JP2023173862A - Printing ink composition for soft packaging laminate, printing method, printed matter and laminate - Google Patents

Abstract

To provide a printing ink composition for soft packaging laminate which has good storage stability, is excellent in printability, and has good pot life of residual ink even if a curing agent is blended according to applications.SOLUTION: A printing ink composition for soft packaging laminate contains A to C of (A) a pigment, (B) a binder resin containing a polyurethane resin having an amino value of 2.07-4.55 mgKOH/g and a hydroxyl value of 5.00-6.70 mgKOH/g, and (C) an organic solvent, wherein the polyurethane resin contains a polyol component, a polyisocyanate component, a monoamino alcohol component, a diamine component and a polyamine component containing polyalkylene polyamine as polymerization components, and the polyurethane resin has a primary amino group and/or a secondary amino group at its terminal and contains a hydroxyl group at its terminal.SELECTED DRAWING: None

Description

The present invention relates to a printing ink composition for flexible packaging laminates. More specifically, the present invention has good storage stability (pigment dispersibility), excellent printability, and good pot life (two-liquid stability) of residual ink even when a hardening agent is added. The present invention relates to a printing ink composition for flexible packaging laminates. In addition, it can contribute to preventing global warming and reducing environmental impact, has good storage stability (pigment dispersibility), excellent printability, and even when a hardening agent is added depending on the application, it can be used to remove residual ink from pots. This invention relates to a printing ink composition for flexible packaging laminates that has good life (two-liquid stability).

BACKGROUND OF THE INVENTION Packaging materials using various plastic films are used for foods, confectionery, household goods, pet food, etc. due to their functionality such as design, economy, content protection, and transportability. Additionally, many packaging materials are printed with gravure or flexographic printing to give them a design and message that appeals to consumers.
In order to obtain these packaging materials, surface printing is performed on the surface of the base film of the packaging material, or an adhesive or anchoring agent is applied as necessary to the printed surface of the base film of the packaging material to form a film. Back printing is performed to laminate the paper.
For back printing, color ink and white ink are sequentially printed on various films such as polyester, nylon, and aluminum foil. Thereafter, polyethylene film, polypropylene film, etc. are laminated on the printed layer of white ink for the purpose of heat sealing by dry laminating using an adhesive or extrusion laminating using an anchor coating agent. (For example, see Patent Document 1).
Furthermore, depending on the application, printing ink made by converting the printing ink into two liquids (two-liquid curable printing ink) has also been proposed (for example, see Patent Document 2).
However, in the disclosed patent, when the printing ink is made into two liquids, there is a problem that the pot life (two liquid stability) and heat resistance (hot peel strength) are insufficient depending on the application.
Furthermore, in recent years, "biomass" has been attracting attention as an industrial resource that is not an exhaustible resource. "Biomass" is "renewable organic resources derived from living organisms, excluding fossil resources." Furthermore, for the purpose of environmental conservation, biomass polymers using biomass as raw materials have been developed since the 1980s. Biomass polymers are considered to be useful as a measure to prevent global warming, and are used in a wide variety of products such as molding, fibers, non-woven fabrics, packaging, toners, inks, paints, films and sheets, foams, coatings, and adhesives. It is expected to be used as a material.
Patent Document 3 discloses a printing ink containing a biopolyurethane resin with a high utilization rate of plant-derived raw materials (for example, see Patent Document 3).
However, even in the disclosed patent, when the printing ink is made into two liquids, the pot life (two liquid stability) and heat resistance (hot peel strength) are insufficient depending on the application.
In order to solve this problem, the polymerization components include a polyol component, a polyisocyanate component, a polyamine component, and a specific amine component having one active amino group having an active hydrogen group and another active hydrogen group. (amino alcohol) and has a polyurethane polyurea structure in which a part of the terminal amino groups are replaced with other active hydrogen groups, in a polyurethane resin with terminal active amino groups, the average number of amino groups per resin molecule is 1.00 or more and 1.90 or less, and a printing ink containing a hardener containing a biopolyurethane resin and an isocyanate compound has been proposed (for example, see Patent Document 4).
However, even when this printing ink was used, there were problems in that the pot life (two-liquid stability) was insufficient and the printability was also insufficient.

Japanese Patent Application Publication No. 5-97959 Japanese Patent Application Publication No. 2017-025143 International Publication No. 2018/199085 JP2022-014668A

A printing ink containing a curing agent containing a biopolyurethane resin and an isocyanate compound described in Patent Document 1, and a printing ink containing a curing agent containing a biopolyurethane resin and a polyisocyanate compound described in Patent Document 4, The pot life (two-liquid stability) of the residual ink was not sufficient, and the printing suitability was also insufficient.
In contrast, the present invention has good storage stability (pigment dispersibility), excellent printability, and even when a hardening agent is added, the pot life of residual ink (two-liquid stability) is good. An object of the present invention is to provide a printing ink composition for flexible packaging laminates. In addition, it can contribute to preventing global warming and reducing environmental impact, has good storage stability, excellent printability, and even when a hardening agent is added depending on the application, the pot life of residual ink (two-component stability) Another object of the present invention is to provide a printing ink composition for laminates for flexible packaging that has good properties.
Furthermore, by using a specific biomass polyurethane resin together with a specific polyurethane resin other than the biomass polyurethane resin, or by using a specific polyurethane resin other than the biomass polyurethane resin, roll contamination at high temperatures and high humidity, impression cylinder stains, etc. An object of the present invention is to provide a printing ink composition for flexible packaging laminates that has improved resistance to ink dissolution during overprinting.

As a result of intensive studies to solve the above problems, the present inventors invented the following specific printing ink composition for flexible packaging laminates.
The invention is as follows.
1. A. pigment,
B. A binder resin containing a polyurethane resin with an amine value of 2.07 to 4.55 mgKOH/g and a hydroxyl value of 5.00 to 6.70 mgKOH/g,
C. Organic solvent,
Contains A to C of
This polyurethane resin contains, as polymerization components, a polyol component, a polyisocyanate component, a monoamino alcohol component, a diamine component, and a polyamine component containing a polyalkylene polyamine component,
This polyurethane resin has a primary amino group and/or a secondary amino group at the end, and contains a hydroxyl group at the end.
Printing ink composition for flexible packaging laminates.
2. The printing ink composition for flexible packaging laminates according to 1, wherein the polyurethane resin contains a biomass polyurethane resin.
3. 3. The printing ink composition for flexible packaging laminates according to 1 or 2, wherein the polyurethane resin contains a hydroxyl group in the molecule.
4. 4. The printing ink composition for flexible packaging laminates according to any one of 1 to 3, which contains a diamine component not having a hydroxyl group and a diamine component having a hydroxyl group as the diamine component.
5. The biomass polyurethane resin includes a biomass polyurethane resin formed by reacting a biomass polyol component and a polyisocyanate component, and the biomass polyol component includes a plant-derived short chain diol component having 2 to 4 carbon atoms and a plant-derived short chain diol component having 2 to 4 carbon atoms. 5. The printing ink composition for flexible packaging laminates according to any one of 1 to 4, which is a biopolyester polyol reacted with a carboxylic acid component.
6. 6. The printing ink composition for flexible packaging laminates according to 5, wherein the plant-derived carboxylic acid component is one or more selected from sebacic acid, succinic acid, and dimer acid.
7. 7. The printing ink composition for flexible packaging laminates according to any one of 1 to 6, which contains a biomass polyurethane resin and the following non-biomass polyurethane resin.
Polyurethane resins that are not biomass are composed of a polyisocyanate component containing dicyclohexylmethane 4,4'-diisocyanate and isophorone diisocyanate, a polymer polyol component containing a polyether polyol component and a polyester polyol component, and a polyamine component. , contains a monoamino alcohol component.
8. A printing method for printing the printing ink composition for flexible packaging laminates according to 1 or 2.
9. A printed matter obtained by printing the printing ink composition for flexible packaging laminates according to 1 or 2.
10. A laminate laminate having a printed layer formed from the printing ink composition for flexible packaging laminates according to 1 or 2.

According to the printing ink composition for flexible packaging laminates of the present invention, it has good storage stability (pigment dispersibility), excellent printability, and even when a hardening agent is blended, the pot life of the residual ink ( 2-liquid stability) is good.
In addition, it can contribute to preventing global warming and reducing environmental impact, has good storage stability (pigment dispersibility), excellent printability, and even when a hardening agent is added depending on the application, it can be used to remove residual ink from pots. Good life (two-liquid stability).
Furthermore, by using a specific biomass polyurethane resin and a polyurethane resin that is not a specific biomass, resistance to roll contamination during high temperature and humidity, impression cylinder staining, and ink leaching during overprinting is improved.

<Printing ink composition for flexible packaging laminate>
The printing ink composition for flexible packaging laminates (hereinafter also referred to as "ink composition" in some cases) of the present invention includes:
1. A. pigment,
B. A binder resin containing a polyurethane resin with an amine value of 2.07 to 4.55 mgKOH/g and a hydroxyl value of 5.00 to 6.70 mgKOH/g,
C. Organic solvent,
Contains A to C of
The polyurethane resin contains, as polymerization components, a polyol component, a polyisocyanate component, a monoamino alcohol component, a diamine component, and a polyamine component containing a polyalkylene polyamine component,
This polyurethane resin has a primary amino group and/or a secondary amino group at the end, and contains a hydroxyl group at the end.
This is a printing ink composition for flexible packaging laminates.
Each will be explained below.

<Pigment>
Examples of pigments include inorganic, organic, and extender pigments that can be used in ink compositions that generally contain organic solvents. Examples of inorganic pigments include titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, navy blue, ultramarine blue, carbon black, and graphite. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments. Examples of extender pigments include calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, and talc.
The content of the pigment is not particularly limited, and may be any content that allows colored printing to be performed with the ink composition. The pigment may be contained in the ink composition in an amount of 0.5 to 50.0% by mass. When the pigment content is less than 0.5% by mass, the printed area tends to be insufficiently colored. On the other hand, if the pigment content exceeds 50.0% by mass, printability tends to be insufficient.

<Polyurethane resin with an amine value of 2.07 to 4.55 mgKOH/g and a hydroxyl value of 5.00 to 6.70 mgKOH/g>
The polyurethane resin in the present invention contains, as polymerization components, a polyol component, a polyisocyanate component, a monoamino alcohol component, and a polyamine component further containing a diamine component and a polyalkylene polyamine. That is, this polyurethane resin has a primary amino group and/or a secondary amino group and a hydroxyl group at the end of the molecule. In other words, this polyurethane resin is formed by reacting components including a polyol component, a polyisocyanate component, a monoamino alcohol component, and a polyamine component containing a diamine component and a polyalkylene polyamine component.
Furthermore, preferably, the polymerization components include a polyol component, a polyisocyanate component, a monoamino alcohol component, a diamine component containing a diamine component not having a hydroxyl group and a diamine component having a hydroxyl group, and a polyalkylene polyamine. Contains a polyamine component. That is, this polyurethane resin has a primary amino group and/or a secondary amino group at the end of the molecule, and a hydroxyl group within the molecule and at the end of the molecule. In other words, this polyurethane resin contains a polyol component, a polyisocyanate component, a monomonoamino alcohol component, a diamine component containing a diamine component not having a hydroxyl group and a diamine component having a hydroxyl group, and a polyalkylene polyamine component. It is made by reacting components containing a polyamine component.
The polyurethane resin may be either a biomass polyurethane resin or a petroleum-derived polyurethane resin that is not biomass. Furthermore, from an environmental point of view, 3.0 to 100% by mass, preferably 10.0 to 100% by mass, may be biomass polyurethane resin, and this biomass polyurethane resin is made by reacting a biopolyester polyol component and a polyisocyanate component. Contains a resin with a structured structure.
Furthermore, the biopolyester polyol component can basically include a biopolyester polyol obtained by reacting a plant-derived short chain diol component having 2 to 4 carbon atoms with a plant-derived carboxylic acid component.

The polyurethane resin of the present invention has an amine value of 2.07 to 4.55 mgKOH/g and a hydroxyl value of 5.00 to 6.70 mgKOH/g. From the viewpoint of storage stability, printability, and pot life (two-liquid stability) of the residual ink composition when a curing agent is blended, it is necessary to have at least a primary amino group or a secondary amino group at the end. It contains either one and contains a hydroxyl group at the end.
Among these, the amine value is preferably 2.50 mgKOH/g or more, more preferably 3.00 mgKOH/g or more, and preferably 4.40 mgKOH/g or less, and more preferably 4.00 mgKOH/g or less. Furthermore, the hydroxyl value is preferably 5.20 mgKOH/g or more, more preferably 5.50 mgKOH/g or more. Moreover, 6.30 mgKOH/g or less is preferable, and 6.00 mgKOH/g or less is more preferable.

(Polyurethane resin)
The polyurethane resin may be either a biomass polyurethane resin or a petroleum-derived polyurethane resin that is not biomass. In the present invention, a case in which a biomass polyurethane resin is contained will be explained in detail. As the petroleum-derived polyurethane resin that is not biomass, petroleum-derived polyurethane resins other than the biomass polyurethane resins that can be used in combination as described in the biomass polyurethane resins described below can be used.
(Biomass polyurethane resin)
In the present invention, 3.0 to 100% by mass, preferably 10.0 to 100% by mass of the above polyurethane resin is biomass polyurethane resin. The remaining 0 to 97.0% by mass, preferably 0 to 90.0% by mass, is petroleum-derived polyurethane resin. In addition, from an environmental point of view, the biomass polyurethane resin is preferably contained in the binder resin in terms of solid content of 10.0% by mass or more, more preferably 40.0% by mass or more, and 100% by mass. It is even more preferable.
The biomass polyurethane resin in the present invention will be explained below.
The biomass polyurethane resin in the present invention is a resin obtained by reacting a biopolyester polyol component, a polyisocyanate component, a polyamine component under the following conditions, and a monoamino alcohol component as polymerization components.
- Bio-polyester polyol component From an environmental standpoint, the bio-polyester polyol component is preferably a bio-polyester polyol obtained by reacting a plant-derived short chain diol component having 2 to 4 carbon atoms with a plant-derived carboxylic acid component.
Examples of short-chain diols having 2 to 4 carbon atoms derived from plants include 1,3-propanediol, 1,4-butanediol, ethylene glycol, diethylene glycol, and the like. These may be used in combination.

Examples of the above plant-derived carboxylic acid components include sebacic acid, succinic acid, lactic acid, glutaric acid, dimer acid, and azelaic acid. These may be used in combination.
Preferred are sebacic acid, succinic acid, and dimer acid.
Furthermore, it is more preferable that sebacic acid and succinic acid are included. The mass ratio of sebacic acid and succinic acid is preferably sebacic acid/succinic acid = 10/90 to 90/10.

- Polyisocyanate component The polyisocyanate component is not particularly limited. For example, the polyisocyanate component includes aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate, aliphatic diisocyanate compounds such as hexamethylene diisocyanate, and α , α, α', α'-tetramethylxylylene diisocyanate and other aromatic aliphatic diisocyanate compounds. Furthermore, polyisocyanate components derived from biomass can also be used.
The ratio of the polyisocyanate component to the polymeric polyol component used is preferably such that the isocyanate group/hydroxyl group equivalent ratio (isocyanate index (I.I.)) is 1.2 to 1.8.

- Monoamino alcohol component The monoamino alcohol component functions as a reaction terminator, and examples include monoethanolamine, diethanolamine, monopropanolamine, monoisopropanolamine, diisopropanolamine, and 1-amino-2,3-propanediol. As a result, the biomass polyurethane resin has a hydroxyl group at the molecular end.

- Polyamine component The polyamine component functions as a chain extender and a reaction terminator, and contains a diamine component and a polyalkylene polyamine component. More preferably, it contains a diamine component containing a diamine component not having a hydroxyl group and a diamine component having a hydroxyl group, and a polyamine component containing a polyalkylene polyamine component.
Diamine components include diamines that do not have hydroxyl groups, such as aliphatic diamines such as ethylene diamine, propylene diamine, tetramethylene diamine, and hexamethylene diamine, and alicyclic diamines such as isophorone diamine and 4,4'-dicyclohexylmethane diamine. , N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)propylenediamine, N,N'-di(2-hydroxyethyl)ethylenediamine, etc. Examples include diamine components such as diamines having
Examples of the polyalkylene polyamine component include polyalkylene polyamines such as diethylene triamine and triethylene tetramine.
In the present invention, diamines having a hydroxyl group are preferably used in combination with diamines not having a hydroxyl group in order to improve resolubility. As the diamines having no hydroxyl group, diamines having an alicyclic structure and no hydroxyl group are preferred.
Furthermore, in the present invention, a polyalkylene polyamine component is further used in combination in order to improve the cohesive force and storage stability (pigment dispersibility) of the biomass polyurethane resin.
In the present invention, it is more preferable to use polyalkylene polyamine, diamines having a hydroxyl group, and alicyclic diamines having no hydroxyl group together with the monoethanolamine described above.

(Components that can be added as necessary during synthesis of biomass polyurethane resin)
During the synthesis of the biomass polyurethane resin of the present invention, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, and triethylene glycol, glycerin, etc. may be used as chain extenders, if necessary. As triol compounds and reaction terminators, monoalcohols such as methanol and ethanol, and alkylamines such as n-propylamine, n-butylamine and di-n-butylamine can be used. By using a triol compound such as glycerin, a biomass polyurethane resin having a hydroxyl group in the side chain can also be obtained.
Biomass polyurethane resin is made by reacting each of the above components, and even when a curing agent is added depending on the storage stability, printability, and application, it is difficult to use the final product in terms of the pot life (two-liquid stability) of residual ink. Contains at least one of a primary amino group or a secondary amino group, and contains a hydroxyl group at the end, more preferably a hydroxyl group in the molecule and at the end of the molecule, and has an amine value of 2.07 to 4.55 mgKOH/g , the hydroxyl value should be 5.00 to 6.70 mgKOH/g.

As a method for producing biomass polyurethane resin, for example, any of the following (1) to (5) can be adopted.
(1) A diamine component is added as a chain extender to a urethane prepolymer having an isocyanate group at the end, which is obtained by reacting a biomass polyol component and a polyisocyanate component, and the chain is extended to obtain a urethane prepolymer having an isocyanate group at the end. After that, a monoamino alcohol component is reacted as a reaction terminator, and then a polyamine component is added and reacted to form a compound containing at least either a primary amino group or a secondary amino group at the end and a hydroxyl group at the end. A method for obtaining biomass polyurethane resin containing
(2) A diamine component is added as a chain extender to a urethane prepolymer having an isocyanate group at the end, which is obtained by reacting a biomass polyol component and a polyisocyanate component, and the chain is extended to obtain a urethane prepolymer having an isocyanate group at the end. After that, a monoamino alcohol component, which is a reaction terminator, and a polyamine component are simultaneously added and reacted. How to obtain biomass polyurethane resin.
(3) A polyamine compound that acts as a chain extender and a reaction terminator, and a monoamino alcohol component that is a reaction terminator are added to the urethane prepolymer having an isocyanate group at the end, which is obtained by reacting a biomass polyol component and a polyisocyanate component. A method for obtaining a biomass polyurethane resin containing at least one of a primary amino group or a secondary amino group at the terminal, and a hydroxyl group at the terminal, by adding and reacting at the same time, carrying out chain elongation and reaction termination at the same time.
(4) A monoamino alcohol component, which is a reaction terminator, is added to the urethane prepolymer having an isocyanate group at the end, which has been made by reacting a biomass polyol component and a polyisocyanate component, and then a polyamine compound is added to cause chain elongation. A method for obtaining a biomass polyurethane resin containing at least one of a primary amino group or a secondary amino group at its terminal, and a hydroxyl group at its terminal, by simultaneously stopping the reaction.
(5) A part of the polyamine compound is added to the urethane prepolymer having an isocyanate group at the end, which is obtained by reacting a biomass polyol component and a polyisocyanate component, to perform chain extension, and then a monoamino alcohol component, which is a reaction terminator, is added. is added to cause a reaction, then the remaining polyamine compound is added to simultaneously elongate the chain and terminate the reaction, and the polyamine compound contains at least either a primary amino group or a secondary amino group at the end, and a hydroxyl group at the end. How to obtain biomass polyurethane resin.
In the methods for obtaining a biomass polyurethane resin in (1) to (5) above, a polyurethane resin containing a hydroxyl group in the molecule can be obtained by using diamines having a hydroxyl group as the polyamine component.

Petroleum-derived polyurethane resins other than biomass polyurethane resins that can be used in combination will be explained.
The petroleum-derived polyurethane resin contains a polymeric polyol component, a polyisocyanate component, a polyamine component under the following conditions, and a monoamino alcohol component as polymerization components. In other words, it is formed by reacting a polymeric polyol component, a polyisocyanate component, a polyamine component under the following conditions, and a component containing a monoamino alcohol component. Examples of the petroleum-derived polyurethane resin include petroleum-derived polyurethane resins that satisfy the following conditions (1) and (2).
(1) Contains at least either a primary amino group or a secondary amino group at the end, and a hydroxyl group at the end.
(2) The amine value is 2.07 to 4.55 mgKOH/g, and the hydroxyl value is 5.00 to 6.70 mgKOH/g.
The polyamine component contains a diamine component and a polyalkylene polyamine. Furthermore, preferably, the following conditions (3), (4), and (5) are satisfied.
(3) The diamine component contains a diamine component that does not have a hydroxyl group and a diamine component that has a hydroxyl group.
(4) The polyurethane resin contains a polyisocyanate component including dicyclohexylmethane 4,4'-diisocyanate and isophorone diisocyanate, a high molecular polyol component, a polyamine component, and a monoamino alcohol component as polymerization components.
(5) The polymer polyol component contains a polyether polyol component and a polyester component.

- Polymer polyol component Examples of the polymer polyol compound component include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyether diol compounds such as alkylene oxide adducts of bisphenol A such as ethylene oxide and propylene oxide, and adipic acid. , sebacic acid, phthalic anhydride, etc., and one or more dibasic acids such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, etc. Examples include polyester diol compounds such as polyester diols and polycaprolactone diols obtained by condensing one or more glycols. More preferably, they are used in combination due to printability.
Furthermore, in addition to the above-mentioned polymeric diol compound components, alkanediols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene Low-molecular-weight diol compound components such as glycol, propylene glycol, 1,4-butanediol, and 1,3-butanediol can be used alone or in combination of two or more.

・Polyisocyanate component Polyisocyanate compounds include aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate, aliphatic diisocyanate compounds such as hexamethylene diisocyanate, and α , α, α', α'-tetramethylxylylene diisocyanate and the like can be used singly or in combination of two or more.
As the polyisocyanate component, dicyclohexylmethane 4,4'-diisocyanate and isophorone diisocyanate are used in combination from the viewpoint of resistance to roll contamination at high temperature and high humidity, impression cylinder staining, and ink dissolution during overprinting. The mass ratio of dicyclohexylmethane 4,4'-diisocyanate and isophorone diisocyanate is preferably in the range of dicyclohexylmethane 4,4'-diisocyanate/isophorone diisocyanate = 95/5 to 10/90.
The ratio of the polyisocyanate component to the polymeric polyol component used is such that the isocyanate group/hydroxyl group equivalent ratio (isocyanate index (I.I.)) is 1.2 to 2.3.

- Polyamine component The polyamine component functions as a chain extender and a reaction terminator, and contains a diamine component and a polyalkylene polyamine component. More preferably, it contains a diamine component containing a diamine component not having a hydroxyl group and a diamine component having a hydroxyl group, and a polyamine component containing a polyalkylene polyamine component.
Diamine components include aliphatic diamines such as ethylene diamine, propylene diamine, tetramethylene diamine, and hexamethylene diamine; diamines that do not have hydroxyl groups such as isophorone diamine; and alicyclic diamines such as 4,4'-dicyclohexylmethane diamine. , N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)propylenediamine, N,N'-di(2-hydroxyethyl)ethylenediamine, and other diamines having a hydroxyl group.
Examples of the polyalkylene polyamine component include polyalkylene polyamines such as diethylene triamine and triethylene tetramine.
In the present invention, preferably, diamines having a hydroxyl group are used in combination with diamines not having a hydroxyl group in order to improve resolubility. As the diamines having no hydroxyl group, diamines having an alicyclic structure and no hydroxyl group are preferred.
Furthermore, in the present invention, a polyalkylene polyamine component is further used in combination in order to improve the cohesive force and storage stability (pigment dispersibility) of the biomass polyurethane resin.
In the present invention, it is more preferable to use polyalkylene polyamine, diamines having a hydroxyl group, and alicyclic diamines having no hydroxyl group together with the monoethanolamine described above.

- Monoamino alcohol component Examples of monoamino alcohol components include monoethanolamine, diethanolamine, monopropanolamine, monoisopropanolamine, diisopropanolamine, and 1-amino-2,3-propanediol, which are used as reaction terminators. be done. As a result, the petroleum-derived polyurethane resin has a hydroxyl group at the molecular end.

(Components that can be added as necessary during the synthesis of petroleum-derived polyurethane resins other than biomass polyurethane resins)
When synthesizing petroleum-derived polyurethane resins, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, and triethylene glycol, and triols such as glycerin are used as chain extenders as necessary. As the compound and reaction terminator, monoalcohols such as methanol and ethanol, and alkylamines such as n-propylamine, n-butylamine and di-n-butylamine can be used. By using a triol compound such as glycerin, a petroleum-derived polyurethane resin having a hydroxyl group in the side chain can also be obtained.
Petroleum-derived polyurethane resin is made by reacting the above components, and even when a curing agent is added depending on the storage stability, printing suitability, and use, the pot life (two-liquid stability) of the residual ink is Contains at least one of a primary amino group or a secondary amino group at the terminal, and a hydroxyl group at the terminal, more preferably a hydroxyl group in the molecule and at the terminal, and has an amine value of 2.07 to 4.55 mgKOH/ g, and the hydroxyl value should be 5.0 to 6.70 mgKOH/g.

As a method for producing a non-biomass polyurethane resin using only petroleum-derived components, for example, any of the following (1) to (4) can be adopted.
(1) A polyamine component was added as a chain extender to a urethane prepolymer having an isocyanate group at the end, which was obtained by reacting a polyol component and a polyisocyanate component, and the chain was extended to obtain a urethane prepolymer having an isocyanate group at the end. After that, a monoamino alcohol component is reacted as a reaction terminator, and then a polyamine component is reacted, and the polyamine component contains at least either a primary amino group or a secondary amino group at the end, and a hydroxyl group at the end. How to obtain polyurethane resin.
(2) A polyamine component was added as a chain extender to a urethane prepolymer having an isocyanate group at the end, which was obtained by reacting a polyol component and a polyisocyanate component, and the chain was extended to obtain a urethane prepolymer having an isocyanate group at the end. Then, as a reaction terminator, a monoamino alcohol component and a polyamine component are simultaneously added and reacted to form a polyurethane containing at least one of a primary amino group or a secondary amino group at the end and a hydroxyl group at the end. How to get resin.
(3) A polyamine compound that functions as a chain extender and a reaction terminator, and a monoamino alcohol component that is a reaction terminator are simultaneously added to a urethane prepolymer having an isocyanate group at the end, which is obtained by reacting a polyol component and a polyisocyanate component. A method for obtaining a polyurethane resin containing at least one of a primary amino group or a secondary amino group at the terminal and a hydroxyl group at the terminal by simultaneously carrying out chain elongation and reaction termination.
(4) A monoamino alcohol component as a reaction terminator is added to the urethane prepolymer having an isocyanate group at the end, which has been reacted with a polyol component and a polyisocyanate component, and reacted. Then, a polyamine compound is added to cause chain extension and reaction. A method for obtaining a polyurethane resin containing at least one of a primary amino group or a secondary amino group at the terminal, and a hydroxyl group at the terminal, by simultaneously carrying out termination.
(5) A part of the polyamine compound is added to the urethane prepolymer having an isocyanate group at the end, which is obtained by reacting a polyol component and a polyisocyanate component, to perform chain extension, and then a monoamino alcohol component, which is a reaction terminator, is added. and react, then add the remaining polyamine compound to simultaneously elongate the chain and terminate the reaction, and contain at least one of a primary amino group or a secondary amino group at the end, and a hydroxyl group at the end. How to obtain polyurethane resin.
In the methods for obtaining polyurethane resins (1) to (5), polyurethane resins containing hydroxyl groups in the molecule can be obtained by using diamines having hydroxyl groups as the polyamine component.

The printing ink composition for flexible packaging of the present invention uses a biomass polyurethane resin and a non-biomass polyurethane resin that uses only petroleum-derived components in accordance with the performance required of the printing ink composition for flexible packaging laminates. The molecular weight, chemical structure, and equivalent ratio of each component may be adjusted as appropriate based on the desired hardness of the polyurethane resin.

<Binder resin that can be used in combination>
Binder resins that can be used in combination with the polyurethane resin of the present invention include vinyl chloride/vinyl acetate copolymer, nitrified cotton, cellulose acetate propionate resin, other cellulose derivatives, polyamide resin, acrylic resin, dimer acid resin, and maleic resin. Resins such as acid resins, petroleum resins, terpene resins, ketone resins, copal resins, and polypropylene oxides can be used, and can be appropriately selected depending on the use of the ink composition.

- Organic solvent Examples of organic solvents used in the ink composition of the present invention include toluene, ketone-based organic solvents (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester-based organic solvents (e.g., methyl acetate, ethyl acetate, etc.) n-propyl acetate, n-butyl acetate, isobutyl acetate, etc.), alcoholic organic solvents (methanol, ethanol, n-propanol, isopropanol, butanol, etc.), and hydrocarbon solvents (toluene, methylcyclohexane, etc.) can be used.
In addition, in consideration of environmental issues and the printability and drying properties of the ink, a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent is used as the organic solvent for the ink composition during printing. It is preferable to use the organic solvent in a range of 50/50 to 95/5, preferably 60/40 to 85/15.
Furthermore, from the viewpoint of printability of the ink, it is preferable that the ink composition at the time of printing contains 5.0% by mass or more, preferably 15.0% by mass or more of propyl acetate.

- Water Water is blended in an amount of 0.1 to 10.0% by mass in the ink composition of the present invention in order to impart fluidity to the ink composition.
The content of water in the ink composition may be 0.1% by mass or more, and preferably 1.0% by mass or more. Further, the content of water in the ink composition is preferably 9.0% by mass or less. When the water content is less than 0.1% by mass, the ink composition tends to have a high viscosity. On the other hand, when the water content exceeds 10.0% by mass, the ink composition tends to lose its balance.

・Additives added as necessary Additives added as necessary include rosin and its derivatives, chlorinated polypropylene, adhesion improvers such as dammar resin, silica particles, polyethylene wax, fatty acid amide, etc. Examples include antiblocking agents, pigment dispersants, crosslinking agents, lubricants, leveling agents, surfactants, antistatic agents, antifoaming agents, etc., and can be appropriately selected depending on the use of the ink composition.

(vinyl chloride/vinyl acetate copolymer)
When the pigment is not sufficiently dispersed by just containing a polyurethane resin, or when improving the adhesion or lamination suitability of metallized films, printing ink compositions for flexible packaging laminates may contain vinyl chloride/vinyl acetate copolymer. It is preferable that coalescence be used in combination. The vinyl chloride/vinyl acetate copolymer may be a copolymer of vinyl chloride and vinyl acetate monomers conventionally used in gravure printing ink compositions. Among them, a copolymer of vinyl chloride monomer and vinyl acetate monomer has a hydroxyl group, preferably a vinyl chloride/vinyl acetate copolymer having 50 to 200 hydroxyl groups, in the organic solvent system of an environmentally friendly ink. suitable. A vinyl chloride/vinyl acetate copolymer having such a hydroxyl group can be obtained by saponifying a part of the acetate ester moiety.
In the case of a vinyl chloride/vinyl acetate copolymer having a hydroxyl group obtained by saponifying a part of the acetate ester moiety, a structural unit based on the reactive site of vinyl chloride in the molecule (formula 1 below), vinyl acetate 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 acetate (formula 2 below) and the structural unit based on the saponification of the reaction site of vinyl acetate (formula 3 below). In other words, the structural units based on the reactive sites of vinyl chloride impart toughness and hardness to the resin film, the structural units based on the reactive sites of vinyl acetate impart adhesiveness and flexibility, and the structural units based on the reactive sites of vinyl acetate impart saponification. The structural units based on the .
Formula 1 -CH ₂ -CHCl-
Formula 2 -CH ₂ -CH(OCOCH ₃ )-
Formula 3 -CH ₂ -CH(OH)-
Specific examples of vinyl chloride/vinyl acetate copolymers having such hydroxyl groups include Solvine A, AL, TA5R, TA2, TA3, TAO, TAOL, C, CH, CN, CNL, etc. manufactured by Nissin Chemical Industry Co., Ltd. can be mentioned.
A polyurethane resin having a primary amino group or a secondary amino group at the terminal, an amine value of 2.07 to 4.55 mgKOH/g, and a hydroxyl group at the terminal, and a vinyl chloride/vinyl acetate copolymer. The total content is preferably 5 to 20% by mass in the printing ink composition for flexible packaging laminates.

(nitrified cotton, cellulose acetate propionate resin)
In the printing ink composition for flexible packaging laminates of the present invention, nitrified cotton and cellulose acetate propionate resin may be used in combination to improve blocking resistance.
Nitrified cotton is preferably contained in an amount of 0.1 to 2.0% by mass in the printing ink composition for flexible packaging laminates. The cellulose acetate propionate resin is preferably contained in an amount of 0.1 to 3.0% by mass in the printing ink composition for flexible packaging laminates.

(nitrified cotton)
As the nitrified cotton, nitrified cotton conventionally used in gravure printing ink compositions can be used. Nitrified cotton is obtained as a nitric acid ester in which three hydroxyl groups in the six-membered ring of anhydrous glucopyranose groups in natural cellulose are replaced with nitric acid groups by reacting natural cellulose with nitric acid. Nitrified cotton that can be used in the present invention preferably has a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90. Specific examples of the nitrified cotton include SS1/2, SS1/4, SS1/8, TR1/16, NC RS-2, (KCNC, KOREA CNC LTD), and the like.

(cellulose acetate propionate resin)
As the cellulose acetate propionate resin, cellulose acetate propionate resin conventionally used in gravure printing ink compositions may be used.
Cellulose acetate propionate resin is obtained by triesterifying cellulose with acetic acid and propionic acid and then hydrolyzing it. Generally, resins containing 0.6 to 2.5% by weight of acetylation, 42.0 to 46.0% by weight of propionation, and 1.8 to 5.0% by weight of hydroxyl groups are commercially available. A specific example of the cellulose acetate propionate resin is cellulose acetate propionate manufactured by Kanto Kagaku Co., Ltd., and the like.

(Other binder resins)
Furthermore, the ink composition of the present invention may be used as other binder resins such as cellulose acetate butyrate resin, acrylic resin, polyamide resin, rosin, rosin derivative, adhesive resin, etc. within a range where performance does not deteriorate and in consideration of cost. may be added as a supplement.

(Adhesion improver)
<Chlorinated polypropylene>
As the chlorinated polypropylene, one having a degree of chlorination of 20 to 50% is preferably used. When the degree of chlorination is within the above range, the chlorinated polypropylene has excellent compatibility with organic solvents and excellent adhesion to films. In the present invention, the degree of chlorination is defined as 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 5,000 to 200,000. When the weight average molecular weight is within the above range, the chlorinated polypropylene has excellent adhesive properties and excellent solubility in organic solvents. Moreover, when using chlorinated polypropylene, it is preferable to use it at 3.0 mass % or less in terms of solid content mass % of the ink composition.

(Dammar resin)
Dammar resin, also written as dammar or dammar, is a type of natural resin derived from plants. Specifically, it is a type of natural resin obtained from plants of the family Dipterocarpaceae or Orchidaceae that grow in Southeast Asia such as Malaysia and Indonesia. When using Dammar resin, it is dissolved in a suitable organic solvent to form a varnish. Since Dammar resin does not contain chlorine, chlorine can be eliminated or reduced compared to when a chlorinated polyolefin resin is used in the printing ink composition. Moreover, when using Dammar resin, it is preferable to use it at 3.0 mass % or less in terms of solid content mass % of the ink composition.

(Anti-blocking agent)
(Silica particles)
Examples of the silica particles include natural products, synthetic products, crystalline, non-crystalline, hydrophobic, and hydrophilic ones. The silica particles preferably have an average particle diameter of 1.0 to 5.0 μm (the average particle diameter of the silica particles means the particle diameter at 50% (D50) of the integrated value in the particle size distribution, and is calculated using the Coulter Counter method. ). The silica particles may be hydrophilic silica having a hydrophilic functional group on its surface, or may be hydrophobic silica made hydrophobic by modifying the hydrophilic functional group with an alkylsilane or the like. Among these, hydrophilic silica particles are preferred. The ink composition containing hydrophilic silica particles also has the effect of promoting wetting and spreading of the ink during overprinting and improving the overprinting effect (hereinafter sometimes referred to as "trapping property"). When silica particles are used, they are used in the ink composition in an amount of 3.0% by mass or less, preferably 1.0% by mass or less.

(polyethylene wax)
The polyethylene wax used has an average particle size in the range of 1.0 to 3.0 μm (the average particle size means the particle size measured with #1 Honeywell Microtrac UPA). When the particle size of the polyethylene wax is within the above range, the ink composition has excellent slip properties, blocking properties, and trapping properties. Moreover, when using polyethylene wax, the content in the ink composition is preferably 1.5% by mass or less.

(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 a fatty acid and an amide group. Examples of fatty acid amides include monoamides, substituted amides, bisamides, methylolamides, and esteramides, and the fatty acid amide is at least one selected from the group consisting of monoamides, substituted amides, and bisamides because it improves blocking resistance. It is preferable. The amount of fatty acid amide used in the ink composition is preferably 1% by mass or less.

- Monoamide: Monoamide is represented by the following general formula (1).
General formula (1) R ₁ -CONH ₂
(In the formula, _R1 represents a 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: The substituted amide is represented by the following general formula (2).
General formula (2) R ₂ -CONH-R ₃
(In the formula, R ₂ and R ₃ represent 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) R ₄ -CONH-R ₅ -HNCO-R ₆
General formula (4) R ₇ -NHCO-R ₈ -CONH-R ₉
(In the formula, R ₄ , R ₆ , R ₇ , and R ₉ represent residues obtained by removing COOH from a fatty acid, and may be the same or different. R ₅ and R ₈ are alkylene groups having 1 to 10 carbon atoms. or represents an arylene group, which may be the same or different.)
Specific examples of bisamides include methylene bisstearamide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, and hexamethylene bisstearic acid amide. , hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N,N'-distearyladipic acid amide, N,N'- Examples include 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) R ₁₀ -CONHCH ₂ OH
(In the formula, _R10 represents a 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.

- Esteramide: Esteramide is represented by the following general formula (6).
General formula (6) R ₁₁ -CONH-R ₁₂ -OCO-R ₁₃
(In the formula, R ₁₁ and R ₁₃ represent a residue obtained by removing COOH from a fatty acid, and may be the same or different, and R ₁₂ represents an alkylene group or arylene group having 1 to 10 carbon atoms.)
Specific examples of esteramides include stearylamide ethyl stearate, oleylamide ethyl stearate, and the like.

The melting point of the fatty acid amide is preferably 50°C to 150°C.
Further, 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 saturated fatty acids having 18 to 22 carbon atoms are preferable. More preferred are unsaturated fatty acids. More preferred saturated fatty acids are lauric acid, palmitic acid, stearic acid, behenic acid, and hydroxystearic acid, and even more preferred unsaturated fatty acids are oleic acid and erucic acid.

(Antistatic agent)
As the antistatic agent, known antistatic agents conventionally used in gravure printing inks can be used. Specific examples include coconut alkylbis(hydroxyethyl)methyl nitrate, coconut bis(hydroxyethyl)methyl chloride, quaternary ammonium salt compound (sulfate), monoalkyltrimethylammonium chloride, monoalkylbenzyldimethylammonium chloride, Examples include quaternary ammonium salts (hydrochlorides) such as dialkyldimethylammonium chloride, thiocyanates, alkylimidazolines, and alkylimidazoliums. When using an antistatic agent, the content of the antistatic agent in the ink composition is preferably 3.0% by mass or less.

<Curing agent>
As the curing agent, those conventionally used in ink compositions for laminating flexible packaging can be used. Specifically, polyfunctional isocyanate compounds such as biuret, isocyanurate, and adduct can be used, including 24A-100, 22A-75, TPA-100, TSA-100, TSS-100, TAE-100, TKA-100, P301-75E, E402-808, E405-70B, AE700-100, D101, D201, A201H (manufactured by Asahi Kasei Corporation), Mytec Y260A (manufactured by Mitsubishi Chemical Corporation), CORONATE HX, CORONATE HL , CORONATE L (manufactured by Tosoh Corporation), and Desmodule N75MPA/X (manufactured by Bayer Corporation). It is preferable that the curing agent is added to the ink composition for laminating flexible packaging in a solid content of 0.7 to 2.4%. The amount and type of curing agent are appropriately selected and blended depending on the type and use of the ink composition for laminating flexible packaging to be used.

<Method for manufacturing the ink composition of the present invention>
The method for producing the printing ink composition for flexible packaging laminates of the present invention is not particularly limited. For example, the ink composition may include A. pigment, B. A polyurethane resin having a primary amino group and/or a secondary amino group at the end and a hydroxyl group at the end, C. After dispersing and kneading components such as an organic solvent and water using various known dispersion and kneading devices such as a bead mill, ball mill, sand mill, attritor, roll mill, and pearl mill, water and various optional components are added. , can be prepared by stirring and mixing. The resulting printing ink composition for flexible packaging laminates has a viscosity of 10 to 1000 mPa·s by adjusting the content of each component and the combination of binder resin and organic solvent. The curing agent can be added just before printing when producing the ink, but from the viewpoint of stability it is preferably added just before printing.

When used during gravure printing, if the printing ink composition for flexible packaging laminates does not contain a curing agent, add the curing agent and stir to obtain an appropriate viscosity according to the printing conditions at the ambient temperature during printing. Specifically, organic solvents such as ester solvents and alcohol solvents are Preferably, it is diluted with a solvent.
At this time, the content of the polyurethane resin of the present invention is not particularly limited. For example, the content of the polyurethane resin in the printing ink composition for flexible packaging laminates is preferably 1.5% by mass or more, more preferably 6.0% by mass or more. Moreover, 17.0 mass % or less is preferable, and 15.0 mass % or less is more preferable. When the content of polyurethane resin is less than 1.5% by mass, storage stability tends to decrease. On the other hand, when the content of the polyurethane resin exceeds 17.0% by mass, the viscosity of the ink composition tends to increase. When the polyurethane resin is contained within the above content range, the resulting printing ink composition for flexible packaging laminates is similar to conventional ink compositions even when printed using a shallow plate cylinder. , can exhibit good print density, printability and lamination suitability.
As the binder resin of the present invention, in addition to polyurethane resin, vinyl chloride/vinyl acetate copolymer, nitrified cotton, cellulose acetate propionate resin, and other binder resins may be used in combination.

<Printing method and printed matter using the ink composition of the present invention>
In the printing method using the ink composition of the present invention, for example, the ink composition is printed one or more times on a resin film, which is a base material for a known laminate, by a known method such as gravure printing. Next, if necessary, another ink composition is printed on any part of the surface side of the printing ink layer formed by these printings by a known method such as gravure printing, and then dried with a dryer. Printed matter obtained by this method is also included in the present invention.
Examples of the base resin film used at this time include stretched and unstretched polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, vinylon, and styrene. Furthermore, regarding these resin films, it is also possible to use films obtained by processing such as coating and kneading of an antifogging agent, surface coating and kneading of a matting agent, and the like.
Further, as the resin film, a film formed by laminating a barrier layer formed by metal vapor deposition and coating with a barrier resin on various printing plastic films, etc. can be used.

(Method for obtaining a laminate (laminate processed product) using a printing ink composition for flexible packaging laminates)
Next, a method for obtaining a laminated product using the ink composition of the present invention will be explained.
In the laminated product of the present invention, for example, first, a printing ink composition for flexible packaging laminates of a color other than white is printed on a resin film one or more times using a gravure printing method. Next, a white printing ink composition for flexible packaging laminates is optionally gravure printed on the surface side of the colored ink layer for flexible packaging laminates formed by these printings (lower layer side when viewed from the surface layer after final lamination). Print using this method and dry using a dryer.

A laminated product for packaging bags and the like can be obtained by laminating a resin film or the like by various laminating methods on the side of the obtained printed matter that is coated with the white ink composition for flexible packaging laminates.
Methods for obtaining this laminated product include an extrusion lamination method in which a titanium-based, urethane-based, imine-based, polybutadiene-based anchor coating agent, etc. is coated on the surface of the printed matter, and then molten polymer is laminated thereon; The dry lamination method involves applying an adhesive diluted to an appropriate viscosity with an organic solvent to the surface of the printed material, and then laminating the film-like polymer thereon. A non-sol lamination method can be used.
The extrusion lamination method described above is a method in which an anchor coating agent such as titanium, urethane, imine, or polybutadiene is coated on the surface of the printed matter as necessary, and then molten polymer is laminated using a known extrusion lamination machine. In addition, it is also possible to use molten resin as an intermediate layer and laminate it with other materials in the form of a sandwich.

As the molten polymer used in the extrusion lamination method, conventionally used resins such as low density polyethylene, ethylene-vinyl acetate copolymer, polypropylene, etc. can be used. Among these, the effects of the present invention are enhanced when low density polyethylene is used, which is likely to be oxidized and generate carbonyl groups during melting.
In addition, in the dry lamination method described above, a urethane-based or isocyanate-based adhesive diluted with an organic solvent to an appropriate viscosity is applied to the surface of the printed matter, and after drying, a film-like polymer is pasted using a known dry laminating machine. This is a method to match. The non-sol laminating method is a method in which a urethane-based adhesive, an isocyanate-based adhesive, or the like is applied to the surface of a printed matter, and then a film-like polymer is laminated using a known dry laminating machine. As the resin for the film used in the dry lamination method and the non-sol lamination method, polyethylene, unstretched polypropylene, etc. can be used. In particular, for packaging materials used in retort applications, aluminum foil can be sandwiched between the base material and the resin film to be laminated. Such laminated products can also be used for boiling and retort applications after being made into bags and filled with contents.
The resin film used at this time is not particularly limited. Resin films include, for example, polyester films such as polyethylene terephthalate (PET), polylactic acid, and polycaprolactone, various printing plastic films such as nylon and vinylon, and barrier films made by coating these various printing plastic films with metal vapor deposition and barrier resin. A film or the like having laminated layers can be used.

Hereinafter, the present invention will be explained in more detail with reference to Examples. The present invention is not limited to these examples at all. In addition, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass."

<Biomass polyurethane resin varnish>
<Production example of polyurethane resin varnish 1 (biomass polyurethane, amine value 5.66 mgKOH/g, hydroxyl value 4.37 mgKOH/g)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 396.10 parts by mass of ethyl acetate and 169.80 parts by mass of isopropyl alcohol, 7.09 parts by mass of isophorone diamine, 0.31 parts by mass of monoethanolamine, and N-( 1.44 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 1 (solid content 30% by mass).

<Production example of polyurethane resin varnish 2 (biomass polyurethane, amine value 4.51 mgKOH/g, hydroxyl value 5.24 mgKOH/g)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 395.40 parts by mass of ethyl acetate and 169.40 parts by mass of isopropyl alcohol, 6.45 parts by mass of isophoronediamine, 0.61 parts by mass of monoethanolamine, and N-( 1.31 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 2 (solid content 30% by mass).

<Production example of polyurethane resin varnish 3 (biomass polyurethane, amine value 3.36 mgKOH/g, hydroxyl value 6.12 mgKOH/g)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 393.40 parts by mass of ethyl acetate and 168.60 parts by mass of isopropyl alcohol, 5.81 parts by mass of isophorone diamine, 0.92 parts by mass of monoethanolamine, and N-( 1.18 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 3 (solid content 30% by mass).

<Production example of polyurethane resin varnish 4 (biomass polyurethane, amine value 2.84 mgKOH/g, hydroxyl value 6.57 mgKOH/g)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 394.20 parts by mass of ethyl acetate and 169.00 parts by mass of isopropyl alcohol, 5.49 parts by mass of isophorone diamine, 1.07 parts by mass of monoethanolamine, and N-( 1.12 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 4 (solid content 30% by mass).

<Production example of polyurethane resin varnish 5 (biomass polyurethane, amine value 2.20 mgKOH/g, hydroxyl value 7.01 mgKOH/g)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 393.80 parts by mass of ethyl acetate and 168.80 parts by mass of isopropyl alcohol, 5.17 parts by mass of isophoronediamine, 1.22 parts by mass of monoethanolamine, and N-( 1.05 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 5 (solid content 30% by mass).

<Production example of polyurethane resin varnish 6 (biomass polyurethane, amine value 1.38 mgKOH/g, hydroxyl value 6.13 mgKOH/g, no diethylenetriamine)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,3-propanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 394.10 parts by mass of ethyl acetate and 168.90 parts by mass of isopropyl alcohol, 5.81 parts by mass of isophorone diamine, 0.92 parts by mass of monoethanolamine, and N-( 1.18 parts by mass of 2-hydroxyethyl)ethylenediamine was added and reacted to obtain polyurethane resin varnish 6 (solid content 30% by mass).

<Production example of polyurethane resin varnish 7 (biomass polyurethane, amine value 3.36 mgKOH/g, hydroxyl value 6.12 mgKOH/g, dimer acid as acid component)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 200 parts by mass of polyester diol with an average molecular weight of 2000 obtained from dimer acid (derived from plants) and 1,3-propanediol (derived from plants), 33.30 parts by mass of isophorone diisocyanate was charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 393.40 parts by mass of ethyl acetate and 168.60 parts by mass of isopropyl alcohol, 5.81 parts by mass of isophorone diamine, 0.92 parts by mass of monoethanolamine, and N-( 1.18 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 7 (solid content 30% by mass).

<Production example of polyurethane resin varnish 8 (biomass polyurethane, amine value 3.36 mgKOH/g, hydroxyl value 6.12 mgKOH/g, diethylene glycol as glycol component)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, the average obtained from sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and diethylene glycol (derived from plants) 200 parts by mass of polyester diol having a molecular weight of 2000 and 33.30 parts by mass of isophorone diisocyanate were charged, and the mixture was reacted at 100 to 105°C for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 393.40 parts by mass of ethyl acetate and 168.60 parts by mass of isopropyl alcohol, 5.81 parts by mass of isophorone diamine, 0.92 parts by mass of monoethanolamine, and N-( 1.18 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 8 (solid content 30% by mass).

<Production example of polyurethane resin varnish 9 (biomass polyurethane, amine value 3.36 mgKOH/g, hydroxyl value 6.12 mgKOH/g, ethylene glycol as glycol component)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, add sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and ethylene glycol (derived from plants). 200 parts by mass of polyester diol having an average molecular weight of 2000 and 33.30 parts by mass of isophorone diisocyanate were charged, and the mixture was reacted at 100 to 105°C for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 393.40 parts by mass of ethyl acetate and 168.60 parts by mass of isopropyl alcohol, 5.81 parts by mass of isophorone diamine, 0.92 parts by mass of monoethanolamine, and N-( 1.18 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 9 (solid content 30% by mass).

<Production example of polyurethane resin varnish 10 (biomass polyurethane, amine value 3.36 mgKOH/g, hydroxyl value 6.12 mgKOH/g, 1,4-butanediol as glycol component)>
Sebacic acid (derived from castor oil)/succinic acid (derived from plants) = 70/30 (mass ratio) and 1,4-butanediol (derived from plants) were placed in a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube. ) and 33.30 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 393.40 parts by mass of ethyl acetate and 168.60 parts by mass of isopropyl alcohol, 5.81 parts by mass of isophorone diamine, 0.92 parts by mass of monoethanolamine, and N-( 1.18 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 10 (solid content 30% by mass).

<Polyurethane resins other than biomass polyurethane resins>
<Production example of polyurethane resin varnish 1 that is not biomass polyurethane resin (polyurethane that is not biomass, amine value 5.66 mgKOH/g, hydroxyl value 4.37 mgKOH/g)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 100 parts by mass of 3-methyl-1,5-pentylene adipate diol with an average molecular weight of 2000 and 100 parts by mass of polypropylene glycol with an average molecular weight of 2000. , 16.67 parts by mass of isophorone diisocyanate and 19.67 parts by mass of hydrogenated MDI were charged, and the mixture was reacted at 100 to 105°C for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 406.6 parts by mass of ethyl acetate and 174.26 parts by mass of isopropyl alcohol, 7.09 parts by mass of isophoronediamine, 0.31 parts by mass of monoethanolamine, and N-( 1.44 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added to stop the reaction, and polyurethane resin varnish 1 (solid content 30% by mass) was obtained.

<Production example of polyurethane resin varnish 2 that is not biomass polyurethane resin (non-biomass polyurethane, amine value 4.51 mgKOH/g, hydroxyl value 5.24 mgKOH/g)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 100 parts by mass of 3-methyl-1,5-pentylene adipate diol with an average molecular weight of 2000 and 100 parts by mass of polypropylene glycol with an average molecular weight of 2000. , 16.67 parts by mass of isophorone diisocyanate and 19.67 parts by mass of hydrogenated MDI were charged, and the mixture was reacted at 100 to 105°C for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 404.80 parts by mass of ethyl acetate and 173.49 parts by mass of isopropyl alcohol, 6.45 parts by mass of isophoronediamine, 0.61 parts by mass of monoethanolamine, and N-( 1.31 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 2 (solid content 30% by mass).

<Production example of polyurethane resin varnish 3 that is not biomass polyurethane resin (non-biomass polyurethane, amine value 3.36 mgKOH/g, hydroxyl value 6.12 mgKOH/g)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 100 parts by mass of 3-methyl-1,5-pentylene adipate diol with an average molecular weight of 2000 and 100 parts by mass of polypropylene glycol with an average molecular weight of 2000. , 16.67 parts by mass of isophorone diisocyanate and 9.67 parts by mass of hydrogenated MDI were charged, and the mixture was reacted at 100 to 105° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 397.91 parts by mass of ethyl acetate and 170.53 parts by mass of isopropyl alcohol, 5.81 parts by mass of isophorone diamine, 0.92 parts by mass of monoethanolamine, and N-( 1.18 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 3 (solid content 30% by mass).

<Production example of polyurethane resin varnish 4 that is not biomass polyurethane resin (polyurethane that is not biomass, amine value 2.84 mgKOH/g, hydroxyl value 6.57 mgKOH/g)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 100 parts by mass of 3-methyl-1,5-pentylene adipate diol with an average molecular weight of 2000 and 100 parts by mass of polypropylene glycol with an average molecular weight of 2000. , 16.67 parts by mass of isophorone diisocyanate and 19.67 parts by mass of hydrogenated MDI were charged, and the mixture was reacted at 100 to 105°C for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 397.29 parts by mass of ethyl acetate and 170.27 parts by mass of isopropyl alcohol, 5.49 parts by mass of isophorone diamine, 1.07 parts by mass of monoethanolamine, and N-( 1.12 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 4 (solid content 30% by mass).

<Production example of polyurethane resin varnish 5 that is not a biomass polyurethane resin (polyurethane that is not a biomass, amine value 2.20 mgKOH/g, hydroxyl value 7.01 mgKOH/g)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 100 parts by mass of 3-methyl-1,5-pentylene adipate diol with an average molecular weight of 2000 and 100 parts by mass of polypropylene glycol with an average molecular weight of 2000. , 16.67 parts by mass of isophorone diisocyanate and 19.67 parts by mass of hydrogenated MDI were charged, and the mixture was reacted at 100 to 105°C for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 396.41 parts by mass of ethyl acetate and 170.00 parts by mass of isopropyl alcohol, 5.17 parts by mass of isophorone diamine, 1.22 parts by mass of monoethanolamine, and N-( 1.05 parts by mass of 2-hydroxyethyl)ethylenediamine and 0.29 parts by mass of diethylenetriamine were added and reacted to obtain polyurethane resin varnish 5 (solid content 30% by mass).

<Production example of polyurethane resin varnish 6 that is not biomass polyurethane resin (non-biomass polyurethane, amine value 4.40 mgKOH/g, hydroxyl value 6.10 mgKOH/g, no polyalkylene polyamine)>
In a four-necked flask equipped with a stirrer, a cooling tube, and a nitrogen gas introduction tube, 100 parts by mass of 3-methyl-1,5-pentylene adipate diol with an average molecular weight of 2000 and 100 parts by mass of polypropylene glycol with an average molecular weight of 2000. , 16.67 parts by mass of isophorone diisocyanate and 19.67 parts by mass of hydrogenated MDI were charged, and the mixture was reacted at 100 to 105°C for 6 hours while introducing nitrogen gas. After cooling to near room temperature and adding 397.44 parts by mass of ethyl acetate and 170.33 parts by mass of isopropyl alcohol, 5.81 parts by mass of isophorone diamine, 0.92 parts by mass of monoethanolamine, and N-( 1.18 parts by mass of 2-hydroxyethyl)ethylenediamine was added and reacted to obtain polyurethane resin varnish 6 (solid content 30% by mass).

<Production example of printing ink composition for flexible packaging laminate>
Pigment (phthalocyanine blue C.I. Pigment Blue 15:4), each polyurethane resin varnish, vinyl chloride/vinyl acetate copolymer (Solvine TA-3, Nissin Kagaku Kogyo Co., Ltd.) were mixed with Red Devil's paint conditioner. Then, a solvent (the paint conditioner and the solvent were combined to form a mixed solution) was added to prepare printing inks for flexible packaging laminates of Examples and Comparative Examples shown in Tables 1 and 2. A composition was obtained.

(vinyl chloride/vinyl acetate copolymer)
Solvine TA-3, Nissin Chemical Industry Co., Ltd.
(Rosin and its derivatives)
Polymerized rosin: acid value 160mgKOH/g
(chlorinated polypropylene)
40 parts by mass of chlorinated polypropylene (solid content 50%) with 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 chlorinated polypropylene with a solid content of 20%.
(Silica particles)
Average particle size: 4.5μm
(polyethylene wax)
Average particle size: 2.11μm
(Mixed solvent)
Ethyl acetate/propyl acetate/isopropyl alcohol = 50/30/20
(hardening agent)
Curing agent 1: Isophorone diisocyanate (IPDI)/trimethylolpropane (TMP) adduct product (solid content 40%)
Curing agent 2: Hexamethylene diisocyanate (HDI) biuret product (solid content 40%)
Curing agent 3: xylene diisocyanate (XDI)/trimethylolpropane (TMP) adduct product (solid content 40%)

(evaluation)
Performance evaluation of the printing ink compositions for flexible packaging laminates of each of the Examples and Comparative Examples obtained above was performed by the following method, and the evaluation results are shown in Table 1.
<Performance evaluation of ink composition>
(Storage stability (pigment dispersibility))
The printing ink compositions for flexible packaging laminates of each of the Examples and Comparative Examples obtained above were collected in a glass bottle and stored at an ambient temperature of 60°C for 14 days. From the presence or absence of pigment sedimentation, the ink quality was determined. Storage stability was evaluated.
○: No sedimentation is observed, and the storage stability of the ink is good.
△: Slight sedimentation is observed, and the storage stability of the ink is somewhat poor. ×: Sedimentation is observed, and the storage stability of the ink is poor.

(Two-liquid stability)
The printing ink compositions for flexible packaging laminates of each of the Examples and Comparative Examples obtained above were collected in a glass bottle, 3 parts by mass of each curing agent was added to 100 parts by mass of each ink, and the compositions were stored at 40°C for 3 days. Zahn Cup No. Based on the change in viscosity measured in 3, the two-liquid stability of the ink was evaluated according to the following evaluation criteria.
(Evaluation criteria)
〇: Viscosity change is less than 2 seconds
△: Viscosity change is 2 seconds or more and less than 5 seconds
×: Viscosity change for 5 seconds or more (print evaluation)
To 100 parts by mass of each of the printing ink compositions for flexible packaging laminates listed in Table 3, 3 parts by mass of a curing agent and 50 parts by mass of a mixed solvent were further added to the formulations in Table 1 to dilute the composition and reduce the viscosity. After adjusting to 15 seconds using Rigosha Zahn Cup No. 3, printing speed was 150 m/min on the treated surface of OPP, PET, and NY using a gravure printing machine equipped with an engraving plate (printing plate, Helio 175 lines/inch). I printed it with . The temperature during printing was 25° C. and the humidity was 50%.

<About the film>
PET: Polyethylene terephthalate film with corona discharge treatment on one side, Toyobo Co., Ltd., E-5102, thickness 12 μm
OPP: Biaxially oriented polypropylene film, Toyobo Co., Ltd., P-2161, thickness 30 μm
NY: Nylon film, Toyobo Co., Ltd., N-1102, thickness 15 μm

(Guide roll removed)
After printing under the conditions described in the above printing evaluation, a test was conducted to see if the ink composition adhered to the guide roll (the guide roll was removed) to evaluate printability. In addition, once the ink composition adheres to the guide roll, it transfers again to the printing surface and causes stains, so if "guide roll removal" occurs, it will have a negative effect on obtaining decorative prints. . Then, the presence or absence of the ink coating on the printed matter coming off due to the guide roll of the gravure printing machine was visually evaluated. In this evaluation, the temperature and humidity during printing were respectively 10° C., 30%, 25° C., 50%, and 30° C., 80%.
〇：Nothing △：Something with something ×：Something with something

(Adhesiveness)
After printing under the conditions described in the print evaluation above, adhere cellophane tape to the printed surface of each printed material and evaluate adhesiveness from the ratio of the area where the ink film peels off from the adherend when peeled off. did.
○: No peeling at all △: Peeling area is less than 20% ×: Peeling area is 20% or more

<Blocking resistance>
After printing under the conditions described in the above print evaluation, the printed surface of each obtained printed matter and the corona discharge treated surface of each film were overlapped, and a load of 3 kg/cm ² was applied, and a temperature of 45°C was applied for 24 hours. I left it for a while. Thereafter, the ink surface and film surface were peeled off, and the transfer of the ink film to the film surface was evaluated.
○: Peels off without resistance and has no transfer of ink film.
△: There is resistance but no ink film transfer at all.
×: Less than 50% migration of ink film was observed.

(Retort suitability)
Under the conditions described in the above print evaluation, each printed matter was printed one day after printing on polyethylene terephthalate (PET) and nylon (NY), and then applied an amount of urethane adhesive (Takelac) with a solid content of 2.0 g/ ^m2. After applying A-616/Takenate A-65 (Mitsui Chemicals SKC Polyurethane Co., Ltd.), a non-stretched polypropylene film (RXC-22, 60 μm thick, Mitsui Chemicals Tohcello Co., Ltd.) was laminated using a dry laminating machine, and the film was heated at 40°C. A dry laminate was obtained by leaving it for 3 days. This dry laminate was made into a bag, filled with a mixture of 90% water and 10% salad oil, and then melt-sealed.The product printed on PET was immersed in pressurized hot water at 135°C for 60 minutes. Retort suitability was evaluated based on the presence or absence of lamina floating. The same tests and evaluations were carried out except that the temperature was 120°C for those printed in NY. Through this evaluation, lamination suitability can be confirmed and retort suitability can be evaluated.
〇: No laminate floating at all
△: Pinhole-like or thin and short laminate floating in some parts
×: Long streak-like lami floating can be seen on the entire surface.

Examples 1 to 11 listed in Table 1 and Examples 12 to 14 listed in Table 2 have excellent storage stability (pigment dispersibility) and two-liquid stability. Comparative Examples 1 and 4 whose amine value and hydroxyl value are outside the range of the present invention, Comparative Examples 2 and 5 whose hydroxyl value is outside the range of the present invention, and Comparative Examples 2 and 5 whose amine value is outside the range of the present invention, as listed in Tables 1 and 2. According to Comparative Examples 3 and 6, which were outside the middle range, the storage stability (pigment dispersibility) or two-liquid stability was poor.
In addition, according to Examples 1 to 3, 8 to 9, and 12 to 14 shown in Table 3, and Examples 15 to 19, which are mixtures thereof, although not listed in the table, storage stability (pigment dispersibility) ) and two-liquid stability, and exhibited excellent effects in various printability. In particular, according to Examples 15 to 19, the guide roll removal (30° C., 80%) was even better.

Claims (10)

A. pigment,
B. A binder resin containing a polyurethane resin with an amine value of 2.07 to 4.55 mgKOH/g and a hydroxyl value of 5.00 to 6.70 mgKOH/g,
C. Organic solvent,
Contains A to C of
This polyurethane resin contains, as polymerization components, a polyol component, a polyisocyanate component, a monoamino alcohol component, a diamine component, and a polyamine component containing a polyalkylene polyamine component,
This polyurethane resin has a primary amino group and/or a secondary amino group at the end, and contains a hydroxyl group at the end.
Printing ink composition for flexible packaging laminates. The printing ink composition for flexible packaging laminates according to claim 1, wherein the polyurethane resin contains a biomass polyurethane resin. The printing ink composition for flexible packaging laminates according to claim 1 or 2, wherein the polyurethane resin contains a hydroxyl group in the molecule. The printing ink composition for flexible packaging laminates according to claim 1 or 2, which contains a diamine component not having a hydroxyl group and a diamine component having a hydroxyl group as the diamine component. The biomass polyurethane resin includes a biomass polyurethane resin formed by reacting a biomass polyol component and a polyisocyanate component, and the biomass polyol component includes a plant-derived short chain diol component having 2 to 4 carbon atoms and a plant-derived short chain diol component having 2 to 4 carbon atoms. The printing ink composition for flexible packaging laminates according to claim 1 or 2, which is a biopolyester polyol reacted with a carboxylic acid component. 6. The printing ink composition for flexible packaging laminates according to claim 5, wherein the plant-derived carboxylic acid component is one or more selected from sebacic acid, succinic acid, and dimer acid. The printing ink composition for flexible packaging laminates according to claim 1 or 2, comprising a biomass polyurethane resin and the following non-biomass polyurethane resin.
Polyurethane resins that are not biomass are composed of a polyisocyanate component containing dicyclohexylmethane 4,4'-diisocyanate and isophorone diisocyanate, a polymer polyol component containing a polyether polyol component and a polyester polyol component, and a polyamine component. , contains a monoamino alcohol component. A printing method for printing the printing ink composition for flexible packaging laminate according to claim 1 or 2. A printed matter printed with the printing ink composition for flexible packaging laminate according to claim 1 or 2. A laminate laminate having a printing layer formed from the printing ink composition for flexible packaging laminates according to claim 1 or 2.