阅读说明：本技术 涂布剂、涂布有该涂布剂的层叠体、包装材料和加工品 (Coating agent, laminate coated with same, packaging material, and processed product ) 是由 中村英美 神山达哉 武田美穗 小林裕季 菅野勉 于 2020-03-23 设计创作，主要内容包括：本发明提供一种涂布剂、使用该涂布剂而得到的水蒸气阻隔性优异的层叠体、包装材料、加工品,对于所述涂布剂来说,能够利用简便的装置容易地形成尽管为薄膜也仍然能够赋予优异的水蒸气阻隔性的涂布层。通过包含含酸基的烯烃树脂(A1)、异氰酸酯化合物(B1)、有机溶剂的双组分型涂布组合物、涂布有该涂布剂的层叠体、使用了涂布有该涂布剂的层叠体的包装材料、加工品来解决课题。(The invention provides a coating agent, and a laminate, a packaging material and a processed product which are obtained by using the coating agent and have excellent water vapor barrier property. The problem is solved by a two-component type coating composition containing an acid group-containing olefin resin (A1), an isocyanate compound (B1) and an organic solvent, a laminate coated with the coating agent, and a packaging material and a processed product using the laminate coated with the coating agent.)

1. A two-component type coating agent comprising: an acid group-containing olefin resin (A1), an isocyanate compound (B1), and an organic solvent.

2. The two-component type coating agent according to claim 1, wherein the isocyanate compound comprises an aliphatic isocyanate.

3. The two-component type coating agent according to claim 1 or 2, further comprising an acid anhydride.

4. The two-component type coating agent according to any one of claims 1 to 3, further comprising a curing accelerator.

5. The two-component type coating agent according to any one of claims 1 to 4, further comprising a lubricant.

6. The two-component type coating agent according to any one of claims 1 to 5, further comprising an anti-blocking agent.

7. The two-component type coating agent according to any one of claims 1 to 6, further comprising a tackifier.

8. A laminate having a cured coating film of the two-component coating agent according to any one of claims 1 to 7 on a substrate.

9. A packaging material comprising the laminate of claim 8.

10. A packaging material obtained by molding the laminate according to claim 8.

Technical Field

The present invention relates to a coating agent capable of imparting excellent water vapor barrier properties, and a laminate, a packaging material, and a processed product coated with the coating agent and having water vapor barrier properties.

Background

Packaging containers for storing various foods, medicines, and the like are manufactured by molding or forming a thermoplastic resin film such as polyethylene terephthalate (PET), nylon (Ny), polypropylene (PP), or paper. When packaging moisture-proof products, it is necessary to perform moisture-proof processing on these packaging containers.

As the moisture-proof processing method, there are a method of melting and laminating a moisture-proof material on a base material, and a method of applying (or impregnating) a coating liquid containing a moisture-proof material, and the latter is more advantageous in terms of being able to be made thin and easy to handle. As materials having moisture-proof properties, materials described in patent documents 1 to 3 are known.

Disclosure of Invention

Problems to be solved by the invention

However, the inventions described in patent documents 1 to 3 are not sufficient in moisture resistance, and in patent documents 1 and 2, the application to the base material must be heated to a temperature higher than the melting point of the resin composition, and a special application device and a complicated application process are required.

The present invention has been made in view of such circumstances, and relates to a coating agent capable of imparting excellent water vapor barrier properties, and a laminate, a packaging material, and a processed product coated with the coating agent.

Means for solving the problems

The present invention relates to a two-component type coating agent comprising: an acid group-containing olefin resin (A1), an isocyanate compound (B1), and an organic solvent.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the coating agent of the present invention, a coating layer having excellent water vapor barrier properties despite being a thin film can be easily formed by a simple apparatus. In addition, the laminate, packaging material and processed product coated with the coating agent have excellent water vapor barrier properties.

Detailed Description

< coating agent >

The coating agent of the present invention is a two-component type coating agent comprising a first agent comprising an acid group-containing olefin resin (a1) and a second agent comprising an isocyanate compound (B1). Hereinafter, each component of the agent of the present invention will be described in detail.

(first agent)

The first agent contains an olefin resin (a1) containing an acid group as the resin (a). Examples of the acid group included in the acid group-containing olefin resin (a1) include a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, and a phosphoric acid group. The acid group-containing resin may include only 1 kind of the acid group-containing resin, or may include 2 or more kinds of the acid group-containing resin.

Examples of the acid group-containing olefin resin include homopolymers or copolymers of acid group-containing monomers, copolymers of acid group-containing monomers and olefin monomers, and acid group-containing monomer modifications of polyolefins.

The acid group-containing monomer used in the preparation of the homopolymer or copolymer of an acid group-containing monomer is preferably an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride. Specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohexa-4-ene-1, 2-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride, 1, 2, 3, 4, 5, 8, 9, 10-octahydronaphthalene-2, 3-dicarboxylic anhydride, 2-oct-1, 3-diketospiro [4.4] non-7-ene, bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, methylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic anhydride, methyl-5-norbornene-2, 3-dicarboxylic anhydride, methyl-2, 3-dicarboxylic anhydride, and mixtures thereof, 5-norbornene-2, 3-dicarboxylic anhydride, and the like.

As the acid group-containing monomer used in the preparation of the copolymer of the acid group-containing monomer and the olefin-based monomer, the same monomers as those used in the preparation of the homopolymer or copolymer of the acid group-containing monomer described above can be used. Can be used alone, or in combination of 2 or more. Maleic anhydride is preferably used.

The olefin monomer used for the preparation of the copolymer of the acid group-containing monomer and the olefin monomer includes olefins having 2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, hexene, and vinylcyclohexane. Among these, olefins having 3 to 8 carbon atoms are preferable, propylene and 1-butene are more preferable, and propylene and 1-butene are preferably used in combination, particularly, from the viewpoint of excellent resistance to solvents and adhesion to substrates, particularly, from the viewpoint of satisfactory adhesion to resin films described later and solvent resistance.

In order to prepare a copolymer of the acid group-containing monomer and the olefin-based monomer, other compounds having an ethylenically unsaturated group, such as styrene, butadiene, isoprene, etc., may be used in combination with the acid group-containing monomer and the olefin-based monomer.

As the acid group-containing monomer used in the preparation of the acid group-containing monomer modification of polyolefin, the same monomer as the acid group-containing monomer used in the preparation of the homopolymer or copolymer of the above acid group-containing monomer can be used. Can be used alone, or in combination of 2 or more. Maleic anhydride is preferably used.

Examples of the polyolefin used for the production of the modified acid group-containing monomer of the polyolefin include homopolymers or copolymers of olefins having 2 to 8 carbon atoms, copolymers of olefins having 2 to 8 carbon atoms with other monomers, and examples thereof include polyethylene such as High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), and linear low density polyethylene resins, polypropylene, polyisobutylene, poly (1-butene), poly (4-methyl-1-pentene), polyvinylcyclohexane, ethylene-propylene block copolymers, ethylene-propylene random copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-hexene copolymers, propylene-1-butene copolymers and other α -olefin copolymers, ethylene-vinyl acetate copolymers, and the like, Ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate-methyl methacrylate copolymers, ionomer resins, and the like. Among these, in particular, from the viewpoint of good adhesion, a homopolymer of an olefin having 3 to 8 carbon atoms and a copolymer of two or more olefins having 3 to 8 carbon atoms are preferable, and a homopolymer of propylene or a propylene-1-butene copolymer is more preferable, and in particular, a propylene-1-butene copolymer is preferable from the viewpoint of excellent resistance to a solvent and excellent adhesion.

Examples of the method for modifying a polyolefin with an acid group-containing monomer include graft modification and copolymerization. Specific examples of the method for reacting an acid group-containing monomer with a polyolefin by graft modification include the following methods: a method of melting polyolefin and adding an acid group-containing monomer (graft monomer) thereto to cause a graft reaction; a method in which a polyolefin is dissolved in a solvent to prepare a solution, and a graft monomer is added thereto to cause a graft reaction; a method of mixing a polyolefin dissolved in an organic solvent with a graft monomer, heating the mixture at a temperature not lower than the softening temperature or the melting point of the polyolefin, and simultaneously performing radical polymerization and dehydrogenation in a molten state.

In order to graft-copolymerize the graft monomer efficiently in any case, it is preferable to carry out the grafting reaction in the presence of a radical initiator. The grafting reaction is usually carried out at 60-350 ℃. The amount of the radical initiator used is usually in the range of 0.001 to 1 part by weight based on 100 parts by weight of the polyolefin before modification.

The weight average molecular weight of the acid group-containing olefin resin is preferably 40000 or more in order to improve the adhesion. In order to ensure appropriate fluidity, the weight average molecular weight of the acid group-containing olefin resin is preferably 150000 or less.

In the present application, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by Gel Permeation Chromatography (GPC) under the following conditions.

A measuring device: HLC-8320GPC, manufactured by Tosoh corporation

Column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel1000HXL manufactured by Tosoh Co

A detector: RI (differential refractometer)

Data processing: Multi-STATION GPC-8020model II manufactured by Tosoh corporation

The measurement conditions were as follows: column temperature 40 deg.C

Solvent tetrahydrofuran

Flow rate 0.35 ml/min

The standard is as follows: monodisperse polystyrene

Sample preparation: a tetrahydrofuran solution was filtered through a microfilter at a concentration of 0.2 mass% in terms of solid content of the resin (100. mu.l)

The acid group-containing olefin resin is preferably crystalline. The melting point of the acid group-containing olefin resin is preferably 50 ℃ or higher, more preferably 60 ℃ or higher, and further preferably 65 ℃ or higher. The melting point of the acid group-containing olefin resin is preferably 120 ℃ or lower, more preferably 100 ℃ or lower, and still more preferably 90 ℃ or lower.

The melting point of the acid group-containing olefin resin was measured by DSC (differential scanning calorimetry). Specifically, the temperature was raised from the temperature decreased arrival temperature to the temperature increased arrival temperature at 10 ℃/min, then the heat history was removed by cooling to the temperature decreased arrival temperature at 10 ℃/min, and then the temperature was again raised to the temperature increased arrival point at 10 ℃/min. The peak temperature at the second temperature rise was defined as the melting point. The temperature-lowering arrival temperature is set to a temperature 50 ℃ or higher lower than the crystallization temperature, and the temperature-raising arrival temperature is set to a temperature 30 ℃ or higher than the melting point temperature. The temperature reached by the temperature decrease and the temperature reached by the temperature increase are determined by test measurement.

Specific examples of such an olefin resin containing an acid group include maleic anhydride-modified polypropylene, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylate-maleic anhydride terpolymers, and the like. Examples of commercially available products of the acid group-containing olefin resin include "MODIC" series manufactured by Mitsubishi chemical corporation, "ADMER" series manufactured by Mitsui chemical corporation, "UNISTOLE" series, TOYOTAC "series manufactured by Toyo chemical corporation," YOUMEX "series manufactured by Sanyo chemical corporation," REXPEARL "series manufactured by Japanese polyethylene corporation," REXPEARL ET "series, PRIMCOR series manufactured by Dow chemical corporation," NUCREL "series manufactured by Du Pont polymerization chemical corporation, and" BONDINE "series manufactured by ARKEMA.

As the acid group-containing olefin resin (A1), other resins than those mentioned above can be used, and examples thereof include TAFTEC M series manufactured by Asahi Kasei corporation, and Kraton FG series manufactured by Kraton Polymers Japan corporation.

In the first agent, as the resin (a), a resin (a2) having no reactive functional group may be contained in addition to the olefin resin (a1) having an acid group. The resin (a2) is preferably a crystalline olefin resin. When the resin (a2) is a crystalline olefin resin, the solvent resistance of the coating agent is improved.

Examples of the resin (A2) include homopolymers or copolymers of olefins having 2 to 8 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, hexene, and vinylcyclohexane, and copolymers of olefins having 2 to 8 carbon atoms with other monomers, and specifically include polyethylene such as High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), and linear low density polyethylene resins, polypropylene, polyisobutylene, poly (1-butene), poly (4-methyl-1-pentene), polyvinylcyclohexane, ethylene-propylene block copolymers, ethylene-propylene random copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-hexene copolymers, and α -olefin copolymers, Ethylene-methyl methacrylate copolymers, propylene-1-butene copolymers, and the like. Among these, homopolymers of olefins having 3 to 8 carbon atoms and copolymers of olefins having 2 or more carbon atoms and 3 to 8 carbon atoms are preferable, homopolymers or copolymers of propylene are more preferable, and homopolymers of propylene are even more preferable, from the viewpoint of improving solvent resistance.

The weight average molecular weight of the resin (a2) is preferably 2000 to 200000, from the viewpoint of high solubility in a solvent and improved coatability. The weight average molecular weight of the resin (A2) is more preferably 20000 to 180000, and still more preferably 40000 to 160000.

The melting point of the resin (A2) is preferably 50 to 100 ℃. The electrolytic resistance can be more reliably improved by setting the melting point to 50 ℃ or higher, and the coatability can be satisfactorily maintained by setting the melting point to 100 ℃ or lower. The melting point of the resin (A2) is more preferably 60 to 95 ℃, and still more preferably 70 to 90 ℃.

The solid acid value of the first agent is preferably 1mgKOH/g or more, more preferably 5mgKOH/g or more, and preferably 200mgKOH/g or less, more preferably 165mgKOH/g or less. When the ratio is 200mgKOH/g or less, flexibility is excellent, and when the ratio is 1mgKOH/g or more, heat resistance is good.

The acid value of the first agent can be calculated as follows: FT-IR (FT-IR 4200, manufactured by Nippon Denshoku Co., Ltd.) was used, and the coefficient (f) obtained from a calibration curve prepared using a chloroform solution of maleic anhydride and the expansion and contraction peak (1780 cm) of the acid anhydride ring of maleic anhydride in the maleic anhydride-modified polyolefin solution were used^-1) Absorbance of (I) and stretching peak of carbonyl group of maleic acid (1720 cm)^-1) The absorbance (II) of (2) was calculated by the following formula. In the following formula, the molecular weight of maleic anhydride was 98.06 and the molecular weight of potassium hydroxide was 56.11.

[ mathematical formula 1]

(second agent)

The second agent contains an isocyanate compound (B1) as a so-called curing agent (B) which is reactive with the acid group-containing olefin resin (a 1). The isocyanate compound (B1) is not particularly limited as long as it has a plurality of isocyanate groups in one molecule, and conventionally known compounds can be used. Specific examples thereof include aliphatic diisocyanates such as butane-1, 4-diisocyanate, butene-diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2, 4, 4-trimethylhexamethylene diisocyanate, 1, 3, 6-hexamethylene triisocyanate, octamethylene diisocyanate, 1, 8-diisocyanate-4-isocyanatomethyloctane, 1, 6, 11-undecane triisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, lysine diisocyanate, and lysine ester diisocyanate;

alicyclic diisocyanates such as cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4 '-diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4, 4' -diisocyanate, norbornane diisocyanate and the like;

aromatic diisocyanates such as 1, 5-naphthalene diisocyanate, 4 ' -diphenylmethane diisocyanate, 4 ' -diphenyldimethylmethane diisocyanate, 4 ' -dibenzyl diisocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-tolylene diisocyanate, and 2, 6-tolylene diisocyanate.

Compounds derived therefrom, that is, isocyanurate bodies, adduct bodies, biuret types, uretdione bodies, allophanate bodies of the above isocyanates, prepolymers having an isocyanate residue (oligomers obtained from a diisocyanate and a polyol), or composites thereof may also be used.

As the curing agent (B), a compound obtained by reacting a part of the isocyanate groups of the above polyfunctional isocyanate compound with a compound having reactivity with isocyanate groups may be used. Examples of the compound having reactivity with an isocyanate group include amino group-containing compounds such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, dibutylamine, ethylenediamine, benzylamine, and aniline: hydroxyl group-containing compounds such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, octanol, 2-ethylhexanol, dodecanol, ethylene glycol, propylene glycol, benzyl alcohol, phenol, and the like: compounds having an epoxy group such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol glycidyl ether, and cyclohexanedimethanol diglycidyl ether: and carboxylic acid-containing compounds such as acetic acid, butyric acid, caproic acid, caprylic acid, succinic acid, adipic acid, sebacic acid, and phthalic acid.

Among them, aliphatic isocyanates such as isophorone diisocyanate and hexamethylene diisocyanate are preferably used from the viewpoint of excellent storage stability and adhesion to a base material; compounds derived from aliphatic isocyanates. The isocyanate compound (B1) preferably has a composition of 9 or more of an aliphatic isocyanate or a compound derived from an aliphatic isocyanate. The isocyanate compound (B1) may be an aliphatic isocyanate compound or a compound derived from an aliphatic isocyanate compound.

In addition to the isocyanate compound (B1), the second agent may contain a compound (B2) having reactivity with the acid group-containing olefin resin (a1) described later, and in this case, the proportion of the isocyanate compound (B1) in the curing agent (B) is preferably 4 or more. The proportion of the isocyanate compound (B1) in the curing agent (B) is more preferably 5 or more, and still more preferably 8 or more. The curing agent (B) may be all the isocyanate compound (B1).

The second agent may be used in combination with a compound (B2) other than the isocyanate compound (B1) having reactivity with the acid group-containing olefin resin (a 1). Examples of the other compound (B2) that can be used in combination with the isocyanate compound (B1) include epoxy compounds, aziridinyl group-containing compounds, carbodiimides, oxazolines, amino resins, and the like.

Examples of the epoxy compound include polyglycidyl ether type epoxy resins of aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, diglycerol, sorbitol, spiro glycol, and hydrogenated bisphenol a;

bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol AD epoxy resin;

aromatic epoxy resins such as novolak phenol resins and novolak phenol resins, which are glycidyl ethers of cresol novolak resins;

polyglycidyl ethers of polyhydric alcohols which are ethylene oxide or propylene oxide adducts of aromatic polyhydric compounds such as bisphenol a, bisphenol F, bisphenol S, and bisphenol AD;

polyglycidyl ether type epoxy resins of polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; cyclic aliphatic polyepoxy resins such as bis (3, 4-epoxycyclohexylmethyl) adipate and 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexyl formate;

polyglycidyl ester type epoxy resins of polycarboxylic acids such as propane tricarboxylic acid, butane tetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid, and trimellitic acid;

diepoxy resins of hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α -pinene and vinylcyclohexene;

epoxy resins of diene polymers such as polybutadiene and polyisoprene;

glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl bisaminomethylcyclohexane, diglycidyl aniline, and tetraglycidyl m-xylylenediamine;

epoxy resins containing heterocyclic rings such as triazine and hydantoin.

These epoxy resins may be used alone, or 2 or more kinds may be used in combination.

The epoxy compound (B1) is preferably an epoxy compound having 2 or more epoxy groups and 1 or more hydroxyl groups in 1 molecule and having a weight average molecular weight of 3000 or less.

Examples of the aziridinyl group-containing compound include N, N '-hexamethylene-1, 6-bis (1-aziridinecarboxamide), N' -diphenylmethane-4, 4 '-bis (1-aziridinecarboxamide), trimethylolpropane-tris- β -aziridinylpropionate), N' -toluene-2, 4-bis (1-aziridinecarboxamide), triethylenemelamine, trimethylolpropane-tris- β (2-methylaziridine) propionate, bis-isophthaloyl-1-2-methylaziridine, tris-1-aziridinyloxyphosphine oxide, tris-1-2-methylaziridine phosphine oxide, and the like.

Examples of the carbodiimide include N, N '-di-o-toluyl carbodiimide, N' -diphenyl carbodiimide, N '-di-2, 6-dimethylphenyl carbodiimide, N' -bis (2, 6-diisopropylphenyl) carbodiimide, N '-dioctyldecyl carbodiimide, N-toluyl-N' -cyclohexyl carbodiimide, n, N '-di-2, 2-t-butylphenyl carbodiimide, N-toluoyl-N' -phenylcarbodiimide, N '-di-p-aminophenylcarbodiimide, N' -di-p-hydroxyphenylcarbodiimide, N '-dicyclohexylcarbodiimide, N' -di-p-toluoyl-carbodiimide, and the like.

Examples of the oxazoline include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2, 5-dimethyl-2-oxazoline, mono-oxazoline compounds such as 2, 4-diphenyl-2-oxazoline, 2 '- (1, 3-phenylene) -bis (2-oxazoline), 2' - (1, 2-ethylene) -bis (2-oxazoline), 2 '- (1, 4-butylene) -bis (2-oxazoline), and 2, 2' - (1, 4-phenylene) -bis (2-oxazoline).

Examples of the amino resin include melamine resin, benzoguanamine resin, and urea resin.

When the second agent contains a compound (B2) having reactivity with the acid group-containing olefin resin (a1), the amount of the second agent blended is preferably 6 or less, more preferably 5 or less, and still more preferably 2 or less of the curing agent (B).

The amount of the curing agent (B) is preferably adjusted so that the mass of the solid component of the curing agent (B) per the mass of the solid component of the resin (A) contained in the first part is 1/1 to 1/10.

The amount of the curing agent (B) is preferably adjusted so that the equivalent ratio of the acid group (a) contained in the first agent to the functional group (B) contained in the curing agent and having reactivity with the acid group (B) (functional group (B)/acid group (a)) is 1 to 10. When the acid group (a) is an acid anhydride group, it is calculated as 2 equivalents.

(organic solvent)

The coating agent of the present invention can exhibit appropriate coatability while securing fluidity by further mixing an organic solvent with the above components. The organic solvent may contain only either the first agent or the second agent, or both. It may be added while mixing the first agent with the second agent. Such an organic solvent is not particularly limited as long as it can be removed by volatilization by heating in the drying step at the time of coating with the coating agent, and examples thereof include aromatic organic solvents such as toluene and xylene; aliphatic organic solvents such as n-hexane and n-heptane; alicyclic organic solvents such as cyclohexane and methylcyclohexane; halogen-based organic solvents such as trichloroethylene, dichloroethylene, chlorobenzene, and chloroform; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; alcohol solvents such as ethanol, methanol, n-propanol, 2-propanol (isopropanol), butanol, and hexanol; ether solvents such as diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane, and butyl carbitol; glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and propylene glycol monomethyl ether; and glycol ester solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate, and these solvents may be used alone or in combination of 2 or more.

From the viewpoint of excellent solubility of the acid group-containing olefin resin (a1), a mixed solvent of an alicyclic organic solvent and an ester solvent is preferably used, and a mixed solvent of methylcyclohexane and ethyl acetate is particularly preferably used. Further, in order to improve the solubility of the acid group-containing olefin resin (a1), a mixed solvent of an alicyclic organic solvent and an ester solvent and an alcohol solvent may be used. In this case, the alcohol solvent is preferably isopropanol, 2-butanol or the like.

In order to improve the solubility of the isocyanate compound (B1), an aromatic organic solvent or a ketone solvent may be used in combination with a mixed solvent of an alicyclic organic solvent and an ester solvent. In this case, toluene is preferably used as the aromatic organic solvent, and methyl ethyl ketone is preferably used as the ketone solvent.

The amount of the organic solvent used is preferably 5 to 30% by mass of the resin (a) relative to the total mass of the resin (a) and the organic solvent. This makes it possible to produce a coating agent having excellent coatability and excellent wettability to a film.

(other Compounds)

The coating agent of the present invention may contain various additives such as acid anhydride, curing accelerator, other resin (other than the resin (a)), plasticizer, lubricant, antiblocking agent, matting agent, thermoplastic elastomer, reactive elastomer, phosphoric acid compound, and silane coupling agent, as required. The content of these additives may be appropriately adjusted within a range not impairing the function of the coating agent of the present invention.

Examples of the acid anhydride include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, and unsaturated carboxylic acid anhydrides, and 1 or 2 or more species may be used in combination. More specifically, examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyhexamic anhydride, polyazelaic anhydride, polysebacic anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexanedicarboxylic anhydride, methylcyclohexanetetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride, chlorendic anhydride, nadic anhydride, methylnadic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1, 2-dicarboxylic anhydride, 3, 4-dicarboxy-1, 2, 3, 4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1, 2, 3, 4-tetrahydro-1-naphthalene succinic dianhydride, and the like.

Further, as the acid anhydride, an acid anhydride obtained by modifying the above compound with a diol may be used. Examples of the diol that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; polyether glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol. Further, a copolymerized polyether diol of two or more kinds of these diols and/or polyether diols may also be used.

The amount of the acid anhydride blended is preferably 0.01 parts by mass or more, more preferably 0.8 parts by mass or more, per 100 parts by mass of the resin (a). The amount of the acid anhydride blended is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 1.5 parts by mass or less, per 100 parts by mass of the resin (a).

Examples of the curing accelerator include organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-butylphenyl) phosphine, diphenylphosphine, and phenylphosphine, and imidazole compounds such as 2-methylimidazole, 1, 2-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole; tertiary amines such as triethylamine, triethylenediamine, N' -methyl-N- (2-dimethylaminoethyl) piperazine, 1, 8-diazabicyclo [5.4.0] undecene (DBU), 1, 5-diazabicyclo [4.3.0] -nonene, and 6-dibutylamino-1, 8-diazabicyclo [5.4.0] undecene, and compounds obtained by converting these tertiary amines into amine salts using phenol, octanoic acid, quaternary tetraphenylborate, etc.; cationic catalysts such as triallylsulfonium hexafluoroantimonate and diallyliodionium hexafluoroantimonate. These may be used alone, or 2 or more of them may be used in combination. It is preferable to use at least 1 selected from the group consisting of organophosphine compounds and imidazole compounds.

The amount of the curing accelerator is preferably 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin (a) of the first part.

Examples of the other resin include rosin-based or rosin ester-based resins, terpene-based or terpene-phenol-based resins, saturated hydrocarbon resins, coumarone-based resins, coumarone-indene-based resins, styrene-based resins, xylene-based resins, phenol-based resins, petroleum-based resins, and the like. These may be used alone or in combination of two or more. Among them, styrene resin is preferably used.

Examples of the styrene resin include homopolymers of styrene monomers such as homopolymers of styrene and homopolymers of α -methylstyrene; copolymers of styrene and alpha-methylstyrene; copolymers of styrene monomers such as styrene and alpha-methylstyrene and polymerizable aliphatic monomers; copolymers of styrene monomers such as styrene and α -methylstyrene with polymerizable aromatic monomers.

The melting point of the styrene resin is preferably in the range of 80 to 140 ℃ and the weight average molecular weight is preferably in the range of 800 to 3000.

The amount of the styrene resin blended is preferably 0.01 to 1.5 parts by mass per 100 parts by mass of the resin (A).

Examples of the plasticizer include polyisoprene, polybutene, and process oil, and examples of the thermoplastic elastomer include reactive elastomers such as styrene-butadiene copolymer (SBS), hydrogenated styrene-butadiene copolymer (SEBS), SBBS, hydrogenated styrene-isoprene copolymer (SEPS), styrene block copolymer (TPS), and olefin elastomer (TPO), and elastomers obtained by acid-modifying these elastomers.

Examples of the lubricant include fatty acid amide waxes such as oleamide, erucamide, stearamide, behenamide, ethylene bis oleamide, and ethylene bis erucamide; animal and vegetable oil waxes such as rice wax, palm wax, candelilla wax, mutton tallow wax, beeswax, whale oil, and beef tallow; petroleum waxes such as vaseline, paraffin wax, microcrystalline wax, polyethylene wax, polypropylene wax, PTFE wax, and linear higher alcohols; and silicones such as dimethylpolysiloxane and modified silicones such as dimethylpolysiloxane in which at least 1 side chain methyl group of the dimethylpolysiloxane is substituted with an organic group other than a methyl group (e.g., a methanol group, a polyether group, or an alkyl group having 2 or more carbon atoms).

Examples of the anti-blocking agent include inorganic particles such as silica, alumina, calcium oxide, calcium carbonate, calcium sulfate, calcium silicate, magnesium carbonate, precipitated barium sulfate, clay, and carbon black; and organic particles such as acrylic resins, urethane resins, styrene resins, epoxy resins, amide resins, and crosslinked products thereof. These may be used alone or in combination of two or more.

The anti-blocking agent preferably has an average particle diameter of 0.5 to 10 μm, more preferably 0.5 to 5 μm.

The anti-blocking agent also exhibits an effect as a so-called matting agent for suppressing the gloss of a cured coating film of the coating agent to give a natural appearance.

The amount of the antiblocking agent blended is preferably 50% by mass or less based on the total amount of the resin (A) and the antiblocking agent.

Examples of the phosphoric acid compound include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid and hypo リン acid (hypophosphoric acid), condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid and superphosphoric acid, and monoesters, diesters, monoesters, monopropyl, monobutyl, mono-2-ethylhexyl, monophenyl, monomethyl, monoethyl, monopropyl, monobutyl, mono-2-ethylhexyl, monophenyl, di-2-ethylhexyl, diphenyl orthophosphate, dimethyl, diethyl, dipropyl, dibutyl, di-2-ethylhexyl and diphenyl phosphites, and monoesters, diesters of these compounds, Monoesters and diesters of condensed phosphoric acids and alcohols, for example, products obtained by adding an epoxy compound such as ethylene oxide or propylene oxide to the above phosphoric acids, and epoxy phosphoric esters obtained by adding the above phosphoric acids to aliphatic or aromatic diglycidyl ethers.

Examples of the silane coupling agent include aminosilanes such as γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethyldimethoxysilane, and N-phenyl- γ -aminopropyltrimethoxysilane; epoxy silanes such as beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-glycidoxypropyltriethoxysilane; vinyl silanes such as vinyltris (β -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and γ -methacryloxypropyltrimethoxysilane; hexamethyldisilazane, gamma-mercaptopropyltrimethoxysilane, and the like.

These components may be blended in advance with the first agent or the second agent, or may be added when the first agent and the second agent are mixed.

The coating agent of the present invention can be prepared by mixing the above components. In this case, the respective components may be mixed at the same time to prepare a coating agent, but from the viewpoint of excellent stability and workability of the coating agent, it is preferable to prepare a two-component type coating agent in which components other than the curing agent (B) (second agent) are mixed in advance to prepare a premix, and the curing agent (B) is mixed when the coating agent is used.

The coating agent of the present invention can easily form a coating layer having excellent water vapor barrier properties even though it is a thin film, by a simple apparatus.

< layered product >

The laminate of the present invention is obtained by applying the coating agent of the present invention to a substrate. The coating agent of the present invention has excellent coatability on various substrates, and can be used for coating or impregnating paper, synthetic paper, thermoplastic resin film, steel sheet, aluminum foil, wood, woven cloth, nonwoven cloth, gypsum board, wood board, and the like, and can form a coating layer by removing a solvent. Among them, the thermoplastic resin composition is preferably used for paper, synthetic paper, and thermoplastic resin film.

Examples of the thermoplastic resin film include polyolefin films such as polyethylene terephthalate (PET) films, polystyrene films, polyamide films, polyacrylonitrile films, polyethylene films (LLDPE: low density polyethylene films and HDPE: high density polyethylene films), polypropylene films (CPP: unstretched polypropylene films and OPP: biaxially stretched polypropylene films), polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films, which are commonly used for food applications. They may be subjected to a stretching treatment. As a stretching treatment method, generally, a resin is melt-extruded by an extrusion film-forming method or the like to be formed into a sheet, and then simultaneously biaxially stretched or sequentially biaxially stretched. In the case of sequential biaxial stretching, the stretching treatment in the longitudinal direction is usually performed first, and then the stretching in the transverse direction is performed. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used. Further, a film in which a deposition layer of a metal such as aluminum or stainless steel or a metal oxide such as silica or alumina is laminated on the lamination film may be used.

Further, films commonly used for industrial applications, including polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, polyvinyl alcohol, ABS resin, norbornene resin, cycloolefin resin, polyimide resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, ethylene-vinyl acetate copolymer, and the like, may be mentioned.

The thickness of the base film is not particularly limited, and is usually in the range of 1 to 500. mu.m.

Further, the coating agent of the present invention may be applied to a laminate obtained by bonding two or more of these substrates with an adhesive. The coating agent of the present invention is excellent in water vapor barrier properties and solvent resistance, and therefore, for example, water vapor and solvent can be prevented from entering an adhesive layer for bonding substrates to each other, and the adhesive strength of a laminate can be maintained for a long period of time.

More specific examples of the laminate include:

(1) substrate film 1/adhesive layer 1/sealant film

(2) Substrate film 1/adhesive layer 1/metal vapor deposition unstretched film

(3) Substrate film 1/adhesive layer 1/metal vapor-deposited stretched film

(4) Transparent vapor-deposited stretched film/adhesive layer 1/sealant film

(5) Substrate film 1/adhesive layer 1/substrate film 2/adhesive layer 2/sealant film

(6) Substrate film 1/adhesive layer 1/Metal vapor deposition stretched film/adhesive layer 2/sealant film

(7) Substrate film 1/adhesive layer 1/transparent vapor-deposited stretched film/adhesive layer 2/sealant film

(8) Substrate film 1/adhesive layer 1/metal layer/adhesive layer 2/sealant film

(9) Substrate film 1/adhesive layer 1/substrate film 2/adhesive layer 2/metal layer/adhesive layer 3/sealant film

(10) Substrate film 1/adhesive layer 1/metal layer/adhesive layer 2/substrate film 2/adhesive layer 3/sealant film

(11) Substrate film 1/adhesive layer 1/substrate film 2, and the like, but are not limited thereto.

Examples of the base film 1 used in the composition (1) include an OPP film, a PET film, and a nylon film. As the base film 1, a base film coated for improving gas barrier properties, ink receptivity when a printing layer described later is provided, or the like can be used. Commercially available base film 1 to which coating is applied includes a K-OPP film, a K-PET film, and the like. Examples of the sealant film include a CPP film and an LLDPE film. The printed layer may be provided on the surface of the substrate film 1 on the adhesive layer 1 side (when a coated substrate film is used as the substrate film 1, the surface of the coated layer on the adhesive layer 1 side). The printing layer is formed by a general printing method conventionally used for printing a polymer film, using various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, inkjet ink, and the like.

Examples of the base film 1 used in the structures (2) and (3) include an OPP film and a PET film. As the metal deposition unstretched film, a VM-CPP film obtained by performing metal deposition of aluminum or the like on a CPP film can be used, and as the metal deposition stretched film, a VM-OPP film obtained by performing metal deposition of aluminum or the like on an OPP film can be used. In the same manner as in the configuration (1), a printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1.

Examples of the transparent vapor-deposited stretched film used in the configuration (4) include films obtained by vapor deposition of silica or alumina on an OPP film, a PET film, a nylon film, or the like. For the purpose of protecting an inorganic deposition layer of silica or alumina, a film coated on the deposition layer may be used. The sealant film may be the same as that of the composition (1). The printing layer may be provided on the surface of the transparent vapor-deposited stretched film on the side of the adhesive layer 1 (in the case of using a base film coated on the inorganic vapor-deposited layer, the surface of the coating layer on the side of the adhesive layer 1). The method of forming the printed layer is the same as in the configuration (1).

The substrate film 1 used in the configuration (5) includes a PET film and the like. The base film 2 may be a nylon film. The sealant film may be the same as that of the composition (1). In the same manner as in the configuration (1), a printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1.

The substrate film 1 of the composition (6) may be the same as those of the compositions (2) and (3). Examples of the metal vapor-deposited stretched film include a VM-OPP film and a VM-PET film obtained by vapor-depositing a metal such as aluminum on an OPP film and a PET film. The sealant film may be the same as that of the composition (1). In the same manner as in the configuration (1), a printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1.

The substrate film 1 constituting (7) may be a PET film. The transparent vapor-deposited stretched film may be the same as that of the composition (4). The sealant film may be the same as that of the composition (1). In the same manner as in the configuration (1), a printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1.

Examples of the base film 1 constituting (8) include a PET film and a nylon film. Examples of the metal layer include aluminum foil. The sealant film may be the same as that of the composition (1). In the same manner as in the configuration (1), a printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1.

Examples of the base film 1 constituting the components (9) and (10) include a PET film. The base film 2 may be a nylon film. Examples of the metal layer include aluminum foil. The sealant film may be the same as that of the composition (1). In the same manner as in the configuration (1), a printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1.

The substrate film 1 constituting (11) may be a PET film. Examples of the base film 2 include a PET film and a polyvinylidene fluoride film.

In these configurations, the coating agent of the present invention is applied to, for example, the outer side of the base film 1 (the surface of the base film 1 opposite to the side on which the sealant film is disposed), and a coating layer may be disposed at another position.

Further, so-called inline coating may be performed in which the coating agent of the present invention is applied to an unstretched film and the coated film is stretched.

Further, the thermoplastic resin film is preferably subjected to corona discharge treatment. Silica, alumina, or the like may be deposited by evaporation, or a gas barrier coating such as an oxygen barrier layer may be laminated.

When paper is used as the substrate, a moisture-proof paper can be produced. As the base paper, kraft paper, lining paper, coated paper, and board paper can be mentioned.

When synthetic paper is used as the base material, moisture-proof synthetic paper can be produced. The structure of the synthetic paper is not particularly limited. Therefore, the structure may be a single-layer structure or a multilayer structure. Examples of the multilayer structure include a two-layer structure of a base material layer and a surface layer, a three-layer structure of a base material layer and a surface layer on the front and back surfaces thereof, and a multilayer structure in which another resin film layer is present between the base material layer and the surface layer. Each layer may or may not contain an inorganic filler or an organic filler. Further, a microporous synthetic paper having a plurality of fine pores may also be used.

The method for applying the coating agent of the present invention to a substrate is not particularly limited, and gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain coating, spray coating, dip coating, brush coating, and the like can be used. The amount of the coating agent to be applied may be determined as appropriate depending on the substrate. In the case where the substrate is a thermoplastic resin film, the thickness of the coating layer in the present invention is desirably at least more than 0.1 μm in order to sufficiently improve the water vapor barrier property. From the viewpoint of water vapor barrier properties, a thick coating layer is preferable, but the present invention is characterized in that the water vapor barrier properties are exhibited even if the coating layer is thin, and therefore, if the coating agent of the present invention is used, the characteristics of the substrate can be utilized and the water vapor barrier properties can be improved. Therefore, the thickness of the coating layer of the present invention is preferably 0.1 to 10 μm, more preferably 0.2 to 8 μm, and particularly preferably 0.3 to 7 μm.

In addition, the base material isWhen a substrate such as paper, woven fabric, knitted fabric, or nonwoven fabric into which a coating agent is impregnated is used, it is difficult to evaluate the coating amount based on the film thickness, and therefore, the coating quality after drying is used for evaluation. The coating mass after drying is only 1 to 200g/m²The above range may be used.

After the coating agent of the present invention is applied to a substrate, the drying temperature when the solvent is dried is preferably 40 to 150 ℃, more preferably 40 to 130 ℃, and still more preferably 40 to 120 ℃. Preferably, an aging step is further provided after drying. The curing conditions may be appropriately adjusted at 25 to 100 ℃ for 12 to 240 hours.

Further, another base material may be further bonded to the coating layer of the laminate treated with the coating agent of the present invention. The combinable substrate may be used by appropriately selecting a metal foil such as aluminum, or the like, in addition to the above-mentioned substrates such as a thermoplastic resin film, paper, synthetic paper, wood, woven cloth, knitted cloth, nonwoven cloth, or the like, and may be the same or different. Further, the laminates of the present invention may be combined with each other.

As a method for attaching another substrate, the coating layer may be attached to another substrate with an adhesive, or another substrate may be laminated on the coating layer by extrusion lamination or the like.

< packaging Material and processed article >

The laminate of the present invention is excellent in water vapor barrier properties and therefore can be used for applications such as paper cups, moisture-proof corrugated paper, moisture-proof paper, and water vapor barrier films; packaging of objects that are not resistant to water drops, moisture; packaging of objects requiring prevention of diffusion of internal moisture to the outside, such as wet tissues; and various applications such as a front sheet and a back sheet of a solar cell, which require prevention of deterioration of a base material due to moisture after long-term use.

Further, the laminate of the present invention is also excellent in solvent resistance, and therefore, can be preferably used for packaging materials such as shampoo and hair conditioner. Such contents may deteriorate the adhesive layer and cause a decrease in adhesive strength, and if a coating layer formed from the coating agent of the present invention is provided between the adhesive layer and the contents, deterioration of the adhesive layer can be suppressed.

The laminate of the present invention can be suitably used for various applications such as extrusion packaging for storing foods, medical products, daily necessities, strap packaging, packaging material for battery packaging materials, packaging material for capacitor packaging materials, and the like by molding.