP adsorption amount 45 ml / 100 g, specific surface area 45 m ² / g, PH9
・ PR146 (Pigment Red 146)
・ PB 15: 4 (Pigment Blue 15: 4)
・ Titanium oxide

(Adhesion improver)
<Chlorinated polypropylene>
40 parts by mass of chlorine polypropylene (solid content 50%) having a degree of chlorination of 40% and a number average molecular weight of 100,000 and 60 parts by mass of methylcyclohexane were mixed and stirred to obtain a chlorinated polypropylene varnish having a solid content of 20%.
<Rosin and its derivatives>
Polymerized rosin: Acid value 160 mgKOH / g
(Anti-blocking agent)
<Silica particles>
Average particle size 4.5 μm
<Polyethylene wax>
Average particle size: 12 μm
<Fatty acid amide>
Ethylene bisstearic acid amide <mixture 1, mixture 2>
By mass ratio, ethyl acetate / propyl acetate / IPA (isopropyl alcohol) = 50/25/25

<Production example of gravure printing ink composition base material for film>
Pigment (neutral carbon black), polyurethane resin varnish (A), vinyl chloride / vinyl acetate copolymer resin having a hydroxyl group and / or vinyl chloride / acrylic copolymer resin having a hydroxyl group, and a paint conditioner manufactured by Red Devil. The polyurethane resin varnish (B), the adhesion improver, the blocking inhibitor, the mixed solution 1, and water were added to the composition of the black ink for flexible packaging laminating of Examples and Comparative Examples shown in Table 2. I got something.

<Manufacturing example of indigo ink composition base material for laminating for flexible packaging>
A pigment (CIPB15: 4), a polyurethane resin varnish (A), a vinyl chloride / vinyl acetate copolymer resin having a hydroxyl group, and / or a vinyl chloride / acrylic copolymer resin having a hydroxyl group, manufactured by Red Devil. Knead using a paint conditioner, and further add a polyurethane resin varnish (B), an adhesion improver, an antiblocking agent, a mixed solution 1, and water, and then add the laminate printing indigo color for flexible packaging of the examples shown in Table 2. An ink composition was obtained.

<Production example of gravure red ink composition base material for film>
A paint conditioner manufactured by Red Devil Co., Ltd. uses a pigment (CI PR146), a polyurethane resin varnish (A), a vinyl chloride / vinyl acetate copolymer resin having a hydroxyl group, and / or a vinyl chloride / acrylic copolymer resin having a hydroxyl group. The polyurethane resin varnish (B), the adhesion improver, the blocking inhibitor, the mixed solution 1, and water were further added to prepare the laminate printing red ink composition for flexible packaging shown in Table 2. Obtained.

(Ink storage stability)
The gravure printing ink composition base material for each film obtained above was collected in a glass bottle, stored at an atmospheric temperature of 60 ° C. for 14 days, and then the storage stability of the ink was evaluated from the presence or absence of pigment precipitation visually confirmed. did.

<Manufacturing of laminated body 1>
100 parts by mass of each of the black ink composition for flexible packaging laminate, the indigo ink composition for soft packaging laminate, and the red ink composition for flexible packaging laminate is diluted with the mixed solution 2 according to the formulation shown in Table 2 to adjust the viscosity. It was adjusted to 15 seconds with Zahn Cup No. 3 manufactured by Rigosha. Using a gravure printing machine, the black ink composition for flexible packaging laminate, the gravure indigo ink composition for flexible packaging laminate, or the red ink composition for flexible packaging laminate is printed and dried on the treated surface of various films under the following conditions. A printed matter for laminating was obtained. At the time of printing, the guide roll was evaluated. Using the obtained laminated printed matter, blocking resistance, adhesiveness, and retort resistance were evaluated. 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 printing machine
Coating speed: 150m / min
Printing plate: Direct 175 lines 28 μm Solid plate Drying temperature: 55 ° C

<Various films>
PET (film): Polyethylene terephthalate film with corona discharge treatment on one side, manufactured by Toyobo Co., Ltd., E-5101, thickness 12 μm
OPP: Biaxially stretched polypropylene film treated with corona discharge, 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 on one side (trade name: Fine Barrier AT-R, manufactured by Reiko Co., Ltd.)
Tech Barrier: PET film with silica vapor deposition on one side (trade name: Tech Barrier TXR, manufactured by Mitsubishi Plastics)
A-OP: Stretched polypropylene film with polyvinyl alcohol coated 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.)
IB-PET (PET film with aluminum vapor deposition, trade name: IB-PET-PUB, manufactured by Dai Nippon Printing Co., 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.)

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

(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 after applying a load of 15 kg / cm ² and leaving at 40 ° C. for 12 hours, each film was peeled off. The blocking resistance was evaluated from the state of time.
A: There is no resistance when the film is peeled off, and the ink does not peel off from the printed surface B: There is resistance when the film is peeled off, but the ink does not peel off from the printed surface C: Resistance when the film is peeled off Ink peels off from the printed surface

(Retort resistance)
A urethane-based adhesive (Takelac A-616 / Takenate A-65, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) with a solid content of 2.0 g / m ² is applied to each printed matter one day after printing, and then dried. An unstretched polypropylene film (RXC-3, thickness 60 μm, manufactured by Tohcello Co., Ltd.) was laminated with a laminating machine and left at 40 ° C. for 3 days to obtain a dry laminate. 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 and sealed, and then pressed at 135 ° C. for a PET film and 120 ° C. for a film other than a PET film. The retort resistance was evaluated from the presence or absence of floating of the laminated film when immersed in hot water for 30 minutes.
A: No lambs floating at all C: Pinhole-shaped or partially thin and short lambs floats-: The film used for printing does not have retort suitability, so the retort suitability test was not performed.

According to the examples according to the present invention, it was possible to obtain an ink composition having excellent storage stability, and more widely, adhesiveness to various films, blocking resistance and retort resistance.
On the other hand, according to Comparative Example 1 containing the polyurethane resin (A) having a high urethane group concentration and Comparative Example 2 in which the polyurethane resin (B) has a high urethane group concentration, the ink composition is inferior in adhesiveness and retort resistance. It became a thing. Further, according to Comparative Example 3 in which the amount of the polyurethane resin (A) is too large in view of the mass ratio of the polyurethane resin (A) and the polyurethane resin (B), the adhesiveness to some films and the blocking resistance to all the films tested were improved. The result was inferior.
Further, according to Comparative Example 4 in which the amount of the polyurethane resin (B) was too large in view of the mass ratio of the polyurethane resin (A) and the polyurethane resin (B), the ink composition was inferior in adhesiveness and retort resistance.
Further, according to Comparative Examples 5 and 6 containing no polyurethane resin (B), the adhesiveness to some base materials was inferior.

Claims (12)

A printing ink composition for lamination containing a pigment, a binder resin, and an organic solvent. The binder resin is a polyurethane resin having a urethane group concentration of 0.3 to 2.4 mmol / g and a urea bond having an amino group at the terminal. (A), polyurethane resin (B) having a urethane group concentration of 2.0 to 6.0 mmol / g and having no urea bond and having a mass average molecular weight of 1,000 to 6,000, and vinyl chloride / vinyl acetate having a hydroxyl group. Laminate printing for packaging containing a copolymer resin and / or a vinyl chloride / acrylic copolymer resin having a hydroxyl group, and the mass ratio of the polyurethane resin (A) to the polyurethane resin (B) is 95: 5 to 50:50. Ink composition. The first aspect of claim 1, wherein the polyurethane resin (A) has a urethane group concentration of 0.5 to 1.3 mmol / g, and the polyurethane resin (B) has a urethane group concentration of 3.5 to 5.5 mmol / g. Laminate printing ink composition for flexible packaging. The laminate printing ink composition for flexible packaging according to claim 1 or 2, wherein the polyurethane resin (A) has an amine value of 1.0 to 15.0 mgKOH / g. The total mass content of the polyurethane resin (A) and the polyurethane resin (B), the vinyl chloride / vinyl acetate copolymer resin having a hydroxyl group, and the vinyl chloride / acrylic copolymer resin having a hydroxyl group is 100/0 to 0. The laminate printing ink composition for flexible packaging according to any one of claims 1 to 3 according to 45/55. The laminated printing ink composition for flexible packaging according to any one of claims 1 to 4, wherein the polyurethane resin (A) and / or the polyurethane resin (B) is a biomass polyurethane resin. The laminate printing ink composition for flexible packaging according to any one of claims 1 to 5, wherein the pigment is a neutral carbon, a phthalocyanine pigment, or PR146. The laminate printing ink composition for flexible packaging according to any one of claims 1 to 6, which contains at least one selected from an adhesion improver and an antiblocking agent. The laminated printing ink composition for flexible packaging according to claim 7, which contains an adhesion improver and an antiblocking agent. The adhesion improver is at least one selected from rosin and its derivatives, chlorinated polypropylene, and dammar resin, and the blocking inhibitor is silica particles, polyethylene wax, fatty acid amide, cellulose acetate propionate resin, cellulose acetate butyrate resin. The laminate printing ink composition for flexible packaging according to claim 7 or 8, which is at least one selected from nitrocellulose. The laminate printing ink composition for flexible packaging according to any one of claims 1 to 9, wherein the organic solvent is a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent. The laminated printing ink composition for flexible packaging according to any one of claims 1 to 10, further comprising water. The laminated printing ink composition for flexible packaging according to any one of claims 1 to 11, further comprising a glycol ether-based organic solvent.