JP6902194B2 - Aqueous emulsions and coatings, cured products and laminates - Google Patents

Description

The present invention relates to aqueous emulsions and coatings, cured products and laminates.

Patent Document 1 describes an aqueous emulsion containing an acid-modified chlorinated polyolefin that can be used as an adhesive. However, such an aqueous emulsion could not adhere to the adherends or to the adherends with sufficient strength.

Japanese Unexamined Patent Publication No. 2007-31473

There is a demand for an aqueous emulsion capable of adhering the adherends to or against the adherends with sufficient strength.

The present invention includes the following inventions.
[1] An aqueous emulsion containing chlorinated rubber having a chlorine atom content of 45% by mass or more, a compound having one or more polymerizable groups, and water.
[2] The aqueous emulsion according to [1], wherein the content of the compound having a polymerizable group is 50 to 10000 parts by mass with respect to 100 parts by mass of the chlorinated rubber.
[3] Water is contained as the dispersion medium, and the mixture contains water.
The aqueous emulsion according to [1] or [2], which comprises a mixture of the chlorinated rubber and the compound having a polymerizable group as a dispersoid.
[4] The aqueous emulsion according to any one of [1] to [3], wherein the dispersoid is in a liquid state.
[5] The aqueous emulsion according to any one of [1] to [4], wherein at least a part of the chlorinated rubber is dissolved in the dispersoid.
[6] The aqueous emulsion according to any one of [1] to [5], which comprises a solution in which at least a part of the chlorinated rubber is dissolved in the compound having a polymerizable group as a dispersoid.
[7] The aqueous emulsion according to any one of [1] to [6], wherein the compound having a polymerizable group is a liquid at 23 ° C. at atmospheric pressure.
[8] The aqueous emulsion according to any one of [1] to [7], wherein the compound having a polymerizable group is a compound having an ethylenically unsaturated double bond.
[9] The aqueous emulsion according to any one of [1] to [8], which further contains a surfactant.
[10] The aqueous emulsion according to any one of [1] to [9], which further contains a photopolymerization initiator.
[11] The aqueous emulsion according to any one of [1] to [10], which further contains a light stabilizer.
[12] The aqueous emulsion according to any one of [1] to [11], which further contains an ultraviolet curable oligomer.
[13] The aqueous emulsion according to any one of [1] to [12], which further contains a fluorescent whitening agent.
[14] The aqueous emulsion according to any one of [1] to [13], which further contains a leveling agent.
[15] The aqueous emulsion according to any one of [3] to [14], wherein the volume-based median diameter of the dispersoid is 10 μm or less.
[16] The aqueous emulsion according to any one of [1] to [15], wherein the chlorinated rubber does not have a carboxy group and a carboxylic acid anhydride structure.
[17] The total amount of the mass part of the chlorinated rubber and the mass part of the compound having a polymerizable group is relative to the total amount of the chlorinated rubber, the compound having the polymerizable group and the mass part of water. , 0.1% by mass to 70% by mass. The aqueous emulsion according to any one of [1] to [16].
[18] A coating film formed by any of the above-mentioned aqueous emulsions.
[19] The cured product of the coating film according to [18].
[20] The cured product according to [19], one or more adhesive layers, and the second base material are laminated in this order on a first base material made of an olefin polymer. Laminated body.
[21] On a first base material made of an ethylene-vinyl acetate copolymer, a cured product according to [19], a layer or more of an adhesive layer on the first base material, and a second base material are formed. Laminated bodies laminated in this order.
[22] The laminate according to [20] or [21], wherein the adhesive layer and the second base material are laminated via the cured product according to [19].

According to the present invention, the adherends can be adhered to the adherends or the adherends with sufficient strength.

In one embodiment, the aqueous emulsion of the present invention mainly comprises a chlorinated rubber and a compound having a polymerizable group. The aqueous emulsion usually contains water as a dispersion medium. The aqueous emulsion of the present invention is useful as a water-based adhesive.
<Chlorinated rubber>
The chlorinated rubber is a chlorinated rubber having a chlorine atom content of 45% by mass or more. The chlorinated rubber may be one type or a combination of two or more types.

The chlorinated rubber may or may not have a melting point, but preferably has a melting point. The melting point is preferably 100 ° C. or higher, more preferably 200 ° C. or higher, and even more preferably 240 ° C. or higher. Further, it is preferably 350 ° C. or lower, and more preferably 300 ° C. or lower.

The chlorine atom content of the chlorinated rubber is preferably 45 to 90% by mass, more preferably 55 to 90% by mass, and further preferably 60 to 80% by mass.

As the chlorinated rubber, one having no carboxy group and a carboxylic acid anhydride structure can be used. When such a chlorinated rubber is used in the aqueous emulsion of the present invention, particularly when the aqueous emulsion is used as the aqueous adhesive, the concern about deterioration of the water resistance of the aqueous adhesive becomes extremely small and is effective. Specifically, it is preferable to use a carboxylic acid anhydride such as maleic anhydride that has not been acid-modified.

The chlorinated rubber is not particularly limited as long as it is chlorinated natural rubber or synthetic rubber, but specifically, chlorinated natural rubber, chlorinated butadiene rubber, chlorinated butyl rubber, chlorinated isoprene rubber, butadiene / halogen. Cyclic conjugated diene adduct, chlorinated butadiene styrene copolymer, brominated poly (2,3-dichloro-1,3-butadiene) and α-haloacrylonitrile-co-2,3-dichloro-1,3-butadiene Examples thereof include copolymers. A copolymer or rubber containing a hydrocarbon group having 4 or more carbon atoms as a raw material is preferable. More preferably, it is a chlorinated natural rubber, a chlorinated isoprene rubber and a chlorinated butadiene rubber.

As a method for chlorinating natural rubber or synthetic rubber, a conventionally known method can be adopted. For example, a method of dissolving natural rubber or synthetic rubber in a chlorinated organic solvent such as carbon tetrachloride or monochlorobenzene or an organic solvent such as toluene and blowing chlorine gas; a state in which natural rubber or synthetic rubber is suspended or emulsified in water. Method of blowing chlorine gas with; method of introducing chlorine gas while irradiating ultraviolet rays while suspending or emulsifying natural rubber or synthetic rubber in water; chlorinating with natural rubber or synthetic rubber and liquid under low temperature pressurization Examples thereof include a method of directly chlorinating by contacting with chlorine. Further, the coagulated solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then chlorinated, or the coagulated solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then emulsified and dispersed to volatilize the solvent. It can also be chlorinated in a fresh state. When chlorinating natural rubber, chlorine gas can be blown into the latex-like natural rubber to chlorinate it.
For example, polyisoprene, a surfactant, and an acid such as hydrochloric acid, sulfuric acid, or nitric acid are added to water, emulsified, and then chlorine gas is blown into the water to obtain uniformly chlorinated polyisoprene.

The polystyrene-equivalent weight average molecular weight of the chlorinated rubber is usually 1000 or more, preferably 3000 or more, more preferably 5000 or more, and further preferably 10000 or more. Further, it is usually 400,000 or less, preferably 200,000 or less. The polystyrene-equivalent weight average molecular weight can be measured by gel permeation chromatography (GPC).
Within such a range, sufficient adhesive strength can be ensured when the aqueous emulsion of the present invention is used as the aqueous adhesive, and excessive increase in viscosity can be suppressed to adhere to the adherend. Sufficient sex can be ensured.

Examples of the chlorinated rubber include commercially available products and those manufactured according to any known method. Commercially available products include Supercron (registered trademark) CR-10, CR-20 (Nippon Paper Industries, Ltd.), Pergut S-5, Pergut S-10, Pergut S-20, Pergut S-40, Pergut S-90. , Pergut S-130, Pergut S-170 (Bayer Material Science Co., Ltd.), Alloprene (registered trademark) R10, R20, R40 (manufactured by ICI UK) and the like. Known methods include, for example, the method described in Japanese Patent No. 2660478.

<Compound with polymerizable group>
The compound having a polymerizable group is, for example, a vinyl group, an allyl group, a propenyl group, a vinylidene group, a vinylene group (meth) acrylic group, a (meth) acryloyl group, a vinyl ether group, a vinyl benzyl ether group as a polymerizable group. , (Meta) acrylic oxy group, (meth) allylamide group, styryloxy group, styrylamide group, isocyanate group, thioisocyanate group, carboxyl group, alcoholic or phenolic hydroxyl group, silanol group, alicyclic epoxy group, epoxy group , Glycidyl group, cyclic ether group such as oxetane group, and other ring-opening polymerizable groups. These groups may contain only one type or two or more types, or may contain only one type or two or more types.
Examples of the compound having a polymerizable group include a compound having an ethylenically unsaturated double bond, an epoxy compound, an oxetane compound, a glycidyl ether compound and the like. These compounds may be used alone or in combination of two or more.
As the compound having a polymerizable group, a compound having one or more ethylenically unsaturated double bonds is preferable.

The compound having an ethylenically unsaturated double bond has preferably 1 to 10 ethylenically unsaturated double bonds, more preferably 1 to 6, still more preferably 1 to 3, and even more preferably 1 to 1. I have two.

Examples of the compound having one ethylenically unsaturated double bond include heterocyclic ethylenically unsaturated compounds (for example, N-vinyl-nitrogen-containing heterocycles such as N-methylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam. Compounds; heterocyclic (meth) acrylates such as morpholin (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and glycidyl (meth) acrylate), N-vinylformamide, N-vinylacetamide, dialkylaminoethyl (meth) acrylate ( For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate), N, N'-dimethylacrylamide, alkoxy (poly) alkylene glycol (meth) acrylate (eg, methoxyethylene (meth) acrylate, ethoxy-diethylene glycol (eg) Meta) acrylate, methoxypolyethylene (meth) acrylate, butoxypolyethylene (meth) acrylate, etc.), phenoxyalkyl (meth) acrylate (for example, 2-phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, etc.), alkylphenoxymethyl (Meta) acrylate (eg, nonylphenoxyethyl (meth) acrylate, etc.), phenoxy (poly) alkylene glycol (meth) acrylate (eg, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth)) Acrylate, etc.), Alkylphenoxy (poly) alkylene glycol (meth) acrylate (eg, nonylphenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, etc.), Alkyl (meth) acrylate (eg, methyl (meth) acrylate, etc.) ) Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, stearyl (meth) acrylate , Acrylate (meta ) Acrylate, behenyl (meth) acrylate, etc.), (meth) acrylate having an alicyclic skeleton (for example, cyclohexyl (meth) acrylate, 4 (1,1-dimethylethyl) cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbonyl (meth) acrylate, cyanonorbornyl (meth) acrylate, menthyl (meth) acrylate , Fentyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl adamantyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] deca-8-yl = (meth) acrylate, tricyclo [5.2. 1.0 ^2,6 ] Deca-4-methyl = (meth) acrylate, cyclodecyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, isobornyl (meth) acrylate, bornyl (meth) acrylate, Dicyclopentadiene (meth) acrylate, dicyclopentenyloxyalkyl (meth) acrylate, tricyclodecanyloxyethyl (meth) acrylate, isobolmiloxyethyl (meth) acrylate, etc.), aralkyl (meth) acrylate (eg, benzyl) (Meta) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, etc.), hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxy-o-phenylphenolpropyl (meth) acrylate, 2-( Meta) Acryloyloxyethyl-2-hydroxyethylphthalic acid, glycerin mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, 2-hydroxyethyl (Meta) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, polypropylene grease Cole mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol-propylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc.), poly ε-caprolactone mono (meth) acrylate , Mono [2- (meth) acryloyloxyethyl] acid phosphate, halogen-containing (meth) acrylate (eg, tolfluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, perfluoro Octylethyl (meth) acrylate, N, N, N-trimethyl-N- (2-hydroxy-3methacryloyloxypropyl) -ammonium chloride, etc.), silicone-containing (meth) acrylate (eg, (meth) acrylic-modified organopolysiloxane) , 3- (meth) Acrylicoxypropyltrimethoxysilane, 3- (meth) Acrylateoxypropyltriethoxysilane, 3- (meth) acrylicoxypropylmethyldimethoxysilane, 3- (meth) acrylicoxypropylmethyldiethoxysilane, etc. ), Aromatic vinyl compounds (eg, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-methoxystyrene) , Vinyl benzoate, etc.), unsaturated carboxylic acid glycidyl esters-containing (meth) acrylates (eg, glycidyl (meth) acrylates, glycidyl methacrylates, 3,4-epoxybutyl (meth) acrylates, (3,4-epoxycyclohexyl)) Methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc.), aliphatic vinyl compounds (eg, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, etc.), Unsaturated amides or unsaturated imides (eg, acrylamide, methacrylicamide, diacetone (meth) acrylamide, α-chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N- (2-) (Hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylicamide, maleimide, etc.), acrylonitrile, methacrylonitrile, α-chloroacrylonite A macromonomer having a monoacryloyl group or a monomethacryloyl group at the end of the ryl and a polymer (for example, polystyrene, polymethylacrylate, polymethylmethacrylate, polyn-butylacrylate, polyn-butylmethacrylate, polysilicone, etc.) And so on.

Examples of the compound having two ethylenically unsaturated double bonds include di (meth) acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate and (polyoxy) alkylene glycol. Di (meth) acrylate (for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene gillicol di (meth) acrylate, polyethylene glycol -Propylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) ) Acrylate, alkoxylated neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, alkoxy Hexadiol di (meth) acrylate, Pentandiol di (meth) acrylate, 3-Methyl-pentanediol di (meth) acrylate, Glycerindi (meth) acrylate, Trimethylol propandi (meth) acrylate, Pentaerythritol di (meth) ) Acrylate), di (meth) acrylate of alkylene oxide (eg, ethylene oxide, propylene oxide, etc.) adduct of bisphenol A (eg, di (meth) acrylate of 2,2-bis (2-hydroxyethoxyphenyl) propane) Etc.), di (meth) acrylates having bridging ring hydrocarbon groups (eg, cyclohexanedimethanol di (meth) acrylates, di (meth) acrylates of tricyclodecanedimethylol (eg, tricyclodecanedimethanol di (eg) (Meta) acrylate), dicyclopentadiene (meth) acrylate, etc.), bifunctional epoxy resin (meth) acrylic Allic acid adduct (eg, (meth) acrylic acid adduct of 2,2-bis (glycidyloxyphenyl) propane, bisphenol A diglycidyl ether methacrylic acid adduct, etc.), glycerindi (meth) acrylate, silicone-containing (meth) ) Acrylate (for example, (meth) acrylic-modified organopolysiloxane, etc.), diacetone acrylic amide, and the like.

Examples of the compound having three or more ethylenically unsaturated double bonds include trimethylolpropanetri (meth) acrylate, trimethylolpropanetrioxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth). ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropanetetraacrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, tris (acryloyloxy) Isocyanurate, Tris (2-acryloyloxyethyl) isocyanurate, Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, Tris (hydroxypropyl) isocyanurate tri (meth) acrylate, Triallyl trimellitic acid, Examples thereof include triallyl isocyanurate and silicone-containing (meth) acrylate (for example, (meth) acrylic-modified organopolysiloxane).

Among them, the compound having one or more ethylenically unsaturated double bonds is preferably a compound having 5 to 25 carbon atoms, more preferably a compound having 6 to 18 carbon atoms, and further preferably 8 to 16 carbon atoms. It is a compound of.

Examples of the epoxy compound include phenylglycidyl ether, p-tert-butylphenylglycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2. -Epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, bisphenol A diglycidyl ether, Neopentyl glycol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxy-6- Methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxiside, ethylene Glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butane Didiol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylpropan triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiendi Examples thereof include oxide, limonendioxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane and the like.

Among them, as the epoxy compound, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are more preferable, from the viewpoint of excellent curing speed.

Examples of the oxetane compound include 2-hydroxymethyl-2-methyloxetane, 2-hydroxymethyl-2-ethyloxetane, 2-hydroxymethyl-2-propyloxetane, 2-hydroxymethyl-2-butyloxetane, and 1,4-bis. [(3-Ethyl-3-oxetanylmethoxy) methyl] benzene and the like can be mentioned.

Examples of the glycidyl ether compound include 1,4-butanediol glycidyl ether, 1,6-hexanediol glycidyl ether, cyclohexanedimethanol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerin polyglycidyl ether, and diethylene glycol diglycidyl ether. ..

The compound having a polymerizable group may be a compound which is solid at 23 ° C., but a compound which is liquid under atmospheric pressure is preferable. Liquids include solutions, emulsions, suspensions, colloids and the like. Due to such properties, a uniform aqueous emulsion can be obtained.

The compound having a polymerizable group contained in the aqueous emulsion of the present invention is usually 50 to 10000 parts by mass, preferably 100 to 10000 parts by mass, and more preferably 200 to 100 parts by mass with respect to 100 parts by mass of the chlorinated rubber. It is 5000 parts by mass, more preferably 400 to 5000 parts by mass.

The aqueous emulsion of the present invention may contain a polymerization inhibitor. The polymerization inhibitor may be any one that delays or stops the radical reaction. Polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monoesterides, N-nitrosodiphenylamine, phenothiazine, 4-t-butylcatechol, N-phenylnaphthylamine, 2,6-di-t-butyl-p-methylphenol. , 2,5-di-t-butylhydroquinone, 1,4-benzoquinone, 2,6-di-t-butyl-1,4-benzoquinone, methyl-p-benzoquinone, 2,5-diphenyl-p-benzoquinone, Examples thereof include 4-methoxyphenol, chloranyl, pyrogallol, 2-oxydiphenylamine, phenothiazine and the like.

Commercially available polymerization inhibitors include Kinopower QS-10, Kinopower QS-20, Kinopower QS-30, Kinopower QS-40, Kinopower QS-W10 (manufactured by Kawasaki Kasei Chemicals, Inc.), Metoquinoneflakes, Nonflex Alba, MH, Examples thereof include TBH, PBQ, tolucinone, and TBQ (manufactured by Seiko Kagaku Co., Ltd.).

The polymerization inhibitor also has an aspect of maintaining high storage stability of the composition and ensuring curability. Therefore, in consideration of such an action, the amount of the polymerization inhibitor added is preferably 0 with respect to 100 parts by mass, which is the total of the mass part of the chlorinated rubber and the mass part of the compound having a polymerizable group. It is .005 to 0.4 parts by mass, more preferably 0.01 to 0.3 parts by mass, further preferably 0.02 to 0.2 parts by mass, and particularly preferably 0.035 to 0.2 parts by mass. The polymerization inhibitor is preferably dissolved in a compound having a polymerizable group.

<Water>
As the water contained in the aqueous emulsion of the present invention, tap water or deionized water is usually used. The amount of water contained in the aqueous emulsion is not particularly limited, and may be any amount as long as the chlorinated rubber and the compound having a polymerizable group can be present as a uniform dispersion medium.

<Additives>
In the aqueous emulsion of the present invention, various additives can be added in addition to the above-mentioned chlorinated rubber and the compound having a polymerizable group. Additives include surfactants, photopolymerization initiators, light stabilizers, UV curable oligomers, fluorescent whitening agents, leveling agents, basic compounds, organic solvents, cross-linking agents, photosensitizers, and other resins. Phenolic stabilizers, phosphite stabilizers, amine stabilizers, amide stabilizers, anti-aging agents, weather-resistant stabilizers, preservatives, anti-settling agents, antioxidants, heat stabilizers, rocking agents, thickening agents Agents, antifoaming agents, viscosity modifiers, weather resistant agents, pigment dispersants, antistatic agents, lubricants, nucleating agents, flame retardants, oils, dyes, curing agents; transition metal compounds such as titanium oxide (rutyl type) and zinc oxide Pigments such as carbon black; glass fiber, carbon fiber, potassium titanate fiber, wolastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, kaolin, fine powder silica, mica, calcium silicate, water Examples thereof include inorganic or organic fillers such as aluminum oxide, magnesium hydroxide, aluminum oxide, magnesium oxide, alumina and Celite.

These additives and the like may constitute a dispersoid of an aqueous emulsion. In this case, at least a part of the chlorinated rubber may be dissolved in the dispersoid. Here, the fact that at least a part of the chlorinated rubber is dissolved in the dispersoid means that at least a part of the chlorinated rubber is dissolved in at least one component among the components forming the dispersoid. To do. For example, when the aqueous emulsion of the present invention is filtered through a filter having a pore size of 0.50 μm, the filtrate may contain at least a part of chlorinated rubber. The chlorinated rubber contained in the filtrate is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, based on 100 parts by mass of the chlorinated rubber contained in the aqueous emulsion before filtration. Even more preferably, it is 70% by mass or more.
Filtration with a filter is preferably carried out after heating to a temperature equal to or higher than the melting point of the compound having a polymerizable group contained in the aqueous emulsion.

When the chlorinated rubber contains other resins, it is preferable that at least a part of the chlorinated rubber is dissolved in a compound having a polymerizable group or a dispersoid, but at least one of the additives such as other resins. The part may be dissolved in a compound having a polymerizable group or a dispersoid.
Filtration with a filter is preferably carried out after heating to a temperature equal to or higher than the melting point of the compound having a polymerizable group contained in the aqueous emulsion.

When the above additives are added to the aqueous emulsion of the present invention, all of the additives may be mixed with the dispersoid in the aqueous emulsion or may be mixed with water. The term "mixed" means that it may be dispersed or dissolved.

<Surfactant>
The surfactant is preferably one that acts as an emulsifier. Examples of the surfactant include cationic, anionic, amphoteric and nonionic surfactants, and preferably anionic and nonionic surfactants. The surfactant may be used alone or in combination of two or more.

Examples of the anionic surfactant include amino acid condensates of higher fatty acids such as sodium fatty acid such as sodium palmitate, sodium ether carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, sodium lauroyl sarcosin, and sodium N-lauroyl glutamate, and higher grades. Higher fatty acid ester sulfonates such as alkyl sulfonates and lauric acid ester sulfonates, dialkyl sulfosuccinates such as dioctyl sulfosuccinate, higher fatty acid amide sulfonates such as oleic acid amide sulfonic acid, sodium dodecylbenzene sulfonate. , Alkylaryl sulfonate such as diisopropylnaphthalene sulfonate, formalin condensate of alkylaryl sulfonate, higher alcohol sulfate such as pentadecane-2-sulfate, polyoxy such as dipolyoxyethylene dodecyl ether phosphate Ethylene alkyl phosphate ester, lignin sulfonate, polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate, polyoxyethylene nonylpropenylphenyl ether ammonium sulfate, bis (polyoxyethylene polycyclic phenyl ether) bismethacrylate sulfate , Alkylallyl succinate sulfonic acid sodium salt, polyoxyalkylene alkenyl ether ammonium sulfate, 2-sodium sulfoethyl methacrylate, alkoxypolyethylene glycol maleic acid ester, higher alcohol sulfate ester salt, higher carboxylate, alkylbenzene sulfonate, poly Oxyethylene alkyl sulfate salt, polyoxyethylene alkyl phenyl ether sulfate salt and vinyl sulfosuccinate, poly (meth) sodium acrylate, poly (meth) ammonium acrylate, (meth) acrylic acid- (meth) acrylate ester co-weight Examples thereof include coalescence, styrene-maleic acid copolymer, styrene-maleic acid copolymer ammonium salt, styrene-maleic acid half ester copolymer ammonium salt, sodium carboxymethyl sulfonic acid and sodium naphthalene sulfonate formalin condensate.

Cationic surfactants include alkylamine hydrochlorides such as dodecylamine hydrochloride, alkylquaternary ammonium salts such as alkyldimethylbenzylammonium salts, alkylisoquinolinium salts, dialkylmorpholinium salts, benzethonium chloride, and poly. Alkylammonium salts such as alkylvinylpyridinium salt, dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkylammonium salt, allyltri Examples thereof include alkylammonium salts, diallyldialkylammonium salts, and polydiallyldimethylammonium chlorides.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene glyceryl monofatty acid. Estel, polyoxypropylene glycol monofatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene fatty acid ester, higher fatty acid glycerin ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene Included are block polymers, polyoxyethylene fatty acid amides, alkylolamides, polyoxyethylene alkylamines, and polyoxyethylene alkanediols, alkoxypolyethylene glycol methacrylates. Polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene fatty acid amide, polyalkylene polyamine alkylene oxide adduct, polyalkylene polyimine alkylene oxide adduct, polyvinylpyrrolidone, dicyandiamide polyalkylene polyamine condensate, polyethylene glycol, polyvinyl alcohol And so on.

Examples of the amphoteric tenside include N-laurylalanine, N, N, N-trimethylaminopropionic acid, N, N, N-trihydroxyethylaminopropionic acid, N-hexyl-N, N-dimethylaminoacetic acid, and the like. Examples thereof include 1- (2-carboxyethyl) pyrimidinium betaine, lecithin, lauryl betaine and lauryldimethylamine oxide.

Commercially available surfactants include Emar 0, Emar 10G, Emar 2F paste, Emar 20C, Emar E-27C, Emar 270J, Emar E-27C, Neoperex GS, Neoperex G-15, Neoperex G-25. , Neoperex G-65, Latemuru PD-104, Perex OT-P, Perex TR, Perex SS-L, Perex SS-H, Demor N, Demor EP, Emargen 102KG, Emargen 104P, Emargen 105, Emargen 106, Emargen 108 , Emargen 404, Emargen 130K, Emargen 147, Emargen LS-106, Emargen LS-110, Emargen A-60, Emargen 109P, Emargen 350, Latemul PD-420, Leodor 430V, Emanon 1112, Emanon CH-25, Amit 102, Acetamine 86, Coatamine 24P, Anchtor 24B, Neoperex No. 6 Powder, Latemuru E-1000A, Perex OT-P, Emargen LS-114, Emargen 210P, Emargen 220, Emargen 306P, Emargen 320P, Emargen 408, Emargen 409PV, Emargen 420, Anchor 86B and Anchor 20BS (manufactured by Kao), Neugen EA-177, Neugen XL-40, Neugen TDS-30, Neugen TDX-80, Neugen LP-80, DKS NL-15, DKS NL-50, DKS NL-80, DKS NL-110, DKS NL-180, Neugen TDS-70, Neugen TDS-100, Neugen ET-83, Neugen ET-160, Neugen YX-400, Hytenol NF-08, Hytenol 227L, Plysurf A212C, Plysurf A210D, Neocol P, Monogen Y-100 , Catiogen TML, Aqualon KH-10, Aqualon KH-1025, Aqualon HS-10, Aqualon RN-20, Aqualon RN-30, Pittscol K-17L and Pittscol V-7154 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeca Pluronic F108, Adeca Pluronic L-61, Adeca Pluronic 17R-2 (manufactured by ADEKA) Eleminor JS-20, Eleminor RS-3000, Sanmorin OT-70 and Caribon EN-200 (manufactured by Sanyo Kasei Kogyo), Clarepovar PVA- 103, Clarepoval PVA-105, Clarepoval PVA-117, Clarepoval PVA-217, Clarepoval PVA-205, Clarepoval PVA-203, Clarepoval PVA-210, Clarepoval PVA-235, Clarepoval PVA-403, Clarepoval PVA-405, Clarepoval PVA-417, Clarepoval M-205, Clarepoval MP-203, Clarepoval KL-506 and Clarepoval KL-318 (manufactured by Clare), Akumalim AKM-511-60, Akumalim AKM -0531, Polystar OM, Pronon # 102 (manufactured by Nichiyu Co., Ltd.) and the like can be mentioned.

The aqueous emulsion of the present invention preferably contains a surfactant. When a surfactant is contained, if the content is an amount effective for forming an aqueous emulsion, the adhesiveness of the aqueous emulsion is good, but it has a mass part of the chlorinated rubber and a polymerizable group. It is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less with respect to 100 parts by mass in total with the mass parts of the compound. The lower limit of the amount of surfactant is preferably at least 1 part by mass.

<Photopolymerization initiator>
A photopolymerization initiator is a compound that produces an active species by the action of light, a photoradical generator that generates an active radical by the action of light, a photoacid generator that generates an acid by the action of light, and a photoacid generator that generates an acid by the action of light. Examples thereof include a photobase generator that generates a base.

Examples of the photoradical generator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, sulfonic acid derivatives, onium salts (iodonium salts, sulfonium salts, etc.), carboxylic acid esters and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, 4-methylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butyl). Peroxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone and the like.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane. -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[ 4- (2-Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methylpropiophenone and 2-hydroxy-2-methyl-1- [4- (1- (1-) Methylvinyl) phenyl] Propane-1-one oligomers and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2 -(5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3 , 5-Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like can be mentioned.

Examples thereof include sulfonic acid derivatives, onium salts (iodonium salt, sulfonium salt, etc.), carboxylic acid esters, etc., which will be described later.

As the photoradical generator, a commercially available one can be used. Commercially available photoradical generators include Irgacure® 907, 184, 651, 819, 250, 2959, 127, 754 and 369 (BASF Japan Ltd.), Sakeol® BZ, Z. And BEE (Seiko Kagaku Co., Ltd.), Kayacure (registered trademark) BP100 (Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), ADEKA PUTMER SP-152 and SP-170 ((() ADEKA Corporation), TAZ-A and TAZ-PP (Nippon Sibel Hegner Co., Ltd.), TAZ-104 (Sanwa Chemical Co., Ltd.), Darocur (registered trademark) 1173, MBF (BASF Japan Co., Ltd.), etc. Be done.
These photoradical generators may be used alone or in combination.
Specific examples of the combination include Irgacure® 500 (1-hydroxy-cyclohexyl-phenyl-ketone / benzophenone: 50/50%) and Irgacure® 1700 (bis (2,6-dimethoxybenzoyl) -2). , 4,4-trimethylpentylphosphine oxide / 2-hydroxy-2-methylphenylpropan-1-one: 25/75%) and Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone: 25/75%) (BASF Japan Co., Ltd.) and the like.

Examples of the photoacid generator include sulfonic acid derivatives, onium salts, carboxylic acid esters and the like.

Examples of the sulfonic acid derivative include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidesulfonates such as trifluoromethylsulfonate derivatives, benzoinsulfonates, and 1-oxy-2-hydroxy-3. -Propyl alcohol sulfonates, pyrogallol trisulfonates, benzyl sulfonates can be mentioned. Specifically, diphenyldisulfone, ditosyldisulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xysilylsulfonyl) diazomethane, phenylsulfonylbenzoyldiazomethane, bis (cyclohexylsulfonyl) methane, benzointosylate. 1,2-Diphenyl-2-hydroxypropyl tosylate, 1,2-di (4-methylmercaptophenyl) -2-hydroxypropyl tosylate, pyrogallol methyl sulfonate, pyrogallol ethyl sulfonate, 2,6-dinitrophenyl methyl tosi Examples thereof include lat, ortho-nitrophenylmethyl tosylate, and para-nitrophenyl tosylate.

Examples of the onium salt include tetrafluoroborate (BF ^4- ), hexafluorophosphate (PF ^6- ), hexafluoroantimonate (SbF ^6- ), hexafluoroarsenate (AsF ^6- ), and hexachloroantimonate (SbC ^{l6). -} ), Tetraphenyl borate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO ^4- ), trifluoromethanesulphonate ion (CF ₃ SO ^3- ), fluorosulphon A sulfonium salt or an iodonium salt having an anion such as an acid ion (FSO ^3- ), a toluene sulphonate ion, a trinitrobenzene sulphonate anion, or a trinitrotoluene sulphonate anion can be used.

Examples of the sulfonium salt include triphenylsulfonium hexafluoroacylnate, triphenylsulfonium hexafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluobenzyl) borate, methyldiphenylsulfonium tetrafluoroborate, and methyldiphenylsulfonium. Tetrax (pentafluorobenzyl) borate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritoylsulfonium hexafluorophosphate, anisyldiphenylsulfonium hexa Hexafluolantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-butoxyphenyldiphenylsulfoniumtetrakis (pentafluorobenzyl) borate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, tris (4-phenoxyphenyl) sulfonium hexafluoro Phosphate, di (4-ethoxyphenyl) methylsulfonium hexafluoroarsenate, 4-acetylphenyldiphenylsulfonium tetrafluoroborate, 4-acetylphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, tris (4-thiomethoxyphenyl) sulfonium hexate Fluorophosphate, di (methoxysulfonylphenyl) methylsulfonium hexafluoroantimonate, di (methoxynaphthyl) methylsulfonium tetrafluoroborate, di (methoxynaphthyl) methylsulfonium tetrax (pentafluorobenzyl) borate, di (carbomethoxyphenyl) methylsulfonium Hexafluorophosphate, (4-octyloxyphenyl) diphenylsulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, tris (dodecylphenyl) sulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, 4 − Acetamide phenyldiphenylsulfonium tetrafluoroborate, 4-acetamidophenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, dimethylna Futylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, trifluoromethyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, phenylmethylbenzylsulfonium hexafluorophosphate, 10-methylphenoxatiinium hexafluorophosphate, 5- Methylthiantrenium hexafluorophosphate, 10-phenyl-9,9-dimethylthioxanthenium hexafluorophosphate, 10-phenyl-9-oxothioxanthenium xantenium tetrafluoroborate, 10-phenyl-9-oxothio Xanthenium tetrakis (pentafluorobenzyl) borate, 5-methyl-10-oxothiatrenium tetrafluoroborate, 5-methyl-10-oxothiatrenium tetrakis (pentafluorobenzyl) borate, and 5-methyl-10,10- Examples thereof include dioxothiatrenium hexafluorophosphate.

Examples of the iodonium salt include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate, and [4- (2-). Hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2-hydroxy-n-tetrade) Syroxy) Phenyl] Phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-t- Butylphenyl) iodonium trifluorosulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexa Fluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate, di (dodecylphenyl) iodonium hexafluoroantimonate, di (dodecylphenyl) iodonium trifurate, diphenyliodonium bisulfate, 4,4'-dichlorodiphenyliodonium bisul Fate, 4,4'-dibromodiphenyliodonium bisulfate, 3,3'-dinitrodiphenyliodonium bisulfate, 4,4'-dimethyldiphenyliodonium bisulfate, 4,4'-bissuccinimide diphenyliodonium bisulfate, 3-nitro Diphenyliodonium bisulfate, 4,4'-dimethoxydiphenyliodonium bisulfate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, (4-octyloxyphenyl) phenyliodonium tetrakis (3,5-bis-trifluoromethyl) Phenyl) Borate and the like can be mentioned.

As the other onium salt, an aromatic diazonium salt can be used, and for example, p-methoxybenzenediazonium hexafluoroantimonate or the like can be used.

Commercially available onium salts include Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI-L110. , SI-L147 (above, manufactured by Sanshin Kagaku Kogyo Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above, manufactured by Union Carbide), Adecaoptomer SP-150, SP- 151, SP-170, SP-171, SP-172 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 and Irgacure250 (manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-2369. , CI-2064 (above, manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, manufactured by Sartmer), DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI-105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI- 105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (and above) , Midori Kagaku Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (all manufactured by Nippon Kayaku Co., Ltd.), IBPF, IBCF (manufactured by Sanwa Chemical Co., Ltd.) CD1012 ( Sartmer), IBPF, IBCF (above, Sanwa Chemical Co., Ltd.), BBI-101, BBI-102, BBI-103, BBI-109 (above, Midori Chemical Co., Ltd.), UVE1014 (general electronics) RHODORSIL-PI2074 (manufactured by Rhodia), WPI-113, WPI-116 (manufactured by Wako Junyaku Co., Ltd.) and the like.

In addition, J. Polymer Science: Part A: Polymer Chemistry, Vol. 31, 1473-1482 (1993), J. Mol. Polymer Science: Part A: Polymer Chemistry, Vol. Diaryliodonium salts that can be prepared by the methods described in 31, 1483-1491 (1993) can also be used. These can be used alone or in combination of two or more.

Examples of the carboxylic acid ester include 1,8-naphthalenedicarboxylic acid imidemethylsulfonate, 1,8-naphthalenedicarboxylic acid imidetosyl sulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate, and 1,8-naphthalenedicarboxylic acid imide camphor. Sulfonate, imidephenyl succinate, imide tosyl succinate, imide trifluoromethyl succinate, imide camphor succinate, imide trifluoro phthalate, cis-5-norbornene-end-2,3-dicarboxylic acid imide Examples thereof include trifluoromethylsulfonate.

Examples of the photobase generator include acyclic acyloxyimino compounds, acyclic carbamoyloxime compounds, carbamoyl hydroxylamine compounds, carbamate compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, and nitrobenzyl carbamate compounds. Examples thereof include a sulfonamide compound, an imidazole derivative compound, an amineimide compound, a pyridine derivative compound, an α-aminoacetophenone derivative compound, a quaternary ammonium salt derivative compound, an α-lactone ring derivative compound, an amineimide compound, and a phthalimide derivative compound. These can be used alone or in combination of two or more.

When the aqueous emulsion of the present invention contains a photopolymerization initiator, the content thereof is stable with respect to 100 parts by mass, which is the total of the mass part of the chlorinated rubber and the mass part of the compound having a polymerizable group. From the viewpoint of reactivity and odor, it is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.

<Light stabilizer>
Examples of the light stabilizer include an ultraviolet absorber and a hindered amine-based light stabilizer. The light stabilizer may be used alone or in combination of two or more.

Examples of the ultraviolet absorber include salicylic acids (for example, phenylsalicylate, pt-butylphenylsalicylate, p-octylphenylsalicylate, etc.) and benzophenones (for example, a2,4-dihydroxybenzophenone oxalate, 2-hydroxy). -4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'- Dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, etc.), benzotriazoles (eg, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5) '-Tert-Butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5' -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5 '-Ditert-amylphenyl) benzotriazole, 2-{(2'-hydroxy-3', 3 ", 4", 5 ", 6" -tetrahydrophthalimidemethyl) -5'-methylphenyl} benzotriazole, etc.) , Triazines (eg, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2,4-dihydroxyphenyl-4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine , 2,4-Bis (2-Hydroxy-4-propyloxyphenyl) -6- (2,4-Dimethylphenyl) -1,3,5-Triazine, 2- (2-Hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-Triazine, 2- [2-Hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-Triazine) and oxalic acid anilides (eg, N- (2-ethylphenyl) -N'-(2-ethoxy-5-t-butylphenyl) oxalate diamide, N- (2-ethylphenyl) -N'-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethoxy-2'-ethyl-oxalic acid bisanilide, oxalic acid diamide having an aryl group which may be substituted on the nitrogen atom, etc.), etc. Can be mentioned.

Examples of hindered amine-based light stabilizers include ester group-containing piperidines (eg, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4). -Acryloyloxy-2,2,6,6-tetramethylpiperidine, etc.), ether group-containing piperidines (eg, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, etc.), amide group-containing piperidines (eg 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidin, bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1,6-dicarbamate, etc.), and high molecular weight piperidine polycondensates (eg, dimethyl succinate). -1- (2-Hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6 6-Pentamethyl-4-piperidinol and tridecyl alcohol condensate, etc.) and the like.

When the aqueous emulsion of the present invention contains a light stabilizer, the content thereof is preferably 15 parts by mass or less with respect to 100 parts by mass, which is the total of the mass parts of the chlorinated rubber and the mass part of the compound having a polymerizable group. It is more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less.

<UV curable oligomer>
Examples of the ultraviolet curable oligomer include urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate oligomer and the like. The UV curable oligomers may be used alone or in combination.

As the urethane acrylate oligomer, a commercially available one can be used. Commercially available urethane acrylate oligomers include CN929, CN965, CN968, CN981A75, CN985B88, CN991, CN970AH75, CN975, CN992, CN994 and CN9165 (manufactured by Sartmer), U-4HA and U-6HA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). , AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

Commercially available epoxy acrylate oligomers can be used. Examples of commercially available epoxy acrylate oligomers include CN116, CN120B60, CN120M50, CN131B, CN132, CN137, CN152, and CN2102E (manufactured by Sartmer).

Commercially available polyester acrylate oligomers can be used. Examples of commercially available polyester acrylate oligomers include CN292, CN2259, CN2262, CN2270, CN2271E, CN2272, CN2273, CN2276, CN2279, CN2285, CN2298, CN2300, CN2301, CN2302, CN2303, and CN2304 (manufactured by Sartmer). These polyester acrylate oligomers may be used alone or in combination.

When the aqueous emulsion of the present invention contains an ultraviolet curable oligomer, the content thereof is preferably 20 parts by mass with respect to 100 parts by mass, which is the total of the parts by mass of the chlorinated rubber and the parts by mass of the compound having a polymerizable group. It is 5 parts by mass or less, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.

<Optical brightener>
Optical brighteners include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-alkylimide, bisbenzoxazolylethylene, 1,4-bis. Examples thereof include (2-benzoxazolyl) naphthalene and dialkylstilbene. Commercially available fluorescent whitening agents include Kayahor 3BS Liq. , Kayahor TAC Liq. , Kayaphor HBC Liq. , Kayalight B, Kayaphor AS 150, Kayaphor CR 200, Kayaphor JB Liq., Mikawite ATN conc. (Manufactured by Nippon Kayaku Co., Ltd.), TINOPAL OB, TINOPAL NFW Liquid (manufactured by BASF), Hakkol P, Hakkol PHD, Hakkol RF, Hakkol PSR, Hakkol PSR-B, Hakkol CHP-B, Hakkol CHP-B, Hakkol D, Hakkol BE conc, Hakkol SG conc 150, Hakkol TH-100, Hakkol S-100, Hakkol RX-1, Hakkol OW-11, Hakkol OW-10extra, Hakkol KIP H / C, Hakkol KIP H / C Examples thereof include Hakkol PMS H / C (manufactured by Showa Kagaku Kogyo Co., Ltd.), Nikkafluor SB conc, Nikkafluor KB, Nikkafluor OB, Nikkabright CX H / C (manufactured by Nippon Kayaku Kogyo Co., Ltd.) and the like. The fluorescent whitening agents may be used alone or in combination.

When the aqueous emulsion of the present invention contains a fluorescent whitening agent, the content thereof is preferably 5 with respect to 100 parts by mass, which is the total of the parts by mass of the chlorinated rubber and the parts by mass of the compound having a polymerizable group. It is not less than parts by mass, more preferably 3 parts by mass or less, and further preferably 1 part by mass or less.

<Leveling agent>
As the leveling agent, Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), BYK300, BYK306, BYK310, BYK320, BYK330, BYK346, BYK349, BYK-333, BYK-345, BYK-347, BYK-348, BYK-378 (manufactured by Big Chemie Japan), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (manufactured by Shinetsu Chemical Industry Co., Ltd.), Surflon SC-101, Surfron KH-40 (manufactured by AGC Seimi Chemical Co., Ltd.), Futergent 222F, Futergent 251 and FTX-218 (manufactured by Neos), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (manufactured by Mitsubishi Materials), Megafuck F- 171 、 Megafuck F-177, Megafuck F-475, Megafuck F-556, Megafuck R-30 (manufactured by DIC), Adecacol W-193, Adecacol W-287, Adecacol W-288, Adecacol W-304 (Made by ADEKA), SN Wet 366, Nopco 38-C, SN Disper Sand 5468, SN Disper Sand 5034, SN Disper Sand 5027, SN Disper Sand 5040, SN Disper Sand 5020 (San Nopco) Fluoroalkyl benzenesulfonate, full Oralkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylamino Sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, poly Oxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyo Examples thereof include xyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, alkyldiphenyl ether disulfonate and the like.

When the aqueous emulsion of the present invention contains a leveling agent, the content thereof is preferably 20 parts by mass or less with respect to 100 parts by mass in total of the mass parts of the chlorinated rubber and the mass part of the compound having a polymerizable group. It is more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less.

<Base compound>
Examples of the basic compound include ammonia, organic amine compounds and metal hydroxides. Ammonia or an organic amine compound is preferred.

Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-. Examples thereof include diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. Preferably, it is N, N-dimethylethanolamine.
Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide and the like.
Basic compounds are readily available on the market.

When the aqueous emulsion of the present invention contains a basic compound, the content thereof is preferably 20 parts by mass with respect to 100 parts by mass, which is the total of the parts by mass of the chlorinated rubber and the parts by mass of the compound having a polymerizable group. It is 10 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less.

<Organic solvent>
Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol and n-propanol. , Isopropyl alcohol and alcohols such as n-butanol; glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol; Cellsolve-based solvents; glycol-based solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and 3-methoxy-3-methyl-1-butanol; and ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate). ), Glycol ester solvents such as diethylene glycol monobutyl ether acetate and diethylene glycol monoethyl ether acetate and the like. These may be used alone or in combination.

When the aqueous emulsion of the present invention contains an organic solvent, the content thereof is 100 parts by mass, which is the total of the mass parts of the chlorinated rubber and the mass part of the compound having a polymerizable group, from the viewpoint of odor. It is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, further preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less.

<Crosslinking agent>
By including the cross-linking agent, the adhesiveness, the water resistance of the adhesive layer and the solvent resistance of the adhesive layer tend to be further improved.
Examples of the cross-linking agent include epoxy compounds, polyisosianate compounds, oxazoline compounds, aziridine compounds, carbodiimide compounds, active methylol compounds, active alkoxymethyl compounds, metal chelate, hydrazide compounds, hydrazine compounds and the like.
Preferred are aliphatic polyisosianate compounds, carbodiimide compounds, oxazoline group-containing compounds, hydrazide compounds, and hydrazine compounds. Of these, aqueous (water-soluble or water-dispersible) ones are more preferable. These cross-linking agents may be used alone or in combination.

Examples of the polyisocyanate compound include hexamethylene diisocyanate (HDI), 4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), and oligomers or polymers thereof.
Specifically, Sumijuru (registered trademark) N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, 44V10, 44V20 made by Sumika Bayer Urethane. And E 21-1, Death Modules (registered trademarks) manufactured by Sumitomo Bayer Urethane Co., Ltd. N3100, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547 and DA- L, E14 and E22, Bayer Urethane (registered trademark) 304 and XP2655, BASF (BASONAT (registered trademark)) PLR8878 and HW-100, Takeda Pharmaceutical Company Limited (registered trademark) ) WD720, WD725 and WD730, Duranate (registered trademark) WB40-100, WB40-80D and WX-1741 manufactured by Asahi Kasei Kogyo Co., Ltd. can be mentioned.

Specific examples of the carbodiimide-based cross-linking agent include Nisshinbo Chemical Co., Ltd .: Carbodilite (SV-02, V-02, V-02-L, V-04, E-01, E-02) and the like. Can be mentioned.

Specific examples of hydrazide compound cross-linking agents include Otsuka Chemical Co., Ltd .: ADH (adipic acid dihydrazide), SDH (sebacate dihydrazide), DDH (dodecandiohydrazide), IDH (isophthalic acid dihydrazide), SAH. (Hydrazide salicylate) and the like.

Specific examples of the hydrazine compound cross-linking agent include Otsuka Chemical Co., Ltd .: hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine monobromide, hydrazine carbonate and the like.

When the aqueous emulsion of the present invention contains a cross-linking agent, the content thereof is preferably 30 parts by mass with respect to 100 parts by mass, which is the total of the mass parts of the chlorinated rubber and the mass part of the compound having a polymerizable group. It is less than or equal to, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.

<Photosensitizer>
The photosensitizer can be appropriately selected according to the wavelength to be enhanced. The effective excitation wavelength range is usually 450 nm or less, preferably 250 to 380 nm. Examples of the photosensitizer include triethanolamine, triisopropanolamine, 4,4-diethylaminobenzophenone, 2-dimethylaminoethyl benzoate, ethyl 4-dimethylaminoethyl benzoate and isoacyl 4-dimethylaminobenzoate. ..

When the aqueous emulsion of the present invention contains a photosensitizer, the content thereof is preferably 15 with respect to 100 parts by mass, which is the total of the parts by mass of the chlorinated rubber and the parts by mass of the compound having a polymerizable group. It is not less than parts by mass, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less.
<Other resins>
The aqueous emulsion of the present invention may contain other resins as long as the intended properties are not impaired.
Other resins include ethylene-vinyl ester resin, styrene-maleic acid resin, resin having a structural unit derived from α-olefin having 2 to 20 carbon atoms, chlorinated and modified products thereof, (meth) acrylic resin, and polystyrene. , Polyvinyl acetate, polyurethane, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic acid ester copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, chloride Vinylidene- (meth) acrylic acid ester copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, resin having a structural unit derived from chlorinated α-olefin having 2 to 20 carbon atoms, ethylene-vinyl ester resin, polyurea, acrylonitrile Butadiene styrene resin, chloroprene resin, acid-modified chloroprene resin, butyl rubber, chlorinated butyl rubber, brominated butyl rubber, modified rubber, styrene- (meth) acrylic acid resin, synthetic rubber, natural rubber, styrene-butadiene resin, butadiene resin, poly Examples thereof include (meth) acrylonitrile resin, (meth) acrylamide resin, polyester resin, modified nylon resin, epoxy resin, styrene-based block copolymer, and oligomers thereof. Of the above, the rubber containing a chlorine atom is preferably a rubber having a chlorine atom content of less than 45% by mass. These may be in the form of solids (eg, resin powders) or in the form of emulsions.

The ethylene-vinyl ester resin is a copolymer containing a polymer composed of an ethylene unit and a vinyl ester unit. Examples of the vinyl ester unit include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl ester of a tertiary carboxylic acid having 8 to 10 carbon atoms, and so-called vinyl versatic acid (for example, manufactured by Shell Chemical Co., Ltd., trade name: Veova (registered trademark)). ) 10) and the like, such as an alkyl acid vinyl ester and the like. Among the vinyl ester units, vinyl acetate is preferable. When vinyl acetate is used as the vinyl ester unit, the copolymer becomes an ethylene-vinyl acetate copolymer (hereinafter, may be abbreviated as "EVA").

For example, the ethylene-vinyl acetate copolymer has various properties depending on the vinyl acetate content and the like, but includes various vinyl acetate content and shapes (film, block, fiber, foam). The ethylene-vinyl acetate copolymer may contain a polymer such as polyolefin. Preferred polyolefins include ethylene-octene copolymers, ethylene-butene copolymers, polypropylene and polyethylene.

The ethylene-vinyl ester resin may contain a monomer unit copolymerizable with the ethylene unit and the vinyl ester unit in addition to the ethylene unit and the vinyl ester unit. Examples of the monomer unit include vinyl halides such as vinyl chloride, monomers having a functional group such as a small amount of amide group, and (meth) acrylic acid ester.
Examples of the ethylene-vinyl ester resin copolymer include VINNOL E15 / 45, E15 / 45M, E15 / 48A, H15 / 42, H15 / 50, H11 / 59, H14 / 36, H40 / 50, H40 / 55, and H40 /. 60, H30 / 48M (Wacker Chemie AG) and the like can be mentioned.
The ethylene-vinyl ester resin and its copolymer may be in the form of an emulsion. Such an emulsion may be produced by emulsion polymerization of the monomers constituting the ethylene unit and the vinyl ester unit, or a commercially available emulsion may be used. Examples of the ethylene-vinyl ester resin copolymer emulsion include Sumikaflex® 201HQ, 303HQ, 355HQ, 400HQ, 401HQ, 408HQ, 410HQ, 450HQ, 455HQ, 456HQ, 460HQ, 465HQ, 467HQ, 7400HQ, 470HQ. 478HQ, 510HQ, 520HQ, 710, 752, 755, SDX-5100, 801HQ, 808HQ, 830, 850HQ, 900HL and 3950 (above, manufactured by Sumitomo Chemical Co., Ltd.), Vanflex OM-4000 and OM-4200 (above) , Co., Ltd.), Polymer (registered trademark) EVA AD-2, AD-3, AD-4, AD-5, AD-51, AD-56, AD-59 and P-900 (above, Showa High School) Polymer Co., Ltd.), Denka EVA Tex (registered trademark) # 20, # 30, # 40M, # 60, # 81 and # 82 (all manufactured by Denki Kagaku Kogyo Co., Ltd.) and the like.

Examples of the styrene-maleic acid resin include Araster 700 and 703S (manufactured by Arakawa Chemical Industries, Inc., SMA (registered trademark) 1000, SMA (registered trademark) 2000, SMA (registered trademark) 3000 (Cray Valley's). VE-1122 (Seikou PMC Co., Ltd.) and the like can be mentioned as examples of the styrene-maleic acid resin emulsion.

Examples of α-olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. , 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptene, 1-octadecene, 1-nonadecene, 1-eicosene, vinylcyclohexane and the like. Ethylene and propylene are preferred.

Resins having a structural unit derived from α-olefin having 2 to 20 carbon atoms include polyethylene (PE), high density polyethylene (HDPE), medium density polypropylene (MDPE), low density polyethylene (LDPE), and linear low density. Homopolymers such as polyethylene, ultra-high molecular weight polyethylene and polypropylene (PP), isotactic (isotactic) polypropylene, syndiotactic polypropylene and atactic polypropylene, ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene Α-Olefin copolymers such as -1-butene copolymer, ethylene-1-octene copolymer and ethylene-1-hexene copolymer, α-olefin having 2 to 20 carbon atoms and the α- Examples thereof include a copolymer of an olefin and a copolymerizable monomer. Further, the copolymer of the α-olefin having 2 to 20 carbon atoms and the monomer copolymerizable with the α-olefin may contain one kind of each monomer, or may contain two or more kinds of each monomer. It may be a thing.

The resin having a structural unit derived from α-olefin having 2 to 20 carbon atoms may be any of a homopolymer, a random copolymer, a block copolymer, and a graft copolymer. Further, it may be one having a low molecular weight or a high molecular weight with a peroxide or the like.

As a modified product of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a resin having a structural unit derived from an α-olefin having a prime number of 2 to 20 is modified with α, β-unsaturated carboxylic acids and the like. Examples include modified products.

The modification rate of the modified product modified by α, β-unsaturated carboxylic acids and the like is usually 0.1 to 10% by mass, preferably 0.2 to 10% by mass, based on 100% by mass of the copolymer before modification. It is 5% by mass, more preferably 0.2 to 4% by mass.

Examples of α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids (maleic acid, itaconic acid, citraconic acid, etc.) and α, β-unsaturated carboxylic acid esters (methyl maleate, methyl itaconate, etc.). , Methyl citraconic acid, etc.), α, β-unsaturated carboxylic acid anhydride (maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, etc.). Further, a modified product obtained by combining these α, β-unsaturated carboxylic acids may be used. These may be carboxylic acid anhydrides, hydrolyzed carboxylic acids, or a mixture thereof.

Such a modified product is a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms or a copolymer of an α-olefin having 2 to 20 carbon atoms and a monomer copolymerizable with the α-olefin. , A method of adding α, β-unsaturated carboxylic acids and the like after melting, a method of adding α, β-unsaturated carboxylic acids and the like after dissolving in a solvent such as toluene and xylene, and the like. Manufactured by a known method.

As the modification rate of the resin having a structural unit derived from a chlorinated α-olefin having 2 to 20 carbon atoms, the chlorine atom content is preferably 5 to 80 with respect to 100% by mass of the copolymer before modification. It is by mass, more preferably 40 to 75% by mass. More preferably, it is 55 to 70% by mass.

Chlorination of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is carried out by dissolving or dispersing a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms in a solvent to obtain a mixture. It can be obtained by chlorinating a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms by a method of blowing chlorine gas or the like.

Examples of the monomer copolymerizable with the α-olefin having 2 to 20 carbon atoms include α, β-unsaturated carboxylic acid and its anhydride, a metal salt of α, β-unsaturated carboxylic acid, and α, β-unsaturated carboxylic acid. Examples thereof include acid esters, vinyl esters, vinyl ester saponified products, cyclic olefins, vinyl aromatic compounds, polyene compounds (dienes and the like), (meth) acrylonitrile, vinyl halides, amides and billinidene halides. These may be used alone or in combination for copolymerization.

Examples of α, β-unsaturated carboxylic acid and its anhydride include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, monomethyl maleate, monoethyl maleate, and maleic acid. Examples thereof include an acid half ester, a maleic acid half amide, an itaconic acid half ester, and an itaconic acid half amide. Of these, acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
Examples of the metal salt of α, β-unsaturated carboxylic acid include salts of monovalent metals such as lithium, sodium and potassium, and salts of polyvalent metals such as magnesium, calcium and zinc. Specific examples thereof include sodium salt and magnesium salt of (meth) acrylic acid.
Examples of α, β-unsaturated carboxylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl acrylate, and maleic acid. Examples thereof include esterified products of dimethyl and methacrylic acid and alcohol. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferable.

Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatic acid and the like. Of these, vinyl acetate is preferable.
Examples of the vinyl ester saponified product include vinyl alcohol obtained by saponifying vinyl ester with a basic compound or the like.

As the cyclic olefin, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2 -Dihydrodicyclopentadiene, 5-chloronorbornene, cyclopentene, cyclohexene, cycloheptene, vinylcyclohexane and the like can be mentioned.

Vinyl aromatic compounds include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene and vinylnaphthalene. And so on.

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

Aliphatic conjugated polyene compounds include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-methyl-. Examples thereof include 1,3-decadene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-octadene and 2,3-dimethyl-1,3-decadien.

Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclohexadiene, 2-chloro-1, Examples thereof include 3-butadiene, 2-chloro-1,3-pentadiene and 2-chloro-1,3-cyclohexadiene.

Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,9-decadien, 3,3-dimethyl-1,4-hexadiene, and 5-ethyl-1. , 4-Heptadien, 4-Methyl-1,4-Octadiene, 5-Methyl-1,4-Octadiene, 4-Ethyl-1,4-Octadiene, 4-Methyl-1,4-Nonadiene, 5-Methyl-1 , 4-Decadien, 6-methyl-1,6-undecadien and 4-ethylidene-12-methyl-1,11-pentadecadien and the like.

Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 1,4-divinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, and methyltetrahydroindene.

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

Examples of the copolymer having a structural unit derived from α-olefin having 2 to 20 carbon atoms include an ethylene-acrylic acid copolymer, an ethylene unsaturated carboxylic acid copolymer such as an ethylene-methacrylic acid copolymer, and the above-mentioned ethylene. -Ionomer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene / methyl methacrylate, in which some or all of the carboxyl groups of the unsaturated carboxylic acid copolymer are neutralized with the above metal. Polymers, ethylene-isobutyl acrylate copolymers, ethylene-unsaturated carboxylic acid ester copolymers such as ethylene-n-butyl acrylate copolymers, isobutyl ethyl acrylate-methacrylic acid copolymers, ethylene-acrylic Ethylene-unsaturated carboxylic acid ester / unsaturated carboxylic acid copolymer such as n-butyl acid-methacrylic acid copolymer and ionomer in which some or all of its carboxyl groups are neutralized with the above metal, ethylene-vinyl acetate copolymer Examples thereof include an ethylene-vinyl ester copolymer such as a coalescence.

Examples of the resin having a structural unit derived from α-olefin having 2 to 20 carbon atoms and its modified product include Melsen (registered trademark) HH-6410M, H-6051, H-6960, H-6820 and H-6822X. (Tosoh Co., Ltd.), Eval (registered trademark) L171B, F171B, H171B, E105B and G156B (Clare Co., Ltd.), Soanol (registered trademark) D2908, DT2904, DC3212, DC3203, E3808, ET3803, A4412, AT4403, BX , 16DX, D2908H4 and A4412H4 (Nippon Synthetic Chem Industry Co., Ltd.), Soaredin (registered trademark) PG505 (Nippon Synthetic Chem Industry Co., Ltd.), NISSO (registered trademark) PB (Nippon Sotatsu Co., Ltd.), Polytail (registered trademark) ) H (Mitsubishi Chemical Co., Ltd.), Epaul (registered trademark) (Idemitsu Kosan Co., Ltd.), OREVAC (registered trademark) G1821, OE808 and OE825 (Alchema Co., Ltd.), LOTADAR MAH2210, 3200, P3 3200, 3210 , 4210, 6200, 3410, 3430 and 4720 (Alchema Co., Ltd.), BONDINE (registered trademark) LX4110, HX8210, TX8030, HX8290, HX8410 and AX8390 (Alchema Co., Ltd.), OREVAC (registered trademark) T9314, T9318 and G18211. (Alchema Co., Ltd.), Umex (registered trademark) 2000 (Sanyo Kasei Kogyo Co., Ltd.), Aurolen (registered trademark) 100S and 200T (Nippon Synthetic Chemical Industry Co., Ltd.) and the like.
The resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a modified product thereof may be in the form of an emulsion. Such an emulsion may be produced by emulsifying a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a modified product thereof, or a commercially available one may be used. Examples of emulsions of resins having structural units derived from α-olefins having 2 to 20 carbon atoms and modified products thereof include Arrowbase (registered trademark) SA-1200, SB-1200, SE-1200, and SB-1010 (Unitica). (Co., Ltd.), Aptolock (registered trademark) BW-5550 (Mitsubishi Chemical Co., Ltd.), Aurolen (registered trademark) AE-202, AE-301 (Nippon Paper Industries, Ltd.), Aquatex (registered trademark) EC -1200, EC-1700, AC-3100, MC-4400, HA-1100, 909 (Chuo Rika Kogyo Co., Ltd.) and the like can be mentioned.

Resins having structural units derived from chlorinated α-olefins having 2 to 20 carbon atoms include Eraslen (registered trademark) 401A and 303B (Showa Denko Co., Ltd.), Hardlen (registered trademark) CY-9122P, and CY-. 9124P, HM-21P, M-28P, F-2P, F-6P, F-69, 13-LP, 13-LLP, 14-LWP, 14-WL-P, 15-LP, 15-LLP, 16- LP, DX-526P, DX-530P and BS-40 (Toyobo Co., Ltd.), and Supercron (registered trademark) 803L, 803MW, 814HS, 390S, HE-305, HE-505, HE-510, HE- 515, HE-910, HE-915, HE-1070, HE-1200, HP-205, HP-215, HP-620 (Nippon Paper Chemicals Co., Ltd.) and the like can be mentioned.
The resin having a structural unit derived from a chlorinated α-olefin having 2 to 20 carbon atoms may be in the form of an emulsion. Such an emulsion may be produced by emulsifying a resin having a structural unit derived from a chlorinated α-olefin having 2 to 20 carbon atoms, or a commercially available one may be used. Emulsions of resins having structural units derived from chlorinated α-olefins having 2 to 20 carbon atoms include, for example, Haadren® EW-5303, EH-801, EW-5504, EZ-1000 and EZ-. 2000 (Toyobo Co., Ltd.), Supercron (registered trademark) E-604, E-480T, E-415 (Nippon Paper Chemicals Co., Ltd.) and the like can be mentioned.

Polyurethane is a polymer composed of urethane bonds and is usually obtained by the reaction of alcohol (-OH) and isocyanate (-NCO). The polyurethane foam includes polyurethane foamed by a volatile solvent such as carbon dioxide or chlorofluorocarbon generated by the reaction of isocyanate with water.
Commercially available polyurethane can be used. For example, Nippon Polyurethane Industry Co., Ltd. 3110, 3116, 3016, 3113, 3124, 3126, 3230 (Nippon Polyurethane Industry Co., Ltd.) and the like can be mentioned. Commercially available water-soluble urethanes include, for example, Dispacol® U-42, U-53, U-54, U-56, KA-8488, KA-8584, KA-8755, KA-8756 and KA-. 8766 (Sumitomo Bayer Urethane Co., Ltd.), Hydran (registered trademark) HW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP-60LM and AP-80 (DIC Co., Ltd.), Yupren (registered trademark) UXA-306, UXA-307, Permarin UA-150, Permarin UA-200, Permarin UA-300, Permarin UA-310 and Eucoat UWS-145 (Sanyo Kasei Kogyo Co., Ltd.) )), Superflex® 107M, 110, 126, 130, 150, 160, 210, 300, 361, 370, 410, 420, 460, 500M, 700, 750, 820 and 860 (Daiichi Kogyo Seiyaku Co., Ltd. HUX-401, HUX-420A, HUX-380, HUX-561, HUX-210, HUX-822, HUX-895 and HUX-830 (ADEKA Corporation), etc. Can be mentioned.

Polyvinyl chloride can be obtained by suspension polymerization or bulk polymerization of vinyl chloride.
Examples of the polyvinyl chloride include hard polyvinyl chloride, semi-hard polyvinyl chloride, and soft polyvinyl chloride. A soft polyvinyl chloride is preferable.
Examples of polyvinyl chloride include Kanevinyl S-400, PSH-180, PSL-180 Kaneka Corporation) and the like. Examples of the polyvinyl chloride emulsion include Vinibran 701, 700, 711 (Nissin Chemical Industry Co., Ltd.) and the like.

Chlorinated polyvinyl chloride is a polyvinyl chloride resin chlorinated by a chlorination method such as a gas phase or a liquid phase. Examples of the polyvinyl chloride-based resin include a vinyl chloride homopolymer and a vinyl chloride copolymer. Examples of the monomer constituting the copolymer of vinyl chloride together with vinyl chloride include ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylic acid ester, maleic acid ester and the like. Examples of the chlorinated polyvinyl chloride include Sekisui PVC-HA (Sekisui Chemical Co., Ltd.).

Examples of polyvinylidene chloride include Saran X05253-16 (manufactured by Dow Chemical Co., Ltd.), a resin for Saran Wrap (registered trademark) (manufactured by Asahi Kasei Corporation), and the like. Examples of the polyvinylidene chloride emulsion include Diofan 193D, A736, A036, A050, A063, B204, A115 (manufactured by Solvay) and the like.

Examples of the vinyl chloride-vinylidene chloride copolymer resin include IXAN SGA-1 (manufactured by Solvay) and the like.

Examples of the vinylidene chloride- (meth) acrylic acid ester copolymer resin include IXAN PVS-109, 801 and 815, Diofan A586, A602 and A610 (manufactured by Solvay).

The chloroprene-based resin is obtained by polymerizing chloroprene synthesized by dehydrochloric acid of dichlorobutene obtained by chlorination of butadiene, or copolymerizing it with another monomer. Examples of such other monomers include isoprene, butadiene, dichlorobutadiene, styrene, acrylonitrile, acrylic acid esters, methacrylic acid esters, acrylic acid, methacrylic acid, itaconic acid and the like.

The acid-modified chloroprene resin can be obtained by graft-copolymerizing the above chloroprene-based resin with at least one selected from α, β-unsaturated carboxylic acid and its anhydride. Examples of the α, β-unsaturated carboxylic acid and its acid anhydride include those exemplified as a modified product of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms.

Examples of the chloroprene-based resin and the acid-modified chloroprene resin include Skyprene (registered trademark) G-42, G-40S, G-55, G-40, S-1, G-40T, B-30S, and Y-31. (Tosoh Co., Ltd.), Showprene (registered trademark) W, AF, WHV, WXJ, WB (Showa Denko KK), and Denka Chloroprene (registered trademark) A-30, A-70, A-90, A- 91, M-130L, DCR-11 (Electrochemical Industry Co., Ltd.) and the like can be mentioned. Emulsions of chloroprene-based resins and acid-modified chloroprene resins include Skyperene® GFL-820, GFL-890, GFL-280, LA-502, LA-660, SL-360, SL-390 and SL-590. (Tosoh Co., Ltd.), Shoprene (registered trademarks) 115, 571, 572, 650, 671A, 750, SD78 and SD77S (Showa Denko KK), and Denca chloroprene (registered trademarks) LA-50 and LC-501 ( Electrochemical Industry Co., Ltd.)) and the like.

Examples of the chlorinated butyl rubber include EnjayButyl HT10-66 (manufactured by Enjay Chemical Co., Ltd.), JSR CHLOROBUTYL 1066 (manufactured by JSR Corporation), and HT1066 (manufactured by ExxonMobil).

Examples of the brominated butyl rubber include JSR BROMOBUTYL 2255 and 2244 (manufactured by JSR Corporation) and Exxon bromobutyl 2255 (exxon mobile chemical company).

Examples of the modified rubber include a chlorinated or brominated modified copolymer of a copolymer of isomonoolefin and paramethylstyrene, and examples of a commercially available product include Expro50 (manufactured by Exxon).

Examples of the styrene-based block copolymer include a block copolymer composed of a diene block and a styrene block. Specifically, both styrene-butadiene block copolymer (SB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-butadiene-butylene-styrene. Examples thereof include a polymer (SBBS) or a hydrogenated product of these block copolymers, a styrene / isobutylene-styrene triblock copolymer (SIBS), and a styrene-isobutyrene block copolymer (SIB). Such a hydrogenated additive is a block copolymer in which all of the styrene block and the diene block are hydrogenated, or a block copolymer in which only the diene block is hydrogenated, or a part of the styrene block and the diene block. It may be a partially hydrogenated product such as a hydrogenated block copolymer.

Other resins may contain water-soluble resins such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose and hydroxyethyl cellulose in order to further enhance the stability of the aqueous emulsion.

Further, the other resin may include a pressure-sensitive resin or a resin having a function as a pressure-sensitive adhesive. Examples of such resins include rosins, terpene resins, petroleum-based resins obtained by polymerizing petroleum fractions having 5 carbon atoms and their hydrogenated resins, petroleum-based resins obtained by polymerizing petroleum distillates having 9 carbon atoms, and hydrogenating thereof. Examples thereof include resins, other petroleum-based resins, kumaron resins, and inden resins. Specifically, rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumalized rosin and their glycerin esters, pentaerythritol esters, methyl esters, triethylene glycol esters, phenolic modified products and their esters. Rosin compounds such as terpene polymers; terpene polymers such as terpene polymers, terpene phenols, β-pinene polymers, aromatic-modified terpene polymers, α-pinene polymers, terpene-based hydrogenated resins; petroleum distillates with 5 carbon atoms Examples thereof include petroleum-based resins obtained by polymerizing the above, petroleum-based resins obtained by polymerizing petroleum distillates having 9 carbon atoms, and hydrogenated resins thereof; petroleum-based resins such as maleic acid-modified products and fumaric acid-modified products, and chlorinated paraffins.

Terpene resins include YS resin PX, PXN, YS polystar, Mighty Ace, YS resin TO, TR and Clearon P, M, K (Yasuhara Chemical Co., Ltd.), Tamanol 803L, 901 (Arakawa Chemical Industry Co., Ltd.) and , Teltac 80 (Nippon Terpen Chemical Co., Ltd.) and the like. Examples of the terpene resin emulsion include Tamanol E-200NT and E100 (Arakawa Chemical Industry Co., Ltd.).

Examples of the chlorinated paraffin include Empara (registered trademark) 70, 50, AR-500 (Ajinomoto Fine-Techno Co., Ltd.), Toyoparax (registered trademark) 250, 265, 270, 150, A50 (Tosoh Co., Ltd.) and the like. Be done.

Other resins may be contained alone or in combination of two or more.
Other resins are readily available on the market.
The aqueous emulsion of the present invention may contain other resins as long as its properties are not impaired, and the content thereof is 100, which is the sum of the mass parts of the chlorinated rubber and the mass parts of the compound having a polymerizable group. It is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less with respect to parts by mass. Other resins may be mixed with the aqueous emulsion of the present invention in the form of an emulsion, or may be emulsified together with a chlorinated rubber and a compound having a polymerizable group to form an aqueous emulsion.

<Thickener>
Thickeners can be used to adjust the viscosity of aqueous emulsions. Thickeners include Adecanol® UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH-541VF, UH-550, UH-752 and H-756VF (ADEKA CORPORATION), and SN thickener 920, 922,924,926,929-S, A-801, A-806, A-812, A-813, Examples thereof include A-818, 621N, 636, 601 and 603, 612, 613, 615, 618, 621N, 630, 634, 636 and 4050 (San Nopco Ltd.).

<Form of aqueous emulsion>
The aqueous emulsion of the present invention preferably contains a chlorinated rubber and a compound having a polymerizable group as a mixture. The mixture is a state in which a chlorinated rubber and a compound having a polymerizable group are mixed, a state in which the chlorinated rubber is dispersed or swollen in a compound having a polymerizable group, and at least a part of the chlorinated rubber is a polymerizable group. Includes the state of being dissolved in a compound having.

The fact that at least a part of the chlorinated rubber is dissolved in the compound having a polymerizable group means that when the mixture of the chlorinated rubber and the compound having a polymerizable group is filtered through a filter having a pore size of about 0.50 μm, the filtrate is obtained. It suffices if at least a part of chlorinated rubber is contained therein. The chlorinated rubber contained in the filtrate is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, based on 100 parts by mass of the chlorinated rubber contained in the aqueous emulsion before filtration. Even more preferably, it is 70% by mass or more.
Filtration with a filter is preferably carried out after heating to a temperature equal to or higher than the melting point of the compound having a polymerizable group contained in the aqueous emulsion.

Examples of the method of mixing the chlorinated rubber and the compound having a polymerizable group include a method of mixing the chlorinated rubber and the compound having a polymerizable group using a mixer. The mixing temperature is usually 25 to 100 ° C. The mixing time is preferably as short as possible. Examples of the mixer include a Banbury mixer, a Henschel mixer, a homomixer and the like.

The mixture of the chlorinated rubber and the compound having a polymerizable group is preferably contained as a dispersoid. Here, the dispersoid means particles dispersed in water. In this case, the dispersoid may be a solid under atmospheric pressure of 23 ° C., but is preferably a liquid.
When the dispersoid is a liquid, it is sufficient that at least one or more of the components constituting the dispersoid have fluidity, and the dispersoid may contain a solid component or an insoluble component.
When the dispersoid is a liquid and has fluidity, the fluidity may be high or low. This is because the stability of the aqueous emulsion tends to improve when the fluidity is low, and the adhesiveness tends to improve when the fluidity is high.

The total content of the mass part of the chlorinated rubber and the mass portion of the compound having a polymerizable group is preferably 0.1 with respect to the total mass of the chlorinated rubber, the compound having a polymerizable group and water. It is ~ 70% by mass, more preferably 1 to 70% by mass, and further preferably 2% to 60% by mass. By setting it within the above range, the adhesiveness becomes good. In particular, when the content is 30% by mass or more, the stability of the aqueous emulsion becomes good. Therefore, it is more preferably 30% by mass to 60% by mass, further preferably 40% by mass to 60% by mass, and even more preferably 45% by mass to 60% by mass.

The dispersoid in the aqueous emulsion has a volume-based median diameter of preferably 10 μm or less, more preferably 0.01 to 5 μm, still more preferably 0.01 to 2 μm, and even more preferably 0.01. It is ~ 1 μm. If it is within the above range, the static stability becomes good.
The volume-based median diameter is a particle diameter corresponding to a value of the integrated particle diameter distribution of 50% on a volume basis, and means a median diameter measured on a volume basis unless otherwise specified.
The average particle size of the dispersoid can be measured by a laser diffraction particle size measuring device LA-950V2 manufactured by HORIBA, Ltd.

<Manufacturing method of aqueous emulsion>
The aqueous emulsion of the present invention can be produced by a known method. For example, it can be produced by a post-emulsification method (for example, a forced emulsification method, a self-emulsification method, a phase inversion emulsification method, etc.) in which a chlorinated rubber and a compound having a polymerizable group are dispersed in a dispersion medium such as water.

For example, a chlorinated rubber and a compound having a polymerizable group are added to the reactor (additives may be optionally added), mixed, and then water and / or a solvent is further added, and an optional surfactant is added. , A method of emulsifying by heating and stirring after adding an additive such as a photopolymerization initiator can be mentioned.

Examples of the reactor include a container provided with a heating device and a stirrer capable of applying a force such as a shearing force to the contents. A closed container or a pressure-resistant container is preferable. A general stirrer can be used. Examples of such a reactor include a pressure resistant autoclave with a stirrer. Stirring may be performed under normal pressure or reduced pressure. The rotation speed of the stirrer is usually 50 to 20000 rpm.

The mixing temperature and the heating / stirring temperature are usually 10 to 90 ° C., preferably 15 to 80 ° C., more preferably 15 to 60 ° C., and usually 25 to 100 ° C.
Mixing and / or heating and stirring may be performed using a mixer such as a Banbury mixer, a Henschel mixer, or a homomixer in addition to the above-mentioned stirrer.

For example, additives such as photopolymerization initiators, cross-linking agents, organic solvents, basic compounds, thickeners, leveling agents and the like may be added before adding water and / or solvent, or water and / or solvent. It may be added after the addition or after the emulsification. In particular, light stabilizers, UV curable oligomers, optical brighteners, photosensitizers and other resins are preferably added before adding water and / or solvent.
An aqueous emulsion having a large particle size may be obtained by pre-emulsifying in advance, and an aqueous emulsion having a small particle size may be obtained by high-pressure shearing with an apparatus such as a high-pressure homogenizer or a high-pressure homogenizer.

After emulsification, if the obtained aqueous emulsion contains an organic solvent, it is preferable to remove the organic solvent. The removal of the organic solvent is usually carried out by distilling off under reduced pressure.

When a surfactant is used in the production of the aqueous emulsion, the surfactant may be separated and removed from the obtained aqueous emulsion. The separation and removal of the surfactant can be carried out by, for example, a centrifuge, a filtration filter having pores whose average pore size is smaller than the average particle size of the aqueous emulsion, or an ultrafiltration membrane. However, the separation and removal of the surfactant may only reduce the amount of the surfactant.
Further, the obtained aqueous emulsion is preferably cooled. By cooling, an aqueous emulsion composed of fine dispersoids can be obtained. It is preferable that the cooling is not rapid cooling but gentle cooling such as leaving at room temperature. As a result, a fine and homogeneous aqueous emulsion can be obtained without agglutination of the resin or the like during the cooling process.

<Use of aqueous emulsion>
As described above, the aqueous emulsion of the present invention is useful as a composition constituting an aqueous adhesive or the like. Further, it may be used as a composition for forming as a coating film or a coating film by an aqueous emulsion on an adherend. Water-based adhesives, coating films, coating films and the like are usually used as dried products or cured products. In particular, the water-based adhesive effectively exerts its function in the form of a coating film formed by an aqueous emulsion or a cured product thereof.

The adherend (including the first base material and the second base material) to be coated, coated, and bonded is made of wood, plywood, medium density fiber board (MDF), particle board, fiber board, or the like. Materials: Cotton cloth, cotton-containing fiber, linen cloth, rayon and other cellulose materials: Polyurethane (polyurethane derived from ethylene as the main component), polypropylene (polyurethane derived from propylene as the main component), Polyethylenes such as polystyrene (polyethylene whose main component is a structural unit derived from styrene), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), (meth) acrylic resin polyester, polyether, polyvinyl chloride, polyurethane , Polyurethane foam, ethylene-vinyl acetate copolymer (EVA), foamed EVA, polyamide resin such as nylon 6, nylon 66 or other plastic materials such as foams thereof; polyurethane-based, polyamide-based and polyamino acid-based synthetic leather; Examples include ceramic materials such as glass and ceramics; and metal materials such as iron, stainless steel, copper, and aluminum. These may be composite materials composed of a plurality of components. Further, it may be a kneaded molded product of an inorganic filler such as talc, silica or activated carbon, carbon fiber or the like and a plastic material.
Among them, adhesion between cellulose-based materials and plastic materials, polyvinyl chloride, ethylene-vinyl acetate copolymers, cotton-containing fibers, nylon resins, olefin-based polymers, polyurethane, rubber, styrene-based blocks such as styrene-butadiene rubber, etc. It can be suitably used for adhering polymers and synthetic leather. Examples of the shape of these materials include various shapes such as a film, a sheet, and a block shape, but a film and a sheet shape are preferable.

The olefin-based polymer is a resin obtained by polymerizing an olefin, and examples thereof include homopolymers and copolymers having a structural unit derived from an α-olefin having 2 to 20 carbon atoms. Examples of the olefin polymer include those exemplified by the above-mentioned other resins.
In addition, examples of the resin constituting the adherend include those exemplified by the other resins.

The cotton-containing fiber may be a 100% cotton fiber, or may be a blended fiber of cotton and other natural fibers and / or chemical fibers. Other natural fibers include wool, silk, hemp and the like. Examples of chemical fibers include synthetic fibers (for example, polyamide fibers such as polyester and nylon), semi-synthetic fibers (cellulose fibers such as acetate, protein fibers such as Promix), and regenerated fibers (rayon, cupra, polynosic, etc.). Cellular fibers) and inorganic fibers (carbon fibers, glass fibers) and the like can be mentioned.
Examples of the shape of the cotton-containing fiber include woven fabric, knitted fabric, non-woven fabric, knitted fabric, felt, film, block shape and the like.

Nylon resin is a so-called polyamide resin, which is a polymer composed of amide bonds. Specific examples thereof include nylon 6, nylon 6, 6, nylon 4, 6, nylon 11, nylon 12, and the like. The nylon resin may have any shape such as a film, a block, a fiber, or a foam.

As the rubber, for example, diene rubbers such as natural rubber, thermoplastic rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, acronitrile-butadiene rubber, chloroprene rubber, and butyl rubber are mainly used. In preparing the rubber composition, these diene-based rubbers may be used alone or in combination of two or more. If necessary, a reinforcing agent such as clay, carbon black or silica, a silane coupling agent, an antiaging agent, a softening agent, zinc oxide, stearic acid, a vulcanization accelerator, a vulcanizing agent, sulfur and the like are appropriately blended. You may.

Synthetic leather includes both synthetic leather and artificial leather in a narrow sense. That is, synthetic leather obtained by applying a synthetic resin to a natural or synthetic fabric or the like may be used, or artificial leather obtained by impregnating a fabric such as microfiber (usually a non-woven fabric) with a synthetic resin may be used. Artificial leather obtained by impregnating a cloth (usually a non-woven fabric) with a synthetic resin and further applying the synthetic resin may be used. Examples of these synthetic resins include polyurethane-based resins, polyamide-based resins, and polyamino acid-based resins. A polyurethane resin is preferable.

The aqueous emulsion of the present invention is effective for adhering materials such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes (hereinafter, may be referred to as adherends). Can be used for. In particular, for adhering constituent materials (adhesive bodies) such as scabbard, insole, and outer sole in footwear such as men's shoes such as sports shoes, town shoes, and business shoes, women's shoes, and industrial work shoes. It is suitable as an adhesive for. The surface of these adherends may be smooth or may have irregularities. Further, the surface of the adherend may be subjected to a primer treatment for enhancing the adhesion of an adhesive or the like. Examples of the primer treatment include blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and formation of an anchor layer.

As a method of adhering the adherend, a coating film obtained by drying the aqueous emulsion of the present invention, an adhesive layer, and the adherend (second base material) are placed on the adherend (first base material). A method of laminating in this order can be mentioned.

First, an aqueous emulsion is applied to the surface of the first substrate, optionally the second substrate.
Any known coating method can be used for coating. For example, methods such as 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 and spatula coating can be used.

After applying the aqueous emulsion to the first substrate, the obtained coating film may be dried or heat-treated, and then may be irradiated with electromagnetic waves.

When the drying or heat treatment is performed, the water or solvent can be removed by the drying or heat treatment to form a coating film.
The heating temperature is about 30 to 150 ° C., preferably about 40 to 80 ° C.
The heating time is about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes.
Before and after the heat-drying treatment, the first base material may be further treated by leaving it (natural drying) or using an ordinary hot air circulation type oven, an infrared heater, electromagnetic waves such as ultraviolet rays, or the like. In this case, the heating temperature and time for pre-drying can be appropriately adjusted according to the characteristics of the base material, the composition of the aqueous emulsion to be used, and the like. For example, the same conditions as above can be mentioned.

The aqueous emulsion may be applied and dried only once, or may be applied twice or more. The same method may be combined or different methods may be combined for the coating method and the drying method.

In the case of electromagnetic wave processing, examples of the light source include a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, an arc lamp, and a laser. Preferred examples thereof include metal halide lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and low-pressure mercury lamps. The irradiation amount is usually 5 mW / cm2 to 2000 mW / cm2 as the peak illuminance, preferably 10 mW / cm2 to 2000 mW / cm2, and the integrated irradiation amount is usually 20 to 3000 mJ / cm2, preferably 100 to 2500 mJ / cm2. is there.

The surface of the first substrate may be primed before the aqueous emulsion is applied to the adherend. Examples of the primer treatment include blast treatment, chemical treatment, degreasing treatment, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and anchor layer formation treatment.

In the coating film after drying, it is preferable that 95% by mass or more of the water contained in the aqueous emulsion is removed. Adhesiveness can be ensured within this range.

The thickness of the coating film after drying includes a thickness such that the thickness after the drying treatment is about 0.01 to 300 μm, preferably about 0.01 to 200 μm, and more preferably about 0.01 to 50 μm. ..

Next, an adhesive is applied to at least one of the first base material and the second base material to which the aqueous emulsion is applied, and heat-drying treatment is performed. These coating and heat-drying treatments need to be performed only once on at least one of the first base material and the second base material, but the adhesive may be applied and heat-dried on both sides at least once. ..
Conditions such as the adhesive coating method, coating thickness, heat treatment method, temperature and time can be appropriately changed. The same conditions as those for coating and drying the aqueous emulsion described above may be selected, or different conditions may be selected.

When the adhesive is applied to both the first base material and the second base material, the adhesive layer does not have to be the same adhesive to the first base material and the second base material. Considering the adhesiveness between the two, it is preferable to use the same adhesive. The adhesive may be the aqueous emulsion used above or a commercially available adhesive.
The thickness of the adhesive layer can be appropriately adjusted depending on the composition of the adhesive used, the material and form of the base material, and the like. For example, the thickness after the drying treatment may be about 0.01 to 300 μm, preferably about 0.01 to 200 μm.

The surface of the second substrate may be primed before the aqueous emulsion is applied to the adherend. The primer treatment can be appropriately selected from the above.

The method of laminating the surfaces of the first base material and the second base material coated with the aqueous emulsion and / or the adhesive may be either a mechanical operation or a manual method.
At the time of bonding, heat, pressure, or both may be applied. When heat is applied, it is necessary to set the temperature range so that the first base material, the second base material, and the adhesive layer do not deteriorate, preferably about 120 ° C. or lower, more preferably about 100 ° C. or lower. Is. The heat load may be performed by using the above-mentioned ordinary hot air circulation type oven, infrared heater, microwave oven or the like. The pressure when the pressure is applied includes ^{about 100 g / cm 2} or more, and less than the pressure at which the shapes of the first base material and the second base material are deformed. When heat and / or pressure is applied, the time may be, for example, about 1 second to 10 days.

Examples of the first base material and the second base material include those similar to those of the adherend described above. Among them, the equipment in which the first base material is an olefin polymer or an ethylene / vinyl acetate copolymer is preferable, and the second base material is polyvinyl chloride, synthetic leather, rubber, cotton-containing fiber and polyolefin. A substrate selected from the group consisting of polymers is preferred.

The adhesive layer can be obtained by removing water, a solvent, or the like from polyurethane, a rubber-based adhesive, an acrylic adhesive, an epoxy adhesive, or the like by heat-drying, electromagnetic wave treatment, or the like.

Examples of the polyurethane include those similar to those described above.
Examples of the rubber-based adhesive include natural rubber, chloroprene rubber, styrene-butadiene copolymer rubber (SBR), isobutylene rubber, butyl rubber, styrene-isoprene-styrene block copolymer rubber (SIS), and styrene-butadiene-styrene block. Examples thereof include polymerized rubber (SBS), butadiene-acrylonitrile copolymer rubber (NBR), and butadiene rubber (BR). These may be used alone or in combination of two or more. Further, in addition to these rubber components, an adhesion-imparting resin such as a rosin resin, a terpene resin, or a petroleum resin may be mixed.

As the acrylic adhesive, a copolymer of an acrylic acid ester and / or a methacrylic acid ester as an adhesive component and a functional group monomer component and an agglomerating component copolymerizable therewith can be preferably exemplified. This copolymer may be crosslinked with an isocyanate-based cross-linking agent, a chelate-based cross-linking agent, an epoxy-based cross-linking agent, or the like.
Examples of the acrylate ester include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, and 2-ethylhexyl acrylate. N-octyl acrylate, n-lauryl acrylate and the like can be preferably exemplified. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate and 2-ethylhexyl methacrylate. N-octyl methacrylate, n-lauryl methacrylate and the like can be preferably exemplified.

Functional group monomer components that can be copolymerized with acrylic acid ester and / or methacrylic acid ester include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; acrylic. Hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl acid acid, hydroxybropil acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate; acrylamide, methacrylic acid, N-methylolacrylamide, N-methylolmethacrylate, N-butoxy N-substituted or unsubstituted acrylamides such as methyl acrylamide and N-butoxymethacrylic amide; acrylic acids such as glycidyl methacrylate and glycidyl methacrylate; glycidyl esters of methacrylic acid; acrylonitrile and the like can be preferably exemplified.

The epoxy adhesive is a compound having an average of 1 or more epoxy groups per molecule, which is used as a component of an ordinary epoxy resin adhesive. Examples of useful epoxy resins include epoxy resins obtained from bisphenol A and epichlorohydrin, polyglycidyl ethers obtained from bisphenol F and epichlorohydrin, or hydrides bisphenol A and epichlorohydrin. In addition, oxazolidone-modified epoxy resin, novolak type epoxy resin, polyfunctional phenol type epoxy resin, various halogenated epoxy resins, glycidyl ester type epoxy resin, polyglycol type epoxy resin, cyclic aliphatic epoxy resin and the like can also be used. .. These epoxy resins can be used alone or in combination of two or more.

The polyurethane, rubber-based adhesive, acrylic adhesive, and epoxy adhesive may be in the form of an adhesive such as water-based, solvent-based, or hot melt.

The adhesive constituting the adhesive layer may contain a resin or an additive other than the above-mentioned adhesive.
Examples of the resin that may be contained in the adhesive layer include a polyolefin resin, polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), and polytetrafluoroethylene (PTFE). Examples thereof include polymers and copolymers such as acrylonitrile butadiene styrene resin (ABS resin) and AS resin, and modified polymers and modified products. These may be used alone or in combination of two or more.
Further, a pressure-sensitive resin or a resin that exhibits a function as a pressure-sensitive adhesive may be used.
Examples of such resins include rosins, terpene resins, petroleum-based resins obtained by polymerizing petroleum distillates having 5 carbon atoms and hydrogenated resins thereof, petroleum-based resins obtained by polymerizing petroleum distillates having 9 carbon atoms, and the like. Examples thereof include hydrogenated resins, other petroleum-based resins, kumaron resins, inden resins, and polyurethane resins.
Additives that may be contained in the adhesive layer include surfactants, photopolymerization initiators, light stabilizers, UV curable oligomers, fluorescent whitening agents, leveling agents, basic compounds, organic solvents, cross-linking agents, etc. Photosensitizers, other resins, phenol-based stabilizers, phosphite-based stabilizers, amine-based stabilizers, amide-based stabilizers, anti-aging agents, weather-resistant stabilizers, anti-settling agents, antioxidants, heat stabilizers, Preservatives, rocking agents, thickeners, defoaming agents, viscosity modifiers, weathering agents, pigment dispersants, antistatic agents, lubricants, nucleating agents, flame retardants, oils, dyes, hardeners; titanium oxide (rutyl type) ) And transition metal compounds such as zinc oxide; pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers, wolastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, kaolin, fine Examples thereof include inorganic or organic fillers such as powdered silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, alumina and Celite.

The coating film of the aqueous emulsion, the dried product of the coating film, and the cured product thereof preferably have a shear viscosity of less than 200 Pa · s. In this range, the adhesiveness tends to improve. The shear viscosity is determined by a rotary leometer using a cone plate (angle 2 °) when the shear rate is 1s-1 and the measurement temperature is 25 ° C (the melting point of the compound having a polymerizable group is higher than 25 ° C). Can be measured at a temperature 10 ° C. higher than the melting point of the compound having a polymerizable group).
The dried product of the aqueous emulsion preferably removes 95% by mass or more of the mass of water contained in the aqueous emulsion. Thereby, the influence of water on the shear viscosity can be suppressed and a desired shear viscosity can be obtained.

Examples of the aqueous emulsion of the present invention will be described in detail below. Parts and% in the example mean mass-based unless otherwise specified.
The chlorine content of the chlorinated rubber and the polymer is a value measured by a flask combustion-ion chromatograph method.
The component concentration of the aqueous emulsion is the mass of the total content of the mass part of the chlorinated rubber and the mass part of the compound having a polymerizable group with respect to the total mass of the chlorinated rubber, the compound having a polymerizable group and water. It is a value calculated by the concentration (mass%).
The median diameter of the dispersoid is a value measured by a laser diffraction particle size measuring device LA-950V2 manufactured by HORIBA, Ltd. Unless otherwise specified, it is the value of median diameter (unit: μm) measured on a volume basis.

The static stability was evaluated by allowing the obtained aqueous emulsion to stand at room temperature for 1 week and observing the aqueous emulsion. When phase separation was not visually confirmed in the aqueous emulsion, it was judged that the static stability was good.
◯: No change ×: Phase separation was visually confirmed

The chlorinated rubber, the compound having a polymerizable group, the photopolymerization initiator, the surfactant, the light stabilizer, the ultraviolet curable oligomer, the fluorescent whitening agent and the organic solvent in the production example and the evaluation example are as follows.
Chlorinated rubber 1: Pergut S20 (Bayer, chlorine content 58.8% by mass or more)
Chlorinated rubber 2: Pergut S40 (Bayer, chlorine content 65.5% by mass or more)
Chlorinated rubber 3: Pergut S10 (Bayer, chlorine content 64.1% by mass or more)
Chlorinated rubber 4: Pergut S5 (Bayer, chlorine content 61.2% by mass or more)

Polymer 1: Shoprene W (Showa Denko KK, chloroprene rubber, chlorine content 37.8% by mass)
Polymer 2: Shoprene AF (Showa Denko KK, chloroprene rubber, chlorine content 38.1% by mass)
Polymer 3: VINNOL E15 / 45 (Wacker Chemie AG, vinyl chloride / vinyl acetate copolymer resin)

Resin aqueous dispersion 1: Arrow base SD (Unitica, modified polyolefin resin aqueous dispersion, solid content 25%)
Resin aqueous dispersion 2: Shoprene SD77S (Showa Denko, chloroprene rubber, solid content 55%)
Resin aqueous dispersion 3: Auroralen AE-202 (Nippon Paper Industries, Inc., modified polyolefin resin aqueous dispersion, solid content 30%)
Resin aqueous dispersion 4: Aquatex HA-1100 (Chuo Rika Kogyo Co., Ltd., ethylene / vinyl acetate copolymer resin, solid content 45%)
Resin aqueous dispersion 5: Viniblanc 700 (Nisshin Chemical Industry Co., Ltd., vinyl chloride resin aqueous dispersion, solid content 30%)
Resin aqueous dispersion 6: DiofanTM A063 (Solvay Specialty Polymers Japan, Inc., vinylidene chloride resin aqueous dispersion, solid content 55%)

Compound with polymerizable group 1: Dodecyl methacrylate (containing 970 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound 2: 1,6-hexanediol dimethacrylate having a polymerizable group (containing 60 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound with polymerizable group 3: Stearyl methacrylate (containing 200 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound with polymerizable group 4: 2-ethylhexyl methacrylate (containing 25 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound 5 with polymerizable group: Cyclohexyl methacrylate (containing 50 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound with polymerizable group 6: 2-Ethylhexyl acrylate (containing 100 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound 7 with polymerizable group: Diacetone acrylamide (containing 100 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound with polymerizable group 8: Neopentyl glycol diglycidyl ether (Tokyo Chemical Industry Co., Ltd.)
Compound 9 with polymerizable group: Blemmer VA (containing 200 ppm 4-methoxyphenol, NOF CORPORATION)

Compound 10 with polymerizable group: Dodecyl acrylate (containing 100 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound 11: 1,6-hexanediol diacrylate having a polymerizable group (containing 100 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound 12 having a polymerizable group: Cyclohexyl acrylate (containing 100 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound 13 with polymerizable group: Polyethylene glycol dimethacrylate (containing 200 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound with polymerizable group 14: SR489 (containing 170 ppm of 4-methoxyphenol, Arkema)
Compound 15 with polymerizable group: SR340 (containing 200 ppm 4-methoxyphenol and 200 ppm 1,4-benzenediol, Arkema)
Compound 16 with polymerizable group: CN131 (4-methoxyphenol 800 ppm, Arkema)
Compound 17 with polymerizable group: NK ester DCP (containing 200 ppm 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)
Compound with polymerizable group 18: NK ester A-200 (containing 100 ppm 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)

Photopolymerization Initiator 1: 2-Hydroxy-2-methylpropiophenone (Tokyo Chemical Industry Co., Ltd.)
Photopolymerization Initiator 2: 1-Hydroxycyclohexylphenyl ketone (Tokyo Chemical Industry Co., Ltd.)
Photopolymerization Initiator 3: 2- [2- (5-Methylfuran-2-yl) Vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine (Tokyo Chemical Industry Co., Ltd.)

Surfactant 1: Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)
Surfactant 2: Latemul E-1000A (30% aqueous solution, Kao Corporation)
Surfactant 3: Neugen EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.)
Surfactant 4: DKS NL-180 (Daiichi Kogyo Seiyaku Co., Ltd.)
Surfactant 5: Kuraray Poval 217 (Kuraray Co., Ltd.)
Surfactant 6: Kuraray Poval 205 (Kuraray Co., Ltd.)
Surfactant 7: ADEKA PLRONIC F108 (ADEKA CORPORATION)
Surfactant 8: Emargen 102KG (Kao Corporation)
Surfactant 9: Emargen 109P (Kao Corporation)
Surfactant 10: Emargen 150 (Kao Corporation)

Basic compound 1: N, N-dimethylethanolamine (Tokyo Chemical Industry Co., Ltd.)
Light stabilizer 1: TINUVIN 1130 (BASF)
Light stabilizer 2: TINUVIN 123 (BASF)
UV curable oligomer 1: AH-600 (Kyoeisha Chemical Co., Ltd.)
UV curable oligomer 2: UA-306H (Kyoeisha Chemical Co., Ltd.)

Optical brightener 1: 1,4-bis (2-benzoxazolyl) naphthalene (Tokyo Chemical Industry Co., Ltd.)
Optical brightener 2: Kayaphor SN (Nippon Kayaku Co., Ltd.)
Optical brightener 3: Nikkafluor OB (Nippon Kagaku Kogyo Co., Ltd.)

Organic solvent 1: Toluene (Wako Pure Chemical Industries, Ltd., special grade reagent)
Organic solvent 2: 2-butanone (Wako Pure Chemical Industries, Ltd., special grade reagent)
Organic solvent 3: 2-propanol (Wako Pure Chemical Industries, Ltd., special grade reagent)
Leveling agent 1: BYK-349 (Big Chemie Japan)
Cross-linking agent: adipic acid dihydrazide (Tokyo Chemical Industry Co., Ltd.)
In each table, these components are represented by parts by mass.

<Manufacturing example 1>
In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux cooling tube, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)) was added as a compound having a polymerizable group, and dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.). ) 60 parts and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry Co., Ltd.), and 190 parts of tetrahydrofuran (Hayashi Junyaku, reagent special grade) are charged and stirred at 60 ° C. to dissolve and bring to room temperature. After cooling, a trahydrofuran solution of chlorinated rubber 1 and a compound having a polymerizable group was prepared.
3 parts of surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)) was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an ion-exchanged aqueous solution of surfactant 1.
At room temperature, in a tetrahydrofuran solution of the chlorinated rubber 1 and the compound having a polymerizable group, an ion exchange aqueous solution of the surfactant 1, and 2 parts of N, N-dimethylethanolamine as the basic compound 1 (Tokyo Chemical Industry Co., Ltd.) Was charged, stirred and mixed. Next, TK Robomix (manufactured by PRIMIX Corporation) equipped with the stirrer homomixer MARKII was prepared. The resulting mixture was stirred at 16000 rpm for 2 minutes to give a milky white aqueous emulsion. The obtained aqueous emulsion was put into an eggplant flask, distilled off under reduced pressure with an evaporator, and filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-1). The non-volatile content concentration of the obtained aqueous emulsion (E-1) was 45%. Each added component is shown in Table 1-1.

<Manufacturing example 2>
An aqueous emulsion (E) was used in the same manner as in Production Example 1 except that 90 parts of dodecyl methacrylate was used in place of the compound having a polymerizable group used in Production Example 1 and 5 parts of Aqualon KH-10 was used in place of the surfactant. -2) was obtained. The non-volatile content concentration of the obtained aqueous emulsion (E-2) was 47%. Each added component is shown in Table 1-1.

<Manufacturing example 3>
In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux cooling tube, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)) and dodecyl methacrylate as a compound having a polymerizable group (Tokyo Chemical Industry Co., Ltd.) 45 parts and 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry Co., Ltd.) were charged, and 190 parts of tetrahydrofuran (Hayashi Junyaku, reagent special grade) were charged, stirred at 60 ° C. to dissolve, and cooled to room temperature. Then, a trahydrofuran solution of the chlorinated rubber 1 and the compound having a polymerizable group was prepared.
5 parts of surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)) was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an ion-exchanged aqueous solution of surfactant 1.
At room temperature, in a tetrahydrofuran solution of the chlorinated rubber 1 and the compound having a polymerizable group, an ion exchange aqueous solution of the surfactant 1, and 2 parts of N, N-dimethylethanolamine as the basic compound 1 (Tokyo Chemical Industry Co., Ltd.) Was added, stirred and mixed. Further, 5 parts of a photopolymerization initiator 1 (2-hydroxy-2-methylpropiophenone (Tokyo Chemical Industry Co., Ltd.)) was added, and the mixture was stirred and mixed. Next, TK Robomix (manufactured by PRIMIX Corporation) equipped with the stirrer homomixer MARKII was prepared. The resulting mixture was stirred at 16000 rpm for 2 minutes to give a milky white aqueous emulsion. The obtained aqueous emulsion was put into an eggplant flask, distilled off under reduced pressure with an evaporator, and filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-3). The non-volatile content concentration of the obtained aqueous emulsion (E-3) was 43%. Each added component is shown in Table 1-1.

<Manufacturing example 4>
In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)) and dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) as a compound having a polymerizable group. 60 parts and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry Co., Ltd.) were charged, stirred at 60 ° C. to dissolve, and cooled to room temperature.
3 parts of surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)) was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an ion-exchanged aqueous solution of surfactant 1.
At room temperature, in a mixed solution of chlorinated rubber 1 and a compound having a polymerizable group, an ion exchange aqueous solution of surfactant 1 and 2 parts of N, N-dimethylethanolamine as basic compound 1 (Tokyo Chemical Industry Co., Ltd.) Was added, stirred and mixed. Next, TK Robomix (manufactured by PRIMIX Corporation) equipped with the stirrer homomixer MARKII was prepared. The resulting mixture was stirred at 16000 rpm for 2 minutes to give a milky white aqueous emulsion. Next, using a high-pressure homogenizer (manufactured by SMT Co., Ltd.) LAB1000, the aqueous emulsion obtained by performing one treatment at 800 bar was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-4). Each added component is shown in Table 1-2.

<Manufacturing Examples 5 to 14>
Using the chlorinated rubber by mass shown in Tables 1-2 and Table 1-3, a compound having a polymerizable group, a surfactant, a basic compound 1, and ion-exchanged water, an aqueous solution is used in the same manner as in Production Example 4. Emulsions (E-5) to (E-14) were obtained.

<Manufacturing example 15>
In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)) and dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) as a compound having a polymerizable group. 60 parts and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry Co., Ltd.) were charged, stirred at 60 ° C. to dissolve, and cooled to room temperature.
5 parts of surfactant 2 (Latemuru (registered trademark) E-1000A (30% aqueous solution, Kao Corporation)) is placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C., and the ion-exchanged aqueous solution of surfactant 2 is dissolved. Was prepared.
At room temperature, an ion-exchanged aqueous solution of the surfactant 2 was added to a mixed solution of the chlorinated rubber 1 and the compound having a polymerizable group, and further, 2 parts of N, N-dimethylethanolamine (Tokyo) as the basic compound 1. Kasei Kogyo Co., Ltd.) was added, and the mixture was stirred and mixed. To this, 1 part of a photopolymerization initiator 1 (2-hydroxy-2-methylpropiophenone (Tokyo Chemical Industry Co., Ltd.)) was added, and the mixture was stirred and mixed. Next, TK Robomix (manufactured by PRIMIX Corporation) equipped with the stirrer homomixer MARKII was prepared. The resulting mixture was stirred at 16000 rpm for 2 minutes to give a milky white aqueous emulsion. Next, using a high-pressure homogenizer (manufactured by SMT Co., Ltd.) LAB1000, the aqueous emulsion obtained by performing one treatment at 800 bar was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-15). Each added component is shown in Table 1-4.

<Manufacturing Examples 16 to 20>
Using the chlorinated rubber by mass shown in Table 1-4, a compound having a polymerizable group, a surfactant, a basic compound 1, a photopolymerization initiator and ion-exchanged water, an aqueous solution is used in the same manner as in Production Example 15. Emulsions (E-16) to (E-20) were obtained.

<Manufacturing Examples 21 to 50>
Using the chlorinated rubber content by mass, the compound having a polymerizable group, the surfactant, the basic compound 1 and the ion-exchanged water shown in Tables 1-5 to 1-8 in the same manner as in Production Example 4. Aqueous emulsions (E-21) to (E-50) were obtained.

<Manufacturing Examples 51-60>
The mass of the light stabilizer, ultraviolet curable oligomer or fluorescent whitening agent 1 shown in Tables 1-9 and 1-10 was added at the same time as the chlorinated rubber 1, and the masses shown in Tables 1-9 and 1-10 were added. Aqueous emulsion (E-51) in the same manner as in Production Example 4, except that a chlorinated rubber, a compound having a polymerizable group, a surfactant, a basic compound 1, a leveling agent 1, and ion-exchanged water were added. ~ (E60) was obtained. Each added component is listed in Tables 1-9 and 1-10.

<Manufacturing example 61>
In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux cooling tube, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)) and dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) as a compound having a polymerizable group. 60 parts, 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry Co., Ltd.) and 20 parts of organic solvent 1 (toluene (Wako Pure Chemical Industry Co., Ltd., special grade reagent)) were charged and dissolved by stirring at 60 ° C. It was cooled to room temperature.
5 parts of surfactant 2 (Latemuru (registered trademark) E-1000A (30% aqueous solution, Kao Corporation)) is placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C., and the ion-exchanged aqueous solution of surfactant 2 is dissolved. Was prepared.
At room temperature, a mixed solution of chlorinated rubber 1, a compound having a polymerizable group and toluene, an ion exchange aqueous solution of surfactant 2, and 2 parts of N, N-dimethylethanolamine as basic compound 1 (Tokyo Chemical Industry Co., Ltd.) ) Was added, and the mixture was stirred and mixed. To this, 5 parts of a photopolymerization initiator 1 (2-hydroxy-2-methylpropiophenone (Tokyo Chemical Industry Co., Ltd.)) was added, and the mixture was stirred and mixed. Next, TK Robomix (manufactured by PRIMIX Corporation) equipped with the stirrer homomixer MARKII was prepared. The resulting mixture was stirred at 16000 rpm for 2 minutes to give a milky white aqueous emulsion. Next, using a high-pressure homogenizer (manufactured by SMT Co., Ltd.) LAB1000, the aqueous emulsion obtained by performing one treatment at 800 bar was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-61). Each added component is listed in Table 1-11.

<Manufacturing Examples 62 to 66>
By the same method as in Production Example 61, except that the photopolymerization initiator 1 used in Production Example 61 is not used, parts of the chlorinated rubber shown in Table 1-11, a compound having a polymerizable group, and a surfactant , Basic compound 1, organic solvent and ion-exchanged water were used to obtain aqueous emulsions (E-61) to (E-66).

<Manufacturing example 67>
In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)) and dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) as a compound having a polymerizable group. 60 parts and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry Co., Ltd.) were charged, stirred at 60 ° C. to dissolve, and cooled to room temperature.
3 parts of surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)) was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an ion-exchanged aqueous solution of surfactant 1.
At room temperature, in a mixed solution of the chlorinated rubber 1 and a compound having a polymerizable group, an ion exchange aqueous solution of the surfactant 1 and 2 parts of N, N-dimethylethanolamine (Tokyo Chemical Industry Co., Ltd.) as the basic compound 1 were added. It was added, stirred and mixed. Next, TK Robomix (manufactured by PRIMIX Corporation) equipped with the stirrer homomixer MARKII was prepared. The resulting mixture was stirred at 5000 rpm for 2 minutes to give a milky white aqueous emulsion. The obtained aqueous emulsion was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-67). Each added component is listed in Table 1-12.

<Manufacturing Examples 68 to 69>
Using parts of the chlorinated rubber shown in Table 1-12, a compound having a polymerizable group, a surfactant, a basic compound 1, and ion-exchanged water, an aqueous emulsion (E-68) was used in the same manner as in Production Example 67. )-(E-69) were obtained.

<Comparative manufacturing example 1>
An aqueous emulsion (S-1) was obtained in the same manner as in Production Example 11 except that the polymer 1 (Shoprene W (Showa Denko KK)) was used for the chlorinated rubber 1 used in Production Example 11.

<Comparative manufacturing example 2>
An aqueous emulsion (S-2) was obtained in the same manner as in Production Example 11 except that the polymer 2 (Shoprene AF (Showa Denko)) was used for the chlorinated rubber 1 used in Production Example 11.

<Comparative manufacturing example 3>
An aqueous emulsion (S-3) was obtained in the same manner as in Production Example 65 except that the polymer 1 (Shoprene W (Showa Denko KK)) was used for the chlorinated rubber 1 used in Production Example 65.

<Manufacturing Examples 70 to 139>
Add the aqueous emulsion, photopolymerization initiator, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan Co., Ltd.) and ion-exchanged water in parts by mass shown in Tables 2-1 to 2-7, and use a three-one motor. The mixture was stirred to obtain water-based adhesives (F1) to (F70) containing the aqueous emulsion obtained in the production example.
Hereinafter, as one embodiment of the aqueous emulsion of the present invention, a form further containing an additive more suitable as an adhesive is described as "water-based adhesive".

<Manufacturing Examples 140 to 149>
Aqueous emulsion, photopolymerization initiator, compound having a polymerizable group, light stabilizer, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan Co., Ltd.), cross-linking agent, by mass shown in Table 2-8. The organic solvent and ion-exchanged water were mixed and stirred with a three-one motor to obtain water-based adhesives (F71) to (F80) containing the aqueous emulsion obtained in the production example.

<Manufacturing example 150>
In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)) and polymer 3 (VINNOL E15 / 45 (Wacker Chemie AG, Germany)) 1 60 parts of dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry Co., Ltd.) were charged as a compound having a polymerizable group, and dissolved by stirring at 60 ° C. It was cooled to room temperature.
3 parts of surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)) was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an ion-exchanged aqueous solution of surfactant 1.
At room temperature, in a mixed solution of chlorinated rubber 1 and a compound having a polymerizable group, an ion exchange aqueous solution of surfactant 1 and 2 parts of N, N-dimethylethanolamine as basic compound 1 (Tokyo Chemical Industry Co., Ltd.) Was added, stirred and mixed. Next, TK Robomix (manufactured by PRIMIX Corporation) equipped with the stirrer homomixer MARKII was prepared. The resulting mixture was stirred at 16000 rpm for 2 minutes to give a milky white aqueous emulsion. Next, using a high-pressure homogenizer (manufactured by SMT Co., Ltd.) LAB1000, the aqueous emulsion obtained by performing one treatment at 800 bar was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-70). Each added component is listed in Table 2-9.

<Manufacturing Examples 151 to 157>
Three-one motor by mixing the aqueous emulsion, resin aqueous dispersion, photopolymerization initiator, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan, Inc.) and ion-exchanged water in parts by mass shown in Table 2-10. The water-based adhesives (F81) to (F87) containing the aqueous emulsion obtained in the production example were obtained.

<Manufacturing Examples 158 to 194>
The photopolymerization initiator or fluorescent whitening agent by mass shown in Tables 2-11 and 2-12 was added at the same time as the chlorinated rubber 1, and the chlorinated rubber by mass shown in Tables 2-11 and 2-12. , Aqueous emulsions (E-71) to (E107) were obtained in the same manner as in Production Example 4 except that a compound having a polymerizable group, a surfactant, a basic compound 1 and ion-exchanged water were added.

<Manufacturing example 195 to 231>
Aqueous emulsion, photopolymerization initiator, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan Co., Ltd.) and ion-exchanged water of the mass parts shown in Table 2-13 are added and stirred with a three-one motor to produce a production example. Water-based adhesives (F88) to (F124) containing the aqueous emulsion obtained in the above were obtained.

<Manufacturing example 232>
Polyurethane emulsion (Dispacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.), Isocyanate (Death Module (registered trademark) N3300, Sumika Bayer Urethane Co., Ltd.), Leveling Agent 1 (BYK (registered trademark) )-349 and Big Chemie Japan Co., Ltd. were mixed so as to have a non-volatile content ratio of 100 parts: 5 parts: 1 part to obtain an aqueous emulsion (E200).

<Comparative Manufacturing Examples 4 to 6>
Aqueous emulsion, photopolymerization initiator, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan Co., Ltd.) and ion-exchanged water of the mass parts shown in Table 2-14 are mixed, stirred by a three-one motor, and water-based. Adhesives (H1) to (H3) were obtained.

<Evaluation example 1>
The water-based adhesive (F1) is applied to M-EVA (foam of ethylene-vinyl acetate copolymer), which is the first base material, using a brush (application amount: weight after drying: about 3 g / m ^2). ), And dried at 70 ° C. for 5 minutes, and irradiated with ultraviolet rays with a conveyor-type UV irradiation device (Igraphics Co., Ltd., Eye Grandage ECS-4011GX) to obtain M-EVA (A). (Lamp: High-pressure mercury lamp, Lamp output: 3 kW, Lamp height: 110 mm, Conveyor speed: 276 m / min, Integrated light intensity: 1100 mJ / cm ² (Ultraviolet integrated light meter UVICURE PLUS II, UV-A measurement value, Fusion UV Systems Japan KK)
Subsequently, an aqueous emulsion (E200) was applied to soft polyvinyl chloride and M-EVA (A) using a brush (application amount: weight after drying: about 50 g / m ² ), and dried in an oven at 70 ° C. for 5 minutes. did. Then, the obtained soft polyvinyl chloride and the coated surfaces of the aqueous emulsion (E200) of M-EVA (A) were bonded to each other, crimped by hand, and further crimped with a press at 3 MPa for 20 seconds. As a result, a laminate (1) was obtained in which an adhesive layer made of soft polyvinyl chloride and E200, an adhesive layer irradiated with ultraviolet rays, and M-EVA as a first base material were laminated in this order.

The obtained laminate (1) was left at room temperature for 24 hours, and then using a tensile tester (manufactured by Shimadzu Corporation, Autograph), the peeling speed was 50 mm / min, the peeling angle was 180 degrees, and the temperature was room temperature. The adhesiveness between M-EVA and soft polyvinyl chloride in the laminate was evaluated by measuring the peel strength. The results are shown in Table 3-1.
◯: Peeling strength 55 N / inch or more.
X: Peeling strength is less than 55 N / inch.

<Evaluation Examples 2-79>
Laminated body (2) in the same manner as in Evaluation Example 1 except that the water-based adhesive (F1) of Evaluation Example 1 was changed to any of the water-based adhesives (F1) to (F37) and (F39) to (F80). )-(79) were obtained.
The adhesiveness of the laminated body was evaluated in the same manner as in Evaluation Example 1. The results are shown in Tables 3-1 to 3-8.

<Evaluation example 80>
Same as Evaluation Example 1 except that the water-based adhesive (F1) of Evaluation Example 1 was changed to the water-based adhesive (F38) and the amount of the water-based adhesive applied to M-EVA was changed to about 1 g / m ^2. A laminate (80) was obtained.
The adhesiveness of the laminated body was evaluated in the same manner as in Evaluation Example 1. The results are shown in Table 3-9.

<Evaluation example 81>
The water-based adhesive (F1) of Evaluation Example 1 was changed to the water-based adhesive (F70) and irradiated with ultraviolet rays once (lamp: high-pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 276 m / min, integrated light volume: 1100 mJ / cm2 (ultraviolet integrated light meter UVICURE PLUS II, UV-A measurement value, Fusion UV Systems
Japan K. K. After that, a laminated body (81) was obtained in the same manner as in Evaluation Example 1 except that it was further irradiated with ultraviolet rays under the same conditions once.
The adhesiveness of the laminated body was evaluated in the same manner as in Evaluation Example 1. The results are shown in Table 3-10.

The laminated bodies (1) to (81) generally showed a sufficiently high peel strength of 55 N / inch or more.

<Evaluation example 82>
Apply the water-based adhesive (F1) to M-EVA (foam of ethylene-vinyl acetate copolymer) using a brush (coating amount: about 3 g / m ² after drying), and 5 at 70 ° C. After drying for a minute, M-EVA (A) was obtained by irradiating with ultraviolet rays with a conveyor type UV irradiation device (Eiglandage ECS-4011GX manufactured by Eye Graphics Co., Ltd.). (Lamp: High-pressure mercury lamp, Lamp output: 3 kW, Lamp height: 110 mm, Conveyor speed: 276 m / min, Integrated light intensity: 1100 mJ / cm ² (Ultraviolet integrated light meter UVICURE PLUS II, UV-A measurement value, Fusion UV Systems Japan KK)
Subsequently, an aqueous emulsion (E200) was applied to cotton canvas (Johoku Kogyo Co., Ltd.) using a brush (application amount: weight about 50 g / m ² after drying), and oven-dried at 70 ° C. for 5 minutes. (A) was obtained. An aqueous emulsion (E200) is applied to the obtained cotton canvas (A) and M-EVA (A) using a brush (application amount: about 50 g / m ² after drying), and an oven at 70 ° C. for 5 minutes. It was dry. Then, the coated surfaces of the obtained cotton canvas (A) and M-EVA (A) of the aqueous emulsion (E200) were bonded to each other, crimped by hand, and further crimped with a press at 3 MPa for 20 seconds. As a result, a laminated body (82) in which an adhesive layer made of cotton canvas and E200, an adhesive layer irradiated with ultraviolet rays, and M-EVA were laminated in this order was obtained.

<Evaluation example 83>
Apply the water-based adhesive (F1) to M-EVA (foam of ethylene-vinyl acetate copolymer) using a brush (coating amount: about 3 g / m ² after drying), and 5 at 70 ° C. After drying for a minute, M-EVA (A) was obtained by irradiating with ultraviolet rays with a conveyor type UV irradiation device (Eiglandage ECS-4011GX manufactured by Eye Graphics Co., Ltd.). (Lamp: High-pressure mercury lamp, Lamp output: 3 kW, Lamp height: 110 mm, Conveyor speed: 276 m / min, Integrated light intensity: 1100 mJ / cm ² (Ultraviolet integrated light meter UVICURE PLUS II, UV-A measurement value, Fusion UV Systems Japan KK)
Subsequently, an acetone solution (2% by mass) of trichloroisocyanuric acid was applied to a rubber substrate (Shinei Kako Co., Ltd.) with a brush (application amount: about 0.5 g / m ² after drying), and at 70 ° C. for 5 minutes. It was dried in an oven to obtain a rubber substrate (A). An aqueous emulsion (E200) is applied to the obtained rubber base material (A) and M-EVA (A) using a brush (application amount: about 50 g / m ² after drying), and at 70 ° C. for 5 minutes. It was dried in the oven. Then, the coated surfaces of the obtained rubber base material (A) and M-EVA (A) of the aqueous emulsion (E200) were bonded to each other, crimped by hand, and further crimped with a press at 3 MPa for 20 seconds. As a result, a laminated body (83) in which an adhesive layer composed of a rubber base material (A) and E200, an adhesive layer irradiated with ultraviolet rays, and M-EVA were laminated in this order was obtained.

<Evaluation example 84>
Apply the water-based adhesive (F1) to M-EVA (foam of ethylene-vinyl acetate copolymer) using a brush (coating amount: about 3 g / m ² after drying), and 5 at 70 ° C. After drying for a minute, M-EVA (A) was obtained by irradiating with ultraviolet rays with a conveyor type UV irradiation device (Eiglandage ECS-4011GX manufactured by Eye Graphics Co., Ltd.). (Lamp: High-pressure mercury lamp, Lamp output: 3 kW, Lamp height: 110 mm, Conveyor speed: 276 m / min, Integrated light intensity: 1100 mJ / cm ² (Ultraviolet integrated light meter UVICURE PLUS II, UV-A measurement value, Fusion UV Systems Japan KK)
Subsequently, an aqueous emulsion (E200) was applied to synthetic leather (Johoku Kogyo Co., Ltd.) and M-EVA (A) using a brush (application amount: weight after drying: about 50 g / m ² ), and 5 at 70 ° C. Oven dried for minutes. Then, the obtained synthetic leather (Johoku Kogyo Co., Ltd.) and the coated surfaces of the aqueous emulsion (E200) of M-EVA (A) were bonded to each other, crimped by hand, and further crimped with a press at 3 MPa for 20 seconds. As a result, a laminated body (84) in which an adhesive layer made of synthetic leather (Johoku Kogyo Co., Ltd.) and E200, an adhesive layer irradiated with ultraviolet rays, and M-EVA were laminated in this order was obtained.

The obtained laminates (82) to (84) were left at room temperature for 24 hours, and then using a tensile tester (manufactured by Shimadzu Corporation, Autograph), the peeling speed was 50 mm / min, and the peeling angle was 180 degrees. At room temperature, the adhesiveness of M-EVA to the cotton canvas, rubber base material or synthetic leather in the laminate was evaluated by measuring the peel strength. The results are shown in Table 3-11.
◯: Peeling strength 55 N / inch or more.
X: Peeling strength is less than 55 N / inch.

<Evaluation example 85>
1.01 g of the aqueous emulsion (E-4) obtained in Production Example 4 is diluted 10-fold with ion-exchanged water and filtered using a membrane filter 1 (manufactured by ADVANTEC TOYO, manufactured by nitrocellulose, pore diameter 0.45 μm). And obtained a filtrate. When methanol was added to the obtained filtrate, a precipitate was formed. The precipitate was collected by filtration using a membrane filter 2 (ADVANTEC TOYO, PTFE, pore size 0.50 μm), and further adhered to the membrane filter 2 and the membrane filter 2 with methanol (Wako Pure Chemical Industries, Ltd., reagent special grade). The precipitate was washed. The precipitate attached to the membrane filter 2 and the membrane filter 2 was dried under reduced pressure (10 hPa) at 22 ° C. for 24 hours, and the precipitate adhered to the membrane filter 2 was dissolved in THF. GPC measurement of the obtained THF solution and IR measurement of the substance obtained by drying the THF solution were performed. As a result, chlorinated rubber 1 was detected. Of 100 parts by mass of the chlorinated rubber 1 contained in the aqueous emulsion obtained in Production Example 4, the mass of the chlorinated rubber 1 contained in the aqueous emulsion after filtration was 96 mass as a result calculated from the GPC measurement result. %Met.

<Evaluation example 86>
The shear viscosity of the composition obtained by drying the aqueous emulsion of Production Example 4 at 70 ° C. for 30 minutes was measured at 25 ° C. and a shear rate of 1s-1 with a rotary rheometer using a cone plate (angle 2 °). did. The shear viscosity was 23 Pa · s.

<Evaluation example 87>
The shear viscosity of the composition obtained by drying the aqueous emulsion of Production Example 14 at 70 ° C. for 30 minutes was measured at 25 ° C. and a shear rate of 1s-1 with a rotary rheometer using a cone plate (angle 2 °). did. The shear viscosity was 46 Pa · s.

<Evaluation example 88>
The shear viscosity of the composition obtained by drying the aqueous emulsion of Production Example 28 at 70 ° C. for 30 minutes was measured at 56 ° C. and a shear rate of 1s-1 with a rotary rheometer using a cone plate (angle 2 °). did. The shear viscosity was 12 Pa · s.

<Evaluation examples 89-91>
In Evaluation Example 1, "M-EVA (Ethylene-Vinyl Acetate Copolymer Foam)" used as the first base material is shown in the "First Base Material" column of Table 3-12 below. Laminates 89 to 91 were obtained in the same manner as in Evaluation Example 1 except that they were replaced with.

The obtained laminate was left at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corporation, Autograph), the laminate was subjected to a peeling speed of 50 mm / min, a peeling angle of 180 degrees, and room temperature. The adhesiveness between the first substrate and the soft polyvinyl chloride was evaluated by measuring the peel strength. The results are shown in Table 3-12.
◯: Peeling strength 55 N / inch or more.
X: Peeling strength is less than 55 N / inch.

ＰＥ／ＥＶＡ＝６０／４０：ポリエチレン／エチレン−酢酸ビニル共重合体を６０／４０（ＰＥ／ＥＶＡ＝６０／４０）で重合させた発泡体
ＰＥ／ＳＥＢＳ＝５０／５０：ポリエチレン／スチレン−エチレン−ブチレン−スチレンブロック共重合体を５０／５０（ＰＥ／ＳＥＢＳ＝５０／５０）で重合させた発泡体
ＳＢＢＳ：スチレン−ブタジエン−ブチレン−スチレンブロック共重合体（ＳＢＢＳ）で重合させた発泡体

PE / EVA = 60/40: A foam obtained by polymerizing a polyethylene / ethylene-vinyl acetate copolymer at 60/40 (PE / EVA = 60/40) PE / SEBS = 50/50: Polyethylene / styrene-ethylene- Foam obtained by polymerizing a butylene-styrene block copolymer at 50/50 (PE / SEBS = 50/50) SBBS: Foam polymer polymerized with a styrene-butadiene-butylene-styrene block copolymer (SBBS)

<Evaluation Examples 92-98>
Laminates (92) to (98) were obtained in the same manner as in Evaluation Example 1 except that the water-based adhesive (F1) of Evaluation Example 1 was changed to any of the water-based adhesives (F81) to (F87). ..
The adhesiveness of the laminated body was evaluated in the same manner as in Evaluation Example 1. The results are shown in Table 3-13.
◯: Peeling strength 55 N / inch or more.
X: Peeling strength is less than 55 N / inch.

<Evaluation examples 99 to 135>
Laminates (99) to (135) were obtained in the same manner as in Evaluation Example 1 except that the water-based adhesive (F1) of Evaluation Example 1 was changed to any of the water-based adhesives (F88) to (F124). ..
The adhesiveness of the laminated body was evaluated in the same manner as in Evaluation Example 1. The results are shown in Table 3-14.
◯: Peeling strength 55 N / inch or more.
X: Peeling strength is less than 55 N / inch.

<Comparative Examples 1 to 3>
Comparative laminates (1) to (3) were obtained in the same manner as in Evaluation Example 1 except that the water-based adhesive (F1) of Evaluation Example 1 was changed to any of the water-based adhesives (H1) to (H3). It was.
The adhesiveness of the laminated body was evaluated in the same manner as in Evaluation Example 1. The results are shown in Table 3-15.

比較積層体（１）〜（３）は総じて、５５Ｎ／ｉｎｃｈ未満の低い剥離強度を示した。

The comparative laminates (1) to (3) generally showed low peel strength of less than 55 N / inch.

The aqueous emulsion of the present invention can be usefully used as an adhesive or as a coating film in order to adhere the adherends to the adherends with sufficient strength.

Claims (19)

Chlorinated rubber obtained by chlorinating natural rubber or synthetic rubber and having a chlorine atom content of 55% by mass or more and 90% by mass or less, a compound having one or more polymerizable groups, and water. Aqueous emulsion containing
The content of the compound having a polymerizable group with respect to 100 parts by mass of the chlorinated rubber is 50 to 10,000 parts by mass.
The compound having a polymerizable group is a compound having an ethylenically unsaturated double bond.
An aqueous emulsion for adhering an adherend made of an olefin polymer, which is an emulsion after mixing the chlorinated rubber and the compound having a polymerizable group. Chlorinated rubber obtained by chlorinating natural rubber or synthetic rubber and having a chlorine atom content of 55% by mass or more and 90% by mass or less, a compound having one or more polymerizable groups, and water. Aqueous emulsion containing
The content of the compound having a polymerizable group with respect to 100 parts by mass of the chlorinated rubber is 50 to 10,000 parts by mass.
The compound having a polymerizable group is a compound having an ethylenically unsaturated double bond.
An aqueous emulsion for adhering an adherend made of an ethylene-vinyl acetate copolymer, which is an emulsion after mixing the chlorinated rubber and the compound having a polymerizable group. Contains water as a dispersion medium
The aqueous emulsion according to claim 1 or 2, which comprises a mixture of the chlorinated rubber and the compound having a polymerizable group as a dispersoid. The aqueous emulsion according to claim 3 , wherein the dispersoid is in a liquid state. Aqueous emulsion according to free Murrell claim 3 or 4 as a dispersoid in a state that at least a portion of said chlorinated rubber is dissolved in the compound having a polymerizable group. The aqueous emulsion according to any one of claims 1 to 5 , wherein the compound having a polymerizable group is a liquid at 23 ° C. at atmospheric pressure. The aqueous emulsion according to any one of claims 1 to 6 , further comprising a surfactant. The aqueous emulsion according to any one of claims 1 to 7 , further comprising a photopolymerization initiator. The aqueous emulsion according to any one of claims 1 to 8 , further comprising a light stabilizer. The aqueous emulsion according to any one of claims 1 to 9 , further comprising an ultraviolet curable oligomer. The aqueous emulsion according to any one of claims 1 to 10 , further comprising a fluorescent whitening agent. The aqueous emulsion according to any one of claims 1 to 11 , further comprising a leveling agent. The aqueous emulsion according to any one of claims 3 to 12 , wherein the volume-based median diameter of the dispersoid is 10 μm or less. The aqueous emulsion according to any one of claims 1 to 13 , wherein the chlorinated rubber does not have a carboxy group and a carboxylic acid anhydride structure. The total amount of the mass part of the chlorinated rubber and the mass part of the compound having a polymerizable group is 0. The aqueous emulsion according to any one of claims 1 to 14 , which is 1% by mass to 70% by mass. A coating film or cured product formed by the aqueous emulsion according to any one of claims 1 to 15. The coating film or cured product according to claim 16 , an adhesive layer of one or more layers, and a second base material are laminated in this order on a first base material made of an olefin polymer. Laminated body. The coating film or cured product according to claim 16 , an adhesive layer of one layer or more, and a second base material are formed on a first base material made of an ethylene-vinyl acetate copolymer. Laminated bodies laminated in this order. The laminate according to claim 17 or 18 , wherein the adhesive layer and the second base material are laminated via the coating film or the cured product according to claim 16.