JP2021127430A - Laminate adhesive composition and easy-to-tear laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminate adhesive composition and a laminate having good laminating suitability, and a laminate adhesive and a laminate which can contribute to prevention of global warming and reduction of environmental load.
A main agent containing a polyol compound and a curing agent containing a trifunctional isocyanate compound having an isocyanurate ring are contained.
Laminate adhesive in which the solid content ratio of the polyol compound to the trifunctional isocyanate compound having an isocyanurate ring is polyol compound: trifunctional isocyanate compound having an isocyanurate ring = 1: 0.1 to 1: 1.5. Composition.
[Selection diagram] None

Description

The present invention relates to a laminate adhesive and a laminate.

Packaging materials using various plastic films are used for foods, confectionery, household goods, pet foods, etc. because of their functions such as design, economy, content protection, and transportability. In addition, many packaging materials are gravure-printed or flexographic-printed with the intention of giving them a design and message that appeals to consumers.
In order to obtain these packaging materials, a front print printed on the surface of the base film of the packaging material, or an adhesive or an anchoring agent is applied to the printed surface of the base film of the packaging material as necessary, and the film is applied. Back-printing is performed by laminating the film.

As back printing, color ink and white ink are sequentially printed on various films such as polyester, nylon, and aluminum foil. After that, a polyethylene film, a polypropylene film, or the like is laminated on the print 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. (See, for example, Patent Document 1).
The obtained laminate is used as a laminate bag for foods such as confectionery, soup, and miso soup. These laminated bags are opened by human hands to remove the contents during use. Here, if the tearability is poor, it is necessary to apply excessive force at the time of opening, and as a result, the product is cut in an unintended direction, resulting in a problem that the contents are spilled. Therefore, good tearability is required.
In particular, the portion where the ink is printed tends to have inferior tearability because the bonding force between the ink layer and the adhesive layer is inferior to that of the plain portion.
As a means for improving the tearability, the applicant proposes to increase the equivalent ratio of the hydroxyl group and the polyisocyanate group of the polyol compound used for the adhesive layer to 1: 3 to 1:18.
However, further improvement in tearability, prevention of global warming, and reduction of environmental load are required.

Japanese Unexamined Patent Publication No. 05-097959 JP-A-2018-8422

An object of the present invention is to obtain a laminate adhesive composition and laminate having good laminating suitability, and a laminate adhesive and laminate that can contribute to prevention of global warming and reduction of environmental load.

As a result of diligent studies to solve the above problems, the present inventors have invented the following laminate adhesive composition and laminate.
The present invention has the following configuration.
1. 1. It contains a main agent containing a polyol compound and a curing agent containing a trifunctional isocyanate compound having an isocyanurate ring.
Laminate adhesive in which the solid content ratio of the polyol compound to the trifunctional isocyanate compound having an isocyanurate ring is polyol compound: trifunctional isocyanate compound having an isocyanurate ring = 1: 0.1 to 1: 1.5. Composition.
2. The laminate adhesion according to 1. Agent composition.
3. 3. The laminated adhesive composition according to 1 or 2, wherein the curing agent contains a trifunctional isocyanate compound having an isocyanurate ring obtained by nurate 1,5-pentamethylene diisocyanate derived from a vegetable oil.
4. The laminate adhesive composition according to any one of 1 to 3, wherein the polyol compound is a biomass compound.
5. The polyol compound is a biomass polyester polyol compound whose acid component and / or glycol component is a biomass component, and / or the polyol compound is a biomass polyester polyol whose raw material is a biomass polyester polyol whose acid component and / or glycol component is a biomass component. The laminate adhesive composition according to any one of 1 to 4 which is a polyol.
6. 5. The laminate adhesive composition according to 5, wherein the acid component is at least one selected from biomass-derived sebacic acid, succinic acid, dimer acid, and azelaic acid.
7. 5. The laminate adhesive composition according to 5 or 6, wherein the glycol component is propanediol derived from biomass.
8. It is an easily tearable laminate including a base film layer, an adhesive layer composed of the laminate adhesive composition according to any one of 1 to 7, and a sealant layer, and the adhesive layer is 1 per square meter of the easily tearable laminate. Easy-to-tear laminate formed to weigh more than .5 grams.
9. 8. The easily tearable laminate according to 8, which includes a printing layer made of an ink composition.
The ink composition in 10.9 contains a pigment, a binder resin, an organic solvent, and water, and the binder resin is an easily tearable laminate containing a polyurethane resin.
11. 9. The easily tearable laminate according to 9 or 10, which contains a vinyl chloride-vinyl acetate copolymer as a binder resin.
12. The easily tearable laminate according to any one of 9 to 11, further comprising a polyfunctional isocyanate compound as a curing agent.
13. 12. The tearable laminate according to 12, wherein the content of the curing agent is 1 to 5% by mass with respect to the ink composition.
14. The polyurethane resin is
A biomass polyurethane resin obtained by reacting a biopolyester polyol component with an organic diisocyanate component is contained, and at least one of a primary amino group and a secondary amino group is contained at the terminal, and the biopolyester polyol component is a dicarboxylic acid. It is a reaction product of diol and diol, and does not contain an organic acid having 3 or more active hydrogen groups having a molecular weight of 300 or less in one molecule, or contains the dicarboxylic acid so as to be 3000 ppm or less with respect to the dicarboxylic acid. Any of 10 to 13 characterized in that at least one of the acid and the diol is derived from a plant, and the content of the biomass polyurethane resin is 5 to 100% by mass in the polyurethane resin. The easily tearable laminate described.
15. The easily tearable laminate according to any one of 8 to 14, wherein the base film layer and the sealant layer are made of a biomass-derived resin.

The laminated adhesive composition and the laminate of the present invention use a trifunctional isocyanate compound having an isocyanurate ring as a curing agent for the laminated adhesive composition. Therefore, the tearability is improved. Furthermore, by using a vegetable oil component as the main agent and the curing agent, it is possible to contribute to prevention of global warming and reduction of environmental load. Further, by incorporating a curing agent in the printing ink, the tearability is further improved.

Hereinafter, the laminated adhesive composition and the laminated body of the present invention will be described in more detail.
<Laminate adhesive composition>
The laminate adhesive composition of the present invention is a laminate adhesive composition containing a polyol compound as a main agent and a curing agent containing a trifunctional isocyanate compound having an isocyanurate ring as a curing agent. Then, the main agent and the curing agent are mixed and reacted to form an adhesive layer.

(Trifunctional isocyanate compound having an isocyanurate ring)
In the present invention, as the trifunctional isocyanate compound having an isocyanurate ring used as a curing agent, a trifunctional isocyanate compound having an isocyanurate ring obtained by nucleolating an isocyanate having two isocyanate groups in the molecule can be used.
Of these, a trifunctional isocyanate compound having an isocyanurate ring derived from vegetable oil is preferable from the environmental point of view. Specifically, nucleolated diisocyanate diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate, lysine diisocyanate, 1,5-pentamethylene diisocyanate and the like can be exemplified.
Among them, a trifunctional isocyanate compound having an isocyanurate ring obtained by nurate 1,5-pentamethylene diisocyanate derived from vegetable oil is preferable.

(Polyol compound)
Examples of the polyol compound having at least two or more hydroxyl groups in the molecule used in the present invention include polyurethane polyols, polyester polyols, polyether polyols, acrylic polyols, etc., and two or more such polyol compounds are mixed. You may use it. Of these, polyurethane polyols, polyester polyols and polyether polyols, whose glass transition temperature and storage elastic modulus can be easily controlled, are preferable.
Among these, a biomass-derived polyester polyol and a biomass polyurethane polyol made from a biomass polyester polyol as a raw material are preferable.
Biomass polyester polyol is obtained by reacting dicarboxylic acid with diol from the viewpoint of contributing to prevention of global warming and reduction of environmental load by increasing the biomass component in the laminate adhesive composition. There is no particular limitation.
The biomass polyurethane polyol using the biomass polyester polyol as a raw material is obtained by reacting the polyol containing the biomass polyester polyol with a polyfunctional isocyanate compound, and the biomass polyurethane polyol is not particularly limited.

Polyethylene polyols include 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, succinic acid, adipic acid, azelaic acid, dimer acid and sebacin. Obtained by condensing a dibasic acid such as acid or phthalic anhydride with glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol and 3-methyl-1,5-pentanediol. These are various high molecular weight diol compounds such as polyester diol compounds such as polyester diols and polycaprolactone diols.
From an environmental point of view, a biomass polyol is preferable, and specifically, a biomass polyester polyol in which an acid component and / or a glycol component is a biomass component and / or a biomass polyester polyol in which an acid component and / or a glycol component is a biomass component is used as a raw material. Biomass polyurethane polyol.

The glycol component is a plant-derived short-chain diol component or the like, and 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 raw material by the following method. 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 a plant resource (for example, 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 useful by-products 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.
Further, ethylene glycol can be produced from bioethanol obtained by a conventional method via ethylene.

The acid component is a plant-derived dicarboxylic acid component or the like, and is not particularly limited. As an example, the dicarboxylic acid component is one selected from sebacic acid, succinic acid, lactic acid, glutaric acid, azelaic acid, dimer acid and the like. These may be used together. Among these, the dicarboxylic acid component is sebacic acid, succinic acid, or azelaic 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. , It is preferable to contain at least one selected from the group consisting of dimeric acid.

The biopolyester polyol may contain an organic acid having three or more active hydrogen groups in one molecule and having a molecular weight of 300 or less. 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 organic acid component having three or more active hydrogen groups in one molecule and having a molecular weight of 300 or less may be contained as an impurity in succinic acid or the like, or may be newly added. By containing such an organic acid component, when higher resistance is required, blocking property and retort property are likely to be satisfactorily developed. When malic acid is contained, it is preferably contained in an amount of 100 to 10000 ppm, more preferably 300 to 2000 ppm, based on the total mass of the dicarboxylic acid components.
The biomass polyol component is an appropriate condensation reaction of a plant-derived short-chain diol component, a plant-derived carboxylic acid component, and an organic acid component having a molecular weight of 300 or less having three or more active hydrogen groups in one molecule, if necessary. It is preferable that the biopolyester polyol can be produced as a plant-derived biopolyester polyol.
These polyester polyols include alkanediols such as trimethylolpropane, 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, and ethylene glycol as raw material polyol compounds. , Propylene glycol, 1,4-butanediol, 1,3-butanediol and other low molecular weight diol compounds may be used in combination.

The biomass polyurethane polyol using the biomass polyester polyol as a raw material is obtained by reacting the polyol containing the biomass polyester polyol with a polyfunctional isocyanate compound.
Examples of the polyfunctional isocyanate compound include aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as dicyclohexylmethane 4,4'-diisocyanate, 1,4-cyclohexanediisocyanate and isophorone diisocyanate, and hexamethylene diisocyanate. Examples thereof include aliphatic diisocyanate compounds and aromatic aliphatic diisocyanate compounds such as α, α, α', α'-tetramethylxylylene diisocyanate. These organic diisocyanate compounds can be used alone or in combination of two or more.

(Amount of a polyol compound and a trifunctional isocyanate compound having an isocyanurate ring)
In the laminate adhesive composition of the present invention, the compounding of the polyol compound in the main agent and the trifunctional isocyanate compound having an isocyanurate ring in the curing agent is the solid content ratio of the polyol compound and the trifunctional isocyanate compound having an isocyanurate ring. Is a polyol compound: a trifunctional isocyanate compound having an isocyanurate ring = 1: 0.1 to 1: 1.5, preferably 1: 0.3 to 1: 0.7. Within this range, excellent tearability can be obtained.

(Form of Laminate Adhesive Composition)
The laminated adhesive composition of the present invention may be either a solvent-free type or a solvent type.
In the case of the solvent type, the organic solvent is not particularly limited. For example, the organic solvent includes toluene, a ketone-based organic solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), an ester-based organic solvent (methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, etc.). ), Alcohol-based organic solvent (methanol, ethanol, n-propanol, isopropanol, butanol, etc.), and hydrocarbon-based solvent (toluene, methylcyclohexane, etc.) may be used. Among these, the organic solvent is preferably a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent in consideration of dealing with environmental problems, printability and drying property of the adhesive. In this case, the ratio of the ester-based organic solvent to the alcohol-based organic solvent is preferably in the range of ester-based organic solvent / alcohol-based organic solvent = 50/50 to 95/5.
When an organic solvent is used, its content is preferably 5% by mass or more in the adhesive composition from the viewpoint of excellent coatability of the obtained adhesive composition. The amount of the organic solvent used is preferably 30% by mass or less. When the amount of the organic solvent used is less than 5% by mass, the effect of blending the organic solvent used for the purpose of reducing the viscosity may be reduced. Further, when the amount of the organic solvent used exceeds 30% by mass, even if the biopolyester polyol compound reacts with diisocyanate, it may take a long time to sufficiently solidify. The organic solvent preferably contains propyl acetate. Propyl acetate is preferably contained in an adhesive composition in an amount of 1.0% by mass or more.

(Other additives)
The adhesive of the present invention includes a silane coupling agent to enhance heat resistance, phosphoric acid or a derivative thereof to enhance acid resistance, a catalyst, an antioxidant, an ultraviolet absorber, an antioxidant, an antifungal agent, and an increase. Additives such as thickeners, plasticizers, fillers and antifoaming agents can be added as needed.

Next, the laminated body of the present invention will be described.
The laminate of the present invention contains a base film layer, a printing layer made of an ink composition, an adhesive layer made of a laminated adhesive composition, and a sealant layer, if necessary.
Specific examples of the method for obtaining the laminate of the present invention include, for example, a base film containing a base material containing a polyol compound and a trifunctional isocyanate compound having an isocyanurate ring after printing with printing ink, if necessary. It can be obtained by applying a laminate adhesive composition containing a curing agent to be coated and further laminating a sealant layer.

<Base film layer, sealant layer>
Examples of the base material of the base film layer and the sealant layer of the present invention include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, biaxially stretched polypropylene, and non-rolled shaft polypropylene. Polyethylene, nylon, polystyrene, polyvinyl chloride, polycarbonate, polyvinyl alcohol, ethylene vinyl acetate copolymer resin film or sheet and polyvinylidene chloride or polyvinyl chloride coated polyethylene, polypropylene, polyester, nylon, cellophane and other films. And aluminum foil, copper foil and the like. Further, if necessary, the surfaces of the first film base material and the second film base material can be subjected to pretreatment such as corona treatment, ozone treatment, and frame treatment.
As the base material of the base film layer, biaxially stretched polypropylene, polyester, stretched nylon and the like are preferable from the viewpoint of water resistance, heat resistance and impact resistance, and from the viewpoint of moisture resistance and gas blocking property.
From an environmental point of view, a biomass-derived resin, particularly a biomass polyester film or the like, is particularly preferable.
The base material of the sealant layer is not particularly limited as long as it is a base material that can be melted by heat and fused to each other, but from the viewpoint of cold resistance, impact resistance, and low temperature sealing property, low density polyethylene and linear low Dense polyethylene, unrolled polypropylene and the like are preferable. From an environmental point of view, low-density polyethylene containing biomass polyolefin, linear low-density polyethylene, unrolled polypropylene and the like are particularly preferable.

<Ink composition for forming a print layer>
The ink composition preferably contains a pigment, a polyurethane resin as a binder resin, a biomass polyurethane resin from an environmental point of view, an organic solvent, and water. In order to improve the tearability, it is preferable to further contain a curing agent.
The constituent components of the ink composition will be described below.

(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, dark blue, ultramarine blue, 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, copper phthalocyanine pigments, condensed polycyclic pigments and the like.
The content of these pigments in the ink composition is usually about 1 to 50% by mass.

(Binder resin)
The binder resin includes a polyurethane resin. Further, from the environmental point of view, the polyurethane resin may contain a biomass polyurethane resin. The biomass polyurethane resin is preferably contained in the polyurethane resin in an amount of 10% by mass or more, more preferably 40% by mass or more in terms of solid content.
Further, the binder resin further contains a vinyl chloride / vinyl acetate-based copolymer and / or a vinyl chloride / acrylic-based copolymer.

(Biomass polyurethane resin)
The biomass polyurethane resin will be described.
The biomass polyurethane resin is a polyurethane resin containing components derived from biomass (derived from plants). Since the biomass polyurethane resin can contribute to the prevention of global warming and the reduction of the environmental load compared to the case of using other depleting resources, a urethane prepolymer is synthesized by the reaction of the biopolyol component and the isocyanate component, and the urethane prepolymer is synthesized. It is preferably a biopolyurethane resin obtained by reacting a chain extender and a reaction terminator as needed, 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 for 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 raw material by the following method. 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 a plant resource (for example, 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 useful by-products 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. Further, ethylene glycol can be produced from bioethanol obtained by a conventional method via ethylene. The plant-derived carboxylic acid component is not particularly limited. For example, the carboxylic acid component is sebacic acid, succinic acid, lactic acid, glutaric acid, azelaic 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. Further, from the viewpoint of adhesiveness of the laminate, it is preferable to contain an organic acid having 3 or more active hydrogen groups having a molecular weight of 300 or less in one molecule. As an example, the organic acid component having three or more active hydrogen groups having a molecular weight of 300 or less in one molecule is malic acid, succinic acid, tartaric acid and the like. These may be used together. The content of the organic acid component having three or more active hydrogen groups having a molecular weight of 300 or less in one molecule is preferably 3000 ppm or less with respect to the dicarboxylic acid. Further, 3000 ppm or less is more preferable, and 100 to 2000 ppm is further preferable with respect to the total amount of sebacic acid and succinic 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 biomass polyester polyol is obtained by directly dehydrating and condensing plant-derived sebacic acid, plant oil-derived succinic acid, and dicarboxylic acid with malic acid of 3000 ppm or less and plant-derived 1,3-propanediol. Is obtained.

Examples of the organic diisocyanate compound include aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as dicyclohexylmethane 4,4'-diisocyanate, 1,4-cyclohexane diisocyanate and isophorone diisocyanate, and hexamethylene diisocyanate. Examples thereof include aliphatic diisocyanate compounds and aromatic aliphatic diisocyanate compounds such as α, α, α', α'-tetramethylxylylene diisocyanate. These organic diisocyanate compounds can be used alone or in combination of two or more. Of these, alicyclic diisocyanates, aliphatic diisocyanates and aromatic aliphatic diisocyanates are more preferable.
The ratio of the organic diisocyanate compound to the biopolyol used is such that the equivalent ratio of isocyanate group: hydroxyl group (isocyanate index) is usually 1.2: 1 to 3.0: 1, more preferably 1.3: 1 to 1. It is a range of 2.0: 1. When the above isocyanate index is smaller than 1.2, it tends to be a flexible polyurethane resin, and the blocking resistance and the like may be low when the ink composition of the present invention is printed. In this case, another hard resin It may be necessary to use in combination with.

As the chain extender, known chain extenders used in polyurethane resins as ink binders 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 biomass polyurethane resin does not gel.

Examples of the reaction terminator to be introduced having a primary amino group and a secondary amino group at the end of the biomass polyurethane resin include aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, and hexamethylenediamine, isophoronediamine, and 4 , 4'-Alicyclic diamines such as dicyclohexylmethanediamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylene diamine, aromatic aliphatic diamines such as xylenediamine, N- (2) Examples of diamines having a hydroxyl group such as −hydroxyethyl) ethylenediamine and N- (2-hydroxyethyl) propylenediamine 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 biomass polyurethane resin include alkanolamines such as monoethanolamine and diethanolamine, and hydroxyl groups such as N- (2-hydroxyethyl) ethylenediamine and N- (2-hydroxyethyl) propylenediamine. Diamines 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.

When the above-mentioned preferable biomass polyurethane resin has a specific functional group, the laminate of the present invention has excellent adhesiveness and laminate suitability.
The biomass polyurethane resin preferably has at least one selected from a primary amino group and a secondary amino group at the end of the molecule, and more preferably has a hydroxyl group.
When the polyurethane resin has an amino group, the amine value is preferably 1 to 10 mgKOH / g. If the amine value is less than 1 mgKOH / g, the adhesiveness of the laminate of the present invention to the film may be lowered, and further, the laminating suitability may be lowered. If the amine value exceeds 10 mgKOH / g, printing may be performed. Blocking resistance at times may be reduced.
In the present invention, the amine value means the amine value per 1 g of solid content, and a potentiometric titration method (for example, COMITE (AUTO TITRA TOR COM-900, BURET B-900, BURET B-900,) is used using a 0.1 N hydrochloric acid aqueous solution. TISTATIONK-900), manufactured by Hiranuma Sangyo Co., Ltd.), and then converted to the equivalent of potassium hydroxide.
As the method for producing the biomass polyurethane resin, a known method for producing a polyurethane resin can be used as it is by using the above materials. Further, if the molecular weight, chemical structure, and equivalent ratio of each component are different, the hardness of the obtained biomass polyurethane resin is also different. Therefore, it is possible to adjust the laminating suitability of the laminate by appropriately combining these components. be.
The mass average molecular weight of the biomass polyurethane resin is preferably 10,000 to 70,000, more preferably 20,000 to 60,000.

(Polyurethane resin)
The polyurethane resin is a polyurethane resin having at least one selected from a primary amino group and a secondary amino group at the end of the molecule. More preferably, it is a polyurethane resin having a hydroxyl group and having at least one selected from a primary amino group and a secondary amino group at the end of the molecule. As these polyurethane resins, 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.
Examples of the organic diisocyanate compound include aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as dicyclohexylmethane 4,4'-diisocyanate, 1,4-cyclohexane diisocyanate and isophorone diisocyanate, and hexamethylene diisocyanate. Examples thereof include aliphatic diisocyanate compounds and aromatic aliphatic diisocyanate compounds such as α, α, α', α'-tetramethylxylylene diisocyanate. These organic diisocyanate compounds can be used alone or in combination 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 adducts 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 such as polyesterdiols and polycaprolactone diols obtained by subjecting two or more kinds to a condensation reaction can be mentioned. These high molecular weight diol compounds can be used alone or in combination of two or more.
Further, in addition to the above polymer diol compound, alkanediol such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4- Low molecular weight diol compounds such as butanediol and 1,3-butanediol can be used alone or in combination of two or more.

In the reaction for 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 person who uses a polyether diol compound as the polymer diol compound. However, the solubility of the obtained polyurethane resin tends to be high, which is preferable in that a wide range of ink designs can be performed according to the required performance.
The ratio of the organic diisocyanate compound to the polymer diol compound is such that the equivalent ratio of isocyanate groups: hydroxyl groups (isocyanate index) is usually 1.2: 1 to 3.0: 1, more preferably 1.3:. It is in the range of 1 to 2.0: 1. When the above isocyanate index is smaller than 1.2, it tends to be a flexible polyurethane resin, and the blocking resistance and the like may be low when the ink composition of the present invention is printed. In this case, another hard resin It may be necessary to use in combination with.

As the chain extender, known chain extenders used in polyurethane resins as ink binders 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.

Examples of the reaction terminator for introducing a primary amino group and a secondary amino group at the end of the polyurethane resin include aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine and hexamethylenediamine, isophoronediamine, 4,4. '-Alicyclic diamines such as dicyclohexylmethanediamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylenediamine, aromatic aliphatic diamines such as xylenediamine, N- (2-hydroxy) Examples thereof include diamines having a hydroxyl group such as ethyl) ethylenediamine and N- (2-hydroxyethyl) propylene diamine. 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. Kind 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.

When the above-mentioned preferable polyurethane resin has a specific functional group, the printing ink composition for a film of the present invention has excellent laminating suitability in a laminated body.
In particular, the polyurethane resin preferably has at least one selected from a primary amino group and a secondary amino group at the end of the molecule, and more preferably has a hydroxyl group.
When the polyurethane resin has an amino group, the amine value is preferably 1 to 10 mgKOH / g. If the amine value is less than 1 mgKOH / g, the adhesiveness of the printing ink composition for film of the present invention to the film may be lowered, and the laminating suitability may be further lowered, so that the amine value is 10 mgKOH / g. If it exceeds, the blocking resistance may decrease.
In the present invention, the amine value means the amine value per 1 g of solid content, and a potentiometric 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), a value converted to the equivalent of potassium hydroxide after measurement by Hiranuma Sangyo Co., Ltd.).

(Vinyl chloride / vinyl acetate copolymer)
The vinyl chloride / vinyl acetate-based copolymer contains vinyl chloride monomer and vinyl acetate monomer, which have been conventionally used in gravure printing ink compositions, as essential components, and vinyl propionate, monochloroacetate, and versatic, 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.
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)-
The vinyl chloride / vinyl acetate copolymers used in the ink composition of the present invention have various types of vinyl chloride / vinyl acetate copolymers in the molecule from the viewpoints of solubility in organic solvents and printability described later and improvement of tearability. It may have a functional group.
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, solvers A, AL, TA5R, TA2, TA3, TAO, TAOL (manufactured by Nisshin Chemical Industry Co., Ltd.) and the like are preferably used.

(Vinyl chloride / acrylic copolymer)
The vinyl chloride / acrylic copolymer contains a copolymer of vinyl chloride and an acrylic monomer as a main component, 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 Octadecyl 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) Acrylic Acid Hydroxyalkyl Esters such as (Meta) Acrylic Acid 3-Hydroxybutyl, (Meta) Acrylic Acid 4-Hydroxybutyl, (Meta) Acrylic Acid 6-Hydroxyhexyl, (Meta) Acrylic Acid 8-Hydroxyoctyl , Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycol mono (meth) acrylate such as 1,4-cyclohexanedimethanol mono (meth) acrylate, caprolactone modified (meth) acrylate, hydroxyethyl acrylamide, etc. Can be mentioned.
Further, as the acrylic monomer, an acrylic monomer having a functional group other than a hydroxyl group can also be used. Examples of the functional group other than the hydroxyl group include a carboxyl group, an amide bond group, an amino group, an alkylene oxide group and the like.

The vinyl chloride / acrylic copolymer preferably has a mass average molecular weight of 10,000 to 70,000.
Further, the vinyl chloride / acrylic copolymer is 50 to 200 mgKOH / g from the viewpoint of improving the solubility in an environment-friendly solvent as the organic solvent, the adhesiveness to the base material, and the tearability. It is preferable to have a hydroxyl group so as to become.
When a vinyl chloride / vinyl acetate copolymer and / or a vinyl chloride / acrylic copolymer is used as the binder, the ink composition of the present invention contains a vinyl chloride / vinyl acetate copolymer (vinyl chloride / vinyl acetate copolymer). And / or vinyl chloride / acrylic copolymer) and biomass polyurethane resin / (vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / acrylic copolymer) = 100/0 to 45/55 ( It can be contained in a mass ratio), preferably 100/0 to 70/30.
By using the biomass polyurethane resin in combination with the vinyl chloride / vinyl acetate copolymer and / or the vinyl chloride / acrylic copolymer, the laminate of the present invention has excellent laminating suitability.
If the biomass 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 vinyl chloride / The proportion of the 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.

(Hardener)
In the present invention, it is preferable to contain a curing agent in order to improve the tearability. A polyfunctional isocyanate compound can be used as the curing agent. Specifically, trifunctional polyfunctional isocyanate compounds such as burette, isocyanurate, and adduct, and bifunctional diisocyanate compounds can be used. Specifically, 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 Co., Ltd.), Coronate CORONATE HX, Coronate CORONATE HL, Coronate CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.), Death Module N75MPA / X (manufactured by Bayer), A-50, A-3, A- 65, Stavio D-376N (manufactured by Mitsui Chemicals, Inc.), H-7 (manufactured by Rock Paint Co., Ltd.) and the like can be exemplified. Of these, it is preferable to use a trifunctional or higher functional isocyanate compound. From an environmental point of view, it is preferable to use a polyfunctional isocyanate compound derived from vegetable oil. The amount of the curing agent used is preferably 1 to 5% by mass with respect to the ink composition. The curing agent is preferably added and mixed at the time of printing.

Further, in the present invention, one kind selected from the adhesion improver and the blocking inhibitor, preferably the adhesion improver and the blocking inhibitor, is applied to the ink composition as long as the performance intended by the present invention is not deteriorated. It is preferable to use them together.
(Adhesion improver)
Examples of the adhesion improver include rosin and its derivatives, chlorinated polypropylene, dammar resin and the like, and it is desirable to contain at least one selected from rosin and its derivatives, more preferably two or more.

(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 with a conjugated double bond, one to the aromatic and the other to the 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 in offset printing inks. The rosin-modified phenol resin can be obtained by a known production method.
(4) Rosin ester: An ester resin derived from rosin, which has been used as a tackifier (tack fire) for adhesives and adhesives for a long time.
(5) Rosin-modified maleic acid resin: A rosin to which maleic anhydride is added and reacted, and if necessary, a hydroxyl group-containing compound such as glycerin is esterified with no hydroxyl group and grafted.
(6) Polymerized rosin: A derivative containing a dimerized resin acid derived from a natural resin rosin.
In addition, known rosins and rosin derivatives can also be used, and these can be used not only alone but also in combination.
Further, the acid value of rosin and its rosin derivative is preferably 120 mgKOH / g or more. When the acid value is 120 mgKOH / g or more, the laminate strength of the laminate 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 to 3.0% by mass in terms of the solid content by mass of the ink composition.

(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, chlorinated polypropylene having a degree of chlorination of more than 50 tends to have low 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 a reduced adhesiveness to the film. 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 to 3.0% by mass in terms of the solid content mass% of the ink composition.

(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 it, dissolve it in a suitable organic solvent to make a varnish. Since the dammar resin does not contain chlorine, chlorine can be eliminated or reduced as compared with the case where chlorinated polypropylene 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 ink composition.

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

(Silica particles)
Examples of the silica particles include natural products, synthetic products, and crystalline, amorphous, hydrophobic, and hydrophilic particles. The silica particles preferably have an average particle size of 1.0 to 5.0 μm (the average particle size of the silica particles means a particle size at an integrated value of 50% (D50) in the particle size distribution, and is a Coulter counter method. Can be obtained by). The silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or hydrophobic silica obtained by modifying the hydrophilic functional group with 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 ink composition.

(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. If the particle size of the polyethylene wax is smaller than 1.0 μm, the slipperiness and blocking property at the time of forming the laminate are lowered, and if the particle size is larger than 20 μm, the trapping property is lowered. The content of polyethylene wax in the 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.

(Nitrified cotton)
As the nitricized cotton, nitricized cotton conventionally used in a gravure printing ink composition can be used. The nitric acid 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) and the like. The amount of nitrified cotton used is preferably in the range of 0.1 to 2.0% by mass in the ink composition 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. The cellulose acetate propionate resin is preferably used in the range of 0.1 to 3.0% by mass in the ink composition depending on the type of pigment.

(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 a degree of acetylation of 2 to 30% by mass, a degree of butyrylation of 17 to 53% by mass, and a degree of hydroxyl groups of 1 to 5% by mass 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 ink composition 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 fatty acid amides include monoamides, substituted amides, bisamides, methylolamides, ester amides, etc., and are composed of monoamides, substituted amides, and bisamides in order to improve blocking resistance during printing during the preparation of laminates. It is preferably at least one selected from the group. The amount of the fatty acid amide used is preferably in the range of 0.01 to 1% by mass in the ink composition.
Monoamide: Monoamide is represented by the following general formula (1).
General formula (1) R ₁ −CONH ₂
(In the formula, R ₁ 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, and erucic acid amide.
-Substitution amide: The substitution 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 the substituted amide include N-oleyl palmitate 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) 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 fatty acids _{, and may be the same or different, and R 5} and R ₈ are alkylene groups having 1 to 10 carbon atoms. Or represents an allylene group.)
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) R _10- CONHCH ₂ OH
(In the formula, R ₁₀ represents a residue obtained by removing COOH from fatty acid.)
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) R _11- CONH-R _12- OCO-R ₁₃
(In the formula, R ₁₁ and R ₁₃ represent residues obtained by removing COOH from fatty acids, and may be the same or different, and R ₁₂ 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.
Further, as the fatty acid constituting the fatty acid amide, a saturated fatty acid having 12 to 22 carbon atoms and / or an unsaturated fatty acid having 16 to 25 carbon atoms is preferable, 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 ester-based organic solvents, alcohol-based organic solvents, and ketone-based organic solvents mixed solvents, or ester-based organic solvents and alcohol-based organic solvents mixed solvents that are more compatible with environmental issues. It is preferable to use it.
Further, the ink composition of the present invention preferably contains 0.1 to 20% by weight of a glycol ether-based organic solvent in 100% by weight of the organic solvent in order to improve the wettability and spreadability of the laminate during printing. .. Specific examples of glycol ether-based organic solvents 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.

(water)
The ink composition of the present invention preferably contains water from the viewpoints of alleviating printing defects due to static electricity during printing for producing a laminate, 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 ink composition.

(Other materials)
Various additives such as pigment dispersants, antistatic agents, and plasticizers can be further added to the ink composition of the present invention.

As a method for producing an ink composition using the above constituent materials, a known method can be used. Specifically, various dispersion / kneading devices such as high-speed mixers, ball mills, sand mills, and attritors, which have conventionally generally used a mixture of pigments, binder resins, organic solvents, and, if necessary, pigment dispersants, are used. It is produced by kneading using and further adding and mixing a predetermined additive. Then, by adjusting the content of each solid content material and the combination of the polyurethane resin and the organic solvent, the viscosity is adjusted to 10 to 1000 mPa · s, and then a curing agent is added at the time of printing from the viewpoint of stability over time. Specifically, the outflow time of Zahn Cup No. 3 is 12 to 23 seconds, preferably about 14 to 16 seconds for high-speed printing so that the viscosity becomes appropriate according to the printing conditions at the atmospheric temperature during printing. An ink composition can be obtained by adding an organic solvent and stirring until the result becomes.

(Laminate Adhesive Composition and Adhesive Method for Forming Adhesive Layer)
As the laminate adhesive composition, those described above can be used.
As a method for adhering using the laminated adhesive composition of the present invention, a known method can be adopted. A means can be adopted in which the laminate adhesive composition is mixed in advance, the ink composition is printed on the base film, applied to the printed surface, and then bonded to the other surface.
Further, the laminate adhesive composition may be mixed at the same time as the application.
As the coating means, a known means can be adopted, and a blade coater, a roll coater, a gravure coater, a discharge from a nozzle, or the like can be adopted.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "mass%" and "part" means "parts by mass". In addition, the number of the amount of each material in the table is also "part by mass".

<Laminate adhesive composition>
(Hardener)
Curing agent 1: A trifunctional isocyanate compound having an isocyanurate ring obtained by nurate 1,5-pentamethylene diisocyanate derived from vegetable oil. Curing agent 2: Takelac A-50 (solid content 75%, manufactured by Mitsui Chemicals, Inc.)

(Main agent)
・ Non-biomass-based main agent 1:
A-515 (solid content 50%, manufactured by Mitsui Chemicals, an aliphatic urethane ester-based polyol)

・ Biomass-based main agent 2:
Sebacic acid (derived from castor oil) / succinic acid (derived from plants) = 70/30 (mass ratio) and malic acid (sebacic acid + succinic acid) in a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube. (Contains 700 ppm), 300 parts by mass of polyesterdiol having an average molecular weight of 2000 obtained from 1,3-propanediol (derived from a plant), 5.7 parts by mass of trimethylolpropane, and 28.5 parts by mass of ethyl acetate. It was heated at 50 ° C. for 30 minutes. A mixed solution of 26.3 parts of tolylene diisocyanate and 28.5 parts of ethyl acetate was placed in a dropping funnel, which was added dropwise to a four-necked flask over 5 minutes, and then reacted at 70 ° C. for 1.5 hours. Then, 0.101 parts by mass of titanium tetrabutoxide was added, the temperature was raised to 90 ° C., and the reaction was carried out for 5 hours. The reaction solution was diluted with ethyl acetate to obtain the main agent 2 of a biomass polyol having a solid content of 70% and a mass average molecular weight of 23,000.

Main agent 3:
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, sebacic acid (derived from castor oil) / succinic acid (derived from plant) / dimer acid (derived from vegetable oil) = 60/30/10 (mass ratio) 300 parts by mass of polyester diol with an average molecular weight of 2000 and 5.7 parts by mass of trimethylol propane obtained from sebacic acid (containing 700 ppm with respect to sebacic acid + succinic acid + dimer acid) and 1,3-propanediol (derived from a plant). , 28.5 parts by mass of ethyl acetate was added, and the mixture was heated at 50 ° C. for 30 minutes. A mixed solution of 26.3 parts of tolylene diisocyanate and 28.5 parts of ethyl acetate was placed in a dropping funnel, which was added dropwise to a four-necked flask over 5 minutes, and then reacted at 70 ° C. for 1.5 hours. Then, 0.101 parts by mass of titanium tetrabutoxide was added, the temperature was raised to 90 ° C., and the reaction was carried out for 5 hours. The reaction solution was diluted with ethyl acetate to obtain the main agent 3 of a biomass polyol having a solid content of 70% and a mass average molecular weight of 25,000.

Main agent 4
Sebacic acid (derived from castor oil) / dimer acid (derived from vegetable oil) = 70/30 (mass ratio) and 1,3-propanediol (plant) in a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube. 300 parts by mass of polyesterdiol having an average molecular weight of 2000, 5.7 parts by mass of trimethylolpropane, and 28.5 parts by mass of ethyl acetate obtained from the above were added and heated at 50 ° C. for 30 minutes. A mixed solution of 26.3 parts of tolylene diisocyanate and 28.5 parts of ethyl acetate was placed in a dropping funnel, which was added dropwise to a four-necked flask over 5 minutes, and then reacted at 70 ° C. for 1.5 hours. Then, 0.101 parts by mass of titanium tetrabutoxide was added, the temperature was raised to 90 ° C., and the reaction was carried out for 5 hours. The reaction solution was diluted with ethyl acetate to obtain the main agent 4 of a biomass polyol having a solid content of 70% and a mass average molecular weight of 22,000.

(Laminate adhesive compositions of Examples 1 to 8 and Comparative Examples 1 and 2)
Hardener: A trifunctional isocyanate compound having an isocyanurate ring obtained by nurate 1,5-pentamethylene diisocyanate derived from vegetable oil, a main agent, and ethyl acetate are stirred and mixed so as to have the ratio shown in Table 1 to prepare a laminate adhesive composition. Manufactured.
(Laminate Adhesive of Comparative Example 3)
Table 1 shows urethane-based curing agent (Takelac A-616 (solid content 62%) / Takenate A-65 (solid content 100%), solid content ratio = 9.92 / 1, manufactured by Mitsui Chemicals, Inc.), main agent, and ethyl acetate. The mixture was stirred and mixed so as to have a ratio of 1 to 3 to produce a laminated adhesive composition.

<Printing ink>
<Production example of polyurethane resin varnish A (non-biomass polyurethane, with amine value and hydroxyl group)>
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 200 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 17.6 parts by mass of isophorone diisocyanate, and hydrogenated MDI21 .0 parts by mass was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. Allow to cool to near room temperature, add 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol, add 8.2 parts by mass of isophorone diamine to extend the chain, and add 0.35 parts by mass of monoethanolamine to react. After that, 1.3 parts by mass of isophorone diamine and 0.6 parts by mass of diethylenetriamine were added to terminate the reaction to obtain a polyurethane resin varnish A (solid content: 30% by mass).

<Production example of polyurethane resin varnish B (biomass polyurethane, with amine value and hydroxyl group)>
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, a cooling tube and a nitrogen gas introduction tube. ), 200 parts by mass of polyesterdiol having an average molecular weight of 2000, 17.6 parts by mass of isophorone diisocyanate, and 21.0 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. Allow to cool to near room temperature, add 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol, add 8.2 parts by mass of isophorone diamine to extend the chain, and add 0.35 parts by mass of monoethanolamine to react. After that, 1.3 parts by mass of isophorone diamine and 0.6 parts by mass of diethylenetriamine were added to terminate the reaction to obtain a polyurethane resin varnish B (solid content: 30% by mass).

<Production example of polyurethane resin varnish C (biomass polyurethane, with amine value and hydroxyl group)>
Sebacic acid (derived from castor oil) / succinic acid (derived from plants) / azelaic acid = 60/30/10 (mass ratio) and 1,3- in a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube. 200 parts by mass of polyesterdiol having an average molecular weight of 2000 obtained from propanediol (derived from a plant), 17.6 parts by mass of isophorone diisocyanate, and 21.0 parts by mass of hydrogenated MDI were charged, and 6 hours at 100 to 105 ° C. while introducing nitrogen gas. It was reacted. Allow to cool to near room temperature, add 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol, add 8.2 parts by mass of isophorone diamine to extend the chain, and add 0.35 parts by mass of monoethanolamine to react. After that, 1.3 parts by mass of isophorone diamine and 0.6 parts by mass of diethylenetriamine were added to terminate the reaction to obtain a polyurethane resin varnish C (solid content: 30% by mass).

<Production example of polyurethane resin varnish D (biomass polyurethane, with amine value and hydroxyl group)>
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, a cooling tube and a nitrogen gas introduction tube. ), 140 parts by mass of polyester diol having an average molecular weight of 2000, 55 parts by mass of polypropylene glycol having an average molecular weight of 2000, 5 parts by mass of polyethylene glycol having an average molecular weight of 2000, 17.6 parts by mass of isophorone diisocyanate, and 21.0 parts by mass of hydrogenated MDI. The mixture was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. Allow to cool to near room temperature, add 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol, add 8.2 parts by mass of isophorone diamine to extend the chain, and add 0.35 parts by mass of monoethanolamine to react. After that, 1.3 parts by mass of isophorone diamine and 0.6 parts by mass of diethylenetriamine were added to terminate the reaction to obtain a polyurethane resin varnish D (solid content: 30% by mass).

(Pigment)
Titanium oxide (vinyl chloride / vinyl acetate resin)
Solveine TA-3, manufactured by Nissin Chemical Industry Co., Ltd.
(Vinyl chloride / acrylic copolymer)
Vinyl chloride / 2-hydroxypropyl acrylate = 84/16 and weight average molecular weight of 45,000 were dissolved in propyl acetate to prepare a varnish having a solid content of 30% by mass.
(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 1 having a solid content of 20%.
(Rosin and its derivatives)
Polymerized rosin: Acid value 160 mgKOH / g
(Silica particles)
Average particle size: 4.5 μm
(Polyethylene wax)
Average particle size: 12 μm
(Hardener)
Isophorone diisoanate adduct compound (100% solid content)
(Mixed Solvents 1 and 2)
Ethyl acetate / propyl acetate / isopropyl alcohol = 50/30/20 mixed solvent

<Manufacturing example of printing ink composition for lamination>
Each pigment, polyurethane resin varnishes A to D, vinyl chloride / vinyl acetate-based copolymer (solvine TA-3, manufactured by Nisshin Kagaku Kogyo Co., Ltd.), vinyl chloride / acrylic copolymer, etc. Knead using a paint conditioner manufactured by Red Devil, and add at least one selected from rosin and its derivatives, chlorinated polypropylene, silica, polyethylene wax, ethylene bisstearic acid amide, nitrified cotton, mixed solvent 1, and water. , The printing ink compositions for laminating of Examples and Comparative Examples shown in Table 1 were obtained.

<Manufacturing method of laminated body>
100 parts by mass of each ink composition is diluted with 50 parts by mass of the mixed solvent 2, a curing agent is added, and Rigocup NO. The viscosity was adjusted to 15 seconds in 3. Each printing ink composition for lamination is printed on the treated surface of various films using a gravure printing machine under the following conditions and dried to obtain the printed matter for lamination of Examples 1 to 17 and Comparative Examples 1 to 3 containing a curing agent. Obtained.
(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

<Performance evaluation>
Each laminating printing ink composition containing a curing agent is printed on the treated surface of a base film (manufactured by Toyobo Co., Ltd., N-1102, thickness 15 μm) with a gravure printing machine equipped with an engraving plate (Helio 175 lines). Printing was performed at a speed of 100 m / min to obtain a printed matter.

<Dry laminate>
Each of the above printed matter was coated with each adhesive shown in Table 1 so as to have a solid content of 3 g / m ^2, and a sealant film (manufactured by Toyobo Co., Ltd., L-4104) was laminated with a dry laminating machine. Laminates of Examples 1 to 17 and Comparative Examples 1 to 3 were obtained.

<Dry laminate strength>
^{After applying each laminated adhesive composition in an amount of 2.0 g / m 2 in} solid content to the printed surface of each printed matter one day after printing, a non-stretched polypropylene film (RXC-3, A dry laminate having a thickness of 60 μm (manufactured by Mitsui Chemicals Tohcello Co., Ltd.) was bonded and left at 40 ° C. for 3 days to obtain a dry laminate. A sample of the dry laminate was cut into a width of 15 mm, and the T-type peel strength was measured using a peel tester manufactured by Yasuda Seiki Seisakusho. The peel strength is a measured value in units of g / 15 mm.

(Easy tearability evaluation)
After each of the laminates of Examples 1 to 17 and Comparative Examples 1 to 3 obtained by dry lamination was allowed to cool at 40 ° C. for 2 days, a cut was made with a cutter, and the easiness of tearing when torn by hand was evaluated.
○: Tear without resistance ○ ⁻ : Slightly resist but tear △: Resistant but tear ×: Sealant stretches and does not tear

Table 2 shows the results obtained by adopting the laminate adhesive compositions shown in Examples and Comparative Examples shown in Table 1 and combining them with each laminate printing ink composition.
A laminate formed by using a laminate adhesive composition according to the present invention and forming a printing ink layer has sufficiently high lamination strength and excellent tearability. On the other hand, according to Comparative Example 1 in which the content of the trifunctional isocyanate compound is low and Comparative Example 3 in which the trifunctional isocyanate compound is not used, the tearability is inferior, and conversely, Comparative Example 2 in which the content of the trifunctional isocyanate compound is high. According to the report, the lamination strength was inferior.

Claims (15)

It contains a main agent containing a polyol compound and a curing agent containing a trifunctional isocyanate compound having an isocyanurate ring.
Laminate adhesive in which the solid content ratio of the polyol compound to the trifunctional isocyanate compound having an isocyanurate ring is polyol compound: trifunctional isocyanate compound having an isocyanurate ring = 1: 0.1 to 1: 1.5. Composition. The first aspect of claim 1, wherein the solid content ratio of the polyol compound and the trifunctional isocyanate compound having an isocyanurate ring is the polyol compound: the trifunctional isocyanate compound having an isocyanurate ring = 1: 0.3 to 1: 0.7. Laminate adhesive composition. The laminated adhesive composition according to claim 1 or 2, wherein the curing agent contains a trifunctional isocyanate compound having an isocyanurate ring obtained by nurate 1,5-pentamethylene diisocyanate derived from vegetable oil. The laminate adhesive composition according to any one of claims 1 to 3, wherein the polyol compound is a biomass compound. The polyol compound is a biomass polyester polyol compound whose acid component and / or glycol component is a biomass component, and / or the polyol compound is a biomass polyester polyol whose raw material is a biomass polyester polyol whose acid component and / or glycol component is a biomass component. The laminate adhesive composition according to any one of claims 1 to 4, which is a polyol. The laminated adhesive composition according to claim 5, wherein the acid component is at least one selected from biomass-derived sebacic acid, succinic acid, dimer acid, and azelaic acid. The laminate adhesive composition according to claim 5 or 6, wherein the glycol component is propanediol derived from biomass. An easily tearable laminated body including a base film layer, an adhesive layer composed of the laminate adhesive composition according to any one of claims 1 to 7, and a sealant layer, and the adhesive layer is an easily tearable laminated body 1 square meter. Easy-to-tear laminate formed to weigh 1.5 grams or more per unit. The easily tearable laminate according to claim 8, which includes a printing layer made of an ink composition. The ink composition according to claim 9 contains a pigment, a binder resin, an organic solvent, and water, and the binder resin is an easily tearable laminate containing a polyurethane resin. The easily tearable laminate according to claim 9 or 10, which contains a vinyl chloride-vinyl acetate copolymer as a binder resin. The easily tearable laminate according to any one of claims 9 to 11, further comprising a polyfunctional isocyanate compound as a curing agent. The tearable laminate according to claim 12, wherein the content of the curing agent is 1 to 5% by mass with respect to the ink composition. The polyurethane resin is
It contains a biomass polyurethane resin obtained by reacting a biopolyester polyol component with an organic diisocyanate component, and contains at least one of a primary amino group and a secondary amino group at the terminal.
The biopolyester polyol component is a reaction product of a dicarboxylic acid and a diol, and does not contain an organic acid having three or more active hydrogen groups having a molecular weight of 300 or less in one molecule, or is relative to the dicarboxylic acid. It is characterized in that at least one of the dicarboxylic acid and the diol is derived from a plant, and the content of the biomass polyurethane resin is 5 to 100% by mass in the polyurethane resin. The easily tearable laminate according to any one of claims 10 to 13. The easily tearable laminate according to any one of claims 8 to 14, wherein the base film layer and the sealant layer are made of a biomass-derived resin.