WO2015194617A1

WO2015194617A1 - Aqueous emulsion, coating film, hardened product and laminate

Info

Publication number: WO2015194617A1
Application number: PCT/JP2015/067554
Authority: WO
Inventors: 肥後　睦子; 史哲松岡
Original assignee: 住友化学株式会社
Priority date: 2014-06-20
Filing date: 2015-06-18
Publication date: 2015-12-23
Also published as: JPWO2015194617A1; CN106459596A; TW201606001A; KR20170020775A

Abstract

Provided is an aqueous emulsion that is capable of sufficiently strong adhesion to an object to be adhered, and is capable of adhering objects to be adhered to each other with sufficient strength.　The aqueous emulsion includes a reactive surfactant (A) represented by formula (I), a halogen atom-containing polymer (B), and water (C). (In formula (I), R¹ represents a hydrogen atom, a C1-20 alkyl group, a C6-20 aryl group, a C7-20 aralkyl group or a carboxyl group, R² represents a C1-20 alkylene group, a C6-30 arylene group or the like, or a combination thereof, R³ represents a hydrogen atom or a methyl group, Z represents a hydrogen atom, a C1-10 alkyl group, a C-10 alkoxy group or -SO₃M (M being a hydrogen atom, an alkali metal or the like) and n is an integer of 0-30.)

Description

Aqueous emulsion and coating film, cured product and laminate

The present invention relates to an aqueous emulsion, a coating film, a cured product, and a laminate.

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 adherends or adherends with sufficient strength.

JP 2007-31473 A

There is a need for an aqueous emulsion that can adhere an adherend with sufficient strength. There is also a need to maintain a more stable aqueous emulsion.

The present invention includes the following inventions.
[1] The aqueous emulsion of the present invention contains a reactive surfactant (A) represented by the following formula (I), a polymer (B) containing a halogen atom, and water (C).

[In the formula (I),
R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group or a carboxyl group having 7-20 carbon atoms,
R ² represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 30 carbon atoms, or a polyalkylene oxide group and a combination thereof, and the methylene group contained in the alkylene group is an oxygen atom or a carbonyl group. May be replaced,
The polyalkylene oxide group contains 1 to 30 alkylene oxide units having 1 to 8 carbon atoms;
R ³ represents a hydrogen atom or a methyl group,
Z represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or —SO ₃ M (M is a hydrogen atom, NH ₄ or an alkali metal);
n represents an integer of 0 to 30. ]
[2] The reactive surfactant (A) is preferably a surfactant represented by the following formula (II).

[In the formula (II),
R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carboxyl group,
R ³ represents a hydrogen atom or a methyl group,
R ⁴ represents a single bond or an alkylene group having 1 to 4 carbon atoms,
X represents a carbonyloxy group or an oxycarbonyl group,
R ⁵ represents a linear or branched alkylene group having 1 to 12 carbon atoms, and the methylene group contained in the alkylene group may be replaced with an oxygen atom or a carbonyl group.
Z represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or —SO ₃ M (M is a hydrogen atom, NH ₄ or an alkali metal). ]
[3] Furthermore, it is preferable to contain the compound (D) which has a polymeric group.
[4] The content of the compound (D) having a polymerizable group with respect to 100 parts by mass of the polymer (B) containing a halogen atom is preferably 50 to 10,000 parts by mass.
[5] It is preferable that a mixture of a polymer (B) containing a halogen atom and a compound (D) having a polymerizable group is included as a dispersoid.
[6] The dispersoid is preferably a liquid.
[7] It is preferable that at least a part of the polymer (B) containing a halogen atom is dissolved in the dispersoid.
[8] It is preferable that a solution in which at least a part of the polymer (B) containing a halogen atom is dissolved in the compound (D) having a polymerizable group is included as a dispersoid.
[9] The compound (D) having a polymerizable group is preferably liquid at 23 ° C. and atmospheric pressure.
[10] The compound (D) having a polymerizable group is preferably a compound having an ethylenically unsaturated double bond.
[11] It is preferable that a photopolymerization initiator is further contained.
[12] It is preferable that a light stabilizer is further contained.
[13] Further, it preferably contains an ultraviolet curable oligomer.
[14] It is preferable that a fluorescent whitening agent is further included.
[15] It is preferable that a leveling agent is further contained.
[16] The volume-based median diameter of the dispersoid is preferably 2 μm or less.
[17] The total content of the polymer (B) containing a halogen atom and the mass part of the compound (D) having a polymerizable group has a polymer (B) containing a halogen atom and a polymerizable group. The content is preferably 0.1% by mass to 70% by mass with respect to the total mass of the compound (D) and water (C).
[18] The polymer (B) containing a halogen atom is preferably made of a halogenated rubber.
[19] The polymer (B) containing a halogen atom is preferably made of a chlorinated rubber.
[20] A coating film formed from the aqueous emulsion of any one of [1] to [19].
[21] A cured product of the coating film according to [20].
[22] A cured product according to [21], one or more adhesive layers, and a second substrate are laminated in this order on a first substrate made of an olefin polymer. Laminated body.
[23] On the first substrate made of an ethylene / vinyl acetate copolymer, the cured product according to [21], one or more adhesive layers thereon, and a second substrate A laminated body laminated in this order.
[24] A method for forming a coating film, comprising applying the aqueous emulsion according to any one of [1] to [19] onto a substrate and drying.
[25] A coating film obtained by the method according to [24].

According to the present invention, adherends or adherends can be bonded to each other with sufficient strength. Moreover, it becomes possible to maintain an aqueous emulsion much more stably.

The aqueous emulsion of the present invention mainly contains a reactive surfactant (A) represented by the following formula (I), a polymer (B) containing a halogen atom, and water (C).

[In the formula (I),
R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carboxyl group,
R ² represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 30 carbon atoms, or a polyalkylene oxide group and a combination thereof, and the methylene group contained in the alkylene group is an oxygen atom or a carbonyl group. May be replaced,
The polyalkylene oxide group contains 1 to 30 alkylene oxide units having 1 to 8 carbon atoms;
R ³ represents a hydrogen atom or a methyl group,
Z represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or —SO ₃ M (M is a hydrogen atom, NH ₄ or an alkali metal);
n represents an integer of 0 to 30. ]
Moreover, it is preferable that the aqueous emulsion of this invention contains the compound (D) which has a polymeric group further. The aqueous emulsion of the present invention is useful as an aqueous adhesive.

<Reactive surfactant (A)>
In the formula (I), examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, n-pentyl group, n-hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group. Group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl and the like.
Examples of the aralkyl group represented by R ¹ include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.
Examples of the alkylene group having 1 to 10 carbon atoms represented by R ² include divalent groups corresponding to the groups exemplified as the alkyl group of R ¹ .
Examples of the arylene group represented by R ² include phenylene group, naphthylene group, anthrylene group, p-methylphenylene group, p-tert-butylphenylene group, p-adamantylphenylene group, tolylene group, xylylene group, cumenyl group, mesitylene group. Group, biphenylene group, phenanthrylene group, 2,6-diethylphenylene group, 2-methyl-6-ethylphenylene and the like.
Examples of the alkyl group having 1 to 10 carbon atoms represented by Z include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include n-hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group and decyl group.
Examples of the alkoxy group having 1 to 10 carbon atoms represented by Z include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and decyloxy group. The
The polyalkylene oxide group includes an alkylene oxide unit having 1 to 8 carbon atoms, and examples thereof include polyethylene oxide, polypropylene oxide, polybutylene oxide, and polypentylene oxide. In the present specification, a functional group composed of only one alkylene oxide unit also corresponds to a “polyalkylene oxide group” for convenience.

The reactive surfactant (A) may be any of cationic, anionic, amphoteric and nonionic surfactants as long as it has the structure of the above formula (I), more preferably anionic or nonionic. It is a surfactant.

Examples of the reactive surfactant represented by the formula (I) include polyoxyethylene alkyl ether, sulfosuccinic acid ester salt of polyoxyethylene alkyl ether, sulfuric acid ester salt of polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, Polyoxyethylene phenyl ether sulfosuccinate ester salt, polyoxyethylene phenyl ether sulfate ester salt, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether sulfosuccinate ester salt, polyoxyethylene alkyl phenyl ether sulfate ester salt , Polyoxyethylene aralkyl phenyl ether, sulfosuccinic acid ester salt of polyoxyethylene aralkyl phenyl ether, polyoxyethylene aralkyl phenyl ether Kilphenyl ether sulfate ester salt, polyoxyethylene alkylphenyl ether phosphate ester salt, polyoxyethylene alkylphenyl ether aliphatic or aromatic carboxylate, acidic phosphoric acid (meth) acrylate ester emulsifier, rosin Various types such as acid anhydride-modified products of glycidyl ester acrylate are exemplified. Furthermore, the thing which replaced polyoxyethylene with what block-copolymerized or random-copolymerized polyoxypropylene or polyoxyethylene and polyoxypropylene is also mentioned.

As these commercial products, for example, “SE-10N”, “NE-10”, “NE-20”, “NE-30”, “Adekaria soap SR-10”, “Adekaria soap SR-” 20 ”,“ Adekaria Soap ER-20 ”(trade name, manufactured by Asahi Denka Kogyo Co., Ltd.),“ AQUALON RN-10 ”,“ AQUALON RN-20 ”,“ AQUALON RN-50 ”,“ AQUALON HS-10 ” , “AQUALON KH-05”, “AQUALON KH-10” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), “Latemul K-180”, “Latemuru S-120”, “Latemuru S-180P”, “Latemuru” “S-180A”, “Latemul PD-420”, “Latemuru PD-430”, “Latemuru PD-450” (trade name, manufactured by Kao Corporation), “Antox MS-60”, “Antokko” "SAD", "Antox MS-2N", "Antox 2N", "Antox LMA-10", "Antox LMA-20", "Antox LMA-27", "Antox EMH-20" “Antox LMH-20”, “Antox SMH-20” and the like are typical examples.

These reactive surfactants are preferably polyoxyethylene phenyl ether type from the viewpoint of emulsifying properties, and it is particularly preferable to use unsaturated sulfonates having a structure in which 5 to 20 moles of alkylene oxide chains are polymerized. preferable.

The above formula (I) is preferably a reactive surfactant represented by the following formula (II).

[In the formula (II),
R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carboxyl group,
R ³ represents a hydrogen atom or a methyl group,
R ⁴ represents a single bond or an alkylene group having 1 to 4 carbon atoms,
X represents a carbonyloxy group or an oxycarbonyl group,
R ⁵ represents a linear or branched alkylene group having 1 to 16 carbon atoms, and the methylene group contained in the alkylene group may be replaced with an oxygen atom or a carbonyl group.
Z represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or —SO ₃ M (M is a hydrogen atom, NH ₄ or an alkali metal). ]
When R ⁴ is a single bond, X is preferably a carbonyloxy group, R ⁵ is more preferably a linear alkyl group having 1 to 12 carbon atoms, and a methylene group contained in the linear alkyl group Is more preferably replaced by an oxygen atom or a carbonyl group.
When the R ⁴ is an alkyl group having 1 to 4 carbon atoms, X is preferably an oxycarbonyl group, preferably R ⁵ is an alkylene group which is branched having 1 to 16 carbon atoms, alkylene groups the branch Is more preferably replaced by an oxygen atom, a carbonyl group or both groups.

Among the above formulas (II), a reactive surfactant represented by the following formula (III) or formula (IV) is more preferable.

[In formula (III), R ¹ , R ³ and Z represent the same meaning as defined for formula (I),
R ⁶ represents an alkyl having 1 to 16 carbon atoms, and the methylene group contained in the alkyl group may be replaced with an oxygen atom or a carbonyl group. ]
In the formula (III), R ⁶ preferably contains an ester (—COO—) bond.

[In formula (IV), R ¹ , R ³ and Z represent the same meaning as defined for formula (I),
R ⁷ represents a linear or branched alkylene group having 1 to 8 carbon atoms, and the methylene group contained in the alkylene group may be replaced with an oxygen atom, a carbonyl group, or both groups. ]

In the formula (IV), R ⁷ is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms.

Further, the reactive surfactant represented by the formula (I) may be represented by the following formula (V).

[In formula (V), R ¹ , R ³ and Z represent the same meaning as defined in formula (I),
R ⁸ is an alkylene group or an arylene group having 6 to 30 carbon atoms having 1 to 8 carbon atoms, alkylenedioxy group having 1 to 8 carbon atoms, arylene dioxy group, or OAr ¹ having 6 to 30 carbon atoms - alkylene radical - Represents a group represented by OAr ² O (wherein, Ar ¹ group and Ar ² each independently represents an aryl group which may be substituted with an aliphatic hydrocarbon group),
The methylene group contained in the alkylene group may be replaced with an oxygen atom or a carbonyl group,
m and n each independently represents an integer of 1 to 30. ]
R ⁸ is preferably an arylene group having 6 to 26 carbon atoms, more preferably a divalent arylene group containing two or more benzene rings.

The reactive surfactant represented by the formula (I) may be represented by the following formula (VI).

[In formula (VI), R ¹ , R ³ and Z represent the same meaning as defined in formula (I);
R ¹⁰ represents a single bond or an alkyleneoxy group,
n and l each independently represents an integer of 1 to 30. ]

The reactive surfactant represented by the formula (I) may be represented by the following formula (VII).

[In formula (VII), R ¹ , R ³ and Z represent the same meaning as defined in formula (I);
R ⁹ represents an alkyl group having 1 to 12 carbon atoms, and the methylene group contained in the alkyl group may be replaced with an oxygen atom or a carbonyl group,
n represents an integer of 1 to 30. ]

The aqueous emulsion of the present invention may contain a surfactant other than the surfactant represented by the formula (I). Surfactants other than the surfactant represented by the formula (I) will be described later.

<Polymer containing halogen atom (B)>
Examples of the polymer (B) containing a halogen atom include halides of olefin polymers, halides of vinyl copolymers, and halogenated rubbers. Preferably, it is a halogenated rubber. As a halogen atom used for halogenation, chlorine and bromine are preferable, and chlorine is more preferable.

The olefin polymer is a resin obtained by polymerizing an olefin, and has, for example, a homopolymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a structural unit derived from an α-olefin having 2 to 20 carbon atoms. A copolymer is mentioned.

Examples of the α-olefin 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-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and vinylcyclohexane.

The homopolymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is a homopolymer polymerized from an α-olefin having 2 to 20 carbon atoms, and examples thereof include polyethylene, polypropylene, and polybutene.

Examples of polyethylene include high density polyethylene, medium density polyethylene, low density polyethylene, ultra low density polyethylene, linear low density polyethylene, and ultra high molecular weight polyethylene.

Examples of the polypropylene include isotactic (isotactic) polypropylene, syndiotactic polypropylene, and atactic polypropylene.

Examples of the copolymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms include ethylene-unsaturated carboxylic acid copolymers such as ethylene-acrylic acid copolymer and ethylene-methacrylic acid copolymer, and the ethylene -Ionomer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer, wherein some or all of the carboxyl groups of the unsaturated carboxylic acid copolymer are neutralized with the above metals. Polymer, ethylene-isobutyl acrylate copolymer, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate-methacrylic acid copolymer, ethylene-acrylic Ethylene-unsaturated carboxylic acid ester such as n-butyl-methacrylic acid copolymer Ionomer in which part or all of the saturated carboxylic acid copolymer and its carboxyl group neutralized with the metal, ethylene - vinyl ester copolymer, and the like - ethylene such as vinyl acetate copolymer. Specifically, an α-olefin copolymer such as ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer or a modified copolymer thereof, Examples thereof include a copolymer with a copolymerizable monomer, a modified copolymer thereof, or a mixture of two or more thereof.

The ethylene-vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, and has different properties depending on the vinyl acetate content. Such ethylene-vinyl acetate copolymers include those having various vinyl acetate contents and shapes (films, blocks, fibers, foams). The ethylene-vinyl acetate copolymer may contain a polymer such as polyolefin. Preferred polyolefins include ethylene-octene copolymers, ethylene-butene copolymers, polypropylene and polyethylene.

Examples of the monomer copolymerizable with α-olefin include unsaturated carboxylic acid, unsaturated carboxylic acid salt, unsaturated carboxylic acid ester, unsaturated carboxylic acid amide, vinyl ester, carbon monoxide and the like. More specifically, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, itaconic anhydride, lithium of these unsaturated carboxylic acids, sodium, Salts of monovalent metals such as potassium, salts of polyvalent metals such as magnesium, calcium and zinc, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, nbutyl acrylate, isooctyl acrylate, methyl methacrylate , Ethyl acrylate, isobutyl methacrylate, dimethyl maleate and other unsaturated carboxylic acid esters, vinyl acetate, vinyl propionate and other vinyl esters, carbon monoxide, sulfur dioxide and the like.

In the copolymer of α-olefin and a copolymerizable monomer, the copolymerizable monomer and α-olefin may be used alone or in combination of two or more.

The halide of the olefin polymer may be an acid-modified halogenated polyolefin. The acid-modified halogenated polyolefin is obtained by graft copolymerizing at least one selected from polypropylene and a propylene-α-olefin copolymer with at least one selected from α, β-unsaturated carboxylic acid and its anhydride. After obtaining the modified polyolefin, it is obtained by halogenating the acid-modified polyolefin.

Here, the propylene-α-olefin copolymer is a copolymer of propylene as a main component and α-olefin. Examples of α-olefins include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 4-methyl-1-pentene. Examples include α-olefins having 2 or 4 to 20 carbon atoms.

α, β-unsaturated carboxylic acid and its acid anhydride include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, Examples include hymic anhydride. Among these, maleic anhydride and itaconic anhydride are preferable.

The content of the component derived from the α, β-unsaturated carboxylic acid and its acid anhydride in the acid-modified halogenated polyolefin is preferably 0.6 to 10% by mass. When it is 10% by mass or less, the hydrophilicity of the acid-modified halogenated polyolefin is lowered, and the water resistance of the coating film obtained from the target composition may be improved. On the other hand, when the content is 0.4% by mass or more, the dispersibility of the acid-modified halogenated polyolefin in water becomes stable and an aqueous emulsion can be easily produced.

Halogenation can be performed, for example, by dissolving a polyolefin or an acid-modified polyolefin in a halogen-based solvent and blowing a halogen gas in the presence or absence of a radical generator.

<Halogenated rubber>
One kind of halogenated rubber may be used, or two or more kinds thereof may be combined. Examples of the halogen atom used for the halogenation include chlorine and bromine, with chlorine being preferred.

The halogenated rubber may or may not have a melting point, but preferably has a melting point. Melting | fusing point becomes like this. Preferably it is 100 degreeC or more, More preferably, it is 200 degreeC or more, More preferably, it is 240 degreeC or more. Moreover, it is preferably 350 ° C. or lower, more preferably 300 ° C. or lower.

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

The halogenated rubber preferably does not have a carboxy group and a carboxylic anhydride structure. Thus, by making the halogenated rubber free of carboxy group or carboxylic anhydride structure, even when the aqueous emulsion of the present invention is used as a water-based adhesive, it effectively prevents a decrease in water resistance of the water-based adhesive. can do.

The halogenated rubber is not particularly limited as long as it is a halogenated natural rubber or synthetic rubber. Specifically, chlorinated natural rubber, brominated natural rubber, chlorinated butadiene rubber, brominated butadiene rubber, chlorinated rubber are used. Butyl rubber, brominated butyl rubber, chlorinated isoprene rubber, brominated isoprene rubber, butadiene / halogenated 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 copolymer. Preferred are halogenated natural rubber, halogenated isoprene rubber, and halogenated butadiene rubber. Particularly preferred are chlorinated natural rubber, chlorinated isoprene rubber and chlorinated butadiene rubber. In preparing the halogenated rubber, these diene rubbers may be used alone or in combination of two or more. If necessary, reinforcing agents such as clay, carbon black or silica, silane coupling agents, anti-aging agents, softeners, zinc white, stearic acid, vulcanization accelerators, vulcanizing agents, sulfur, etc. may be blended appropriately. Also good.

As a method of halogenating natural rubber or synthetic rubber, a conventionally known method can be employed. For example, a method in which natural rubber or synthetic rubber is dissolved in a chlorinated organic solvent such as carbon tetrachloride or monochlorobenzene, or an organic solvent such as toluene, and halogen gas is blown; a state in which natural rubber or synthetic rubber is suspended or emulsified in water A method in which halogen gas is blown in; a method in which halogen gas is introduced and halogenated while irradiating ultraviolet rays in a state where natural rubber or synthetic rubber is suspended or emulsified in water; natural rubber or synthetic rubber and liquid under low temperature pressure Examples thereof include a method of directly halogenating by contacting with halogen. In addition, the aggregated and solidified natural rubber or synthetic rubber may be halogenated after being dissolved in an organic solvent, or the aggregated and 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 halogenated in a wet state. When natural rubber is halogenated, it can be halogenated by blowing halogen gas into latex natural rubber.

For example, polyisoprene, a surfactant and an acid such as hydrochloric acid, sulfuric acid or nitric acid are added to water and emulsified, and then uniformly halogenated polyisoprene can be obtained by blowing halogen gas.

The halogenated rubber has a polystyrene equivalent weight average molecular weight of usually 1000 or more, preferably 3000 or more, more preferably 5000 or more, and further preferably 10,000 or more. Moreover, it is 400000 or less normally, Preferably it is 200000 or less. The weight average molecular weight in terms of polystyrene can be measured by gel permeation chromatography (GPC).

By setting it as such a range, when the aqueous emulsion of the present invention is used as a water-based adhesive, sufficient adhesive strength can be secured, and an excessive increase in viscosity can be suppressed to adhere to an adherend. Sufficient sex can be secured.

Among the halogenated rubbers, chlorinated rubber is preferable. 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 Co., Ltd.), Pergut S-5, Pergut S-10, Pergut S-20, Pergut S-40, Pergut S-90 Pergut S-130, Pergut S-170 (Bayer MaterialScience), Alloprene (registered trademark) R10, R20, R40 (manufactured by ICI UK) and the like. As a well-known method, the method of patent 2660478 is mentioned, for example.

<Water (C)>
The water (C) contained in the aqueous emulsion of the present invention is usually tap water or deionized water. The water contained in the aqueous emulsion is not particularly limited, and a dispersoid containing a polymer (B) containing a halogen atom and, optionally, a compound (D) having a polymerizable group is present as a uniform dispersion medium. Any amount can be used.

<Compound having a polymerizable group (D)>
The compound having a polymerizable group includes, for example, a vinyl group, an allyl group, a propenyl group, a vinylidene group, a vinylene group (meth) acryl group, a (meth) acryloyl group, a vinyl ether group, a vinyl benzyl ether group as the polymerizable group. , (Meth) acryloxy 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 A ring-opening polymerizable group such as a cyclic ether group such as glycidyl group and oxetane group. These groups may contain only 1 type, or 2 or more types, and may contain only 1 type or 2 or more types.
Examples of the compound (D) having a polymerizable group include compounds having an ethylenically unsaturated double bond, epoxy compounds, oxetane compounds, glycidyl ether compounds, 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 at least one ethylenically unsaturated double bond is preferable.

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

Compounds 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). Compound: heterocyclic (meth) acrylate such as morpholine (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 (for example, methoxyethylene (meth) acrylate, Ethoxy-diethylene glycol (meth) acrylate, methoxypolyethylene (meth) acrylate, butoxypolyethylene (meth) acrylate, etc.), phenoxyalkyl (meth) acrylate (for example, 2-phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, etc.) Alkylphenoxymethyl (meth) acrylate (eg, nonylphenoxyethyl (meth) acrylate), phenoxy (poly) alkylene glycol (meth) acrylate (eg, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene) Glycol (meth) acrylate), alkylphenoxy (poly) alkylene glycol (meth) acrylate (for example, Nylphenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, etc.), alkyl (meth) acrylate (eg, methyl (meth) 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, cetyl (meta Acrylate, behenyl (meth) acrylate, etc.), (meth) acrylates 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, phenylnorbornyl (meth) acrylate, cyanonorbornyl (meth) acrylate, menthyl (meth) acrylate, fenchyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl adamantyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] dec-8-yl = (meth) acrylate, tricyclo [ .2.1.0 ^2,6] dec-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, isobornyloxyethyl (meth) acrylate, etc.), aralkyl (meth) acrylate ( For example, benzyl (meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, etc.), hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl) Chill (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxy-o-phenylphenol Propyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, glycerol mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentanediol mono (Meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, polypropylene glycol (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, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, perfluorooctyl Ethyl (meth) acrylate, N, N, N-trimethyl-N- (2-hydroxy-3methacryloyloxypropyl) -ammonium chloride, etc.), silicone-containing (meth) acrylates (for example, ( T) Acrylic modified organopolysiloxane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acrylic Oxypropylmethyldiethoxysilane, 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 ester-containing (meth) acrylates (for example, glycidyl (meth) acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth) acrylate, ( 3, -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) Ethers), unsaturated amides or unsaturated imides (for example, acrylamide, methacrylamide, diacetone (meth) acrylamide, α-chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N -(2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide and maleimide), acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, In addition, a macromonomer having a monoacryloyl group or a monomethacryloyl group at the end of a polymer (for example, polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, polysilicone, etc.) Can be mentioned.

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, (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 glycol 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 Rate, 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, alkoxylated hexanediol di (meth) acrylate, pentanediol di (meth) acrylate, 3-methyl-pentanediol di (meth) Acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, etc.), alkylene oxide (eg, ethylene oxide, propylene oxide, etc.) adduct of bisphenol A di (meth) Acrylate (eg, di (meth) acrylate of 2,2-bis (2-hydroxyethoxyphenyl) propane), di (meth) acrylate having a bridged cyclic hydrocarbon group (eg, cyclohexanedimethanol di (meth)) Acrylate, di (meth) acrylate of tricyclodecane dimethylol (eg tricyclodecane dimethanol di (meth) acrylate), dicyclopentadiene di (meth) acrylate, dimethylol-tricyclodecane diacrylate Rate), (meth) acrylic acid adducts of bifunctional epoxy resins (for example, (meth) acrylic acid adducts of 2,2-bis (glycidyloxyphenyl) propane, bisphenol A diglycidyl ether methacrylic acid adducts, etc.) ), Glycerin di (meth) acrylate, silicone-containing (meth) acrylate (for example, (meth) acryl-modified organopolysiloxane), diacetone acrylate, and the like.

Examples of the compound having three or more ethylenically unsaturated double bonds include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, tris (acryloyloxy) Isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate tri (meth) Examples include acrylate, tris (hydroxypropyl) isocyanurate tri (meth) acrylate, triallyl trimellitic acid, triallyl isocyanurate, and silicone-containing (meth) acrylates (for example, (meth) acryl-modified organopolysiloxane). It is done.

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 this.

Examples of the epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl 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 Tellurium, 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 diepoxide, diethylene glycol ( , 4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, and the like.

Especially, as an epoxy compound, an aromatic epoxide and an alicyclic epoxide are preferable and an alicyclic epoxide is more preferable from a viewpoint of being excellent in a cure rate.

Examples of oxetane compounds include 2-hydroxymethyl-2-methyloxetane, 2-hydroxymethyl-2-ethyloxetane, 2-hydroxymethyl-2-propyloxetane, 2-hydroxymethyl-2-butyloxetane, and 1,4-bis And [(3-ethyl-3-oxetanylmethoxy) methyl] benzene.

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, diethylene glycol diglycidyl ether, and the like. .

The compound (D) having a polymerizable group is preferably a compound that is liquid at 23 ° C. and atmospheric pressure. Liquids include solutions, emulsions, suspensions, colloids and the like. Due to these properties, a uniform aqueous emulsion can be obtained.

The compound (D) having a polymerizable group may be solid at 23 ° C., but is preferably a compound that is liquid at atmospheric pressure. Liquids include solutions, emulsions, suspensions, colloids and the like. Due to these properties, a uniform aqueous emulsion can be obtained.

When the aqueous emulsion of the present invention contains the compound (D) having a polymerizable group, the content thereof is usually 50 to 10,000 parts by mass with respect to 100 parts by mass of the polymer (B) containing a halogen atom, The amount is preferably 100 to 10000 parts by mass, more preferably 200 to 5000 parts by mass, and still more preferably 400 to 5000 parts by mass.

The aqueous emulsion of the present invention may contain a polymerization inhibitor. Any polymerization inhibitor may be used as long as it delays or stops the radical reaction. Specific examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, monoester of hydroquinone, 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, Examples include 4-benzoquinone, methyl-p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 4-methoxyphenol, chloranil, pyrogallol, 2-oxydiphenylamine, and phenothiazine.

Commercially available polymerization inhibitors include Kinopower QS-10, Kinopower QS-20, Kinopower QS-30, Kinopower QS-40, Kinopower QS-W10 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.), Metoquinone Flakes, Nonflex Alba, MH , TBH, PBQ, tolquinone, TBQ (manufactured by Seiko Chemical Co., Ltd.) and the like.

The polymerization inhibitor also has an aspect of maintaining a high storage stability of the composition and ensuring the curability. Therefore, in consideration of such actions and the like, the addition amount of the polymerization inhibitor is preferably 0 with respect to 100 parts by mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. 0.005 to 0.4 parts by mass, more preferably 0.01 to 0.3 parts by mass, still more 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 the compound having a polymerizable group.

<Additives>
The aqueous emulsion of the present invention includes various additives in addition to the reactive surfactant (A), the polymer (B) containing a halogen atom, water (C) and the compound (D) having a polymerizable group. Can be added. Additives include surfactants, photopolymerization initiators, light stabilizers, UV curable oligomers, fluorescent brighteners, leveling agents, basic compounds, organic solvents, crosslinking agents, photosensitizers, other resins, Phenol stabilizer, phosphite stabilizer, amine stabilizer, amide stabilizer, anti-aging agent, weathering stabilizer, antiseptic, anti-settling agent, antioxidant, thermal stabilizer, thixotropic agent, thickening Agents, antifoaming agents, viscosity modifiers, weathering agents, pigment dispersants, antistatic agents, lubricants, nucleating agents, flame retardants, oil agents, dyes, curing agents; transition metal compounds such as titanium oxide (rutile type) and zinc oxide Pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers, wollastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, kaolin, fine powder silica, mica, silicic acid Calcium, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, inorganic or organic fillers such as alumina and Celite, and the like.

These additives and the like may constitute a dispersoid of the aqueous emulsion. In this case, at least a part of the polymer (B) containing a halogen atom may be dissolved in the dispersoid. Here, at least a part of the polymer (B) containing a halogen atom is dissolved in the dispersoid means that at least a part of the polymer (B) containing a halogen atom forms a dispersoid. It means that it is dissolved in at least one component. For example, when the aqueous emulsion of the present invention is filtered through a filter having a pore size of 0.5 μm, the filtrate may contain at least a part of the polymer (B) containing a halogen atom. The polymer (B) containing a halogen atom contained in the filtrate is preferably 1% by mass or more, more preferably 100 parts by mass of the polymer (B) containing a halogen atom contained in the aqueous emulsion before filtration. Is 10% by mass or more, more preferably 30% by mass or more, and still more preferably 70% by mass or more.
Filtration with a filter is preferably performed 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 polymer (B) containing a halogen atom contains other resins, at least a part of the polymer (B) containing a halogen atom is dissolved in the compound (D) or dispersoid having a polymerizable group. However, at least a part of other additives such as resins may be dissolved.
Filtration with a filter is preferably performed after heating to a temperature equal to or higher than the melting point of the compound (D) having a polymerizable group contained in the aqueous emulsion.

In addition, when adding the said additive to the aqueous | water-based emulsion of this invention, all the additives may be mixed with the dispersoid in an aqueous | water-based emulsion, and may be mixed with water. Mixing means dispersed, swollen, or dissolved.

<Surfactant>
The aqueous emulsion of the present invention may contain a surfactant other than the reactive surfactant (A) represented by the above formula (I). The surfactant preferably acts as an emulsifier. Examples of the surfactant include cationic, anionic, amphoteric and nonionic surfactants, and preferred are anionic and nonionic surfactants. Surfactants may be used alone or in combination of two or more.

Anionic surfactants include fatty acid sodium such as sodium palmitate, sodium ether carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, amino acid condensate of higher fatty acid such as sodium lauroyl sarcosine, sodium N-lauroyl glutamate, Alkyl sulfonates, higher fatty acid ester sulfonates such as 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 Alkyl aryl sulfonates such as diisopropyl naphthalene sulfonate, formalin condensates of alkyl aryl sulfonates, pentadecane-2-sulfate, etc. Secondary alcohol sulfate, polyoxyethylene alkyl phosphate such as dipolyoxyethylene dodecyl ether phosphate, lignin sulfonate, polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate, polyoxyethylene nonylpropenyl Ammonium phenyl ether sulfate, bis (polyoxyethylene polycyclic phenyl ether) bismethacrylate sulfate, alkyl allyl succinate sulfonate sodium salt, polyoxyalkylene alkenyl ether ammonium sulfate, 2-sodium sulfoethyl methacrylate, alkoxy polyethylene glycol maleate , Higher alcohol sulfates, higher carboxylates, alkylbenzene sulfonates, polyoxygens Lenalkyl sulfate salt, polyoxyethylene alkylphenyl ether sulfate salt and vinyl sulfosuccinate, sodium poly (meth) acrylate, ammonium poly (meth) acrylate, (meth) acrylic acid- (meth) acrylic acid ester copolymer Styrene-maleic acid copolymer, styrene-maleic acid copolymer ammonium salt, styrene-maleic acid half ester copolymer ammonium salt, sodium carboxymethylcellulose and sodium naphthalene sulfonate formalin condensate.

Cationic surfactants include alkylamine hydrochlorides such as dodecylamine hydrochloride, alkyl quaternary ammonium salts such as alkyldimethylbenzylammonium salts, alkylisoquinolinium salts, dialkylmorpholinium salts, benzethonium chloride, Alkylvinylpyridinium salts, alkylammonium salts such as 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 chloride.

Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl mono fatty acid. Ester, 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 Block polymer, polyoxyethylene fatty acid amide, alkylolamide, polyoxye Alkylene alkyl amines, and polyoxyethylene alkanediol, alkoxy polyethylene glycol methacrylate, and the like. Polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene fatty acid amide, polyalkylene polyamine alkylene oxide adduct, polyalkylene polyimine alkylene oxide adduct, polyvinyl pyrrolidone, dicyandiamide polyalkylene polyamine condensate, polyethylene glycol, polyvinyl alcohol Etc.

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

Commercially available surfactants include EMAL 0, EMAL 10G, EMAL 2F paste, EMAL 20C, EMAL E-27C, EMAL 270J, EMAL E-27C, Neoperex GS, Neoperex G-15, Neoperex G-25 , Neoperex G-65, Latemul PD-104, Perex OT-P, Perex TR, Perex SS-L, Perex SS-H, Demol N, Demol EP, Emulgen 102KG, Emulgen 104P, Emulgen 105, Emulgen 106, Emulgen 108 Emulgen 404, Emulgen 130K, Emulgen 147, Emulgen LS-106, Emulgen LS-110, Emulgen A-60, Emulgen 109P, Emulgen 350, Rheodor 430V, Emanon 1112, Emanon CH-25, Amit 102, Acetamine 86, Coatamine 24P, Anhitole 24B, Neoperex No. 6 powder, Latemul E-1000A, Perex OT-P, Emulgen LS-114, Emulgen 210P, Emulgen 220, Emulgen 306P, Emulgen 320P, Emulgen 408, Emulgen 409PV, Emulgen 420, Amphital 86B and Amphital 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, Haitenol NF-08, Haitenol 227L, Prisurf A212C, Plastic Surf A210D, Neocor P, Monogen Y-100, Cathogen TML, Pitzkor K-17L and Pitzkor V-7154 (Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Pluronic F108, Adeka Pluronic L-61, Adeka Pluronic 17R-2 ( ADEKA) Eleminol JS-20, Eleminol RS-3000, Sanmorin OT-70 and Caribbon EN-200 (Sanyo Chemical Industries), Kuraray Poval PVA-103, Kuraray Poval PVA-105, Kuraray Poval PVA-117, Kuraray POVAL PVA-217, KURARAY POVAL PVA-205, KURARAY POVAL PVA-203, KURARAY POVAL PVA-210, KURARAY POVAL PVA-235, KURARAY POVAL PVA-403, KURARAY POVAL PVA-405 Kuraray Poval PVA-417, Kuraray Poval M-205, Kuraray Poval MP-203, Kuraray Poval KL-506 and Kuraray Poval KL-318 (manufactured by Kuraray), Akumalim AKM-1511-60, Akumalim AKM-053, Polystar OM and Examples include Pronon # 102 (manufactured by NOF Corporation).

The content of the surfactant that may be contained in the aqueous emulsion of the present invention is the sum of the mass part of the polymer (B) containing a halogen atom and the mass part of the compound (D) having a polymerizable group. The amount is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less with respect to 100 parts by mass. The lower limit of the amount of surfactant is preferably at least 1 part by mass. By setting it as this range, adhesiveness can be improved more.

<Photopolymerization initiator>
A photopolymerization initiator is a compound that generates an active species by the action of light, a photo radical generator that generates an active radical by the action of light, a photo acid generator that generates an acid by the action of light, and the action of light. Examples include photobase generators that generate bases.

Examples of the photo radical generator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, sulfonic acid derivatives, onium salts (such as iodonium salts and sulfonium salts), and carboxylic acid esters.

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, additional methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert -Butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 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] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone and 2-hydroxy-2-methyl-1- [4- (1- And an oligomer of methylvinyl) phenyl] propan-1-one.

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

Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 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- (furan-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- [ - such as (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples include sulfonic acid derivatives, onium salts (such as iodonium salts and sulfonium salts), carboxylic acid esters, and the like described later.

A commercially available thing can be used as a photoradical generator. Commercially available photoradical generators include Irgacure (registered trademark) 907, 184, 651, 819, 250, 2959, 127, 754 and 369 (BASF Japan Co., Ltd.), Seikol (registered trademark) BZ, Z And BEE (Seiko Chemical Co., Ltd.), Kayacure (registered trademark) BP100 (Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adekaoptomer SP-152 and SP-170 (( ADEKA), TAZ-A and TAZ-PP (Nihon Shibel Hegner Co., Ltd.), TAZ-104 (Sanwa Chemical Co., Ltd.), Darocur (registered trademark) 1173 and MBF (BASF Japan Co., Ltd.) It is done.
These photo radical generators may be used alone or in combination.
Specific examples of the combination include Irgacure (registered trademark) 500 (1-hydroxy-cyclohexyl-phenyl-ketone / benzophenone: 50/50%), Irgacure (registered trademark) 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 Ltd.).

Examples of photoacid generators include sulfonic acid derivatives, onium salts, and carboxylic acid esters.

Examples of the sulfonic acid derivatives include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidesulfonates such as trifluoromethylsulfonate derivatives, benzoinsulfonates, 1-oxy-2-hydroxy-3 Mention may be made of sulfonates of propyl alcohol, pyrogallol trisulfonates, benzyl sulfonates. Specifically, diphenyldisulfone, ditosyldisulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xylylsulfonyl) diazomethane, phenylsulfonylbenzoyldiazomethane, bis (cyclohexylsulfonyl) methane, benzoin tosylate 1,2-diphenyl-2-hydroxypropyl tosylate, 1,2-di (4-methylmercaptophenyl) -2-hydroxypropyl tosylate, pyrogallol methyl sulfonate, pyrogallol ethyl sulfonate, 2,6-dinitrophenyl methyl tosylate And lato, ortho-nitrophenyl methyl tosylate, para-nitrophenyl tosylate and the like.

Examples of onium salts include tetrafluoroborate (BF ⁴⁻ ), hexafluorophosphate (PF ⁶⁻ ), hexafluoroantimonate (SbF ⁶⁻ ), hexafluoroarsenate (AsF ⁶⁻ ), hexachloroantimonate (SbCl ^{6). -} ), Tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO ⁴⁻ ), trifluoromethanesulfonate ion (CF ₃ SO ³⁻ ), fluorosulfone acid ion (FSO ^3-), using toluene sulfonic acid ion, trinitrobenzene sulfonic acid anion, a sulfonium salt or iodonium salt having an anion such as trinitrotoluene sulfonate anion It can be.

Examples of the sulfonium salt include triphenylsulfonium hexafluoroacylate, triphenylsulfonium hexafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorobenzyl) borate, methyldiphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium. Tetrakis (pentafluorobenzyl) borate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritoylsulfonium hexafluorophosphate, anisyldiphenyls Honium hexahexafluoroantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-butoxyphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, tris (4-phenoxyphenyl) Sulfonium hexafluorophosphate, di (4-ethoxyphenyl) methylsulfonium hexafluoroarsenate, 4-acetylphenyldiphenylsulfonium tetrafluoroborate, 4-acetylphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, tris (4-thiomethoxyphenyl) ) Sulfonium hexafluorophosphate, di (methoxysulfonyl) Nyl) methylsulfonium hexafluoroantimonate, di (methoxynaphthyl) methylsulfonium tetrafluoroborate, di (methoxynaphthyl) methylsulfonium tetrakis (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-acetamidophenyldiphenylsulfonium tetrafluoro Borate, 4-acetamidophenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, dimethyl Naphthylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, trifluoromethyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, phenylmethylbenzylsulfonium hexafluorophosphate, 10-methylphenoxathinium hexafluorophosphate, 5-methyl Thianthrenium hexafluorophosphate, 10-phenyl-9,9-dimethylthioxanthenium hexafluorophosphate, 10-phenyl-9-oxothioxanthenium xanthenium tetrafluoroborate, 10-phenyl-9-oxothioki Santenium tetrakis (pentafluorobenzyl) borate, 5-methyl-10-oxothiatrenium teto Tetrafluoroborate, 5-methyl-10-oxo-thia Torre tetrakis (pentafluorobenzyl) borate, and 5-methyl-10,10-and di-oxo-thia tray hexafluorophosphate and the like.

Examples of the iodonium salt include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate, [4- (2- Hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2-hydroxy-n-tetrade Siloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium hexafluoro Phosphate, bis (4-tert-butylphenyl) iodonium trifluorosulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoro Borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate, di (dodecylphenyl) iodonium hexafluoroantimonate, di (dodecylphenyl) iodonium triflate, diphenyliodonium bissulfate, 4,4'-dichlorodiphenyliodonium bisulphate, 4,4'-dibromodiphenyliodonium bisulphate , 3,3'-dinitrodiphenyliodonium bisulphate, 4,4'-dimethyldiphenyliodonium bisulphate, 4,4'-bissuccinimide diphenyliodonium bisulphate, 3-nitrodiphenyliodonium bisulphate, 4,4'-dimethoxy Examples thereof include diphenyliodonium bisulphate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, (4-octyloxyphenyl) phenyliodonium tetrakis (3,5-bis-trifluoromethylphenyl) borate.

As other onium salts, aromatic diazonium salts can be used, for example, p-methoxybenzenediazonium / hexafluoroantimonate.

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 (manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990 (manufactured by Union Carbide), Adekaoptomer SP-150, SP- 151, SP-170, SP-171, SP-172 (Asahi Denka Kogyo Co., Ltd.), Irgacure 261, Irgacure 250 (Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-2439 CI-2064 (Nippon Soda Co., Ltd.), CD-1010, CD-10 1, CD-1012 (above, manufactured by Sartomer), 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 (above, manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, manufactured by Nippon Kayaku Co., Ltd.), IBPF, IBCF (Sanwa Chemica CD1012 (manufactured by Sartomer), IBPF, IBCF (above, manufactured by Sanwa Chemical Co., Ltd.), BBI-101, BBI-102, BBI-103, BBI-109 (above, Midori Chemical Co., Ltd.) And UVE1014 (manufactured by General Electronics), RHODORSIL-PI2074 (manufactured by Rhodia), WPI-113, WPI-116 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

J. Polymer Science: Part A: Polymer Chemistry, Vol. 31, 1473-1482 (1993), J.A. Polymer Science: Part A: polymer Chemistry, Vol. 31, 1483-1491 (1993) can also be used diaryl iodonium salts that can be produced. These can be used alone or in combination of two or more.

As the carboxylic acid ester, 1,8-naphthalenedicarboxylic acid imidomethyl sulfonate, 1,8-naphthalenedicarboxylic acid imidotosyl sulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate, 1,8-naphthalenedicarboxylic acid imide camphor Sulfonate, succinimide phenyl sulfonate, succinimide tosyl sulfonate, succinimide trifluoromethyl sulfonate, succinimide camphor sulfonate, phthalic imide trifluorosulfonate, cis-5-norbornene-endo-2,3-dicarboxylic imide Examples thereof include trifluoromethyl sulfonate.

Examples of the photobase generator include acyclic acyloxyimino compounds, acyclic carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, Examples include sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, α-lactone ring derivative compounds, amine imide compounds, and phthalimide derivative compounds. 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 is the sum of the mass part of the polymer (B) containing a halogen atom and the mass part of the compound (D) having a polymerizable group. From the viewpoints of stability, reactivity, and odor, 100 parts by mass is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and even more preferably. Is 5 parts by mass or less.

<Light stabilizer>
Examples of the light stabilizer include an ultraviolet absorber and a hindered amine light stabilizer. A light stabilizer may be used independently and may be used in combination of 2 or more type.

Examples of the ultraviolet absorber include salicylic acids (eg, phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, etc.), benzophenones (eg, oxalic acid 2,4-dihydroxybenzophenone, 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 (for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5) '-Ter -Butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-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′-di) tert-amylphenyl) benzotriazole, 2-{(2′-hydroxy-3 ′, 3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl} benzotriazole, etc.), triazines (For example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy Loxy-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 Ruphenyl) -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-tert-butylphenyl) oxalic acid diamide, N- (2-ethylphenyl)) -N '-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethoxy-2'-ethyl-oxalic acid bisanilide, oxalic acid diamides having an aryl group optionally substituted on the nitrogen atom, etc.) Is mentioned.

Examples of hindered amine light stabilizers include ester group-containing piperidines (for example, 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 (for example, 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 (for example, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1,6-di As well as high molecular weight piperidine polycondensates (for example, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensates such as succinate, , 2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, etc.).

When the aqueous emulsion of the present invention contains a light stabilizer, the content is 100 parts by mass of the total of the part by mass of the polymer (B) containing a halogen atom and the part (D) having a polymerizable group. On the other hand, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less. By setting it as this range, adhesiveness can be improved more.

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

A commercially available urethane acrylate oligomer can be used. Examples of commercially available urethane acrylate oligomers include CN929, CN965, CN968, CN981A75, CN985B88, CN991, CN970AH75, CN975, CN992, CN994 and CN9165 (Sartomer), U-4HA and U-6HA (manufactured by Shin-Nakamura Chemical 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.

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

A commercially available polyester acrylate oligomer 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. 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 a total of 100 parts by mass of the polymer (B) containing a halogen atom and the compound (D) having a polymerizable group. Preferably it is 20 mass parts or less with respect to a mass part, More preferably, it is 15 mass parts or less, More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less. By setting it as this range, adhesiveness can be improved more.

<Fluorescent brightener>
Examples of fluorescent brighteners include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-alkylimide, bisbenzoxazolylethylene, 1,4-bis (2-Benzoxazolyl) naphthalene, dialkylstilbene and the like. Commercially available optical brighteners include Kayahor 3BS Liq. Kayahor TAC Liq. Kayahor HBC Liq. , Kayalight B, Kyaphor AS 150, Kyaphor CR 200, Kyaphor JB Liq., Mikawhite ATN conc. (Manufactured by Nippon Kayaku Co., Ltd.), TINOPAL OB, TINOPAL NFW Liqid (manufactured by BASF), Hakkol P, Hakkol PHD, Hakkol RF, Hakkol PSR, Hakkol PSR-B, Hakkol CYP-B, Hakkol PY-2000, Hakkol PY-2000 D, Hakkol BE conc, Hakkol SG conc 150, Hakkol TH-100, Hakkol S-100, Hakkol RX-1, Hakkol OW-11, Hakkol OW-10 extra, Hakkol KIP H / C, Hakol KIP H / C, Hakol Hakkol PMS H / C (made by Showa Chemical Co., Ltd.), Nikkafluor SB conc, Nikkafluor KB, Nikkafluor OB Nikka bright CX H / C (manufactured by Nippon Chemical Industry Co., Ltd.) and the like. The optical brighteners may be used alone or in combination.

When the aqueous emulsion of the present invention contains a fluorescent brightening agent, the content is the sum of the parts by mass of the polymer (B) containing a halogen atom and the parts by mass of the compound (D) having a polymerizable group. Preferably it is 5 mass parts or less with respect to 100 mass parts, More preferably, it is 3 mass parts or less, More preferably, it is 1 mass part or less. By setting it as this range, adhesiveness can be improved more.

<Leveling agent>
As a 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 BYK Japan) KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (manufactured by AGC Seimi Chemical Co., Ltd.), Footgent 222F, footage 251, FTX-218 (manufactured by Neos), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (Mitsubishi Materials), MegaFuck F- 171 、 Me Fuck F-177, Mega Fuck F-475, Mega Fuck F-556, Mega Fuck R-30 (manufactured by DIC), Adeka Coal W-193, Adeka Coal W-287, Adeka Coal W-288, Adeka Coal W-304 (ADEKA) Manufactured), SN wet 366, Nopco 38-C, SN disperse sand 5468, SN disperse sand 5034, SN disper sand 5027, SN disperse sand 5040, SN disper sand 5020 (San Nopco) fluoroalkylbenzene sulfonate, fluoroalkyl carboxylic acid Acid salt, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis Reoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether , Polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palm Tate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxye Ren sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonates, or alkyl diphenylether disulfonic acid salts.

When the aqueous emulsion of the present invention contains a leveling agent, the content is 100 parts by mass of the total of the parts by mass of the polymer (B) containing a halogen atom and the compounds (D) having a polymerizable group. On the other hand, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less. By setting it as this range, adhesiveness can be improved more.

<Basic compound>
As a basic compound, ammonia, an organic amine compound, a metal hydroxide, etc. are mentioned, for example. Preferably, it is ammonia or an organic amine compound.

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

When the aqueous emulsion of the present invention contains a basic compound, the content thereof is a total of 100 parts by mass of the polymer (B) containing a halogen atom and the compound (D) having a polymerizable group. Preferably it is 20 mass parts or less with respect to a mass part, More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less. By setting it as this range, adhesiveness can be improved more.

<Organic solvent>
Examples of organic solvents 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. Alcohols such as isopropyl alcohol and n-butanol; glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol; methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary butyl ether) and butyl carbitol Cellosolve solvents; diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and 3-methyl And glycol solvents such as xyl-3-methyl-1-butanol; and glycol ester solvents such as ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate. It is done. These may be used alone or in combination.

When the aqueous emulsion of the present invention contains an organic solvent, the content is 100 parts by mass of the total of the parts by mass of the polymer (B) containing a halogen atom and the compound (D) having a polymerizable group. On the other hand, from the viewpoint of odor, 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 10 parts by mass or less.

<Crosslinking agent>
By including a crosslinking agent, there exists a tendency which adhesiveness, the water resistance of an adhesive bond layer, and the solvent resistance of an adhesive bond layer improve more.
Examples of the crosslinking agent include epoxy compounds, polyisocyanate compounds, oxazoline compounds, aziridine compounds, carbodiimide compounds, active methylol compounds, active alkoxymethyl compounds, metal chelates, hydrazide compounds, and hydrazine compounds.
Preferred are aliphatic polyisocyanate compounds, carbodiimide compounds, oxazoline group-containing compounds, hydrazide compounds, and hydrazine compounds. Of these, aqueous (water-soluble or water-dispersible) ones are more preferable. If necessary, these crosslinking 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, Sumidur (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 Module (registered trademark) N3100, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547 and DA-, manufactured by Sumitomo Bayer Urethane Co., Ltd. L, E14 and E22, Bihijoule (registered trademark) 304 and XP2655 manufactured by Sumitomo Bayer Urethane Co., Ltd., BASONAT (registered trademark) PLR8878 and HW-100 manufactured by BASF, Takenate (registered trademark) manufactured by Takeda Pharmaceutical Company Limited ) WD720, WD7 5 and WD730, Asahi Chemical Industry Co. Duranate (registered trademark) WB40-100, include WB40-80D and WX-1741 or the like.

Specific examples of carbodiimide-based crosslinking agents include Nisshinbo Chemical Co., Ltd .: Carbodilite (SV-02, V-02, V-02-L, V-04, E-01, E-02), etc. Can be mentioned.

Specific examples of hydrazide compound crosslinking agents include: Otsuka Chemical Co., Ltd .: ADH (adipic acid dihydrazide), SDH (sebacic acid dihydrazide), DDH (dodecanediohydrazide), IDH (isophthalic acid dihydrazide), SAH. (Salicylic acid hydrazide) and the like.

Specific examples of the hydrazine compound crosslinking agent include Otsuka Chemical Co., Ltd .: hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine monohydrobromide, hydrazine carbonate, and the like.

When the aqueous emulsion of the present invention contains a crosslinking agent, the content is 100 parts by mass of the total of the parts by mass of the polymer (B) containing a halogen atom and the compounds (D) having a polymerizable group. On the other hand, it is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

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

When the aqueous emulsion of the present invention contains a photosensitizer, the content is the sum of the parts by mass of the polymer (B) containing a halogen atom and the parts by mass of the compound (D) having a polymerizable group. Preferably it is 15 mass parts or less with respect to 100 mass parts, More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts 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, (meth) acrylic resin, polystyrene, polyvinyl acetate, polyurethane, ethylene-vinyl ester resin, polyurea, acrylonitrile butadiene styrene resin, butyl rubber, modified rubber. , Styrene- (meth) acrylic resin, synthetic rubber, natural rubber, styrene-butadiene resin, butadiene resin, poly (meth) acrylonitrile resin, (meth) acrylamide resin, polyester resin, modified nylon resin, epoxy resin, styrene block Examples thereof include copolymers and oligomers thereof.

The ethylene-vinyl ester resin is a copolymer containing a polymer composed of ethylene units and vinyl ester units. Examples of vinyl ester units include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl esters of tertiary carboxylic acids having 8 to 10 carbon atoms, and so-called vinyl versatates (for example, trade name: Veova (registered trademark) manufactured by Shell Chemical Co., Ltd.). And alkyl acid vinyl esters such as 10). Of the vinyl ester units, vinyl acetate is preferred. When vinyl acetate is used as the vinyl ester unit, the copolymer is an ethylene-vinyl acetate copolymer (hereinafter abbreviated as “EVA”).

For example, ethylene-vinyl acetate copolymers have various vinyl acetate contents and shapes (films, blocks, fibers, foams), although the properties differ depending on the vinyl acetate content and the like. The ethylene-vinyl acetate copolymer may contain a polymer such as polyolefin. Preferred polyolefins include ethylene-octene copolymers, ethylene-butene copolymers, polypropylene and polyethylene.

In addition to ethylene units and vinyl ester units, the ethylene-vinyl ester resin may contain monomer units copolymerizable therewith. Examples of the monomer unit include vinyl halides such as vinyl chloride, monomers having a small amount of a functional group such as an amide group, and (meth) acrylic acid esters.
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, H40 / 60, H30 / 48M (Wacker Chemie AG) and the like.
The ethylene-vinyl ester resin and the copolymer thereof may be in the form of an emulsion. Such an emulsion may be produced by emulsion polymerization of monomers constituting the ethylene units and vinyl ester units, or commercially available ones may be used. Examples of the emulsion of the ethylene-vinyl ester resin copolymer include Sumikaflex (registered trademark) 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 Polysol (registered trademark) EVA AD-2, AD-3, AD-4, AD-5, AD-51, AD-56, AD-59 and P-900 (above, Showa High) (Molecular Co., Ltd.) Denka EVA-Tex (registered trademark) # 20, # 30, # 40M, # 60, # 81 and # 82 (manufactured by Denki Kagaku Kogyo Co., Ltd.).

Examples of the styrene-maleic resin include Alastar 700 and 703S (manufactured by Arakawa Chemical Industries, Ltd., SMA (registered trademark) 1000, SMA (registered trademark) 2000, SMA (registered trademark) 3000 (manufactured by Cray Valley's Company). Etc.

Examples of the α-olefin 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-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and vinylcyclohexane. Preferably, they are ethylene and propylene.

Examples of the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms include polyethylene (PE), high density polyethylene (HDPE), medium density polyethylene (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 a 1-butene copolymer, an ethylene-1-octene copolymer and an ethylene-1-hexene copolymer, and an α-olefin having 2 to 20 carbon atoms and the α-olefin Copolymers of monomers copolymerizable with olefins It is below. Further, the copolymer of an α-olefin having 2 to 20 carbon atoms and a monomer copolymerizable with the α-olefin may contain one type of each monomer or two or more types. It may be a thing.

The resin having a structural unit derived from an 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 reduced in molecular weight or 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, the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is modified with an α, β-unsaturated carboxylic acid or the like. Modified products.

The modification rate of the modified product modified with α, β-unsaturated carboxylic acid or the like is usually 0.1 to 10% by mass, preferably 0.2 to 0.2% with respect to 100% by mass of the copolymer before modification. 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.), α, β-unsaturated carboxylic acid esters (methyl maleate, methyl itaconate) ), Α, β-unsaturated carboxylic anhydrides (maleic anhydride, itaconic anhydride, citraconic anhydride, etc.). A modified product obtained by combining these α, β-unsaturated carboxylic acids may also be used. These may be carboxylic anhydrides, carboxylic acids formed by hydrolysis, or a mixture thereof.

Such a modified product includes 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 and modifying α, β-unsaturated carboxylic acids after melting, a method of modifying by dissolving α, β-unsaturated carboxylic acids after dissolving in a solvent such as toluene and xylene, etc. It is produced by a known method.

The modification rate of the chlorinated resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is such that the chlorine atom content is preferably 5 to 80 with respect to 100% by mass of the copolymer before modification. % 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 performed by dissolving or dispersing the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms in a solvent. 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.

Monomers copolymerizable with α-olefins having 2 to 20 carbon atoms include α, β-unsaturated carboxylic acids and anhydrides, metal salts of α, β-unsaturated carboxylic acids, α, β-unsaturated carboxylic acids, and the like. Examples 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 halogenated vinylidenes. These may be used alone or in combination for copolymerization.

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, maleic Examples include acid half esters, maleic acid half amides, itaconic acid half esters, itaconic acid half amides, and the like. 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. Specifically, the sodium salt and magnesium salt of (meth) acrylic acid are mentioned.
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, maleic acid Examples include esterified products of dimethyl and methacrylic acid and alcohol. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferred.

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

Examples of the cyclic olefin include 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.

Examples of vinyl aromatic compounds include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, and vinylnaphthalene. Etc.

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, and aromatic non-conjugated polyene compounds. . These may have a substituent 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 include 1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-octadiene, and 2,3-dimethyl-1,3-decadiene.

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 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-decadiene, 3,3-dimethyl-1,4-hexadiene, 5-ethyl-1 , 4-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1 4, 4-decadiene, 6-methyl-1,6-undecadiene, 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 an α-olefin having 2 to 20 carbon atoms include ethylene-unsaturated carboxylic acid copolymers such as ethylene-acrylic acid copolymer and ethylene-methacrylic acid copolymer, and the ethylene -Ionomer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer, wherein some or all of the carboxyl groups of the unsaturated carboxylic acid copolymer are neutralized with the above metals. Polymer, ethylene-isobutyl acrylate copolymer, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate-methacrylic acid copolymer, ethylene-acrylic Ethylene-unsaturated carboxylic acid ester such as n-butyl-methacrylic acid copolymer Ionomer in which part or all of the saturated carboxylic acid copolymer and its carboxyl group neutralized with the metal, ethylene - vinyl ester copolymer, and the like - ethylene such as vinyl acetate copolymer.

Specific examples of the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and modified products thereof include Mersen (registered trademark) H H-6410M, H-6051, H-6960, H-6820 and H-6822X (Tosoh Corporation), EVAL (registered trademark) L171B, F171B, H171B, E105B and G156B (Kuraray Co., Ltd.), Soarnol (registered trademark) D2908, DT2904, DC3212, DC3203, E3808, ET3803, A4412, AT4403, BX, 16DX, D2908H4 and A4412H4 (Nippon Synthetic Chemical Industry Co., Ltd.), Soresin (registered trademark) PG505 (Nippon Synthetic Chemical Industry Co., Ltd.), NISSO (registered trademark) PB (Nippon Soda Co., Ltd.), Polytail (Registered trademark) H (Mitsubishi Chemical Corporation), Epaul R) (manufactured by Idemitsu Kosan (Ltd.)), OREVAC (R) G 18211, OE808 and OE825 (Arkema (Ltd.)), LOTADAR
MAH2210, 3200, P3 3200, 3210, 4210, 6200, 3410, 3430 and 4720 (Arkema Corp.), BONDINE (registered trademark) LX4110, HX8210, TX8030, HX8290, HX8410 and AX8390 (Arkema Corp.), OREVAC ( (Registered trademark) T9314, T9318 and G1821 (Arkema Co., Ltd.), Umex (registered trademark) 2000 (Sanyo Chemical Industry Co., Ltd.), Auroren (registered trademark) 100S and 200T (Nippon Paper Chemical Co., Ltd.), etc. Can be mentioned.

Examples of the resin having a structural unit derived from a chlorinated α-olefin having 2 to 20 carbon atoms include Eraslen (registered trademark) 401A and 303B (Showa Denko KK).

Polyurethane is a polymer composed of urethane bonds and is usually obtained by the reaction of alcohol (—OH) and isocyanate (—NCO). In the polyurethane, the urethane foam includes a polyurethane foamed by a volatile solvent such as carbon dioxide or freon produced by a reaction between an isocyanate and water.

A commercially available polyurethane can be used. Examples of commercially available water-soluble urethanes include DISPAROL (registered trademark) U-42, U-53, U-54, U-56, KA-8484, KA-8484, 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 Corporation), Uprene (registered trademark) UXA-306, UXA-307, Permarin UA-150, Permarin UA-200, Permarin UA-300, Permarin UA-310, and Ucourt UWS-145 (Sanyo Chemical Industries, Ltd.) )), Superflex (registered trademark) 107M, 110, 126, 130, 150, 160, 210, 00, 361, 370, 410, 420, 460, 500M, 700, 750, 820 and 860 (Daiichi Kogyo Seiyaku Co., Ltd.), and Adekabon titer (registered trademark) HUX-401, HUX-420A, HUX-380 , HUX-561, HUX-210, HUX-822, HUX-895, and HUX-830 (Adeka Co., Ltd.), NIPPON (registered trademark) 3110, 3116, 3016, 3113, 3124, 3126, 3230 (Nippon Polyurethane Industry ( Etc.).

Polyvinyl chloride is obtained by a method such as suspension polymerization or bulk polymerization of vinyl chloride.
Examples of the polyvinyl chloride include hard polyvinyl chloride, semi-rigid polyvinyl chloride, and soft polyvinyl chloride. Preferably, it is soft polyvinyl chloride.
Examples of the polyvinyl chloride include Kanevinyl S-400, PSH-180, PSL-180 (Kaneka).

Chlorinated polyvinyl chloride is obtained by chlorinating a polyvinyl chloride resin by a chlorination method such as a gas phase or a liquid phase. Examples of the polyvinyl chloride resin include a vinyl chloride homopolymer and a vinyl chloride copolymer. Examples of the monomer constituting the vinyl chloride copolymer 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 polyvinylidene chloride include SARAN X05253-16 (manufactured by Dow Chemical Co., Ltd.), a resin for saran wrap (registered trademark) (manufactured by Asahi Kasei Co., Ltd.), Diofan 193D, A736, A036, A050, A063, B204, A115 and the like. Can be mentioned.

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

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

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

The acid-modified chloroprene resin is obtained by graft copolymerizing the above chloroprene resin with at least one selected from α, β-unsaturated carboxylic acids and anhydrides thereof. Examples of α, β-unsaturated carboxylic acids and acid anhydrides thereof include those exemplified as modified products of resins having structural units derived from α-olefins having 2 to 20 carbon atoms.

Examples of the chloroprene resin and acid-modified chloroprene resin include Skyprene (registered trademark) GFL-820, GFL-890, GFL-280, LA-502, LA-660, SL-360, SL-390, and SL-590. And SL-590, G-42, G-40S, G-55, G-40S-1, G-40T, B-30S, Y-31 (Tosoh Corp.), Shopreen (registered trademark) W, AF, WHV, WXJ, WB, 115, 571, 572, 650, 671A, 750, SD78 and SD77 (Showa Denko), and Denkachloroprene (registered trademark) A-30, A-70, A-90, A- 91, M-130L, DCR-11, LA-50, and LC-501 (Electrochemical Industry Co., Ltd.).

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

Examples of the brominated butyl rubber include JSR BROMOBUTYL５５2255, 2244 (manufactured by JSR), Exxon bromobutyl 2255 (ExxonMobil Chemical).

Examples of the modified rubber include a chlorinated or brominated modified copolymer of a copolymer of isomonoolefin and paramethylstyrene, and a commercially available product is Expro 50 (manufactured by Exxon).

Examples of the styrene block copolymer include a block copolymer composed of a diene block and a styrene block. Specifically, styrene-butadiene block copolymer (SB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), or hydrogenation of these block copolymers Styrene / isobutylene-styrene triblock copolymer (SIBS), and styrene-isobutylene diblock copolymer (SIB). Such a hydrogenated product 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 include water-soluble resins such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, and hydroxyethyl cellulose in order to further improve the stability of the aqueous emulsion.

Further, as other resins, an adhesive resin or a resin having a function as a tackifier may be contained. Examples of such resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and hydrogenated resins thereof. Examples thereof include resins, other petroleum resins, coumarone resins, and indene resins. Specifically, rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin and their glycerin ester, pentaerythritol ester, methyl ester, triethylene glycol ester, phenol modified product and ester thereof Rosins such as fluorides; terpene polymers, terpene phenols, β-pinene polymers, aromatic modified terpene polymers, α-pinene polymers, terpene hydrogenated resins, and other terpene resins; C5 petroleum fractions Petroleum resins obtained by polymerizing petroleum resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and hydrogenated resins thereof; petroleum resins such as maleic acid modified products and fumaric acid modified products, chlorinated paraffins, etc. .

Examples of terpene resins include Yasuhara Chemical Co., Ltd .: YS Resin PX / PXN, YS Polyster, Mighty Ace, and YS Resin TO / TR and Clearon P / M / K, Arakawa Chemical Industries, Ltd .: Tamanol 803L / 901, and Nippon Terpene Chemical Co., Ltd .: Teltac 80 etc. are mentioned.

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 Corp.), and the like. It is done.

Other resin may be individual and may be contained in combination of 2 or more type.
Other resins can be easily obtained from the market.

In the case where the aqueous emulsion of the present invention contains other resins, the content thereof is a total of 100 parts by mass of the polymer (B) containing halogen atoms and the compound (D) having a polymerizable group. Preferably it is 100 mass parts or less with respect to a mass part, More preferably, it is 50 mass parts or less, More preferably, it is 30 mass parts or less, More preferably, it is 20 mass parts or less. Other resins may be mixed with the aqueous emulsion of the present invention in the form of an emulsion, or may be emulsified with a polymer (B) containing a halogen atom and a compound (D) having a polymerizable group to form an aqueous emulsion. Good.

<Thickener>
Thickeners can be used to adjust the viscosity of the aqueous emulsion. As a thickener, Adecanol (registered trademark) 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), and SN thickener 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A-813, A-818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, and 4050 (San Nopco).

<Form of aqueous emulsion>
In the aqueous emulsion of the present invention, the polymer (B) containing a halogen atom and the compound (D) having a polymerizable group are preferably contained as a mixture. A mixture is a state in which a polymer containing a halogen atom and a compound having a polymerizable group are mixed, and a polymer (B) containing a halogen atom is dispersed or swollen in a compound (D) having a polymerizable group. A state in which at least a part of the polymer (B) containing a halogen atom is dissolved in a compound having a polymerizable group.

That at least a part of the polymer (B) containing a halogen atom is dissolved in the compound having a polymerizable group means that a mixture of the polymer (B) containing a halogen atom and a compound having a polymerizable group is used. When filtering with a filter having a pore size of about 0.5 μm, the filtrate may contain at least a part of the polymer (B) containing a halogen atom. The polymer (B) containing a halogen atom contained in the filtrate is preferably 1% by mass or more, more preferably 100 parts by mass of the polymer (B) containing a halogen atom contained in the aqueous emulsion before filtration. Is 10% by mass or more, more preferably 30% by mass or more, and still more preferably 70% by mass or more.
Filtration with a filter is preferably performed 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.

As a method of using a polymer (B) containing a halogen atom and a compound (D) having a polymerizable group as a mixture, a polymer (B) containing a halogen atom and a compound (D) having a polymerizable group can be used. And the like are mixed 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, and a homomixer.

The mixture of the polymer (B) containing a halogen atom and the compound (D) having a polymerizable group is preferably contained as a dispersoid. Here, dispersoid means particles dispersed in water. In this case, the dispersoid may be a solid at 23 ° C. and atmospheric pressure, but is preferably a liquid.
The dispersoid is liquid as long as at least one of the components constituting the dispersoid has 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. Preferably, the dispersoid is preferably a liquid at 23 ° C. and atmospheric pressure.
The total content of the mass part of the polymer (B) containing a halogen atom and the mass part of the compound having a polymerizable group is a polymer (B) containing a halogen atom, a compound having a polymerizable group, and water. Is preferably from 0.1 to 70% by mass, more preferably from 1 to 70% by mass, and even more preferably from 2% to 60% by mass. Adhesiveness becomes favorable by setting it as the said range. 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 still 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. ~ 1 μm. When it is within the above range, the stationary stability is good.

The volume-based median diameter is a particle diameter corresponding to a cumulative particle diameter distribution value 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 with a laser diffraction particle size measuring device LA-950V2 manufactured by HORIBA Corporation.

<Method for producing aqueous emulsion>
The aqueous emulsion of the present invention can be produced by a known method. For example, a post-emulsification method (for example, forced emulsification method, self-emulsification method, phase inversion emulsification method) in which a polymer (B) containing a halogen atom and a compound (D) having a polymerizable group are dispersed in a dispersion medium such as water. Etc.).

For example, a polymer (B) containing a halogen atom and a compound (D) having a polymerizable group are added to a reactor (optionally an additive may be added), and after mixing, water and / or Alternatively, a method of emulsifying by adding a solvent and optionally adding additives such as a surfactant and a photopolymerization initiator and then stirring with heating can be mentioned.

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

The mixing temperature and the heating and 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, and a homomixer in addition to the above-described stirrer.

For example, additives such as a photopolymerization initiator, a crosslinking agent, an organic solvent, a basic compound, a thickener, and a leveling agent may be added before adding water and / or a solvent, and water and / or a solvent may be added. You may add after adding, and may add after emulsification. In particular, the light stabilizer, ultraviolet curable oligomer, fluorescent whitening agent, photosensitizer, 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 performing high-pressure shearing using an apparatus such as a high-pressure homogenizer or a high-pressure homojetter.

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

In the production of the aqueous emulsion, when a surfactant is used, the surfactant may be separated and removed from the obtained aqueous emulsion. Separation and removal of the surfactant can be performed by, for example, a centrifugal separator, a filtration filter having an average pore size 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.
Furthermore, it is preferable to cool the obtained aqueous emulsion. By cooling, an aqueous emulsion composed of a fine dispersoid can be obtained. It is preferable that the cooling be performed slowly, for example, by leaving it at room temperature instead of rapid cooling. Thereby, a fine and homogeneous aqueous emulsion can be obtained without aggregation of 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. Moreover, you may use as a composition for forming in a to-be-adhered body as a coating film or a coating film by an aqueous emulsion. A water-based adhesive, a coating film, a coating film, and the like are usually used as a dried product or a cured product. In particular, the water-based adhesive effectively exhibits its function in the form of a coating film formed from an aqueous emulsion or a cured product thereof.

<Adherent>
Wood, plywood, medium density fiberboard (MDF), particle board, fiber board, etc. as adherends (including the first base material and the second base material) to be coated, covered and adhered Cellulosic materials such as cotton cloth, cotton-containing fibers, linen and rayon; polyethylene (polyolefins mainly composed of structural units derived from ethylene), polypropylene (polyolefins composed mainly of structural units derived from propylene), Polyolefins such as polystyrene (polyolefins mainly composed of structural units derived from styrene), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), (meth) acrylic resin polyester, polyether, polyvinyl chloride, polyurethane , Urethane foam, ethylene-vinyl acetate copolymer (EV ), Plastic materials such as foamed EVA, nylon 6, nylon 66 and other polyamide-based resins or foams thereof; polyurethane-based, polyamide-based and polyamino acid-based synthetic leather; ceramic materials such as glass and ceramics; and iron, stainless steel, Examples thereof include metal materials such as 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 and the like and a plastic material.
Among them, adhesion between cellulosic materials and plastic materials, polyvinyl chloride, ethylene-vinyl acetate copolymers, cotton-containing fibers, nylon resins, olefin polymers, polyurethane, rubber, styrene butadiene rubber and other styrene block copolymers. It can be suitably used for adhesion of polymers and synthetic leather. Examples of the shape of these materials include various types such as a film, a sheet, or a block, and preferably a film and a sheet.
The styrenic block copolymer is a block copolymer comprising a diene block and a styrene block, and specifically includes a styrene-butadiene block copolymer (SB) and a styrene-butadiene-styrene block copolymer. (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-butylene-styrene copolymer (SBBS) or hydrogenated products of these block copolymers, styrene / isobutylene-styrene triblock copolymer Examples thereof include a combination (SIBS) and a styrene-isobutylene diblock copolymer (SIB). Such a hydrogenated product 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.

The olefin 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. As an olefin polymer, what was illustrated by said other resin is mentioned.
Examples of the resin constituting the adherend include those exemplified above for the other resins.

The cotton-containing fibers may be 100% cotton fibers, or may be blended fibers of cotton and other natural fibers and / or chemical fibers. Other natural fibers include wool, silk and hemp. 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.) Cellulosic fibers) and inorganic fibers (carbon fibers, glass fibers) and the like.
Examples of the shape of the cotton-containing fiber include woven fabric, knitted fabric, nonwoven fabric, knitted fabric, felt, film, and block shape.

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

As the rubber, for example, natural rubber, thermoplastic rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber and the like are mainly used. In preparing the rubber composition, these diene rubbers may be used alone or in combination of two or more. If necessary, reinforcing agents such as clay, carbon black or silica, silane coupling agents, anti-aging agents, softeners, zinc white, stearic acid, vulcanization accelerators, vulcanizing agents, sulfur, etc. are appropriately blended. May be.

Synthetic leather includes both synthetic leather and artificial leather in the narrow sense. In other words, it may be a synthetic leather obtained by applying a synthetic resin to a natural or synthetic fabric, or may be an artificial leather obtained by impregnating a synthetic resin into a fabric (usually a nonwoven fabric) such as a microfiber, such as a microfiber. Artificial leather obtained by impregnating a fabric (usually a nonwoven fabric) with a synthetic resin and further applying the synthetic resin may be used. Examples of these synthetic resins include polyurethane resins, polyamide resins, and polyamino acid resins. A polyurethane resin is preferable.

The aqueous emulsion of the present invention is effective for bonding materials (hereinafter sometimes referred to as adherends) such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes. Can be used for In particular, to bond construction materials (adherents) such as underwear, 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. The surface of these adherends may be smooth or may have irregularities. Moreover, you may give the primer process for improving adhesion | attachment, such as an adhesive agent, to those surfaces. 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, anchor layer formation, and the like.

<Application method>
As a method for adhering the adherend, the adherend (first substrate) and a coating film obtained by drying the aqueous emulsion of the present invention, an adhesive layer, and an adherend (second substrate) are used. ) In this order. Specifically, the following methods are mentioned.

First, an aqueous emulsion is applied to the surface of the first substrate, optionally the second substrate. In addition, any application | coating method can be utilized for application | coating of the aqueous emulsion to the surface of a 1st base material and a 2nd base material. The coating film is applied by a method 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, brushing and spatula coating. It can be formed by applying an adhesive to one or both surfaces of the body.

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

In the case of performing drying or heat treatment, the coating film can be formed by removing water or solvent by drying or heat treatment.
An example of the heating temperature is about 30 to 150 ° 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 substrate may be further treated by leaving (natural drying) or using a normal hot air circulation oven, an infrared heater, electromagnetic waves such as ultraviolet rays, and the like. In this case, the heating temperature and time in the preliminary drying can be appropriately adjusted according to the characteristics of the substrate, the composition of the aqueous emulsion to be used, and the like. For example, the same conditions as mentioned above can be mentioned.

Application and drying of the aqueous emulsion may be performed only once or may be performed twice or more. As the coating method and the drying method, the same method may be combined, or different methods may be combined.

In the case of electromagnetic wave treatment, examples of the light source include a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, an arc lamp, and a laser. Preferably, a metal halide lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, and a low pressure mercury lamp are mentioned. Irradiation dose is usually ^{5mW / cm 2 ~ 2000mW / cm} 2 as a peak irradiance, preferably ^{10mW / cm 2 ~ 2000mW / cm} 2, integrated irradiation amount is usually 20 ~ 3000mJ / cm ^2, preferably 100 ˜2500 mJ / cm ² .

Before applying the aqueous emulsion to the adherend, the surface of the first substrate may be subjected to a primer treatment. 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 water contained in the aqueous emulsion is removed. Adhesiveness is securable by setting it as this range.

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

Next, an adhesive is applied to at least one of the first substrate and the second substrate to which the aqueous emulsion is applied, and is heat-dried. These application and heat drying treatments may be performed only once on at least one of the first base material and the second base material, but one or more times of application and heat drying of the adhesive may be performed on both.
The adhesive application method, application thickness, heat treatment method, temperature, time, and other conditions can be changed as appropriate. The same conditions as the application and drying of the aqueous emulsion described above may be selected, or different conditions may be selected.

When applying the adhesive to both the first substrate and the second substrate, the adhesive layer may not be the same adhesive for the first substrate and the second substrate, Considering the adhesiveness of both, it is preferable to use the same adhesive. The water-based emulsion used above may be sufficient as an adhesive agent, and a commercially available adhesive agent may be sufficient as it.
The thickness of the adhesive layer can be appropriately adjusted depending on the composition of the adhesive used, the material and form of the substrate, and the like. For example, the thickness after drying is about 0.01 to 300 μm, preferably about 0.01 to 200 μm.

Before applying the aqueous emulsion to the adherend, the surface of the second substrate may be subjected to a primer treatment. The primer treatment can be appropriately selected from the above.

As a method of bonding the surfaces of the first substrate and the second substrate to which the aqueous emulsion and / or adhesive is applied, either a mechanical operation or a manual method may be used.
When bonding, heat, pressure or both may be applied. In the case of applying heat, it is necessary to set the temperature range in which the first base material, the second base material, and the adhesive layer do not deteriorate, preferably about 120 ° C. or less, more preferably about 100 ° C. or less. It is. The heat load may be performed using the above-described normal hot air circulation type oven, infrared heater, microwave oven, or the like. As a pressure in the case of applying a pressure, about 100 g / cm < ² > or more is mentioned, and less than the pressure which the shape of a 1st base material and a 2nd base material deform | transforms. In the case of applying heat and / or pressure, the time is, for example, about 1 second to 10 days.

Examples of the first base material and the second base material are the same as the adherend described above. Among them, the first base material is preferably an equipment made of an olefin polymer or an ethylene / vinyl acetate copolymer, and the second base material is polyvinyl chloride, synthetic leather, rubber, cotton-containing fiber, and polyolefin base. A substrate selected from the group consisting of polymers is preferred.

The adhesive layer can be obtained, for example, by removing water, solvent, etc. from polyurethane, rubber adhesive, acrylic adhesive, epoxy adhesive, etc. by performing heat drying, electromagnetic wave treatment, or the like.

Examples of the polyurethane include the same ones as described above.
Examples of rubber adhesives 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 copolymer. Examples thereof include polymer rubber (SBS), butadiene-acrylonitrile copolymer rubber (NBR), and butadiene rubber (BR). These may be used alone or in combination of two or more. 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.

Preferred examples of the acrylic adhesive include a copolymer of an acrylic ester and / or a methacrylic ester as an adhesive component, a functional group monomer component copolymerizable therewith, and an aggregating component. This copolymer may be crosslinked with an isocyanate crosslinking agent, a chelate crosslinking agent, an epoxy crosslinking agent, or the like.
Examples of acrylic esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, Preferred examples include n-octyl acrylate and n-lauryl acrylate. Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, Preferred examples include n-octyl methacrylate and n-lauryl methacrylate.

Examples of the functional group monomer component copolymerizable 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 Acrylic acid or hydroxyalkyl ester of methacrylic acid such as hydroxyethyl acid, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-butoxy N-substituted or unsubstituted acrylamide such as methyl acrylamide and N-butoxy methacrylamide; glycidyl ester of acrylic acid or methacrylic acid such as glycidyl methacrylate and glycidyl methacrylate; Preferable examples include acrylonitrile.

The epoxy adhesive is a compound having an average of one or more epoxy groups per molecule used as a component of a normal 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, hydrogenated bisphenol A and epichlorohydrin, and the like. In addition, oxazolidone-modified epoxy resins, novolac type epoxy resins, polyfunctional phenol type epoxy resins, various halogenated epoxy resins, glycidyl ester type epoxy resins, polyglycol type epoxy resins, cycloaliphatic epoxy resins, and the like can also be used. . These epoxy resins can be used alone or in admixture of two or more.

Polyurethane, rubber adhesives, acrylic adhesives, and epoxy adhesives may be in the form of adhesives such as water-based, solvent-based, and hot melt.

The adhesive which comprises an adhesive bond layer may contain resin other than the adhesive agent mentioned above, and an additive.
Examples of the resin that may be contained in the adhesive layer include polyolefin resin, polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE), Examples include various 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.
Moreover, you may use resin which exhibits the function as an adhesive resin or a tackifier.
Examples of such resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and Examples thereof include hydrogenated resins, other petroleum resins, coumarone resins, indene 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, crosslinking agents, Photosensitizers, other resins, phenolic stabilizers, phosphite stabilizers, amine stabilizers, amide stabilizers, anti-aging agents, weathering stabilizers, preservatives, antisettling agents, antioxidants, heat Stabilizer, thixotropic agent, thickener, antifoaming agent, viscosity modifier, weathering agent, pigment dispersant, antistatic agent, lubricant, nucleating agent, flame retardant, oil agent, dye, curing agent; titanium oxide (rutile type) ) And transition metal compounds such as zinc oxide; pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers, wollastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, kaolin, fine End silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, inorganic or organic fillers such as alumina and Celite, and the like.

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 was measured with a rotary rheometer using a cone plate (angle 2 °) with a shear rate of 1 s-1 and a measurement temperature of 25 ° C. (when 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 dry product of the aqueous emulsion preferably excludes 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. Unless otherwise indicated, the part and% in an example mean a mass reference | standard.
The halogen atom content of the polymer containing a halogen atom and the compound having a polymerizable group is a value measured by a flask combustion-ion chromatography method.
The component concentration of the aqueous emulsion is such that the polymer containing a halogen atom and the compound having a polymerizable group have a total content of the mass part of the polymer containing a halogen atom and the mass part of the compound having a polymerizable group. It is the value which calculated the mass concentration (mass%) with respect to the mass which added water.
The median diameter of the dispersoid is a value measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA Corporation. Unless otherwise specified, it is a median diameter value (unit: μm) measured on a volume basis.

The standing stability was evaluated by allowing the obtained aqueous emulsion to stand at room temperature for 3 weeks and observing the aqueous emulsion. When phase separation was not visually confirmed in the aqueous emulsion, it was judged that the standing stability was good.
○: No change ×: Phase separation was confirmed visually

Polymers containing halogen atoms, compounds having polymerizable groups, photopolymerization initiators, surfactants, ultraviolet curable oligomers, fluorescent brighteners and organic solvents in Production Examples and Evaluation Examples are as follows.
Polymer 1 containing halogen atom 1: Chlorinated rubber (Product name: Pergut S20 (Bayer, chlorine content 58.8% by mass or more))
Polymer 2 containing halogen atom: Chlorinated rubber (Product name: Pergut S40 (Bayer, chlorine content of 65.5% by mass or more))
Polymer 3 containing halogen atom: Polyvinyl chloride (Product name: low molcular weight (Aldrich))
Polymer 4 containing halogen atom: Chlorinated polyolefin resin (Product name: Hardren HM-21P, manufactured by Toyobo Co., Ltd., chlorine content 21 mass%)
Polymer 5 containing halogen atom: Chlorinated polyolefin resin (product name: HARDREN F-6P, manufactured by Toyobo Co., Ltd., chlorine content 20 mass%)
Polymer 6 containing halogen atom: Chloroprene resin (Product name: Shoprene W, Showa Denko KK, chlorine content 37.8% by mass, aqueous emulsion)
Polymer 7 containing halogen atom: Solution of chloroprene resin (Product name: No-Tape NP9820, No-Tape Kogyo Co., Ltd.)

Compound 1 having polymerizable group: dodecyl methacrylate (containing 970 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd., reagent grade)
Compound having a polymerizable group 2: 1,6-hexanediol dimethacrylate (containing 4-ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd., reagent grade)
Compound 3 having a polymerizable group: stearyl methacrylate (containing 200 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound 4 having a polymerizable group: 2-ethylhexyl methacrylate (containing 25 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound 5 having a polymerizable group: cyclohexyl methacrylate (containing 50 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound 6 having a polymerizable group: Ethoxylated isocyanuric acid triacrylate (Product name: A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Compound 7 having a polymerizable group: diacetone acrylamide (containing 100 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound 8 having a polymerizable group: Neopentyl glycol diglycidyl ether (Tokyo Chemical Industry Co., Ltd.)

Reactive 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 (manufactured by Kuraray Co., Ltd.)
Surfactant 6: Kuraray Poval 205 (manufactured by Kuraray Co., Ltd.)
Surfactant 7: Adeka Pluronic F108 (manufactured by ADEKA)
Surfactant 8: Kuraray Poval M-205 (manufactured by Kuraray Co., Ltd.)
Surfactant 9: Kuraray Poval MP-203 (manufactured by Kuraray Co., Ltd.)
Surfactant 10: Kuraray Poval KL-318 (manufactured by Kuraray Co., Ltd.)
Surfactant 11: Kuraray Poval CM318 (manufactured by Kuraray Co., Ltd.)
Surfactant 12: Pitzkor K-30 (Daiichi Kogyo Seiyaku Co., Ltd.)
Surfactant 13: Sun artist H-PN (manufactured by Saneigen FFI Co., Ltd.)
Surfactant 14: Aquarim AKM-053 (manufactured by NOF Corporation)
Reactive surfactant 15: Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.)
Reactive surfactant 16: Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.)

Photopolymerization initiator 1: 2-hydroxy-2-methylpropiophenone (Tokyo Chemical Industry Co., Ltd.)
Photopolymerization initiator 2: 1-hydroxy-cyclohexyl phenyl 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.)

Leveling agent 1: BYK-349 (Big Chemie Japan)
Basic compound 1: N, N-dimethylethanolamine (Tokyo Chemical Industry Co., Ltd.)
UV curable oligomer 1: AH-600 (Kyoeisha Chemical Company)
UV curable oligomer 2: UA-306H (Kyoeisha Chemical Co., Ltd.)
Optical brightener: 1,4-bis (2-benzoxazolyl) naphthalene (Tokyo Chemical Industry Co., Ltd.)
In each table, these components are expressed in parts by mass.

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

<Production Examples 2 to 27>
As shown in the following Table 1-1 and Table 1-2, aqueous emulsions (E-2) to (E-27) were obtained in the same manner as in Production Example 1, except that the mixing ratio of each component was different.

<Production Example 28>
In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of polymer 4 containing a halogen atom (Hardylene HN-21P (Toyobo Co., Ltd.)), a compound having a polymerizable group, polymerizable 90 parts of compound 4 having a group (2-ethylhexyl methacrylate (Tokyo Kasei Kogyo Co., Ltd.)) is added, 50 parts of tetrahydrofuran (Hayashi Junyaku, reagent grade) is added, and the mixture is stirred and dissolved at 60 ° C., and cooled to room temperature. Then, a tetrahydrofuran solution of the polymer component 4 and the compound 4 having a polymerizable group was prepared.
In addition, 3 parts of reactive surfactant 15 (AQUALON HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.)) is placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. An exchange aqueous solution was prepared.
At room temperature, an ion exchange aqueous solution of the reactive surfactant 15 is added to a tetrahydrofuran solution of the polymer 4 containing a halogen atom and the compound 4 having a polymerizable group, and further, the basic compound 1 (N, N— 2 parts of dimethylethanolamine (Tokyo Kasei Kogyo Co., Ltd.) was added and stirred, and then mixed with TK Robotics (manufactured by PRIMIX) with a stirrer homomixer MARKII and stirred at 16000 rpm for 2 minutes to give a milky white An aqueous emulsion was obtained. 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-28). The obtained aqueous emulsion (E-28) had a nonvolatile content concentration of 50%. Each added component is listed in Table 1-3.

<Production Examples 29 to 44>
As shown in Table 1-3 below, aqueous emulsions (E-29) to (E-44) were obtained in the same manner as in Production Example 28 except that the mixing ratio of each component was different.

<Production Examples 45 to 47>
As shown in Table 1-4 below, aqueous emulsions (E-45) to (E-47) were obtained in the same manner as in Production Example 1, except that the mixing ratio of each component was different.

<Production Examples 48 to 49>
As shown in Table 1-5 below, aqueous emulsions (E-48) to (E-49) were obtained in the same manner as in Production Example 1 except that the mixing ratio of each component was different.

<Production Example 50>
Polyurethane emulsion (Disquacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.), Isocyanate (Desmodur (registered trademark) N3300, Sumika Bayer Urethane Co., Ltd.), Leveling agent 1 (BYK (registered trademark)) ) -349, Big Chemie Japan Co., Ltd.) was mixed at a nonvolatile content ratio of 100 parts: 5 parts: 1 part to obtain an aqueous emulsion (E200).

<Production Examples 51 to 99>
Aqueous emulsions (E-1) to (E-49), photopolymerization initiator 1, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan), ion exchange, in parts by mass shown in Table 2-1. Water was added and the mixture was stirred with a three-one motor to obtain aqueous adhesives (F1) to (F49) containing the aqueous emulsion obtained in the production example.
Hereinafter, as an embodiment of the aqueous emulsion of the present invention, a form further containing an additive more suitable as an adhesive is referred to as an “aqueous adhesive”.

<Evaluation Examples 1 to 49>
Apply the water-based adhesives (F1 to F49) prepared in Production Examples 51 to 99 to M-EVA (ethylene-vinyl acetate copolymer foam), which is the first substrate, using a brush. Amount: about 3 g / m ² after drying), dried at 150 ° C. for 5 minutes, and irradiated with ultraviolet rays by a conveyor-type UV irradiation device (eye graphics ECS-4011GX, manufactured by Eye Graphics Co., Ltd.). (A) was obtained. (Lamp: high pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 276 m / min, integrated light quantity: 1100 mJ / cm ² (UV integrated light meter UVICURE PLUS II, UV-A measurement value, FusionUV Systems Japan) KK)
Subsequently, the aqueous emulsion (E200) to the soft polyvinyl chloride and M-EVA (A), was applied using a brush (coating amount: weight after drying about ^{50 g} / m 2), oven dried 5 minutes at 120 ° C. did. Thereafter, the coated surfaces of the obtained soft polyvinyl chloride and M-EVA (A) of the aqueous emulsion (E200) were bonded to each other, pressed by hand, and further pressed by a press at 3 MPa for 20 seconds. Thus, laminates 1 to 49 were obtained in which an adhesive layer made of soft polyvinyl chloride and E200, an adhesive layer irradiated with ultraviolet rays, and a first substrate (M-EVA) were laminated in this order.

The obtained laminate was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corp., Autograph), the peel rate was 50 mm / min, the peel angle was 180 degrees, and the room temperature was The adhesion between M-EVA and soft polyvinyl chloride was evaluated by measuring peel strength. The results are shown in Table 3-1.
○: Peel strength 55 N / inch or more.
X: Peel strength less than 55 N / inch.

<Evaluation Examples 50 to 52>
In Evaluation Example 1, “M-EVA (ethylene-vinyl acetate copolymer foam)” used as the first base material is shown in the column “First base material” in Table 3-2 below. Laminated bodies 50 to 52 were obtained in the same manner as in Evaluation Example 1 except that the difference was changed to.

The obtained laminate was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corp., Autograph), the peel rate was 50 mm / min, the peel angle was 180 degrees, and the room temperature was The adhesion between the first substrate and soft polyvinyl chloride was evaluated by measuring peel strength. The results are shown in Table 3-2.
○: Peel strength 55 N / inch or more.
X: Peel strength less than 55 N / inch.

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

Laminated bodies 1 to 44 produced using the water-based adhesives F1 to F44 generally exhibited sufficiently high peel strength of 55 N / inch or more. In addition, the laminates 51 to 53 produced by changing the first substrate of the laminate 1 like the materials of the evaluation examples 51 to 53 have a sufficiently high peel strength of 55 N / inch or more, like the laminate 1. Indicated.

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

Claims

An aqueous emulsion comprising a reactive surfactant (A) represented by the following formula (I), a polymer (B) containing a halogen atom, and water (C).

[In the formula (I),
R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carboxyl group,
R 2 represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 30 carbon atoms, or a polyalkylene oxide group and a combination thereof, and the methylene group contained in the alkylene group is an oxygen atom or a carbonyl group. May be replaced,
The polyalkylene oxide group contains 1 to 30 alkylene oxide units having 1 to 8 carbon atoms;
R 3 represents a hydrogen atom or a methyl group,
Z represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or —SO 3 M (M is a hydrogen atom, NH 4 or an alkali metal);
n represents an integer of 0 to 30. ]
The aqueous emulsion according to claim 1, wherein the reactive surfactant (A) is a surfactant represented by the following formula (II).

[In the formula (II),
R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carboxyl group,
R 3 represents a hydrogen atom or a methyl group,
R 4 represents a single bond or an alkylene group having 1 to 4 carbon atoms,
X represents a carbonyloxy group or an oxycarbonyl group,
R 5 represents a linear or branched alkylene group having 1 to 12 carbon atoms, and the methylene group contained in the alkylene group may be replaced with an oxygen atom or a carbonyl group.
Z represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or —SO 3 M (M is a hydrogen atom, NH 4 or an alkali metal). ]
Furthermore, the aqueous emulsion of Claim 1 or 2 containing the compound (D) which has a polymeric group.
The aqueous emulsion according to claim 3, wherein the content of the compound (D) having a polymerizable group is from 50 to 10,000 parts by mass with respect to 100 parts by mass of the polymer (B) containing a halogen atom.
The aqueous emulsion according to claim 3 or 4, comprising a mixture of a polymer (B) containing a halogen atom and a compound (D) having a polymerizable group as a dispersoid.
The aqueous emulsion according to claim 5, wherein the dispersoid is a liquid.
The aqueous emulsion according to claim 5 or 6, wherein at least a part of the polymer (B) containing a halogen atom is dissolved in the dispersoid.
The aqueous emulsion according to any one of claims 3 to 7, comprising a solution in which at least a part of the polymer (B) containing a halogen atom is dissolved in the compound (D) having a polymerizable group as a dispersoid.
The aqueous emulsion according to any one of claims 3 to 8, wherein the compound (D) having a polymerizable group is a liquid at 23 ° C under atmospheric pressure.
The aqueous emulsion according to any one of claims 3 to 9, wherein the compound (D) having a polymerizable group is a compound having an ethylenically unsaturated double bond.
The aqueous emulsion according to any one of claims 1 to 10, further comprising a photopolymerization initiator.
The aqueous emulsion according to any one of claims 1 to 11, further comprising a light stabilizer.
The aqueous emulsion according to any one of claims 1 to 12, further comprising an ultraviolet curable oligomer.
The aqueous emulsion according to any one of claims 1 to 13, further comprising an optical brightener.
The aqueous emulsion according to any one of claims 1 to 14, further comprising a leveling agent.
The aqueous emulsion according to any one of claims 5 to 15, wherein the volume-based median diameter of the dispersoid is 2 µm or less.
The total amount of the polymer (B) containing a halogen atom and the mass part of the compound (D) having a polymerizable group is such that the polymer (B) containing a halogen atom and the compound having a polymerizable group (D ) And water (C), the aqueous emulsion according to any one of claims 3 to 16 in an amount of 0.1 to 70% by mass.
The aqueous emulsion according to any one of claims 1 to 17, wherein the polymer (B) containing a halogen atom comprises a halogenated rubber.
The aqueous emulsion according to any one of claims 1 to 17, wherein the polymer (B) containing a halogen atom comprises a chlorinated rubber.
A coating film formed from the aqueous emulsion according to any one of claims 1 to 19.
21. A cured product of the coating film according to claim 20.
A laminate obtained by laminating the cured product according to claim 21, one or more adhesive layers, and a second substrate in this order on a first substrate made of an olefin polymer. body.
A cured product according to claim 21, a further one or more adhesive layers, and a second substrate are laminated in this order on a first substrate made of an ethylene / vinyl acetate copolymer. Laminated body.
A method for forming a coating film, comprising coating the aqueous emulsion according to any one of claims 1 to 19 on a substrate and drying.
A coating film obtained by the method according to claim 24.