JP2009000924A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate having a coating layer that develops superior adhesion between polypropylene and polyester, polyethylene and polyester and between molded articles, sheets and films of various resins and that exhibits water resistance. <P>SOLUTION: The laminate is manufactured by coating and drying a coating material containing a water dispersion comprising a propylene-based elastomer and/or a styrene-based elastomer, a polyester and/or an acrylic resin and/or a urethane resin, and water, or comprising a water dispersion comprising an ethylene-based elastomer and/or a styrene-based elastomer, a polyester and/or an acrylic resin and/or a urethane resin, and water. Accordingly, the coating layer exhibits excellent adhesion between polypropylene and polyester and between polyethylene and polyester and in mutually bonding molded articles, sheets and films of various resins and also exhibits water resistance, having the effects not encountered before, and it can be used for wide industrial applications. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to various olefinic resins and polyesters obtained by coating and drying various elastomers, polyester and / or acrylic resins and / or urethane resins, and a coating material containing an aqueous dispersion composed of water. The present invention relates to a laminate having a coating layer excellent in adhesion to water and water resistance.

Conventionally, polyolefins and polyesters have many advantages such as generally high productivity and various moldability, light weight and rust prevention, etc., so interior and exterior of automobiles and ships, various packaging materials, home appliances, etc. It is widely used as furniture, miscellaneous goods, building materials, etc.
In particular, polypropylene, polyethylene, and polyester are used in a wide range of fields, and these are often used in multiple layers. As a method for adhering these, an adhesive such as a solvent-based, aqueous-based, or hot melt is used.
Recently, water-based adhesives have been developed due to increasing awareness of environmental problems. A method of dispersing a kneaded material composed of a thermoplastic resin and a water-soluble polymer in water (Patent Document 1), an olefin Proposed are a method of obtaining a water dispersion by melt-kneading a saponified resin and saponified polyvinyl alcohol (Patent Document 2), an aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer (Patent Document 3), and the like. .
Japanese Patent Laid-Open No. 51-12835 JP-A-56-2149 JP 2000-72879 A

However, these use water-soluble materials and surfactants to make them water-based, or use many functional groups with high polarity and high hydrophilicity, so that the water resistance of the coating film and the adhesion to the olefin substrate are low. The problem of deteriorating arises.
An object of the present invention is to improve the above-mentioned problems and provide a laminate having a polyolefin. Specifically, it is excellent in molded products, sheets and films of various resins of polypropylene and polyester, polyethylene and polyester. Another object of the present invention is to provide a laminate having a coating layer that exhibits excellent adhesion and water resistance.

  As a result of intensive studies and studies to achieve the above object, the present inventors have found that a propylene elastomer and / or a styrene elastomer, a polyester and / or acrylic resin and / or a urethane resin, water, It is obtained by coating and drying a coating material containing an aqueous dispersion consisting of: excellent adhesion to propylene resin and polyester, excellent water resistance, or ethylene elastomer and / or styrene elastomer and polyester It is obtained by coating and drying a coating material containing an aqueous dispersion comprising acrylic resin and / or urethane resin and water, and having excellent adhesion to ethylene resin and polyester and water resistance. As a result, the present invention has been completed.

That is, the present invention is specified by the following (1) to (5).
(1) A water dispersion comprising a propylene elastomer (A) and / or a styrene elastomer (C), a polyester (D) and / or an acrylic resin (E) and / or a urethane resin (F), and water. A laminate comprising a coating layer obtained by coating and drying a coating material to be contained, wherein one base material is a propylene-based resin and the other base material is polyester.
(2) An aqueous dispersion composed of ethylene elastomer (B) and / or styrene elastomer (C), polyester (D) and / or acrylic resin (E) and / or urethane resin (F), and water. A laminate comprising a coating layer obtained by coating and drying a coating material containing, wherein one substrate is made of an ethylene-based resin and the other substrate is made of polyester.
(3) The coating material contains an aqueous dispersion of petroleum hydrocarbon resin (G) and / or rosin resin (H) and / or terpene resin (I) (1 ) Or (2).
(4) Propylene elastomer (A) and / or styrene elastomer (C) 10 to 90 parts by weight, polyester (D) and / or acrylic resin (E) and / or urethane resin (F) 10 to 90 parts by weight Part, petroleum hydrocarbon resin (G) and / or rosin resin (H) and / or terpene resin (I) 0-50 parts by weight, (A) and / or (C), (D) And / or (E) and / or (F), (G) and / or (H) and / or (I), wherein the total is 100 parts by weight. The laminated body as described in 1).
(5) 10 to 90 parts by weight of ethylene elastomer (B) and / or styrene elastomer (C) and 10 to 90 weights of polyester (D) and / or acrylic resin (E) and / or urethane resin (F) Part, and petroleum hydrocarbon resin (G) and / or rosin resin (H) and / or terpene resin (I) 0 to 50 parts by weight, (B) and / or (C), (D) And / or (E) and / or (F), (G) and / or (H) and / or (I), wherein the total is 100 parts by weight. The laminated body as described in 2).

  According to the present invention, polypropylene and polyester, polyethylene and polyester, molded products of various resins, sheets, films having excellent adhesiveness between water and water, and having an unprecedented action and effect in a wide range of industrial applications. Can be used.

Details of the present invention will be described below.
[Propylene Elastomer (A)]
Examples of the propylene-based elastomer (A) used in the present invention include polypropylene, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / 1-butene / ethylene copolymer, propylene / ethylene / 1-butene. Examples thereof include an α-olefin alone or two or more types of copolymers containing a propylene component of 50 mol% or more, represented by a copolymer.
Among these, the weight average molecular weight (hereinafter abbreviated as Mw. The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard) is usually 10,000 to 700. In the range of 30,000, preferably 30,000 to 500,000.

[Ethylene elastomer (B)]
Examples of the ethylene elastomer (B) used in the present invention include polyethylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-butene / propylene copolymer, ethylene / propylene / 1-butene. Examples thereof include an α-olefin alone or two or more types of copolymers containing 50 mol% or more of an ethylene component, which is represented by a copolymer.
Among these, the weight average molecular weight (hereinafter abbreviated as Mw. The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard) is usually 10,000 to 700. In the range of 30,000, preferably 30,000 to 500,000.

[Styrene elastomer (C)]
Examples of the styrene elastomer (C) used in the present invention include hydrogenated styrene-conjugated diene block copolymers, hydrogenated styrene-conjugated diene random copolymers, and the like. Examples of the constitution of the hydrogenated product of the polymer include a hydrogenated product of a styrene-conjugated diene diblock copolymer, a hydrogenated product of a styrene-conjugated diene-styrene triblock copolymer, and the like. Examples of the conjugated diene used here include butadiene and isoprene.

Among these, a hydrogenated styrene-isoprene-styrene triblock copolymer, a hydrogenated styrene-butadiene-styrene triblock copolymer, and a hydrogenated styrene-butadiene random copolymer are preferred. .
The content of styrene used here is usually in the range of 2 to 60% by weight, more preferably 3 to 45% by weight.
The weight average molecular weight (hereinafter abbreviated as Mw) is preferably in the range of 10,000 to 700,000, and a hydrogenated product of styrene-isoprene-styrene copolymer or triblock copolymer of styrene-butadiene-styrene. In the combined hydrogenated product, 10,000 to 500,000 is preferable. Moreover, in the hydrogenated product of a styrene-butadiene copolymer, 10,000-700,000, Furthermore, 50,000-500,000 are preferable.

Said elastomer can be used individually or in combination of 2 or more types.
The propylene-based elastomer (A), the ethylene-based elastomer (B), and the styrene-based elastomer (C) are prepared by the following method using a salt of the acid-modified polyolefin (J) and / or a salt of the higher fatty acid (K). Can be dispersed in water.

As the salt of the acid-modified polyolefin (J) used in the present invention, a group of a carboxylic acid salt bonded to a polyolefin polymer chain (including a carboxylic acid group in the case of a partially neutralized product or a partially saponified product), It is an olefin resin containing 0.05 to 5 mmol, preferably 0.1 to 4 mmol as —COO— groups per gram of resin.
The acid-modified polyolefin (J) is, for example, a single monomer having a neutralized or non-neutralized carboxylic acid group and / or a saponified or unsaponified carboxylic acid ester. The monomer can be obtained by graft copolymerization.

  The molecular weight of the acid-modified polyolefin (J) is preferably a single olefin or a copolymer of two or more having a number average molecular weight (Mn) measured by GPC in the range of 500 to 10,000. Specific examples of olefins include ethylene, propylene, butene, pentene, hexene, octene and the like. Among these, in the case of propylene-based elastomer (A), propylene homopolymer and propylene / olefin copolymer are used, and in the case of ethylene-based elastomer (B), ethylene homopolymer and ethylene / olefin copolymer are used in styrene In the case of the elastomer (C), an ethylene homopolymer, a propylene homopolymer, an ethylene / olefin copolymer, and a propylene / olefin copolymer are preferable.

Examples of the monomer having a neutralized or non-neutralized carboxylic acid group and the monomer having a saponified or non-saponified carboxylic acid ester group include, for example, ethylenically unsaturated carboxylic acid , Anhydrides thereof or esters thereof.
Examples of the ethylenically unsaturated carboxylic acid (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic ^TM (Endoshisu as its anhydride -Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, and the like, as unsaturated carboxylic acid ester, methyl of the above ethylenically unsaturated carboxylic acid, Examples include monoesters or diesters such as ethyl or propyl. These monomers can be used alone or in combination.

In order to produce a modified product by graft copolymerization of a graft monomer selected from the above monomers with a grafted polymer, various conventionally known methods can be employed. Examples thereof include a method of melting a grafted polymer and adding a graft monomer and graft copolymerizing, or a method of dissolving in an organic solvent and adding a graft monomer and graft copolymerizing. In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a polymerization initiator (L-1).
The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The ratio of the polymerization initiator used is usually in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the grafted polymer.

  As a polymerization initiator (L-1) used here, di-tert-butyl peroxide, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide , Lauroyl peroxide, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide , Tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert-butylperoxide) hexane, tert -Butylbenzoate, tert-butylpe Organic peroxides such as phenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumene hydroperoxide, azobisisobutyronitrile, 4,4′- And azo compounds such as azobis (4-cyanopentanoic acid) and 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) propioamide). These can be used alone or in admixture of two or more.

  Among these polymerization initiators, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5- ( Dialkyl peroxides such as tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

Examples of the basic substance (M) used for neutralization and saponification include alkali metals such as sodium and potassium, inorganic amines such as hydroxylamine and ammonium hydroxide, organic amines such as methylamine and ethanolamine, ammonia, sodium oxide, Mention may be made of sodium peroxide, alkali metal and alkaline earth metal oxides, hydroxides, weak salts of alkaline earth metals such as sodium carbonate and the like.
As the carboxylic acid group or carboxylic acid ester group neutralized or saponified with a basic substance, a carboxylic acid alkali metal salt such as sodium carboxylate or potassium carboxylate or ammonium carboxylate is preferred.

  The salt of higher fatty acid (K) used in the present invention is preferably a salt of a fatty acid having 25 to 60 carbon atoms, more preferably an alkali metal salt, alkaline earth metal salt or amine of a fatty acid having 25 to 40 carbon atoms. Salts, and alkali metal salts of montanic acid and oleic acid are preferable.

The salt of higher fatty acid (K) may contain a higher fatty acid and / or an ester of higher fatty acid in addition to the salt of higher fatty acid. The alcohol residue constituting the ester preferably has 2 to 30 carbon atoms, and particularly preferably 6 to 20 carbon atoms. Residues can be linear or branched. A mixture of different carbon numbers may be used. Specific examples of the alcohol residue include residues of higher alcohols such as cetyl alcohol, stearyl alcohol, and oleyl alcohol. Montanic acid ester wax and montan wax are particularly suitable.
The salt of higher fatty acid (K) can be obtained by neutralizing the higher fatty acid and / or saponifying the higher fatty acid ester. In this case, it may be a partially neutralized product or a partially saponified product in which fatty acids or fatty acid esters not neutralized or saponified coexist. Examples of the basic substance that can be used for neutralization and saponification are the same as those mentioned for the salt of the acid-modified polyolefin (J).

  Furthermore, in order to improve the dispersion stability in water, various surfactants (N) can be used. For example, anionic surfactants such as alkyl naphthalene sulfonates and metal soaps (Zn, Al, Na, K salts), nonionic surfactants such as fatty acid monoglycerides, alkyl ammonium chlorides, amphoteric surfactants and water-soluble surfactants And valent metal salts. These surfactants can be used individually by 1 type or in mixture of 2 or more types. The amount of the surfactant (N) used is preferably about 0.05 to 40% by weight, more preferably 0.1 to 20% by weight, and particularly preferably 0.1 to 10% by weight with respect to various elastomers.

In the aqueous dispersion of various elastomers used in the present invention, it is desirable to contain the respective components in a certain quantitative ratio range. That is, the salt of acid-modified polyolefin (J) and / or the salt of higher fatty acid (K) is desirably contained in an amount of 0.5 to 30% by weight, preferably 1 to 20% by weight, based on 100 parts by weight of various elastomers. .
Further, the surfactant (N) added as desired is preferably blended in an amount of 0.1 to 40 parts by weight, particularly 0.2 to 20 parts by weight, per 100 parts by weight of various elastomers.

  The water content is 1 to 25% by weight, preferably 1 to 20% by weight, based on various elastomers. When the water content is less than 1% by weight, phase inversion (the resin solid content is changed from a continuous phase to a dispersed phase by water) hardly occurs, and a suitable aqueous dispersion cannot be obtained. If it exceeds 25% by weight, the aqueous dispersion has fluidity. That is, by setting the content within the range of 1 to 25%, an apparently solid aqueous dispersion can be obtained.

  The above-mentioned aqueous dispersion is obtained by melt-kneading the various elastomers and the acid-modified polyolefin and / or the fatty acid and / or the fatty acid ester, adding a basic substance (M) and water, and further melt-kneading. , Neutralization and / or saponification and dispersion (phase inversion) of the elastomer into the aqueous phase, or water in advance as a basic substance in the acid-modified polyolefin and / or the fatty acid and / or the fatty acid ester. Is added, and neutralized and / or saponified, melted and kneaded with the elastomer, further added with water, and melt-kneaded to disperse the elastomer into the aqueous phase (phase inversion). It is preferable to be manufactured.

The former method is preferred because it is simple and a uniform particle size can be obtained. The melt kneading means used for phase inversion may be any known means, but preferably a kneader, a Banbury mixer, or a multi-screw extruder can be exemplified.
The ratio of the basic substance addition amount for neutralization or saponification is 60 to 200%, preferably 80 to 170% of the total carboxylic acid or carboxylic acid ester.
Moreover, although the water dispersion obtained by melt-kneading and phase inversion contains 1 to 25% of water, it can be obtained with this water content or by adding water to this to lower the viscosity. .

[Polyester (D)]
Examples of the polyester (D) used in the present invention include polyesters such as aromatic polyesters, aliphatic polyesters, saturated polyesters and unsaturated polyesters. These are mainly polycondensates of an acid component monomer (O) and an alcohol component monomer (P).

  Examples of the acid component monomer (O) include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acids, 4,4′-diphenyldicarboxylic acid, trimellitic acid, trimesic acid, pyromellitic acid, benzoic acid, p-oxy Benzoic acid, p- (hydroxyethoxy) benzoic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, suberic acid, brassic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, 1,4 -Use cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, hexahydroorthophthalic acid, tricyclodecanedicarboxylic acid, tetrahydroterephthalic acid, and tetrahydroorthophthalic acid, or methyl esters or anhydrides of these acids. be able to. Among these, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, trimellitic anhydride are preferably used, and these acid component monomers can be used alone or in combination.

  Examples of the alcohol component monomer (P) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1 , 4-butanediol, 1,2-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-2-butyl- 1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol, polypropylene glycol, poly Tetramethylene glycol, trimethylo Propane, trimethylolethane, glycerin, pentaerythritol, bisphenol-based ethylene oxide adduct, bisphenol-based propylene oxide adduct, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1, 3-cyclohexanediol, hydrogenated bisphenol A, spiroglycol, tricyclodecanediol, tricyclodecane dimethanol, resorcinol, 1,3-bis (2-hydroxyethoxy) benzene, etc. are used, among which ethylene glycol, diethylene glycol, tri Ethylene glycol, 1,4-butanediol, and neopentyl glycol are preferably used, and these alcohol component monomers are used alone or in combination. It is possible.

  The polyester used in the present invention can be produced by a known method such as a melt polymerization method, a solution polymerization method, or a solid phase polymerization method. The method for dispersing the obtained polyester in water is not particularly limited, but the polyester containing a functional group that can be neutralized with a basic substance such as an acid is dissolved in an organic solvent (Q), and the basic polyester is dissolved. After neutralizing with substance (M), after removing organic solvent (Q) or dissolving in organic solvent (Q) and mechanically shearing in the presence of emulsifier (R) and dispersing in water A method of removing the organic solvent (Q), a method of melt kneading with the emulsifier (R), adding an aqueous solution of water or a basic substance (M) thereto, and dispersing the resin raw material in water, or the above Examples of the method are the same as those for obtaining an aqueous dispersion of various elastomers.

  Examples of the organic solvent (Q) used in the present invention include aromatic hydrocarbons such as xylene, toluene, and ethylbenzene, ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3 methoxy Organic solvents such as ester solvents such as butyl acetate and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be used, and a mixture of two or more of these may be used.

In the method of neutralizing these acids and the like with a basic substance, the acid value of the polyester is preferably 1 to 80 KOHmg / g, more preferably 3 to 70 KOHmg / g.
In addition, in the method of using the emulsifier (R) in the presence of the organic solvent (Q) or the method of melt kneading with the emulsifier (R), the amount of the emulsifier is preferably in the range of 0.1 to 25 parts by weight, The range of 0.5 to 20 parts by weight is preferable.
Examples of the emulsifier (R) used here include acid-modified polyolefin (J), surfactant (N), carboxymethylcellulose, polyacrylic acid, polyvinyl alcohol, sulfonate-containing polyester (S), and the like. Two or more kinds may be used in combination.

  The sulfonate-containing polyester (S) used in the present invention is mainly a polycondensate of an acid component monomer (O) and an alcohol component monomer (P), but a sulfonic acid bonded to a polymer. It is a polyester containing a salt. As the sulfonic acid-containing monomer, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (p-sulfophenoxy) isophthalic acid, 5- (sulfopropoxy) isophthalic acid, 4-sulfonaphthalene-2, 7-dicarboxylic acid, sulfopropylmalonic acid, sulfosuccinic acid, 2-sulfobenzoic acid, 3,2-sulfobenzoic acid, 5-sulfosalicylic acid and methyl esters of these carboxylic acids, and metal salts and ammonium salts of these sulfonic acids Among them, a sodium salt of 5-sulfoisophthalic acid or a sodium salt of dimethyl 5-sulfoisophthalic acid is preferably used.

In addition, these sulfonic acid-containing component monomers are used in an amount corresponding to that the sulfonate-containing polyester is contained at a concentration of 0.1 to 1.5 mmol equivalent in terms of —SO ₃ ^— group per gram of polymer. It is preferable to use an amount corresponding to containing at a concentration of 0.2 to 1.0 mmol equivalent.
The melt-kneading means used in the present invention may be any known means, but preferred examples include a kneader, a Banbury mixer, a single-screw extruder, and a twin-screw extruder.

[Acrylic resin (E)]
The acrylic resin (E) used in the present invention is a resin comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers, As these copolymerizable monomers, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl ( (Meth) acrylate, stearyl (meth) acrylate , Tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl ( (Meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic acid esters such as diethylaminoethyl (meth) acrylate, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Hydroxyl group-containing vinyls such as 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, Carboxylic group-containing vinyls such as crylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, and monoesterified products thereof, glycidyl (meth) acrylate , Epoxy group-containing vinyls such as methyl glycidyl (meth) acrylate, isocyanate group-containing vinyls such as vinyl isocyanate and isopropenyl isocyanate, aromatics such as styrene, α-methylstyrene, vinyltoluene and t-butylstyrene Vinyls, acrylamides, methacrylamides, N-methylol methacrylamides, N-methylol acrylamides, diacetone acrylamides, maleic amides and other amides, vinyl acetates, vinyl propionates, etc. Esters, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (methacrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, Aminoalkyl (meth) acrylates such as N, N-dibutylaminoethyl (meth) acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate, styrene sulfonic acid, sodium styrene sulfonate, 2-acrylamido-2-methyl Unsaturated sulfonic acids such as propanesulfonic acid, unsaturated phosphoric acids such as mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) acid phosphate, other acrylonitrile, methacrylonitrile, 2-methyl Carboxyethyl acrylate, 2-ethoxyethyl acrylate, ethylene, _propylene, alpha-olefin C 4 _{-C 20,} 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6, Examples include 6-tetramethyl-4-piperidyl (meth) acrylate and 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole. Moreover, the macromonomer etc. which have the said monomer or its copolymer in a segment, and have a vinyl group at the terminal can also be used.

Examples of the copolymerizable monomer comprising other copolymerizable monomers used in the present invention include carboxylic anhydrides such as maleic anhydride and citraconic anhydride.
Moreover, description like the methyl (meth) acrylate described here shows methyl acrylate and methyl methacrylate.

  As a method for producing an aqueous dispersion of a resin comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers used in the present invention, Although not limited, for example, a basic substance (M) is added to a resin solution obtained by solution polymerization in which a copolymerizable monomer and a polymerization initiator (L-1) are polymerized in an organic solvent (Q). , A method of removing an organic solvent after adding ion-exchanged water, an emulsion polymerization method of polymerizing a copolymerizable monomer in the presence of a surfactant (N) and a polymerization initiator (L-2) in water, and the like. A resin obtained by removing a solvent of a resin solution obtained by a method or a solution polymerization in which a copolymerizable monomer and a polymerization initiator (L-1) are polymerized in an organic solvent (Q) is used for the above various elastomers. Manufactured by a method of dispersing in water, such as by obtaining a water dispersion can do.

The method for obtaining a resin comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers according to the present invention. The monomer must contain an acidic group that can be neutralized with a basic substance (M). Specifically, the acid value of the resin using the carboxyl group-containing vinyls described in the copolymerizable monomer is preferably 4 KOHmg / g or more, and more preferably 7 KOHmg / g or more. When the acid value is less than 4 KOHmg / g, the hydrophilicity becomes low and it becomes difficult to make it water-based. The acid value described above is a value in a resin (solid) excluding a solvent.
It is used to synthesize a resin comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group of the present invention and other copolymerizable monomers.

Moreover, as a polymerization initiator (L-2), persulfates, such as ammonium persulfate, potassium persulfate, and sodium persulfate, hydrogen peroxide, the polymerization initiator (L-1) described above, or these and iron Examples include metal ions such as ions and redox initiators in combination with reducing agents such as sodium sulfoxylate, formaldehyde, sodium pyrosulfite, sodium hydrogen sulfite, L-ascorbic acid, Rongalite, etc., one or two of these The above can be used.
The amount of these polymerization initiators used is usually 0.1 to 10% by weight based on the total amount of monomers.
Furthermore, in order to improve the stability to water, said surfactant (N) can be used.

  As a resin comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers used in the present invention, the Tg measured by DSC is −60 ° C. -80 degreeC is preferable, More preferably, it is -30 degreeC-50 degreeC. Further, the weight average molecular weight by GPC is preferably 1000 to 500000, and more preferably 5000 to 200000.

[Urethane resin (F)]
Examples of the polyfunctional isocyanate compound that is a component constituting the urethane resin (F) used in the present invention include various aliphatic polyisocyanates such as ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and octamethylene diisocyanate. Isocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato- n-butylidene) pentaerythritol, diisocyanate dimate Such as alicyclic polyisocyanate, phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane -2,4,4'-triisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenyl ether diisocyanate, and other aromatic polyisocyanates, thiodiethyl diisocyanate, thiopropyl diisocyanate, thiodihexyl diisocyanate, dimethylsulfone diisocyanate, etc. Sulfur-containing aliphatic isocyanate, diphenyl sulfide-2,4'-diisocyanate, diph Aromatic disulfide isocyanates such as phenyl sulfide-4,4'-diisocyanate, aliphatic disulfide isocyanates such as diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide-5,5'-diisocyanate Aromatic sulfone isocyanate such as diphenylsulfone-4,4′-diisocyanate, diphenylsulfone-3,3′-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester, etc. Sulfonic acid ester isocyanate, 4,4'-dimethylbenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-dimethoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate And sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate, 1,4-dithian-2,5-diisocyanate, and the like.

  In addition, these alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, burette-modified products, dimerization or trimerization reaction products are also used. However, polyfunctional isocyanate compounds other than the above compounds may be used. Moreover, these polyfunctional isocyanate compounds can also be used by 1 type, or 2 or more types of mixtures.

  Of the above compounds, the obtained resin, and the yellowing resistance, thermal stability, light stability of the film after coating it and forming a film, or the availability of a polyfunctional isocyanate compound From the aspect, aliphatic polyisocyanates and alicyclic polyisocyanate compounds are preferable, and among them, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,5-bisisocyanate methylnorbornane, 2,6- Bisisocyanatomethylnorbornane and derivatives thereof are particularly preferred.

Examples of the active hydrogen compound having at least two active hydrogen groups capable of reacting with the polyfunctional isocyanate compound per molecule include the following. Polyol compound: ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,3-butanediol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, Pentaerythritol, dipentaerythritol, sorbitol, erythritol, hexanetriol, triglycerose, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, cyclopentanediol, cyclohexanediol, tricyclo [5.2.1.0 ^2,6 ] Aliphatic polyols such as decane-dimethanol, bicyclo [4.3.0] -nonanediol, dicyclohexanediol , Aromatic polyols such as dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, bisphenol S, halogenated polyols such as dibromoneopentyl glycol, polyester polyol, polyethylene glycol, polyether polyol, Polythioether polyols, polyacetal polyols, polycarbonate polyols, polycaprolactone polyols, silicon polyols, flanged methanol, and condensation reactions of organic acids such as oxalic acid, adipic acid, acetic acid, phthalic acid, isophthalic acid, and pyromellitic acid with the above polyols Product, addition reaction between the polyol and alkylene oxide such as ethylene oxide or propylene oxide Product, addition reaction product of alkylene polyamine and alkylene oxide, 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol valeric acid, 3 1,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, and their caprolactone-modified products, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, and the like.

  Among these, a polyester polyol having a polyester skeleton is preferable in terms of adhesion.

  In addition, polyamino compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, hexamethylenediamine, cyclohexylenediamine, phenylenediamine, tolylenediamine and xylenediamine, and α-amino acids such as serine, lysine and histidine should also be used. Can do.

  In the present invention, the active hydrogen compound is preferably a straight-chain compound having no branched skeleton, and further, a polyester polyol, polyether polyol, polycarbonate polyol having a melting point (Tm) of 40 ° C. or lower, It is preferable to use 50 parts by weight or more and 98 parts by weight or less of polycaprolactone polyol, polyolefin polyol and copolymers or mixtures thereof in 100 parts by weight of all active hydrogen compounds. When the amount is less than 50 parts by weight, the texture of the film obtained from the aqueous coating material tends to deteriorate, and when it exceeds 98 parts by weight, the film strength and hardness tend to decrease. These compounds may be used alone or in combination of two or more.

  In addition, in order to stably disperse the urethane resin (F) used in the present invention in water, known materials and stabilization techniques can be used, but one kind of carboxyl group, sulfonyl group and ethylene oxide group is used in the molecule. It preferably has at least one, and more preferably has at least one carboxyl group and / or sulfonyl group.

  Examples of constituents for introducing these atomic groups include 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol valeric acid, 3,4- Examples include, but are not limited to, diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, polyethylene glycol, polyaddition product of ethylene oxide and propylene oxide, and a polymer of ethylene glycol and the active hydrogen compound. It is not something. By introducing these atomic groups into the molecule, the mechanical stability of the resin and the miscibility with other components tend to be improved.

  The preferred amount when using the carboxyl group and / or sulfonyl group-containing compound is such that the acid value in terms of solid content of the urethane resin aqueous dispersion is in the range of 2 to 35 KOHmg / g, more preferably 3 to 30 KOHmg / g. It is. If the acid value is less than the above range, the mechanical stability of the resin tends to be high.

  Although the manufacturing method of a urethane resin (F) is not specifically limited, The following methods are mentioned. A polyfunctional isocyanate compound, a compound having an active hydrogen group capable of reacting with an isocyanate group in the active hydrogen compound, an active hydrogen group capable of reacting with an isocyanate group in the compound, and a carboxyl group in the molecule; Urethane having an isocyanate group at the molecular end by reacting at least one compound having a sulfonyl group or an ethylene oxide group at an equivalent ratio such that the isocyanate group is excessive in the presence or absence of a suitable organic solvent. A prepolymer is produced, and then the prepolymer having a carboxyl group and / or a sulfonyl group is neutralized with a neutralizing agent such as a tertiary amine, and then this neutralized prepolymer is added with a chain extender-containing agent. After putting it into an aqueous solution and reacting it, if the system contains an organic solvent, it can be removed. Obtained by the above method, the method obtained by reacting the unneutralized urethane prepolymer obtained by the above method with an aqueous solution containing a neutralizing agent and containing a chain extender, and the above method In the neutralized urethane prepolymer, an aqueous solution having a chain extender is added and reacted, or in the unneutralized urethane prepolymer obtained by the above method, a neutralizing agent is contained, and There is a method of adding an aqueous solution having a chain extender and reacting to obtain an aqueous dispersion.

  The neutralizing agent used in the present invention is not particularly limited, but alkanolamines such as N, N-dimethylethanolamine and N, N-diethylethanolamine, N-methylmorpholine, and N-ethyl. Tertiary amines such as morpholine, pyridine, N-methylimidazole, ammonia, trimethylamine, triethylamine, alkali metals such as lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide Examples of the compound include quaternary ammonium compounds such as tetramethylammonium hydroxide, and these compounds can be used alone or as a mixture of two or more.

  The use amount of the neutralizing agent is preferably 0.5 to 3 equivalents, more preferably 0.7 to 1 with respect to 1 equivalent of carboxyl group and / or sulfonyl group in the polyurethane resin having the carboxyl group and / or sulfonyl group. .5 equivalents. If it is less than the above range, the stability of the urethane resin (F) in water tends to be lowered.

  Examples of the chain extender used in the present invention include water, ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, butylenediamine, hexamethylenediamine, cyclohexylenediamine, piperazine, 2-methylpiperazine, phenylenediamine, and tolylenediamine. , Xylenediamine, α, α′-methylenebis (2-chloroaniline), 3,3′-dichloro-α, α′-biphenylamine, m-xylenediamine, isophoronediamine, NBDA (trade name, Mitsui Chemicals, Inc.) N-methyl-3,3'-diaminopropylamine, and polyamines such as an adduct of diethylenetriamine and acrylate or a hydrolysis product thereof are suitable.

  Examples of the solvent used in obtaining the aqueous dispersion of the urethane resin (F) include ketones such as methyl ethyl ketone and acetone, esters such as methyl acetate and ethyl acetate, tetrahydrofuran, and the like. The solvent is not particularly limited as long as it is not higher than ° C. These solvents can be used alone or in a mixed state of two or more. Use of a solvent having a boiling point exceeding 100 ° C., that is, exceeding the boiling point of water, makes it difficult to completely remove only the solvent from the solution after forming the aqueous dispersion, and the high boiling point solvent remains in the film. When it is unavoidably used for performance, it is preferably used in an amount of 10 parts by weight or less with respect to 100 parts by weight of the aqueous dispersion of the urethane resin (F).

  Moreover, the water dispersion of the urethane resin (F) used by this invention can be used also as a modified body by making it react with other components, such as another monomer and a resin component. Furthermore, in the aqueous dispersion of the urethane resin (F) obtained in the present invention, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, methacrylamide, styrene, acrylonitrile, butadiene, vinyl acetate, ethylene, It can also be used as a composite obtained by polymerizing at least one monomer such as propylene, itaconic acid, maleic acid and the like.

Among the aqueous dispersions of the urethane resin (F) thus obtained, the elongation at break is preferably 0.1 to 800%.
Furthermore, in order to improve the stability to water, said surfactant (N) can be used.

[Petroleum hydrocarbon resin (G)]
Examples of the petroleum hydrocarbon resin (G) used in the present invention include an aliphatic petroleum resin whose main raw material is a C5 fraction of tarnaphtha, an aromatic petroleum resin whose main raw material is a C9 fraction, and those Copolymeric alicyclic. C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) C9 fraction copolymerized resin), styrene, indene, coumarone, coumarone indene resin containing dicyclopentadiene, etc., and condensation of ρ-tertiarybutylphenol and acetylene. Examples thereof include alkylphenol resins typified by products, xylene resins obtained by reacting o-xylene, ρ-xylene, and m-xylene with formalin. These can be used alone or in combination of two or more. Among these, petroleum hydrocarbon resins having a weight average molecular weight of 1,000 to 50,000 as measured by GPC are preferable, and 1,500 to 30,000 are particularly preferable. Moreover, what has a polar group in these resin is still more preferable.

[Rosin resin (H)]
Examples of the rosin resin (H) used in the present invention include modified rosin modified with natural rosin, polymerized rosin, maleic acid, fumaric acid, (meth) acrylic acid and the like. Examples of the rosin derivative include esterified products, phenol-modified products and esterified products of the above rosins, and hydrogenated products thereof can also be mentioned.

[Terpene resin (I)]
Examples of the terpene resin (I) used in the present invention include resins comprising α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, and the like. Α-pinene, β-pinene, Examples thereof include aromatic-modified terpene resins obtained by polymerizing aromatic monomers such as styrene on limonene, dipentene, and the like, and hydrogenated products thereof can also be mentioned. Among these, terpene phenol resins, aromatic modified terpene resins, and hydrogenated products thereof are preferable.

  In the present invention, petroleum hydrocarbon resin (G), rosin resin (H), and terpene resin (I) can be used in combination.

  These can be used by mixing those dispersed in water by a known method, but propylene elastomer (A), ethylene elastomer (B), styrene elastomer (C) and polyester (D). It can also be used after being mixed with acrylic resin (E) or urethane resin (F) and then dispersed in water.

  In the present invention, when one base material is a propylene-based resin and the other base material is a polyester, the propylene-based elastomer (A) and / or the styrene-based elastomer (C) described above is 10 to 90 parts by weight, 10 to 90 parts by weight of polyester (D) and / or acrylic resin (E) and / or urethane resin (F), petroleum hydrocarbon resin (G) and / or rosin resin (H) and / or terpene System resin (I) comprising 0 to 50 parts by weight, (A) and / or (C), (D) and / or (E) and / or (F), (G) and / or (H) and / or Or it is preferable to mix so that the total sum of (I) may be 100 weight part, (A) and / or (C) 20-80 weight part, (D) and / or (E) and / or ( F) 20-80 weight And (G) and / or (H) and / or (I) 0 to 50 parts by weight, and (A) and / or (C), (D) and / or (E) and / or (F) ), (G) and / or (H) and / or (I) are more preferably mixed so that the total amount is 100 parts by weight.

  Moreover, when one base material consists of ethylene-type resin and the other base material consists of polyester, ethylene-type elastomer (B) and / or (C) 10-90 weight part as described above, (D) and (E) and / or (F) 10 to 90 parts by weight and (G) and / or (H) and / or (I) 0 to 50 parts by weight, (B) and / or (C) , (D) and / or (E) and / or (F), (G) and / or (H) and / or (I) are preferably mixed so that the total amount is 100 parts by weight, B) and / or (C) 20 to 80 parts by weight, (D) and / or (E) and / or (F) 20 to 80 parts by weight, (G) and / or (H) and / or ( I) 0 to 50 parts by weight, (B) and / or (C), (D) and / or It is more preferable to be mixed in a (E) and / or (F), the total sum 100 parts by weight of (G) and / or (H) and / or (I).

  The shape of the substrate used in the present invention is not particularly limited, but at least one is preferably a sheet or a film.

  Other slipperiness imparting agents (for example, synthetic wax, natural wax, etc.), tackiness imparting agents, crosslinking agents, film forming aids, leveling agents, viscoelasticity modifiers, wetting agents, flame retardants (if necessary) For example, phosphorus-containing resins such as ammonium polyphosphate, phosphate esters, melamine, zinc borate, magnesium hydroxide, etc.), stabilizers, rust inhibitors, fungicides, UV absorbers, weathering stabilizers, heat stabilizers , Foaming agent, antifoaming agent, wetting agent, coagulant, gelling agent, anti-aging agent, softening agent, plasticizer, flavoring agent, anti-sticking agent, mold release agent, anti-settling agent, antioxidant, charging Inhibitors, dyes, pigments (eg, titanium white, bengara, phthalocyanine, carbon black, permanent yellow, etc.), fillers (eg, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate) Additives such as kaolin, mica, asbestos, mica, calcium silicate), organic solvents, oils (mineral lubricants, mineral oils, synthetic oils, vegetable oils, etc.) are added to the extent that the object of the present invention is not impaired. May be.

These additives may be used alone or in combination of two or more. Such an additive may be used when the various elastomers obtained above are dispersed in water, or may be added after being dispersed in water.
Moreover, the hardening | curing agent which can react with active hydrogen and / or a hydroxyl group can be used for the composition which has active hydrogen and / or a hydroxyl group among this invention.

  For example, a laminate having a urethane bond can be obtained by mixing with a curing agent having an isocyanate group in the molecule. Examples of the curing agent include Takenate WB series (produced by Mitsui Takeda Chemical Co., Ltd.) in which an isocyanate group is treated with a blocking agent such as oximes, lactams, and phenols, and Elastron BN. Series (Daiichi Kogyo Seiyaku Co., Ltd.) etc. are mentioned.

  A resin synthesized from at least one of melamine, urea, benzoguanamine, glycoluril, and formaldehyde and formaldehyde, for example, a part of a methylol group by a lower alcohol such as methanol, ethanol, propanol, isopropanol, butanol, and isobutanol. Alternatively, amino resins which are all alkyl etherified can also be used as the curing agent.

  Furthermore, an oxazoline compound can also be used as a curing agent. Examples of the curing agent include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2- Examples thereof include isopropenyl-4-methyl-2-oxazoline.

The curing agent capable of reacting with the coating material of the present invention and active hydrogen and / or hydroxyl group can be used in an arbitrary ratio.
When the curing agent capable of reacting with active hydrogen and / or hydroxyl group is a curing agent having an isocyanate group, the mixing ratio of active hydrogen and isocyanate group is 0.5: 1.0 to 1.0: The range of 0.5 is preferable, and the range of 0.8: 1.0 to 1.0: 0.8 is more preferable.
When the curing agent capable of reacting with active hydrogen and / or a hydroxyl group is an amino resin, the weight ratio of the coating material / amino resin solid of the present invention is 95/5 to 20/80. The range of 90/10 to 60/40 is more preferable.

  Furthermore, when the curing agent capable of reacting with active hydrogen and / or hydroxyl group is an oxazoline compound, the weight ratio of the coating material / amino resin solid of the present invention is used in the range of 95/5 to 20/80. Is preferable, and the range of 90/10 to 60/40 is more preferable.

The mixture of the curing agents described above can be applied and cured as it is, but a reactive catalyst can be used in combination as required.
The method for applying the material of the present invention is not particularly limited, and can be performed by a method such as spraying, curtain coater, flow coater, roll coater, gravure coater, brush coating, or dipping. The application can usually be carried out easily at room temperature, and the drying method after application is not particularly limited, and it can be dried by an appropriate method such as natural drying or heat forced drying.
The thickness of the coating layer is not particularly limited because it is appropriately selected depending on the use of the laminate.

These laminates exist in a state of being sandwiched between a propylene-based resin and polyester, an ethylene-based resin and polyester, and a propylene-based resin and ethylene-based resin, and at least one of these base materials is a film or a sheet It is preferable.
Moreover, a coating layer can also be provided on the uncoated side of these laminates. If the base material is a propylene-based resin, apply a propylene-based elastomer; if the base material is an ethylene-based resin; apply an ethylene-based elastomer; Thus, a laminated body can be configured.

Hereinafter, although the manufacturing method and various test examples of the composition of this invention are given and demonstrated further, this invention is not limited at all by these Examples.
Aqueous dispersion of propylene-based elastomer (A) The aqueous dispersion of propylene-based elastomer (A) is a propylene-based elastomer (A), 100 parts by weight of a propylene-butene-ethylene copolymer (Degussa Japan Co., Ltd., VESTOPLAST 792), A biaxial screw in which 10 parts by weight of maleic anhydride-modified polypropylene wax (manufactured by Mitsui Chemicals, high wax NP0555A) as acid-modified polypropylene (J) and 3 parts by weight of potassium oleate as higher fatty acid (K) are mixed It is supplied at a rate of 3000 g / hour from the hopper of an extruder (Ikegai Iron Works Co., Ltd., PCM-30, L / D = 40), and 20% of potassium hydroxide from the supply port provided in the vent portion of the extruder. The aqueous solution was continuously supplied at a rate of 90 g / hour, and the heating temperature was 210. In was continuously extruded. The extruded resin mixture could be cooled to 110 ° C. with a jacketed static mixer installed at the extruder port and further poured into 80 ° C. warm water. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm (measured by Microtrac).

Aqueous dispersion of ethylene elastomer (B) The aqueous dispersion of propylene elastomer (A), except that the propylene elastomer (A) was changed to an ethylene-butene copolymer (Tafmer A20085, manufactured by Mitsui Chemicals, Inc.). An aqueous dispersion of an ethylene elastomer (B) was obtained in the same manner as above. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.

A propylene-based elastomer (A) except that the water-dispersed propylene-based elastomer (A) of the styrene-based elastomer (C) was changed to a hydrogenated product of styrene-butadiene block copolymer (Taftec H1041 manufactured by Asahi Kasei Chemicals Corporation). The aqueous dispersion of styrene-based elastomer (C) was obtained in the same manner as the aqueous dispersion of The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.

300 parts by weight of toluene and 300 parts by weight of polyester-based elastomer (Toyobo Co., Ltd., Byron 500) were added to a flask equipped with an aqueous dispersion stirrer of polyester (D-1), a thermometer, a reflux cooling device, and a nitrogen introduction tube. The mixture was charged and dissolved by heating under reflux. 500 parts by weight of this solution, 375 parts by weight of distilled water, and 1.5 parts by weight of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation, Neoperex F-25) are mixed and stirred for 15 minutes at a rotational speed of 10,000 rpm to obtain an emulsion. Got. Toluene in this emulsion was distilled off under reduced pressure with an evaporator to obtain an aqueous dispersion of a polyester elastomer (D-1). The obtained aqueous dispersion had a yield of 98%, a solid content concentration of 45%, a pH of 7, and an average particle size of 0.6 μm.

A polyester (D-2) aqueous dispersion stirrer, thermometer, reflux condenser, and four-necked flask equipped with a nitrogen introduction tube were mixed with 40 parts by weight of terephthalic acid, 50 parts by weight of isophthalic acid, and sodium 5-sulfoisophthalate. 10 parts by weight, 100 parts by weight of ethylene glycol, and 0.1 parts by weight of dibutyltin oxide were added, the temperature was gradually raised from 140 ° C. to 220 ° C., and the ester exchange reaction was carried out over 6 hours while removing the generated water. It was. Next, a polycondensation reaction was performed over 2 hours under reduced pressure while raising the temperature from 220 ° C. to 250 ° C. to obtain polyester D-2-1.

  70 parts by weight of Byron 500, 30 parts by weight of polyester D-2-1 and 1 part by weight of sodium dodecylbenzenesulfonate as a surfactant were mixed into a twin screw extruder (Ikegai Iron Works, PCM -30, L / D = 40) from a hopper at a rate of 101 g / hr, water is continuously fed at a rate of 30 g / hr from a feed port provided in the vent of the extruder, and the heating temperature Continuous extrusion at 240 ° C. The extruded resin mixture was cooled to 90 ° C. with a jacketed static mixer installed in the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion of a polyester elastomer (D-2). . The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 5, and an average particle size of 0.6 μm.

A four-necked flask equipped with an aqueous dispersion stirrer of acrylic resin (E), a thermometer, a reflux condenser, and a nitrogen introduction tube was charged with 500 parts by weight of toluene and 100 parts by weight of ethyl acetate, and the atmosphere was 85 under a nitrogen gas atmosphere. The temperature was raised to ° C. Then, 150 parts by weight of methyl methacrylate, 120 parts by weight of ethyl acrylate, 30 parts by weight of 2-hydroxyethyl acrylate, 10 parts by weight of methacrylic acid and 3 parts by weight (hereinafter abbreviated as PBO) as a copolymerization monomer. The mixture was fed for 4 hours to react. After 1 hour and 2 hours from the end of the feed, 0.2 parts by weight of PBO was added and reacted for 2 hours from the last addition to obtain a resin solution. The resulting resin solution is neutralized with triethylamine to theoretically 100%, deionized water is added so that the non-volatile content is 40%, and then toluene and ethyl acetate are removed under reduced pressure. An aqueous dispersion of an acrylic resin having a solid content of 40%, a pH of 8, and an average particle size of 0.3 μm was obtained.

In a four-necked flask equipped with an aqueous dispersion stirrer of urethane resin (F), a thermometer, a reflux cooling apparatus with a stuck din, and a nitrogen introduction tube, 20 parts of adipic acid, 15 parts of isophthalic acid, 13 parts of phthalic acid, Charge 10 parts of 1,3-butanediol and 42 parts of trimethylolpropane, heat to 150-230 ° C. in a nitrogen stream, and perform a dehydration reaction. After the reaction, 10 parts of ethyl acetate and 20 parts of toluene are added. 76% of polyester was obtained.

  In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 67.0 parts by weight of the polyester, 21.0 parts by weight of 2,2-dimethylolbutanoic acid, 1,4-butane 12.4 parts by weight of diol, 96.3 parts by weight of hexamethylene diisocyanate, and 374.0 parts by weight of methyl ethyl ketone were charged and reacted at 90 ° C. for 6 hours in a nitrogen gas atmosphere. Thereafter, the mixture was cooled to 60 ° C., triethylamine was added so that the neutralization degree was 100%, and the mixture was mixed at this temperature for 30 minutes. The obtained prepolymer was mixed and stirred with 1275.7 parts by weight of 0.86% hexamethylenediamine aqueous solution, and then methylethylketone was removed at 60 ° C. under reduced pressure to obtain a solid content of 30%, a pH of 8, and an average particle size. An aqueous dispersion of urethane resin having a diameter of 0.2 μm was obtained.

In a flask equipped with an aqueous dispersion stirrer of a petroleum hydrocarbon resin (G), a thermometer, a reflux cooling device, and a nitrogen introduction tube, 300 parts by weight of hexane, petroleum resin (manufactured by Mitsui Chemicals, Highlets T-480X ) Was added and dissolved by heating under reflux. 500 parts by weight of this solution, 250 parts by weight of distilled water, and 1.5 parts by weight of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation, Neopelex F-25) were mixed and stirred at a rotational speed of 10,000 rpm for 15 minutes. Subsequently, 0.7 part by weight of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., Hibiswaco 304) was added and mixed by stirring to obtain an emulsion. Hexane in this emulsion was distilled off under reduced pressure with an evaporator to obtain an aqueous dispersion of petroleum hydrocarbon resin (G). The obtained aqueous dispersion had a yield of 98%, a solid content concentration of 50%, a pH of 8, and an average particle size of 0.6 μm.

Example 1
30 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 70 parts by weight of an aqueous dispersion of propylene elastomer (A) and 50% aqueous solution 2 of Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.) under stirring 7 parts by weight were dropped and mixed in order to obtain a coating material. The obtained coating material was coated on a polypropylene film with a bar coater so that the film thickness after drying was 5 μm, and then dried at 90 ° C. for 5 minutes. The obtained film was cut into a strip of 15 mm width, a polyethylene terephthalate film cut into the same shape was bonded to the coated surface, and thermally bonded by applying a pressure of 1 kg / cm 2 at 150 ° C. for 3 seconds to obtain a laminate. It was.

Example 2
The coating material is blended in the order of 50 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 50 parts by weight of an aqueous dispersion of a propylene elastomer (A), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A laminated body was obtained in the same manner as in Example 1 except that it was changed.

Example 3
The coating material is blended in the order of 70 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 30 parts by weight of an aqueous dispersion of a propylene elastomer (A), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A laminated body was obtained in the same manner as in Example 1 except that it was changed.

Example 4
The coating material is 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 18 parts by weight of an aqueous dispersion of a petroleum hydrocarbon resin (G), and 50 parts by weight of an aqueous dispersion of a propylene-based elastomer (A). A laminate was obtained in the same manner as in Example 1, except that the composition was changed to a blend of 2.7 parts by weight of a 50% aqueous solution of Olfine E1010.

Example 5
Coating material is 30 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 18 parts by weight of superester E720 (manufactured by Arakawa Chemical Co., Ltd.) which is an aqueous dispersion of rosin resin (H), and propylene. A laminate was obtained in the same manner as in Example 1 except that the composition was changed in the order of 50 parts by weight of the aqueous dispersion of elastomer (A) and 2.7 parts by weight of 50% aqueous solution of Olfine E1010.

Example 6
The coating material is 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 18 parts by weight of Nanolet R1050 (manufactured by Yashara Chemical Co., Ltd.) which is an aqueous dispersion of a terpene resin (I), and a propylene elastomer (A ) And a mixture obtained in the order of 2.7 parts by weight of a 50% aqueous solution of Olfine E1010, a laminate was obtained in the same manner as in Example 1.

Example 7
Super coating that is 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 9 parts by weight of an aqueous dispersion of a petroleum hydrocarbon resin (G), and an aqueous dispersion of a rosin resin (H). The same method as in Example 1 except that 9 parts by weight of ester E720, 50 parts by weight of an aqueous dispersion of propylene-based elastomer (A), and 2.7 parts by weight of 50% aqueous solution of Olphine E1010 were changed in this order. A laminate was obtained.

Example 8
Nanolet which is 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 9 parts by weight of an aqueous dispersion of a petroleum hydrocarbon resin (G), and an aqueous dispersion of a terpene resin (I). The same method as in Example 1 except that R1050 was changed to 9 parts by weight, 50 parts by weight of an aqueous dispersion of propylene-based elastomer (A), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A laminate was obtained.

Example 9
The coating material is 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 9 parts by weight of Superester E720, which is an aqueous dispersion of a rosin resin (H), and an aqueous dispersion of a terpene resin (I). Example 1 except that 9 parts by weight of Nanolet R1050 as a body, 50 parts by weight of an aqueous dispersion of propylene-based elastomer (A), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010 were mixed in this order. The laminated body was obtained by the same method.

Example 10
The coating material is 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 4.5 parts by weight of an aqueous dispersion of a petroleum hydrocarbon resin (G), and an aqueous dispersion of a rosin resin (H). 9 parts by weight of a certain super ester E720, 4.5 parts by weight of Nanolet R1050, which is an aqueous dispersion of terpene resin (I), 50 parts by weight of an aqueous dispersion of propylene-based elastomer (A), and a 50% aqueous solution of Olfine E1010 A laminated body was obtained in the same manner as in Example 1 except that the composition was changed to that blended in the order of 2.7 parts by weight.

Example 11
The coating material is blended in the order of 50 parts by weight of an aqueous dispersion of a polyester elastomer (D-2), 50 parts by weight of an aqueous dispersion of a propylene elastomer (A), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A laminated body was obtained in the same manner as in Example 1 except that it was changed.

Example 12
The coating material was blended in the order of 56.3 parts by weight of an aqueous dispersion of acrylic resin (E), 50 parts by weight of an aqueous dispersion of propylene-based elastomer (A), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A laminated body was obtained in the same manner as in Example 1 except that it was changed to one.

Example 13
The coating material was blended in the order of 75 parts by weight of an aqueous dispersion of urethane resin (F), 50 parts by weight of an aqueous dispersion of propylene-based elastomer (A), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. Except having changed, the laminated body was obtained by the same method as Example 1.

Example 14
The coating material is 30 parts by weight of an aqueous dispersion of urethane resin (F), 18 parts by weight of an aqueous dispersion of petroleum hydrocarbon resin (G), 50 parts by weight of an aqueous dispersion of propylene-based elastomer (A), Olfin E1010 A laminate was obtained in the same manner as in Example 1 except that the mixture was changed to 2.7 parts by weight of a 50% aqueous solution.

Example 15
The coating material is 30 parts by weight of an aqueous dispersion of urethane resin (F), 18 parts by weight of superester E720 which is an aqueous dispersion of rosin resin (H), and 50 parts by weight of an aqueous dispersion of propylene elastomer (A). A laminate was obtained in the same manner as in Example 1, except that the composition was changed in the order of 2.7 parts by weight of olphine E1010 and 2.7 parts by weight of Olfin E1010.

Example 16
30 parts by weight of an aqueous dispersion of urethane resin (F), 18 parts by weight of Nanolet R1050, which is an aqueous dispersion of terpene resin (I), and 50 parts by weight of an aqueous dispersion of propylene-based elastomer (A) A laminate was obtained in the same manner as in Example 1, except that the composition was changed to a blend of 2.7 parts by weight of a 50% aqueous solution of Olfine E1010.

Example 17
The coating material is an aqueous dispersion of polyester elastomer (D-1) 30 parts by weight, an aqueous dispersion of acrylic resin (E) 22.5 parts by weight, an aqueous dispersion of propylene elastomer (A) 50 parts by weight, A laminate was obtained in the same manner as in Example 1, except that the composition was changed in the order of 2.7 parts by weight of 50% aqueous solution of Olfine E1010.

Example 18
The coating material is 30 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 30 parts by weight of an aqueous dispersion of urethane resin (F), 50 parts by weight of an aqueous dispersion of propylene elastomer (A), Olfin E1010. A laminate was obtained in the same manner as in Example 1 except that the mixture was changed to 2.7 parts by weight of a 50% aqueous solution.

Example 19
The coating material was made of 33.8 parts by weight of an aqueous dispersion of acrylic resin (E), 30 parts by weight of an aqueous dispersion of urethane resin (F), 50 parts by weight of an aqueous dispersion of propylene-based elastomer (A), and Olfine E1010. A laminate was obtained in the same manner as in Example 1 except that the blend was made in the order of 2.7 parts by weight of 50% aqueous solution.

Example 20
The coating material is 30 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 11.3 parts by weight of an aqueous dispersion of acrylic resin (E), 15 parts by weight of an aqueous dispersion of urethane resin (F), propylene A laminate was obtained in the same manner as in Example 1, except that the composition was changed in the order of 50 parts by weight of the aqueous dispersion of the elastomer (A) and 2.7 parts by weight of the 50% aqueous solution of Olfine E1010.

Example 21
The coating material is blended in the order of 50 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 50 parts by weight of an aqueous dispersion of a styrene elastomer (C), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A laminated body was obtained in the same manner as in Example 1 except that it was changed.

Example 22
The coating material is 30 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 50 parts by weight of an aqueous dispersion of propylene elastomer (A), 20 parts by weight of an aqueous dispersion of styrene elastomer (C), Olfin A laminate was obtained in the same manner as in Example 1 except that it was changed to one blended in the order of 2.7 parts by weight of 50% aqueous solution of E1010.

Example 23
As a coating material, 30 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 18 parts by weight of Nanolet R1050, which is an aqueous dispersion of terpene resin (I), and an aqueous dispersion of propylene elastomer (A) Example 1 except that 50 parts by weight, Takenate WD-720 (manufactured by Mitsui Takeda Chemical Co., Ltd.) as a curing agent was blended in the order of 10 parts by weight and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. The laminated body was obtained by the same method.

Example 24
The coating material used in Example 1 was coated on the outside of the polypropylene film of the laminate obtained in Example 1 with a bar coater so that the film thickness after drying was 5 μm, and then dried at 90 ° C. for 5 minutes. To obtain a laminate.

Example 25
To 30 parts by weight of the aqueous dispersion of the polyester elastomer (D-1), 70 parts by weight of the aqueous dispersion of the ethylene elastomer (B) and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010 are added dropwise in order. Thus, a coating material was obtained. The obtained coating material was coated on a polyethylene film with a bar coater so that the film thickness after drying was 5 μm, and then dried at 90 ° C. for 5 minutes. The obtained film was cut into a strip of 15 mm width, a polyethylene terephthalate film cut into the same shape was bonded to the coated surface, and thermally bonded by applying a pressure of 1 kg / cm 2 at 150 ° C. for 3 seconds to obtain a laminate. It was.

Example 26
The coating material is blended in the order of 50 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 50 parts by weight of an aqueous dispersion of ethylene elastomer (B), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A layered product was obtained in the same manner as in Example 21 except that it was changed to the above.

Example 27
The coating material was blended in the order of 70 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 30 parts by weight of an aqueous dispersion of ethylene elastomer (B), and 2.7 parts by weight of a 50% aqueous solution of Olfin E1010. A layered product was obtained in the same manner as in Example 21 except that it was changed to the above.

Example 28
The coating material is 30 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 18 parts by weight of an aqueous dispersion of petroleum hydrocarbon resin (G), and 50 parts by weight of an aqueous dispersion of ethylene elastomer (B). A laminate was obtained in the same manner as in Example 21 except that the composition was changed to 2.7 parts by weight of 50% aqueous solution of Olfine E1010.

Example 29
As a coating material, 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 18 parts by weight of Superester E720, which is an aqueous dispersion of a rosin resin (H), and an aqueous dispersion of an ethylene elastomer (B) A laminate was obtained in the same manner as in Example 21, except that the composition was changed in the order of 50 parts by weight of the body and 2.7 parts by weight of the 50% aqueous solution of Olfine E1010.

Example 30
As a coating material, 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 18 parts by weight of Nanolet R1050, which is an aqueous dispersion of a terpene resin (I), and an aqueous dispersion of an ethylene elastomer (B) A laminate was obtained in the same manner as in Example 21 except that the blend was made in the order of 50 parts by weight and 2.7 parts by weight of 50% aqueous solution of Olfine E1010.

Example 31
Super coating that is 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 9 parts by weight of an aqueous dispersion of a petroleum hydrocarbon resin (G), and an aqueous dispersion of a rosin resin (H). The same method as in Example 1, except that the ester E720 was changed to 9 parts by weight, 50 parts by weight of an aqueous dispersion of the ethylene elastomer (B), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A laminate was obtained.

Example 32
Nanolet which is 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 9 parts by weight of an aqueous dispersion of a petroleum hydrocarbon resin (G), and an aqueous dispersion of a terpene resin (I). The same method as in Example 1 except that R1050 was changed to 9 parts by weight, 50 parts by weight of an aqueous dispersion of ethylene-based elastomer (B), and 2.7 parts by weight of 50% aqueous solution of Olfine E1010. A laminate was obtained.

Example 33
The coating material is 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 9 parts by weight of Superester E720, which is an aqueous dispersion of a rosin resin (H), and an aqueous dispersion of a terpene resin (I). Example 1 except that Nanolet R1050 was changed to a blend of 9 parts by weight, 50 parts by weight of an aqueous dispersion of ethylene-based elastomer (B), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. The laminated body was obtained by the same method.

Example 34
The coating material is 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 4.5 parts by weight of an aqueous dispersion of a petroleum hydrocarbon resin (G), and an aqueous dispersion of a rosin resin (H). 9 parts by weight of a certain super ester E720, 4.5 parts by weight of Nanolet R1050, which is an aqueous dispersion of terpene resin (I), 50 parts by weight of an aqueous dispersion of ethylene elastomer (B), and a 50% aqueous solution of Olfine E1010 A laminated body was obtained in the same manner as in Example 1 except that the composition was changed to that blended in the order of 2.7 parts by weight.

Example 35
The coating material is blended in the order of 50 parts by weight of an aqueous dispersion of polyester elastomer (D-2), 50 parts by weight of an aqueous dispersion of ethylene elastomer (B), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A layered product was obtained in the same manner as in Example 21 except that it was changed to the above.

Example 36
The coating material was blended in the order of 56.3 parts by weight of an aqueous dispersion of acrylic resin (E), 50 parts by weight of an aqueous dispersion of ethylene-based elastomer (B), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A laminated body was obtained in the same manner as in Example 21 except that the structure was changed.

Example 37
The coating material was blended in the order of 75 parts by weight of an aqueous dispersion of urethane resin (F), 50 parts by weight of an aqueous dispersion of ethylene-based elastomer (B), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A laminated body was obtained in the same manner as in Example 21 except for the change.

Example 38
The coating material was 30 parts by weight of an aqueous dispersion of urethane resin (F), 18 parts by weight of an aqueous dispersion of petroleum hydrocarbon resin (G), 50 parts by weight of an aqueous dispersion of ethylene elastomer (B), Olfin E1010 A layered product was obtained in the same manner as in Example 21, except that the mixture was changed to a mixture of 2.7 parts by weight of a 50% aqueous solution.

Example 39
The coating material is 30 parts by weight of an aqueous dispersion of urethane resin (F), 18 parts by weight of Superester E720, which is an aqueous dispersion of rosin resin (H), and 50 parts by weight of an aqueous dispersion of ethylene elastomer (B). A laminate was obtained in the same manner as in Example 21, except that the composition was changed to a blend of 2.7 parts by weight of 50 parts aqueous solution of Olfin E1010.

Example 40
The coating material is 30 parts by weight of an aqueous dispersion of urethane resin (F), 18 parts by weight of Nanolet R1050, which is an aqueous dispersion of terpene resin (I), and 50 parts by weight of an aqueous dispersion of ethylene elastomer (B). A laminate was obtained in the same manner as in Example 21 except that the composition was changed to 2.7 parts by weight of 50% aqueous solution of Olfine E1010.

Example 41
The coating material is an aqueous dispersion of 30 parts by weight of polyester elastomer (D-1), an aqueous dispersion of acrylic resin (E) of 22.5 parts by weight, an aqueous dispersion of ethylene elastomer (B) of 50 parts by weight, A laminate was obtained in the same manner as in Example 21 except that the composition was changed in the order of 2.7 parts by weight of 50% aqueous solution of Orphin E1010.

Example 42
The coating material is 30 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 30 parts by weight of an aqueous dispersion of urethane resin (F), 50 parts by weight of an aqueous dispersion of ethylene elastomer (B), Olfin E1010. A layered product was obtained in the same manner as in Example 21, except that the mixture was changed to a mixture of 2.7 parts by weight of a 50% aqueous solution.

Example 43
The coating material is made of 33.8 parts by weight of an aqueous dispersion of acrylic resin (E), 30 parts by weight of an aqueous dispersion of urethane resin (F), 50 parts by weight of an aqueous dispersion of ethylene-based elastomer (B), and Olfine E1010. A laminate was obtained in the same manner as in Example 21, except that the blend was made in the order of 2.7 parts by weight of 50% aqueous solution.

Example 44
The coating material is 30 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 11.3 parts by weight of an aqueous dispersion of acrylic resin (E), 15 parts by weight of an aqueous dispersion of urethane resin (F), ethylene A laminate was obtained in the same manner as in Example 21, except that the composition was changed in the order of 50 parts by weight of the aqueous dispersion of the elastomer (B) and 2.7 parts by weight of the 50% aqueous solution of Olfine E1010.

Example 45
The coating material is blended in the order of 50 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 50 parts by weight of an aqueous dispersion of a styrene elastomer (C), and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. A layered product was obtained in the same manner as in Example 21 except that it was changed to the above.

Example 46
The coating material is 30 parts by weight of an aqueous dispersion of polyester elastomer (D-1), 50 parts by weight of an aqueous dispersion of ethylene elastomer (B), 20 parts by weight of an aqueous dispersion of styrene elastomer (C), Olfin A laminate was obtained in the same manner as in Example 21, except that the composition was changed in the order of 2.7 parts by weight of 50% aqueous solution of E1010.

Example 47
As a coating material, 30 parts by weight of an aqueous dispersion of a polyester elastomer (D-1), 18 parts by weight of Nanolet R1050, which is an aqueous dispersion of a terpene resin (I), and an aqueous dispersion of an ethylene elastomer (B) A laminate was obtained in the same manner as in Example 21, except that 50 parts by weight and Takenate WD-720 as a curing agent were mixed in the order of 10 parts by weight and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. It was.

Example 48
The coating material used in Example 21 was coated on the outside of the polyethylene film of the laminate obtained in Example 21 with a bar coater so that the film thickness after drying was 5 μm, and then dried at 90 ° C. for 5 minutes. To obtain a laminate.

Comparative Example 1
A laminate was obtained in the same manner as in Example 1 except that the blend was made in the order of 100 parts by weight of an aqueous dispersion of propylene-based elastomer (A) and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010.

Comparative Example 2
A laminate was obtained in the same manner as in Example 1 except that the blend was made in the order of 100 parts by weight of an aqueous dispersion of ethylene-based elastomer (B) and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010.

Comparative Example 3
A laminate was obtained in the same manner as in Example 1, except that the mixture was formulated in the order of 100 parts by weight of an aqueous dispersion of styrene elastomer (C) and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010.

Comparative Example 4
A laminate was obtained in the same manner as in Example 1, except that the blend was made in the order of 100 parts by weight of an aqueous dispersion of the polyester elastomer (D-1) and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. It was.

Comparative Example 5
A laminate was obtained in the same manner as in Example 1 except that the blend was made in the order of 100 parts by weight of the aqueous dispersion of acrylic resin (E) and 2.4 parts by weight of 50% aqueous solution of Olfine E1010.

Comparative Example 6
A laminate was obtained in the same manner as in Example 1 except that the mixture was changed to 100 parts by weight of an aqueous dispersion of urethane resin (F) and 1.8 parts by weight of 50% aqueous solution of Olfine E1010.

Comparative Example 7
A laminate was obtained in the same manner as in Example 18 except that the blend was made in the order of 100 parts by weight of an aqueous dispersion of propylene-based elastomer (A) and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010.

Comparative Example 8
A laminate was obtained in the same manner as in Example 18 except that the blend was made in the order of 100 parts by weight of an aqueous dispersion of ethylene-based elastomer (B) and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010.

Comparative Example 9
A laminate was obtained in the same manner as in Example 18, except that the mixture was formulated in the order of 100 parts by weight of an aqueous dispersion of styrene elastomer (C) and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010.

Comparative Example 10
A laminate was obtained in the same manner as in Example 18 except that the blend was made in the order of 100 parts by weight of an aqueous dispersion of the polyester elastomer (D-1) and 2.7 parts by weight of a 50% aqueous solution of Olfine E1010. It was.

Comparative Example 11
A laminate was obtained in the same manner as in Example 18 except that the blend was made in the order of 100 parts by weight of an aqueous dispersion of acrylic resin (E) and 2.4 parts by weight of 50% aqueous solution of Olphine E1010.

Comparative Example 12
A laminate was obtained in the same manner as in Example 18 except that the mixture was changed in the order of 100 parts by weight of an aqueous dispersion of urethane resin (F) and 1.8 parts by weight of 50% aqueous solution of Olfine E1010.

[Evaluation and results]
<Various evaluations>
Measurement of peel strength After peeling off the end of a strip with a width of 15 mm, the end is pulled in the direction of 180 ° at a speed of 50 mm / min, and the peel strength is measured. If the peel strength is 300 g / 15 mm or more, ○, 150 g / Evaluations were made with a value of 15 mm or more and less than 300 g / 15 mm as Δ and a value of less than 300 g / 15 mm as x.

Hot water resistance test The test piece obtained above was immersed in warm water adjusted to 40 ° C for 240 hours, and the same peel strength measurement was performed.

Cross-cut peel test According to the cross-cut peel test method described in JIS-K-5400, a cross-cut was applied to the coated surfaces of Examples 24 and 48, and Cellotape (registered trademark) was pasted on the cross cut. Then, it pulled immediately in 90 degree direction and made it peel, and evaluated by the number of grids which were not peeled among 100 grids.

Claims (5)

A coating containing an aqueous dispersion composed of a propylene-based elastomer (A) and / or a styrene-based elastomer (C), a polyester (D) and / or an acrylic resin (E) and / or a urethane resin (F), and water. A laminate comprising a coating layer obtained by coating and drying a work material, wherein one base material is a propylene-based resin and the other base material is polyester. Coating containing an aqueous dispersion composed of ethylene elastomer (B) and / or styrene elastomer (C), polyester (D) and / or acrylic resin (E) and / or urethane resin (F), and water. A laminate comprising a coating layer obtained by coating and drying a work material, wherein one base material is made of an ethylene-based resin and the other base material is made of polyester. The coating material contains an aqueous dispersion of petroleum hydrocarbon resin (G) and / or rosin resin (H) and / or terpene resin (I). The laminated body as described in. 10 to 90 parts by weight of propylene-based elastomer (A) and / or styrene-based elastomer (C), 10 to 90 parts by weight of polyester (D) and / or acrylic resin (E) and / or urethane resin (F), Petroleum hydrocarbon resin (G) and / or rosin resin (H) and / or terpene resin (I) consisting of 0 to 50 parts by weight, (A) and / or (C), (D) and / or 2. The coating material according to claim 1, wherein the total of (E) and / or (F), (G) and / or (H) and / or (I) is 100 parts by weight. The laminated body of description. 10 to 90 parts by weight of an ethylene elastomer (B) and / or a styrene elastomer (C), 10 to 90 parts by weight of a polyester (D) and / or an acrylic resin (E) and / or a urethane resin (F), Petroleum hydrocarbon resin (G) and / or rosin resin (H) and / or terpene resin (I) consisting of 0 to 50 parts by weight, (B) and / or (C), (D) and / or 3. The coating material according to claim 2, wherein the total of (E) and / or (F), (G) and / or (H) and / or (I) is 100 parts by weight. Laminated body.