TW201302950A - Aqueous adhesive and laminate structure - Google Patents

Abstract

An objective of this invention is to provide an aqueous adhesive having excellent adhesion for adhesiving ethylene/ethylene acetate copolymer and cotton-containing fiber, and an ethylene/ethylene acetate copolymer/adhesion layer/cotton-containing fiber laminate structure. The present aqueous adhesive for adhesiving ethylene/ethylene acetate copolymer and cotton-containing fiber contains a polymer which contains 1 or more structure units derived from an α -olefin having a carbon number of 2 to 20; Furthermore, the aqueous adhesive preferably contains a surfactant represented by the following formula (I) and water. (In the formula, X represents a hydrogen atom or -SO3M (M is a hydrogen atom, NH4 or an alkali metal ). n represents an integer of 1 to 3. m represents an integer of 1 to 100.)

Description

Aqueous adhesive and laminated structure

This invention relates to aqueous binders and laminate constructions for use in ethylene/vinyl acetate copolymers and cotton-containing fibers.

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

(previous technical literature) (Non-patent literature)

Non-Patent Document 1: Japanese Adhesives, "Next Handbook (4th Edition)", published by the Nikkan Kogyo Shimbun, December 28, 2007, 98 pages

Among the conventional aqueous adhesives, in particular, the adhesion of ethylene/vinyl acetate copolymer to cotton-containing fibers may not be satisfactory.

The invention includes the following invention.

[1]. An aqueous adhesive for use in a polymer comprising a vinyl/vinyl acetate copolymer and a cotton-containing fiber, and comprising a structural unit having one or more kinds of α-olefins 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 is a hydrogen atom, NH ₄ or an alkali metal). n represents an integer of 1 to 3. m represents an integer of 1 to 100.)

[3] The aqueous adhesive according to [2], wherein the surfactant contains two or more kinds of surfactants in which X is a hydrogen atom and a surfactant in which X is -SO ₃ M.

[4] The aqueous adhesive according to [2] or [3] wherein -SO ₃ M in the aforementioned surfactant is SO ₃ NH ₄ .

The aqueous binder according to any one of the above aspects, wherein the polymer has a structural unit derived from the α-olefin having 2 to 20 carbon atoms, and more than one or more a group selected from the group consisting of an α-olefin having 2 to 20 carbon atoms, an α, β-unsaturated carboxylic acid ester, an α, β-unsaturated carboxylic anhydride, and vinyl acetate different from the α-olefin having 2 to 20 carbon atoms. a copolymer of structural units of the monomers.

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

[A] The aqueous adhesive according to any one of [1] to [6] wherein the polymer has a structural unit derived from ethylene and one or more selected from the group consisting of α, β-unsaturated Group of carboxylic acid esters and α,β-unsaturated carboxylic acids a copolymer of structural units of the monomers.

[A] The aqueous adhesive according to any one of [1] to [7] wherein the polymer has at least one selected from the group consisting of: (a) ethylene-propylene copolymerization , propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer, ethylene-propylene-1-butene copolymer, etc. An α-olefin copolymer or a modified product thereof; or a mixture of two or more of the above; (b) an ethylene-propylene copolymer, a propylene-1-butene copolymer, an ethylene-1-butene copolymer, and ethylene An α-olefin copolymer such as a 1-octene copolymer, an ethylene-1-hexene copolymer or an ethylene-propylene-1-butene copolymer or a maleic anhydride modified product thereof; or two of these a mixture of the above; (c) a copolymer of an 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 with α, β- a copolymer of a carboxylic acid 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 substance thereof; A mixture of two or more kinds.

[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], which comprises It is selected from the group consisting of terpene polymer, terpene phenol, β-pinene polymer, aromatic modified terpene polymer, α-pinene polymer, and terpene hydrogenated resin. Terpene resin.

[13] The aqueous adhesive according to any one of [1] to [10] which further comprises a polyurethane resin; and is selected from a terpene polymer, a terpene phenol, a β-pinene polymer, an aromatic A terpene-based resin composed of a group consisting of a terpene polymer, an α-pinene polymer, and a terpene-based hydrogenated resin.

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

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

[16] The aqueous adhesive according to any one of [1] to [14] which is selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), and two different Isocyanate of the group consisting of hexamethylene cyanate (HDI), phenyl diisocyanate (XDI) and such oligomers or polymers.

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

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

[A] 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, 0.1 to 20 parts by weight, or 100 parts by weight of the total resin constituting the aqueous emulsion. 0.1 to 10 parts by weight of the aforementioned surfactant.

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

[A] The aqueous adhesive according to any one of [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, Obtained by autoemulsion or phase-transfer method.

[22] A laminated structure comprising a first substrate comprising an ethylene/vinyl acetate copolymer, and an adhesive layer comprising a polymer having one or more types of structural units derived from an α-olefin having 2 to 20 carbon atoms; The second substrate including the cotton-containing fiber is laminated in order.

[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 a water-based adhesive agent for adhering to each other, in particular, an ethylene/vinyl acetate copolymer and a cotton-containing fiber, and a laminate 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 inter-substrate adhesive composed of various materials, and is particularly suitable for the subsequent attachment of an ethylene/vinyl acetate copolymer to a cotton-containing fiber.

The laminate structure of the present invention will comprise an ethylene/vinyl acetate copolymer. The first substrate, 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 substrate including a cotton-containing fiber are laminated in this order.

In the laminated structure, the subsequent layer is sandwiched between the substrates composed of various materials, in particular, sandwiched between the laminated structures of the ethylene/vinyl acetate copolymer and the cotton-containing fibers. Next, the layer is a layer obtained by an adhesive, especially an aqueous adhesive, and if the solvent contains a solvent, it is a layer formed by evaporating the solvent.

Here, the ethylene/vinyl acetate copolymer (hereinafter referred to as "first substrate") is generally a copolymer of ethylene and vinyl acetate at a high temperature and a high pressure, and the properties of the copolymer are due to the content ratio of vinyl acetate. And different. The ethylene/vinyl acetate copolymer is used in a variety of applications, including various vinyl acetate content ratios and forms (films, blocks, fibers, foams).

The ethylene/vinyl acetate copolymer may be used in combination with a polyolefin or the like. Preferred polyolefins are exemplified by ethylene-octene copolymers, ethylene-butene copolymers, polypropylene and polyethylene.

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

Ethylene/vinyl acetate copolymerization of the aqueous binder of the present invention Examples of the form of the object and the cotton-containing fiber include various forms such as a woven fabric, a knitted fabric, a non-woven fabric, a jersey fabric, a felt, a film, and a block.

The aqueous adhesive of the present invention can function as an adhesive for an adhesive, an adhesive, an adhesive, a heat sealant, a paint, a primer for a paint, a binder for an ink, an adhesive, and a modifier for an emulsion. It is used as an adhesive for the use of an ethylene/vinyl acetate copolymer and a cotton-containing fiber for films, sheets, construction materials, building materials, automobile parts, electric/electronic products, packaging materials, clothing, boots, and the like.

Among them, in sports shoes, casual shoes, leather shoes and other gentleman's boots and women's boots, and further for industrial work boots and other shoes, suitable as a material for the upper, midsole, outsole, etc. The adhesive used between the vinyl acetate copolymer material and the cotton-containing fibrous material.

The size, thickness, shape, and the like of the ethylene/vinyl acetate copolymer and the cotton-containing fiber can be appropriately adjusted in accordance with the purpose of use of the laminated structure.

The surface of the ethylene/vinyl acetate copolymer and the cotton-containing fiber may be smooth or have irregularities.

Further, a primer treatment may be applied to the surface of the first substrate and/or the second substrate in order to improve adhesion to an adhesive or the like. Examples of the primer treatment include sand blasting, drug treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, formation of a lower layer, and the like.

<adhesive agent>

The subsequent agent contains a polymer having one or more types of 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, is a structural unit having one or more kinds of α-olefins 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-ten Hepene, 1-octadecene, 1-nonenylene, 1-eicosene, ethylene cyclohexane, and the like. Preferred are ethylene, propylene, 1-butene and the like.

The polymer containing more than one type of structural unit derived from an α-olefin having 2 to 20 carbon atoms is preferably polyethylene (PE), high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene. a monomeric polymer (LDPE), polypropylene (PP), or the like; an ethylene-propylene copolymer, a propylene-1-butene copolymer, an ethylene-1-butene copolymer, an ethylene-1-octene An α-olefin copolymer such as a copolymer, an ethylene-1-hexene copolymer, an ethylene-propylene-1-butene copolymer or a modified product thereof; a copolymer with a copolymerizable monomer or a modified product thereof; Or a mixture of two or more of these. In the copolymer of the copolymerizable monomer, the copolymerizable monomer and the alpha olefin may be used singly 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 a peroxide or the like.

The total structural unit of the α-olefin-based polymer is 100 mol%, and for example, it is preferable to contain a structural unit derived from propylene: a structure derived from 1-butene. The unit is 71 to 99 mol%: 1 to 29 mol% of the copolymer or the modified product, more preferably 80 to 99 mol%: 1 to 20 mol% of the copolymer or its modified product, More preferably, it contains 90 to 99 mol%: 1 to 10 mol% of a copolymer or a modified product thereof. The copolymer is preferably a copolymer having no substantial melting peak 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.

For example, the ethylene structural unit derived therefrom: preferably from 5 to 20 mol% of the structural unit derived from propylene: 80 to 95 mol% of the copolymer or modified product thereof, more preferably 5 to 19 mol% The copolymer of 81 to 95 mol% or a modified substance thereof is more preferably a copolymer containing 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 of 1 J/g or more, or a heat of crystallization of 1 J/g or more, which is observed by differential scanning calorimetry (DSC) in a temperature range of -100 to 200 °C. The crystallization peak.

For example, a structural unit derived from ethylene: a structural unit derived from propylene: a structural unit derived from 1-butene preferably from 1 to 99 mol%: 99 to 1 mol%: 99 to 1 mol% of copolymerization More preferably, it contains 5 to 80 mol%: 90 to 2 mol%: 90 to 1 mol% of the copolymer or its modified product, and more preferably 10 to 40 mol%: 85 to 5 mol%: 60 to 2 mol% of a copolymer 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 produced by a metallocene system, for example, in the case of Japanese Laid-Open Patent Publication No. SHO-58-19309, No. 60-35005, and the like (see, for example, European Patent Publication No. 1211287).

Further, the above propylene-1-butene copolymer or the modified product and the ethylene-propylene copolymer or the modified product thereof are preferably blended in a weight ratio of from 1 to 99:99 to 1, more preferably from 5 to 95. : 95 to 5 blenders, and more preferably 10 to 90: 90 to 10 blenders.

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 acid (Maleic acid, iaconic acid, citraconic acid, etc.), α, β- Unsaturated carboxylic acid esters (methyl maleate, methyl itaconate, methyl pyrophosphate, etc.), α, β-unsaturated carboxylic anhydrides (maleic anhydride, itaconic anhydride, pyrophosphonic 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 material include a method in which an α-olefin-based polymer is added and then α or β-unsaturated carboxylic acid is added, and the α-olefin-based polymer is dissolved in a solvent such as toluene or xylene. A known method such as a method of modifying an α, β-unsaturated carboxylic acid or the like. Further, when the structural unit derived from the α,β-unsaturated carboxylic anhydride is contained in the modified product, the acid anhydride group may be maintained, or the open ring may be contained, or both the acid anhydride group and the open ring may be contained.

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.

The copolymerizable monomer may, for example, be 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, a vinyl ester saponified product, or a cyclic olefin. A vinyl aromatic compound, a polyene compound (diene or the like), (meth)acrylonitrile, a vinyl halide, a halogenated vinylidene or the like. These may be used alone or in combination of two or more.

Further, 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, and crotonic acid. For example, a half ester of an unsaturated dicarboxylic acid, a hemidecylamine, etc. are mentioned. 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, butyl (meth)acrylate, and (meth)acrylic acid rings. Examples of the oxypropyl ester and 2-hydroxyethyl acrylate include esterified products 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, pivalic acid vinyl, and monobasic fatty acid B. Surfic acid vinyl or 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-propyl norbornene, 5,6-dimethyl norbornene, and 1- Methyl norbornene, 7-methylnordecene, 5,5,6-trimethylnordecene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidene Alkene, 5-ethylene norene, 1,4,5,8-dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene (1,4,5,8- Dimethano-1,2,3,4,4a,5,8,8a-octahydronaph thalene), 2-methyl-1,4,5,8-dimethylene-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2, 3-dimethyl-1,4,5,8-dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8 -Dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethylene-1,4,5,8-dimethylene-1,2,3 ,4,4a,5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethylene-1,2,3,4,4a,5,8,8a-octahydrogen Naphthalene, 1,5-dimethyl-1,4,5,8-dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-cyclohexyl-1, 4,5,8-Dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethylene -1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethylene-1,2,3,4,4a, 5,8,8 A-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronordecene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro -6-trifluoromethylnordecene, 5-chloromethylnordecene, 5-methoxynordecene, 5,6-dicarboxynorpentene anhydride, 5-dimethylaminonordecene , 5-cyanopentene, cyclopentene, 3-methylcyclopentene, 4-methyl Cyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methyl Cyclohexene, 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, dibromostyrene, and 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, an alicyclic non-conjugated polyene compound, and a fragrance. A family of non-conjugated polyene compounds and the like. These may have a substituent of an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group or the like.

Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isobutylene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, and 2-isopropyl group. -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-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.

Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, and 2,3-dimethyl-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-cyclohexadiene, etc. .

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-hexane Alkene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4-heptadiene, 5-B Base-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 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-ethyl-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-propane Base-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-decadiene, 5-methyl-1,4-decadiene, 4 -ethyl- 1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-B Base-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-anthracene Diene, 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-癸二 Alkene, 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-methyl- 1,8-undecadiene, 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-pentadecatriene, 5,9,13-trimethyl-1 ,4,8,12-tetradecadiene, 8,14,16-trimethyl-1,7,14-hexadecanetriene, 4-ethylene-12-methyl-1,11- Pentadecene and the like.

Examples of the alicyclic non-conjugated polyene compound include ethylene cyclohexane, ethylene cyclohexene, 5-ethylene-2-northene, 5-ethylidene-2-northene, 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-isopropylidene- 5-northene, 6-chloromethyl-5-isopropenyl-2-northene, 1,4-divinylcyclohexane, 1,3-diethylenecyclohexane, 1,3-diethylene Cyclopentane, 1,5-diethylenecyclooctane, 1-propenyl-4-ethenecyclohexane, 1,4-dipropenylcyclohexane, 1-propenyl-5-vinylcyclooctane, 1 , 5-dipropenylcyclooctane, 1-propenyl-4-isopropenylcyclohexane, 1-isopropenyl-4-ethenecyclohexane, 1-isopropenyl-3-ethenecyclopentane, Methyltetrahydroindene or the like.

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

The modified product of the copolymer with the copolymerizable monomer is, for example, as described above, and examples thereof include modified substances derived from α, β-unsaturated carboxylic acids. At this time, the phase For 100 parts by weight of the copolymer with the copolymerizable monomer, the mass is usually from 0.1 to 10 parts by weight, preferably from 0.2 to 5 parts by weight, more preferably from 0.2 to 4 parts by weight.

And a monomeric lipid copolymer copolymerizable with an α-olefin, specifically, for example, (i) an ethylene-vinyl acetate copolymer, the saponified product or a partially saponified product, or an ethylene-vinyl acetate copolymer. Maleic anhydride modified product; (ii) ethylene-(meth)acrylic acid copolymer; (iii) ethylene-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 propylene-propylene Ethylene-vinyl acetate-(meth)acrylate copolymer of ester, ethylene-vinyl acetate copolymer-methyl (meth)acrylate, etc.; (vi) ethylene-ethyl (meth)acrylate-maleic anhydride copolymer Ethylene-(meth)acrylate-maleic anhydride; (vii) ethylene-(meth)acrylate of ethylene-(meth)acrylic acid butyl acrylate-methyl (meth) acrylate copolymer, etc. (meth) acrylate copolymer; (viii) a copolymer of the metal salts; and (ix) a blend of two or more of the copolymers, and the like.

The polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, particularly the copolymer of the above (i) to (vii), preferably has a melt flow rate at 190 ° C and a load of 2160 g. 0.01 to 500g/10 The score is preferably from 0.01 to 400 g/10 minutes.

The polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, particularly the copolymer of the above (i) to (vii) preferably has 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.

The polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is preferably a structural unit having an α-olefin derived from 2 to 20 carbon atoms, and α derived from at least one selected from the group consisting of carbon atoms 2 to 20 a copolymer of structural units of a monomer having a carbon number of 2 to 20, an α, an α, β-unsaturated carboxylic acid ester, an α, β-unsaturated carboxylic acid anhydride, or a vinyl acetate group; Preferably, it has a structural unit derived from ethylene and a group consisting of one or more selected from the group consisting of α-olefins having 3 to 20 carbon atoms, α, β-unsaturated carboxylic acid esters, α, β-unsaturated carboxylic anhydrides, and vinyl acetate. a copolymer of a structural unit of a monomer; more preferably, it has a structural unit derived from ethylene and a group consisting of one or more selected from the group consisting of α, β-unsaturated carboxylic acid esters and α, β-unsaturated carboxylic acids. a copolymer of structural units of monomers.

Specifically, it is preferably (i) an ethylene-vinyl acetate copolymer, the saponified or partially saponified product, or a maleic anhydride modified product of an ethylene-vinyl acetate copolymer; (ii) an ethylene-(meth)acrylic acid copolymer. (iii) ethylene-(meth) acrylate copolymer; (v) ethylene-vinyl acetate-(meth) acrylate copolymer; (vi) ethylene-(meth) acrylate-maleic anhydride copolymer (vii) an ethylene-(meth) acrylate-(meth) acrylate copolymer. More preferably (ia) 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 are, in particular, copolymers containing structural units derived from a carbon number of 2 to 20, more preferably ethylene.

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

<Other resins>

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

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

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

Examples of such a resin include rosin, terpene resin, petroleum resin which polymerizes a petroleum fraction of carbon number 5, hydrogenated resin thereof, and carbon. The petroleum-based resin in which the petroleum distillation component of the number 9 is polymerized, the hydrogenated resin, other petroleum-based resin, coumarone resin, enamel resin, urethane resin, and the like.

Specific examples thereof include rosin, polymeric rosin, disproportionated turpentine, hydrogenated rosin, maleated turpentine, fumarate rosin, and the like, glycerol ester, neopentyl ester, methyl ester, triethylene glycol ester, a phenolic modified substance and a rosin such as the esterified product; a terpene polymer, a terpene phenol, a β-pinene polymer, an aromatic modified terpene polymer, an α-pinene polymer, a terpene hydrogenated resin, etc. a terpene resin; a petroleum resin which polymerizes a petroleum fraction of carbon number 5; a petroleum resin which polymerizes a petroleum distillation component having a carbon number of 9; and a hydrogenated resin; a maleic acid modified product and a reversed butene A petroleum-based resin such as an acid-modified material; a polyisocyanate compound and a polyol compound to be described later, and a urethane resin which can react with other compounds, etc., may be mentioned as necessary.

Among them, preferred are, for example, terpene 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. A commercially available product of any of the types such as the Japanese terpene chemical company.

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 water-soluble or water-insoluble, but is preferably water-insoluble.

In general, a polyurethane resin can react a polyisocyanate compound with a polyol compound, and can be obtained by repeating the reaction with other compounds. reaction For example, a method such as an acetone method, a prepolymer mixing method, a ketimine method, a hot melt dispersion method, or the like can be mentioned.

The polyisocyanate compound may, for example, be an organic polyisocyanate compound having two or more isocyanate groups in a molecule generally used in the production of polyurethane. For example, 1,4-tetramethylene diisocyanate, hexamethylene 1,6-diisocyanate (HDI), hexamethylene 2,2,4-trimethyldiisocyanate, 3-isocyanate A 3-,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexyl-2,4-diisocyanate, methylcyclohexyl-2,6-di Isocyanate, xylene diisocyanate (XDI), 1,3-bis(isocyanate)methylcyclohexane, tetramethylxylene diisocyanate, trans-cyclohexane-1,4-diisocyanate, quaternary acid diisocyanate Aliphatic diisocyanates such as (lysine diisocyanate); 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI), diphenylmethane-4,4'-diisocyanate (MDI), 1,5'-cycloalkane diisocyanate, tolidine diisocyanate, diphenylmethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3- An aromatic diisocyanate such as a phenyl diisocyanate; an isocyanate triisocyanate, triphenylmethane triisocyanate, 1,6,11-undecane triisocyanate, 1,8-isocyanate-4,4-iso Acid ester methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, adduct of trimethylolpropane and toluene diisocyanate, trimethylolpropane and 1,6- A triisocyanate or the like such as an adduct of hexamethylene diisocyanate. These may be used alone or in combination of two or more.

The polyol compound can be exemplified by the use of a usual polyurethane. A compound having two or more hydroxyl groups in the subunit. 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 diol, polypropylene glycol, polytetramethylene ether glycol, etc.; from adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid, isophthalic acid, anti-butyl a dicarboxylic acid such as enedic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid or sebacic acid, and ethylene glycol, diethylene glycol, propylene glycol, 1,4- Butylene glycol, 1,6-hexanediol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, Polyester polyols obtained from polyol compounds such as 1,3-propanediol, tripropylene glycol, trimethylolpropane, glycerin, etc.; polycaprolactone polyol, poly-β-methyl-δ-valerolactone, etc. Lactone-based polyester polyols; polybutadiene polyols or hydrogenated products thereof, polycarbonate polyols, polythioether polyols, polyacrylate polyols, and the like.

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

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.

The neutralizing agent may, for example, be a tertiary amine compound such as triethylamine or triethanolamine; an inorganic basic compound such as sodium hydroxide; ammonia or the like.

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 a sulfonyl group, a carboxyl group, a hydroxyl group, a primary amino group (-NH ₂ ), and a secondary amine group ( (NH), etc., a compound having one or more active hydrogens which are reactive with an isocyanate group (hereinafter referred to as "a compound containing a hydrophilic group").

Examples of the hydrophilic group-containing compound include, for example, 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, and N-(2). a sulfonic acid-containing compound such as -aminoethyl)-2-aminoethyl sulfonic acid; 2,2-dimethylol lactic acid, 2,2-dimethylolpropionic acid, 2,2-dihydroxyl 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 possible to extend the chain and adjust the molecular weight as necessary, and a compound different from the hydrophilic group-containing compound may be used in combination, and the compound has an activity of reacting with an isocyanate compound in the molecule. hydrogen. Examples of such a compound include polyamine compounds such as ethylene diamine, 1,4-butane diamine, and hexamethylenediamine; polyhydric alcohols containing tertiary amines such as triethanolamine; methanol, ethanol, butanol, and the like. Monools, etc.

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

For example, a polyurethane dispersion (or an aqueous polyurethane solution) in which a polyurethane resin is dispersed or dissolved in water can be cited. The content of the polyurethane resin in the polyurethane dispersion may be, for example, about 10 to 70% by weight, preferably about 20 to 60% by weight. More preferably, it is about 30 to 60% by weight, still more preferably about 30 to 55% by weight.

The polyurethane dispersion may further contain an organic solvent which does not contain an isocyanate reactive group, such as ethyl acetate, acetone, methyl ethyl ketone, N-methyl pyrrolidone 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 matter in the polyurethane dispersion.

The water-soluble urethane resin may, for example, be Dispercoll U-42, U-53, U-54, U-56, KA-8481, KA-8584, KA-8755, KA-8756, manufactured by Sumitomo Bayerium Co., Ltd. , KA-8766; DIC (Stock Company) HYDRAN HW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP-60LM, AP-80; Sanyo Chemical Industrial (stock company) UPRENE UXA-306, UXA-307, PARMALIN UA-150, PARMALIN UA-200, PARMALIN UA-300, PARMALIN UA-310, UCOAT UWS-145; SuperFlex made by First Industrial Pharmaceutical Co., Ltd. 107M, 110, 126, 130, 150, 160, 300, 361, 370, 410, 420, 460, 700, 750, 820; ADEKA company's Bon-Tighter 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 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 weight ratio) is preferably from 5:95 to 95:5, more preferably from 5:95 to 95:5, still more preferably from 5:95 to 80:20.

These resins may be emulsions or may be emulsified with a polymer having a structural unit derived from an a-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 salt). And the like, but among them, a hydrogen atom, -SO ₃ H or -SO ₃ NH _{4 is} preferred.

When two or more types of surfactants are combined, X may be the same and n and/or M may be different, and it is preferred that the combination n and/or M are the same or different and X is different. Specifically, X is a combination of a 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 . 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.), and LATEMUL E-1000A (manufactured by Kao Co., Ltd.) represented by the following formula (A), and is represented by the following formula (B). NOIGEN EA-177 (manufactured by First Industrial Pharmaceutical Co., Ltd.) and the like.

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

For example, the anionic surfactant may, for example, be a sulfate ester of a higher alcohol, a higher alkyl sulfonate, a higher carboxylate, an alkylbenzenesulfonate, a polyoxyethylene alkyl sulfate, or a polyoxyethylene alkylbenzene. Ethyl ether sulfate, vinyl sulfosuccinate, and the like.

Examples of the cationic surfactant include alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt; alkylpyridines such as cetylpyridinium salt and mercaptopyridinium salt; a salt; an alkylene trialkylammonium salt, a dialkylalkylene dialkylammonium salt, a propenyltrialkylammonium salt, a dipropylenedialkylammonium salt, and the like.

Examples of the nonionic surfactant include polyoxyethyl alkyl ethers such as polyoxyethylene propylene ether, polyoxyethyl alkylphenyl ethers, polyethylene glycol fatty acid esters, and oxygen. a compound having a polyoxyethyl structure such as an ethyloxypropyl block copolymer, a polyoxyethyl fatty acid decylamine or an oxyethyl-oxypropyl copolymer, and a sorbent such as a polyoxyethyl sorbitan fatty acid ester Alcohol derivatives and the like.

The amphoteric surfactant may, for example, be lauryl betaine or dodecyldimethylamine oxide.

Interface activity with respect to 100 parts by weight of the resin constituting the aqueous binder The content of the agent 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 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 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 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 in combination, the weight is preferably from 1 to 99:99 to 1, more preferably from 5 to 95:95 to 5, More preferably, it is from 10 to 90:90 to 10, especially from 30:70 to 90:10, from 40:60 to 90:10, and from 50:50 to 90:10.

<alkaline compound>

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

The basic compound is preferably a neutralized carboxyl group such as ammonia, an organic amine compound, a metal hydroxide or the like. 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 volatilized 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, iminodipropylamine, ethylamine, and diethylamine. Amine, 3-ethoxypropylamine, 3-diethylaminopropylamine, second butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, Monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like. Among them, preferred is N,N-dimethylethanolamine and the like.

The metal hydroxide may, for example, be lithium hydroxide, potassium hydroxide or sodium hydroxide.

When the aqueous binder contains a basic compound, the content 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, aromatic hydrocarbons such as toluene or xylene; aliphatic hydrocarbons such as hexane; ethyl acetate and butyl acetate. Ester and other esters; methyl ethyl ketone, methyl isobutyl ketone and other ketones; methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol and other alcohols; ethylene glycol, diethylene glycol, three Glycol solvent such as ethylene glycol or propylene glycol; methyl cellosolve, 赛路苏, butyl 赛路苏, II Acetone, a racemic solvent such as MTBE (methyl tert-butyl ether) or butyl carbitol; diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether a glycol solvent such as 3-methoxy-3-methyl-1-butanol; ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene glycol monobutyl ether acetate An organic solvent such as a glycol ester solvent such as an ester or diethylene glycol monoethyl ether acetate. 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 is usually from 0.01 to 30 parts by weight, preferably from 0.01 to 10 parts by weight, per 100 parts by weight of the resin constituting the aqueous adhesive.

<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-precipitant, antioxidant, thermal stabilizer, light stabilizer, etc.; stabilizer, tackifier, dispersant, defoamer, viscosity modifier, weathering agent, pigment, pigment dispersant, antistatic agent Additives such as slip agents, nucleating agents, flame retardants, oil agents, dyes, hardeners, crosslinkers, etc.; transition metal compounds such as titanium oxide (rutile), zinc oxide, and pigments such as carbon black; glass Fiber, carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, kaolin, fine powder of cerium oxide, mica, calcium citrate, aluminum hydroxide, Any component such as inorganic or organic fillers such as magnesium hydroxide, aluminum oxide, magnesium oxide, aluminum oxide, 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 water content 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, and more preferably 85 parts by weight, based on the total amount of the aqueous adhesive. % or less, more preferably 80% by weight or less, still more preferably 70% by weight or less.

(tackifier)

In order to adjust the viscosity of the mixture, a tackifier can be used. Examples of the tackifier include ADEKANOL UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, and UH-540 manufactured by ADEKA Co., Ltd. UH-541VF, UH-550, UH-752, H-756VF; SN thickener 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A-813, A-made by SANNOPCO 818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, 4050, and the like.

(Dispersant)

A dispersant may be used in order to improve the wettability of the coated substrate. 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, BYK-347, and BYK-made by BYK. 348, BYK-349, BYK-378: NONOCO WET 50, SN WET 366, NOPCO 38-C, SN DisperSant 5468, 5034, 5027, 5040, 5020, etc. manufactured by SANNOPCO.

(hardener)

Examples of the curing agent include diphenylmethane diisocyanate (MDI), isocyanate diisocyanate (TDI), hexamethylene diisocyanate (HDI), and diisocyanate diisocyanate. A base ester (XDI) and such oligomers or polymers. Specific examples include SUMIJOUR 44V20, SUMIJOURN 3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, etc., which are manufactured by Bayer urethane.

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>

The method for producing the aqueous binder may, for example, be a method known in the art, for example, an emulsification method (for example, a forced emulsification method, a self-emulsification method, a phase emulsification method, etc.) after the resin is polymerized and then dispersed in an aqueous medium. .

Specifically, for example, (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, followed by heating and stirring, and before and after reconstituting Optionally adding water and/or solvent and stirring; (2) adding an emulsified resin, any solvent and stirring in a kneading machine, then heating and melting, and adding a surfactant, water and/or solvent thereto, and then adding Heating and stirring, and adding water and/or solvent arbitrarily before and after stirring. 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 a stirrer capable of imparting 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. Stirring 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 necessary.

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

Preferably, after stirring, the solvent is distilled off from the resulting dispersion (preferably reduced pressure or pressurized). The method of distilling off can utilize the methods well known in the art. law. The degree of pressure reduction or pressurization may be, for example, 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 the mold can be used.

The method of emulsification using an extruder is to mix the emulsified resin and the surfactant and continuously supply it by the funnel or the supply port of the extruder, and heat and melt the kneading, and then the squeezing is performed by the squeezing. Water is supplied to the supply port of at least one of the compression zone, the metering zone, and the degassing zone of the press, and is continuously pressed by the die after the screw is kneaded.

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 a range as far as desired, 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, for example, be a filtration filter using a centrifugal separator, a pore having an average pore diameter smaller than the average particle diameter of the aqueous binder (preferably a fine filtration membrane having an average pore diameter of 0.05 to 0.5 μm). ) or methods such as ultrafiltration membranes.

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 such as standing at normal temperature can be cited. Thereby using the tree during the cooling process The fat or the like does not aggregate, and a fine and homogeneous aqueous adhesive can be obtained.

The particle size of the dispersion contained in the aqueous adhesive of the present invention 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, based on the number, and it is allowed to stand still. Good sex.

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-based intermediate diameter corresponds to a particle having a cumulative particle diameter distribution of 50% on a volume basis. path. For the purpose of special explanation, the value of the median diameter measured on a number basis is shown.

Further, it is also possible to filter, for example, using a filter having various pore diameters or the like as necessary.

When the aqueous binder contains a plurality of types of dispersions (for example, a polymer having a structural unit derived from an α-olefin, a urethane resin, or the like), the particle diameter of each dispersion is preferably the same. The degree of the same 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 the ethylene/vinyl acetate copolymer (first substrate) and the cotton-containing fiber (second substrate).

First, it is preferred to apply an adhesive to both of the first substrate and the second substrate.

The coating method is a known film forming method, and examples thereof include any of an ethylene/vinyl acetate copolymer and a cotton-containing fiber, and it is preferred to apply an adhesive to both surfaces and leave it at a temperature near room temperature as necessary. , drying, or a heat treatment for drying and baking.

According to the composition of the adhesive, which is formed by extrusion molding into a coating film form, or can be applied to various substrate surfaces and dried, the obtained coating film is sandwiched between the ethylene/vinyl acetate copolymer and the cotton-containing fiber. And pressurize (or heat) and then.

Coating methods include, for example, gravure roll coating, reverse roll coating, bar coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, Dip coating, brush coating method, plate coating method, and the like.

Further, before the application of the 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 and dried to be treated as a primer. 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 performing the primer treatment, the aqueous adhesive used may be used alone or in combination of two or more. The primer treatment can be carried out only once or twice. 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 non-thermal drying such as natural drying, air drying, or usual hot air circulation type oven, infrared or far infrared heater, electromagnetic wave (for example, electromagnetic wave with a frequency band of 2.45±0.02 GHz), or microwave oven. Wait and proceed. The heating temperature and the heating time can be appropriately adjusted depending on the properties of the substrate, the composition of the adhesive, and the like. For example, the heating temperature is, for example, 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 It takes about 5 seconds to 10 minutes.

The application and drying of the subsequent agent 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, frequency bands of different electromagnetic waves can be combined.

The bonding of the first and second substrates can be carried out under heat, pressure or simultaneous load. The temperature range in which the first base material and the second base material and the subsequent layer are not deteriorated when heated is preferably about 120 ° C or lower, more preferably about 100 ° C or lower. The heat can be carried out using the above-described usual hot air circulation type oven, infrared heater, microwave oven or the like. The pressure at the time of the load pressure is, for example, about 100 g/cm ² or more, and the pressure at which the shape of the first base material and the second base material is not deformed is not 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) may be applied to the obtained laminated structure, and the load pressure may be restored.

The thickness of the coating film formed by using the adhesive can be appropriately adjusted depending on the form of the ethylene/vinyl acetate copolymer and the cotton-containing fiber of the object. 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 of the polymer contains a proportion

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

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 is about 20%)

(2) limiting viscosity (limiting viscosity, intrinsic Viscosity) [η]

It was carried out at 135 ° C using a Ubbelohde viscometer. The tetrahydronaphthalene solution of the polymer having a polymer concentration c of 0.6, 1.0, and 1.5 mg/mL per tetralin unit volume 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 three values obtained was taken as the specific viscosity (η sp) of the concentration. The value of η sp /c is extrapolated to the value of the origin as the ultimate viscosity [η].

(3) Molecular weight distribution

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

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 peaks and crystallization peaks

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

(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 the temperature was maintained for 5 minutes.

(ii) Next, the temperature was lowered from -200 ° C at a temperature drop rate of 10 ° C /min at 200 ° C, and maintained for 5 minutes after the end of the temperature drop. The peak observed in (ii) is a crystallization peak, and it is confirmed whether or not there is 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 the dissolution peak of the crystal, and it is confirmed whether or not there is a dissolution peak having a peak area of 1 J/g or more.

(5) Dissolution index (MFR)

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

(6) Change the quality

The modified mass of maleic anhydride was prepared by dissolving 1.0 g of the sample in 20 mL of xylene, and re-precipitating the sample by re-precipitating the sample solution while stirring in 300 mL of methanol, and then vacuum-drying the recovered sample (80 ° C, 8 hours), a film having a thickness of 100 μm was produced by a hot press, and the infrared absorption spectrum of the obtained film was measured, and the amount of maleic anhydride was adjusted by mass absorption at around 1780 cm ^-1 .

(7) Non-volatile ingredients

The measurement method is based on JIS K-6828.

(8) Particle diameter of aqueous emulsion

The value measured by the laser diffraction particle diameter measuring device LA-950V2 manufactured by HORIBA. Unless otherwise specified, the particle diameter 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 sometimes 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 a toluene solution of triisobutylaluminum (TIBA) [10 parts of TIBA, 20% by TOSOH ‧ Akzo (supply company)], followed by the addition of diethyl decyl (tetramethylcyclopentadiene) (3 - 0.001 part of tert-butyl-5-methyl-2-phenoxy)titanium dichloride was dissolved in 87 parts of dehydrated toluene, and 0.03 part of dimethylanilinium (pentafluorophenyl) borate was dissolved in The 122 parts of toluene were dehydrated and stirred for 2 hours. Will get the opposite The solution was added to 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 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 premixing, 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, and 100 parts of a polymer (B-2-1) [ethylene/propylene copolymer (LICOCENE PP 1602, ethylene: propylene = 15 mol%: 85 mol%)], 50 parts of maleic anhydride, 2,4,8,10-tetrabutylbutyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]diphenyl And [d,f][1,3,2] two 1,4,8,10-trtra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1 , 3, 2] dioxaphosphepin) (Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd.) 1 part, heated and stirred at 140 ° C to obtain a solution, then added 2 parts of di-tert-butyl peroxide, and continued to stir at the same temperature 5 The reaction takes place in an hour. In addition, an oil bath is used for heating. After completion of the reaction, the contents were cooled to room temperature and added to 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 obtain a polymer (B-2-2) which was 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 observed 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 crystal 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, in the temperature range of -100 to 200 ° C, the polymer (B-2-3) was observed to have a crystal melting peak of 1 J/g or more and a crystal peak having a heat of crystallization of 1 J/g or more.

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

After the stirrer, the thermometer, the dropping funnel, the reflux cooling tube, and the reduced pressure were placed in the separable flask reactor having a capacity of 21, the gas in the reactor was replaced with nitrogen. To the flask was added dry toluene 1 l 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 sometimes referred to as TIBA) to the reactor, a dimethyl fluorenyl group (2,3,4,5-tetramethyl ring) as a polymerization catalyst was added to the reactor. Pentadiene) (3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride 0.005 mmol. After 15 seconds, 0.025 mmol of triphenylmethyltetrakis(pentafluorophenyl)borate was added to the reactor to initiate polymerization. As a result of the 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, no crystal melting peak having a heat of crystal fusion of 1 J/g or more and a crystal peak having a heat of crystallization of 1 J/g or more were 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 Water-Based Emulsion>

In a separable flask reaction vessel having a stirrer, a thermometer, and a reflux condenser tube, 200 parts of toluene as a solvent and 100 parts of a polymer (B-1-2) as a copolymer were added at 80 ° C. Stir and dissolve solution. 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 the reaction mixture was stirred with a dispersion wing, and 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 obtained aqueous emulsion (E-1) had a particle diameter (number basis) of 0.61 μm and a nonvolatile content concentration of 36%.

<Production Example 2 of Water-Based 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 obtained aqueous emulsion (E-2) had a particle diameter (number basis) of 0.25 μm and a nonvolatile content concentration of 38%.

<Production Example 3 of Water-Based 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. Place The particle size (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 Water-Based 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 obtained aqueous emulsion (E-4) had a particle diameter (number basis) of 0.21 μm and a nonvolatile content of 36%.

<Production Example 5 of Water-Based 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 obtained aqueous emulsion (E-5) had a particle diameter (number basis) of 0.13 μm and a nonvolatile content of 36%.

<Production Example 6 of Water-Based 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 Water-Based Emulsion>

An aqueous emulsion was produced in the same manner as in <Production Example 1 of the 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 obtained aqueous emulsion (E-7) had a particle diameter (number basis) of 0.21 μm and a nonvolatile content of 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 <Production Example 1 of the aqueous emulsion>, an aqueous emulsion was produced in the same manner as in the case of the <. The obtained aqueous emulsion (E-8) had a particle diameter (number basis) of 0.09 μm and a nonvolatile content concentration of 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-4-1) [BONDINE AX8390 (manufactured by ARKEMA)] was used as the copolymer. The obtained aqueous emulsion (E-9) had a particle diameter (number basis) of 0.11 μm and a nonvolatile content concentration of 42%.

<Production Example 10 of Water-Based Emulsion>

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

<Production Example 11 of aqueous emulsion>

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

<Production Example 12 of aqueous emulsion>

In addition to using 50 parts of a polymer (B-4-3), an adhesive resin (terpene phenol, TAMANOL 803L, manufactured by Arakawa Chemical Co., Ltd.), 50 parts of a substituted polymer (B-1-2), 100 parts, and <aqueous emulsion Production Example 1> An aqueous emulsion (E-12) was produced in the same manner. The particle size (number basis) of the obtained aqueous emulsion is 0.20 μm, the concentration of non-volatile components was 33%.

<Production Example 13 of aqueous emulsion>

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

<Production Example 14 of aqueous emulsion>

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

<Water-based 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 size of 0.7 μm and a nonvolatile content of 45%.

<Water-based emulsion (E-16)>

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

<Water-based emulsion (E-17)>

An aqueous emulsion of EVA copolymer (EC-1800, manufactured by Central Chemical Industry Co., Ltd.) (E-17). The aqueous emulsion had a particle diameter of 1.7 μm and a nonvolatile content of 45%.

<Water-based emulsion (E-18)>

An aqueous emulsion of ethylene/epoxypropyl 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 Water-Based Emulsion>

An aqueous emulsion (E-18) and an aqueous emulsion of terpene phenol (TAMANOLE-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended in an amount of 67 parts by weight: 33 parts to prepare an aqueous emulsion (E-19).

<Water-based 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 size of 0.7 μm and a nonvolatile content of 55%.

<Production Example 21 of aqueous emulsion>

An aqueous emulsion (E-20) and an aqueous emulsion of terpene phenol (TAMANOLE-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended in an amount of 67 parts by weight: 33 parts to prepare an aqueous emulsion (E-21).

<Water-based 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 size of 0.8 μm and a nonvolatile content of 55%.

<Production Example 23 of Water-Based Emulsion>

An aqueous emulsion (E-22) and an aqueous emulsion of terpene phenol (TAMANOLE-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended in an amount of 67 parts by weight: 33 parts to prepare an aqueous emulsion (E-23).

<Water-based 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 size of 0.9 μm and a nonvolatile content concentration of 50%.

<Production Example 25 of Water-Based Emulsion>

An aqueous emulsion (E-24) and an aqueous emulsion of terpene phenol (TAMANOLE-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended in an amount of 67 parts by weight: 33 parts to prepare an aqueous emulsion (E-25).

<Water-based 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 size of 0.7 μm and a nonvolatile content of 55%.

<Production Example 27 of Water-Based Emulsion>

An aqueous emulsion (E-26) and an aqueous emulsion of terpene phenol (TAMANOLE-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended in an amount of 67 parts by weight: 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 (TAMANOLE-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended in an amount of 67 parts by weight: 33 parts to prepare an aqueous emulsion (E-28).

<Production Example 29 of aqueous emulsion>

An aqueous emulsion (E-9) and an aqueous emulsion of terpene phenol (TAMANOLE-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended in an amount of 67 parts by weight: 33 parts to prepare an aqueous emulsion (E-29).

<Production Example 30 of Water-Based Emulsion>

An aqueous emulsion (E-8) and an aqueous emulsion of terpene phenol (TAMANOLE-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended in an amount of 67 parts by weight: 33 parts to prepare an aqueous emulsion (E-30).

<Water-based 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 size of 0.6 μm and a nonvolatile content concentration of 52%.

<Production Example 32 of Water-Based Emulsion>

An aqueous emulsion (E-31) and an aqueous emulsion of terpene phenol (TAMANOLE-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended in an amount of 67 parts by weight: 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 100 parts of ethylene/propylene copolymer (B-2-4), 50 parts of substituted polymer (B-1-2), Production Example 1 of 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 Water-Based Emulsion>

An aqueous emulsion (E-13) was prepared by blending an aqueous emulsion (E-13) with terpene phenol (TAMANOLE-200NT, manufactured by Arakawa Chemical Co., Ltd.) in a nonvolatile ratio of 67 parts: 33 parts. .

<Production Example 35 of Water-Based Emulsion>

The temperature in the cell of LABO PLASTOMILL was set to 95 °C. 3.12 g of the copolymer (B-1-2) was sealed in the liquid 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 oxyethylene oxypropylene bulk copolymer (weight average molecular weight: 15500: Pluronic F108: manufactured by Asahi Kasei Co., Ltd.) and 0.21 g of water were added as an emulsifier, and the temperature in the liquid bath was maintained at 95 ° C. , while mixing for 300 minutes per minute and mixing for 3 minutes (shear speed 1173 seconds ^-1 ). After the kneading, the contents were taken out, warm water of about 70 ° C was placed, and stirred and dispersed in a container to obtain an aqueous emulsion (E-35) having a volume of 0.43 μm in the middle of the volume of the dispersion.

<Production Examples 36 to 38 of aqueous emulsion>

Using the copolymer and the surfactant shown in Table 1 in the weight ratio shown in Table 1, the emulsions (E-36) to (E-38) were obtained in substantially the same manner as in <Production Example 1 of the aqueous emulsion>. ).

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 First Industrial Pharmaceutical Co., Ltd.)

<Production Example 39 of Water-Based 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 N3300, manufactured by SBU Co., Ltd.) were used. The non-volatile component ratio is 100 parts: 100 parts: 100 parts: 5 parts are blended to obtain an aqueous emulsion (E-39).

<Production Example 40 of Water-Based 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 N3300, manufactured by SBU Co., Ltd.) were used. The non-volatile content ratio is 100 parts: 100 parts: 200 parts: 10 parts are blended to obtain an aqueous emulsion (E-40).

<Production Example 41 of Water-Based 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 N3300, manufactured by SBU Co., Ltd.) were used. The non-volatile component ratio was 100 parts: 100 parts: 1600 parts: 41 parts were blended to obtain an aqueous emulsion (E-41).

<Production Example 42 of Water-Based 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 N3300, manufactured by SBU Co., Ltd.) were used. The non-volatile component ratio is 100 parts: 100 parts: 100 parts: 15 parts are blended to obtain an aqueous emulsion (E-42).

<Production Example 43 of Water-Based 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 N3300, manufactured by SBU Co., Ltd.) were used. The non-volatile component ratio is 100 parts: 100 parts: 200 parts: 20 parts are blended to obtain an aqueous emulsion (E-43).

<Production Example 44 of Water-Based Emulsion>

An aqueous emulsion (E-44) was obtained by blending a polyurethane emulsion (Dispercoll U-54, manufactured by SBU Co., Ltd.) and isocyanate (Desmodur N3300, manufactured by SBU Co., Ltd.) in a nonvolatile content ratio of 100 parts: 5 parts.

<Production Example 45 of Water-Based Emulsion>

Aqueous emulsion (E-36), polyurethane emulsion (Dispercoll U-54, manufactured by SBU Co., Ltd.), isocyanate (Desmodur, manufactured by SBU Co., Ltd.) N3300) is formulated as an aqueous emulsion (E-45) in a ratio of 100 parts by weight: 100 parts: 5 parts.

<Production Example 46 of Water-Based Emulsion>

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

<Production Examples 47 to 63 of Water-Based Emulsions>

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

Copolymers and surfactants in the table.

Copolymer P1: C2 (ethylene) / EVA (ethylene / vinyl acetate copolymer) / MAH (maleic anhydride) copolymer (OREVAC T9314, manufactured by ARKEMA)

Copolymer P2: C2/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, Inc.)

Copolymer T1: Thermally decomposable 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) (LATEMULE-1000A, 30% aqueous solution, manufactured by Kao Corporation)

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

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

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

<Stabilization for 5 days of standing>

The obtained aqueous emulsion is placed in a 250 ml plastic container and allowed to stand at room temperature. The appearance change was observed after 5 days. The evaluation criteria are as follows. The results are shown in Table 4-1 and Table 4-2.

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

×: Aggregation or precipitation, phase separation occurred.

Test examples 15 to 64

The aqueous emulsions (E-15) to (E-35) were uniformly dispersed by visual observation, and did not cause aggregation, precipitation, phase separation, etc. under long-term storage, and showed good stability.

When the aqueous emulsions (E-36) to (E-63) were allowed to stand for 5 days in the same manner as described above, aggregation, precipitation, and phase separation were not observed, and they were in a good state.

<Example A: Evaluation of Adhesion of M-EVA by Aqueous Adhesive 1>

In each of the aqueous emulsions (nonvolatile content ratio) obtained in the production example of the aqueous emulsion, ADEKANOL UH-420 (ADEKA Corporation) was added as a tackifier in the amounts shown in Table 5 (nonvolatile content ratio, unit: parts by weight). As a dispersing agent, NOPCOWET 50 (manufactured by SANNOPCO Co., Ltd.) was prepared by dissolving water in a manner of making the nonvolatile content of the mixture 40% and stirring it with a three-one motor to obtain an aqueous adhesive.

The obtained aqueous adhesive of Table 5 was applied to 100% cotton canvas using a glass rod (coating amount: weight after drying: about 60 g/m ² ), and naturally dried for 20 minutes, and the resulting canvas was placed in a microwave oven (Panasonic) Company system, NE-EH212, frequency 2.455GHz), 30 seconds electromagnetic wave treatment at 750W.

Further, each of the aqueous adhesives was applied to M-EVA (foam of ethylene/vinyl acetate copolymer) using a bar coater No. 75 (winding diameter: 75 × 25 μm) (coating amount: weight after drying) On the 70 g/m ² ), the obtained M-EVA was placed in a microwave oven, and subjected to electromagnetic wave treatment at 750 W for 110 seconds.

Each of the water-based adhesives was applied to cotton canvas and M-EVA again (the amount of cotton canvas coating: about 40 g/m ² after drying, and the amount of M-EVA coating: about 80 g/m ² after drying). The obtained cotton canvas and M-EVA were placed in a microwave oven and subjected to electromagnetic wave treatment at 750 W for 30 seconds.

Next, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA are adhered to each other and pressed.

The thus obtained cotton/adhesion layer/M-EVA laminate structure was again placed in a microwave oven, and subjected to electromagnetic wave treatment at 750 W for 110 seconds. Immediately removed from the microwave oven and pressed by hand.

The obtained laminated structure 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 drawing tester (autograph manufactured by Shimadzu Corporation), thereby evaluating the laminated structure. The closeness. The results are shown in Table 5.

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

×: The peel strength was less than 10 N/inch.

Examples A28 to A49

The aqueous adhesives of the above aqueous emulsions (E-15) to (E-34) and (E-35) are excellent in adhesion to various substrates.

<Example B: Evaluation of Adhesion of M-EVA by Aqueous Adhesive 2>

In each of the aqueous emulsions (nonvolatile content ratio) obtained in the production example of the aqueous emulsion, ADEKANOL UH-756VF (ADEKA Co., Ltd.) was added as a tackifier in the amounts shown in Table 6 (nonvolatile content ratio, unit: parts by weight). The NOPCOWET 50 (manufactured by SANNOPCO Co., Ltd.) as a dispersing agent was prepared by dissolving water in a manner such that the nonvolatile content of the mixture was 40%, and stirring with a stirrer to obtain an aqueous adhesive B1 and an aqueous adhesive B2, respectively.

The obtained aqueous adhesive B2 was applied to 100% cotton canvas using a glass rod (coating amount: dry weight: about 130 g/m ² ), and naturally dried for 20 minutes, and the resulting canvas was placed in a microwave oven (MICRO Electronics Co., Ltd.) System, 9KW microwave oven, frequency 2.45GHz), 30 seconds electromagnetic wave treatment with 3000W.

Further, the aqueous adhesive B1 was applied to M-EVA (coating amount: weight after drying to about 30 g/m ² ) using a bar coater No. 75 (winding diameter: 75 × 25 μm), and the obtained M-EVA was obtained. Put it into the microwave oven and perform electromagnetic wave treatment for 110 seconds at 3000W.

The aqueous adhesive B2 was applied to cotton canvas and M-EVA respectively (the amount of cotton canvas coating: about 60 g/m ² after drying, and the amount of M-EVA coating: about 30 g/m ² after drying). The obtained cotton canvas and M-EVA were placed in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 15 seconds.

Next, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA are adhered to each other and pressed.

The thus obtained cotton/adhesion layer/M-EVA laminate structure was again placed in a microwave oven, and subjected to electromagnetic wave treatment at 3900 W for 120 seconds. Immediately removed from the microwave oven and pressed by hand.

Each of the obtained laminated structures was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was carried out in the same manner as the above-described method and evaluation criteria. The results are shown in Table 6.

<Example C: Evaluation of Adhesion of M-EVA by Aqueous Adhesive 3>

In each of the emulsions (nonvolatile content ratio) obtained in the production example of the aqueous emulsion, ADEKANOL UH-756VF (made by Adeka Co., Ltd.) as a tackifier was added in an amount (nonvolatile content ratio, unit: parts by weight) as shown in Table 7 The NOPCOWET 50 (manufactured by SANNOPCO Co., Ltd.) as a dispersing agent was prepared by dissolving water in a manner such that the nonvolatile content of the mixture was 40%, and stirring with a stirrer to obtain an aqueous adhesive C1 and an aqueous adhesive C2.

The obtained aqueous adhesive C2 described in Table 7 was applied to 100% cotton canvas (coating amount: dry weight: about 130 g/m ² ) using a glass rod, and naturally dried for 20 minutes, and the resulting canvas was placed. The microwave oven was subjected to electromagnetic wave treatment for 30 seconds at 3000W.

Further, each of the aqueous adhesives C1 shown in Table 7 was applied to M-EVA using a bar coater No. 75 (weight coating amount after drying: about 30 g/m ² ), and the obtained M-EVA was placed. Into the microwave oven, 170 seconds of electromagnetic wave treatment at 5000W.

Applying the aqueous adhesive C2 to the obtained cotton canvas and M-EVA respectively (the amount of cotton canvas coating: weight after drying is about 70 g/m ² , the amount of coating of M-EVA: the weight after drying is about 30 g/M 2 ), The cotton canvas was placed in a hot air oven at 80 ° C for about 15 minutes, and the M-EVA was placed in a hot air oven at 80 ° C for about 10 minutes, and the coated surface of the aqueous adhesive was applied while being warmed.

The obtained cotton/adhesive layer/M-EVA laminate structure was again placed in a hot air dryer, heat-treated at 80 ° C for 10 minutes, and taken out by a dryer, and then pressed by hand.

The obtained laminated structure was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was evaluated by the same method and evaluation criteria as described above. The results are shown in Table 7.

<Example D: Evaluation of Adhesion of M-EVA by Aqueous Adhesive 4>

In 100 parts by weight of each of the aqueous emulsions (nonvolatile content ratio) obtained in the production example of the aqueous emulsion, ADEKANOL UH-420 was added as a tackifier in the amounts shown in Table 8 (nonvolatile content ratio, unit: parts by weight). (made by Adeka Co., Ltd.), NOPCOWET 50 (manufactured by SANNOPCO Co., Ltd.) as a dispersing agent, and water-mixed with a stirrer so that the nonvolatile content of the mixture is 40%, and the aqueous adhesive D is obtained.

The obtained aqueous adhesive D of Table 7 was applied to 100% cotton canvas (coating amount: dry weight: about 130 g/m ² ) using a glass rod, and naturally dried for 1 hour.

Further, the aqueous adhesive D was applied to M-EVA (foam of ethylene/vinyl acetate copolymer) using a bar coater No. 75 in the same manner as in the application of cotton (weight coating after drying) Amount: about 30 g/m ² ), the obtained M-EVA was naturally dried for 1 hour. Thereafter, it was coated with a glass rod (cotton canvas: weight after drying: about 70 g/m ² , M-EVA coating amount: dry weight: about 30 g/m ² ) on cotton canvas and M-EVA, and placed in a microwave oven. Electromagnetic wave treatment was performed at 750 W for 30 seconds.

Next, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA were adhered to each other and pressed.

The thus obtained cotton/adhesive layer/M-EVA laminate structure was again placed in a microwave oven, and subjected to electromagnetic wave treatment at 750 W for 110 seconds. It is taken out by the dryer and then pressed by hand. Thereby, a laminated structure composed of a cotton/adhesion layer/M-EVA is obtained.

Place the laminated structure at room temperature for 24 hours to be the same as above The adhesion of the laminated structure was evaluated by the method and the evaluation criteria. The results are shown in Table 8.

<Example F: Evaluation of Adhesion and Heat Resistance of M-EVA by Aqueous Adhesive 5>

First, as the aqueous emulsion (E-36) to (E-38) (nonvolatile content ratio, unit: parts by weight) obtained in the production example of the aqueous emulsion as in Table 9-1, it will be used as the terpene of the adhesive resin 1. An aqueous phenol emulsion (TAMANOL E-200NT, manufactured by Arakawa Chemical Co., Ltd.) and an aqueous urethane emulsion (Dispercoll U-54, manufactured by SBU Co., Ltd.) as an adhesive resin 2 were blended in a nonvolatile ratio of 100:100:100. , ADEKANOL UH-756VF (made by Adeka), as a viscosity-increasing agent, NOPCOWET 50 as a dispersing agent (manufactured by SANNOPCO Co., Ltd.), Desmodur N3300 (manufactured by SBU Co., Ltd.) as a crosslinking agent, and water-mixed with a stirrer so as to have a nonvolatile content of the mixture of 40%, to obtain aqueous binders F1 to F10.

The obtained aqueous adhesive (F10) of Table 9-1 was coated with a glass rod (coating amount: weight after drying: about 130 g/m ² ) on a 100% cotton canvas, and after 20 minutes of natural drying, it was carried out at 3000 W. Second electromagnetic wave processing.

Further, each of the aqueous adhesives (F1) to (F9) was applied to M-EVA (foam of ethylene/vinyl acetate copolymer) using a bar coater No. 75 (coating amount: weight after drying was about 30 g) On /m ² ), the obtained M-EVA was subjected to electromagnetic wave treatment at 3000 W for 110 seconds. Thereafter, it was coated with a glass rod water-based adhesive (F10) (amount of cotton canvas coating: weight after drying: about g/m ² , M-EVA coating amount: weight after drying: about g/m ² ) On the M-EVA, the M-EVA was subjected to electromagnetic wave processing at 3000 W for 15 seconds.

Next, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA were bonded to each other, and subjected to electromagnetic wave treatment at 3900 W for 120 seconds. Then press it with your hand. Thereby, a laminated structure composed of a cotton/adhesion layer/M-EVA is obtained.

The obtained laminated structure was allowed to stand at room temperature for 24 hours, and then the peeling strength was measured at a peeling speed of 50 mm/min and a peeling angle of 180 degrees using a drawing tester (autograph manufactured by Shimadzu Corporation), thereby evaluating the laminated structure. The closeness. The results are shown in Table 9-2.

○: The peel strength was 70 N/inch or more.

×: The peel strength was less than 70 N/inch.

The obtained laminated structure was allowed to stand at room temperature for 24 hours, and then the peeling strength was measured using a drawing tester (Toyo Seiki, STROGRAPH T) at a set temperature of 60 ° C in the tank, a peeling speed of 50 mm/min, and a peeling angle of 180 degrees. Thereby, the heat resistance of the laminated structure was evaluated. The results are shown in Table 9-2.

○: The peel strength was 15 N/inch or more.

×: The peel strength was less than 15 N/inch.

<Example G: Evaluation of Adhesion of M-EVA by Aqueous Adhesive 6>

First, in 100 parts by weight of an aqueous emulsion (E-36) (nonvolatile content ratio, unit: parts by weight) obtained in the production example of an aqueous emulsion, an aqueous emulsion of terpene phenol as an adhesive resin (TAMANOL E-200NT) 50 parts of a non-volatile content ratio of 100:50, and added 2 parts by weight of ADEKANOL UH-420UH (made by Adeka Co., Ltd.) as a tackifier, NOPCOWET as a dispersing agent 50 parts (manufactured by SANNOPCO Co., Ltd.) 8 parts by weight, and water-mixed with a stirrer so as to make the non-volatile content of the mixture 40%, to obtain an aqueous adhesive G1.

The obtained aqueous adhesive G1 was applied (coating amount: dry weight: about 167 g/m ² ) to a 100% cotton canvas using a glass rod, and naturally dried for 1 hour. Thereafter, the aqueous adhesive G1 was again applied (coating amount: weight after drying was about 100 g/m ² ).

Further, the aqueous adhesive G1 was applied (coating amount: weight after drying to about g/m ² ) to M-EVA (foam of ethylene/vinyl acetate copolymer) using a bar coater No. 75.

After the canvas and the M-EVA were naturally dried for one hour, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA were bonded to each other, and electromagnetic wave treatment was performed at 3900 W for 150 seconds. Then press it with your hand. Thereby, a laminated structure composed of a cotton/adhesion layer/M-EVA is obtained.

The obtained laminated structure was allowed to stand at room temperature for 24 hours, and then the peeling strength was measured at a peeling speed of 50 mm/min and a peeling angle of 180 degrees using a drawing tester (autograph manufactured by Shimadzu Corporation), thereby evaluating the laminated structure. The closeness. And the peel strength is better than 10N/inch. result.

(industrial availability)

The ethylene/vinyl acetate copolymer and the cotton-containing fiber can be firmly adhered to according to the aqueous adhesive of the present invention. Further, a laminate structure of an ethylene/vinyl acetate copolymer/adhesion layer/cotton fiber excellent in adhesion can also be provided.

Claims (23)

An aqueous binder for use in a polymer comprising an ethylene/vinyl acetate copolymer and a cotton-containing fiber, and having a structural unit having one or more kinds of α-olefins having 2 to 20 carbon atoms. The aqueous adhesive according to claim 1, which further comprises a surfactant represented by the following formula (I). (wherein, X represents a hydrogen atom or -SO ₃ M (M is a hydrogen atom, NH ₄ or an alkali metal); n represents an integer of 1 to 3; m represents an integer of 1 to 100). The aqueous adhesive according to claim 2, wherein the surfactant contains two or more types of a surfactant in which X is a hydrogen atom and a surfactant in which X is -SO ₃ M. The aqueous adhesive according to claim 2, wherein the -SO ₃ M in the surfactant is 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 carbon number of 2 to 20, and a selected from the carbon number One or more monomers of a group consisting 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 A copolymer of structural units. The aqueous adhesive according to any one of claims 1 to 5, wherein the polymer has a structural unit derived from ethylene and A copolymer of structural units of one or more monomers selected from the group consisting of α-olefins having 3 to 20 carbon atoms, α, β-unsaturated carboxylic acid esters, α, β-unsaturated carboxylic anhydrides, and vinyl acetate. 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, β- A copolymer of structural units of one or more monomers of a group consisting of unsaturated carboxylic acids. The aqueous adhesive according to any one of claims 1 to 7, wherein the polymer has at least one selected from the group consisting of: (a) an ethylene-propylene copolymer, propylene- Α-olefin copolymerization such as 1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer, ethylene-propylene-1-butene copolymer Or a modified substance thereof; or a mixture of two or more of the above; (b) an ethylene-propylene copolymer, a propylene-1-butene copolymer, an ethylene-1-butene copolymer, an ethylene-1-octene An α-olefin copolymer such as a 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; a copolymer of α-olefin and vinyl acetate or a modified product thereof; or a mixture of two or more thereof; (d) a copolymer of an α-olefin and a (meth) acrylate with an α, β-carboxylic acid or a modified substance; or a mixture of two or more thereof; and (e) an α-olefin and a (meth) acrylate and a maleic anhydride a copolymer or a modified substance thereof; 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 is selected from the group consisting of terpene polymers, terpene phenols, β-pinene polymers, aromatic modified terpene polymers, and α. a terpene-based resin composed of a terpene polymer and a 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 a terpene polymer, a terpene phenol, a β-pinene polymer, an aromatic modified terpene A terpene-based resin composed of a polymer, an α-pinene polymer, and a terpene-based hydrogenated resin. 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 further comprises an isocyanate. The aqueous adhesive according to any one of claims 1 to 14, which is selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), and diisocyanate Methyl ester (HDI), An isocyanate of a group consisting of benzene diisocyanate (XDI) and such oligomers or polymers. 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 contains 0.1 to 50 parts by weight, 0.1 to 20 parts by weight or 0.1 to 10 parts by weight based on 100 parts by weight of the whole resin constituting the aqueous emulsion. 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, from 10 to 90:90. Up to 10, 30:70 to 90:10, 40:60 to 90:10 or 50:50 to 90:10 containing the surfactant represented by the formula (A) and the surfactant represented by the formula (B), An aqueous adhesive according to any one of claims 1 to 20, which is obtained by dispersing the resin after polymerizing the thermoplastic resin. It is obtained by an emulsification method, a forced emulsification method, an auto-emulsification method or a phase-transfer emulsification method in an aqueous medium. A laminated structure comprising a first substrate comprising an ethylene/vinyl acetate copolymer, an adhesive layer comprising 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 material The second substrate of the fiber is laminated in order. 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.