JP2020189901A - Laminate adhesive and laminate - Google Patents

Abstract

To solve the problem that conventional polyurethane resins are not intended for resources conservation and environmental load reduction, and the problem that it is unknown whether it can be processed into a laminate adhesive when using a plant-derived raw material.SOLUTION: A two-component laminate adhesive includes a biomass polyester polyol whose acid component and/or glycol component is a biomass component, and an isocyanate compound.SELECTED DRAWING: None

Description

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

Biomass is attracting attention with the goal of conserving resources and reducing the environmental burden. Environmental load reduction activities are being carried out in various industries and industries. "Biomass" is "renewable, biologically-derived organic resources excluding fossil resources." In addition, for the purpose of environmental conservation, biomass polymers using biomass as a raw material have been developed since the 1980s. Biomass polymers are considered to be useful as measures to prevent global warming, and are expected as materials for a wide variety of products such as molding processes, fibers, non-woven fabrics, packaging, and adhesives.
However, as described in Patent Documents 1 and 2, although a laminating adhesive containing a curing agent containing a polyisocyanate component and a main agent containing a polyol component is known, the above-mentioned biomass polymer is used. That has not been done.

Japanese Patent No. 6317428 Japanese Unexamined Patent Publication No. 2014-004799

However, the polyurethane resins described in Patent Documents 1 and 2 do not contribute to resource conservation and reduction of environmental load, and plant-derived raw materials are raw materials even if the composition labeling of the raw materials is the same as that of petroleum-derived raw materials. As a result of using, the performance of the adhesive may differ, and it was unclear whether it was possible to make a laminated adhesive.

The present inventors have found that the above problems can be solved by forming an adhesive formed by laminating with the following two-component laminate adhesive and the two-component laminate adhesive, and have come to solve the present invention. It was.
That is, the present invention
1. 1. A two-component laminate adhesive composed of a main agent containing a biomass polyurethane resin made from a biomass polyester polyol whose acid component and / or glycol component is a biomass component, and a curing agent containing an isocyanate compound.
2. 2. The two-component laminate adhesive according to 1, wherein the acid component and the glycol component are biomass components.
3. 3. The two-component laminate adhesive according to 1 or 2, wherein the acid component is at least one selected from biomass-derived sebacic acid, succinic acid, and dimer acid.
4. The two-component laminate adhesive according to any one of 1 to 3, wherein the glycol component is a biomass-derived propanediol.
5. The biomass polyester polyol component is a biopolyester polyol obtained by reacting a plant-derived short-chain diol component, an organic acid component having three or more active hydrogen groups having a molecular weight of 300 or less in one molecule, and a plant-derived carboxylic acid component. The two-component laminate adhesive according to any one of 1 to 4.
6. The two liquids according to any one of 1 to 5 in a laminate in which a film substrate, a printing layer composed of an ink composition, an adhesive layer composed of an adhesive, and a second film substrate are laminated in this order. A laminate characterized by being an adhesive.
The ink composition in 7.6 contains a pigment, a binder resin, an organic solvent, and water, the binder resin contains a polyurethane resin, and the polyurethane resin contains a biopolyester polyol component and an organic diisocyanate component. The biopolyester polyol component contains at least one of a primary amino group or a secondary amino group at the terminal, and is a reaction product of a dicarboxylic acid and a diol. It 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 it so as to be 3000 ppm or less with respect to the dicarboxylic acid, and at least one of the dicarboxylic acid and the diol is contained. A laminate that is derived from a plant and has a content of the biomass polyurethane resin of 5 to 100% by mass in the polyurethane resin.
According to the present invention, a two-component laminate that can contribute to prevention of global warming and reduction of environmental load, has good pigment dispersibility, and exhibits excellent blocking resistance and laminating suitability even when used for flexible packaging. An adhesive and a laminated adhesive could be obtained.

According to the present invention, even if a specific biomass-derived laminated adhesive is adopted, it is possible to unexpectedly obtain an adhesive having good practicality like a commercially available laminated adhesive.

The two-component laminate adhesive and the laminate of the present invention are intended for use in packaging foods and the like for flexible packaging. The two-component laminated adhesive composition and the laminate will be described in detail.
First, a two-component laminated adhesive will be described.
<Two-component laminate adhesive>
The two-component laminate adhesive of the present invention is a two-component adhesive containing a biomass polyester polyol as a main agent and an organic diisocyanate compound as a curing agent. Then, the main agent and the curing agent are mixed and reacted to form an adhesive layer, and the adhesive layer is cured to form a polyurethane resin, which exhibits adhesiveness.

(Biomass polyester polyol used as the main agent)
The biomass polyester polyol used as the main agent is obtained by reacting a dicarboxylic acid with a diol from the viewpoint of contributing to prevention of global warming and reduction of environmental load because the biomass component in the two-component laminate adhesive increases. , Biomass polyester polyol is not particularly limited.
The biomass polyester polyol includes polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyetherdiol compounds such as ethylene oxide of bisphenol A and alkylene oxide adducts such as propylene oxide, and adipic acid, sebacic acid, phthalic anhydride and the like. Polycaprolactone diols, polyester diols obtained by condensing a basic acid with glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol. Various high molecular weight diol compounds such as polyester diol compounds. And one or more of these compounds are obtained from plant-derived compounds and / or plant-derived compounds.

The plant-derived short-chain diol component 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 plant resources (such as corn). Compared with the 1,3-propanediol compound produced by the EO production method, the 1,3-propanediol compound produced by a bio-method such as the above fermentation method has a useful by-product such as lactic acid in terms of safety. It can be obtained and the manufacturing cost can be kept low. 1,4-Butanediol can be produced by obtaining succinic acid obtained by producing glycol from plant resources and fermenting it, and hydrogenating it.
In addition, ethylene glycol can be produced from bioethanol obtained by a conventional method via ethylene.

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

The biopolyester polyol may contain an organic acid having a molecular weight of 300 or less and having three or more active hydrogen groups in one molecule. The organic acid component is not particularly limited. As an example, the organic acid component having three or more active hydrogen groups in one molecule and having a molecular weight of 300 or less is malic acid, succinic acid, tartaric acid and the like. These may be used together. The 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 contain alkanediols such as trimethylolpropane, 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, and ethylene glycol as the raw material polyol components. , Propylene glycol, 1,4-butanediol, 1,3-butanediol and other low molecular weight diol compounds may be used in combination.

(Diisocyanate compound used as a curing agent)
In the present invention, the diisocyanate compound used as a curing agent is not particularly limited. Aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate, aliphatic diisocyanate compounds such as tetramethylene diisocyanate and hexamethylene diisocyanate, and diphenylmethane diisocyanate and xylylene diisocyanate. Arophilic aliphatic diisocyanate compounds such as α, α, α'and α'-tetramethylxylylene diisocyanate can be used. Further, these diisocyanate compounds can be mixed and used.

(Biomass isocyanate compound)
In the present invention, plant-derived biomass isocyanate can be adopted as the diisocyanate compound. This is obtained by converting a plant-derived divalent carboxylic acid into a terminal amino group by acid amidation and reduction, and further reacting with phosgene to convert the amino group into an isocyanate group. By adopting biomass isocyanate, it can further contribute to the prevention of global warming and the reduction of environmental load.
Examples of plant-derived biomass isocyanates include diimmerate diisocyanate (DDI), octamethylene diisocyanate, and decamethylene diisocyanate. A plant-derived isocyanate compound can also be obtained by converting a plant-derived amino acid into an isocyanate group using a plant-derived amino acid as a raw material. For example, lysine diisocyanate (LDI) is obtained by methyl esterifying the carboxyl group of lysine and then converting the amino group to an isocyanate group. Further, 1,5-pentamethylene diisocyanate is obtained by decarboxylating the carboxyl group of lysine and then converting the amino group into an isocyanate group.
Further, a polymer or oligomer obtained by polymerizing the above-mentioned isocyanate compound and diol compound so that the terminal becomes an isocyanate group can also be used.

(Amount of biomass polyester polyol and diisocyanate mixed)
In the two-component laminate adhesive of the present invention, the composition of the biomass polyester polyol in the main agent and the diisocyanate in the curing agent is the ratio of the number of OH groups in the biomass polyester polyol and the number of NCO groups in the diisocyanate (isocyanate index). ) Is preferably the number of NCO groups / the number of OH groups = 1.2 to 3.0. Further, it is more preferably 1.3 or more. Further, the isocyanate index is more preferably 2.0 or less. Within this range, there is a high possibility that excellent blocking properties and laminating suitability will be obtained.
When the isocyanate index is less than 1.2, the polyurethane resin which is the adhesive layer after curing tends to be softened. As a result, the ink composition tends to have reduced blocking resistance and the like.

(Form of two-component laminated adhesive)
The two-component laminate adhesive 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. As an 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.), hydrocarbon-based solvent (toluene, methylcyclohexane, etc.) may be used. Among these, it is preferable that the organic solvent is 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 and diisocyanate react with each other, 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 for enhancing heat resistance, an oxygen acid or a derivative of phosphorus for enhancing acid resistance, a catalyst, an antioxidant, an ultraviolet absorber, an antioxidant, a fungicide, and the like. Additives such as thickeners, plasticizers, fillers and antifoaming agents can be added as needed.
The silane coupling agent is not limited to the following examples, for example, trialkoxysilane having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-aminopropyltriethoxysilane, and N- (2- (2-). Aminoethyl) Trialkoxysilane having an amino group such as 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxy Examples thereof include trialkoxysilane having a glycidyl group such as propyltriethoxysilane.
The amount of the silane coupling agent added is preferably 0.1 to 5.0% by weight, more preferably 0.2 to 3.0% by weight, based on the solid content of the adhesive.
The oxygen acid of phosphorus may be any acid having at least one free oxygen acid, for example, phosphoric acids such as hypophosphoric acid, phosphoric acid, orthophosphoric acid, hypophosphoric acid, metaphosphoric acid, and the like. Examples thereof include condensed phosphoric acids such as pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid. Examples of the derivative of phosphorus oxygen acid include those obtained by partially esterifying phosphorus oxygen acid with alcohols in a state where at least one free oxygen acid is left. Examples of these alcohols include fatty alcohols such as methanol, ethanol, ethylene glycol and glycerin, and aromatic alcohols such as phenol, xylenol, hydroquinone, catechol and fluoroglycinol. The oxygen acid of phosphorus or a derivative thereof may be used in combination of two or more. The amount of phosphorus oxygen acid or a derivative thereof added is preferably 0.01 to 10% by weight, more preferably 0.01 to 5.0% by weight, based on the solid content of the adhesive, and is 0. It is particularly preferably 0.02 to 1.0% by weight.

Next, the laminated body of the present invention will be described.
The laminate of the present invention is a laminate in which the first film substrate, the printing layer composed of the ink composition, the adhesive layer composed of the adhesive, and the second film substrate are laminated in this order.
(First and second film substrates)
Examples of the first film base material and the second film base material include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, biaxially stretched polypropylene, and non-rolled shaft polypropylene. Polyester, 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, etc. 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 first film base material, biaxially stretched polypropylene, polyester, stretched nylon and the like are preferable from the viewpoint of water resistance, heat resistance, impact resistance, moisture resistance and gas blocking property.
The second film base material 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 linearity are used. Low density polyethylene and unrolled polypropylene are preferable.

(Ink composition for forming a print layer)
The ink composition preferably contains a pigment, a biomass polyurethane resin as a binder resin, an organic solvent, and water.
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, navy blue, ultramarine, carbon black and graphite, and examples of extender pigments include silica particles, calcium carbonate, kaolin and clay. Examples thereof include barium sulfate, aluminum hydroxide, and talc. Of these, it is preferable to use titanium oxide as the white pigment. Examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, 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. The polyurethane resin may contain a biomass polyurethane resin. From the environmental point of view, 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, it is preferable to contain a polyurethane resin having an amine value and 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 as compared with the case of using other depleting resources, a urethane prepolymer is synthesized by the reaction of the biopolypoly component and the isocyanate component. 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 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 plant resources (such as corn). Compared with the 1,3-propanediol compound produced by the EO production method, the 1,3-propanediol compound produced by a bio-method such as the above fermentation method has a useful by-product such as lactic acid in terms of safety. It can be obtained and the manufacturing cost can be kept low. 1,4-Butanediol can be produced by obtaining succinic acid obtained by producing glycol from plant resources and fermenting it, and hydrogenating it. In addition, ethylene glycol can be produced from bioethanol obtained by a conventional method via ethylene. The plant-derived carboxylic acid component is not particularly limited. As an example, the carboxylic acid component is sebacic acid, succinic acid, lactic acid, glutaric acid, dimer acid and the like. These may be used together. Among these, the carboxylic acid component preferably contains at least one selected from the group consisting of sebacic acid, succinic acid and dimer acid. 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, 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-cyclohexanediisocyanate, and isophorone diisocyanate, and hexamethylene diisocyanate. Examples thereof include aliphatic diisocyanate compounds such as α, α, α', α'-tetramethylxylylene diisocyanate and other aromatic aliphatic diisocyanate compounds. 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 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 thereof include diamines having a hydroxyl group such as −hydroxyethyl) ethylenediamine and N- (2-hydroxyethyl) propylenediamine. 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.
In particular, 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 potential difference titration method (for example, COMITE (AUTO TITTOROR COM-900, BURET B-900, TITSTATIONK) is used using a 0.1 N hydrochloric acid aqueous solution. -900), the value converted to the equivalent of potassium hydroxide after measurement by Hiranuma Sangyo Co., Ltd.).

As the 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. ..
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 that can be used together with the biomass 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-cyclohexanediisocyanate, and isophorone diisocyanate, and hexamethylene diisocyanate. Examples thereof include aliphatic diisocyanate compounds such as α, α, α', α'-tetramethylxylylene diisocyanate and other aromatic aliphatic diisocyanate compounds. 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 adduct such as propylene oxide, adipic acid, sebacic acid, and anhydrous. One or more dibasic acids such as phthalic acid and one of glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol Alternatively, polyesterdiol compounds such as polyesterdiols and polycaprolactone diols obtained by subjecting two or more kinds to a condensation reaction can be mentioned. These polymer diol compounds can be used alone or in combination of two or more.
Further, in addition to the above high molecular weight diol compound, alkanediols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4- Low molecular weight diol compounds such as butanediol and 1,3-butanediol can be used alone or in combination of two or more.
When a mixed solvent system of an ester solvent and an alcohol solvent is used as the organic solvent described later in the reaction for synthesizing the polyurethane resin, a polyether diol compound is used 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 to be introduced having 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, Alicyclic diamines such as 4'-dicyclohexylmethanediamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylene diamine, aromatic aliphatic diamines such as xylenediamine, N- (2- (2- Examples of diamines having a hydroxyl group such as hydroxyethyl) ethylenediamine and N- (2-hydroxyethyl) propylene diamine can be exemplified. Among these, polyamines having a primary amino group such as diethylenetriamine and triethylenetetratriamine are preferable. Examples of the reaction terminator for introducing a hydroxyl group into the polyurethane resin include alkanolamines such as monoethanolamine and diethanolamine, and diamines having hydroxyl groups such as N- (2-hydroxyethyl) ethylenediamine and N- (2-hydroxyethyl) propylenediamine. Can be exemplified. Further, known reaction terminators such as monoamine compounds and monoalcohol compounds can be used. Specifically, monoalkylamines such as n-propylamine and n-butylamine, and dialkylamines such as di-n-butylamine. Kind, monoalcohols such as ethanol can be exemplified.

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 potential difference titration method (for example, COMITE (AUTO TITTOROR COM-900, BURET B-900, TITSTATIONK) is used using a 0.1 N hydrochloric acid aqueous solution. -900), the value converted to the equivalent of potassium hydroxide after measurement by Hiranuma Sangyo Co., Ltd.).

<Vinyl chloride / vinyl acetate copolymer>
The vinyl chloride / vinyl acetate copolymer contains vinyl chloride monomer and vinyl acetate monomer, which have been conventionally used in gravure printing ink compositions, as essential components, and vinyl propionate, monochloroacetate, and versatic, if necessary. A vinyl acetate monomer such as vinyl acetate, vinyl laurate, vinyl stearate, vinyl benzoate, or a monomer having a functional group such as a hydroxyl group can be used as a copolymerization component, which is produced by a known method.
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 copolymer used in the ink composition of the present invention may have various functional groups in the molecule from the viewpoint of solubility in the organic solvent described later and printability. good.
When an environment-friendly solvent is used as the organic solvent, the vinyl chloride / vinyl acetate copolymer preferably has a hydroxyl group of 50 to 200 mgKOH / g. As a commercially available product of such a vinyl chloride / vinyl acetate copolymer, for example, it is preferable to use solvers A, AL, TA5R, TA2, TA3, TAO, TAOL and the like.

<Vinyl chloride / acrylic copolymer>
The vinyl chloride / acrylic copolymer is mainly composed of a copolymer of vinyl chloride and an acrylic monomer, and the form of the copolymer is not particularly limited. For example, the acrylic monomer may be blocked or randomly incorporated in the main chain of polyvinyl chloride, or may be graft-copolymerized in the side chain of polyvinyl chloride.
As the acrylic monomer, a (meth) acrylic acid ester, an acrylic monomer having a hydroxyl group, or the like can be used. Examples of the (meth) acrylic acid ester include a (meth) acrylic acid alkyl ester, and the alkyl group may be linear, branched, or cyclic, but a linear alkyl group is preferable.
For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate. , (Meta) 2-ethylhexyl acrylate, (meth) isooctyl acrylate, (meth) decyl acrylate, (meth) dodecyl acrylate, (meth) tetradecyl acrylate, (meth) hexadecyl acrylate, (meth) acrylate Octadecil and the like can be mentioned.
Examples of acrylic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (Meta) hydroxyalkyl esters such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate , Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycol mono (meth) acrylate such as 1,4-cyclohexanedimethanol mono (meth) acrylate, caprolactone modified (meth) acrylate, hydroxyethyl acrylamide, etc. Can be mentioned.
Further, as the acrylic monomer, an acrylic monomer having a functional group other than a hydroxyl group can also be used. Examples of functional groups other than hydroxyl groups include carboxyl groups, amide bond groups, amino groups, alkylene oxide groups and the like.
The vinyl chloride / acrylic copolymer preferably has a mass average molecular weight of 10,000 to 70,000.
Further, from the viewpoint of solubility in an environmentally friendly solvent as the organic solvent and adhesiveness to the substrate, the vinyl chloride / acrylic copolymer has a hydroxyl group so as to have a hydroxyl group of 50 to 200 mgKOH / g. It is preferable to have.

In the gravure printing ink composition for film of the present invention, a biomass polyurethane resin + polyurethane resin and (vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / acrylic copolymer) are mixed with a biomass polyurethane resin + polyurethane resin. / (Vinyl chloride / vinyl acetate-based copolymer and / or vinyl chloride / acrylic-based copolymer) = 100/0 to 45/55 (mass ratio), preferably 100/0 to 70 / It is 30.
By using the biomass polyurethane resin + 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. ..
When the above biomass polyurethane resin + polyurethane resin / (vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / acrylic copolymer) is less than 45/55, (vinyl chloride / vinyl acetate copolymer and / Alternatively, the proportion of the vinyl chloride / acrylic copolymer) may increase, the printed matter formed by using the ink composition of the present invention may become hard, and the adhesiveness to the film may be insufficient.

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 within a range that does not deteriorate the performance intended by the present invention. 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, more preferably two or more, selected from rosin and its derivatives.

<Rosin and its derivatives>
Examples of the rosin include gum rosin, tall oil rosin, wood rosin and the like. Generally, rosin is an amber, amorphous resin obtained from pine and is a mixture because it is obtained from nature. Dehydroabietic acid may be isolated and used for each component, and these are also defined as rosins in the present invention.
The rosin derivative is a compound obtained by modifying the above rosin, and is specifically listed below.
(1) Hydrogenated rosin: A rosin having improved weather resistance by adding (hydrogenating) hydrogen to a conjugated double bond.
(2) Disproportionated rosin: Disproportionation is the reaction of two molecules of rosin to two molecules of abietic acid having a conjugated double bond, one to an aromatic and the other to a single double bond. It is a modification that becomes a molecule. It is generally inferior in weather resistance to hydrogenated rosin, but has better weather resistance than untreated rosin.
(3) Rosin-modified phenolic resin: Rosin-modified phenolic resin is often used as the main binder for offset printing inks. The rosin-modified phenolic resin can be obtained by a known production method.
(4) Rosin ester: An ester resin derived from rosin, which has long been used as a tackifier (tack fire) for adhesives and adhesives.
(5) Rosin-modified maleic acid resin: A rosin to which maleic anhydride is added and reacted, and if necessary, a hydroxyl group-containing compound such as glycerin is esterified with no hydroxyl group and grafted.
(6) Polymerized rosin: A derivative containing a dimerized resin acid derived from a natural resin rosin.
In addition, known rosins and rosin derivatives can also be used, and these can be used not only alone but also in combination.
Further, the acid value of rosin and its rosin derivative is preferably 120 mgKOH / g or more. When the acid value is 120 mgKOH / g or more, the laminate strength 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 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, when the degree of chlorination exceeds 50, the chlorinated polypropylene tends to have a reduced adhesiveness to the film. In the present invention, the degree of chlorination is defined by the mass% of chlorine atoms in the chlorinated polypropylene resin. Further, the chlorinated polypropylene is preferably a modified or unmodified chlorinated polypropylene having a mass average molecular weight of 5000 to 20000. When the mass average molecular weight is less than 5000, the chlorinated polypropylene tends to have low adhesiveness. On the other hand, when the mass average molecular weight exceeds 200,000, the chlorinated polypropylene tends to have a reduced solubility in an organic solvent. The amount used when blending the chlorinated polypropylene is preferably 0.1 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, dissolve in a suitable organic solvent to make a varnish. Since the dammar resin does not contain chlorine, chlorine can be eliminated or reduced as compared with the case where 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 cotton cotton depending on the kind of pigment.

<Silica particles>
Examples of the silica particles include natural products, synthetic products, crystalline, non-crystalline, hydrophobic, and hydrophilic particles. The silica particles preferably have an average particle size of 1.0 to 5.0 μm (the average particle size of the silica particles means a particle size at an integrated value of 50% (D50) in the particle size distribution, and is a Coulter counter method. Can be obtained by). The silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or hydrophobic silica obtained by modifying the hydrophilic functional group with alkylsilane or the like to make it hydrophobic, but hydrophilic ones are preferable and hydrophilic. The ink containing silica particles also has the effect of promoting the wetting and spreading of the ink during overlay printing and improving the overlay printing effect (hereinafter, may be referred to as "trapping property"). The amount of silica particles used is preferably 0.0 to 3.0% by mass, more preferably 0.1 to 1.0% by mass in the 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.

<Nitrocellulose>
As the nitric acid cotton, nitric acid cotton conventionally used in a gravure printing ink composition can be used. The vitrified cotton is obtained as a nitrate ester in which three hydroxyl groups in the 6-membered ring of the anhydrous glucopyranose group in the natural cellulose are replaced with a nitric acid group by reacting natural cellulose with nitric acid. As the nitricized cotton used in the present invention, one having a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90 is preferably used. Specific examples include SS1 / 2, SS1 / 4, SS1 / 8, TR1 / 16, NCRS-2, (manufactured by KOREA CNC LTD) and the like. The amount of nitrocellulose used is preferably in the range of 0.1 to 2.0% by mass in the 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 acids.)
Specific examples of the monoamide include lauric acid amide, palmitate amide, stearic acid amide, bechenic acid amide, hydroxystearic acid amide, oleic acid amide, erucic acid amide and the like.
-Substitution amide: The substitution amide is represented by the following general formula (2).
General formula (2) 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 palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucate amide and the like.
Bisamide: Bisamide is represented by the following general formula (3) or general formula (4).
General formula (3) 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 arylene 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 acids.)
Specific examples of the methylol amide include methylol palmitate amide, methylol stearic acid amide, methylol bechenic acid amide, methylol hydroxystearic acid amide, methylol oleic acid amide, and methylol erucic acid amide.
-Ester amide: The ester amide is represented by the following general formula (6).
General formula (6) 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.
The fatty acid constituting the fatty acid amide is preferably a saturated fatty acid having 12 to 22 carbon atoms and / or an unsaturated fatty acid having 16 to 25 carbon atoms, and a saturated fatty acid having 16 to 18 carbon atoms and / or 18 to 22 carbon atoms. Unsaturated fatty acids are more preferred. Lauric acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid are particularly preferable as saturated fatty acids, and oleic acid and erucic acid are particularly preferable as unsaturated fatty acids.

(Organic solvent)
Examples of the organic solvent include ketone organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester organic solvents such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate and isobutyl acetate, methanol and ethanol. Alcohol-based organic solvents such as n-propanol, isopropanol and butanol, and hydrocarbon solvents such as toluene and methylcyclohexane can be used.
From the aspect of environmental issues, we use 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 the glycol ether-based organic solvent include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and ethylene glycol. Examples thereof include monoisobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monon-propyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether.

(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 forming 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, for example, a mixture of a pigment, a binder resin, an organic solvent and, if necessary, a pigment dispersant is kneaded using a high-speed mixer, a ball mill, a sand mill, an attritor or the like, and further, thiocyanate is added. It can be obtained by adding and mixing the rest of the material such as the additive of.

(Adhesive that forms an adhesive layer)
As the adhesive, those described above can be used.
(Adhesion method using two-component laminate adhesive)
A known method can be adopted as a method for adhering using the two-component laminated adhesive of the present invention. A means can be adopted in which a two-component laminate adhesive is mixed in advance, the ink composition of the base film is printed, applied to the printed surface, and then bonded to the other surface.
Further, the two-component laminate adhesive 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 "% by mass" and "part" means "part by mass". In addition, the number of the amount of each material in the table is also "part by mass".

(Printing ink)
<Production example of polyurethane resin varnish A (biomass polyurethane, amine value 6.4)>
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, cooling tube and nitrogen gas introduction tube. 200 parts by mass of polyesterdiol with an average molecular weight of 2000, 17.6 parts by mass of isophorone diisocyanate, and 21.0 parts by mass of hydrogenated MDI obtained from 1,3-propanediol (derived from a plant). The reaction was carried out at 100 to 105 ° C. for 6 hours while introducing. 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 polyurethane resin varnish A (solid content 30% by mass, amine value 6.4).

<Production example of polyurethane resin varnish B (biomass polyurethane, amine value 6.4)>
Sebacic acid (derived from castor oil) / succinic acid (derived from plants) / dimer acid (derived from plants) = 60/30/10 (mass ratio) and apples 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 having an average molecular weight of 2000 obtained from an acid (containing 700 ppm with respect to sebacic acid + succinic acid) and 1,3-propanediol (derived from a plant), 17.6 parts by mass of isophorone diisocyanate, hydrogenated MDI 21. 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 polyurethane resin varnish B (solid content 30% by mass, amine value 6.4).

<Production example of polyurethane resin varnish C (biomass polyurethane, amine value 6.4)>
Polyester with an average molecular weight of 2000 obtained from sebacic acid (derived from castor oil) and dimer acid (derived from plants) and 1,3-propanediol (derived from plants) in a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube. 200 parts by mass of diol, 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 C (solid content 30% by mass, amine value 6.4).

<Production example of polyurethane resin varnish D (non-biomass polyurethane, amine value 6.4)>
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 D (solid content 30% by mass, amine value 6.4).

(Pigment)
-Titanium oxide, phthalocyanine blue, C.I. I. 15: 4
(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, weight average molecular weight 45,000) was dissolved in propyl acetate to prepare a varnish having a solid content of 30% by mass.
(Rosin and its derivatives)
Polymerized rosin: Acid value 160 mgKOH / g
(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%.
(Dammal resin)
50 parts of a commercially available natural dammar resin (solid) was dissolved in 50 parts of methylcyclohexane to obtain a dammar resin solution having a solid content of 50%.
(Silica particles)
Average particle size: 4.5 μm
(Polyethylene wax)
Average particle size: 12 μm
(Mixed Solvents 1 and 2)
Ethyl acetate / propyl acetate / isopropyl alcohol = 50/30/20

<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.), and vinyl chloride / acrylic copolymer are blended so as to have the formulations shown in Table 1. Kneaded using a paint conditioner manufactured by Red Devil, and at least one selected from rosin and its derivatives, chlorinated polypropylene, dammar resin, silica, polyethylene wax, ethylene bisstearic acid amide, nitrified cotton, mixed solvent 1, water. Was added to obtain a printing ink composition for laminating of Examples and Reference Examples shown in Table 1.

<Dry Laminate Adhesive Composition>
(Main agent 1)
Sebacic acid (derived from castor oil) / succinic acid (derived from plant) = 70/30 (mass ratio) and malic acid (sebacic acid + succinic acid) in a four-necked flask equipped with a stirrer, cooling tube and nitrogen gas introduction tube. , And 300 parts by mass of polyester diol with an average molecular weight of 2000 obtained from 1,3-propanediol (derived from a plant), 5.7 parts by mass of trimethylol propane, and 28.5 parts by mass of ethyl acetate. It was heated at ° 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 part 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 1 of a biomass polyol having a solid content of 70% and a mass average molecular weight of 23,000.

(Main agent 2)
Sebacic acid (derived from castor oil) / succinic acid (derived from plant) / dimer acid (derived from vegetable oil) = 60/30/10 (mass ratio) and malic acid in a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube. With 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 an 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 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 25,000.

(Main agent 3)
Sebasic acid (derived from castor oil) / dimer acid (derived from vegetable oil) = 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. ), 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 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 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 22,000.

(Laminate Adhesive Composition Examples 1 to 3)
31.6 parts by mass (solid content 70%) of the main agents 1 to 3, 10.5 parts by mass of the curing agent Takenate A5 (MDI / TMP, solid content 10.5%, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), ethyl acetate 57. 9 parts by mass were stirred and mixed to produce Laminate Adhesive Composition Examples 1 to 3.
Example 1 (actual 1) is a laminate adhesive composition using the main agent 1, Example 2 (actual 2) is a laminate adhesive composition using the main agent 2, and a laminate adhesive composition using the main agent 3 is implemented. Example 3 (actual 3) was used.
(Laminate adhesive of reference example)
Commercial product used in the reference example: Urethane adhesive (Takelac A-616 / Takenate A-65, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.)

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

<About film>
PET: Polyethylene terephthalate film with corona discharge treatment on one side, manufactured by Toyobo Co., Ltd., E-5101, thickness 12 μm
OPP: Corona-discharged biaxially stretched polypropylene film, manufactured by Toyobo Co., Ltd. P-2161, thickness 25 μm
NY: Nylon film, manufactured by Toyobo, N-1102, thickness 15 μm

<Dry laminate strength>
After applying the laminate adhesive composition Examples 1 to 3 in an amount of 2.0 g / m ^{2 in} solid content to the printed surface of each printed matter one day after printing, and as a reference example, a commercially available laminate adhesive. An unstretched polypropylene film (RXC-3, thickness 60 μm, manufactured by Tohcello Co., Ltd.) was laminated with a dry laminating machine and left at 40 ° C. for 3 days to obtain a dry laminated matter. 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 Co., Ltd.

<Retort resistance>
The dry laminate obtained for the above dry laminate strength test is made into a bag, filled with a mixture of 90% by weight of water and 10% by weight of salad oil, sealed, and then immersed in hot water at 135 ° C. for 30 minutes. The retort resistance was evaluated based on the presence or absence of floating of the laminated film.
A: No Lami floats can be seen.
B: Pinhole-shaped or partly thin and short lami floats.
C: Long streaky lami floats can be seen on the entire surface.

Reference Examples W1 and W2 using commercially available laminate adhesives are also excellent in dry laminate strength and retort resistance, but each example according to the present invention can also obtain the same effect as the commercially available laminate adhesives. did it.

Claims (7)

A two-component laminate adhesive composed of a main agent containing a biomass polyurethane resin made from a biomass polyester polyol whose acid component and / or glycol component is a biomass component, and a curing agent containing an isocyanate compound. The two-component laminate adhesive according to claim 1, wherein the acid component and the glycol component are biomass components. The two-component laminate adhesive according to claim 1 or 2, wherein the acid component is at least one selected from biomass-derived sebacic acid, succinic acid, and dimer acid. The two-component laminate adhesive according to any one of claims 1 to 3, wherein the glycol component is propanediol derived from biomass. The biomass polyester polyol component is a biopolyester polyol obtained by reacting a plant-derived short-chain diol component, an organic acid component having three or more active hydrogen groups having a molecular weight of 300 or less in one molecule, and a plant-derived carboxylic acid component. The two-component laminate adhesive according to any one of claims 1 to 4. The adhesive according to any one of claims 1 to 5 in a laminate in which a film base material, a printing layer made of an ink composition, an adhesive layer made of an adhesive, and a second film base material are laminated in this order. A laminate characterized by being a two-component adhesive. The ink composition according to claim 6 contains a pigment, a binder resin, an organic solvent, and water, the binder resin contains a polyurethane resin, and the polyurethane resin contains a biopolyester polyol component and an organic diisocyanate component. The biopolyester polyol component contains at least one of a primary amino group or a secondary amino group at the terminal, and is a reaction product of a dicarboxylic acid and a diol. It 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 it so as to be 3000 ppm or less with respect to the dicarboxylic acid, and at least one of the dicarboxylic acid and the diol is contained. A laminate that is derived from a plant and has a content of the biomass polyurethane resin of 5 to 100% by mass in the polyurethane resin.