TW201305294A - Aqueous adhesive and laminate structure - Google Patents

Abstract

The purpose of the invention is to provide an aqueous adhesive having an excellent adhesion for adhering nylon resin and cotton-containing fiber, and provide a laminate structure of nylon resin/adhesive layer/cotton-containing fiber. The aqueous adhesive for adhering nylon resin and cotton-containing fiber comprises a copolymer having at least one kind of structure unit originated from α -olefin having carbon number of 2 to 20, and further preferably comprises a surfactant represented by the following formula (I) and water (wherein, X represents a hydrogen atom or -SO3M(M is a hydrogen atom, NH4 or alkali metal), n represents an integer of 1 to 3, and m represents an integer of 1 to 100.)

Description

Aqueous adhesive and laminated structure

The present invention relates to an aqueous binder and a laminate structure for the subsequent use of a nylon resin and a cotton-containing fiber.

In general, various types of resins are contained in the aqueous adhesive, and the types of the resins and the like are reviewed. In addition, various types and combinations of the base material and the subsequent layer of the laminated structure obtained by adhering the substrates to each other by the adhesive are examined (Non-Patent Document 1).

[Previous Technical Literature] [Non-patent literature]

[Non-Patent Document 1] Japanese adhesive preparation "Next manual (4th edition)" published by Nikkan Kogyo Shimbun, December 28, 2007, 98 pages

In the case of the conventional aqueous adhesive, especially in the case of the adhesion between the nylon resin and the cotton-containing fiber, there is a possibility that it may not be satisfied.

The present invention encompasses the following inventions.

[1] An aqueous adhesive for use in a nylon resin and a cotton-containing fiber, which comprises a polymer having one or more structural units derived from an α-olefin having 2 to 20 carbon atoms.

[2] The aqueous adhesive according to [1], which further comprises a surfactant represented by the following formula (I). (wherein X represents a hydrogen atom or -SO ₃ M (M-based hydrogen atom, NH ₄ or an alkali metal). n represents an integer of 1 to 3. m represents an integer of 1 to 100.)

As the aqueous [3] [2] Next agent, wherein the surfactant system comprises a hydrogen atom of the X interface active agent, and the type -SO 2 X ₃ M-based surfactant of the above.

[4] The aqueous binder according to [2] or [3], wherein the surfactant is -SO ₃ M-based SO ₃ NH ₄ .

[5] The aqueous adhesive according to any one of [1] to [4] wherein the polymer has the aforementioned structural unit derived from an α-olefin having 2 to 20 carbon atoms, and a group of 2 to 20 carbon atoms having 2 to 20 carbon atoms, α,β-unsaturated carboxylic acid esters, α,β-unsaturated carboxylic anhydrides, and vinyl acetate having a carbon number of 2 to 20 A copolymer of structural units of one or more monomers.

[6] The aqueous adhesive according to any one of [1] to [5] wherein the polymer has a structural unit derived from ethylene and an α-olefin derived from a carbon number of 3 to 20, A copolymer of structural units of one or more monomers of the group consisting of α,β-unsaturated carboxylic acid esters, α,β-unsaturated carboxylic anhydrides, and vinyl acetate.

[7] The aqueous adhesive according to any one of [1] to [6] wherein the polymer has a structural unit derived from ethylene and is derived from an α,β-unsaturated carboxylic acid ester and Group of α,β-unsaturated carboxylic acids A copolymer of structural units of the above monomers.

[A] The aqueous adhesive according to any one of [1] to [7] wherein the polymer is at least one selected from the group consisting of: (a) an ethylene-propylene copolymer, Α-olefin such as propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer, ethylene-propylene-1-butene copolymer a copolymer or a modified product thereof; or a mixture of two or more thereof; (b) an ethylene-propylene copolymer, a propylene-1-butene copolymer, an ethylene-1-butene copolymer, an ethylene-1- An α-olefin copolymer such as an octene copolymer, an ethylene-1-hexene copolymer or an ethylene-propylene-1-butene copolymer or a maleic anhydride modified product thereof, or a mixture of two or more thereof; (c) a copolymer of α-olefin and vinyl acetate or a modified product thereof, or a mixture of two or more thereof; (d) an α-olefin and a (meth) acrylate and an α, β-carboxylic acid a copolymer or a modified product thereof, or a mixture of two or more thereof; and (e) a copolymer of an α-olefin and a (meth) acrylate with maleic anhydride or a modified product thereof, or the like a mixture of the above.

[9] The aqueous adhesive according to any one of [1] to [8] wherein the polymer has a melting point of 60 to 110 °C.

[10] The aqueous adhesive according to any one of [1] to [9], which further comprises an adhesive resin.

[11] The aqueous adhesive according to any one of [1] to [10], which further comprises a polyurethane resin or a water-insoluble polyurethane resin.

[12] The aqueous adhesive according to any one of [1] to [10], wherein Containing a polymer selected from the group consisting of terpene polymers, terpene phenols, β-pinene polymers, aromatic modified terpene polymers, α-pinene polymers, and terpene hydrogenated resins. Group of terpene resins.

[13] The aqueous adhesive according to any one of [1] to [10], which further comprises a polyurethane resin, and is selected from the group consisting of terpene polymers, terpene phenols, β-pinene polymers, and aromatic modification. A terpene-based resin in which a terpene polymer, an α-pinene polymer, and a terpene-based hydrogenated resin are grouped.

[14] The aqueous adhesive according to any one of [1] to [10], which further comprises a polyurethane resin and a terpene phenol, or a water-insoluble polyurethane resin and a terpene phenol.

[15] The aqueous adhesive according to any one of [1] to [14], which contains an isocyanate.

[16] The aqueous adhesive according to any one of [1] to [14], which further comprises a selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), and isocyanates in groups of such oligomers or polymers.

[17] The aqueous adhesive according to any one of [1] to [16], which further comprises a basic compound.

[A] The aqueous adhesive according to any one of [1] to [17] wherein the aqueous adhesive contains a dispersion having a particle diameter (number basis) of 0.01 to 1.0 μm.

[19] The aqueous adhesive according to any one of [1] to [18], which is contained in an amount of 0.1 to 50 parts by weight and 0.1 to 20 parts by weight based on 100 parts by weight of all the resins constituting the aqueous emulsion. Or 0.1 to 10 parts by weight The aforementioned surfactant.

[20] The aqueous adhesive according to any one of [1] to [19] wherein the surfactant is in a mass ratio of from 1 to 99:99 to 1, from 5 to 95:95 to 5, From 10 to 90:90 to 10, 30:70 to 90:10, 40:60 to 90:10 or 50:50 to 90:10, the surfactant represented by the formula (A) and the formula (B) are represented. Surfactant.

[A] The aqueous adhesive according to any one of [1] to [20] wherein after the polymerization of the thermoplastic resin, the resin is dispersed in an aqueous medium, followed by emulsification (post-emulsification) ), forced emulsification method, auto-emulsification method or phase-transfer emulsification method.

[22] A laminated structure in which a first substrate comprising a nylon resin, an adhesive layer containing a polymer having one or more structural units derived from an α-olefin having 2 to 20 carbon atoms, and a cotton-containing fiber are sequentially included The second substrate is laminated.

[23] The layered structure according to [22], wherein the layer is a layer formed of the aqueous binder according to any one of [1] to [21].

According to the present invention, it is possible to provide an aqueous binder which is followed by, in particular, a nylon resin and a cotton-containing fiber, and a laminated structure thereof.

The aqueous adhesive of the present invention contains a polymer having one or more structural units derived from an α-olefin having 2 to 20 carbon atoms. The aqueous adhesive can be used as an adhesive between the materials, which is especially suitable for various materials. Next to the nylon resin and the cotton-containing fiber.

The laminated structure of the present invention is a first substrate comprising a nylon resin, an adhesive layer containing a polymer having one or more types of structural units derived from an α-olefin having 2 to 20 carbon atoms, and a cotton-containing fiber. 2 substrate laminate.

In the laminated structure, the subsequent layer is sandwiched between the substrates composed of various materials, in particular, sandwiched between the laminated structure of the nylon resin and the cotton-containing fibers. Next, the layer is a layer obtained by evaporating the water in the adhesive and the solvent in the solvent by a layer obtained by an adhesive, especially an aqueous adhesive.

Here, a nylon resin (hereinafter referred to as a "first substrate"), that is, a polyamine-based resin, is a polymer which is condensed by a guanamine bond, that is, contains various constituent monomers. The type and molecular weight. Specific examples thereof include nylon 6, nylon 6,6, nylon 4, 6, nylon 11, nylon 12 and the like. The nylon resin may have any form such as a film, a block, a fiber, or a foam.

The cotton-containing fiber (hereinafter referred to as the "second substrate") may be a fiber of 100% cotton, and may be a blended fiber of cotton and other natural fibers and/or chemical fibers. Other natural fibers include wool, enamel, hemp, and the like. Examples of the chemical fiber include synthetic fibers (for example, polyester-based fibers such as polyester or nylon), semi-synthetic fibers (cellulose-based fibers such as acetate, and protein-based fibers such as promix), and recycled fibers (嫘萦). (rayon), cupra, cellulosic fibers such as polynosic, inorganic fibers (carbon fibers, glass fibers), and the like.

The form of the cotton-containing fiber of the object of the aqueous adhesive of the present invention, Examples thereof include various forms such as a fabric, a knitted fabric, a non-woven fabric, a knit fabric, a felt, a film, and a block.

The aqueous adhesive of the present invention can exhibit, for example, an adhesive, an adhesive, an adhesive for a binder, a heat sealant, a paint, a primer for a paint, an adhesive for an ink, an adhesive for an adhesive, and a modifier for an emulsion. Function, and as an adhesive for the use of nylon resin and cotton-containing fibers for films, sheets, construction materials, building materials, automotive parts, electrical/electronic products, packaging materials, clothing, shoes, and the like.

Among them, the preferred form is used as a shoe upper, a midsole, an outsole, and the like in sports shoes, casual shoes, business shoes, and the like for men's and women's shoes, and further for industrial work boots and the like. A nylon resin material is used between the nylon resin material and the cotton-containing fiber material.

The size, thickness, shape, and the like of the nylon resin and the cotton-containing fiber can be appropriately adjusted in accordance with the purpose of use of the laminated structure.

The surface of the nylon resin and the cotton-containing fiber may be smooth or have irregularities.

Further, a primer treatment for improving the adhesion of the adhesive or the like may be applied to the surface of the first substrate and/or the second substrate. Examples of the primer treatment include blasting, drug treatment, degreasing, flame treatment, acid treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, formation of an anchor layer, and the like.

<Binder>

The subsequent agent contains a polymer having one or more structural units derived from an α-olefin having 2 to 20 carbon atoms.

<polymer>

The binder of the present invention, particularly the polymer contained in the aqueous binder, has one or more structural units derived from an α-olefin having 2 to 20 carbon atoms.

Examples of the α-olefin having 2 to 20 carbon atoms include ethylene (C2), propylene (C3), 1-butene (C4), 1-pentene, 1-hexene, 1-heptene, and 1 -octene, 1-decene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonenylene, 1-eicosene, ethylene cyclohexane, and the like. Preferred are ethylene, propylene, 1-butene and the like.

A polymer containing structural units derived from an α-olefin having 2 to 20 carbon atoms, preferably polyethylene (PE), high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE). , homopolymer of polypropylene (PP) or the like thereof; ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene- An α-olefin copolymer such as a 1-hexene copolymer or an ethylene-propylene-1-butene copolymer or a modified product thereof; a copolymer with a copolymerizable monomer or a modified substance thereof; or the like The above mixture. In the copolymer of the copolymerizable monomer, the copolymerizable monomer and the alpha olefin may be used alone or in combination of two or more. The form of the copolymer may be, for example, any of random copolymerization, block copolymerization, graft copolymerization, and the like. These may be those which have a low molecular weight and a high molecular weight by an oxide or the like.

The total structural unit of the α-olefin-based polymer is 100% by mole, and for example, a structural unit derived from propylene is included in the following ratio: a structural unit derived from 1-butene, preferably containing a ratio system 71 to 99 mol%: 1 to 29 mol% of a copolymer or a modified product thereof, more preferably a proportion 80 Up to 99% by mole: 1 to 20% by mole of the copolymer or modified substance thereof, and more preferably a copolymer containing 90 to 99% by mole of the ratio: 1 to 10% by mole or a modified product thereof. The copolymer is preferably a copolymer in which a melting peak is not substantially observed. The fact that the melting peak is not substantially observed means that a crystal melting peak having a crystal melting heat of 1 J/g or more is not observed by differential scanning calorimetry (DSC) in a temperature range of -100 to 200 °C.

The ethylene structural unit derived from the following: a structural unit derived from propylene, preferably a copolymer containing a ratio of 5 to 20 mol%: 80 to 95 mol%, or a modified product thereof, more preferably contains The ratio is 5 to 19 mol%: 81 to 95 mol% of the copolymer or the modified product thereof, and more preferably the copolymer having a ratio of 10 to 19 mol%: 81 to 90 mol% or a modified product thereof . The copolymer is preferably a copolymer in which a melting peak is observed. It is observed that the melting peak is a crystal melting peak having a crystal melting heat of 1 J/g or more, or a crystallization heat of 1 J/g, observed by differential scanning calorimetry (DSC) in a temperature range of -100 to 200 °C. The above crystallization peak.

The structural unit derived from ethylene may be exemplified in the following ratio: structural unit derived from propylene: structural unit derived from 1-butene, preferably containing a ratio of 1 to 99 mol%: 99 to 1 mol%: 99 to 1 mol% of a copolymer or a modified product thereof, more preferably a copolymer containing a ratio of 5 to 80 mol%: 90 to 2 mol%: 90 to 1 mol% of a copolymer or a modified product thereof, and more preferably A copolymer containing a ratio of 10 to 40 mol%: 85 to 5 mol%: 60 to 2 mol% or a modified product thereof. The copolymer is preferably a copolymer in which no melting peak is observed.

For the copolymers, for example, a well-known single site (single site) can be used. The catalysts are manufactured by, for example, the above-mentioned Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei.

Further, the weight ratio of the above propylene-1-butene copolymer or its modified product to the ethylene-propylene copolymer or its modified substance is preferably from 1 to 99:99 to 1, more preferably 5 It is more preferably a blend of from 95 to 95:5 to 10, more preferably from 10 to 90:90 to 10.

The modified product of the α-olefin-based polymer may, for example, be a modified product derived from an α,β-unsaturated carboxylic acid. At this time, the mass is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, based on 100 parts by weight of the polymer of the α-olefin.

Examples of the α,β-unsaturated carboxylic acid include α,β-unsaturated carboxylic acids (Maleic acid, iaconic acid, citraconic acid, etc.). α,β-unsaturated carboxylic acid esters (methyl maleate, methyl itaconate, methyl pyroyl citrate, etc.), α,β-unsaturated carboxylic anhydrides (maleic anhydride, itaconic anhydride, caramel) Anhydride, etc.). Further, these α,β-unsaturated carboxylic acids may be used in combination. Among them, α,β-unsaturated carboxylic anhydride is preferred, and maleic anhydride is more preferred.

Examples of such a modified product include a method in which an α-olefin-based polymer is melted, and an α,β-unsaturated carboxylic acid or the like is added to be modified, and the α-olefin-based polymer is dissolved in a solvent such as toluene or xylene. Thereafter, a known method such as a method of modifying an α,β-unsaturated carboxylic acid or the like is added. Further, when the modified material contains a structural unit derived from an α,β-unsaturated carboxylic anhydride, the acid anhydride group may be maintained, or the ring-opener may be contained, and the acid anhydride group may be further included. Both.

Among them, the α-olefin-based polymer is preferably a copolymer of ethylene and one or more kinds of α-olefins having 3 to 20 carbon atoms or a modified product of the copolymer, or a mixture thereof.

Examples of the copolymerizable monomer include an unsaturated carboxylic acid or an anhydride thereof, a metal salt of an α,β-unsaturated carboxylic acid, an α,β-unsaturated carboxylic acid ester, a vinyl ester, and a vinyl ester saponified product. a cyclic olefin, a vinyl aromatic compound, a polyene compound (diene or the like), (meth)acrylonitrile, a vinyl halide, a vinylidene halide or the like. These may be used alone or in combination of two or more.

In the present specification, acrylic acid and methacrylic acid are collectively referred to as (meth)acrylic acid, and acrylate and methacrylic acid ester are collectively referred to as (meth)acrylic acid ester.

Examples of the unsaturated carboxylic acid or an anhydride thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and further unsaturated two. A half ester of a carboxylic acid, a hemiamine or the like. Among them, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferred, and acrylic acid and maleic anhydride are particularly preferred.

The metal salt of the α,β-unsaturated carboxylic acid may, for example, be a sodium salt or a magnesium salt of (meth)acrylic acid.

Examples of the α,β-unsaturated carboxylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate, and (methyl). A glycidyl acrylate, 2-hydroxyethyl acrylate, and further an esterified product of methacrylic acid and an alcohol. Among them, preferred are methyl (meth)acrylate and ethyl (meth)acrylate.

Examples of the vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl neodecanoate and the like. Among them, vinyl acetate is preferred.

The vinyl ester saponified product may, for example, be a vinyl alcohol obtained by saponifying a vinyl ester with a basic compound or the like.

Examples of the cyclic olefin include norbornene, 5-methylnordecene, 5-ethyl norbornene, 5-propylnordecene, 5,6-dimethylnordecene, and 1 -methylnordecene, 7-methylnordecene, 5,5,6-trimethylnordecene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethyleneide Terpene, 5-ethylene decene, 1,4,5,8-dimethyl bridge-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-methyl-1,4 ,5,8-Dimethyl Bridge-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethyl bridge-1,2, 3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethyl bridge-1,2,3,4,4a,5,8, 8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethyl bridge-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethylene-1, 4,5,8-dimethyl bridge-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethyl bridge-1,2, 3,4,4a,5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethyl bridge-1,2,3,4,4a,5,8, 8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethyl bridge-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dichloro- 1,4,5,8-dimethyl bridge-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethyl bridge- 1,2,3,4,4a,5,8,8a-octahydronaphthalene, 1,2-dihydrocyclopentadiene, 5-chloronordecene, 5,5-dichloronorbornene, 5- Fluorine decene , 5,5,6-trifluoro-6-trifluoromethylnordecene, 5-chloromethylnordecene, 5-methoxynordecene, 5,6-dicarboxynordecene anhydride, 5 - dimethylaminopyrene, 5-cyanopyridene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-Dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3 , 4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, ethylene cyclohexane, and the like.

Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, ethylene xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, and dibromostyrene. , fluorostyrene, p-tert-butyl styrene, ethyl styrene, vinyl naphthalene, and the like.

Examples of the polyene compound include a linear or branched aliphatic conjugated polyene compound, an alicyclic conjugated polyene compound, an aliphatic non-conjugated polyene compound, and an alicyclic non-conjugated compound. An olefin compound, an aromatic non-conjugated polyene compound, or the like. These groups may have a substituent such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group or an aralkyloxy group.

Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isobutylene, 2-ethyl-1,3-butadiene, and 2-propyl-1,3-butadiene. 2-isopropyl-1,3-butadiene, 2-hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl- 1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2-methyl-1,3-octadiene, 2-methyl Base-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3-dimethyl- 1,3-octadiene, 2,3-dimethyl-1,3-decadiene, and the like.

The alicyclic conjugate is a polyene compound, and examples thereof include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, and 2,3-dimethyl group. -1,3-cyclopentadiene, 2,3-dimethyl-1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3- Butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3-pentadiene, 2-chloro-1,3-cyclopentadiene, 2-chloro-1,3-ring Hexadiene and the like.

Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, and 1,7. -octadiene, 1,8-decadiene, 1,9-decadiene, 1,13-tetradecadiene, 1,5,9-nonanetriene, 3-methyl-1,4- Hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3-methyl-1, 5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4-heptadiene , 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-g Diene, 3-methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl- 1,6-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-B Base-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6 -ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene , 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-decadiene, 5-methyl-1,4-anthracene Diene , 4-ethyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-anthracene Diene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6 -decadiene, 6-ethyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1 , 7-decadiene, 7-ethyl-1,7-decadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl -1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6- Methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7- Decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1, 8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecenediene, 9-A Base-1,8-undecanediene, 6,10-dimethyl-1,5,9-undecanetriene, 5,9-dimethyl-1,4,8-nonanetriene, 4-Ethylene-8-methyl-1,7-decadiene, 13-ethyl-9-methyl-1,9,12-pentadecanetriene, 5,9,13-trimethyl -1,4,8,12-tetradecadiene, 8,14,16-trimethyl-1,7,14-hexadecanetriene, 4-ethylene-12-methyl-1, 11-pentadecaene and the like.

Examples of the alicyclic non-conjugated polyene compound include ethylene cyclohexane, ethylene cyclohexene, 5-vinyl-2-northene, 5-ethylidene-2-norbornene, and 5 -methylene-2-northene, 5-isopropenyl-2-northene, cyclohexadiene, dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 2- Methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene, 2,3-diisopropylidene-5-norbornene, 2-ethylene-3- Isopropyl-5-norbornene, 6-chloromethyl-5-isopropenyl-2-northene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane , 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1 -allyl-5-vinylcyclooctane, 1,5-diallyl cyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinyl Cyclohexane, 1-isopropenyl-3-vinylcyclopentane, methyltetrahydroindene, and the like.

Examples of the aromatic non-conjugated polyene compound include divinylbenzene and ethylene isopropenylbenzene.

For the modification of the copolymer with the copolymerizable monomer, as described above For example, a modified substance derived from an α,β-unsaturated carboxylic acid or the like can be mentioned. At this time, the mass is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, based on 100 parts by weight of the copolymer with the copolymerizable monomer.

As the copolymer of the α-olefin and the copolymerizable monomer, specifically, (i) an ethylene-vinyl acetate copolymer, a saponified product or a partially saponified product thereof, or an ethylene-vinyl acetate copolymer Maleic anhydride modified product, (ii) ethylene-(meth)acrylic acid copolymer, (iii) ethylene-(meth)acrylic acid butyl acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, etc. (meth) acrylate copolymer, (iv) ethylene-alicyclic α-olefin copolymer such as ethylene-ethylene cyclohexane, (v) ethylene-vinyl acetate copolymer (meth)acrylic acid propyl acrylate, Ethylene-vinyl acetate-(meth)acrylate copolymer such as ethylene-vinyl acetate copolymer (methyl) acrylate, (vi) ethylene such as ethylene-ethyl (meth)acrylate-maleic anhydride copolymer -(Meth)acrylate-maleic anhydride copolymer, (vii) ethylene-(meth)acrylate-ethylene (meth)acrylate-methyl (meth)acrylate copolymer a acrylate copolymer, (viii) a copolymer of the metal salts, and (ix) a blend of two or more of the copolymers, and the like.

Polymerization of structural units having an alpha-olefin from 2 to 20 carbon atoms The copolymer, especially the above (i) to (vii), preferably has a melt flow rate of from 0.01 to 500 g/10 min at 190 ° C and a load of 2160 g, more preferably from 0.01 to 400 g / 10 minutes.

A polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, particularly a copolymer of the above (i) to (vii), preferably having a melting point of 60 to 200 ° C, more preferably 60 to 120 ° C, More preferably, it is 60 to 110 °C. When a polymer having a melting point in this range is used, the permeability or adhesion of the aqueous adhesive to the object can be further enhanced.

A polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, preferably having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and α-from a carbon number selected from 2 to 20 carbon atoms a structural unit of one or more monomers in which a group of olefins having a carbon number of 2 to 20, an α, β-unsaturated carboxylic acid ester, an α, β-unsaturated carboxylic acid anhydride, and a vinyl acetate group More preferably, it has a structural unit derived from ethylene, and is derived from an α-olefin selected from carbon atoms 3 to 20, an α,β-unsaturated carboxylic acid ester, an α,β-unsaturated carboxylic anhydride, and a vinyl acetate. a copolymer of structural units of one or more monomers in a group; more preferably, having a structural unit derived from ethylene, and derived from an α,β-unsaturated carboxylic acid ester and α,β-unsaturated A copolymer of structural units of one or more monomers in which a carboxylic acid is grouped.

Specifically, (i) an ethylene-vinyl acetate copolymer, a saponified or partially saponified product thereof or a maleic anhydride modified product of an ethylene-vinyl acetate copolymer, (ii) an ethylene-(meth)acrylic acid is preferred. Copolymer, (iii) ethylene-(meth) acrylate copolymer, (v) ethylene-vinyl acetate-(meth) acrylate copolymer, (vi) ethylene-(meth) acrylate-maleic anhydride Total Polymer, (vii) ethylene-(meth) acrylate-(meth) acrylate copolymer; more preferably (i) ethylene-vinyl acetate copolymer, (ii) ethylene-(meth)acrylic acid copolymer , (iii) ethylene-(meth) acrylate copolymer, (v) ethylene-vinyl acetate-(meth) acrylate copolymer, (vi) ethylene-(meth) acrylate-maleic anhydride copolymer . Among these, a copolymer containing a structural unit derived from an α-olefin having a carbon number of 2 to 20 (more preferably ethylene) is particularly preferred.

In the aqueous adhesive of the present invention, the content of the polymer can be appropriately adjusted depending on, for example, the type of the polymer to be used, the purpose of use, the desired properties, and the like. For example, from the viewpoint of maintaining the stability of the aqueous adhesive, moderately retaining viscosity, and/or exhibiting good film forming ability and adhesion, the content is preferably from 1 to 60 by weight based on the total amount of the aqueous adhesive. More preferably, it is 3 to 60% by weight, 3 to 50% by weight, still more preferably 5 to 55% by weight.

<Other resins>

The aqueous adhesive of the present invention may contain other resins than the above-mentioned polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms.

Examples of other resins include polyolefin resins other than the above polymers, acrylic resins (PMMA), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), and polyvinyl acetate. (PVAc), polytetrafluoroethylene (PTFE), acrylonitrile butadiene styrene resin (ABS resin), polymers and copolymers such as AS resin, and various resins such as these modified materials. These may be used alone or in combination of two or more.

Further, an adhesive resin or a resin which functions as an adhesion-imparting agent can be used.

Examples of such a resin include, for example, a rosin type, a terpene type resin, a petroleum resin obtained by polymerizing a petroleum fraction of 5, a hydrogenated resin thereof, and a petroleum fraction having a carbon number of 9 Petroleum resins and hydrogenated resins thereof, other petroleum resins, coumarone resins, enamel resins, polyurethane resins, and the like.

Specific examples thereof include rosin, polymeric rosin, disproportionated turpentine, hydrogenated rosin, maleated turpentine, and rosin rosin, and glycerides, pentaerythritol esters, methyl esters, and triethylene glycol esters. Phenolic modified substances and rosins such as esterified products; terpene polymers, terpene phenols, β-pinene polymers, aromatic modified terpene polymers, α-pinene polymers, terpene hydrogenated resins, etc. An olefin resin; a petroleum resin polymerized with a petroleum fraction of 5 carbon atoms; a petroleum resin polymerized with a petroleum fraction of 9 carbon atoms; and a hydrogenated resin thereof; a petroleum resin such as a maleic acid modified product or a fumarate modified product; A polyisocyanate compound to be described later, a polyhydric alcohol compound, and a polyurethane resin obtained by further reacting with other compounds as needed.

Among them, preferred are terpene-based resins and polyurethane resins. As the terpene-based resin, YS RESIN PX/PXN, YS POLY STAR, MIGHTYACE, YS RESIN TO/TR, Clearon P/M/K (manufactured by Yasuhara Chemical Co., Ltd.), TAMANOL 803L/901 (manufactured by Arakawa Chemical Co., Ltd.), and Terutac 80 can be used. (available from Nippon Terpene Chemicals Co., Ltd.) or the like.

The polyurethane resin is preferably in the form of an aqueous emulsion in which the polyurethane is dispersed in water. That is, the polyurethane may be either water-soluble or water-insoluble, but is preferably water-insoluble.

In general, the polyurethane resin can be obtained by reacting a polyisocyanate compound with a polyol compound and further reacting with other compounds as needed. Examples of the reaction include an acetone method, a prepolymer mixing method, a ketimine method, and a hot melt dispersion method.

The polyisocyanate compound is exemplified by an organic polyisocyanate compound which usually has two or more isocyanate groups in the molecule for producing a polyurethane. For example, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 3-isocyanate methyl-3, 5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexyl-2,4-diisocyanate, methylcyclohexyl-2,6-diisocyanate, hydrazine Diisocyanate (XDI), 1,3-bis(isocyanate)methylcyclohexane, tetramethyl decyl diisocyanate, trans-cyclohexane-1,4-diisocyanate, diazonium diisocyanate Diisocyanate) and other aliphatic diisocyanates; 2,4-methylphenylene diisocyanate (TDI), 2,6-methylphenylene diisocyanate (TDI), diphenylmethane-4,4'-diisocyanate (MDI) 1,5'-naphthalene diisocyanate, tolidine diisocyanate, diphenylmethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, Aromatic diisocyanates such as 1,3-phenylene diisocyanate; aminate triisocyanate, triphenylmethane triisocyanate, 1,6,11-undecane triisocyanate, 1,8 - isocyanate-4,4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, adduct of trimethylolpropane and methylphenyl diisocyanate, three A triisocyanate such as an adduct of methylolpropane and 1,6-hexamethylene diisocyanate. These may be used alone or in combination of two or more.

The polyol compound may, for example, be a compound having two or more hydroxyl groups in a molecule which is usually used for producing a polyurethane. Examples thereof include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, and glycerin; Polyether polyols such as alcohol, polypropylene glycol, polytetramethylene ether glycol; from adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid, isophthalic acid, fumaric acid, succinic acid , dicarboxylic acids such as oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, and ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6 - hexanediol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 1,3-propanediol, three a polyester polyol obtained from a polyol compound such as propylene glycol, trimethylolpropane or glycerin; a polycaprolactone polyol; a polylactone polyester polyol such as polyβ-methyl-δ-valerolactone; A polybutadiene polyol or a hydride thereof, a polycarbonate polyol, a polythioether polyol, a polyacrylate polyol, or the like.

In order to enhance the dispersion stability in water, the polyurethane resin is preferably one having a hydrophilic group in the molecule. A polyurethane having a hydrophilic group in its molecule is called an ionomer structure and has its own interface activity. Therefore, there is a tendency to be easily dispersed in water, and the aqueous emulsion of the polyurethane is further emulsified to polymerize the monomer, and the obtained aqueous emulsion has a tendency to improve water resistance.

The hydrophilic group is preferably an anionic group such as a sulfonyl group or a carboxyl group, and more preferably a sulfonyl group. This is because it has a tendency to further improve the water resistance of the aqueous emulsion obtained by emulsion polymerization of the monomer.

The anionic group is usually preferably neutralized by a neutralizing agent.

Examples of the neutralizing agent include a tertiary amine compound such as triethylamine or triethanolamine; an inorganic base compound such as sodium hydroxide; and ammonia.

In order to introduce a hydrophilic group into a molecule, the following compounds are preferably used in the production of a polyurethane. Examples of the compound include a nonionic hydrophilic group having a structural unit derived from polyethylene glycol in the molecule, and having one or more sulfonyl groups, carboxyl groups, hydroxyl groups, primary amine groups (-NH ₂ ), and secondary amine groups ( =NH) A compound such as an active hydrogen which is reactive with an isocyanate group (hereinafter referred to as "a compound containing a hydrophilic group").

Examples of the compound having a hydrophilic group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, and N. a sulfonic acid-containing compound such as (2-aminoethyl)-2-aminoethylsulfonic acid; 2,2-dimethylol lactic acid, 2,2-dimethylolpropionic acid, 2,2-di A carboxylic acid-containing compound or the like such as 2,2-methylol valerianic acid. These may be used alone or in combination of two or more.

When the polyurethane resin is produced as an aqueous emulsion, it is necessary to extend the chain, adjust the molecular weight, and the like, and a compound different from the hydrophilic group-containing compound may be used in combination, and the compound contains a compound which can react with the isocyanate compound in the molecule. Active hydrogen. Examples of such a compound include polyamine compounds such as ethylenediamine, 1,4-butanediamine, and hexamethylenediamine; polyhydric alcohols containing tertiary amines such as triethanolamine; and methanol, ethanol, butanol, and the like. Alcohols, etc.

As the polyurethane resin, a commercially available aqueous polyurethane emulsion and a commercially available water-soluble urethane resin can be used as it is.

For example, a polyamine which disperses or dissolves a polyurethane resin in water can be cited. Ester dispersion (or aqueous polyurethane solution). The content of the polyurethane resin in the polyurethane dispersion may be from about 10 to 70% by weight, preferably from about 20 to 60% by weight, more preferably from about 30 to 60% by weight, still more preferably from about 30 to 55% by weight.

The polyurethane dispersion may also contain an organic solvent which does not contain an isocyanate reactive group, such as ethyl acetate, acetone, methyl ethyl ketone, N-methylpyrrolidone or the like. The amount of the organic solvent is not particularly limited, but may be 0.1 to 100 parts by weight based on 100 parts by weight of the nonvolatile component in the polyurethane dispersion.

Examples of the water-soluble amine ester resin include Dispercoll U-42, U-53, U-54, U-56, KA-8481, KA-8584, KA-8755, KA manufactured by Sumitomo Bayer Urethane Co., Ltd. -8756, KA-8766; HYDRANHW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP-60LM, AP-80, Sanyo, manufactured by DIC Corporation UPRENEUXA-306, UXA-307, PARMALIN UA-150, PARMALIN UA-200, PARMALIN UA-300, PARMALIN UA-310, UCOAT UWS-145 manufactured by Huacheng Industrial Co., Ltd.; SuperFlex manufactured by Daiichi Kogyo Co., Ltd. 107M, 110, 126, 130, 150, 160, 300, 361, 370, 410, 420, 460, 700, 750, 820; ADEKA BONTIGHTER HUX-401, HUX-420A, HUX-380, HUX- 561, Hux-210, HUX-822, HUX-895, HUX-830, etc.

When the aqueous adhesive of the present invention contains other resins, the content thereof is preferably from 1 to 99% by weight, more preferably from 3 to 99% by weight, still more preferably from 5 to 90% by weight, based on the total amount of the aqueous adhesive.

Further, the polymer: other resin (nonvolatile content ratio) is preferably 5:95 to 95:5, more preferably 5:95 to 95:5, and even more preferably 5:95 to 80:20.

These resins may be emulsified or emulsified together with a polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms.

<Surfactant>

The aqueous adhesive of the present invention preferably contains a surfactant which acts generally as an emulsifier. Such a surfactant may, for example, be a cationic, anionic, amphoteric or nonionic surfactant, and among them, an anionic or nonionic surfactant is preferred. It is especially preferred to have the structure of formula (I). The surfactant may be used singly or in combination of two or more kinds, but it is preferred to use two or more types in combination. Among them, it is more preferred to use two or more kinds of surfactants having the structure of the formula (I) in combination.

In the formula (I), X is a hydrogen atom, -SO ₃ M (M is a hydrogen atom, -NH ₄ or an alkali metal), and examples thereof include sulfuric acid and a sulfate (for example, an alkali metal salt such as an ammonium salt or a sodium). And the like, but among them, a hydrogen atom, -SO ₃ H or -SO ₃ NH _{4 is} preferred.

In the case of combining two or more types of surfactants, X may be the same and n and/or m may be different, and it is preferred that the combinations n and/or m are the same or different and X is different. Specifically, a combination of an X-based hydrogen atom and -SO ₃ H, a combination of a hydrogen atom and -SO ₃ NH ₄ , and a combination of -SO ₃ H and -SO ₃ NH ₄ may be mentioned. Among them, a combination of a hydrogen atom and -SO ₃ NH ₄ is preferred.

The surfactant represented by the formula (I) is LATEMUL AD-25 (manufactured by Kao Co., Ltd.), LATEMUL E-1000A (made by Kao Co., Ltd.) represented by the following formula (A), and the following formula (B) ) indicated by NOIGEN EA-177 (manufactured by First Industrial Pharmaceutical Co., Ltd.).

The aqueous adhesive of the present invention may contain a surfactant other than the surfactant represented by the formula (I).

For example, as the anionic surfactant, a sulfate ester of a higher alcohol, a higher alkyl sulfonate, a higher carboxylate, an alkylbenzenesulfonate, a polyoxyethylidene sulfate, a polyoxygen Ethyl ethyl phenyl ether sulfate, vinyl sulfosuccinate, and the like.

Examples of the cationic surfactant include alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt; alkyl groups such as cetylpyridinium salt and mercaptopyridinium salt; Pyridinium salt; alkyloxyalkyltrialkylammonium salt, dioxyalkylene dialkylammonium salt, allyltrialkylammonium salt, diallyldialkylammonium salt, and the like.

In the case of a nonionic surfactant, polyoxyethylene propylene ether, polyoxyethylene propylene ether, polyoxyethylene ethyl phenyl ether, polyethylene glycol fatty acid Ethylene oxide propylene oxide block copolymer, polyoxyalkylene fatty acid decylamine, oxidized ethylidene-oxylated propyl copolymer, etc. A compound of a base structure, a sorbitol derivative such as a polyoxyethylene ethyl sorbitol fatty acid ester, or the like.

As the amphoteric surfactant, lauryl betaine can be mentioned. (lauryl betaine), dodecyl dimethylamine oxide, and the like.

The content of the surfactant is usually 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the resin constituting the aqueous binder.

When the aqueous adhesive of the present invention contains a surfactant other than the surfactant represented by the formula (I), the surfactant represented by the formula (I) and the formula (I) with respect to 100 parts by weight of the resin constituting the aqueous binder The total content of the surfactant other than the surfactant is usually from 0.1 to 50 parts by weight, preferably from 0.1 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight.

When the surfactant represented by the formula (A) and the surfactant represented by the formula (B) are used, the weight ratio is preferably from 1 to 99:99 to 1, more preferably from 5 to 95:95. 5, more preferably 10 to 90: 90 to 10, especially 30:70 to 90:10, 40:60 to 90:10, 50:50 to 90:10.

<alkaline compound>

The aqueous adhesive of the present invention preferably contains a basic compound.

As the basic compound, a carboxyl group neutralized person such as ammonia, an organic amine compound, a metal hydroxide or the like is preferable. Preferred is ammonia or an organic amine compound. In particular, the organic amine compound having a boiling point of 200 ° C or less can be easily scattered by usual drying, and it is preferred to maintain/improve the water resistance and alkali resistance of the coating film when the coating film is formed by using an aqueous binder.

Examples of the organic amine compound include triethylamine, N,N-dimethylethanolamine, aminoethanolamine, N-methyl-N,N-diethanolamine, isopropylamine, and imidobispropane. Amine, ethylamine, diethylamine, 3-ethoxypropyl Amine, 3-diethylaminopropylamine, second butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methyl Morpholine, N-ethylmorpholine and the like. Among them, N,N-dimethylethanolamine or the like is preferred.

Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide, and sodium hydroxide.

When the aqueous binder contains a basic compound, the content thereof is preferably from 1 to 30 parts by weight, more preferably from 2 to 20 parts by weight, still more preferably from 2 to 10 parts by weight, per 100 parts by weight of the resin constituting the aqueous binder. .

<solvent>

The aqueous adhesive agent of the present invention preferably contains no solvent, and may contain, for example, an aromatic hydrocarbon such as toluene or xylene; an aliphatic hydrocarbon such as hexane; an ester such as ethyl acetate or butyl acetate; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, etc. Glycol solvent; methyl cellosolve, 赛路苏, butyl 赛路苏, 二 Acetone, MTBE (methyl tert-butyl ether), butyl carbitol, etc., sulphone solvent; diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl Alcohol solvent such as ethyl ether or 3-methoxy-3-methyl-1-butanol; ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene glycol monobutyl A glycol ester solvent such as a vinyl ether acetate or a diethylene glycol monoethyl ether acetate; or an organic solvent. These may be used alone or in combination of two or more.

When the aqueous adhesive of the present invention contains a solvent, the content thereof is usually 0.01 to 30 parts by weight based on 100 parts by weight of the resin constituting the aqueous adhesive. It is preferably from 0.01 to 10 parts by weight.

<Other ingredients>

The aqueous adhesive of the present invention usually contains water. Further, the phenol-based stabilizer, the phosphorus-based stabilizer, the amine-based stabilizer, the guanamine-based stabilizer, the anti-aging agent, the weathering stabilizer, and the like may be contained as long as the properties of the aqueous adhesive are not impaired. Anti-settling agent, antioxidant, thermal stabilizer, light stabilizer and other stabilizers; shaker, tackifier, dispersant, defoamer, viscosity modifier, weathering agent, pigment, pigment dispersant, antistatic agent, Additives such as slip agent, nucleating agent, flame retardant, oil agent, dye, hardener, cross-linking agent; transition metal compound such as titanium oxide (rutile type) and zinc oxide; pigment such as carbon black; glass fiber , carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass-flake, barium sulfate, clay, kaolin, cerium oxide fine powder, mica, calcium citrate, hydrogen Any component such as inorganic or organic fillers such as alumina, magnesium hydroxide, alumina, magnesia, alumina, and diatomaceous earth.

(water)

The water contained in the aqueous adhesive of the present invention is generally water, ion exchange water or the like. Further, in order to improve the stability of the aqueous adhesive, a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose or hydroxyethyl cellulose may be added.

The content of water is, for example, 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 45% by weight or more, based on the total amount of the aqueous binder. It is 85 wt% or less, more preferably 80 wt% or less, still more preferably 70 wt% or less.

(tackifier)

For the viscosity adjustment of the formulation, a tackifier can be used. As the tackifier, ADEKANOL UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH- by ADEKA Co., Ltd. can be cited. 540, UH-541VF, UH-550, UH-752, H-756VF; SNthickener 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A-813 by SANNOPCO , A-818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, 4050, and the like.

(Dispersant)

In order to improve the wettability of the coated substrate, a dispersing agent can be used. Examples of the dispersing agent include ADEKACOL W-193, W-287, W-288, and W-304 manufactured by ADEKA Co., Ltd.; BYK-333, BYK-345, BYK-346, and BYK-347 manufactured by BYK Corporation. , BYK-348, BYK-349, BYK-378; NONOCO WET50, SN WET366, NOPCO 38-C, SN DisperSant 5468, 5034, 5027, 5040, 5020, etc. manufactured by SANNOPCO.

(hardener)

Examples of the hardener include diphenylmethane diisocyanate (MDI), methyl benzene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and xylene diisocyanate (XDI), which are isocyanate-based hardeners. And such oligomers or polymers. Specifically, SUMIDUR 44V20, SUMIDUR N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, etc. by Bayer Urethane can be mentioned.

The hardener is preferably from 0.1 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight, per 100 parts by weight of the resin constituting the aqueous adhesive. The hardener can be added and dissolved in an organic solvent.

<Method for Producing Aqueous Adhesive>

Examples of the method for producing the aqueous adhesive include a method known in the art, for example, an emulsification method after the resin is polymerized and then dispersed in an aqueous medium (for example, a forced emulsification method, an auto-emulsification method, a phase transfer emulsification method). and many more.

Specifically, it can be exemplified: (1) adding an emulsified resin and a solvent to the reactor and stirring, then heating and dissolving, and adding a surfactant, water and/or a solvent thereto, heating and stirring, and recovering before and after Optionally adding water and/or solvent and stirring; (2) adding an emulsified resin, any solvent in a kneading machine, stirring, heating and melting, and adding a surfactant, water and/or solvent thereto, heating and The mixture is stirred and arbitrarily added with water and/or solvent and stirred. However, at least one water addition is required in the methods (1) and (2).

In the production method of the above (1), the reactor is a container (preferably a sealed and/or pressure-resistant container) having a heating device capable of heating and providing a shearing force to the contents.

The mixer can be used with a conventional mixer. Examples of such a pressure resistant container include a pressure autoclave equipped with a stirrer. The stirring system can be carried out, for example, at either normal pressure or reduced pressure. Further, the number of revolutions of the agitator can be performed, for example, at a number of revolutions of about 50 to 1000 rpm. It is preferred to increase the number of revolutions when performing dispersion/stirring of the aqueous binder as needed.

The heating is usually carried out at 50 to 200 ° C, preferably 60 to 150 ° C, and more preferably 70 to 100 ° C.

After stirring, the solvent is preferably distilled off from the resulting dispersion (preferably reduced pressure or pressurized). The method of distilling off can utilize methods well known in the art. The degree of pressure reduction or pressurization may be about 0.001 to 1 MPa, preferably about 0.001 to 0.5 MPa.

In the production method of the above (2), for example, a roll mill, a kneader, an extruder, an ink roll, a Banbury mixer, or the like can be used. In particular, an extruder or a multi-axis extruder having one or more screws in a casing can be used.

The method of emulsification using an extruder is to mix the emulsified resin and the surfactant, and continuously supply it by a hopper or a supply port of the extruder, heat-melt and knead it, and then borrow it. Water is supplied from a supply port provided in at least one of a compression zone, a metering zone, and a degassing zone of the extruder, and is continuously extruded by a die after being kneaded by a screw.

Further, in the production process of the aqueous adhesive, it is preferred to appropriately add the above-mentioned other components such as components other than the above, other resins, an antifoaming agent, and a viscosity adjusting agent at any time.

Further, in the production step of the aqueous adhesive, it is preferred to use a surfactant in the range obtained, and when the surfactant is excessively used, the excess surfactant can be arbitrarily separated and removed from the obtained aqueous adhesive. The separation and removal of the surfactant may be, for example, a filter using a centrifugal separator and micropores having an average pore diameter smaller than the average particle diameter of the aqueous binder (preferably having a precision of an average pore diameter of 0.05 to 0.5 μm). Filter membrane) or super Filter and other methods.

Further, it is preferred to cool the obtained aqueous adhesive. Thereby, an aqueous adhesive containing fine particles of the resin composition can be obtained. The cooling does not require a particularly low temperature, and a method of leaving it at normal temperature can be cited. Thereby, the resin or the like does not aggregate during the cooling process, and a fine and homogeneous aqueous adhesive can be obtained.

The aqueous binder of the present invention contains the particle diameter of the dispersoid, which is usually 10 μm or less, preferably 0.01 to 10 μm, more preferably 0.01 to 2 μm, still more preferably 0.01 to 1 μm, on a number basis. Set the stability is good.

Here, the particle diameter of the number reference corresponds to a particle diameter of 50% of the cumulative particle diameter distribution on a number basis, and the volume reference median diameter means a cumulative particle diameter distribution based on a volume basis. The value is 50% of the particle size. Unless otherwise stated, it means the value of the intermediate diameter measured on a number basis.

Further, depending on the necessity, for example, a filter having various pore sizes or the like may be used for filtration or the like.

When the aqueous binder contains a plurality of types of dispersoids (for example, a polymer having a structural unit derived from an α-olefin, a polyurethane resin, etc.), the particle diameter of each dispersoid is preferably the same. The same degree is, for example, preferably within ±50% of the particle diameter of the polymer having the structural unit derived from the α-olefin, and more preferably within ±30%.

<Method for Producing Laminated Structure/How to Use Aqueous Adhesive>

The aqueous adhesive of the present invention can be used for a nylon resin (first substrate) and a cotton-containing fiber (second substrate).

First, it is preferred to coat both the first substrate and the second substrate. Cloth adhesive.

The coating method may be a known film forming method, for example, one of a nylon resin and a cotton-containing fiber, preferably coated with an aqueous adhesive of the present invention on both surfaces, and placed at a temperature near room temperature as needed. Drying or performing a heat treatment for drying and baking.

The composition of the aqueous adhesive can be formed by extrusion molding into a coating film, or can be applied to various substrate surfaces and dried; the obtained coating film can also be sandwiched between nylon resin and cotton-containing fiber. Press and press (or heat).

Examples of the coating method include gravure roll coating, reverse roll coating, bar coating, wire bar coating, lip coating, air knife coating, and curtain coating. Curtain flow coating, spray coating, dip coating, brush painting, knife coating, and the like.

Further, before the application of the aqueous adhesive, the primer treatment may be applied to the surface of the first substrate and/or the second substrate as described above.

In particular, when a substrate containing water-absorbent such as cotton fibers is used, an aqueous adhesive can be applied as a primer and dried. Here, the application of the aqueous adhesive can be carried out by the above method. Drying can be carried out by the method described later. In the case of the primer treatment, the aqueous binder to be used may be used alone or in combination of two or more. The primer treatment may be carried out only once or twice or more. Further, different aqueous binders may be used for the first and second substrates, but it is preferred to use the same aqueous binder.

Drying can be carried out by natural drying, air drying, etc., or by using a general hot air circulation type oven, infrared or far infrared heater, electromagnetic wave. (for example, an electromagnetic wave having a frequency band of 2.45 ± 0.02 GHz) is irradiated by a device, a microwave oven, or the like by thermal drying or the like. The heating temperature and the heating time can be appropriately adjusted depending on the characteristics of the substrate, the composition of the aqueous adhesive of the present invention, and the like. For example, the heating temperature is about 30 to 150 ° C, preferably about 40 to 85 ° C. The heating time is, for example, about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, more preferably about 5 seconds to 10 minutes.

The application and drying of the aqueous adhesive may be carried out only once or twice or more. In this case, the coating method and the drying method may be combined with the same method, or different methods may be combined. In addition, electromagnetic waves of different frequency bands can be combined.

The bonding of the first and second substrates can be carried out under load heat, load pressure, or both. When the load is hot, the temperature range in which the first base material and the second base material and the subsequent layer are not deteriorated is preferably about 120 ° C or lower, more preferably about 100 ° C or lower. The heat load can be carried out by using the above-described general hot air circulation type oven, infrared heater, microwave oven or the like. In the case of the load pressure, the pressure may be about 100 g/cm ² or more, and the pressure which does not deform the shape of the first base material and the second base material may be mentioned.

Further, after the first and second base materials are bonded together, the above-mentioned non-thermal drying, thermal drying, or the like (for example, electromagnetic wave irradiation or the like) may be performed on the obtained laminated structure, and the pressure may be applied under a constant load.

The thickness of the coating film formed by using the aqueous adhesive of the present invention can be appropriately adjusted depending on the form of the nylon resin to be coated and the form of the cotton-containing fiber. For example, it is about 0.01 to 300 μm, preferably about 0.01 to 200 μm, more preferably about 0.2 to 200 μm.

(Example)

The invention will be described in more detail below with reference to examples, but the invention is not limited thereto. The parts and % in the examples are based on the weight basis unless otherwise specified.

In the following examples, the physical property measurement was carried out in the following manner.

(1) The structural unit content of the polymer

The measurement results of ¹ H-NMR mass spectrum and ¹³ C-NMR mass spectrum measured by the following conditions were calculated using a nuclear magnetic resonance apparatus (trade name: AC-250, manufactured by Bruker). Specifically, in the ¹³ C-NMR mass spectrum, the ratio of the mass spectrum intensity of the methyl carbon derived from the structural unit of propylene to the mass spectrum intensity of the methyl carbon derived from the structural unit of 1-butene is calculated from the structural unit derived from propylene. The composition ratio of the structural unit derived from 1-butene, followed by the mass spectrum intensity of hydrogen from the methine unit and the methylene unit, and the mass spectrum of hydrogen from the methyl unit in ¹ H-NMR mass spectrometry The composition ratio of the structural unit derived from ethylene, the structural unit derived from propylene, and the structural unit derived from 1-butene was calculated.

¹³ C-NMR (H decoupling)

¹³ C frequency: 150.9MHz

Pulse width: 6.00μsec

Pulse repetition time: 4.0 seconds

Cumulative number: 256 times

Measuring temperature: 137 ° C

Solvent: o-dichlorobenzene-d4 (concentration about 20%)

(2) Ultimate viscosity [η]

It was carried out at 135 ° C using a Ubbelohde viscometer. A tetralin solution of a polymer having a polymer concentration c of 0.6, 1.0, 1.5 mg/mL per unit volume of tetralin was adjusted, and the ultimate viscosity was measured at 135 °C. The measurement was repeated three times at various concentrations, and the average value of the obtained three times was taken as the specific viscosity (η sp) of the concentration, and the value of extrapolating η sp /c to zero was obtained as the ultimate viscosity [η ].

(3) Molecular weight distribution

The measurement was carried out by a colloidal permeation chromatography (GPC) method under the following conditions.

Device: HLC-8121GPC/HT manufactured by TOSOH

Pipe column: TSKgel GMH _HR -H(S)HT 4 made by TOSOH

Temperature: 145 ° C

Solvent: o-dichlorobenzene

Dissolution solvent flow rate: 1.0 ml / min

Sample concentration: 1mg/ml

Determination of injection volume: 300μl

Molecular Weight Standard Material: Standard Polystyrene

Detector: differential refractive index detector

(4) Crystal melting peak and crystallization peak

The measurement was carried out according to the following conditions using a differential scanning calorimeter (DSC220C: input compensation DSC manufactured by Seiko Electronics Co., Ltd.).

(i) A sample of about 5 mg was heated from room temperature to 200 ° C at a temperature increase rate of 30 ° C / min, and maintained for 5 minutes after the end of the temperature rise.

(ii) Next, the temperature was lowered from -200 ° C at a temperature drop rate of 10 ° C / min from 200 ° C, and maintained for 5 minutes after the end of the temperature drop. The peak observed in (ii) is The crystallization peak was confirmed by the presence or absence of a crystallization peak having a peak area of 1 J/g or more.

(iii) Then, the temperature was raised from 200 ° C at a temperature increase rate of 10 ° C / min from -100 ° C. The peak observed in (iii) is a melting peak of the crystal, and it is confirmed whether or not there is a melting peak having a peak area of 1 J/g or more.

(5) Melt flow rate (MFR)

The measurement was carried out in accordance with JIS-K-7210.

(6) Change the quality

The quality of maleic anhydride was changed. 1.0 g of the sample was dissolved in 20 mL of xylene, and the sample solution was dropped into 300 mL of methanol while stirring, and the sample was reprecipitated and recovered, and then the recovered sample was vacuum dried ( At 80 ° C for 8 hours, a film having a thickness of 100 μm was formed by hot pressing, and the infrared absorption spectrum of the obtained film was measured, and the mass of maleic anhydride was adjusted by absorption in the vicinity of 1780 cm ^-1 .

(7) Non-volatile components

This was carried out in accordance with the measurement method of JIS K-6828.

(8) Particle size of aqueous emulsion

The value measured by the laser diffraction particle size measuring device LA-950V2 manufactured by HORIBA. Unless otherwise specified, the particle size is the value of the intermediate diameter measured on a number basis.

<Production Example of Copolymer (B-1-1)>

386 parts of ethylene cyclohexane (hereinafter referred to as VCH) and 3640 parts of toluene were placed in an argon-substituted reactor made of SUS. After heating up to 50 ° C, ethylene was added while being pressurized at 0.6 MPa. Adding toluene solution of triisobutylaluminum (TIBA) [TOSOH‧Akzo (stock company) system TIBA, concentration 20%] 10 parts, followed by the addition of diethyl decyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 0.001 part of dissolved in 87 parts of dehydrated toluene and 0.03 parts of dimethylanilinium (pentafluorophenyl) borate were dissolved in 122 parts of dehydrated toluene, and stirred for 2 hours. The obtained reaction liquid was poured into about 10,000 parts of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and dried under reduced pressure to give 300 parts of copolymer (B-1-1). The copolymer had [η] of 0.48 dl/g, Mn of 15,600, a molecular weight distribution (Mw/Mn) of 2.0, a melting point (Tm) of 57 ° C, a glass transition point (Tg) of -28 ° C, and a VCH in the copolymer. The content ratio of the unit was 13 mol%.

<Production Example of Copolymer (B-1-2)>

0.4 parts of maleic anhydride and 0.04 parts of 1,3-bis(t-butylperoxyisopropyl)benzene were added to 100 parts of the copolymer (B-1-1) copolymer obtained, and after sufficient preparation and mixing, The supply port of the two-axis extruder was supplied and melt-kneaded to obtain a copolymer (B-1-2). Further, the temperature at which the extruder is melt-kneaded is divided into two stages of the first half and the second half of the melt kneading, and the first half is 180 ° C, and the latter half is set to a temperature of 260 ° C to carry out melt kneading. The graft amount of maleic acid of the copolymer (B-1-2) was 0.2%, and the MFR was 180 g/10 min (190 ° C, load: 2.16 kgf).

<Production Example of Copolymer (B-2-2)>

A stirrer, a thermometer, a dropping funnel, a reflux cooling tube were placed in a separable flask reactor having a capacity of 1 L, and the gas in the reactor was replaced with nitrogen. 600 parts of xylene as a solvent, polymer (B-2-1) [ethylene/propylene copolymer (LICOCENE PP 1602, manufactured by Clariant JAPAN Co., Ltd.) was added thereto. Ethylene: propylene = 15 mol%: 85 mol%)] 100 parts, maleic anhydride 50 parts, 2,4,8,10-tetrabutylbutyl-6-[3-(3-methyl-4-hydroxy-5) -1 -butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphane (Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd.) 1 part, heated at 140 ° C The solution was stirred and then 2 parts of di-tert-butyl peroxide was added, and the reaction was continued by stirring at the same temperature for 5 hours. In addition, an oil bath is used for heating. After completion of the reaction, the contents were cooled to room temperature, and poured into 1000 parts of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and dried under reduced pressure to give a polymer (B-2-2) modified with maleic anhydride. The obtained polymer had a Mw of 45,362, an Mn of 23,354, a molecular weight distribution (Mw/Mn) of 1.9, and a maleic acid-modified mass of 0.93%.

Further, the polymer (B-2-1) was in a temperature range of -100 to 200 ° C, and a crystal melting peak having a heat of crystal melting of 1 J/g or more and a crystallization peak having a heat of crystallization of 1 J/g or more were observed.

<Production Example of Copolymer (B-2-4)>

In addition to the use of the polymer (B-2-3) [ethylene/propylene copolymer (LICOCENE PP2602, manufactured by Clariant JAPAN Co., Ltd., ethylene: propylene = 13 mol%: 87 mol%)], with the polymer (B-2-2) In the same manner as in the production example, a polymer (B-2-4) modified with maleic anhydride was obtained. The obtained polymer had Mw of 55115, Mn of 25836, a molecular weight distribution (Mw/Mn) of 2.2, and a maleic acid modified mass of 0.84%.

Further, the polymer (B-2-3) was in a temperature range of -100 to 200 ° C, and a crystal melting peak having a heat of crystal fusion of 1 J/g or more and a crystallization peak having a heat of crystallization of 1 J/g or more were observed.

<Production Example of Copolymer (B-3-1)>

After a stirrer, a thermometer, a dropping funnel, a reflux cooling tube, and a reduced pressure were placed in a separable flask reactor having a capacity of 2 L, the gas in the reactor was replaced with nitrogen. To the flask was added 1 L of dried toluene as a polymerization solvent. Propylene 8NL/min and 1-butene 0.5NL/min were continuously supplied thereto under normal pressure to have a solvent temperature of 30 °C. After adding 1.25 mmol of triisobutylaluminum (hereinafter referred to as TIBA) to the reactor, dimethyl thiol (2,3,4,5-tetramethyl group) as a polymerization catalyst was added to the reactor. Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride 0.005 mmol. After 15 seconds, 0.025 mmol of triphenylmethylphosphonium (pentafluorophenyl)borate was added to the reactor to initiate polymerization. As a result of polymerization for 30 minutes, 155.8 g of a propylene-1-butene copolymer (B-3-1) having a propylene content of 96 mol% was obtained. The obtained polymer had an ultimate viscosity [η] of 2.1 dl/g and a molecular weight distribution (Mw/Mn) of 2.5. Further, in the temperature range of -100 to 200 ° C, any of the crystal melting peak having a heat of crystal fusion of 1 J/g or more and a crystallization peak having a heat of crystallization of 1 J/g or more were not observed.

<Production Example of Copolymer (B-3-2)>

A polymer (B-3-2) modified with maleic anhydride was obtained in the same manner as in the production example of the polymer (B-2-2) except that the polymer (B-3-1) was used. The obtained polymer had a Mw of 49,043, an Mn of 14,267, a molecular weight distribution (Mw/Mn) of 3.4, and a maleic acid-modified mass of 1.79%.

<Production Example 1 of Aqueous Emulsion>

200 parts of toluene as a solvent was added to a 2 L separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux cooling tube. The polymer (B-1-2) of the copolymer was 100 parts, and stirred and dissolved at 80 °C. Then, 17 parts of LATEMUL E-1000A (30% aqueous solution, manufactured by Kao Corporation), 5 parts of NOIGEN EA-177 (manufactured by Daiichi Pharmaceutical Co., Ltd.), and 5 parts of isopropyl alcohol were added as a surfactant for 10 minutes. Mixture. After stirring for 5 minutes, 5 parts of dimethylethanolamine was added and the mixture was stirred for 5 minutes.

Then, the stirring apparatus was changed to TK ROBOMIX (manufactured by PRIMIX Co., Ltd.), and while the reaction mixture was stirred with a dispersion wing, a mixture of 100 parts of isopropyl alcohol and 100 parts of ion-exchanged water was added dropwise over 30 minutes. When fluidity was observed in the reaction mixture, the stirring blade was changed to a homomixer, and 300 parts of ion-exchanged water was added dropwise while stirring to obtain a milky white dispersion.

The obtained dispersion was placed in a 2 L eggplant type flask, and distilled under reduced pressure in an evaporator, and filtered through a mesh of 200 mesh to obtain a polymer (B-1-2) and a surfactant. Aqueous emulsion. The particle diameter (number basis) of the obtained aqueous emulsion (E-1) was 0.61 μm, and the concentration of the nonvolatile component was 36%.

<Production Example 2 of Aqueous Emulsion>

An aqueous emulsion was produced in the same manner as in <Production Example 1 of the aqueous emulsion> except that 100 parts of the polymer (B-2-1) was used as the copolymer. The particle size (number basis) of the obtained aqueous emulsion (E-2) was 0.25 μm, and the concentration of the nonvolatile component was 38%.

<Production Example 3 of Aqueous Emulsion>

An aqueous emulsion was produced in the same manner as in <Production Example 1 of the aqueous emulsion> except that 100 parts of the polymer (B-2-2) was used as the copolymer. The particle diameter (number basis) of the obtained aqueous emulsion (E-3) was 0.22 μm, and the concentration of the nonvolatile component was 39%.

<Production Example 4 of Aqueous Emulsion>

An aqueous emulsion was produced in the same manner as in <Production Example 1 of the aqueous emulsion> except that 100 parts of the polymer (B-2-3) was used as the copolymer. The particle diameter (number basis) of the obtained aqueous emulsion (E-4) was 0.21 μm, and the concentration of the nonvolatile component was 36%.

<Production Example 5 of Aqueous Emulsion>

An aqueous emulsion was produced in the same manner as in <Production Example 1 of the aqueous emulsion> except that 100 parts of the polymer (B-2-4) was used as the copolymer. The particle diameter (number basis) of the obtained aqueous emulsion (E-5) was 0.13 μm, and the concentration of the nonvolatile component was 36%.

<Production Example 6 of Aqueous Emulsion>

An aqueous emulsion was produced in the same manner as in <Production Example 1 of the aqueous emulsion> except that 100 parts of the polymer (B-3-2) was used as the copolymer. The particle diameter (number basis) of the obtained aqueous emulsion (E-6) was 0.33 μm, and the concentration of the nonvolatile component was 34%.

<Production Example 7 of Aqueous Emulsion>

An aqueous emulsion was produced in the same manner as in <Production Example 1 of aqueous emulsion> except that 50 parts of the polymer (B-2-2) and 50 parts of the polymer (B-3-2) were used as the copolymer. The particle diameter (number basis) of the obtained aqueous emulsion (E-7) was 0.21 μm, and the concentration of the nonvolatile component was 35%.

<Production Example 8 of Aqueous Emulsion>

In addition to the use of polymer (B-4-1) [BONDINE HX8140 (ARKEMA) In the same manner as in the production example 1 of the aqueous emulsion, 100 parts of the aqueous emulsion was produced. The particle diameter (number basis) of the obtained aqueous emulsion (E-8) was 0.09 μm, and the concentration of the nonvolatile component was 40%.

<Production Example 9 of Aqueous Emulsion>

An aqueous emulsion was produced in the same manner as in <Production Example 1 of the aqueous emulsion> except that 100 parts of the polymer (B-4-2) [BONDINE AX8390 (manufactured by ARKEMA)] was used as the copolymer. The particle diameter (number basis) of the obtained aqueous emulsion (E-9) was 0.11 μm, and the concentration of the nonvolatile component was 42%.

<Production Example 10 of Aqueous Emulsion>

In addition to using 67 parts of a polymer (B-4-2), 33 parts of an adhesive resin (terpene phenol, TAMANOL 803L, manufactured by Arakawa Chemical Co., Ltd.) to replace 100 parts of the polymer (B-1-2), Production Example 1 of Emulsion> An aqueous emulsion (E-10) was produced in the same manner. The particle diameter (number basis) of the obtained aqueous emulsion was 0.10 μm, and the concentration of the nonvolatile component was 41%.

<Production Example 11 of Aqueous Emulsion>

An aqueous emulsion (E-11) was produced in the same manner as in <Production Example 1 of aqueous emulsion> except that 100 parts of the polymer (B-4-3) [BONDINE HX8290 (manufactured by ARKEMA)] was used as the copolymer. . The particle diameter (number basis) of the obtained aqueous emulsion was 0.18 μm, and the concentration of the nonvolatile component was 39%.

<Production Example 12 of Aqueous Emulsion>

In addition to 50 parts of the polymer (B-4-3), 50 parts of an adhesive resin (terpene phenol, TAMANOL 803L, manufactured by Arakawa Chemical Co., Ltd.) to replace 100 parts of the polymer (B-1-2), Production Example 1 of Emulsion> An aqueous emulsion (E-12) was produced in the same manner. Particle size of the obtained aqueous emulsion (number basis) It was 0.20 μm and the concentration of the nonvolatile component was 33%.

<Production Example 13 of Aqueous Emulsion>

An aqueous emulsification was produced in the same manner as in <Production Example 1 of <Aqueous Emulsion>, except that 100 parts of a polymer (B-4-4) [BONDINE LX4110 (manufactured by ARKEMA)] was used as a copolymer and the reaction temperature was 90 °C. (E-13). The particle diameter (number basis) of the obtained aqueous emulsion was 0.08 μm, and the concentration of the nonvolatile component was 44%.

<Production Example 14 of Aqueous Emulsion>

In addition to 75 parts of a polymer (B-4-4), 25 parts of an adhesive resin (terpene phenol, TAMANOL 803L, manufactured by Arakawa Chemical Co., Ltd.) to replace 100 parts of the polymer (B-1-2), and the reaction temperature was 90 ° C. The aqueous emulsion (E-14) was produced in the same manner as in <Production Example 1 of aqueous emulsion>. The obtained aqueous emulsion had a particle diameter (number basis) of 0.20 μm and a nonvolatile content concentration of 34%.

<Aqueous emulsion (E-15)>

An aqueous emulsion of ethylene/methacrylic acid copolymer (AC-3100, manufactured by Central Chemical Industry Co., Ltd.) (E-15). The aqueous emulsion had a particle diameter of 0.7 μm and a nonvolatile content concentration of 45%.

<Aqueous emulsion (E-16)>

An aqueous emulsion of ethylene/vinyl acetate (EVA) copolymer (HA-1100, manufactured by Central Chemical Industry Co., Ltd.) (E-16). The aqueous emulsion had a particle diameter of 0.8 μm and a nonvolatile content concentration of 45%.

<Aqueous emulsion (E-17)>

An aqueous emulsion of EVA copolymer (EC-1800, manufactured by Central Chemical Industry Co., Ltd.) (E-17). The aqueous emulsion has a particle diameter of 1.7 μm and does not wave. The concentration of the hair component is 45%.

<Aqueous emulsion (E-18)>

An aqueous emulsion of ethylene/glycidyl methacrylate copolymer (SEPOLSION G415, manufactured by Sumitomo Seika Co., Ltd.) (E-18). The aqueous emulsion had a particle diameter of 1.7 μm and a nonvolatile content concentration of 50%.

<Production Example 19 of Aqueous Emulsion>

An aqueous emulsion (E-18) and an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were prepared in such a manner that the nonvolatile content ratio was 67 parts: 33 parts to prepare an aqueous emulsion (E- 19).

<Aqueous emulsion (E-20)>

An aqueous emulsion of ethylene/vinyl acetate copolymer (Sumikaflex 400HQ, manufactured by Sumitomo Chemical Co., Ltd.) (E-20). The aqueous emulsion had a particle diameter of 0.7 μm and a nonvolatile content concentration of 55%.

<Production Example 21 of Aqueous Emulsion>

An aqueous emulsion (E-20) and an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were prepared in such a manner that the nonvolatile content ratio was 67 parts: 33 parts to prepare an aqueous emulsion (E- twenty one).

<Aqueous emulsion (E-22)>

An aqueous emulsion of ethylene/vinyl acetate copolymer (Sumikaflex 401HQ, manufactured by Sumitomo Chemical Co., Ltd.) (E-22). The aqueous emulsion had a particle diameter of 0.8 μm and a nonvolatile content of 55%.

<Production Example 23 of Aqueous Emulsion>

The aqueous emulsion (E-22) and the aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.) have a nonvolatile ratio of 67 parts: 33 Aqueous emulsion (E-23) was prepared by blending in portions.

<Aqueous emulsion (E-24)>

An aqueous emulsion of an ethylene/vinyl acetate copolymer (Sumikaflex 408HQE, manufactured by Sumitomo Chemical Co., Ltd.) (E-24). The aqueous emulsion had a particle diameter of 0.9 μm and a nonvolatile content concentration of 50%.

<Production Example 25 of Aqueous Emulsion>

An aqueous emulsion (E-24) and an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were prepared in such a manner that the nonvolatile content ratio was 67 parts: 33 parts to prepare an aqueous emulsion (E- 25).

<Aqueous emulsion (E-26)>

An aqueous emulsion of ethylene/vinyl acetate copolymer (Sumikaflex 500, manufactured by Sumitomo Chemical Co., Ltd.) (E-26). The aqueous emulsion had a particle diameter of 0.7 μm and a nonvolatile content concentration of 55%.

<Production Example 27 of Aqueous Emulsion>

An aqueous emulsion (E-26) and an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were prepared in such a manner that the nonvolatile content ratio was 67 parts: 33 parts to prepare an aqueous emulsion (E- 27).

<Production Example 28 of Aqueous Emulsion>

An aqueous emulsion (E-11) and an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were prepared by dissolving a nonvolatile content ratio of 67 parts: 33 parts to prepare an aqueous emulsion (E-28). ).

<Production Example 29 of Aqueous Emulsion>

The aqueous emulsion (E-9) and the aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.) have a nonvolatile ratio of 67 parts: 33 An aqueous emulsion (E-29) was prepared by blending in portions.

<Production Example 30 of Aqueous Emulsion>

An aqueous emulsion (E-8) and an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were prepared in such a manner that the nonvolatile content ratio was 67 parts: 33 parts to prepare an aqueous emulsion (E- 30).

<Aqueous emulsion (E-31)>

An aqueous emulsion of ethylene/vinyl acetate/special ester copolymer (Sumikaflex 950HQ, manufactured by Sumitomo Chemical Co., Ltd.) (E-31). The aqueous emulsion had a particle diameter of 0.6 μm and a nonvolatile content concentration of 52%.

<Production Example 32 of Aqueous Emulsion>

An aqueous emulsion (E-31) and an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were prepared in such a manner that the nonvolatile content ratio was 67 parts: 33 parts to prepare an aqueous emulsion (E- 32).

<Production Example 33 of Aqueous Emulsion>

In addition to using 50 parts of propylene/butene copolymer (B-3-2) and 50 parts of ethylene/propylene copolymer (B-2-4) to replace 100 parts of polymer (B-1-2), Production Example 1 of Aqueous Emulsion An aqueous emulsion (E-33) was produced in the same manner. The obtained aqueous emulsion (E-33) had a particle diameter of 0.2 μm (number basis) and a nonvolatile content of 34%.

<Production Example 34 of Aqueous Emulsion>

An aqueous emulsion (E-13) and an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were prepared in such a manner that the nonvolatile content ratio was 67 parts: 33 parts to prepare an aqueous emulsion (E- 34).

<Production Example 35 of Aqueous Emulsion>

The temperature inside the cell of LABO PLASTOMILL was set to 95 °C. 3.12 g of the copolymer (B-1-2) was sealed in the tank, and stirred at 300 rpm for 3 minutes. The highest shear rate at this time is 1173 sec ^-1 . After that, 0.46 g of an oxygen-extended ethyl propyl propyl block copolymer (weight average molecular weight: 15500: Pluronic F108: manufactured by Asahi Kasei Co., Ltd.) and water (0.21 g) were added as an emulsifier, and the temperature in the tank was maintained. At 95 ° C, the mixture was mixed for 3 minutes at 300 rpm (shear speed 1173 sec ^-1 ). After the kneading, the contents were taken out, and warm water of about 70 ° C was placed and stirred and dispersed in a container to obtain an aqueous emulsion (E-35) having an intermediate diameter of 0.43 μm based on the volume of the dispersoid.

<Production Examples 36 to 38 of Aqueous Emulsion>

The copolymers and surfactants shown in Table 1 were used in the weight ratios shown in Table 1, and the emulsions (E-36) to (E) were obtained in substantially the same manner as in Production Example 1 of the aqueous emulsion. -38).

The copolymers and surfactants in Table 1 are as follows.

Copolymer U1: ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE HX8290, manufactured by ARKEMA, melting point: 81 ° C)

Copolymer U2: ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE LX4110, manufactured by ARKEMA, melting point: 107 ° C)

Copolymer U3: ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE HX8210, manufactured by ARKEMA, melting point: 100 ° C)

Surfactant 1: a compound represented by the above formula (A) (LATEMUL E-1000A, 30% aqueous solution, manufactured by Kao Corporation)

Surfactant 2: a compound represented by the above formula (B) (NOIGEN) EA-177, manufactured by Daiichi Pharmaceutical Co., Ltd.)

<Production Example 39 of Aqueous Emulsion>

An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.), a polyurethane emulsion (Dispercoll U-54, manufactured by SBU Co., Ltd.), and an isocyanate (Desmodur, manufactured by SBU Co., Ltd.) N3300) An aqueous emulsion (E-39) was prepared in such a manner that the nonvolatile content ratio was 100 parts: 100 parts: 100 parts: 5 parts.

<Production Example 40 of Aqueous Emulsion>

An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.), a polyurethane emulsion (Dispercoll U-54, manufactured by SBU Co., Ltd.), and an isocyanate (Desmodur, manufactured by SBU Co., Ltd.) N3300) is formulated in an amount of 100 parts by weight: 100 parts: 200 parts: 10 parts to obtain an aqueous emulsion (E-40).

<Production Example 41 of Aqueous Emulsion>

An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.), and a polyurethane emulsion (manufactured by SBU Co., Ltd.) Dispercoll U-54) and isocyanate (Desmodur N3300, manufactured by SBU Co., Ltd.) were formulated in an amount of 100 parts by weight: 100 parts: 1600 parts: 41 parts to obtain an aqueous emulsion (E-41).

<Production Example 42 of Aqueous Emulsion>

An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.), a polyurethane emulsion (Dispercoll U-54, manufactured by SBU Co., Ltd.), and an isocyanate (Desmodur, manufactured by SBU Co., Ltd.) N3300) An aqueous emulsion (E-42) was prepared in such a manner that the nonvolatile content ratio was 100 parts: 100 parts: 100 parts: 15 parts.

<Production Example 43 of Aqueous Emulsion>

An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.), a polyurethane emulsion (Dispercoll U-54, manufactured by SBU Co., Ltd.), and an isocyanate (Desmodur, manufactured by SBU Co., Ltd.) N3300) is prepared in an amount of 100 parts by weight: 100 parts: 200 parts: 20 parts to obtain an aqueous emulsion (E-43).

<Production Example 44 of Aqueous Emulsion>

A polyurethane emulsion (Dispercoll U-54, manufactured by SBU Co., Ltd.) and an isocyanate (Desmodur N3300, manufactured by SBU Co., Ltd.) were prepared so as to have a nonvolatile content ratio of 100 parts: 5 parts to obtain an aqueous emulsion (E-44).

<Production Example 45 of Aqueous Emulsion>

The aqueous emulsion (E-36), the polyurethane emulsion (Dispercoll U-54, manufactured by SBU Co., Ltd.), and the isocyanate (Desmodur N3300, manufactured by SBU Co., Ltd.) were formulated in a nonvolatile content ratio of 100 parts: 100 parts: 5 parts. An aqueous emulsion (E-45) was obtained.

<Production Example 46 of Aqueous Emulsion>

The aqueous emulsion (E-36), the polyurethane emulsion (Dispercoll U-54, manufactured by SBU Co., Ltd.), and the isocyanate (Desmodur N3300, manufactured by SBU Co., Ltd.) were formulated in a nonvolatile content ratio of 100 parts: 200 parts: 10 parts. An aqueous emulsion (E-46) was obtained.

<Production Examples 47 to 63 of Aqueous Emulsion>

The copolymers and surfactants shown in Tables 2 to 3 were used in the weight ratios shown in Tables 2 to 3, and an aqueous emulsion (E) was obtained in substantially the same manner as in Production Example 1 of the aqueous emulsion. -47) to (E-63).

The copolymers and surfactants in the table are as follows.

Copolymer P1: C ₂ (ethylene) / EVA (ethylene / vinyl acetate copolymer) / MAH (maleic anhydride) copolymer (OREVAC T9314, manufactured by ARKEMA)

Copolymer P2: C ₂ /EVA/MAH copolymer (OREVAC T9318, manufactured by ARKEMA)

Copolymer Q1: MAH modified-EVA (OREVAC G18211, manufactured by ARKEMA)

Copolymer R1: EVA partial saponified product (Melthene H6051, manufactured by TOSOH Co., Ltd.)

Copolymer R2: EVA partial saponified product (Melthene H6410M, manufactured by TOSOH Co., Ltd.)

Copolymer R3: EVA partial saponified product (Melthene H6820, manufactured by TOSOH Co., Ltd.)

Copolymer R4: EVA partial saponified product (Melthene H6822X, manufactured by TOSOH Co., Ltd.)

Copolymer R5: EVA partial saponified product (Melthene H6960, manufactured by TOSOH Co., Ltd.)

Copolymer S1: EVA (EVATATE KA-40, manufactured by Sumitomo Chemical Industries, Ltd.)

Copolymer T1: Thermally Degradable Polyethylene (UMX2000, manufactured by Sanyo Chemical Industry Co., Ltd.)

Copolymer U1: ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE HX8290, manufactured by ARKEMA)

Copolymer U2: ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE LX4110, manufactured by ARKEMA)

Surfactant 1: a compound represented by the above formula (A) (LATEMUL E-1000A, 30% aqueous solution, manufactured by Kao Corporation)

Surfactant 2: a compound represented by the above formula (B) (NOIGEN EA-177, manufactured by Dai-ichi Pharmaceutical Co., Ltd.)

Adhesive resin 1: terpene phenol (TAMANOL 803L, manufactured by Arakawa Chemical Co., Ltd.)

<Aqueous emulsion (E-64)>

An aqueous emulsion of ethylene/vinyl acetate/special ester copolymer (Sumikaflex 951HQ, manufactured by Sumitomo Chemical Co., Ltd.) (E-64). The aqueous emulsion had a particle diameter of 0.8 μm and a nonvolatile content of 55%.

The aqueous emulsion obtained in the production example of the above aqueous emulsion was subjected to the following test.

<5-day static stability>

The aqueous emulsion obtained in the production example of the above aqueous emulsion was subjected to the following test.

The obtained aqueous emulsion was placed in a 250 ml plastic container, and the appearance change was observed after standing at room temperature for 5 days. The evaluation criteria are as follows. The results are shown in Table 4 and Table 5.

○: No aggregation, precipitation, and phase separation were observed, and it was in a good state.

×: Aggregation, precipitation, and phase separation occurred.

<Manufacturing Example 1 of Laminated Structure>

In the aqueous emulsion (E-28) (non-volatile content ratio), ADEKANOL UH-420 (manufactured by Adeka Co., Ltd.) as a tackifier was added as a tackifier in the amount described in Table 6 (nonvolatile content ratio) as a dispersing agent. NOPCO WET50 (manufactured by SANNOPCO Co., Ltd.) was stirred with a three-one motor to obtain an aqueous adhesive.

Using a glass rod, the obtained aqueous adhesive was applied to a cotton 100% canvas (coating amount: about 60 g/m ² ), naturally dried for 20 minutes, and the resulting canvas was placed in a microwave oven (NE-EH212, manufactured by Panasonic Co., Ltd.). In the frequency of 2.45 GHz), electromagnetic wave processing was performed at 750 W for 30 seconds.

Applying the obtained aqueous adhesive to cotton canvas and nylon 6 or nylon 66 substrate (cotton canvas coating amount: about 40 g/m ² , nylon 6 or nylon 66 substrate coating amount: about 80 g/m ² ), The resulting cotton canvas and nylon 6 or nylon 66 substrate were placed in a microwave oven and subjected to electromagnetic wave treatment at 300 W for 60 seconds.

Next, the coated surfaces of the obtained aqueous adhesive of the cotton canvas and the nylon 6 or nylon 66 substrate were bonded to each other and pressed by a roll.

Thereby, a laminated structure of cotton/adhesion layer/nylon resin was obtained.

<Manufacturing Example 2 of laminated structure>

In the aqueous emulsion (E-28) (non-volatile content ratio), ADEKANOL UH-420 (manufactured by Adeka Co., Ltd.) as a tackifier was added as a tackifier in the amount described in Table 6 (nonvolatile content ratio) as a dispersing agent. NOPCO WET50 (manufactured by SANNOPCO Co., Ltd.) was stirred with a stirrer to obtain an aqueous binder.

Using a glass rod, the obtained aqueous adhesive was applied to a 100% cotton canvas (coating amount: about 60 g/m ² ), naturally dried for 20 minutes, and the resulting canvas was placed in a microwave oven (manufactured by Panasonic, NE-EH212). In the case, electromagnetic wave processing was performed for 30 seconds at 750W.

The cotton canvas and the nylon 6 substrate were separately coated with the obtained aqueous adhesive (cotton canvas coating amount: about 40 g/m ² , nylon 6 coating amount: about 80 g/m ² ). The obtained cotton canvas was placed in a microwave oven, subjected to electromagnetic wave treatment at 750 W for 60 seconds, and the cotton canvas was taken out. Next, the nylon 6 substrate was placed in a microwave oven and subjected to electromagnetic wave treatment at 500 W for 20 seconds.

Thereafter, the coated surfaces of the obtained aqueous adhesive of the cotton canvas and the nylon 6 substrate were bonded to each other and pressed by a roll.

Thereby, a laminated structure of cotton/adhesion layer/nylon resin was obtained.

<Peel strength test 1 of laminated structure>

The laminated structure obtained above was allowed to stand at room temperature for 24 hours, and then the peeling strength was measured at a peeling speed of 200 mm/min and a peeling angle of 180 degrees using a tensile tester (autograph manufactured by Shimadzu Corporation), thereby evaluating the laminated structure. Adhesiveness. The results are shown in Table 6.

○: The peel strength was 10 N/inch or more.

×: Peel strength is less than 10 N/inch

<Manufacturing Example 3 of Laminated Structure>

The aqueous emulsion obtained by the production example of the aqueous emulsion was applied to a nylon 6 substrate or a nylon 66 substrate by drying at a film thickness of about 10 μm using a glass rod, and was carried out at 120 ° C or 100 ° C for 30 minutes. The heat treatment was carried out to obtain a laminated structure having a layer derived from an aqueous emulsion as a coating film on the surface of a nylon 6 substrate or a nylon 66 substrate.

<Peel strength test 2 of laminated structure>

The respective laminated structures obtained above were allowed to stand at room temperature for 24 hours, and thereafter, 100 cells were cut out in the width of 1 mm in the coating film, and the number of cells remaining completely was calculated by peeling off with a cellophane tap. The adhesion of the coating film after peeling three times with a transparent tape was evaluated. The larger the number (closer to 100), the better the adhesion.

Further, a layered structure can be produced in the same manner as described above, using an aqueous emulsion other than the aqueous emulsions tested in Tables 6 and 7.

Further, in the aqueous emulsion (nonvolatile content ratio) shown in Table 8, ADEKANOL UH-420 (manufactured by Adeka Co., Ltd.) as a tackifier was added in an amount (nonvolatile content ratio) as shown in Table 8 as a tackifier. A dispersant of NOPCO WET50 (manufactured by SANNOPCO Co., Ltd.) was stirred with a stirrer to prepare the following aqueous adhesive.

A laminate structure can also be produced in the same manner as described above using the aqueous binder obtained in Table 8.

(Industry is the possibility of utilization)

By the aqueous adhesive of the present invention, it is possible to provide a laminated structure of a nylon resin/adhesive layer/cotton-containing fiber which can firmly adhere to a nylon resin and a cotton-containing fiber and is excellent in adhesion.

Claims (23)

An aqueous adhesive for use in a nylon resin and a cotton-containing fiber, the aqueous binder comprising a polymer having one or more structural units derived from an α-olefin having 2 to 20 carbon atoms. The aqueous adhesive according to claim 1, further comprising a surfactant represented by the following formula (I); (wherein X represents a hydrogen atom or -SO ₃ M (M-based hydrogen atom, NH ₄ or an alkali metal), n represents an integer of 1 to 3, and m represents an integer of 1 to 100). The aqueous binder according to claim 2, wherein the surfactant is two or more types of a surfactant containing an X-based hydrogen atom and a surfactant of X-SO ₃ M. The aqueous adhesive according to the second or third aspect of the invention, wherein the surfactant is -SO ₃ M-based SO ₃ NH ₄ . The aqueous adhesive according to any one of claims 1 to 4, wherein the polymer has a structural unit derived from the aforementioned α-olefin having 2 to 20 carbon atoms, and is selected from the group consisting of a group of 2 to 20 carbon atoms having 2 to 20 carbon atoms, a ?-olefin, an α,β-unsaturated carboxylic acid ester, an α,β-unsaturated carboxylic anhydride, and a vinyl acetate group A copolymer of structural units of the above monomers. The aqueous connection as described in any one of claims 1 to 5 The above-mentioned polymer has a structural unit derived from ethylene, and an α-olefin selected from carbon atoms 3 to 20, an α,β-unsaturated carboxylic acid ester, an α,β-unsaturated carboxylic anhydride, and an acetic acid. A copolymer of structural units of one or more monomers in which a vinyl ester is grouped. The aqueous adhesive according to any one of claims 1 to 6, wherein the polymer has a structural unit derived from ethylene, and is derived from an α,β-unsaturated carboxylic acid ester and α A copolymer of structural units of one or more kinds of monomers in a group of β-unsaturated carboxylic acids. The aqueous adhesive according to any one of claims 1 to 7, wherein the polymer is at least one selected from the group consisting of: (a) an ethylene-propylene copolymer, propylene Α-olefin system such as 1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer, ethylene-propylene-1-butene copolymer a copolymer or a modified product thereof, or a mixture of two or more thereof; (b) an ethylene-propylene copolymer, a propylene-1-butene copolymer, an ethylene-1-butene copolymer, an ethylene-1-octane An α-olefin copolymer such as an olefin copolymer, an ethylene-1-hexene copolymer or an ethylene-propylene-1-butene copolymer or a maleic anhydride modified product thereof, or a mixture of two or more thereof; c) a copolymer of α-olefin and vinyl acetate or a modified product thereof; or a mixture of two or more thereof; (d) copolymerization of an α-olefin with a (meth) acrylate and an α, β-carboxylic acid Or a modified substance thereof, or a mixture of two or more thereof; and (e) a copolymer of an α-olefin and a (meth) acrylate with maleic anhydride or A modified substance, or a mixture of two or more of these. The aqueous adhesive according to any one of claims 1 to 8, wherein the polymer has a melting point of 60 to 110 °C. The aqueous adhesive according to any one of claims 1 to 9, which further comprises an adhesive resin. The aqueous adhesive according to any one of claims 1 to 10, which further comprises a polyurethane resin or a water-insoluble polyurethane resin. The aqueous adhesive according to any one of claims 1 to 10, which further comprises a terpene polymer, a terpene phenol, a β-pinene polymer, an aromatic modified terpene polymer. A terpene-based resin in the group of α-pinene polymer and terpene-based hydrogenated resin. The aqueous adhesive according to any one of claims 1 to 10, which further comprises a polyurethane resin, and is selected from the group consisting of terpene polymers, terpene phenols, β-pinene polymers, and aromatic modification. A terpene-based resin in which a terpene polymer, an α-pinene polymer, and a terpene-based hydrogenated resin are grouped. The aqueous adhesive according to any one of claims 1 to 10, which further comprises a polyurethane resin and terpene phenol, or a water-insoluble polyurethane resin and terpene phenol. The aqueous adhesive according to any one of claims 1 to 14, which contains an isocyanate. The aqueous adhesive according to any one of claims 1 to 14, which further comprises a selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), and hexamethylene diisocyanate. (HDI), xylene diisocyanate (XDI) and such oligomers or polymers Groups of isocyanates. The aqueous adhesive according to any one of claims 1 to 16, which further comprises a basic compound. The aqueous adhesive according to any one of claims 1 to 17, wherein the aqueous adhesive contains a dispersion having a particle diameter (number basis) of 0.01 to 1.0 μm. The aqueous adhesive according to any one of claims 1 to 18, which is contained in an amount of 0.1 to 50 parts by weight, 0.1 to 20 parts by weight, or 100 parts by weight of the total of the resins constituting the aqueous emulsion. 0.1 to 10 parts by weight of the aforementioned surfactant. The aqueous adhesive according to any one of claims 1 to 19, wherein the aforementioned surfactant is in a mass ratio of from 1 to 99:99 to 1, from 5 to 95:95 to 5,10. From the 90:90 to 10, 30:70 to 90:10, 40:60 to 90:10 or 50:50 to 90:10 mode, the interface represented by the formula (A) and the interface represented by the formula (B) are contained. Active agent The aqueous adhesive according to any one of claims 1 to 20, which is obtained by dispersing the resin in an aqueous medium after polymerizing the thermoplastic resin, followed by an emulsification method, a forced emulsification method, and an autologous method. Emulsification method or The phase transfer emulsification method is obtained. A laminated structure in which a first substrate comprising a nylon resin, an adhesive layer containing a polymer having one or more types of structural units derived from an α-olefin having 2 to 20 carbon atoms, and a second layer containing a cotton-containing fiber are sequentially disposed. Substrate laminate. The layered structure according to claim 22, wherein the adhesive layer is a layer formed of the aqueous adhesive according to any one of claims 1 to 21.