KR20170028310A - Aqueous emulsion, coating film, cured object, and laminate - Google Patents

Abstract

[식 (I) 중, X 는, 질소 원자, CH 또는 나프틸렌기, Y¹ 및 Y² 는, 각각 독립적으로 하이드록실기, -COOR¹, -OCOR², 2-피롤리돈-1-일기, 폴리알킬렌옥사이드 또는 -SO₃M_a (M_a 는 수소 원자, -NH₄ 또는 알칼리 금속) 를 나타내고, m 은 1 ∼ 4 의 정수, p 는, 40 ∼ 2000 의 정수, q 는 0 또는 p 와 q 의 합이 40 ∼ 2000 의 정수가 되는 양의 정수를 나타내며, r 은 0 ∼ 4 의 정수를 나타낸다]
고분자 중합체 : 크로스카르멜로스의 알칼리 금속염 등.There is provided an aqueous emulsion capable of adhering an adherend to an adherend with sufficient strength between adherends.
(A) comprising at least one member selected from the group consisting of a compound containing a structural unit represented by the following formula (I) and / or a polymer polymer, a polymer (B) containing a halogen atom, An aqueous emulsion comprising water (C).

X represents a nitrogen atom, a CH or a naphthylene group, Y ¹ and Y ² each independently represent a hydroxyl group, -COOR ¹ , -OCOR ² , 2-pyrrolidon-1-yl group , a polyalkylene oxide or _a -SO ₃ m denotes a (m is _a hydrogen atom, -NH ₄ or alkali metal), m is an integer of 1 ~ 4, p is an integer of 40 ~ 2000, q is 0 or p And q represents a positive integer which is an integer of 40 to 2000, and r represents an integer of 0 to 4]
Polymer polymers: alkali metal salts of croscarmellose and the like.

Description

AQUEOUS EMULSION, COATING FILM, CURED OBJECT, AND LAMINATE < RTI ID = 0.0 >

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

Patent Document 1 describes an aqueous emulsion comprising an acid-modified chlorinated polyolefin which can be used as an adhesive. However, such an aqueous emulsion can not adhere the adherend to the adherend with sufficient strength.

Japanese Patent Application Laid-Open No. 2007-31473

There is a demand for an aqueous emulsion capable of adhering an adherend with sufficient strength. In addition, it is required to further maintain the aqueous emulsion more stably.

The present invention includes the following inventions.

[1] The aqueous emulsion of the present invention comprises a polymeric surfactant (A) comprising at least one compound selected from the group consisting of a compound containing a structural unit represented by the following formula (I) and / or a polymer polymer, (B) containing an atom, and water (C).

[In the formula (I)

X is a nitrogen atom, CH or naphthylene group,

Y ¹ and Y ² each independently represents a hydroxyl group, -COOR ¹ , -OCOR ² , 2-pyrrolidon-1-yl group, polyalkylene oxide or -SO ₃ M _a (M _a represents a hydrogen atom, NH < ₄ > or an alkali metal,

R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkali metal, -NH ₄ or - (CH ₂ CH ₂ O-) _s -Z (s represents an integer of 1 to 100, An alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a glycidyl group having 3 to 10 carbon atoms, or -SO ₃ M _b (wherein M _b represents a hydrogen atom, -NH ₄ or an alkali metal) , ≪ / RTI >

The polyalkylene oxide preferably contains 1 to 30 alkylene oxide units having 1 to 8 carbon atoms,

R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

m represents an integer of 1 to 4,

p represents an integer of 40 to 2000,

q represents 0 or a positive integer such that the sum of p and q is an integer of 40 to 2000,

r represents an integer of 0 to 4]

Polymeric polymers: alkali metal salts of croscarmellose, alkaline earth metal salts of carboxymethylcellulose, alkali metal salts of carboxymethylcellulose, alkali metal salts of carboxymethylstarch, (methyl) styrene-maleic acid ester copolymers, polyoxyethylene polyoxypropylene block Polymers and polydiallyldimethylammonium chloride

[2] In the compound containing the structural unit represented by the formula (I), q is an integer 0, and is preferably a compound containing a structural unit represented by the following formula (I ').

[In the formula (I '),

m, X and Y ² have the same meanings as defined in formula (I)

[3] It is preferable that the structural unit represented by the formula (I) is a structural unit represented by the formula (II).

[In the formula (II)

p and q satisfy the relationship that p / (p + q) is 0.8 or more and 1 or less]

[4] A surfactant (D) represented by the following formula (III) is further preferable.

[In the formula (III)

R ⁴ represents an alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a polyalkylene oxide group, a (meth) acrylate group having a hydrocarbon group having 1 to 30 carbon atoms, and a combination thereof, And the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group,

The polyalkylene oxide group includes at least 1 and at most 30 alkylene oxide units having 1 to 8 carbon atoms,

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 represents a hydrogen atom, NH ₄ or an alkali metal)

n 'represents an integer of 1 to 40,

[5] The surfactant (D) is preferably a reactive surfactant represented by the following formula (IV).

[In the formula (IV)

R ⁵ 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 ⁶ represents a hydrogen atom or a methyl group,

R ⁷ 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 may be substituted with an oxygen atom or a carbonyl group And,

The polyalkylene oxide group includes at least 1 and at most 30 alkylene oxide units having 1 to 8 carbon atoms,

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;

[6] Further, it is preferable to contain a compound (E) having a polymerizable group.

[7] The content of the polymerizable group-containing compound (E) relative to 100 parts by mass of the polymer (B) containing a halogen atom is preferably 50 to 10000 parts by mass.

[8] It is preferable to include a mixture of a polymer (B) containing a halogen atom and a compound (E) having a polymerizable group as a dispersion.

[9] It is preferable that the dispersion medium is a liquid.

[10] It is preferable that at least a part of the polymer (B) containing a halogen atom is dissolved in the dispersoid.

[11] 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 (E) having a polymerizable group is contained as a dispersion.

[12] The compound (E) having a polymerizable group is preferably a liquid at 23 ° C under atmospheric pressure.

[13] The compound (E) having a polymerizable group is preferably a compound having an ethylenically unsaturated double bond.

[14] In addition, it preferably contains a photopolymerization initiator.

[15] Further, it is preferable to include a light stabilizer.

[16] In addition, it is preferable to include an ultraviolet-curable oligomer.

[17] Further, it is preferable to include a fluorescent whitening agent.

[18] In addition, it is preferable to include a leveling agent.

[19] It is preferable that the median diameter based on the volume of the dispersoid is 2 μm or less.

(B) a halogen atom-containing polymer (B) and a polymerizable group-containing compound (E), the total amount of the halogen atom-containing polymer (B) C) is preferably in the range of 0.1 mass% to 70 mass% with respect to the total mass.

[21] The halogen-containing polymer (B) is preferably a halogenated rubber.

[22] The polymer (B) containing a halogen atom is preferably composed of chlorinated rubber.

[23] A coating film formed of any one of the aqueous emulsions [1] to [22].

[24] A cured product of the coating film described in [23].

[25] A laminate obtained by laminating the cured product described in [24], the adhesive layer having one or more layers thereon, and the second substrate in this order on a first substrate made of an olefinic polymer.

[26] A laminate obtained by laminating a cured product according to [23], an adhesive layer having one or more layers thereon, and a second substrate in this order on a first substrate made of an ethylene / vinyl acetate copolymer.

[27] A method for forming a coating film, which comprises applying an aqueous emulsion of any one of [1] to [22] onto a substrate and drying.

[28] A coated film obtained by the method described in [27].

According to the aqueous emulsion of the present invention, it is possible to adhere the adherend to each adherend with sufficient strength. In addition, the aqueous emulsion can be maintained more stably.

The aqueous emulsion of the present invention comprises a polymeric surfactant (A) comprising at least one compound selected from the group consisting of a compound containing a structural unit represented by the following formula (I) and / or a polymer polymer, (B), and water (C).

[In the formula (I)

X is a nitrogen atom, CH or naphthylene group,

Y ¹ and Y ² each independently represents a hydroxyl group, -COOR ¹ , -OCOR ² , 2-pyrrolidon-1-yl group, polyalkylene oxide or -SO ₃ M _a (M _a represents a hydrogen atom, NH < ₄ > or an alkali metal,

R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkali metal, -NH ₄ or - (CH ₂ CH ₂ O-) _s -Z (s represents an integer of 1 to 100, An alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a glycidyl group having 3 to 10 carbon atoms, or -SO ₃ M _b (wherein M _b represents a hydrogen atom, -NH ₄ or an alkali metal) , ≪ / RTI >

The polyalkylene oxide preferably contains 1 to 30 alkylene oxide units having 1 to 8 carbon atoms,

R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

m represents an integer of 1 to 4,

p represents an integer of 40 to 2000,

q represents 0 or a positive integer such that the sum of p and q is an integer of 40 to 2000,

r represents an integer of 0 to 4]

Polymeric polymers: alkali metal salts of croscarmellose, alkaline earth metal salts of carboxymethylcellulose, alkali metal salts of carboxymethylcellulose, alkali metal salts of carboxymethylstarch, (methyl) styrene-maleic acid ester copolymers, polyoxyethylene polyoxypropylene block Polymers and polydiallyldimethylammonium chloride

The aqueous emulsion of the present invention preferably contains a surfactant (D), and more preferably contains a compound (E) having a polymerizable group. The aqueous emulsion of the present invention is useful as an aqueous adhesive.

≪ Polymeric Surfactant (A) >

The polymer surfactant (A) contained in the aqueous emulsion of the present invention contains at least one member selected from the group consisting of the compound containing the structural unit represented by the formula (I) and / or the polymer polymer. The content of the polymer surfactant (A) contained in the aqueous emulsion of the present invention is preferably 100 parts by mass based on the total of the mass of the polymer (B) containing a halogen atom and the mass of the polymer (E) Preferably 1 to 30 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 1 to 10 parts by mass.

The polymeric surfactant (A) represented by the formula (I) contained in the aqueous emulsion of the present invention is a compound containing a structural unit represented by the formula (I) wherein q is an integer 0, And a structural unit represented by the following formula (1).

[In the formula (I '),

m, X and Y ² have the same meanings as defined in formula (I)

The compound containing the structural unit represented by the above formula (I) may be either a synthetic polymer surfactant having a structural unit represented by the formula (I) or a natural polymer surfactant, which acts as an emulsifier in an aqueous emulsion.

The compound represented by the formula (I) may be any of a cationic, anionic, amphoteric and nonionic surfactant, preferably a cationic or nonionic surfactant, more preferably a cationic, It is a nonionic polymeric surfactant. These polymer surfactants may be used alone or in combination of two or more.

Examples of the alkyl group in the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec- Butyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

Examples of the aromatic hydrocarbon group in the formula (I) include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, A biphenyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group.

Examples of the glycidyl group in the formula (I) include 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, A glycidoxypropyl group, a 4-glycidoxybutyl group, and the like.

Examples of the cyclic alkyl group in the formula (I) include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group and isobornyl group, .

The polyalkylene oxide group in the formula (I) includes an alkylene oxide unit having 1 to 8 carbon atoms in an amount of 1 to 30 and includes, for example, polyethylene oxide, polypropylene oxide, polybutylene oxide, polyphenylene oxide And the like. In the present specification, a functional group composed of only one alkylene oxide unit is also referred to as a "polyalkylene oxide group" for convenience.

Examples of the (meth) acrylate group having a hydrocarbon group of 1 to 30 carbon atoms in the formula (I) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (Meth) acrylate, isobutyl (meth) acrylate, ethylhexyl (meth) acrylate, cyclohexyl mono (meth) acrylate and tricyclodecane.

Examples of the aryl group in the formula (I) include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumenyl group, , Biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group and the like.

Examples of the aralkyl group in the formula (I) include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.

Examples of the alkoxy group in formula (I) include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups. .

The structural unit represented by the formula (I) may be a structural unit represented by the formula (II).

[In the formula (II)

p and q have the same meanings as defined in formula (I)

In the formula (II), p and q are each independently preferably 5 or more and 800 or less, and more preferably 10 or more and 500 or less. Alternatively, it is preferable that q is 0 and p / (p + q) is 0.8 or more and 1 or less. Examples of the compound containing a structural unit represented by the formula (I) include those obtained by modifying the terminal thereof, for example, thiol-modified at the terminal and alkyl-modified at the terminal.

The structural unit represented by the formula (I) may be a structural unit represented by the following formula (I-a).

[In the formula (I-a)

Y 'represents a hydroxyl group, -COOR ¹ , -OCOR ² or 2-pyrrolidon-1-yl group,

R ¹ represents a group represented by a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkali metal, -NH ₄ or -SO ₃ M _b (wherein M _b represents a hydrogen atom, -NH ₄ or an alkali metal)

R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

p represents an integer of 40 to 2000, and a plurality of Y 's are the same or different from each other]

In the formula (Ia), Y 'is preferably -COOR ¹ , more preferably R ¹ is an alkali metal.

The structural unit represented by the formula (I) may be a structural unit represented by the following formula (I-c).

[In the formula (I-c), AO represents an alkylene oxide having 1 to 8 carbon atoms,

R _d represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group,

m2 represents an integer of 1 to 30, and p represents an integer of 40 to 2000)

In the formula (Ic), R _d is preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

The structural unit represented by the formula (I) includes a structural unit represented by the following formula (I-d) wherein m = 1 and X is a naphthylene group as a preferable structural unit.

[In the formula (Id), X 'represents a hydrogen atom, a hydroxyl group or -SO ₃ M _c (M _c represents a hydrogen atom, -NH ₄ or an alkali metal), and p represents an integer of 40 to 2000 ]

In the above formula (Id), it is preferable that X 'is -SO ₃ M _c (M _c represents NH ₄ or an alkali metal).

The structural unit represented by the formula (I) is more preferably a structural unit wherein r = 0, q = 1, m = 1, Y ¹ and Y ² have the same meanings as X ^{1 '} and X ^2' And a structural unit represented by the following formula (I-d ') wherein X is a naphthylene group.

X ^{1 '} and X ^2' each independently represent a hydrogen atom, a hydroxyl group or -SO ₃ M _c (M _c represents a hydrogen atom, -NH ₄ or an alkali metal) And p represents an integer of 40 to 2000,

In the above formula (I-d '), it is preferable that X' is -SO ₃ M _c (M _c represents NH ₄ or an alkali metal).

Examples of commercially available compounds containing the structural unit represented by the formula (I) include CHALOL AN-103P, CHALOL AN-144P, CHALOLOL AH-103P, DKS DISCOAT N-10, DSK DISCOAT N- 14, 40, Lavalin FP, Lavalin FM-P, Cellflow 120, Cellflow 120P, Discool N-509, Discool N-518, Pittschall K-17L, (KA-90) (manufactured by Dai-ichi Kogyo Seiyaku K.K.), Kuraray Poval PVA-103, Kuraray Poval PVA-105, Kuraray Poval PVA-117, Kuraray Poval PVA-217, Kuraray Poval PVA- PVA-403, Kuraray Poval PVA-417, Kuraray Poval 205, Kuraray Poval M-205, Kuraray Poval PVA-210, (Kura-Lea Co.), AKUMARIM AKM-1511-60, AKARA (KURARAYAPOVAL), KURAREA FOUPAL KL-318 Rim AKM-0531, Polyster OM, and Plowon # 102 (manufactured by Nichicon Corporation).

As these polymer surfactants, modified products such as polyvinyl alcohol and partial saponification represented by the formula (II) are preferable, and partial saponification is particularly preferable in view of the water resistance.

≪ Polymer Polymer &

Examples of the polymer polymer include alkali metal salts of croscarmellose, alkaline earth metal salts of carboxymethyl cellulose, alkali metal salts of carboxymethyl cellulose, alkali metal salts of carboxymethyl starch, styrene-maleic acid ester copolymer, polyoxyethylene polyoxypropylene block polymer And polydiallyldimethylammonium chloride. Examples of the alkali metal salt include a sodium salt and a potassium salt. Examples of the alkaline earth metal salt include a calcium salt.

Examples of natural polymer surfactants include cellulose derivatives such as casein, lecithin and hydroxyethyl cellulose, and starch and processed starch. These may be used alone or in combination of two or more. Among them, it is preferable to use carboxymethylcellulose sodium, polyoxyethylene polyoxypropylene block polymer or polydiallyldimethylammonium chloride as the high molecular polymer.

The (methyl) styrene-maleic acid ester copolymer means a methylstyrene-maleic acid ester copolymer or a styrene-maleic acid ester copolymer, and the styrene-maleic acid ester copolymer has a structure represented by the following formula (Ib) Unit. ≪ / RTI >

[Wherein R _b and R _c each independently represent a hydrogen atom, an alkali metal, NH ₄ or a hydrocarbon group of 1 to 18 carbon atoms, and the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group And,

m1 represents an integer of 1 to 30, and n represents an integer of 40 to 2000;

In the formula (Ib), that both of R _b and R _c of either is preferable that the NH _4, and R _b and R _c or may be NH _4. R _b and R _c are more preferably a hydrocarbon group having 3 to 12 carbon atoms, and more preferably a hydrocarbon group having 4 to 10 carbon atoms.

Examples of the high-molecular polymer represented by the formula (I-b) include DKS Discoat N-14 (Daiichi Kogyo Seiyaku Co., Ltd.), Arasta 700 and Arasta 703S (Arakawa Chemical Industries).

It is preferable that the polyoxyethylene polyoxypropylene block polymer includes a structural unit represented by the following formula (I-e).

[In the formula (I-e)

o ', p' and q 'each independently represents an integer of 2 to 2000, and the sum of o', p 'and q' is 20 to 4000. It is preferably an integer, more preferably an integer of 10 to 700.

Examples of the polymer polymer represented by formula (Ie) include adecafluronic F-108, adecafluronic P-103, adecafluronic F-88, adecafluronic F-68, L-61, adecafluronic L-64 and adecafluronic 17R-2 (manufactured by ADEKA).

≪ Halogen atom-containing polymer (B) >

The polymer (B) containing a halogen atom contained in the aqueous emulsion of the present invention preferably has a proportion of carbon atoms in the atoms constituting the main chain of 95% or more, more preferably 97% or more, It is preferably at least 99%. Examples of the polymer constituting the main chain of the polymer (B) include polyolefin, polyvinyl and polyacrylate.

Examples of the halogen-containing polymer (B) include halides of olefin polymers, halides of vinyl copolymers, halogenated rubbers and the like, preferably halogenated rubbers. As the halogen atom used for halogenation, chlorine and bromine are preferable, and chlorine is more preferable.

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

Examples of the? -Olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 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? -Olefin having 2 to 20 carbon atoms is a homopolymer polymerized from an? -Olefin having 2 to 20 carbon atoms, and examples thereof include polyethylene, polypropylene and polybutene.

Examples of the 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? -Olefin having 2 to 20 carbon atoms include an ethylene-unsaturated carboxylic acid copolymer such as an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer, an ethylene-unsaturated carboxylic acid copolymer An ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-isobutyl acrylate copolymer, an ethylene-acrylic acid n-methacrylate copolymer Unsaturated carboxylic acid ester copolymers such as ethylene-isobutyl-methacrylic acid copolymer, ethylene-n-butyl acrylate-methacrylic acid copolymer, ethylene-unsaturated carboxylic acid ester copolymers such as butyl acrylate, A polymeric acid copolymer and an ionomer in which some or all of its carboxyl groups are neutralized with the metal, Ethylene-vinyl ester copolymers such as tylene-vinyl acetate copolymer, and the like. Specifically, there may be mentioned α-olefin copolymers such as ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer and ethylene- A modified copolymer thereof, a copolymer with a copolymerizable monomer or 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 content of vinyl acetate. Such an ethylene-vinyl acetate copolymer also includes various vinyl acetate content and shape (film, block, fiber, foam). The ethylene-vinyl acetate copolymer may contain a polymer such as polyolefin. Preferred polyolefins include ethylene-octene copolymers, ethylene-butene copolymers, polypropylene and polyethylene.

Examples of the monomer copolymerizable with the -olefin include an unsaturated carboxylic acid, a salt of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, an amide of an unsaturated carboxylic acid, a 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 and itaconic anhydride, and lithium, sodium, Salts of monovalent metals such as sodium and potassium; salts of polyvalent metals such as magnesium, calcium and zinc; salts of polyvalent metals such as methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n- butyl acrylate, isooctyl acrylate, methyl methacrylate, Unsaturated carboxylic acid esters such as ethyl acetate, isobutyl methacrylate and dimethyl maleate, vinyl esters such as vinyl acetate and vinyl propionate, carbon monoxide, sulfur dioxide, and the like.

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

The halide of the olefinic polymer may be an acid-modified halogenated polyolefin. The acid-modified halogenated polyolefin is obtained by graft-copolymerizing at least one member selected from an?,? - unsaturated carboxylic acid and anhydride thereof in at least one member selected from polypropylene and a propylene-? -Olefin copolymer to obtain an acid-modified polyolefin And then halogenating the acid-modified polyolefin.

Here, the propylene-? -Olefin copolymer is a copolymer of propylene and an? -Olefin mainly composed of propylene. Examples of the? -olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene and 4-methyl- Of an alpha -olefin having 2 or 4 to 20 carbon atoms.

Examples of the?,? - unsaturated carboxylic acid and its acid anhydride include maleic acid, maleic anhydride, fumaric acid, citraconic anhydride, citraconic anhydride, mesaconic acid, itaconic anhydride, itaconic anhydride, Acid, anhydride anhydride, and the like. Of these, maleic anhydride and itaconic anhydride are preferable.

The content of the component derived from the?,? - unsaturated carboxylic acid and the acid anhydride in the acid-modified halogenated polyolefin is preferably 0.6 to 10% by mass. When the content is 10% by mass or less, the hydrophilicity of the acid-modified halogenated polyolefin is lowered, thereby improving the water resistance of the coating film obtained from the object composition. On the other hand, when the content is 0.6% by mass or more, the acid-modified halogenated polyolefin has a stable dispersibility in water and an aqueous emulsion can be easily produced.

The halogenation can be carried out, 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 halogenated rubber may be used, or two or more halogenated rubbers may be used in combination. Examples of the halogen atom used for halogenation include chlorine and bromine, and chlorine is preferable.

The halogenated rubber may or may not have a melting point, but preferably has a melting point. The melting point is preferably 100 占 폚 or higher, more preferably 200 占 폚 or higher, and still more preferably 240 占 폚 or higher. It is further preferably 350 DEG C or less, and more preferably 300 DEG C or less.

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

The halogenated rubber preferably has neither a carboxyl group nor a carboxylic acid anhydride structure. Thus, even when the aqueous emulsion of the present invention is used as an aqueous adhesive, the water resistance of the aqueous adhesive can be effectively prevented from being lowered, because the halogenated rubber is free of the carboxyl group or the carboxylic anhydride structure.

The halogenated rubber is not particularly limited as long as it is a halogenated natural rubber or synthetic rubber, and specific examples thereof include chlorinated natural rubber, brominated natural rubber, chlorinated butadiene rubber, brominated butadiene rubber, chlorinated butyl rubber, brominated butyl rubber, chlorinated isoprene rubber, Butadiene-styrene copolymer, isoprene rubber, butadiene / halogenated cyclic conjugated diene adduct, chlorinated butadiene styrene copolymer, poly (2,3-dichloro-1,3-butadiene) bromide and? -Haloacrylonitrile- 1,3-butadiene copolymer, and the like. 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. At the preparation of the halogenated rubber, these diene rubbers may be used alone or in combination of two or more. A reinforcing agent such as clay, carbon black or silica, a silane coupling agent, an anti-aging agent, a softening agent, zincation, stearic acid, a vulcanization accelerator, a vulcanizing agent, sulfur and the like may be appropriately added.

As a method of halogenating natural rubber or synthetic rubber, conventionally known methods can be employed. For example, a method of dissolving natural rubber or synthetic rubber in a chlorinated organic solvent such as carbon tetrachloride, monochlorobenzene, or an organic solvent such as toluene, and blowing a halogen gas; A method in which a halogen gas is blown in a state in which natural rubber or synthetic rubber is suspended or emulsified in water; A method of halogenating a natural rubber or a synthetic rubber by introducing a halogen gas while irradiating ultraviolet rays in a state of being suspended or emulsified in water; A method of directly halogenating natural rubber or synthetic rubber with a liquid halogen under a low temperature pressurization, and the like. Alternatively, the natural rubber or synthetic rubber obtained by solidifying the coagulated solid can be dissolved in an organic solvent and then halogenated. Alternatively, the natural rubber or synthetic rubber obtained by solidifying the coagulated solid can be dissolved in an organic solvent, emulsified and dispersed, and the solvent can be halogenated . When the natural rubber is halogenated, the natural rubber on the latex may be halogenated by blowing a halogen gas.

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

The halogenated rubber has a weight average molecular weight in terms of polystyrene of usually 1000 or more, preferably 3000 or more, more preferably 5000 or more, and even more preferably 10000 or more. It is usually 400000 or less, and preferably 200000 or less. The weight average molecular weight in terms of polystyrene can be measured by gel permeation chromatography (GPC).

When the water-based emulsion of the present invention is used in the water-based adhesive in such a range, a sufficient adhesive strength can be ensured and an excessive increase in viscosity can be suppressed and sufficient adhesion to an adherend can be ensured.

Among halogenated rubbers, chlorinated rubbers are preferred. As the chlorinated rubber, there are commercially available products and those produced according to any known method. Examples of commercially available products include Super Clone (registered trademark) CR-10, CR-20 (manufactured by Nippon Paper Industries Co., Ltd.), Pergut S-5, Pergut S-10, Pergut S-20, Pergut S- Gug S-90, Pergut S-130, Pergut S-170 (manufactured by Bayer Material Science), Alloprene (registered trademark) R10, R20, R40 (manufactured by ICI UK) and the like. As a known method, for example, the method described in Japanese Patent No. 2660478 can be mentioned.

&Lt; Water (C) &gt;

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 may be any amount that allows the dispersoid containing the polymer (B) containing a halogen atom and the compound (E) optionally having a polymerizable group to exist as a uniform dispersion medium .

&Lt; Surfactant (D) &gt;

The aqueous emulsion of the present invention preferably contains a surfactant (D) represented by the formula (III). The surfactant (D) is a compound which acts as an emulsifier. By containing such a surfactant (D), the total addition amount of the surfactant in the aqueous emulsion can be reduced, so that the water resistance can be suppressed and the adhesion strength can be suppressed.

[In the formula (III)

R ⁴ represents an alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a polyalkylene oxide group, a (meth) acrylate group having a hydrocarbon group having 1 to 30 carbon atoms, and a combination thereof, The methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group,

The polyalkylene oxide group includes at least 1 and at most 30 alkylene oxide units having 1 to 8 carbon atoms,

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 1 to 40,

The surfactant (D) may be any of cationic, anionic, amphoteric and nonionic surfactants as long as it contains the structural unit of the formula (III), preferably anionic and nonionic surfactants. Lt; / RTI &gt; surfactant. The surfactant may be used alone, or two or more surfactants may be used in combination.

The surfactant (D) is preferably a reactive surfactant represented by the following formula (IV).

In the formula (IV)

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁵ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, , A heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ⁵ include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, Mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group and the like.

Examples of the aralkyl group represented by R ⁵ include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.

As the alkylene group having 1 to 10 carbon atoms represented by R ⁷ , a divalent group corresponding to the group exemplified as the alkyl group for R ⁵ is exemplified.

Examples of the arylene group represented by R ⁷ include a phenylene group, a naphthylene group, an anthrylene group, a p-methylphenylene group, a p-tert-butylphenylene group, a p- , Mesitylene group, biphenylene group, phenanthrylene group, 2,6-diethylphenylene group, 2-methyl-6-ethylphenylene group and the like.

Examples of the alkyl group having 1 to 10 carbon atoms represented by Z 'include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, , A heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group and a decyl group.

Examples of the alkoxy group having 1 to 10 carbon atoms represented by Z 'include a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and decyloxy group.

The polyalkylene oxide group includes one or more alkylene oxide units having 1 to 8 carbon atoms, and includes, for example, polyethylene oxide, polypropylene oxide, polybutylene oxide, and polypentylene oxide. In the present specification, a functional group composed of only one alkylene oxide unit is also referred to as a "polyalkylene oxide group" for convenience.

The reactive surfactant may be any one of cationic, anionic, amphoteric and nonionic surfactants as long as it has the structure of the formula (IV), more preferably anionic or nonionic surfactant .

Examples of the reactive surfactant represented by formula (IV) include polyoxyethylene alkyl ether, sulfosuccinic acid ester salt of polyoxyethylene alkyl ether, sulfuric acid ester salt of polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, polyoxyethylene Sulfosuccinic acid ester salts of polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylphenyl ethers, sulfosuccinic acid ester salts of polyoxyethylene alkylphenyl ethers, poly Oxyethylene aralkylphenyl ether, polyoxyethylene aralkylphenyl ether sulfosuccinic acid ester salt, polyoxyethylene aralkylphenyl ether sulfuric acid ester salt, polyoxyethylene alkylphenyl ether phosphoric acid ester salt, polyoxyethylene alkylphenyl ether Aliphatic or aromatic carboxylic acid salts, acidic Acid (meth) acrylate ester emulsifiers, acid anhydride-modified products of rosin glycidyl ester acrylate, and the like. Further, it is also possible to substitute polyoxyethylene with polyoxypropylene or polyoxyethylene with polyoxypropylene by block copolymerization or random copolymerization.

Examples of commercially available products thereof include "SE-10N", "NE-10", "NE-20", "NE-30", "Adekariasoft SR- Aquaron RN-10, Aquaron RN-20, Aquaron RN-50, AquaRon RN-20 and Aquarion RN-50 were purchased from Asahi Chemical Industry Co., Latex K-180 "," Latex S-120 "and" Latex K-10 "(trade names, manufactured by Dai-ichi Kogyo Seiyaku Co., (Trade name, manufactured by Kao Corporation), "Anotox MS-180P", "Latex S-180A", "Latex PD-420", "Latex PD- Anthox LMA-20 "," Antox LMA-27 "," Anthox LMA-10 "," Antox LMA- EMR-20 "," Antox LMH-20 "," Antox SMH-20 ", Ereminol JS-20, Ereminol RS-3000, Mamolin OT-70 and Carbone EN- Manufactured by Yohsei Kogyo Co., Ltd.), and the like.

As these reactive surfactants, polyoxyethylene phenyl ether-based ones are preferable from the viewpoint of emulsification, and unsaturated sulfonic acid salts having a structure in which alkylene oxide is polymerized in 5 to 20 moles are particularly preferably used.

The formula (IV) is preferably a reactive surfactant represented by the following formula (V).

[In the formula (V)

R ⁵ 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 ⁶ represents a hydrogen atom or a methyl group,

R ⁸ represents a single bond or an alkylene group having 1 to 4 carbon atoms,

Xa represents a carbonyloxy group or an oxycarbonyl group,

R ⁹ represents a linear or branched alkylene group having 1 to 16 carbon atoms, the methylene group contained in the alkylene group may be substituted 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 the R ⁸ have unity sum, Xa is a carbonyl-oxy group is preferable, and R ⁹ is more preferably a straight chain alkyl group of 1 to 12 carbon atoms, with methylene group, an oxygen atom or a carbonyl group contained in these straight-chain alkyl groups And more preferably substituted.

When R ⁸ is an alkyl group having 1 to 4 carbon atoms, Xa is preferably an oxycarbonyl group, and R ⁹ is preferably a branched alkylene group having 1 to 16 carbon atoms, and the methylene group of the branched alkylene group may be an oxygen atom , A carbonyl group, or both groups thereof.

Among the above formula (IV), it is more preferable to be a reactive surfactant represented by the following formula (VI) or (VII).

[In the formula (VI), R ⁵ , R ⁶ and Z 'have the same meanings as defined for the formula (IV)

R ¹⁰ represents alkyl having 1 to 16 carbon atoms, and the methylene group contained in the alkyl group may be substituted with an oxygen atom or a carbonyl group]

[In the formula (VII), R ⁵ , R ⁶ and Z 'have the same meanings as defined for the formula (IV)

R ¹¹ represents a linear or branched alkylene group having 1 to 8 carbon atoms and the methylene group contained in the alkylene group may be substituted with an oxygen atom or a carbonyl group or both groups thereof)

In the formula (VI), it is preferable that R ¹⁰ contains an ester (-COO-) bond. R ¹¹ is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms.

The reactive surfactant represented by the formula (IV) may be represented by the following formula (VIII).

[In the formula (VIII), R ⁵ , R ⁶ and Z 'have the same meanings as defined in the formula (IV)

R ^8a represents an alkylene group having 1 to 8 carbon atoms or an arylene group having 6 to 30 carbon atoms, an alkylenedioxy group having 1 to 8 carbon atoms, an arylene dioxy group having 6 to 30 carbon atoms, or an OAr ¹ -alkylene group-OAr ² O ( Wherein Ar ¹ and Ar ² each independently represent an aryl group which may be substituted with an aliphatic hydrocarbon group,

The methylene group contained in the alkylene group may be substituted with an oxygen atom or a carbonyl group,

ma and na each independently represent an integer of 1 to 30;

The R ^8a is preferably an arylene group having 6 to 26 carbon atoms, more preferably a divalent arylene group containing 2 or more benzene rings.

The reactive surfactant represented by the formula (IV) may be represented by the following formula (IX).

[Wherein R ⁵ , R ⁶ and Z 'have the same meanings as defined in formula (IV), R ^10a represents a single bond or an alkyleneoxy group having 1 to 8 carbon atoms,

na and la each independently represent an integer of 1 to 30,

The reactive surfactant represented by the formula (IV) may be represented by the following formula (X).

[In the formula (X), R ⁵ , R ⁶ and Z 'have the same meanings as defined in the formula (IV)

R ^9a represents an alkyl group having 1 to 12 carbon atoms, the methylene group contained in the alkyl group may be substituted with an oxygen atom or a carbonyl group,

and na represents an integer of 1 to 30;

Specific examples of the surfactant represented by formula (IV) include polyoxyethylene alkyl ether, sulfosuccinic acid ester salt of polyoxyethylene alkyl ether, sulfuric acid ester salt of polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, Sulfosuccinic ester salts of polyoxyethylene phenyl ether, sulfuric acid ester salts of polyoxyethylene phenyl ether, polyoxyethylene alkyl phenyl ether, sulfosuccinic acid ester salts of polyoxyethylene alkyl phenyl ether, sulfuric acid ester salts of polyoxyethylene alkylphenyl ether , Polyoxyethylene aralkylphenyl ether, sulfosuccinic acid ester salt of polyoxyethylene aralkylphenyl ether, sulfuric acid ester salt of polyoxyethylene aralkylphenyl ether, phosphoric acid ester salt of polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl Aliphatic or aromatic carboxylic acid salts of phenyl ethers, acidic (Meth) acrylic acid ester, such as the various types of emulsifiers, rosin glycidyl ester acid anhydride modified product of the acrylate. Further, it is also possible to substitute polyoxyethylene with polyoxypropylene or polyoxyethylene with polyoxypropylene by block copolymerization or random copolymerization.

These products include, for example, SE-10N, NE-10, NE-20, NE-30, Adekariasoft SR-10, Adekariasoft SR- Aquaron RN-10, Aquaron RN-20, Aquaron RN-50, and Aquaron HS (trade name, product of Asahi Kasei Kogyo Co., Ltd.) (Trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), "Lateum K-180", "Latex PD-104", "Latex S , "Latte water PD-420", "Latte water PD-450", "Latte water E-1000A", "Latte water S-180A" Anthox MS-60 "," Antox SAD "," Antox MS-2N "," Antox 2N "," Antox LMA-10 "," Antox LMA- Antotol LMH-20 "," Antox LM-20 "," Ereminol JS-20 "," Eremolin RS-3000 " Mamolin OT-70 and Caribon EN-200 (manufactured by Sanyo Chemical Industries, Ltd.), and the like.

As the surfactants, polyoxyethylene phenyl ether-based surfactants are preferred from the viewpoint of emulsification, and unsaturated sulfonic acid salts having a structure in which alkylene oxide chains are 5 to 20 moles of the alkylene oxide chain are particularly preferably used.

The aqueous emulsion of the present invention may contain a surfactant other than the surfactant represented by the above formula (III). The surfactant other than the surfactant represented by the formula (III) may be any of cationic, anionic, amphoteric and nonionic surfactants, but preferably anionic and nonionic surfactants. The surfactant may be used alone, or two or more surfactants may be used in combination.

Examples of the anionic surfactant include sodium salt of fatty acid such as sodium palmitate, sodium ether carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, sodium lauroyl sarcosinate, sodium N-lauroyl glutamate Higher fatty acid ester sulfonic acid salts such as amino acid condensates of higher fatty acids, higher alkyl sulfonic acid salts and lauric acid ester sulfonic acid salts, dialkylsulfosuccinate salts such as dioctylsulfosuccinate, higher fatty acid amide sulfonic acid salts such as oleic acid amide sulfonic acid, Alkylarylsulfonic acid salts such as sodium dodecylbenzenesulfonate and diisopropylnaphthalenesulfonic acid salt, formalin condensates of alkylarylsulfonic acid salts, higher alcohol sulfuric acid ester salts such as pentadecane-2-sulfate, dipolyoxyethylene dodecylether phosphate Polyoxyethylene alkylphosphoric acid esters such as esters, ligninsulfonic acid salts, polyoxyethylene-1- (allyloxymethyl) alkyl Ammonium polyoxyethylene nonylphenyl ether sulfate, bis (polyoxyethylene polycyclic phenyl ether) bismethacrylate sulfuric acid ester salt, alkyl allyl succinate sulfonic acid sodium salt, polyoxyalkylene alkenyl ether ammonium sulfate, 2 - sodium sulfoethyl methacrylate, alkoxypolyethylene glycol maleic acid esters, sulfuric acid ester salts of higher alcohols, higher carboxylic acid salts, alkyl benzene sulfonic acid salts, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts and (Meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid copolymer ammonium salt, styrene- (meth) acrylate copolymer, Maleic acid half ester copolymer ammonium salt, carboxymethyl cellulose sodium and sodium naphthalenesulfonate And the like can be dried and condensation.

Examples of cationic surfactants include alkylammonium hydrochloride salts such as dodecylamine hydrochloride, alkyl quaternary ammonium salts such as alkyldimethylbenzylammonium salts, alkylisoquinolinium salts and dialkylmorphonium salts, benzalkonium chloride, and polyalkylvinylpyridines Alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridinium salts such as cetylpyridinium salt and decylpyridinium salt, oxyalkylenetrialkylammonium salts, dioxyalkylene dialkylammonium salts, allyltrialkylammonium salts and Diallyldialkylammonium salt, polydiallyldimethylammonium chloride, and the like.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene lanolin alcohols, polyoxyethylene alkylphenol formalin condensates, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene Glyceryl mono fatty acid esters, polyoxypropylene glycol mono fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene castor oil derivatives, polyoxyethylene fatty acid esters, higher fatty acid glycerin esters, sorbitan fatty acid esters, sucrose fatty acid esters, Ethylene polyoxypropylene block polymer, polyoxyethylene fatty acid amide, alkylol amide, polyoxyethylene alkylamine, and polyoxyethylene alkanediol, and alkoxypolyethylene glycol methacrylate. Polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, polyoxyethylene fatty acid amides, polyalkylene polyamine alkylene oxide adducts, and polyalkylene polyimine alkylene oxide adducts.

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

Examples of commercially available surfactants include Emal 0, Emal 10G, Emal 2F paste, Neopellex GS, Neopellex G-15, Neopellex G-25, Neopellex G-65, Pelex OT- Pelex SS-L, Pelex SS-H, Demol N, Demol EP, Leodol 430V, Acetamin 86, Kotamine 24P, Ampytol 24B, Neopellex No. 6 powder, , Armpitol 86B and Armpitol 20BS (manufactured by Kao Corp.), NeoCol P, Monogen Y-100, and Catoggen TML (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

The content of the surfactant (D) contained in the aqueous emulsion of the present invention is preferably such that the amount of the water-soluble emulsion is sufficient to form an aqueous emulsion. However, when the amount of the polymerizable group (B) Is preferably 1 to 30 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of the compound (E)

&Lt; Compound (E) having polymerizable group &gt;

The compound having a polymerizable group is, for example, a compound having a polymerizable group such as 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, (Meth) acryloyl group, styryloxy group, styrylamide group, isocyanate group, thioisocyanate group, carboxyl group, alcoholic or phenolic hydroxyl group, silanol group, alicyclic epoxy group, epoxy group, glycidyl group , Cyclic ether groups such as oxetane groups, and the like. These groups may contain one kind or two or more kinds, and may contain only one or two or more kinds.

Examples of the compound (E) having a polymerizable group include a compound having an ethylenically unsaturated double bond, an epoxy compound, an oxetane compound, and a glycidyl ether compound. 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 ethylenic unsaturated double bond is preferable among them.

The compound having an ethylenically unsaturated double bond preferably has 1 to 10, more preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 to 2, ethylenically unsaturated double bonds Respectively.

Examples of the compound having one ethylenically unsaturated double bond include a heterocyclic ethylenic unsaturated compound (for example, an N-vinyl-nitrogen-containing compound such as N-methylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam Heterocyclic compounds such as heterocyclic (meth) acrylates such as morpholine (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and glycidyl (meth) acrylate), N-vinylformamide, N- (Meth) acrylate, diethylaminoethyl (meth) acrylate), N, N'-dimethylacrylamide, alkoxy (poly (Meth) acrylates such as methoxyethylene (meth) acrylate, ethoxy-diethylene glycol (meth) acrylate, methoxypolyethylene (meth) acrylate, butoxypolyethylene (meth) Acrylate (Meth) acrylate, etc.), phenoxyalkyl (meth) acrylate (e.g., 2-phenoxyethyl (meth) acrylate, phenoxymethyl (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethyleneglycol (meth) acrylate and the like), phenoxy , Phenoxypolyethylene glycol (meth) acrylate), alkylphenoxy (poly) alkylene glycol (meth) acrylates (for example, nonylphenoxypolyethylene glycol (meth) acrylate, para-cumylphenoxyethylene glycol Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i- butyl (meth) acrylate, sec-butyl (meth) acrylate (Meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, isostearyl (meth) acrylate, isostearyl (meth) acrylate, stearyl (meth) acrylate, cetyl Acrylates such as cyclohexyl (meth) acrylate, 4 (1,1-dimethylethyl) cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 3,3,5-trimethylcyclo (Meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbornyl (meth) acrylate, cyanonorbornyl ) Acrylate, pentyl (meth) acrylate, adaman (Meth) acrylate, dimethyl adamantyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] deca-8-yl = (meth) acrylate, tricyclo [5.2.1.0 ^2,6] deca- (Meth) acrylate, dicyclopentyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylate, dicyclopentenyloxyalkyl (meth) acrylate, tricyclodecanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, (Meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate and the like), a hydroxyl group-containing ) Acrylates (e.g., 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy- (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acryloylphosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, polyethyleneglycol mono (meth) acrylate, polyethylene glycol-propylene glycol mono (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) Mono (meth) arc (Meth) acrylates such as mono [2- (meth) acryloyloxyethyl] acid phosphate, halogen containing (meth) acrylates (for example, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoro (Meth) acrylate, perfluorooctylethyl (meth) acrylate, N, N, N-trimethyl-N- (Meth) acryl-modified organopolysiloxane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (E.g., styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p (meth) acryloxypropylmethyldimethoxysilane and the like), aromatic vinyl compounds -Vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-methoxystyrene, benz (Meth) acrylate, glycidyl (meth) acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl (meth) acrylate and the like; unsaturated carboxylic acid glycidyl esters- (Meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc.), aliphatic vinyl compounds (for example, vinyl acetate, vinyl propionate, Unsaturated amides or unsaturated imides (e.g., acrylamide, methacrylamide, diacetone (meth) acrylamide,? -Chloroacrylamide (meth) acrylamide, , N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide And maleimide), acrylonitrile, methacrylamide (Such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysilicon, etc.) And a macromonomer having a monoacryloyl group or a mono-methacryloyl group at the terminal thereof.

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, (Meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate tetraethylene glycol di (meth) acrylate, polyethylene glycol di , Polypropylene glycol di (meth) acrylate, polyethylene glycol-propylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10- Decanediol diacrylate, neopentyl glycol di ( Acrylate, propoxylated neopentyl glycol di (meth) acrylate, alkoxylated neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) (Meth) acrylate such as tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, alkoxylated hexanediol di (meth) acrylate, pentanediol di (Meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, etc.), alkylene oxides of bisphenol A (e.g., ethylene oxide, propylene oxide, (Di (meth) acrylate of 2,2-bis (2-hydroxyethoxyphenyl) propane, etc.), a di (meth) acrylate having a crosslinked cyclic hydrocarbon group ) Acrylate (e.g., cyclohexanedimethanol di (meth) acrylate, di (meth) acrylate of tricyclodecane dimethylol (e.g., tricyclodecanedimethanol di (meth) acrylate) (Meth) acrylic acid adduct of a bifunctional epoxy resin (for example, 2,2-bis (glycidyloxyphenyl) methacrylate, (Meth) acrylic acid adduct, bisphenol A diglycidyl ether methacrylic acid adduct, etc.), glycerin di (meth) acrylate, silicon-containing (meth) acrylate (e.g., Organopolysiloxane, and the like), diacetone acrylamide, and the like.

Examples of the compound having a plurality of ethylenically unsaturated double bonds of 3 or more 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, ditrimethylol propane tetraacrylate, tetramethylol methane tri (meth) acrylate, tetramethylol (Meth) acrylates such as methane tetra (meth) acrylate, tris (acryloyloxy) isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, and tris (2-hydroxyethyl) isocyanurate tri Tri (meth) acrylate, tri (meth) acrylate of tris (hydroxypropyl) isocyanurate, triallyl trimellitic acid, triallyl isocyanurate And silicon-containing (meth) acrylates (e.g., (meth) acryl-modified organopolysiloxane and the like).

Among them, the compound having at least one ethylenically unsaturated double bond is preferably a compound having 5 to 25 carbon atoms, more preferably a compound having 6 to 18 carbon atoms, and more preferably a compound having 8 to 16 carbon atoms.

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 monoxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3- Acryloyloxymethyl cyclohexene oxide, 3-vinylcyclohexene oxide, bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated Bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolak resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether , Number (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, Epoxy-6-methylcyclohexanecarboxylate, 4-epoxy-6-methylcyclohexyl-3 ' (3,4-epoxycyclohexylmethyl) ether of glycols, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, dihexylhydroxyphthalate di-2-ethylhexyl, 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl Ethers, 1,1,3-tetradecadienedioxide, limonene dioxide, 1,2,7 , 8-diepoxy octane, and 1,2,5,6-diepoxy cyclooctane.

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

Examples of the oxetane compound include 2-hydroxymethyl-2-methyloxetane, 2-hydroxymethyl-2-ethyloxetane, 2-hydroxymethyl- Butyloxetane, and 1,4-bis [(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 Diethyl ether, diethyl ether, diethyl ether and diethylene glycol diglycidyl ether.

The compound (E) having a polymerizable group may be solid at 23 占 폚, but a compound which is liquid at atmospheric pressure is preferable. Liquids include solutions, emulsions, suspensions, colloids, and the like. By such properties, a uniform aqueous emulsion can be obtained.

When the compound (E) having a polymerizable group contained in the aqueous emulsion of the present invention is contained, the content thereof is usually 50 to 10000 parts by mass based on 100 parts by mass of the halogen atom-containing polymer (B) Is preferably 100 to 10,000 parts by mass, more preferably 200 to 5,000 parts by mass, and still more preferably 400 to 5,000 parts by mass.

The aqueous emulsion of the present invention may contain a polymerization inhibitor. The polymerization inhibitor may be one that slows or stops the radical reaction. Specific examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, 4-t-butylcatechol, N-phenylnaphthylamine, 2 Di-t-butyl-p-methylphenol, 2,5-di-t-butylhydroquinone, 1,4-benzoquinone, 2,6- Methyl-p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 4-methoxyphenol, chloranil, pyrogallol, 2-oxydiphenylamine and phenothiazine.

As a polymerization inhibitor for commercial products, a polymerization inhibitor such as Quno Power QS-10, Quno Power QS-20, Quno Power QS-30, Quno Power QS-40, Quno Power QS-W10 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.), methoquinone flake, , MH, TBH, PBQ, toluquinone, and TBQ (manufactured by Seiko Chemical).

The polymerization inhibitor also has an aspect of maintaining the storage stability of the composition at a high level and securing the curability. Therefore, the amount of the polymerization inhibitor to be added is preferably 0.005 to 0.4 part by mass, more preferably 0.005 to 0.4 part by mass, per 100 parts by mass in total of the mass part of the chlorinated rubber and the mass part of the compound having a polymerizable group Is preferably from 0.01 to 0.3 parts by mass, more preferably from 0.02 to 0.2 parts by mass, and particularly preferably from 0.035 to 0.2 parts by mass. The polymerization inhibitor is preferably dissolved in a compound having a polymerizable group.

<Additives>

The aqueous emulsion of the present invention may further contain, in addition to the above-mentioned polymer surfactant (A), a polymer (B) containing a halogen atom, water (C), a surfactant (D) Various additives can be added. Examples of the additive include additives such as a photopolymerization initiator, a light stabilizer, an ultraviolet curable oligomer, a fluorescent whitening agent, a leveling agent, a basic compound, an organic solvent, a crosslinking agent, a photosensitizer, other resins, a phenolic stabilizer, a phosphite stabilizer, Amide stabilizer, antioxidant, weathering stabilizer, antiseptic agent, anti-settling agent, antioxidant, heat stabilizer, thixotropic agent, thickener, antifoamer, viscosity adjusting agent, endurance agent, pigment dispersant, antistatic agent, lubricant, , Emulsions, dyes, hardeners; Transition metal compounds such as titanium oxide (rutile type) and zinc oxide; Pigments such as carbon black; Glass fiber, calcium carbonate, calcium carbonate, talc, glass flake, barium sulfate, clay, kaolin, fine powder silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, Inorganic or organic fillers such as magnesium, alumina and celite.

These additives and the like may constitute a dispersion medium of an aqueous emulsion. In this case, at least a part of the halogen-containing polymer (B) may be dissolved in the dispersion. Here, the fact that at least a part of the halogen-containing polymer (B) is dissolved in the dispersoid means that at least a part of the halogen-containing polymer (B) is dissolved in at least one component . For example, when the aqueous emulsion of the present invention is filtered with a filter having a pore diameter of 0.5 탆, it is sufficient that at least a part of the polymer (B) containing a halogen atom is contained in the filtrate. The chlorinated rubber contained in the filtrate is preferably not less than 1 part by mass, more preferably not less than 10 parts by mass, more preferably not less than 10 parts by mass, per 100 parts by mass of the halogen atom-containing polymer (B) contained in the aqueous emulsion before filtration Is not less than 30 parts by mass, and more preferably not less than 70 parts by mass.

The filtration by the filter is preferably carried out after heating the aqueous emulsion to a temperature not lower than the melting point of the compound having a polymerizable group contained in the aqueous emulsion.

In the case where the polymer (B) containing a halogen atom contains other resins, it is preferable that at least a part of the polymer (B) containing a halogen atom is dissolved in the compound (E) having a polymerizable group or the dispersion medium, And at least a part of additives such as other resins may be dissolved.

The filtration by the filter is preferably carried out after heating to the melting point or higher of the compound (E) having a polymerizable group contained in the aqueous emulsion.

When the additive is added to the aqueous emulsion of the present invention, all the additives may be mixed with the dispersoid in the aqueous emulsion or may be mixed with water. Mixing means a dispersed state, a swollen state, or a dissolved state.

&Lt; Photopolymerization initiator &gt;

The photopolymerization initiator is a compound which generates an active species by the action of light and is a photo radical generator which generates an active radical by the action of light, a photoacid generator which generates an acid by the action of light, And a photoacid generator.

Examples of the photo radical generator include a benzoin compound, a benzophenone compound, an alkylphenone compound, an acylphosphine oxide compound, a triazine compound, a sulfonic acid derivative, an onium salt (iodonium salt and a sulfonium salt), a carboxylic acid ester, .

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

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

Examples of the alkylphenone compounds include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- 2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2- Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, and 2-hydroxy-2-methylpropiophenone. -Hydroxy-2-methyl-1- [4- (1-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 the triazine compound 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- (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) -1,3,5-triazine, Ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine And the like.

Sulfonic acid derivatives, onium salts (such as iodonium salts and sulfonium salts), carboxylic acid esters, and the like.

As the photo radical generator, commercially available ones can be used. Commercially available photo-radical generators include Irgacure (registered trademark) 907, 184, 651, 819, 250, 2959, 127, 754 and 369 (BASF Japan) , Z and BEE (Seiko Chemical), Kayacure (registered trademark) BP100 (Nippon Kayaku), Kayacure UVI-6992 (Dow), Adeka Optomer SP-152 TAZ-A and TAZ-PP (Nippon Gibb Hegner), TAZ-104 (Sanwa Chemical), Darocur (registered trademark) 1173 and MBF (BASF Japan) (Trade name).

These photo-radical generating agents may be used alone or in combination.

Specific examples of the combination include Irgacure TM 500 (1-hydroxy-cyclohexyl-phenyl-ketone / benzophenone: 50/50%), Irgacure TM 1700 (bis Trimethylpentylphosphine oxide / 2-hydroxy-2-methylphenylpropan-1-one: 25/75%) and Irgacure (registered trademark) 1800 (bis 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone: 25/75%) (BASF Japan).

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

Examples of the sulfonic acid derivative include imidosulfonates such as disulfone, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes and trifluoromethylsulfonate derivatives, benzoin sulfonates, Sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol, pyrogallol trisulfonates and benzylsulfonates. Specific examples include diphenyldisulfone, ditosyldisulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xylylsulfonyl) diazomethane, phenylsulfonylbenzoyldiazo Methane, bis (cyclohexylsulfonyl) methane, benzoin tosylate, 1,2-diphenyl-2-hydroxypropyl tosylate, 1,2-di (4-methylmercaptophenyl) -2- Tosylate, pyrogallol methylsulfonate, pyrogallol ethylsulfonate, 2,6-dinitrophenylmethyl tosylate, ortho-nitrophenyl methyl tosylate, para-nitrophenyl tosylate and the like.

Examples of the onium salt include tetrafluoroborate (BF ^4- ), hexafluorophosphate (PF ^6- ), hexafluoroantimonate (SbF ^6- ), hexafluoroarsenate (AsF ^6- ) chlor antimonate (SbCl ^6-), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoro-phenyl) borate, perchlorate ion (ClO ^4-), methanesulfonate ion trifluoroacetate (CF ₃ SO ^3-), can use the sulfonium salt or iodonium salt having an anion such as a fluoroalkyl sulfonate ion (FSO ^3-), toluenesulfonic acid ion, trinitrotoluene sulfonic acid anion, trinitrotoluene sulfonic acid anion.

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 hexafluoro Tetrabutylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, , 4-butoxyphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, 4-chlorophenyldiphenylsulfonium hexafluoroantimo (4-ethoxyphenyl) methylsulfonium hexafluoroarsenate, 4-acetylphenyldiphenylsulfonium tetrafluoroborate, 4- (4-phenoxyphenyl) sulfonium hexafluorophosphate, (Pentafluorobenzyl) borate, tris (4-thiomethoxyphenyl) sulfonium hexafluorophosphate, di (methoxysulfonylphenyl) methylsulfonium hexafluoroantimonate, di (Methoxynaphthyl) methylsulfonium tetrafluoroborate, di (methoxynaphthyl) methylsulfonium tetrakis (pentafluorobenzyl) borate, di (carbomethoxyphenyl) methylsulfonium hexafluorophosphate, (3,5-bis-trifluoromethylphenyl) borate, tris (dodecylphenyl) sulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate , 4-acetamide phenyldiphenylsulfonium tetrafluoride (Pentafluorobenzyl) borate, dimethylnaphthylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, trifluoromethyldiphenylsulfonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, (Pentafluorobenzyl) borate, phenylmethylbenzylsulfonium hexafluorophosphate, 10-methylphenoxathiinium hexafluorophosphate, 5-methylthianthrone hexafluorophosphate, 10-phenyl-9 , 9-dimethylthioxanthenium hexafluorophosphate, 10-phenyl-9-oxothioxanthanium citrate tetrafluoroborate, 10-phenyl-9-oxothioxanthanium tetrakis (pentafluorobenzyl) 5-methyl-10-oxothianthrinium tetrafluoroborate, 5-methyl-10-oxothianthrityl tetrakis (pentafluorobenzyl) borate, and 5-methyl-10,10-dioxothyantrhenium hexa Fluoro It may include sulfates, etc.

Examples of iodonium salts include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimo Iodonium trifluoromethanesulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium (Pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoro (tetrafluoroborate) Bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium trifluorosulfonate, bis (Dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecyl Iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate, di (dodecylphenyl) iodonium hexafluoroantimonate, di (dodecylphenyl) iodonium triflate, 4,4'-dichlorodiphenyliodonium bisulfate, 4,4'-dibromodiphenyliodonium bisulfate, 3,3'-dinitrodiphenyl iodonium bisulfate, 4,4'-dibromodiphenyliodonium bisulfate, 4'-dimethyldiphenyliodonium bisulfate, 4,4'-bis-succinimid diphenyl iodonium bisulfate, 3-nitrophenyl iodonium bisulfate, 4,4'-dimethoxydiphenyl iodonium bisulfate , Bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, and (4-octyloxyphenyl) phenyliodonium tetrakis (3,5-bis-trifluoromethylphenyl) borate.

As other onium salts, aromatic diazonium salts can be used, and for example, p-methoxybenzene diazonium hexafluoroantimonate and the like can be used.

Commercially available onium salts include, but are not limited to, acid aids SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI- UVI-6970, UVI-6974, UVI-6990 (manufactured by Union Carbide Co., Ltd.), Adeka Optomer SP-150, Irgacure 250 (manufactured by Ciba Specialty Chemicals), CI-2481, CI-2624 (manufactured by Asahi Kasei Kogyo Co., Ltd.), SP-151, SP-170, SP- , CI-2639, CI-2064 (manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011 and CD-1012 DAI-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI-105, NAI-106, SI- NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NDI-105, BENZOIN TOSYLATE, -109 (manufactured by Midori Kagaku K.K.), PCI-061T, PCI-062T, PCI-020T and PCI-022T (manufactured by NIPPON KAYAKU CO., LTD.), IBPF and IBCF BBI-102, BBI-103, BBI-109 (manufactured by Midori Chemical Co., Ltd.), CD1012 (manufactured by Sato MUSA), IBPF and IBCF (manufactured by Sanwa Chemical Co., (Manufactured by Wako Pure Chemical Industries, Ltd.), UVE1014 (manufactured by General Electric Co., Ltd.), RHODORSIL-PI2074 (manufactured by Rhodia), WPI-113 and WPI-116

Also described in J. Polymer Science: Part A: Polymer Chemistry, Vol. 31, 1473-1482 (1993), J. Polymer Science: Part A: Polymer Chemistry, Vol. 31, 1483-1491 (1993) A diaryliodonium salt which can be produced by the method can also be used. These may be used alone or in combination of two or more.

Examples of the carboxylic acid ester include 1,8-naphthalenedicarboxylic acid imidomethylsulfonate, 1,8-naphthalenedicarboxylic acid imidotylsulfonate, 1,8-naphthalenedicarboxylic acidimidotrifluoromethylsulfone Naphthalene dicarboxylic acid imide camphorsulfonate, succinic acid imidophenylsulfonate, succinic acid imidotylsulfonate, succinic acid imide trifluoromethylsulfonate, succinic acid imide camphorsulfonate, phthalic acid imide Trifluoro sulfonate, cis-5-norbornene-endo-2,3-dicarboxylic acid imidotrifluoromethylsulfonate, and the like.

The photobase generator may be, for example, an acyloxyimino compound of a non-cyclic type, a carbamoyloxime compound of a non-cyclic type, a carbamoylhydroxylamine compound, a carbamic acid compound, a formamide compound, an acetamide compound, a carbamate compound , A benzyl carbamate compound, a nitrobenzyl carbamate compound, a sulfonamide compound, an imidazole derivative compound, an amine imide compound, a pyridine derivative compound, an? -Amino acetophenone derivative compound, a quaternary ammonium salt derivative compound, Derivative compounds, amine imide compounds, phthalimide derivative compounds, and the like. These may be used alone or in combination of two or more.

When the aqueous emulsion of the present invention contains a photopolymerization initiator, the content thereof is preferably 100 parts by mass based on the total of the mass part of the polymer (B) containing a halogen atom and the mass part of the compound (E) 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, still more preferably 5 parts by mass or less, from the viewpoint of stability, reactivity, and odor.

<Light stabilizer>

Examples of the light stabilizer include ultraviolet absorbers and hindered amine light stabilizers. The light stabilizer may be used alone or in combination of two or more.

Examples of the ultraviolet absorber include salicylic acids (for example, phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate and the like), benzophenones (for example, Hydroxybenzophenone, 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 and the like), benzotriazoles (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxyphenyl) benzotriazole, 2- Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5- chlorobenzotriazole, 2- 2'-hydroxy-3 ', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-5'-methylphenyl} benzotriazole, etc.), triazines (such as 2 - {(2'-hydroxy-3 ', 3 ", 4", 5 ", 6" -tetrahydrophthalimidemethyl) For example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy- Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2,4-dihydroxyphenyl-4,6-bis (2,4- (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- Bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) (4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- 4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) -Dimethylphenyl) -1,3,5-triazine) and oxalic anilides (e. G. (2-ethoxyphenyl) -N '- (2-ethoxyphenyl) oxalic acid diamide, N- Oxalic acid diamide, oxalic acid diamide, 2-ethoxy-2'-ethyl-oxalic acid bisanilide, oxalic acid diamide having an aryl group which may be substituted on the nitrogen atom, etc.).

Examples of the hindered amine light stabilizer include ester group-containing piperidines (for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy- Tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, etc.), ether group-containing piperidines (for example, 4-methoxy- , 2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine Pyridine), amide group-containing piperidines (for example, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6- Tetramethyl-4-piperidyl) hexamethylene-1,6-dicarbamate, etc.) and high molecular weight piperidine polycondensates (for example, dimethyl succinate-1- (2-hydroxyethyl) 4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperazine Ridinol and tridecyl alcohol And the like, such as a condensate).

When the aqueous emulsion of the present invention contains a light stabilizer, its content is preferably in the range of preferably 100 parts by mass to 100 parts by mass of the total of the mass of the polymer (B) containing a halogen atom and the mass of the compound (E) 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.

&Lt; UV-curable oligomer &

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

Commercially available urethane acrylate oligomers can be used. Examples of commercially available urethane acrylate oligomers include CN929, CN965, CN968, CN981A75, CN985B88, CN991, CN970AH75, CN975, CN992, CN994 and CN9165 (produced by Sato MUSA), U-4HA and U-6HA (manufactured by Shin Nakamura Chemical Industry Co., , AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G and DAUA-167 (manufactured by Kyowa Chemical Industry Co., Ltd.).

Commercially available epoxy acrylate oligomers may be used. Commercially available epoxy acrylate oligomers include CN116, CN120B60, CN120M50, CN131B, CN132, CN137, CN152 and CN2102E (manufactured by Sato MUSA).

Commercially available polyester acrylate oligomers may 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 have. These polyester acrylate oligomers may be used alone or in combination.

When the aqueous emulsion of the present invention contains an ultraviolet-curable oligomer, the content thereof is preferably 100 parts by mass based on 100 parts by mass of the total of the mass of the polymer (B) containing a halogen atom and the mass of the compound (E) Preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

&Lt; Fluorescent brightening agent &

Examples of the fluorescent brightener include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-alkylimide, bisbenzoxazolylethylene, 4-bis (2-benzoxazolyl) naphthalene, and dialkyl stilbene. Commercially available fluorescent brighteners include Kayahor 3BS Liq., Kayahor TAC Liq., Kayahor HBC Liq., Kayalight B, Kayaphor AS 150, Kayaphor CR 200, Kayaphor JB Liq., Mikawhite ATN conc. B, Hakkol PY-2000, Hakkol PYB-D (manufactured by Nippon Yakuza), TINOPAL OB, and TINOPAL NFW Liqid (manufactured by BASF), Hakkol P, Hakkol PHD, Hakkol RF, Hakkol PSR, Hakkol PSR- , Hakkol BE conc, Hakkol SG conc 150, Hakkol TH-100, Hakkol S-100, Hakkol RX-1, Hakkol OW-11, Hakkol OW-10extra, Hakkol KIP H / C, Hakkol SF, H / C (manufactured by Showa Chemical Industry Co., Ltd.), Nikkafluor SB conc, Nikkafluor KB, Nikkafluor OB, Nikkabright CX H / C (manufactured by Nippon Chemical Industry Co., Ltd.). The fluorescent whitening agent may be used alone or in combination.

When the aqueous emulsion of the present invention contains a fluorescent whitening agent, the content thereof is preferably 100 parts by mass based on the total of the mass part of the polymer (B) containing a halogen atom and the mass part of the compound (E) Preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less.

<Leveling agent>

As the leveling agent, Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (manufactured by Kyowa Chemical Industry Co., Ltd.), BYK300, BYK306, BYK310, BYK320, BYK330, BYK346, BYK349, BYK-333, BYK-345, BYK-347, BYK-348 and BYK-378 (manufactured by Big Chemical Japan), KP-341, KP-358, KP-368 and KF-96-50CS , Surfron SC-101, Surfron KH-40 (manufactured by AGC Seiyaku Chemical Co., Ltd.), Fotogen 222F, Fotogen 251 and FTX-218 (manufactured by Neos Co., Ltd.), KF-50-100CS EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (manufactured by Mitsubishi Materials Corporation), Megapack F-171, Megapack F- Adeka Cole W-287, Adeka Cole W-288, Adeka Cole W-304 (manufactured by ADEKA), and MEKA PARK F-556, SN Disperse Sand 5040, SN Disperse Sand 5040, SN Disperse Sand 5040, SN Disperse Sand 5020 Fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoroalkylpolyoxyethylene ethers, fluoroalkylammonium iodides, fluoroalkylbetaines, fluoroalkylsulfonic acid salts, diglycerin tetrakis (Fluoroalkylpolyoxyethylene 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 lauryl Amines, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitol Sorbitan fatty acid esters, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene Sulfonic acid salts, and alkyldiphenyl ether disulfonic acid salts.

When the aqueous emulsion of the present invention contains a leveling agent, its content is preferably 100 parts by mass or more based on 100 parts by mass of the total of the mass of the halogen atom-containing polymer (B) and the mass of the compound (E) Is not more than 20 parts by mass, more preferably not more than 10 parts by mass, and more preferably not more than 5 parts by mass.

&Lt; Basic compound &gt;

Examples of the basic compound include ammonia, organic amine compounds and metal hydroxides. Preferably, it is an ammonia or an organic amine compound.

Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, Propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, and N- Ethyl morpholine and the like. Preferably, it is N, N-dimethylethanolamine.

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, its content is preferably 100 parts by mass or more per 100 parts by mass of the total of the mass of the polymer (B) containing a halogen atom and the mass of the compound (E) Is not more than 20 parts by mass, more preferably not more than 10 parts by mass, and more preferably not more than 5 parts by mass.

<Organic solvents>

Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; Aliphatic hydrocarbons such as hexane; Esters such as ethyl acetate and butyl acetate; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol and n-butanol; Glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol; Cellosolve solvents such as methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary butyl ether) and butyl carbitol; Glycol solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and 3-methoxy-3-methyl-1-butanol; 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, and the like. These may be used alone or in combination.

When the aqueous emulsion of the present invention contains an organic solvent, the content thereof is preferably 100 parts by mass based on 100 parts by mass of the total of the mass of the halogen atom-containing polymer (B) and the mass of the compound (E) Preferably 100 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, still more preferably 10 parts by mass or less,

<Cross-linking agent>

By including the crosslinking agent, the adhesiveness, the water resistance of the adhesive layer, and the solvent resistance of the adhesive layer tend to be further improved.

Examples of the crosslinking agent include an epoxy compound, a polyisocyanate compound, an oxazoline compound, an aziridine compound, a carbodiimide compound, an active methylol compound, an active alkoxymethyl compound, a metal chelate, a hydrazide compound and a hydrazine compound.

Preferably, the compound is an aliphatic polyisocyanate compound, a carbodiimide compound, an oxazoline group-containing compound, a hydrazide compound, or a hydrazine compound. Among these, water-soluble (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, Sumitra (registered trademark) N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, 44V10, 44V20 and E 21-1, Desmodur (registered trademark) N3100, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487 and XP-2547 manufactured by Sumitomo Bayer Urethane Co., , E14 and E22, Bayer® 304 and XP2655 manufactured by Sumitomo Bayer Urethane Company, BASONAT® PLR8878 and HW-100 manufactured by BASF Corp., Takenate (manufactured by Takeda Chemical Industries, Ltd.) WD720, WD725 and WD730, Dyuranate (registered trademark) WB40-100, WB40-80D and WX-1741 manufactured by Asahi Chemical Industry Co., Ltd., and the like.

V-02, V-02-L, V-04, E-01 and E-02) available from Nisshinbo Chemical Co., Ltd .: CarbodiLite And so on.

Specific examples of the crosslinking agent of the hydrazide compound include 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 cross-linking agent of the hydrazine compound 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, its content is preferably 100 parts by mass or more based on 100 parts by mass of the total of the mass of the polymer (B) containing a halogen atom and the mass of the compound (E) Is not more than 30 parts by mass, more preferably not more than 15 parts by mass, more preferably not more than 10 parts by mass, and even more preferably not more than 5 parts by mass.

<Optical sensitizer>

The photosensitizer can be appropriately selected according to the wavelength to be augmented. The effective excitation wavelength range is usually 450 nm or less, preferably 250 to 380 nm. Examples of the photosensitizer include triethanolamine, triisopropanolamine, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminoethylbenzoate, and 4-dimethylaminobenzoic acid isoacyl.

When the aqueous emulsion of the present invention contains a photosensitizer, the content thereof is preferably 100 parts by mass based on the sum of the mass of the polymer (B) containing a halogen atom and the mass of the polymer (E) 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.

<Other Resins>

The aqueous emulsion of the present invention may contain other resins within a range that does not impair the intended properties.

Examples of the other resin include an ethylene-vinyl ester resin, a styrene-maleic acid resin, a (meth) acrylic resin, polystyrene, a polyvinyl acetate, a polyurethane, an ethylene-vinyl ester resin, a polyurea, an acrylonitrile butadiene styrene resin, , Modified rubber, styrene- (meth) acrylic acid resin, synthetic rubber, natural rubber, styrene-butadiene resin, butadiene resin, poly (meth) acrylonitrile resin, (meth) acrylamide resin, polyester resin, Epoxy resins, styrenic block copolymers and oligomer bodies thereof.

The ethylene-vinyl ester resin is a copolymer containing a polymer comprising an ethylene unit and a vinyl ester unit. Examples of the vinyl ester unit include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl esters of tertiary carboxylic acids having 8 to 10 carbon atoms and so-called vinyl versatate (trade name: Veova (registered trademark) 10), and the like. Among vinylester 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 &quot; EVA &quot;).

For example, the ethylene-vinyl acetate copolymer contains various kinds of vinyl acetate content and shape (film, block, fiber, foam) although the properties are different depending on the content of vinyl acetate. The ethylene-vinyl acetate copolymer may contain a polymer such as polyolefin. Preferred polyolefins include ethylene-octene copolymers, ethylene-butene copolymers, polypropylene and polyethylene.

The ethylene-vinyl ester resin may contain, in addition to the ethylene unit and the vinyl ester unit, a monomer unit copolymerizable therewith. Examples of the monomer unit include a vinyl halide such as vinyl chloride, a monomer having a functional group such as a small amount of an amide group, and a (meth) acrylate.

Examples of the ethylene-vinyl ester resin copolymer include VINNOL E 15/45, E 15/45 M, E 15/48 A, H 15/42, H 15/50, H 11/59, H 14/36, H 40/50, H 40/55, H 40/60 , H30 / 48M (manufactured by 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 prepared by emulsion polymerization of the monomers constituting the ethylene unit and the vinyl ester unit, or a commercially available emulsion may be used. As the emulsion of the ethylene-vinyl ester resin copolymer, for example, Sumikaflex 占 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 (manufactured by Sumitomo Chemical Co., Ltd.), Banflex OM-4000 and OM- AD-5, AD-5, AD-51, AD-56, AD-59 and P-900 (above, manufactured by Kuraray Co., # 60, # 81, and # 82 (manufactured by Denki Kagaku Kogyo Co., Ltd.), and the like.

Examples of the styrene-maleic acid resin include SMA (registered trademark) 1000, SMA (registered trademark) 2000, SMA (registered trademark) 3000 (manufactured by Arakawa Chemical Industries Ltd.) And the like.

Examples of the? -Olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and vinylcyclohexane . Preferably, it is ethylene or propylene.

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

The resin having a structural unit derived from an? -Olefin having 2 to 20 carbon atoms may be any of homopolymers, random copolymers, block copolymers and graft copolymers. In addition, a low molecular weight or a high molecular weight may be obtained by a peroxide or the like.

As a modification of the resin having a structural unit derived from an? -Olefin having 2 to 20 carbon atoms, a resin having a structural unit derived from an? -Olefin having 2 to 20 carbon atoms is modified with?,? -Unsaturated carboxylic acids, Water can be heard.

The modification ratio of the modified product modified with?,? - unsaturated carboxylic acids, etc. is usually from 0.1 to 10% by mass, preferably from 0.2 to 5% by mass, more preferably from 0.2% by mass to 100% by mass of the copolymer before modification To 4% by mass.

Examples of the alpha, beta -unsaturated carboxylic acids include alpha, beta -unsaturated carboxylic acids (such as maleic acid, itaconic acid and citraconic acid), alpha, beta -unsaturated carboxylic acid esters (Such as maleic anhydride, itaconic anhydride, and citraconic anhydride), and the like can be given as examples of the unsaturated carboxylic acid anhydride. Further, they may be modified products obtained by combining these?,? -Unsaturated carboxylic acids. These may be carboxylic acid anhydrides, carboxylic acids formed by hydrolysis, or mixed therewith.

Such a modified product is obtained by melting a copolymer of a resin having a structural unit derived from an? -Olefin having 2 to 20 carbon atoms or a copolymer of an? -Olefin having 2 to 20 carbon atoms and a monomer copolymerizable with the? -Unsaturated carboxylic acids or the like in a solvent such as toluene or xylene and then adding an?,? -Unsaturated carboxylic acid or the like to the solution to modify the solution.

The modification ratio of the resin having a chlorinated C2-C20? -Olefin-derived structural unit is preferably 5 to 80% by mass, more preferably 5 to 80% by mass, relative to 100% by mass of the copolymer before modification By mass is 40 to 75% by mass, and more preferably 55 to 70% by mass.

The chlorination of a resin having a structural unit derived from an? -Olefin having 2 to 20 carbon atoms can be carried out by dissolving or dispersing a resin having a structural unit derived from an -olefin having 2 to 20 carbon atoms in a solvent and blowing a chlorine gas into the resulting mixture By chlorination of a resin having a structural unit derived from an? -Olefin having 2 to 20 carbon atoms.

Examples of the monomer copolymerizable with the? -Olefin having 2 to 20 carbon atoms include?,? - unsaturated carboxylic acids and anhydrides thereof, metal salts of?,? -Unsaturated carboxylic acids,?,? -Unsaturated carboxylic acid esters, (Meth) acrylonitrile, vinyl halide, amide, vinylidene halide, and the like can be given as examples of the vinyl aromatic compound. These may be used singly or in combination for copolymerization.

Examples of the?,? - 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, A half ester of an acid, a half amide of a maleic acid, a half ester of itaconic acid, and a half amide of itaconic acid. Among 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 salts of the?,? - unsaturated carboxylic acids include salts of monovalent metals such as lithium, sodium and potassium, and salts of polyvalent metals such as magnesium, calcium and zinc. Specific examples include sodium salts and magnesium salts of (meth) acrylic acid.

Examples of the?,? -unsaturated carboxylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl -Hydroxyethyl acrylate, dimethyl maleate, esters of methacrylic acid and an alcohol, and the like. Among them, methyl (meth) acrylate and ethyl (meth) acrylate are preferable.

Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and vinyl versatate. Among them, vinyl acetate is preferable.

Examples of the vinyl ester saponification include vinyl alcohol obtained by saponifying a 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, Octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, cyclopentene, cyclohexene, cycloheptene and vinylcyclohexane.

Examples of the vinyl aromatic compound include styrene,? -Methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p- Ethyl styrene and vinyl naphthalene.

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

Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-octadiene and 2,3-dimethyl-1,3-decadiene. have.

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

Examples of the aliphatic nonconjugated polyene compound include 1,4-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,9-decadiene, 3,3- Methyl-1,4-octadiene, 4-methyl-1,4-heptadiene, 4-methyl- 4-nonadiene, 5-methyl-1,4-decadiene, 6-methyl-1,6-undecadiene and 4-ethylidene-12-methyl-1,11-pentadecadien.

Examples of the alicyclic nonconjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 1,4-divinylcyclohexane, 1-isopropenyl- Tetrahydroindene, and the like.

Examples of the aromatic nonconjugated polyene compound include divinylbenzene and vinylisopropenylbenzene.

Examples of the copolymer having a structural unit derived from an? -Olefin having 2 to 20 carbon atoms include an ethylene-unsaturated carboxylic acid copolymer such as an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer, an ethylene-unsaturated carboxylic acid copolymer An ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-isobutyl acrylate copolymer, an ethylene-acrylic acid n-methacrylate copolymer Unsaturated carboxylic acid ester copolymers such as ethylene-isobutyl-methacrylic acid copolymer, ethylene-n-butyl acrylate-methacrylic acid copolymer, ethylene-unsaturated carboxylic acid ester copolymers such as butyl acrylate, A polymeric acid copolymer and an ionomer in which some or all of its carboxyl groups are neutralized with the metal, Ethylene-vinyl ester copolymers such as tylene-vinyl acetate copolymer, and the like.

Specific examples of the resin having a structural unit derived from an? -Olefin having 2 to 20 carbon atoms and modified products thereof include MelSEN (registered trademark) H-6410M, H-6051, H-6960, H-6820 and H- (Registered trademark) D2908, DT2904, DC3212, DC3203, E3808, ET3803, A4412, AT4403 (manufactured by Tosoh Corporation), Eval (registered trademark) L171B, F171B, H171B, E105B and G156B NISSO (registered trademark) PB (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), poly (ethylene terephthalate), polytetrafluoroethylene OEVAC (registered trademark) G 18211, OE808, and OE825 (manufactured by Arc Machinery Co., Ltd.), LOTADAR MAH2210, 3200 (manufactured by Mitsubishi Chemical Corporation), Epol (registered trademark) (Registered trademark) LX4110, HX8210, TX8030, HX8290, HX8410 and AX8390 (Arcema Co., Ltd.), OREVAC (registered trademark), P3 3200, 3210, 4210, 6200, 3410, 3430 and 4720 Trademarks) T9314, T9318 and G18211 (manufactured by Arc Machinery Co., Ltd.), Umex (Registered trademark) 2000 (Sanyo Chemical Industries, Ltd.) and Aurora (registered trademark) 100S and 200T (manufactured by Nippon Paper Chemicals Co., Ltd.).

Examples of the resin having a chlorinated C2-C20? -Olefin-derived structural unit include Erasrene (registered trademark) 401A and 303B (Showa Denko K.K.) and the like.

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

Commercially available polyurethanes may be used. U-54, U-54, U-56, KA-8481, KA-8584, KA-8755, KA-8756 and KA- (HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP-60LM and AP- 300, PERMARINE UA-310, and Yukat UWS-300 (manufactured by DIC Corporation), UXRA-306, UXA-307, PERMARINE UA-150, 110, 126, 130, 150, 160, 210, 300, 361, 370, 410, 420, 460, 500M, 700, 750, 820, HUX-821 and HUX-895 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and Adekbon Titer (registered trademark) HUX-401, HUX-420A, HUX-380, HUX- 830 (ADEKA), Nipolan (registered trademark) 3110, 3116, 3016, 3113, 3124, 3126, 3230 (manufactured by Nippon Polyurethane Industry Co., Ltd.).

Polyvinyl chloride is obtained by suspension polymerization or bulk polymerization of vinyl chloride.

Examples of polyvinyl chloride include hard polyvinyl chloride, semi-rigid polyvinyl chloride, and flexible polyvinyl chloride. Preferably, it is a flexible polyvinyl chloride.

Examples of polyvinyl chloride include carnevinyl S-400, PSH-180, PSL-180 (Kaneka Corporation), and the like.

Chlorinated polyvinyl chloride is chlorinated polyvinyl chloride resin by a chlorination method such as gas phase or liquid phase. Examples of the polyvinyl chloride resin include homopolymers of vinyl chloride and copolymers of vinyl chloride. Examples of the monomer constituting the copolymer of vinyl chloride with vinyl chloride include ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylic acid ester and maleic acid ester.

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

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

Examples of vinylidene chloride- (meth) acrylate copolymer resins include IXAN PVS-109, 801, 815, Diofan A586, A602, A610 (manufactured by Solvay Co., Ltd.) and the like.

The chloroprene-based resin means chloroprene synthesized by dehydrochlorination of dichlorobutene obtained by chlorination of butadiene, which is polymerized alone or copolymerized 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 at least one kind selected from an?,? -Unsaturated carboxylic acid and anhydride thereof with the chloroprene-based resin. Examples of the?,? - unsaturated carboxylic acid and its acid anhydride include those exemplified as a modification of a resin having a structural unit derived from an? -olefin having 2 to 20 carbon atoms.

Examples of the chloroprene resin and the acid-modified chloroprene resin include Skifren (registered trademark) GFL-820, GFL-890, GFL-280, LA-502, LA-660, SL-360, SL- 590 and SL-590, G-42, G-40S, G-55, G-40S-1, G-40T, B-30S, Y- AF, WHV, WXJ, WB, 115, 571, 572, 650, 671A, 750, SD78 and SD77 (Showa Denko K.K.) and Denka chloroprene A- , A-91, M-130L, DCR-11, LA-50 and LC-501 (Denki Kagaku Kogyo K.K.).

Examples of the chlorinated butyl rubber include EnjayButyl HT10-66 (manufactured by Enzyme Chemical Co.), JSR CHLOROBUTYL 1066 (manufactured by JSR Corporation), HT1066 (manufactured by Exxon Mobil Corp.) and the like.

Examples of the brominated butyl rubber include JSR BROMOBUTYL 2255, 2244 (manufactured by JSR Corporation), and Exonbromobutyl 2255 (manufactured by ExxonMobil Chemical Co., Ltd.).

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

As the styrenic block copolymer, there can be mentioned a block copolymer comprising a diene block and a styrene block. Specific examples thereof include styrene-butadiene block copolymer (SB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS) or hydrogenated products of block copolymers thereof, Styrene triblock copolymer (SIBS), and styrene-isobutylene diblock copolymer (SIB). Such a hydrogenated product may be either a hydrogenated block copolymer of a styrene block or a diene block, a partially hydrogenated block copolymer or a partially hydrogenated block copolymer such as a styrene block and a partially hydrogenated block copolymer, Or an additive.

As other resins, a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, and hydroxyethyl cellulose may be contained in order to further enhance the stability of the aqueous emulsion.

The other resin may include a pressure-sensitive adhesive resin or a resin having a function as a tackifier. Examples of such resins include petroleum resins obtained by polymerizing rosin, terpene resins, petroleum fractions of 5 carbon atoms and the hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions containing 9 carbon atoms, , Other petroleum resins, coumarone resins, and indene resins. Specific examples thereof include rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleinized rosin, fumarazine and their glycerin esters, pentaerythritol esters, methyl esters, triethylene glycol esters, phenol-modified products and esters thereof Rosins such as cargo; Terpene resins such as terpene polymers, terpene phenol,? -Pinene polymers, aromatic-modified terpene polymers,? -Pinene polymers, and terpene-based hydrogenated resins; Petroleum resins obtained by polymerizing petroleum oil having 5 carbon atoms, petroleum resins obtained by polymerizing petroleum oil having 9 carbon atoms and hydrogenated resins thereof; Maleic acid-modified products, and fumaric acid-modified products, and chlorinated paraffin.

As terpene resins, YSH Resin PX / PXN, YS Polyster, Mighty Ace and YS Resin TO / TR and Clearon P / M / K, Arakawa Chemical Industries Co., Ltd., 803L / 901 manufactured by Nippon Terpene Chemical Co., Ltd., and Teratak 80 manufactured by Nippon Terpene Chemical Co., Ltd.

250, 265, 270, 150, A50 (manufactured by Tosoh Corporation), and the like can be used as the chlorinated paraffin. .

Other resins may be used alone or in combination of two or more.

Other resins are readily available from the market.

When the aqueous emulsion of the present invention contains other resin, its content is preferably 100 parts by mass or more per 100 parts by mass of the total of the mass of the polymer (B) containing a halogen atom and the mass of the compound (E) Is not more than 100 parts by mass, more preferably not more than 50 parts by mass, more preferably not more than 30 parts by mass, and even more preferably not more than 20 parts by mass. The other resin may be mixed with the aqueous emulsion of the present invention in the emulsion state, or emulsified together with a polymer (B) containing a halogen atom and a compound (E) having a polymerizable group to form an aqueous emulsion.

<Thickener>

Thickening agents can be used to adjust the viscosity of aqueous emulsions. 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 Seeker 920, 922, 924, 926, 929-S, A-801, A-806, A- A-818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636 and 4050 (SANNOPO CO., LTD.).

<Form of aqueous emulsion>

In the aqueous emulsion of the present invention, it is preferable that a polymer (B) containing a halogen atom and a compound (E) having a polymerizable group are contained as a mixture. The mixture is a state in which a polymer containing a halogen atom and a compound having a polymerizable group are mixed, a state in which the polymer (B) containing a halogen atom is dispersed or swollen in a compound (E) having a polymerizable group, And at least a part of the polymer (B) is dissolved in a compound having a polymerizable group.

The phrase "at least a part of the halogen atom-containing polymer (B) is dissolved in the compound having a polymerizable group" means that a mixture of a polymer (B) containing a halogen atom and a compound having a polymerizable group is filtered At least part of the polymer (B) containing a halogen atom may be contained in the filtrate upon filtration. The polymer (B) containing a halogen atom contained in the filtrate is preferably at least 1 part by mass, more preferably at least 1 part by mass, per 100 parts by mass of the halogen atom-containing polymer (B) contained in the aqueous emulsion before filtration 10 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 70 parts by mass or more.

The filtration by the filter is preferably carried out after heating the aqueous emulsion to a temperature not lower than the melting point of the compound having a polymerizable group contained in the aqueous emulsion.

As a method of using a mixture of the halogen atom-containing polymer (B) and the polymerizable group-containing compound (E) as a mixture, the polymer (B) containing a halogen atom and the compound (E) And a method of mixing them. The mixing temperature is usually 25 to 100 占 폚. The mixing time is preferably as short as possible. Examples of the mixer include a Banbury mixer, a Henschel mixer, and a homomixer.

It is preferable that the mixture of the halogen atom-containing polymer (B) and the polymerizable group-containing compound (E) is contained as a dispersion medium. Here, the dispersoid means particles dispersed in water. In this case, the dispersion medium may be solid at 23 占 폚 under atmospheric pressure, but it is preferably liquid.

In the case where the dispersion medium is a liquid, at least one of the components constituting the dispersion medium may have fluidity, and the dispersion medium may contain a solid component or an insoluble component.

When the dispersion quality is liquid and has fluidity, the fluidity may be high or low. When the fluidity is low, the stability of the aqueous emulsion tends to be improved, and when the fluidity is high, the adhesiveness tends to be improved. Preferably, the dispersion medium is liquid at 23 占 폚 under atmospheric pressure.

The content of the total of the halogen atom-containing polymer (B) and the polymerizable group-containing compound in a total amount of the polymer (B) containing a halogen atom, the compound having a polymerizable group, , Preferably from 0.1 to 70 mass%, more preferably from 1 to 70 mass%, and even more preferably from 2 to 60 mass%. Within the above range, adhesiveness is improved. In particular, when the amount is 30% by mass or more, the stability of the aqueous emulsion is improved. Therefore, it is more preferably 30% by mass to 60% by mass, further preferably 40% by mass to 60% by mass, still more preferably 45% by mass to 60% by mass.

The dispersion quality in the aqueous emulsion is preferably 0.01 to 5 占 퐉, more preferably 0.01 to 2 占 퐉, and still more preferably 0.01 To 1 mu m. Within this range, the stationary stability is improved.

The median diameter on a volume basis refers to a median diameter measured on a volumetric basis, unless otherwise specified, and the value of the cumulative particle size distribution is 50% by volume.

The average particle size of the dispersoid can be measured by a laser diffraction particle size analyzer LA-950V2 manufactured by HORIBA, Ltd.

&Lt; Preparation method of aqueous emulsion &gt;

The aqueous emulsion of the present invention can be prepared by a known method. For example, the polymer (B) containing a halogen atom and the compound (E) having a polymerizable group are dispersed in a dispersion medium such as water and then emulsified (for example, a forced emulsification method, a self emulsification method, ). &Lt; / RTI &gt;

For example, a polymer (B) containing a halogen atom and a compound (E) having a polymerizable group may be added to the reactor (optionally, an additive may be added) and then mixed with water and / Optionally adding an additive such as a surfactant or a photopolymerization initiator, and then emulsifying the mixture by heating and stirring.

Examples of the reactor include a heating device and a container provided with a stirrer capable of applying a force such as a shearing force to the contents. Preferably, it is a sealed container or a pressure-resistant container. As the agitator, a general one can be used. Examples of such a reactor include a pressure-resistant autoclave equipped with a stirrer. The agitation may be carried out by either normal pressure or reduced pressure. The number of revolutions of the agitator is usually 50 to 20,000 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 stirring may be carried out 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, or may be added after adding water and / or a solvent , Or may be added after emulsification. In particular, a light stabilizer, an ultraviolet-curable oligomer, a fluorescent whitening agent, a photosensitizer and other resins are preferably added before adding water and / or a solvent.

Pre-emulsification is performed in advance to obtain an aqueous emulsion having a large particle diameter, and high-pressure shearing is performed with a device such as a high-pressure homogenizer or high-pressure homogenizer to obtain an aqueous emulsion having a small particle diameter.

When the obtained aqueous emulsion contains an organic solvent after emulsification, it is preferable to remove the organic solvent. The removal of the organic solvent is usually carried out by distillation under reduced pressure.

When a surfactant is used in the production of the aqueous emulsion, the surfactant may be separated and removed from the resulting aqueous emulsion. Separation and removal of the surfactant can be carried out by, for example, a centrifugal separator, a filtration filter having pores having an average pore diameter smaller than that of the aqueous emulsion, or an ultrafiltration membrane. However, separation and removal of the surfactant may be performed only by reducing the amount of the surfactant.

The obtained aqueous emulsion is preferably cooled. By cooling, an aqueous emulsion composed of a fine dispersion medium can be obtained. The cooling is preferably carried out gently by leaving it at room temperature instead of quenching. As a result, a fine and homogeneous aqueous emulsion can be obtained without aggregation of the resin or the like during the cooling process.

&Lt; Use of aqueous emulsion &gt;

The aqueous emulsion of the present invention is useful as a composition constituting an aqueous adhesive or the like as described above. It may also be used as a composition for forming an applied film or coating film by an aqueous emulsion on an adherend. The aqueous adhesive, the coating film and the coating film are usually used as a dried product or a cured product. Particularly, the water based adhesive effectively exerts its function in the form of a coating film by aqueous emulsion or a cured product thereof.

<Adherend>

Examples of the adherend (including the first substrate and the second substrate) to be coated, covered, or adhered include wood-based materials such as wood, plywood, MDF, particle boards, and fiber boards; Cellulosic materials such as cotton, cotton-containing fibers, abrasion, and rayon; Polyolefins such as polyethylene (polyolefin having a structural unit derived from ethylene as a main component), polypropylene (polyolefin having a structural unit derived from propylene as a main component), polystyrene (polyolefin having a structural unit derived from styrene as a main component) Polyvinyl chloride, polyurethane, foamed urethane, ethylene-vinyl acetate copolymer (EVA), expanded EVA (polyvinyl chloride), polyvinyl chloride, , Nylon 6, nylon 66, or the like, or a foam thereof; Polyurethane-based, polyamide-based and polyamino-based synthetic leather; Ceramics such as glass, ceramics and the like; Iron, stainless steel, copper plate, aluminum and the like. These may be composite materials composed of a plurality of components. In addition, an inorganic filler such as talc, silica or activated carbon, carbon fiber, and the like may be kneaded and molded products of plastic materials.

Among them, adhesion between a cellulose-based material and a plastic material, a styrenic block copolymer such as polyvinyl chloride, an ethylene-vinyl acetate copolymer, a cotton-containing fiber, a nylon resin, an olefinic polymer, a polyurethane, a rubber and a styrene- Synthetic leather and the like. The shape of these materials may be a film, a sheet, or a block or the like, but is preferably a film or a sheet.

The styrenic block copolymer is a block copolymer composed of a diene block and a styrene block. Specifically, the styrene-butadiene block copolymer (SB), the styrene-butadiene-styrene block copolymer (SBS), the styrene- (SBS), styrene-butadiene-butylene-styrene copolymer (SBBS) or a hydrogenated product of a block copolymer thereof, styrene / isobutylene-styrene triblock copolymer (SIBS), styrene- Copolymer (SIB). Such a hydrogenated product may be either a hydrogenated block copolymer of a styrene block or a diene block, a partially hydrogenated block copolymer or a partially hydrogenated block copolymer such as a styrene block and a partially hydrogenated block copolymer, Or an additive.

The olefinic polymer is a resin obtained by polymerizing an olefin, and examples thereof include homopolymers and copolymers having a structural unit derived from an? -Olefin having 2 to 20 carbon atoms. Examples of the olefin polymer include those exemplified above for the other resins.

As the resin constituting the adherend, those exemplified in the other resins can be mentioned.

The surface-containing fiber may be 100% cotton, or may be blended with cotton and other natural fibers and / or chemical fibers. Other natural fibers include wool, silk and hemp. Examples of the chemical fiber include synthetic fibers (e.g., polyamide fibers such as polyester fibers and nylon fibers), semisynthetic fibers (cellulose fibers such as acetate and protein fibers such as pro mix), regenerated fibers , Cellulose fibers such as polynosic fibers) and inorganic fibers (carbon fibers, glass fibers).

Examples of the shape of the surface-containing fiber include a woven fabric, a knitted fabric, a nonwoven fabric, a knitted fabric, a felt, a film or a block.

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

As the rubber, for example, diene rubbers such as natural rubber, thermoplastic rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber and butyl rubber are mainly used. At the time of preparing the rubber composition, these diene rubbers may be used alone or in combination of two or more. A reinforcing agent such as clay, carbon black or silica, a silane coupling agent, an anti-aging agent, a softening agent, zincation, stearic acid, a vulcanization accelerator, a vulcanizing agent, sulfur and the like may be appropriately blended.

Synthetic leather includes both synthetic leather and synthetic leather in consultation. In other words, it may be a synthetic leather obtained by applying a synthetic resin to a natural or synthetic forge or the like, or an artificial leather obtained by impregnating a forge (usually a nonwoven fabric) such as a microfiber with a synthetic resin, Or an artificial leather obtained by impregnating a synthetic resin with a synthetic resin. Examples of the synthetic resin include a polyurethane resin, a polyamide resin, and a polyamino acid resin. Preferably, it is a polyurethane resin.

The aqueous emulsion of the present invention is effective for adhesion of a material such as a film, a sheet, a structural material, a building material, an automobile part, an electric and electronic product, a packaging material, a medical treatment and a footwear (hereinafter sometimes referred to as an adherend) Can be used. Particularly, it is preferable as an adhesive for adhering a constituent material (adherend) such as upper, middle, and lower back in shoe such as shoe shine, sports shoes, town shoe, business shoe, shoe shine, The surface of these adherends may be smooth or have irregularities. In addition, a primer treatment may be applied to their surfaces to increase adhesion of an adhesive or the like. Examples of the primer treatment include blasting, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and formation of an anchor layer.

<Application Method>

As the method of adhering the adherend described above, there can be used a method of laminating an adherend (first base material), a coating film obtained by drying the aqueous emulsion of the present invention, an adhesive layer and an adherend (second base material) . Specifically, the following methods can be mentioned.

First, an aqueous emulsion is applied to the surface of the first substrate, optionally the second substrate. The aqueous emulsion may be applied to the surfaces of the first base material and the second base material by any known coating method. The coating film is formed 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, brush application, And then applying an adhesive to one or both surfaces of the complex.

After coating the first base material with the aqueous emulsion, the obtained coating film may be subjected to drying or heat treatment, and then electromagnetic waves may be further irradiated thereafter.

In the case of drying or heating treatment, the coating film can be formed by removing water or solvent by drying or heat treatment.

The heating temperature is about 30 to 150 占 폚.

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.

The first base material treatment may be performed before or after the heat drying treatment by further leaving (natural drying) or using an electromagnetic wave such as a conventional hot air circulating oven, an infrared heater, or ultraviolet rays. The heating temperature and time in the preliminary drying in this case can be appropriately adjusted depending on the properties of the substrate, the composition of the aqueous emulsion to be used, and the like. For example, the same conditions as described above can be given.

The application and drying of the aqueous emulsion may be carried out only once, or two or more times. The application method and the drying method may be the same or a combination of different methods.

In the case of electromagnetic wave processing, metal halide lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, xenon lamps, arc lamps and lasers can be used as the light source. Preferably, metal halide lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and low-pressure mercury lamps are exemplified. The irradiation dose is usually from 5 to 2000 mW / cm 2, preferably from 10 to 2000 mW / cm 2, and the cumulative dose is usually from 20 to 3000 mJ / cm 2, preferably from 100 to 2500 mJ / Cm &lt; 2 &gt;.

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

It is preferable that at least 95 mass% of the water contained in the aqueous emulsion is removed from the coated film after drying. By setting this range, adhesiveness can be ensured.

The thickness of the coated film after drying is a thickness of about 0.01 to about 300 mu m after the drying treatment, preferably about 0.01 to 200 mu m, and more preferably about 0.01 to 50 mu m.

Subsequently, an adhesive is applied to at least one of the first base material and the second base material coated with the aqueous emulsion, followed by heat drying treatment. These coating and heating and drying treatments may be performed only once in at least one of the first base material and the second base material, but they may be applied to both of them at one or more times and heat dried.

The application method of the adhesive, the thickness of the application, the method of the heat treatment, the conditions such as temperature and time, and the like can be appropriately changed. The same conditions as those for applying and drying the above-described aqueous emulsion may be selected, or different conditions may be selected.

When an adhesive is applied to both the first base material and the second base material, the adhesive layer need not be the same as the first base material and the second base material, but it is preferable to use the same adhesive in consideration of the adhesiveness of the first base material and the second base material Do. The adhesive may be an aqueous emulsion used above, or a commercially available adhesive.

The thickness of the adhesive layer can be appropriately adjusted depending on the composition of the adhesive to be used, the material and the form of the substrate, and the like. For example, the thickness after the drying treatment is about 0.01 to 300 mu m, preferably about 0.01 to 200 mu m.

The surface of the second base material may be subjected to a primer treatment before the aqueous emulsion is applied to the adherend. The primer treatment can be appropriately selected from those described above.

The method of bonding the surfaces of the first base material and the second base material to which the aqueous emulsion and / or the adhesive has been applied may be either a mechanical operation or a manual operation.

And may be performed while applying heat, pressure, or both at the time of conjugation. When heat is applied, the first base material, the second base material and the adhesive layer need to be set in a temperature range in which they do not deteriorate, preferably about 120 ° C or lower, and more preferably about 100 ° C or lower. The heat load may be performed by using the above-described conventional hot-air circulation type oven, infrared heater, microwave oven, or the like. The pressure when the pressure is applied may be about 100 g / cm 2 or more and may be less than the pressure at which the shapes of the first base material and the second base material are deformed. When heat and / or pressure are applied, the time may be, for example, about 1 second to 10 days.

Examples of the first base material and the second base material include the same materials as those described above. Among them, the first substrate is preferably a substrate made of an olefinic polymer or an ethylene-vinyl acetate copolymer, and the second substrate is preferably a polyolefin-based polymer, The substrate to be selected is preferred.

The adhesive layer is obtained, for example, by heat drying or electromagnetic wave treatment from polyurethane, a rubber adhesive, an acrylic adhesive, and an epoxy adhesive to remove water or a solvent.

As the polyurethane, the same ones as mentioned above can be mentioned.

Examples of the rubber adhesives include natural rubber, chloroprene rubber, styrene-butadiene copolymer rubber (SBR), isobutylene rubber, butyl rubber, styrene-isoprene-styrene block copolymer rubber (SIS), styrene-butadiene- Rubber (SBS), butadiene-acrylonitrile copolymer rubber (NBR), and butadiene rubber (BR). These may be used singly or in combination of two or more. In addition to these rubber components, an adhesive resin such as a rosin resin, a terpene resin, or a petroleum resin may be mixed.

As the acrylic adhesive, a copolymer of an acrylate ester and / or a methacrylate ester as a pressure-sensitive adhesive component and a functional group monomer component and an aggregating component copolymerizable therewith can be preferably exemplified. The copolymer may be crosslinked with an isocyanate crosslinking agent, a chelate crosslinking agent, an epoxy crosslinking agent, or the like.

Examples of the acrylic ester include acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, N-lauryl acrylate, and the like can be preferably exemplified. Examples of the methacrylic esters include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, N-hexyl acrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-lauryl methacrylate, and the like.

Examples of the functional monomer component copolymerizable with the acrylic acid ester and / or methacrylic acid ester include?,? - unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; Hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; N-substituted or unsubstituted acrylamides such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-butoxymethylacrylamide and N-butoxy methacrylamide; Glycidyl esters of acrylic acid or methacrylic acid such as glycidyl methacrylate and glycidyl methacrylate; Acrylonitrile and the like can be preferably exemplified.

The epoxy adhesive is a compound having on average at least one epoxy group per molecule, which is used as a component of a conventional epoxy resin-based adhesive. 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, oxazolidin-modified epoxy resins, novolak-type epoxy resins, polyfunctional phenol-type epoxy resins, various halogenated epoxy resins, glycidyl ester type epoxy resins, polyglycol type epoxy resins, and cyclic aliphatic epoxy resins can also be used have. These epoxy resins may be used alone or in combination of two or more.

The polyurethane, the rubber adhesive, the acrylic adhesive and the epoxy adhesive may be in the form of an adhesive such as an aqueous system, a solvent system and a hot melt.

The adhesive constituting the adhesive layer may contain a resin or an additive other than the adhesive described above.

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) Polymers and copolymers such as acrylonitrile butadiene styrene resin (ABS resin) and AS resin, and modified polymers and modified products. These may be blended alone or in combination of two or more.

In addition, a resin exhibiting a function as a pressure-sensitive adhesive resin or a tackifier may be used.

Such resins include, for example, rosins, terpene resins, petroleum resins obtained by polymerizing petroleum oil having 5 carbon atoms, and hydrogenated resins, petroleum resins obtained by polymerizing petroleum oil having 9 carbon atoms, and hydrogenated resins, Other petroleum resin, coumarone resin, indene resin, and polyurethane resin.

Examples of the additive that may be contained in the adhesive layer include a surfactant, a photopolymerization initiator, a light stabilizer, an ultraviolet curable oligomer, a fluorescent brightener, a leveling agent, a basic compound, an organic solvent, a crosslinking agent, a photosensitizer, An antistatic agent, an antistatic agent, an antioxidant, a heat stabilizer, a thixotropic agent, a thickener, a defoaming agent, a viscosity adjusting agent, a lubricant, a pigment dispersant, an antistatic agent, a lubricant , Nucleating agents, flame retardants, emulsions, dyes, hardeners; Transition metal compounds such as titanium oxide (rutile type) and zinc oxide; Pigments such as carbon black; Glass fiber, calcium carbonate, calcium carbonate, talc, glass flake, barium sulfate, clay, kaolin, fine powder silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, And inorganic or organic fillers such as magnesium, alumina and celite.

It is preferable that the coating film of the aqueous emulsion, the dried product of the coating film and the cured product thereof have a shear viscosity of less than 200 Pa · s. In this range, the adhesiveness tends to be improved. The shear viscosity is a rotational rheometer using a cone plate (angle 2 °), and has a shear rate of 1 s -1, a measurement temperature of 25 ° C. (when the melting point of the compound having a polymerizable group is higher than 25 ° C., Lt; RTI ID = 0.0 &gt; 10 C &lt; / RTI &gt;

The dried product of the aqueous emulsion is preferably removed by 95% by mass or more of the mass of water contained in the aqueous emulsion. As a result, the influence of water given to the shear viscosity can be suppressed, and a desired shear viscosity can be obtained.

Example

Hereinafter, an embodiment of the aqueous emulsion of the present invention will be described in detail. Unless otherwise stated, parts and% in the examples mean mass basis.

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 chromatographic method.

The concentration of the component of the aqueous emulsion is preferably such that the mass of the polymer containing the halogen atom and the mass of the compound having the polymerizable group in the total amount of the polymer containing the halogen atom and the polymer containing the polymerizable group The mass concentration (mass%) is calculated.

The median diameter of the dispersion medium is a value measured by a laser diffraction particle size analyzer LA-950V2 manufactured by HORIBA Corporation. Unless otherwise stated, the value of the median diameter measured in terms of volume is (unit: 탆).

The stability of the obtained aqueous emulsion was evaluated by standing the aqueous emulsion for 3 weeks at room temperature and observing the aqueous emulsion. When the phase separation was not visually confirmed in the aqueous emulsion, it was judged that the stability of the solution was good.

○: No change

X: Phase separation was visually confirmed

The polymer containing a halogen atom, the compound having a polymerizable group, the photopolymerization initiator, the surfactant, the ultraviolet-curable oligomer, the fluorescent brightener and the organic solvent in the production examples and the evaluation examples are as follows.

Polymer 1 containing halogen atoms: chlorinated rubber (product name: Pergut S20 (Bayer, chlorine content: 58.8 mass% or more))

Polymer 2 containing halogen atoms: chlorinated rubber (product name: Pergut S40 (Bayer, chlorine content 65.5 mass% or more))

Polymer 3 containing halogen atoms: polyvinyl chloride (trade name: low molcular weight (manufactured by Aldrich))

Polymer 4 containing a halogen atom: Chlorinated polyolefin resin (trade name: Harden HM-21P, manufactured by Toyobo Co., Ltd., chlorine content: 21 mass%)

Polymer 5 containing halogen atoms: chlorinated polyolefin resin (product name: HARDEN F-6P, manufactured by Toyobo Co., Ltd., chlorine content: 20% by mass)

Polymer 6 containing halogen atoms: Chloroprene resin (trade name: Showprene W, Showa Denko K., chlorine content: 37.8% by mass, aqueous emulsion)

Polymer 7 containing a halogen atom: solution of chloroprene resin (product name: NO TAPE NP9820, manufactured by NOFTA Co., Ltd.)

Compound 1 having a polymerizable group 1: methacrylic acid decenyl (containing 970 ppm of 4-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.)

Compound 2 having a polymerizable group: 1,6-hexanediol dimethacrylate (containing 60 ppm of 4-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.)

Compound 3 having a polymerizable group: stearyl methacrylate (containing 200 ppm of 4-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.)

Compound 4 having a polymerizable group: 2-ethylhexyl methacrylate (containing 25 ppm of 4-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.)

Compound 5 having a polymerizable group: cyclohexyl methacrylate (containing 50 ppm of 4-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.)

Compound 6 having a polymerizable group: ethoxy isocyanuric acid triacrylate (trade name: A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)

Compound 7 having a polymerizable group: diacetone acrylamide (containing 100 ppm of 4-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.)

Compound 8 having a polymerizable group: neopentyl glycol diglycidyl ether (manufactured by TOKYO CHEMICAL INDUSTRIES CO., LTD.)

Reactive surfactant 1: Aquarone KH-10 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

Surfactant 2: Latte water E-1000A (30% aqueous solution, Cao Corporation)

Surfactant 3: Neigen EA-177 (Daiichi Kogyo Pharmaceutical Co., Ltd.)

Surfactant 4: DKS NL-180 (Daiichi Kogyo Pharmaceutical Co., Ltd.)

Polymer surfactant 5: Kuraray Poval 217 (manufactured by Kuraray Co., Ltd.)

Polymer surfactant 6: Kuraray Poval 205 (manufactured by Kuraray Co., Ltd.)

Polymer surfactant 7: Adekafluronic F108 (manufactured by ADEKA Corporation)

Polymer surfactant 8: Kuraray Poval M-205 (manufactured by Kuraray Co., Ltd.)

Polymer surfactant 9: Kuraray Fowal MP-203 (manufactured by Kuraray Co., Ltd.)

Polymer surfactant 10: KL-318 (manufactured by Kuraray Co., Ltd.)

Polymeric surfactant 11: CM-318 (manufactured by Kuraray Co., Ltd.)

Polymer surfactant 12: Fitzcor K-30 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

Polymer Surfactant 13: Acid artist H-PN (manufactured by San-Egen Ff. Co., Ltd.)

Polymer Surfactant 14: Aquarim AKM-0531 (manufactured by Nichicon Corporation)

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

Photopolymerization initiator 2: 1-Hydroxy-cyclohexyl phenyl ketone (manufactured by 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 1: BYK-349 (Big Chemie Japan)

Basic compound 1: N, N-dimethylethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

UV curable oligomer 1: AH-600 (Kyoeisha Chemical Co., Ltd.)

UV curable oligomer 2: UA-306H (Kyoeisha Chemical Co., Ltd.)

Fluorescent brightener: 1,4-bis (2-benzoxazolyl) naphthalene (Tokyo Chemical Industry Co., Ltd.)

In each table, these components are expressed as parts by mass.

&Lt; Preparation Example 1 &

10 parts of Polymer 1 (Pergut S20 (Bayer)) containing a halogen atom, 10 parts of a halogen atom-containing polymer 1, and 1 part of a compound having a polymerizable group as a compound having a polymerizable group (meta And 60 parts of a compound having a polymerizable group (1,6-hexanediol dimethacrylate (TOKYO CHEMICAL INDUSTRIES, LTD.)) Were charged, stirred at 60 DEG C to dissolve, cooled to room temperature Respectively.

2 parts of Surfactant 2 (Latex E-1000 (Kao Corporation)) and 5 parts of Polymer Surfactant 5 (Kurara Pawbal 217 (Kuraray Co., Ltd.)) were added to 100 parts of ion-exchanged water, To prepare an ion-exchange water solution of a surfactant.

At room temperature, an ion-exchange water solution of surfactant 2 and polymer surfactant 5 was added to a mixture of polymer 1 containing a halogen atom and a compound having a polymerizable group, and further N, N-dimethylethanolamine (TOKYO CHEMICAL INDUSTRIAL CO., LTD.) Was added and mixed by stirring. Then, a stirrer homomixer MARKII was mounted on a TK Robomix (manufactured by PRIMIX Co., Ltd.) and stirred at 16000 rpm for 2 minutes to obtain a milky white aqueous emulsion . Subsequently, the aqueous emulsion obtained by treating with LAB1000 of high pressure homogenizer (manufactured by SMT Co., Ltd.) once at 800 bar was filtered with a 200-mesh nylon screen to obtain an aqueous emulsion (E-1). Each component added is shown in Table 1-1.

&Lt; Production Examples 2 to 32 &gt;

Aqueous emulsions (E-2) to (E-32) were obtained in the same manner as in Production Example 1 except that the mixing ratios of the respective components were different as shown in Tables 1-1 and 1-2 below.

[Table 1-1]

[Table 1-2]

&Lt; Production Example 33 &gt;

10 parts of a halogen-containing polymer 4 (hyaluronan HN-21P (Toyobo Co., Ltd.)) was added to a separable flask reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and a compound 4 having a polymerizable group (2-ethylhexyl methacrylate (Tokyosho Kagaku Kogyo)), 190 parts of tetrahydrofuran (Hayashi Pure Chemical Industries, Ltd., special grade) was added, and the mixture was stirred at 60 캜 for dissolution. The mixture was cooled to room temperature, And a compound 4 having a polymerizable group were prepared in a tetrahydrofuran solution.

5 parts of Polymer Surfactant 6 (Kuraray Fowal 205 (Kuraray Co., Ltd.)) was added to 100 parts of ion-exchanged water and dissolved by stirring at 90 ° C to prepare an ion-exchange water solution of Polymer Surfactant 6.

At room temperature, an ion-exchanged water solution of a polymeric surfactant 6 was added to a tetrahydrofuran solution of a polymer 4 containing a halogen and a compound 4 having a polymerizable group, and further N, N-dimethylethanolamine 2 (TOKYO CHEMICAL INDUSTRIAL CO., LTD.) Was poured and stirred and mixed. Then, a stirrer homomixer MARKII was attached to TK Robomix (manufactured by PRIMIX Co., Ltd.) and stirred at 16000 rpm for 2 minutes to obtain a milky white aqueous emulsion. The aqueous emulsion thus obtained was placed in an eggplant type flask, subjected to reduced pressure distillation with a separator, and then filtered through a 200 mesh nylon mesh to obtain an aqueous emulsion (E-33). The non-volatile matter concentration of the resulting aqueous emulsion (E-33) was 50%. Each added component is shown in Table 1-3.

&Lt; Preparation Examples 34 to 48 &gt;

Aqueous emulsions (E-34) to (E-48) were obtained in the same manner as in Production Example 33, except that the mixing ratios of the components were different as shown in Table 1-3 below.

[Table 1-3]

&Lt; Preparation Examples 49 to 50 &

Aqueous emulsions (E-49) and (E-50) were obtained in the same manner as in Production Example 1 except that the mixing ratios of the components were different as shown in Table 1-4 below.

[Table 1-4]

The aqueous emulsions (E-1) to (E-48) prepared in Preparation Examples 1 to 48 were allowed to stand at room temperature for 3 weeks, and no phase separation occurred in the aqueous emulsion after 3 weeks. On the other hand, aqueous emulsions (E-49) and (E-50) prepared in Production Examples 49 to 50 were allowed to stand at room temperature for 3 weeks, and phase separation was confirmed in the aqueous emulsion. For this reason, it has become clear that the aqueous emulsions (E-49) and (E-50) are not excellent in stability.

&Lt; Preparation Example 51 &

(Manufactured by Nippon Polyurethane Industry Co., Ltd.), polyurethane emulsion (DisperCol (registered trademark) U-54, manufactured by Sumika Bayer Urethane Co., Ltd.), isocyanate (Desmodur (registered trademark) N3300, -349, manufactured by BICKEMI Japan Co., Ltd.) in an amount of 100 parts: 5 parts: 1 part as a nonvolatile component ratio to obtain an aqueous emulsion (E200).

&Lt; Production Examples 52 to 101 &gt;

Aqueous emulsions (E-1) to (E-50), photopolymerization initiator 1, leveling agent 1 (BYK (registered trademark) -349, Big Chemical Japan Co., Ltd.) And the mixture was stirred with a three-one motor to obtain aqueous adhesives (F1) to (F50) containing the aqueous emulsion obtained in Production Example.

Further, as a mode of the aqueous emulsion of the present invention, a mode further containing an additive suitable as an adhesive is described as &quot; aqueous adhesive &quot;.

[Table 2-1]

<Evaluation Examples 1 to 50>

The water-based adhesives (F1 to F50) prepared in Production Examples 52 to 101 were applied to a first substrate, M-EVA (a foam of ethylene-vinyl acetate copolymer) using a brush (coating amount: about 3 g / M &lt; 2 &gt;), dried at 150 DEG C for 5 minutes, and irradiated with ultraviolet rays to obtain M-EVA (A) with a conveyor type UV irradiator (IGLANDAGE ECS-4011GX manufactured by Eye Graphics Co., Ltd.). (Lamp: high pressure mercury lamp, lamp output: 3 ㎾, lamp height: 110 ㎜, conveyor speed: 276 m / min, cumulative light quantity: 1100 mJ / cm 2 (UVICURE PLUS II, UV-A measurement value, FusionUV Systems Japan KK)

Subsequently, an aqueous emulsion (E200) was applied to flexible polyvinyl chloride and M-EVA (A) using a brush (coating weight: about 50 g / m 2 after drying) and then oven-dried at 120 ° C for 5 minutes. Thereafter, the coated soft polyvinyl chloride and the aqueous emulsion E200 of M-EVA (A) were adhered to each other, pressed by hand, and further pressed with a pressure of 3 MPa for 20 seconds. Thus, stacked layers 1 to 50 in which an adhesive layer composed of flexible polyvinyl chloride and E200, an adhesive layer irradiated with ultraviolet rays, and a first substrate (M-EVA) were laminated in this order were obtained.

The obtained laminate was allowed to stand at room temperature for 24 hours and then stretched at room temperature using a tensile tester (Autograph) manufactured by Shimadzu Corporation) at a stripping rate of 50 mm / -EVA and soft polyvinyl chloride were evaluated by measuring the 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.

[Table 3-1]

<Evaluation Examples 51 to 53>

EVA (foam of ethylene-vinyl acetate copolymer) &quot; used as the first base material in Evaluation Example 1 was changed to the base material described in the &quot; first base material &quot; in the following Table 3-2 The laminated bodies 51 to 53 were obtained in the same manner as in Evaluation Example 1.

The obtained laminate was allowed to stand at room temperature for 24 hours and thereafter stretched using a tensile tester (Autograph) manufactured by Shimadzu Corporation) at a peeling rate of 50 mm / min, a peeling angle of 180 degrees at room temperature, 1 substrate and soft polyvinyl chloride was evaluated by measuring the 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.

[Table 3-2]

PE / EVA = 60/40: Foam obtained by polymerizing polyethylene / ethylene-vinyl acetate copolymer 60/40 (PE / EVA = 60/40)

PE / SEBS = 50/50: Foam obtained by polymerizing polyethylene / styrene-ethylene-butylene-styrene block copolymer 50/50 (PE / SEBS = 50/50)

SBBS: Foam polymerized with styrene-butadiene-butylene-styrene block copolymer (SBBS)

The layered products 1 to 48 produced using the water-based adhesives F1 to F48 exhibited sufficiently high peel strengths of 55 N / inch or more in general. The laminate bodies 52 to 54 produced by changing the first substrate of the laminate body 1 to the materials of the laminate bodies 52 to 54 exhibited sufficiently high peeling strengths of 55 N / inch or more similarly to the laminate body 1.

The aqueous emulsion of the present invention can be usefully used as an adhesive or a coating film because it adheres to an adherend or between adherends with sufficient strength.

Claims (28)

(A) comprising at least one member selected from the group consisting of a compound containing a structural unit represented by the following formula (I) and / or a polymer polymer, a polymer (B) containing a halogen atom, An aqueous emulsion comprising water (C).

[In the formula (I)
X is a nitrogen atom, CH or naphthylene group,
Y ¹ and Y ² each independently represents a hydroxyl group, -COOR ¹ , -OCOR ² , 2-pyrrolidon-1-yl group, polyalkylene oxide or -SO ₃ M _a (M _a represents a hydrogen atom, NH &lt; ₄ &gt; or an alkali metal,
R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkali metal, -NH ₄ or - (CH ₂ CH ₂ O-) _s -Z (s represents an integer of 1 to 100, An alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a glycidyl group having 3 to 10 carbon atoms, or -SO ₃ M _b (M _b is a hydrogen atom, -NH ₄ or an alkali metal) Lt; 2 &gt;),
The polyalkylene oxide preferably contains 1 to 30 alkylene oxide units having 1 to 8 carbon atoms,
R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
m represents an integer of 1 to 4,
p represents an integer of 40 to 2000,
q represents 0 or a positive integer such that the sum of p and q is an integer of 40 to 2000,
r represents an integer of 0 to 4]
Polymer polymers: alkali metal salts of croscarmellose, alkaline earth metal salts of carboxymethyl cellulose, alkali metal salts of carboxymethyl cellulose, alkali metal salts of carboxymethyl starch, (methyl) styrene-maleic acid ester copolymers, polyoxyethylene polyoxypropylene block Polymers and polydiallyldimethylammonium chloride. The method according to claim 1,
An aqueous emulsion, which is a compound containing a structural unit represented by the formula (I), wherein q is an integer 0 and contains a structural unit represented by the following formula (I ').

[In the formula (I '),
m, X, Y ² and p have the same meanings as defined in formula (I) The method according to claim 1,
Wherein the structural unit represented by the formula (I) is a structural unit represented by the formula (II).

[In the formula (II)
p and q satisfy the relationship that p / (p + q) is 0.8 or more and 1 or less] 4. The method according to any one of claims 1 to 3,
An aqueous emulsion further comprising a surfactant (D) represented by the following formula (III).

[In the formula (III)
R ⁴ represents an alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a polyalkylene oxide group, a (meth) acrylate group having a hydrocarbon group having 1 to 30 carbon atoms, and a combination thereof, And the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group,
The polyalkylene oxide group includes at least 1 and at most 30 alkylene oxide units having 1 to 8 carbon atoms,
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 1 to 40, 5. The method of claim 4,
The above-mentioned surfactant (D) is an aqueous emulsion which is a reactive surfactant represented by the following formula (IV).

[In the formula (IV)
R ⁵ 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 ⁶ represents a hydrogen atom or a methyl group,
R ⁷ 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 may be substituted with an oxygen atom or a carbonyl group And,
The polyalkylene oxide group includes at least 1 and at most 30 alkylene oxide units having 1 to 8 carbon atoms,
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; 6. The method according to any one of claims 1 to 5,
Further, an aqueous emulsion containing a compound (E) having a polymerizable group. The method according to claim 6,
Wherein the content of the compound (E) having a polymerizable group is 50 to 10000 parts by mass based on 100 parts by mass of the halogen atom-containing polymer (B). 8. The method according to claim 6 or 7,
An aqueous emulsion comprising, as a dispersoid, a mixture of a polymer (B) containing a halogen atom and a compound (E) having a polymerizable group. 9. The method of claim 8,
An aqueous emulsion in which the dispersion quality is liquid. 10. The method according to claim 8 or 9,
An aqueous emulsion in which at least a part of the polymer (B) containing a halogen atom is dissolved in a dispersion medium. 11. The method according to any one of claims 6 to 10,
An aqueous emulsion comprising, as a dispersoid, a solution in which at least a part of the polymer (B) containing a halogen atom is dissolved in a compound (E) having a polymerizable group. 12. The method according to any one of claims 6 to 11,
Wherein the compound (E) having a polymerizable group is a liquid at 23 DEG C under atmospheric pressure. 13. The method according to any one of claims 6 to 12,
An aqueous emulsion wherein the compound (E) having a polymerizable group is a compound having an ethylenically unsaturated double bond. 14. The method according to any one of claims 1 to 13,
Further, an aqueous emulsion comprising a photopolymerization initiator. 15. The method according to any one of claims 1 to 14,
Additionally, an aqueous emulsion comprising a light stabilizer. 16. The method according to any one of claims 1 to 15,
Additionally, an aqueous emulsion comprising an ultraviolet curable oligomer. 17. The method according to any one of claims 1 to 16,
Further, an aqueous emulsion comprising a fluorescent whitening agent. 18. The method according to any one of claims 1 to 17,
Additionally, an aqueous emulsion comprising a leveling agent. 19. The method according to any one of claims 7 to 18,
An aqueous emulsion having a median diameter of 2 占 퐉 or less based on the volume of a dispersed material. 20. The method according to any one of claims 6 to 19,
(B) containing a halogen atom and the compound (E) having a polymerizable group in the total amount of the halogen atom-containing polymer (B) and the polymerizable group- The aqueous emulsion is 0.1% by mass to 70% by mass with respect to the total mass. 21. The method according to any one of claims 1 to 20,
An aqueous emulsion wherein the polymer (B) containing a halogen atom is a halogenated rubber. 21. The method according to any one of claims 1 to 20,
An aqueous emulsion wherein the polymer (B) containing a halogen atom is composed of a chlorinated rubber. A coating film formed from the aqueous emulsion according to any one of claims 1 to 22. 23. A cured product of a coated film according to claim 23. A laminate obtained by laminating the cured product according to claim 24, an adhesive layer having one or more layers thereon, and a second substrate in this order on a first substrate made of an olefinic polymer. A laminate obtained by laminating a cured product according to claim 24, an adhesive layer having one or more layers thereon, and a second substrate in this order on a first substrate made of an ethylene / vinyl acetate copolymer. A method for forming a coating film, which comprises applying the aqueous emulsion according to any one of claims 1 to 22 on a substrate and drying. 27. A coated film obtained by the method according to claim 27.