JP2013151630A - Aqueous emulsion, method for forming coating film and coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous emulsion excellent in emulsion dispersibility and stability.SOLUTION: An aqueous emulsion includes: (A) two or more surfactants expressed by formula (I); (B) a thermoplastic resin and (C) water, where in formula, X represents a hydrogen atom or -SOM (M is a hydrogen atom, NHor an alkali metal); n denotes an integer of 1 to 3; and m denotes an integer of 1 to 100.

Description

  The present invention relates to an aqueous emulsion, a method for forming a coating film, and a coating film.

  Generally, various surfactants are contained in an aqueous emulsion, and the types and combinations of the surfactants have been studied (Non-patent Document 1).

Takehiko Fujimoto, “Introduction to New Surfactant”, published by Sanyo Kasei Kogyo Co., Ltd., August 1992, p188-205

  Conventional aqueous emulsions may not always be satisfactory with respect to emulsifying dispersibility or stability.

（式中、Ｘは水素原子又は−ＳＯ_３Ｍ（Ｍは水素原子、ＮＨ_４又はアルカリ金属）を示す。ｎは１〜３の整数を表す。ｍは１〜１００の整数を表す。）
（Ｂ）熱可塑性樹脂及び
（Ｃ）水
[２]前記界面活性剤（Ａ）は、Ｘが水素原子である界面活性剤と、Ｘが−ＳＯ_３Ｍである界面活性剤との２種類以上を含む[１]に記載の水性エマルション。
[３]前記界面活性剤（Ａ）は、Ｘが水素原子である界面活性剤と、Ｘが−ＳＯ_３ＮＨ_４である界面活性剤との２種類以上を含む[１]又は[１]に記載の水性エマルション。
[４]前記熱可塑性樹脂（Ｂ）が、炭素数２〜２０のα−オレフィン由来の構造単位を１種類以上含む重合体である[１]〜[３]のいずれか１つに記載の水性エマルション。
[５]粒径（個数基準）０．０１〜１．０μｍの分散質を含有する[１]〜[４]のいずれか１つに記載の水性エマルション。
[６]上記[１]〜[５]のいずれか記載の水性エマルションを基材上に塗工し、乾燥することを特徴とする塗膜の形成方法。
[７]上記[６]に記載の方法で得られた塗膜。 The present invention includes the following inventions.
[1] An aqueous emulsion containing the following (A), (B) and (C).
(A) Two or more kinds of surfactants represented by the following formula (I)

(In the formula, X represents a hydrogen atom or —SO ₃ M (M is a hydrogen atom, NH ₄ or an alkali metal). N represents an integer of 1 to _3. m represents an integer of 1 to 100.)
(B) Thermoplastic resin and (C) water
[2] The aqueous emulsion according to [1], wherein the surfactant (A) includes two or more of a surfactant in which X is a hydrogen atom and a surfactant in which X is —SO ₃ M.
[3] The surfactant (A) includes two or more of a surfactant in which X is a hydrogen atom and a surfactant in which X is —SO ₃ NH ₄ [1] or [1] The aqueous emulsion as described.
[4] The aqueous solution according to any one of [1] to [3], wherein the thermoplastic resin (B) is a polymer containing one or more structural units derived from an α-olefin having 2 to 20 carbon atoms. Emulsion.
[5] The aqueous emulsion according to any one of [1] to [4], which contains a dispersoid having a particle size (number basis) of 0.01 to 1.0 μm.
[6] A method for forming a coating film, which comprises coating the aqueous emulsion according to any one of [1] to [5] on a substrate and drying.
[7] A coating film obtained by the method described in [6] above.

  ADVANTAGE OF THE INVENTION According to this invention, the aqueous emulsion excellent in emulsification dispersibility and stability can be provided.

<Water-based emulsion>
As described above, the aqueous emulsion of the present invention is
(A) two or more kinds of surfactants represented by the above formula (I);
(B) a thermoplastic resin;
(C) Contains water.

<Surfactant (A)>
Surfactant (A) is a substance that generally acts as an emulsifier, and examples thereof include cationic, anionic, amphoteric and nonionic surfactants as long as they have the structure of formula (I). Of these, anionic or nonionic surfactants are preferred. In particular, it is preferable to use two or more kinds of this surfactant in combination.
X in the formula (I) is a hydrogen atom, —SO ₃ M (M is a hydrogen atom, —NH ₄ or an alkali metal), that is, sulfuric acid, sulfate (for example, an alkali metal salt such as ammonium salt or sodium), and the like. Is mentioned. Of these, a hydrogen atom, —SO ₃ H or —SO ₃ NH ₄ is preferable.
As a combination of two or more kinds of surfactants, those having the same X and different n and / or m may be combined, but those having the same or different n and / or m and different X may be combined. preferable. Specifically, X is a combination of a hydrogen atom and —SO ₃ H, a combination of a hydrogen atom and —SO ₃ NH ₄ , or a combination of —SO ₃ H and —SO ₃ NH ₄ . Among these, a combination of a hydrogen atom and —SO ₃ NH ₄ is preferable.

As the surfactant represented by the formula (I), Latemul AD-25 (manufactured by Kao Corporation), Latemuru E-1000A (manufactured by Kao Corporation) represented by the following formula (A), the following formula (B) And Neugen EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.) represented by

The aqueous emulsion of the present invention may contain a surfactant other than the surfactant represented by the formula (I).
For example, the anionic surfactants include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyls. Examples include sulfosuccinate.
Examples of cationic surfactants include alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkylammonium salt , Allyl trialkyl ammonium salt, diallyl dialkyl ammonium salt and the like.
Nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene propylene ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid esters, ethylene oxide propylene oxide block copolymers, polyoxyethylene fatty acid amides, and ethylene oxide. -A compound having a polyoxyethylene structure such as a propylene oxide copolymer and a sorbitan derivative such as a polyoxyethylene sorbitan fatty acid ester.
Examples of amphoteric surfactants include lauryl betaine and lauryl dimethylamine oxide.

The content of the surfactant is usually 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.1 to 100 parts by weight of the resin constituting the aqueous emulsion. 1 to 10 parts by weight.
When the aqueous emulsion of the present invention contains a surfactant other than the surfactant represented by the formula (I), it is represented by the surfactant represented by the formula (I) and the formula (I). The total content with surfactants other than the surfactant is usually 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, with respect to 100 parts by weight of the resin constituting the aqueous emulsion. Yes, more preferably 0.1 to 10 parts by weight.
When the surfactant represented by the formula (A) and the surfactant represented by the formula (B) are used in combination, the weight ratio is preferably 1 to 99:99 to 1, more preferably 5 to 5. 95: 95-5, More preferably, it is 10-90: 90-10, 30: 70-90: 10, 40: 60-90: 10, 50: 50-90: 10 are mentioned especially.

<Thermoplastic resin (B)>
Examples of the thermoplastic resin (B) include polyolefin resin, acrylic resin (PMMA), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene ( Examples thereof include polymers such as PTFE), acrylonitrile butadiene styrene resin (ABS resin), AS resin, and copolymers, and modified products thereof. These may be used alone or in combination of two or more.

Among them, a polyolefin resin that is a polymer including one or more structural units derived from an α-olefin having 2 to 20 carbon atoms is preferable.
Examples of the α-olefin having 2 to 20 carbon atoms include ethylene (C2), propylene (C3), 1-butene (C4), 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-octene, Nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, vinylcyclohexane, etc. Can be mentioned. Preferred are ethylene, propylene, 1-butene and the like.

  Polymers containing structural units derived from α-olefins having 2 to 20 carbon atoms include polyethylene (PE), high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), polypropylene (PP), etc. Homopolymer or modified product thereof; ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer An α-olefin copolymer such as ethylene-propylene-1-butene copolymer or a modified product thereof; a copolymer with a copolymerizable monomer or a modified product thereof; or a mixture of two or more of these. It is preferable. In a copolymer with a copolymerizable monomer, the copolymerizable monomer and α-olefin may be used alone or in combination of two or more. The form of the copolymer may be any of random copolymerization, block copolymerization, graft copolymerization, and the like. These may be those having a low molecular weight or a high molecular weight such as peroxide.

  As the α-olefin polymer, the total structural unit is 100 mol%, for example, the structural unit derived from propylene: the structural unit derived from 1-butene, preferably 71 to 99 mol%: 1 to 29 mol%. Or a modified product thereof, more preferably 80 to 99 mol%: a copolymer or modified product thereof contained in 1 to 20 mol%, more preferably 90 to 99 mol%: 1 to 10 mol % Of copolymers or modified products thereof. This copolymer is preferably a copolymer in which substantially no melting peak is observed. The fact that the melting peak is not substantially observed means that a crystal melting peak having a heat of crystal melting of 1 J / g or more is not observed by differential scanning calorimetry (DSC) in the temperature range of −100 to 200 ° C.

  A structural unit derived from ethylene: a copolymer containing propylene-derived structural units, preferably 5 to 20 mol%: 80 to 95 mol%, or a modified product thereof, more preferably 5 to 19 mol%: 81 to 81 The copolymer or modified product thereof contained at 95 mol%, more preferably, the copolymer or modified product thereof contained at 10 to 19 mol%: 81 to 90 mol%. This copolymer is preferably a copolymer in which a melting peak is observed. A melting peak is observed by means of differential scanning calorimetry (DSC) in the temperature range of −100 to 200 ° C., a crystal melting peak with a crystal melting heat of 1 J / g or more or a crystal with a crystallization heat of 1 J / g or more. This means that a chemical peak is observed.

  Structural unit derived from ethylene: Structural unit derived from propylene: A copolymer containing 1-butene derived structural unit, preferably 1 to 99 mol%: 99 to 1 mol%: 99 to 1 mol% or a modification thereof A copolymer, or a modified product thereof, more preferably 10 to 40 mol%: 85 to 5 mol%, more preferably 5 to 80 mol%: 90 to 2 mol%: 90 to 1 mol%. Examples thereof include a copolymer containing 60 to 2 mol% or a modified product thereof. This copolymer is preferably a copolymer in which no melting peak is observed.

  These copolymers can be produced using, for example, a known single site catalyst (metallocene, etc., for example, see Japanese Patent Application Laid-Open Nos. 58-19309 and 60-35005). For example, see European Patent Publication No. 12111287).

  Further, the above-described propylene-1-butene copolymer or a modified product thereof and the ethylene-propylene copolymer or the modified product thereof are preferably 1 to 99:99 to 1, more preferably 5 to 95 by weight ratio. : 95 to 5, more preferably 10 to 90: 90 to 10 may be blended.

Examples of the modified product of the α-olefin polymer include modified products of α, β-unsaturated carboxylic acids. The amount of modification in this case is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.2 to 4 parts by weight with respect to 100 parts by weight of the α-olefin polymer. It is.
Examples of α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids (maleic acid, itaconic acid, citraconic acid, etc.), α, β-unsaturated carboxylic acid esters (methyl maleate, methyl itaconate). , Citraconic acid methyl, etc.), α, β-unsaturated carboxylic acid anhydrides (maleic anhydride, itaconic anhydride, citraconic anhydride, etc.). Further, these α, β-unsaturated carboxylic acids may be used in combination. Of these, α, β-unsaturated carboxylic acid anhydride is preferable, and maleic anhydride is more preferable.

  Such a modified product is a method in which an α-olefin polymer is melted and then modified by adding α, β-unsaturated carboxylic acids or the like, and the α-olefin polymer is dissolved in a solvent such as toluene or xylene. A known method such as a method in which an α, β-unsaturated carboxylic acid or the like is added and modified after dissolution is exemplified. In addition, when the modified product contains a structural unit derived from an α, β-unsaturated carboxylic acid anhydride, the acid anhydride group may be retained or the ring-opened one may be retained. Both the formed and ring-opened ones may be contained.

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

Examples of the copolymerizable monomer include unsaturated carboxylic acid or its anhydride, metal salt of α, β-unsaturated carboxylic acid, α, β-unsaturated carboxylic acid ester, vinyl ester, vinyl ester saponified product, cyclic olefin, Examples include vinyl aromatic compounds, polyene compounds (such as dienes), (meth) acrylonitrile, halogenated vinyls, and halogenated vinylidenes. You may use these individually or in combination of 2 or more types.
In this specification, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid, and acrylate and methacrylate are collectively referred to as (meth) acrylate.

Examples of unsaturated carboxylic acids or anhydrides include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and unsaturated dicarboxylic acid half esters and half amides. Is mentioned. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
Examples of the metal salt of α, β-unsaturated carboxylic acid include sodium salt and magnesium salt of (meth) acrylic acid.
As α, β-unsaturated carboxylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl acrylate, Examples include esterified products of methacrylic acid and alcohol. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferred.

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

  Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1, 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphth 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene Xene, 4-methylsic Examples include lohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, and vinylcyclohexane.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, Examples include vinyl naphthalene.

  Examples of polyene compounds include linear or branched aliphatic conjugated polyene compounds, alicyclic conjugated polyene compounds, aliphatic non-conjugated polyene compounds, alicyclic non-conjugated polyene compounds, and aromatic non-conjugated polyene compounds. Can be mentioned. 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-isopropyl-1,3-butadiene, 2- Hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3- Hexadiene, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3- Examples include dimethyl-1,3-octadiene and 2,3-dimethyl-1,3-decadiene.

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

  Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9 -Decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4 -Ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4 -Heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene 3-methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene, 4-methyl-1,4- Octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5- Octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6- Octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1 4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1, 5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1, 7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1, 5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1, 6-decadiene, 7-methyl -1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl -1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl -1,8-undecadiene, 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene 13-ethyl-9-methyl-1,9,12-pentadecatriene, 5,9,13-trimethyl-1,4,8,12-tetradecadiene, 8,14,16-trimethyl-1,7 , 14-Hexadeca Lien, 4-ethylidene-12-methyl-1,11-penta decadiene, and the like.

  Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, and 5-isopropenyl-2-norbornene. Cyclohexadiene, dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 6-chloromethyl-5-isopropylenyl-2-norbornene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1 , 5-Divinylcyclooct 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl Examples include -4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, and methyltetrahydroindene.

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

  Examples of the modified product of the copolymer with the copolymerizable monomer include a modified product of α, β-unsaturated carboxylic acids as described above. The amount of modification in this case is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the copolymer with the copolymerizable monomer. 4 parts by weight.

  The polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is preferably a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a carbon number different from that of the α-olefin having 2 to 20 carbon atoms. A structural unit derived from one or more monomers selected from the group consisting of 2 to 20 α-olefin, α, β-unsaturated carboxylic acid ester, α, β-unsaturated carboxylic acid anhydride, and vinyl acetate. More preferably, the copolymer has a structural unit derived from ethylene, an α-olefin having 3 to 20 carbon atoms, an α, β-unsaturated carboxylic acid ester, an α, β-unsaturated carboxylic acid anhydride, and acetic acid. A copolymer having a structural unit derived from one or more monomers selected from the group consisting of vinyl, and more preferably a structural unit derived from ethylene, an α, β-unsaturated carboxylic acid ester and α, β -A copolymer having a structural unit derived from one or more monomers selected from the group consisting of unsaturated carboxylic acids.

As a copolymer of a monomer copolymerizable with α-olefin, specifically,
(i) ethylene-vinyl acetate copolymer, saponified product or partially saponified product thereof, or maleic anhydride-modified product of ethylene-vinyl acetate copolymer,
(ii) an ethylene- (meth) acrylic acid copolymer,
(iii) ethylene- (meth) acrylate copolymers such as ethylene-glycidyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer,
(iv) an ethylene-alicyclic α-olefin copolymer such as ethylene-vinylcyclohexane,
(v) ethylene-vinyl acetate copolymer (glycidyl (meth) acrylate), ethylene-vinyl acetate copolymer (ethylene) -vinyl acetate- (meth) acrylate copolymer such as methyl (meth) acrylate,
(vi) ethylene- (meth) acrylate-maleic anhydride copolymers such as ethylene-ethyl (meth) acrylate-maleic anhydride copolymers,
(vii) ethylene- (meth) acrylate- (meth) acrylate copolymers such as ethylene-glycidyl (meth) acrylate-methyl (meth) acrylate copolymer,
(viii) copolymers of these metal salts, and
(ix) A blend of two or more of these copolymers may be mentioned.

A polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, particularly a copolymer of the above (i) to (vii) has a melt flow rate of 0.01 to 500 g at 190 ° C. under a load of 2160 g. / 10 minutes are preferable, and more preferably 0.01 to 400 g / 10 minutes.
A polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, particularly a copolymer of the above (i) to (vii), preferably has a melting point of 60 to 200 ° C. ° C is more preferable, and 60 to 110 ° C is more preferable. When a polymer having a melting point in this range is used, the permeability or adhesion of the aqueous emulsion to the adherend can be further improved.

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

  In the aqueous emulsion of the present invention, the content of the thermoplastic resin (B) can be appropriately adjusted depending on, for example, the type of thermoplastic resin used, the purpose of use, the performance to be obtained, and the like. For example, from the viewpoint of maintaining the stability of the aqueous emulsion, maintaining the viscosity moderately and / or expressing good film-forming ability, it is preferably 1 to 60% by weight with respect to the total amount of the aqueous emulsion, and more Preferably they are 3-60 weight%, 3-50 weight%, More preferably, it is 5-55 weight%.

<Water (C)>
As water used in the aqueous emulsion of the present invention, tap water, ion-exchanged water or the like is generally used. In order to further improve the stability of the aqueous emulsion, a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, or hydroxyethyl cellulose may be added.
The water content is, for example, 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 45% by weight or more, and preferably 85% by weight or more based on the total amount of the aqueous emulsion. % By weight or less, more preferably 80% by weight or less, still more preferably 70% by weight or less.

<Other resins>
The aqueous emulsion of the present invention may contain other resins other than the thermoplastic resin (B) described above. Such other resins can be used as, for example, an adhesive resin or a tackifier.
Examples of other resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and hydrogens thereof. Examples thereof include additive resins, other petroleum-based resins, coumarone resins, indene resins, polyurethane resins, and the like.

  Specifically, rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin and their glycerin ester, pentaerythritol ester, methyl ester, triethylene glycol ester, phenol modified product and ester thereof Terpenes such as terpenes; terpene polymers, terpene phenols, β-pinene polymers, aromatic-modified terpene polymers, α-pinene polymers, terpene-based hydrogenated resins, etc .; petroleum fractions having 5 carbon atoms Petroleum resins obtained by polymerizing styrene, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and hydrogenated resins thereof; petroleum resins such as maleic acid modified products and fumaric acid modified products; polyisocyanate compounds and polyols described later Polyurea obtained by reacting a compound and, if necessary, another compound Tan resin and the like.

Of these, terpene resins and polyurethane resins are preferable.
Terpene resins are YS Resin PX / PXN, YS Polyster, Mighty Ace, YS Resin TO / TR, Clearon P / M / K (manufactured by Yashara Chemical Co., Ltd.), Tamanol 803L / 901 (manufactured by Arakawa Chemical Co., Ltd.), Teltac 80 (Japan) Any of those commercially available as Terpen Chemical Co., Ltd.) can be used.

The polyurethane resin is preferably in the form of an aqueous emulsion in which polyurethane is dispersed in water. That is, the polyurethane may be either water-soluble or water-insoluble, but is preferably water-insoluble.
Usually, the polyurethane resin can be obtained by reacting a polyisocyanate compound and a polyol compound, and if necessary, other compounds. Examples of the reaction include methods such as an acetone method, a prepolymer mixing method, a ketimine method, and a hot melt dispersion method.

  Examples of the polyisocyanate compound include organic polyisocyanate compounds having two or more isocyanate groups in the molecule, which are used in the production of ordinary polyurethanes. For example, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane 4,4'-diisocyanate, methylcyclohexyl-2,4-diisocyanate, methylcyclohexyl-2,6-diisocyanate, xylylene diisocyanate (XDI), 1,3-bis (isocyanate) methylcyclohexane, tetramethylxylylene diisocyanate, trans Aliphatic diisocyanates such as cyclohexane-1,4-diisocyanate and lysine diisocyanate; 2,4-toluylene diisocyanate (TDI), 2,6-toe Irene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), 1,5′-naphthene diisocyanate, tolidine diisocyanate, diphenylmethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, 1, Aromatic diisocyanates such as 3-phenylene diisocyanate; lysine ester triisocyanate, triphenylmethane triisocyanate, 1,6,11-undecane triisocyanate, 1,8-isocyanate-4,4-isocyanate methyloctane, 1,3, 6-hexamethylene triisocyanate, bicycloheptane triisocyanate, adduct of trimethylolpropane and toluylene diisocyanate And triisocyanates adducts such of trimethylol propane and 1,6-hexamethylene diisocyanate. You may use these individually or in combination of 2 or more types.

  Examples of the polyol compound include compounds having two or more hydroxyl groups in the molecule, which are used for the production of ordinary polyurethane. For example, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, glycerin; polyethylene glycol, polypropylene glycol, polytetramethylene ether Polyether polyols such as glycol; adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid, isophthalic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid Dicarboxylic acids such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,2-propanedio And 1,3-propanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 1,3-propanediol, tripropylene glycol, trimethylolpropane, glycerin and other polyol compounds. Polyester polyols such as polycaprolactone polyol and poly β-methyl-δ-valerolactone; polybutadiene polyol or hydrogenated product thereof, polycarbonate polyol, polythioether polyol, polyacrylate polyol and the like .

  The polyurethane resin preferably has a hydrophilic group in the molecule in order to improve dispersion stability in water. A polyurethane containing a hydrophilic group in its molecule is called an ionomer structure and has a surface-active ability in itself. Therefore, there exists a tendency which is easy to disperse | distribute in water, and there exists a tendency which improves the water resistance of the aqueous emulsion obtained by emulsion-polymerizing a monomer further to the polyurethane aqueous emulsion.

As the hydrophilic group, anionic groups such as a sulfonyl group and a carboxyl group are preferable, and a sulfonyl group is more preferable. This is because there is a tendency to further improve the water resistance of an aqueous emulsion obtained by emulsion polymerization of monomers.
In general, the anionic group is preferably neutralized by a neutralizing agent.
Examples of the neutralizing agent include tertiary amine compounds such as triethylamine and trietalamine; inorganic alkali compounds such as sodium hydroxide; ammonia and the like.

In order to introduce a hydrophilic group into the molecule, it is preferable to use the following compounds during the production of polyurethane. Examples of the compound include a nonionic hydrophilic group such as a structural unit derived from polyethylene glycol in the molecule, and a sulfonyl group, a carboxyl group, a hydroxyl group, a primary amino group (—NH ₂ ), a secondary amino group ( ═NH) and the like (hereinafter also referred to as “hydrophilic group-containing compound”) having at least one active hydrogen having reactivity with an isocyanate group.

  Examples of the hydrophilic group-containing compound include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, and N- (2-aminoethyl) -2. -Sulphonic acid-containing compounds such as aminoethylsulfonic acid; and carboxylic acid-containing compounds such as 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid and 2,2-dimethylolvaleric acid. You may use these individually or in combination of 2 or more types.

  When the polyurethane resin is produced as an aqueous emulsion, it is a compound different from the hydrophilic group-containing compound for the purpose of chain extension, molecular weight adjustment, etc., if necessary, and contains active hydrogen capable of reacting with an isocyanate compound in the molecule. A compound to be used may be used in combination. Examples of such compounds include polyvalent amine compounds such as ethylenediamine, 1,4-butanediamine, and 1,6-hexanediamine; tertiary amine-containing polyhydric alcohols such as triethanolamine, methanol, ethanol, and butanol. And monoalcohols.

As the polyurethane resin, a commercially available polyurethane aqueous emulsion or a commercially available water-soluble urethane resin may be used as it is.
For example, a polyurethane dispersion (or polyurethane aqueous solution) in which a polyurethane resin is dispersed or dissolved in water can be mentioned. As for content of the polyurethane resin in a polyurethane dispersion liquid, about 10 to 70 weight% is mentioned, About 20 to 60 weight% is preferable, About 30 to 60 weight% is more preferable, About 30 to 55 weight% is further more preferable.
The polyurethane dispersion may further contain an organic solvent not containing an isocyanate reactive group, for example, ethyl acetate, acetone, methyl ethyl ketone, N-methylpyrrolidone and the like. The amount of the organic solvent is not particularly limited, but can be 0.1 to 100 parts by weight with respect to 100 parts by weight of the nonvolatile content in the polyurethane dispersion.

  As a water-soluble urethane resin, for example, manufactured by Sumitomo Bayer Urethane Co., Ltd .; DISPARALL U-42, U-53, U-54, U-56, KA-8484, KA-8484, KA-8755, KA-8756 KA-8766, manufactured by DIC Corporation; Hydran HW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP-60LM, AP-80, Sanyo Chemical Manufactured by Kogyo Co., Ltd .; Uprene UXA-306, UXA-307, Permarin UA-150, Permarin UA-200, Permarin UA-300, Permarin UA-310, Yukot UWS-145, Daiichi Kogyo Seiyaku Co., Ltd .; Super Flex 107M, 110, 126, 130, 150, 160, 300, 361, 370, 410, 420, 4 0, 700, 750, 820, manufactured by ADEKA; Adekabon titer HUX-401, HUX-420A, HUX-380, HUX-561, HUX-210, HUX-822, HUX-895, HUX-830, etc. .

When the aqueous emulsion of the present invention contains other resins, the content thereof is preferably 1 to 99% by weight, more preferably 3 to 99% by weight, further based on the total amount of the aqueous adhesive. Preferably it is 5-90 weight%.
The thermoplastic resin (B): other resin (non-volatile content weight ratio) is preferably 5:95 to 95: 5, more preferably 5:95 to 95: 5, and even more preferably 5 : 95 to 80:20.
These resins may be emulsions or emulsified together with the thermoplastic resin (B).

<Basic compound>
The aqueous emulsion of the present invention preferably further contains a basic compound.
As a basic compound, what can neutralize a carboxyl group is preferable, for example, ammonia, an organic amine compound, a metal hydroxide, etc. are mentioned. Preferably, it is ammonia or an organic amine compound. In particular, organic amine compounds having a boiling point of 200 ° C. or less can be easily dispersed by ordinary drying, and maintain / improve the water resistance and alkali resistance of the coating film when an aqueous emulsion is used to form the coating film. This is preferable.
Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, Examples include 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, and N-ethylmorpholine. Of these, N, N-dimethylethanolamine and the like are preferable.
Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide and the like.

  When the aqueous emulsion of the present invention contains a basic compound, the content thereof is preferably 1 to 30 parts by weight, more preferably 2 to 100 parts by weight of the resin constituting the aqueous adhesive. 20 parts by weight, more preferably 2 to 10 parts by weight.

<solvent>
The aqueous emulsion of the present invention preferably does not contain a solvent, but in some cases, in addition to water, for example, aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; ethyl acetate, acetic acid Esters such as butyl; 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), butyl carbitol, diethylene glycol monomethyl ether, triethyleneglycol Glycol solvents such as dimethyl monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether An organic solvent such as a glycol ester solvent such as acetate; You may use these individually or in combination of 2 or more types.
When the aqueous emulsion of the present invention contains a solvent, the content thereof is usually 0.01 to 30 parts by weight, preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin constituting the aqueous adhesive. It is.

<Other ingredients>
Furthermore, the aqueous emulsion of the present invention is a phenol-based stabilizer, a phosphite-based stabilizer, an amine-based stabilizer, an amide-based stabilizer, an anti-aging agent, as necessary as long as the intended properties of the aqueous emulsion are not impaired. Stabilizers such as weathering stabilizers, anti-settling agents, antioxidants, heat stabilizers, light stabilizers; thixotropic agents, thickeners, dispersants, antifoaming agents, viscosity modifiers, weathering agents, pigments, pigment dispersions Additives, antistatic agents, lubricants, nucleating agents, flame retardants, oil agents, dyes, curing agents, crosslinking agents, etc .; transition metal compounds such as titanium oxide (rutile type) and zinc oxide; pigments such as carbon black; glass Fiber, carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate, clay, kaolin, fine powder silica, mica, calcium silicate, water Aluminum, magnesium hydroxide, aluminum oxide, magnesium oxide, alumina, inorganic, such as celite, it may contain optional components such as organic fillers.

(Thickener)
Thickeners can be used to adjust the viscosity of the formulation. As a thickener, manufactured by ADEKA Corporation; Adecanol UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH -541VF, UH-550, UH-752, H-756VF, manufactured by San Nopco; SN thickener 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A-813, A -818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, 4050 and the like.

(Dispersant)
The dispersant can be used for improving the wettability of the coated substrate. As a dispersing agent, ADEKA Co., Ltd. make; Adeka call W-193, W-287, W-288, W-304, BYK make; BYK-333, BYK-345, BYK-346, BYK-347, BYK -348, BYK-349, BYK-378, manufactured by San Nopco; Nopco wet 50, SN wet 366, Nopco 38-C, SN disperse sand 5468, 5034, 5027, 5040, 5020 and the like.

(Curing agent)
Examples of the curing agent include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), and oligomers or polymers thereof, which are isocyanate curing agents. Specifically, Sumika Bayer Urethane Sumidur 44V20, Sumidur N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547 and the like can be mentioned. .
0.1-20 weight part is preferable with respect to 100 weight part of resin which comprises an aqueous | water-based emulsion, and 0.1-10 weight part is more preferable. The curing agent may be added after being dissolved in an organic solvent.

<Method for producing aqueous emulsion>
The aqueous emulsion of the present invention can be produced by a method known in the art, for example, a post-emulsification method (for example, forced emulsification method, self-emulsification method, phase inversion method) after polymerizing the resin and dispersing the resin in an aqueous medium. Emulsification method and the like).
Specifically, (1) The thermoplastic resin (B) and the solvent are charged into the reactor, stirred, heated and dissolved, and the surfactant (A), water (C) and / or solvent are charged into the reactor. , Heating and stirring, and a method in which water (C) and / or solvent is further optionally added before and after this, and (2) a thermoplastic resin (B) and optionally a solvent are added to the kneader and stirring is performed. , Melted by heating, put surfactant (A), water (C) and / or solvent into this, heat and stir, and optionally add water (C) and / or solvent before and after this And the like. However, in any of the methods (1) and (2), water is added at least once.

In the production method of (1) described above, as the reactor, a container (preferably sealed and / or sealed) provided with a heating device capable of being heated and a stirrer capable of applying a shearing force or the like to the contents. Pressure vessel) is used.
A normal stirrer can be used. Examples of such a pressure vessel include a pressure-resistant autoclave with a stirrer. Stirring may be performed, for example, at normal pressure or reduced pressure. Moreover, the rotation speed of a stirrer can be performed with the rotation speed of about 50-1000 rpm, for example. If necessary, it is preferable to increase the rotation speed as the dispersion / stirring of the aqueous emulsion proceeds.
The heating is usually performed at 50 to 200 ° C, preferably 60 to 150 ° C, more preferably 70 to 100 ° C.
After stirring, the solvent is preferably distilled off from the obtained dispersion (preferably reduced pressure or pressurized distillation). As the distillation method here, a method known in the art can be used. The degree of pressure reduction or pressurization is about ± 0.001 to 1 MPa, preferably about ± 0.001 to 0.5 MPa.

  In the production method (2) described above, examples of the kneader include a roll mill, a kneader, an extruder, an ink roll, and a Banbury mixer. In particular, an extruder or a multi-screw extruder having one or more screws in the casing may be used.

  As a method of emulsification using an extruder, a molten thermoplastic resin (B) and a surfactant (A) are mixed, and this is continuously supplied from the hopper or supply port of the extruder, and this is heated and melted. After kneading and further supplying water (C) from at least one supply port provided in a compression zone, a metering zone, a degassing zone, and the like of the extruder, kneading with a screw, continuous extrusion from a die is performed.

In addition, it is preferable to add suitably other components mentioned above, such as components other than the above, other resin, an antifoamer, a viscosity modifier, in the manufacture process of an aqueous emulsion.
Further, in the production process of the aqueous emulsion, the surfactant is preferably used within a desired range. However, when the surfactant is used in excess, it is optionally added from the obtained aqueous emulsion to the excess interface. The active agent may be separated and removed. Separation and removal of the surfactant is, for example, a centrifugal filter, a filtration filter having an average pore size smaller than the average particle size of the aqueous emulsion (preferably having an average pore size of 0.05 to 0.5 μm). Examples thereof include a method using a microfiltration membrane) or an ultrafiltration membrane.
Furthermore, it is preferable to cool the obtained aqueous emulsion. Thereby, the aqueous emulsion containing the fine particle of a resin composition is obtained. The cooling is not particularly required to be performed at a low temperature, and a method of leaving it at room temperature can be mentioned. Thereby, a fine and homogeneous aqueous emulsion can be obtained without aggregation of resin or the like during the cooling process.

The particle size of the dispersoid contained in the aqueous emulsion of the present invention is usually 10 μm or less on a number basis, preferably 0.01 to 10 μm, more preferably 0.01 to 2 μm, and still more preferably 0.01 to 1 μm. And the stationary stability is good.
Here, the number-based particle diameter is a particle diameter corresponding to 50% of the cumulative particle diameter distribution value based on the number, and the volume-based median diameter is 50% of the cumulative particle diameter distribution value based on the volume. Corresponding particle size. Unless otherwise specified, it means a median diameter value measured on a number basis.
Moreover, you may filter using the filter etc. which have various hole diameters as needed, for example.
When a plurality of types of dispersoids are included in the aqueous emulsion (for example, thermoplastic resin (B) and polyurethane resin), the particle diameters of the dispersoids are preferably approximately the same. As the same degree, for example, it is preferably within ± 50% of the particle size of the thermoplastic resin (B), and more preferably within ± 30%.

<Manufacturing method of coating film>
A coating film can be produced using the aqueous emulsion of the present invention.
The coating film is produced by a known film formation method, for example, by applying the aqueous emulsion of the present invention to the surface of various substrates and leaving it at around room temperature as necessary, followed by drying (or heat treatment for drying and baking). ). Depending on the composition of the aqueous emulsion, it can be formed into a coating by extrusion.
Application methods include gravure roll coating, reverse roll coating, bar coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, spatula coating, etc. be able to.

Drying may be natural drying, non-thermal drying such as air drying, or a normal hot-air circulating oven, infrared or far-infrared heater, electromagnetic wave (for example, electromagnetic wave having a frequency band of 2.45 ± 0.02 GHz) irradiation device or electronic It can be performed by heat drying using a range or the like. The heating temperature and the heating time can be appropriately adjusted according to the characteristics of the substrate, the composition of the aqueous emulsion of the present invention, and the like. For example, as heating temperature, about 30-150 degreeC is mentioned, Preferably it is about 40-85 degreeC. 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.
Application and drying of the aqueous emulsion may be performed only once, or may be performed twice or more. At that time, the coating method and the drying method may be combined with each other, or may be combined with different methods. Moreover, you may combine the frequency band from which electromagnetic waves differ.

  The thickness of the coating film formed using the aqueous emulsion of the present invention can be appropriately adjusted depending on its use and the like. For example, about 0.01-300 micrometers is mentioned, Preferably it is about 0.01-200 micrometers, More preferably, it is about 0.2-200 micrometers.

  Base materials include, for example, wood-based materials such as wood, plywood, medium density fiberboard (MDF), particle board, and fiber board; cellulosic materials such as cotton cloth, cotton-containing fibers, linen, and rayon; polyethylene (derived from ethylene) Polyolefins having a structural unit 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), polycarbonate, acrylonitrile / Butadiene / styrene copolymer (ABS resin), (meth) acrylic resin polyester, polyether, polyvinyl chloride, polyurethane, urethane foam, ethylene / vinyl acetate copolymer (EVA), EVA foam, nylon 6, nylon 66 Polyamide etc. Resin or plastic material of the foam, and the like; polyurethanes, polyamide and synthetic leather polyamino acid; glass, ceramic material, ceramic or the like; iron, stainless steel, copper, a metal material such as aluminum and the like. The base material may be a composite material composed of a plurality of materials. Further, an inorganic filler such as talc, silica and activated carbon, a kneaded molded product of carbon fiber or the like and a plastic material may be used.

  Here, the polyurethane is a polymer crosslinked by a urethane bond, and is usually obtained by a reaction between an alcohol (—OH) and an isocyanate (—NCO). The urethane foam is a polyurethane foamed with a volatile solvent such as carbon dioxide or freon produced by a reaction between isocyanate and water used as a crosslinking agent. Semi-rigid polyurethane is used for automobile interiors, and hard polyurethane is used for paints.

These base materials may be subjected to primer treatment in advance. Examples of the primer treatment include blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, anchor layer formation, and the like.
In particular, when using a substrate that can absorb water, such as cotton-containing fibers, as the primer treatment, an aqueous emulsion may be applied and dried. Application | coating of an aqueous emulsion here can utilize the said method, and drying can be performed by the method mentioned later. When performing the primer treatment, the aqueous emulsion to be used may be only one kind or two or more kinds of twice treatment. When two substrates are bonded, different aqueous emulsions may be applied to these substrates, but it is preferable to apply the same one.

<Application>
The aqueous emulsion of the present invention may be used alone or as an adhesive, pressure-sensitive adhesive, adhesive modifier, heat sealant, paint, paint primer, ink binder, pressure-sensitive adhesive, emulsion modifier, etc. Other materials can be combined and used for films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing, and the like.
In particular, because of its excellent adhesiveness, it can be used in applications requiring adhesiveness such as adhesives, pressure-sensitive adhesives, adhesive modifiers, heat sealants, paints, paint primers, and the like.
Above all, for bonding between components such as hood, insole and outer bottom in footwear including men's shoes and women's shoes such as sports shoes, town shoes and business shoes, and industrial work shoes etc. It is suitably used for the use of an adhesive.

In the aqueous emulsion of the present invention, the thermoplastic resin (B) is
(1) a polymer having at least one structural unit derived from an α-olefin having 2 to 20 carbon atoms,
(2) a structural unit derived from an α-olefin having 2 to 20 carbon atoms, an α-olefin having 2 to 20 carbon atoms different from the α-olefin having 2 to 20 carbon atoms, α, β-unsaturated carboxylic acid ester, α , A copolymer having a structural unit derived from one or more monomers selected from the group consisting of β-unsaturated carboxylic acid anhydride and vinyl acetate,
(3) 1 selected from the group consisting of a structural unit derived from ethylene, an α-olefin having 3 to 20 carbon atoms, an α, β-unsaturated carboxylic acid ester, an α, β-unsaturated carboxylic acid anhydride, and vinyl acetate. A copolymer having a structural unit derived from a monomer of at least one species,
(4) Copolymer having a structural unit derived from ethylene and a structural unit derived from one or more monomers selected from the group consisting of α, β-unsaturated carboxylic acid esters and α, β-unsaturated carboxylic acids. Coalescence,
(5) Ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer, ethylene-propylene- An α-olefin copolymer such as 1-butene copolymer or a modified product thereof; or a mixture of two or more of these,
(6) Ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer, ethylene-propylene- An α-olefin copolymer such as 1-butene copolymer or a maleic anhydride modified product thereof; or a mixture of two or more thereof;
(7) Copolymer of α-olefin and vinyl acetate or a modified product thereof; or a mixture of two or more of these,
(8) Copolymer of α-olefin, (meth) acrylate and α, β-carboxylic acid or a modified product thereof; or a mixture of two or more of these; and (9) α-olefin and (meth) acrylate It is preferably at least one selected from the group consisting of a copolymer with maleic anhydride or a modified product thereof; or a mixture of two or more thereof.
The aqueous emulsion of the present invention is preferably such that the thermoplastic resin (B) has a melting point of 60 to 110 ° C.
The aqueous emulsion of the present invention preferably further contains a polyurethane resin or a water-insoluble polyurethane resin.
The aqueous emulsion of the present invention further includes a terpene resin selected from the group consisting of a terpene polymer, a terpene phenol, a β-pinene polymer, an aromatic modified terpene polymer, an α-pinene polymer, and a terpene hydrogenated resin. It is preferable to contain.
The aqueous emulsion of the present invention is further selected from the group consisting of polyurethane resins and terpene polymers, terpene phenols, β-pinene polymers, aromatic modified terpene polymers, α-pinene polymers, and terpene hydrogenated resins. It is preferable to contain a terpene resin.
The aqueous emulsion of the present invention preferably further contains a polyurethane resin and terpene phenol or a water-insoluble polyurethane resin and terpene phenol.
The aqueous emulsion of the present invention preferably further contains an isocyanate.
The aqueous emulsion of the present invention further contains an isocyanate selected from the group consisting of diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI) and oligomers or polymers thereof. It is preferable to do.
The aqueous emulsion of the present invention preferably further contains a basic compound.
In the aqueous emulsion of the present invention, the surfactant is 0.1 to 50 parts by weight, 0.1 to 20 parts by weight or 0.1 to 10 parts by weight with respect to 100 parts by weight of the total resin constituting the aqueous emulsion. It is preferable to include.
In the aqueous emulsion of the present invention, the surfactant is a surfactant represented by the formula (A) and a surfactant represented by the formula (B) in a weight ratio of 1 to 99:99 to 1. 5 to 95:95 to 5, 10 to 90:90 to 10, 30:70 to 90:10, 40:60 to 90:10, or 50:50 to 90:10.
The aqueous emulsion of the present invention is obtained by polymerization of a thermoplastic resin, followed by emulsification, forced emulsification, self-emulsification or phase inversion emulsification after the resin is dispersed in an aqueous medium. Is preferred.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Parts and% in the examples mean weight basis unless otherwise specified.

In the following examples, physical properties were measured by the following method.
(1) Content of structural unit of polymer Based on measurement results of ¹ H-NMR spectrum and ¹³ C-NMR spectrum measured under the following conditions using a nuclear magnetic resonance apparatus (trade name AC-250 manufactured by Bruker). Calculated. Specifically, in the ¹³ C-NMR spectrum, from the ratio of the spectral intensity of the methyl carbon of the structural unit derived from propylene to the spectral intensity of the methyl carbon of the structural unit derived from 1-butene, The composition ratio of the structural unit derived from 1-butene was calculated, and then in the ¹ H-NMR spectrum, from the ratio of the spectral intensity of hydrogen derived from the methine unit and the methylene unit and the spectral intensity of hydrogen derived from the methyl unit, The composition ratio of the structural unit derived from ethylene, the structural unit derived from propylene, and the structural unit derived from 1-butene was calculated.
¹³ C-NMR (H decoupling)
¹³ C frequency: 150.9 MHz
Pulse width: 6.00 μs Pulse repetition time: 4.0 seconds Number of integrations: 256 Measurement temperature: 137 ° C.
Solvent: orthodichlorobenzene-d4 (concentration about 20%)

(2) Intrinsic viscosity [η]
The measurement was performed at 135 ° C. using an Ubbelohde viscometer. A polymer tetralin solution having a polymer concentration c per unit volume of tetralin of 0.6, 1.0, and 1.5 mg / ml was prepared, and the intrinsic viscosity at 135 ° C. was measured. The measurement was repeated three times at each concentration. The average value of the three values obtained was defined as the specific viscosity (ηsp) at that concentration, and the value obtained by extrapolating c of ηsp / c to zero was defined as the intrinsic viscosity [η]. Asked.

(3) Molecular weight distribution It measured by the gel permeation chromatograph (GPC) method on the following conditions.
Device: HLC-8121GPC / HT manufactured by Tosoh Corporation
Column: 4 TSKgel GMH _HR- H (S) HT manufactured by Tosoh Corporation Temperature: 145 ° C
Solvent: o-dichlorobenzene Elution solvent flow rate: 1.0 ml / min Sample concentration: 1 mg / ml
Measurement injection volume: 300 μl
Molecular weight reference material: Standard polystyrene Detector: Differential refraction

(4) Crystal melting peak and crystallization peak Using a differential scanning calorimeter (Seiko Denshi Kogyo's DSC220C: input compensation DSC), measurement was performed under the following conditions.
(I) About 5 mg of the sample was heated from room temperature to 200 ° C. at a rate of temperature increase of 30 ° C./min, and held for 5 minutes after completion of the temperature increase.
(Ii) Next, the temperature was decreased from 200 ° C. to −100 ° C. at a rate of temperature decrease of 10 ° C./min, and held for 5 minutes after the temperature decrease was completed. The peak observed in (ii) was a crystallization peak, and the presence or absence of a crystallization peak having a peak area of 1 J / g or more was confirmed.
(Iii) Subsequently, the temperature was increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. The peak observed in (iii) is the melting peak of the crystal, and the presence or absence of a melting peak having a peak area of 1 J / g or more was confirmed.

(5) Melt flow rate (MFR)
According to JIS-K-7210, the measurement was performed under the conditions of a load of 2.16 kgf and a temperature of 130 ° C.

(6) Modified amount The modified amount of maleic anhydride is obtained by dissolving 1.0 g of a sample in 20 ml of xylene, dropping the sample solution into 300 ml of methanol while stirring to reprecipitate the sample, and then collecting the sample. After vacuum drying (80 ° C., 8 hours), a film having a thickness of 100 μm was prepared by hot pressing, the infrared absorption spectrum of the obtained film was measured, and the amount of maleic anhydride modification was determined by absorption near 1780 cm ^−1. Was quantified.

(7) Non-volatile content It measured by the measuring method according to JISK-6828.
(8) Particle size of aqueous emulsion This is a value measured with a laser diffraction particle size measuring device LA-950V2 manufactured by HORIBA. Unless otherwise specified, the particle diameter is a median diameter value measured on a number basis.

<Production Example of Copolymer (B-1-1)>
386 parts of vinylcyclohexane (hereinafter sometimes referred to as VCH) and 3640 parts of toluene were charged into a SUS reactor substituted with argon. After raising the temperature to 50 ° C., ethylene was charged while being pressurized at 0.6 MPa. 10 parts of a toluene solution of triisobutylaluminum (TIBA) [TIBA concentration 20% manufactured by Tosoh Akzo Co., Ltd.] was charged, followed by diethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl- 2-phenoxy) titanium dichloride 0.001 part dissolved in 87 parts dehydrated toluene and dimethylanilinium tetrakis (pentafluorophenyl) borate 0.03 part dissolved in 122 parts dehydrated toluene were added and stirred for 2 hours. did. The resulting reaction solution was poured into about 10,000 parts of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, 300 parts of copolymer (B-1-1) was obtained. [Η] of the copolymer is 0.48 dl / g, Mn is 15,600, molecular weight distribution (Mw / Mn) is 2.0, melting point (Tm) is 57 ° C., glass transition point (Tg) is − At 28 ° C., the content of VCH units in the copolymer was 13 mol%.

<Example of production of copolymer (B-1-2)>
To 100 parts of the obtained copolymer (B-1-1) copolymer, 0.4 part of maleic anhydride and 0.04 part of 1,3-bis (t-butylperoxyisopropyl) benzene were added. After sufficiently premixing, the mixture was supplied from a supply port of a twin screw extruder and melt kneaded to obtain a copolymer (B-1-2). The temperature of the part of the extruder where the melt kneading was performed was divided into two stages, the first half and the latter half, and the melt kneading was performed at a temperature setting of 180 ° C. in the first half and 260 ° C. in the second half. The copolymer (B-1-2) had a maleic acid graft amount of 0.2% and an MFR of 180 g / 10 min (190 ° C., load: 2.16 kgf).

<Example of production of copolymer (B-2-2)>
A 1 L separable flask reactor was equipped with a stirrer, thermometer, dropping funnel and reflux condenser, and the gas in the reactor was replaced with nitrogen. Here, 600 parts of xylene as a solvent, 100 parts of a polymer (B-2-1) [ethylene / propylene copolymer (LICOCENE PP1602, manufactured by Clariant Japan KK, ethylene: propylene = 15 mol%: 85 mol%)], maleic anhydride 50 parts 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] 1 part of dioxaphosphepine (Sumilyzer GP, manufactured by Sumitomo Chemical Co., Ltd.) was added and heated to 140 ° C. and stirred to obtain a solution. The reaction was continued with stirring. An oil bath was used for heating. After completion of the reaction, the content was lowered to room temperature, poured into 1000 parts of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, a polymer (B-2-2) modified with maleic anhydride was obtained. The obtained polymer had Mw of 45362, Mn of 23354, molecular weight distribution (Mw / Mn) of 1.9, and maleic acid modification amount of 0.93%.
In the polymer (B-2-1), a crystal melting peak with a heat of crystal fusion of 1 J / g or more and a crystallization peak with a heat of crystallization of 1 J / g or more were observed in the temperature range of −100 to 200 ° C. It was.

<Example of production of copolymer (B-2-4)>
The polymer (B-2-2) except that the polymer (B-2-3) [ethylene / propylene copolymer (LICOCENE PP2602, manufactured by Clariant Japan KK, ethylene: propylene = 13 mol%: 87 mol%)] is used. In the same manner as in the above production example, a polymer (B-2-4) modified with maleic anhydride was obtained. Mw of the obtained polymer was 55115, Mn was 25836, molecular weight distribution (Mw / Mn) was 2.2, and maleic acid modification amount was 0.84%.
In the polymer (B-2-3), a crystal melting peak with a heat of crystal fusion of 1 J / g or more and a crystallization peak with a heat of crystallization of 1 J / g or more were observed in the temperature range of −100 to 200 ° C. It was.

<Example of production of copolymer (B-3-1)>
A 2 l separable flask reactor was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and the pressure was reduced, and then the gas in the reactor was replaced with nitrogen. Into this flask, 1 l of dried toluene was introduced as a polymerization solvent. Here, propylene 8 NL / min and 1-butene 0.5 NL / min were continuously fed at normal pressure, and the solvent temperature was 30 ° C. After adding 1.25 mmol of triisobutylaluminum (hereinafter sometimes referred to as TIBA) to the reactor, dimethylsilyl (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-) was used as a polymerization catalyst. 0.005 mmol of 5-methyl-2-phenoxy) titanium dichloride was added to the reactor. 15 seconds later, 0.025 mmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added to the reactor to initiate polymerization. As a result of polymerization for 30 minutes, 155.8 g of a propylene-1-butene copolymer (B-3-1) having a propylene content of 96 mol% was obtained. The obtained polymer had an intrinsic viscosity [η] of 2.1 dl / g and a molecular weight distribution (Mw / Mn) of 2.5. In addition, neither a crystal melting peak with a heat of crystal fusion of 1 J / g or more nor a crystallization peak with a heat of crystallization of 1 J / g or more was observed in the temperature range of −100 to 200 ° C.

<Example of production of copolymer (B-3-2)>
Except for using the polymer (B-3-1), a polymer (B-3-2) modified with maleic anhydride was obtained in the same manner as in the production example of the polymer (B-2-2). . Mw of the obtained polymer was 49043, Mn was 14267, molecular weight distribution (Mw / Mn) was 3.4, and maleic acid modification amount was 1.79%.

<Example 1>
In a 2 l separable flask reaction vessel equipped with a stirrer, thermometer and reflux condenser, 200 parts of toluene as a solvent and 100 parts of a polymer (B-1-2) as a thermoplastic resin were stirred at 80 ° C. Dissolved. Next, as a surfactant, a mixed solution of Latemuru E-1000A (30% aqueous solution, manufactured by Kao Corporation), 5 parts of Neugen EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.) and 5 parts of isopropanol is applied for 10 minutes. And dripped. After further stirring for 5 minutes, 5 parts of dimethylethanolamine was added, and the mixture was further stirred for 5 minutes.
Next, the stirring device was changed to TK Robotics (manufactured by PRIMIX Co., Ltd.), and a mixed solution of 100 parts isopropanol and 100 parts ion-exchanged water was added dropwise over 30 minutes while stirring the reaction mass with a disper blade. When fluidity was observed in the reaction mass, the stirring blade was changed to a homomixer, and 300 parts of ion-exchanged water was added dropwise with stirring to obtain a milky white dispersion.
The obtained dispersion was put into a 2 L eggplant flask, distilled under reduced pressure with an evaporator, and filtered with a 200 mesh nylon net to obtain an aqueous emulsion containing a polymer (B-1-2) and an emulsifier. The obtained aqueous emulsion (E-1) had a particle size (number basis) of 0.61 μm and a nonvolatile content concentration of 36%.

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

<Example 3>
An aqueous emulsion was produced in the same manner as in Example 1 except that 100 parts of the polymer (B-2-2) was used as the thermoplastic resin. The obtained aqueous emulsion (E-3) had a particle size (number basis) of 0.22 μm and a nonvolatile content concentration of 39%.

<Example 4>
An aqueous emulsion was produced in the same manner as in Example 1, except that 100 parts of the polymer (B-2-3) was used as the thermoplastic resin. The obtained water-based emulsion (E-4) had a particle size (number basis) of 0.21 μm and a nonvolatile content concentration of 36%.

<Example 5>
An aqueous emulsion was produced in the same manner as in Example 1 except that 100 parts of the polymer (B-2-4) was used as the thermoplastic resin. The obtained water-based emulsion (E-5) had a particle size (number basis) of 0.13 μm and a nonvolatile content concentration of 36%.

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

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

<Example 8>
An aqueous emulsion was produced in the same manner as in Example 1, except that 100 parts of the polymer (B-4-1) [BONDINE HX8140 (manufactured by ARKEMA)] was used as the thermoplastic resin. The obtained aqueous emulsion (E-8) had a particle size (number basis) of 0.09 μm and a nonvolatile content concentration of 40%.

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

<Example 10>
Instead of using 100 parts of the polymer (B-1-2), 67 parts of the polymer (B-4-2) is used as the thermoplastic resin, and 33 parts of terpene phenol (Tamanol 803L manufactured by Arakawa Chemical Co., Ltd.) is used as the adhesive resin. An aqueous emulsion was produced in the same manner as in <Example 1>. The obtained aqueous emulsion (E-10) had a particle size (number basis) of 0.10 μm and a nonvolatile content concentration of 41%.

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

<Example 12>
Instead of using 100 parts of the polymer (B-1-2), 50 parts of the polymer (B-4-3) is used as the thermoplastic resin, and 50 parts of terpene phenol (Tamanol 803L manufactured by Arakawa Chemical Co., Ltd.) is used as the adhesive resin. An aqueous emulsion was produced in the same manner as in <Example 1>. The obtained aqueous emulsion (E-12) had a particle size (number basis) of 0.20 μm and a nonvolatile content concentration of 33%.

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

<Example 14>
Instead of 100 parts of the polymer (B-1-2), 75 parts of the polymer (B-4-4) is used as the thermoplastic resin, and 25 parts of terpene phenol (Tamanol 803L manufactured by Arakawa Chemical Co., Ltd.) is used as the adhesive resin. An aqueous emulsion was produced in the same manner as in Example 1 except that the temperature was 90 ° C. The obtained aqueous emulsion (E-14) had a particle size (number basis) of 0.20 μm and a nonvolatile content concentration of 34%.

The following tests were conducted on the aqueous emulsions obtained in the above examples.
<Test Example A: Stability for 5 days>
The obtained aqueous emulsion was put into a 250 mL plastic container and allowed to stand at room temperature for 5 days, and then the appearance change was observed. The evaluation criteria were as follows. The results are shown in Tables 1 and 2.
○: Aggregation, precipitation, and phase separation were not observed, and the condition was good.
X: Aggregation, precipitation, and phase separation occurred.

<Test Example A: Evaluation of Adhesion to PP>
A polypropylene plate (thickness 3 mm: hereinafter referred to as a PP plate) is washed with IPA, and the aqueous emulsion obtained in Examples 1 to 7 is barized so that the film thickness after drying becomes 10 μm. It was applied using a coater. This was dried at 80 ° C. for 5 minutes with a hot air dryer, and further heated and dried in an oven at 120 ° C. for 30 minutes to obtain a film.
Based on JIS-K5400 (cross-cut peeling tape method test), the obtained film was cut with a grid-like cut with a gap interval of 1 mm, and then a cellophane tape was stuck on the coating film. Next, one to two minutes after the cellophane tape was applied, one end of the tape was held and peeled off at a right angle to evaluate adhesion. The evaluation criteria were as follows. The results are shown in Table 1.
○: The area of peeling is less than 40% of the square area.
X: The area of peeling is 40% or more of the square area.

<Test Example A: Evaluation of Adhesion to M-EVA>
In each of the aqueous emulsions obtained in Examples 8 to 14, 5 parts (nonvolatile content) of Adecanol U-420 (manufactured by ADEKA) as a thickener and 10 Nopco Wet 50 (manufactured by San Nopco) as a dispersant are used. Part (nonvolatile content ratio) was added and stirred with a three-one motor to obtain an aqueous adhesive.
The obtained water-based adhesive was applied to 100% cotton canvas using a glass rod (application amount: about 60 g / m ² ) and air-dried for 20 minutes. The resulting canvas was made into a microwave oven (manufactured by panasonic) , NE-EH212) and subjected to electromagnetic wave treatment at 750 W for 30 seconds.
Further, each aqueous adhesive obtained in Examples 8 to 14 was applied to M-EVA (ethylene / vinyl acetate copolymer foam) using a glass rod (coating amount: about 70 g / m ² ). The obtained M-EVA was put into a microwave oven and subjected to electromagnetic wave treatment at 750 W for 110 seconds.
Again, each of the cotton canvas and M-EVA was coated with the aqueous adhesives of Examples 8 to 14 (cotton canvas coating amount: about 40 g / m ² , M-EVA coating amount: about 80 g / m ² ). The obtained cotton canvas and M-EVA were placed in a microwave oven and subjected to electromagnetic wave treatment at 750 W for 30 seconds.
Subsequently, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA were bonded together and pressure-bonded.
The cotton / adhesive layer / M-EVA laminated structure thus obtained was again placed in a microwave oven and subjected to electromagnetic wave treatment at 750 W for 110 seconds.
Each obtained laminated structure was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corporation, Autograph), at a peeling rate of 200 mm / min and a peeling angle of 180 degrees, the adhesion of the laminated structure. Evaluated. The evaluation criteria were as follows. The results are shown in Table 2.
○: Peel strength of 10 N / inch or more.
X: Peel strength is less than 10 N / inch.

<Examples 15 to 17>
Using the copolymers and surfactants shown in Table 3 in the weight ratios shown in Table 3, emulsions (E-15) to (E-17) were obtained in substantially the same manner as in <Preparation Example 1 of Aqueous Emulsion>. Obtained.
The copolymers and surfactants in Table 3 are as follows.
Copolymer U1: Ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE HX8290, manufactured by ARKEMA, melting point: 81 ° C.)
Copolymer U2: ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE LX4110, manufactured by ARKEMA, melting point: 107 ° C.)
Copolymer U3: ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE HX8210, manufactured by ARKEMA, melting point: 100 ° C.)
Surfactant 1: Compound represented by the above formula (A) (Latemul E-1000A, 30% aqueous solution, manufactured by Kao Corporation)
Surfactant 2: Compound represented by the above formula (B) (Neugen EA-177, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

<Examples 18 to 27>
As shown in Table 4-1, terpene phenol as the adhesive resin 1 was added to the aqueous emulsions (E-15) to (E-17) (nonvolatile content ratio, unit: parts by weight) obtained in Examples 15 to 17. Aqueous urethane emulsion (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) and adhesive urethane 2 as an aqueous urethane emulsion (Disco Pearl U-54, manufactured by SBU) are blended so that the nonvolatile content ratio is 100: 100: 100. Furthermore, Adecanol UH-756VF (manufactured by ADEKA) is added as a thickener, Nopco Wet 50 (manufactured by San Nopco) is added as a dispersant, and Desmodur N3300 (manufactured by SBU) is added as a crosslinking agent. Prepared with water so that the non-volatile content was 40%, and stirred with a three-one motor to obtain aqueous emulsions (E-18) to (E-27).

<Test Example F: Evaluation 5 for Adhesion to M-EVA and Heat Resistance>
The obtained aqueous emulsion (E-27) shown in Table 4-1 was applied to 100% cotton canvas using a glass rod (coating amount: about 130 g / m ² weight after drying), and after natural drying for 20 minutes. The electromagnetic wave treatment was performed at 3000 W for 30 seconds.
Further, each of the aqueous emulsions (E-18) to (E-26) was added to a bar coater No. 75 (coil diameter: 75 × 25 μm) was applied to M-EVA (ethylene / vinyl acetate copolymer foam) (coating amount: weight after drying about 30 g / m ² ) and obtained. M-EVA was subjected to electron wave treatment at 3000 W for 110 seconds. Thereafter, the aqueous emulsion (E-27) was applied to cotton canvas and M-EVA using a glass rod (cotton canvas coating amount: about 70 g / m ² after drying ^, M-EVA coating amount: about 70 g after drying) / M ² ), and M-EVA was subjected to electromagnetic wave treatment at 3000 W for 15 seconds.
Subsequently, the coated surfaces of the cotton canvas and the aqueous emulsion of M-EVA were bonded together and subjected to electromagnetic wave treatment at 3900 W for 120 seconds. Then, it crimped | bonded by hand. Thereby, a laminated structure composed of cotton / adhesive layer / M-EVA was obtained.

Each of the obtained laminated structures was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corporation, Autograph), at a peeling rate of 50 mm / min and a peeling angle of 180 degrees, the adhesion of the laminated structure. Was evaluated by measuring the peel strength. The results are shown in Table 4-2.
○: Peel strength of 70 N / inch or more.
X: Peel strength is less than 70 N / inch.

Each of the obtained laminated structures was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Toyo Seiki, Strograph T), a set temperature in the tank of 60 ° C., a peeling speed of 50 mm / min, and a peeling angle of 180 degrees Thus, the heat resistance of the laminated structure was evaluated by measuring the peel strength. The results are shown in Table 4-2.
○: Peel strength of 15 N / inch or more.
X: Peel strength is less than 15 N / inch.

<Test Example G: Evaluation 6 of Adhesiveness to M-EVA>
50 parts of an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) as an adhesive resin was added to 100 parts by weight of the aqueous emulsion (E-15) (non-volatile content ratio, unit: parts by weight) obtained in the examples. The non-volatile content ratio is 100: 50, 2 parts by weight of Adecanol UH-420UH (ADEKA) as a thickener, and 8 parts by weight of Nopco Wet 50 (San Nopco) as a dispersant. It was added and prepared with water so that the non-volatile content of the blend was 40%, and stirred with a three-one motor to obtain an aqueous adhesive G1.
The obtained water-based adhesive G1 was applied to 100% cotton canvas using a glass rod (coating amount: weight after drying about 167 g / m ² ), and air-dried for 1 hour. Thereafter, the aqueous adhesive G1 was applied again (application amount: weight after drying of about 100 g / m ² ).
Also, water-based adhesive G1 was applied to bar coater No. 75 was applied to M-EVA (foamed ethylene / vinyl acetate copolymer) (coating amount: weight after drying: about 30 g / m ² ).
After both the canvas and M-EVA were naturally dried for 1 hour, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA were bonded together and subjected to electromagnetic wave treatment at 3900 W for 150 seconds. Then, it crimped | bonded by hand. Thereby, a laminated structure composed of cotton / adhesive layer / M-EVA was obtained.
Each of the obtained laminated structures was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corporation, Autograph), at a peeling rate of 50 mm / min and a peeling angle of 180 degrees, the adhesion of the laminated structure. Was evaluated by measuring the peel strength. Good results were obtained with a peel strength of 10 N / inch or more.

<Example 28>
Aqueous emulsion (E-15), aqueous emulsion of terpene phenol (Tamanol E-200NT, Arakawa Chemical Co., Ltd.), polyurethane emulsion (SBU, Dispacol U-54), isocyanate (SBU, Desmodur N3300) An aqueous emulsion (E-28) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 100 parts: 5 parts.

<Example 29>
Aqueous emulsion (E-15), aqueous emulsion of terpene phenol (Tamanol E-200NT, Arakawa Chemical Co., Ltd.), polyurethane emulsion (SBU, Dispacol U-54), isocyanate (SBU, Desmodur N3300) An aqueous emulsion (E-29) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 200 parts: 10 parts.

<Example 30>
Aqueous emulsion (E-15), aqueous emulsion of terpene phenol (Tamanol E-200NT, Arakawa Chemical Co., Ltd.), polyurethane emulsion (SBU, Dispacol U-54), isocyanate (SBU, Desmodur N3300) An aqueous emulsion (E-30) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 1600 parts: 41 parts.

<Example 31>
Aqueous emulsion (E-15), aqueous emulsion of terpene phenol (Tamanol E-200NT, Arakawa Chemical Co., Ltd.), polyurethane emulsion (SBU, Dispacol U-54), isocyanate (SBU, Desmodur N3300) An aqueous emulsion (E-31) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 100 parts: 15 parts.

<Example 32>
Aqueous emulsion (E-15), aqueous emulsion of terpene phenol (Tamanol E-200NT, Arakawa Chemical Co., Ltd.), polyurethane emulsion (SBU, Dispacol U-54), isocyanate (SBU, Desmodur N3300) An aqueous emulsion (E-32) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 200 parts: 20 parts.

<Example 33>
A polyurethane emulsion (manufactured by SBU, Dispacol U-54) and isocyanate (manufactured by SBU, Desmodur N3300) are blended so that the nonvolatile content ratio is 100 parts: 5 parts to obtain an aqueous emulsion (E-33). It was.

<Example 34>
Aqueous emulsion (E-15), polyurethane emulsion (manufactured by SBU, Dispacol U-54) and isocyanate (manufactured by SBU, Desmodur N3300) are blended so that the nonvolatile content ratio is 100 parts: 100 parts: 5 parts. Thus, an aqueous emulsion (E-34) was obtained.

<Example 35>
Aqueous emulsion (E-15), polyurethane emulsion (manufactured by SBU, Dispacol U-54) and isocyanate (manufactured by SBU, Desmodur N3300) are blended so that the nonvolatile content ratio is 100 parts: 200 parts: 10 parts. Thus, an aqueous emulsion (E-35) was obtained.

<Test Example B: Evaluation 2 for Adhesion to M-EVA>
In each aqueous emulsion (non-volatile content ratio) obtained in the examples, Adecanol UH-756VF (manufactured by ADEKA) as a thickener and Nopco Wet 50 (manufactured by San Nopco) as a dispersant are listed in Table 5 (Non-volatile content ratio, unit: parts by weight) was added and water was prepared so that the non-volatile content of the formulation was 40%, and the mixture was stirred with a three-one motor, and the aqueous adhesive B1 and aqueous adhesive B2 in each test example Got each.
The obtained water-based adhesive B2 was applied to 100% cotton canvas using a glass rod (application amount: weight after drying about 130 g / m ² ) and air-dried for 20 minutes. The resulting canvas was microwaved (Microelectronics company make, 9KW microwave oven, frequency 2.45GHz) It put into electromagnetic waves for 30 seconds at 3000W.
Also, water-based adhesive B1 was applied to bar coater No. 75 was applied to M-EVA (application amount: weight after drying: about 30 g / m ² ), and the obtained M-EVA was put in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 110 seconds.
Again, water-based adhesive B2 was applied to each of cotton canvas and M-EVA (cotton canvas coating amount: weight after drying about 60 g / m ² , M-EVA coating amount: weight after drying about 30 g / m ² ), The obtained cotton canvas and M-EVA were placed in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 15 seconds.
Subsequently, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA were bonded together and pressure-bonded.
The cotton / adhesive layer / M-EVA laminated structure thus obtained was again placed in a microwave oven and subjected to electromagnetic wave treatment at 3900 W for 120 seconds. Immediately removed from the microwave and crimped by hand.
The obtained laminated structure was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was evaluated by the same method and evaluation criteria as described above. The results are shown in Table 5.

<Test Example C: Evaluation 3 for Adhesiveness to M-EVA>
In each emulsion (non-volatile content ratio) obtained in the examples, Adecanol UH-756VF (manufactured by ADEKA) as a thickener and Nopco Wet 50 (manufactured by San Nopco) as a dispersant are contained in the amounts shown in Table 6 (Non-volatile content ratio, unit: parts by weight) was added, and water was prepared so that the non-volatile content of the formulation was 40%, and the mixture was stirred with a three-one motor. C2 was obtained.
The obtained water-based adhesive C2 shown in Table 6 was applied to 100% cotton canvas using a glass rod (weight application amount after drying: about 130 g / m ² ), and air-dried for 20 minutes to obtain. The canvas was subjected to electromagnetic wave treatment in a microwave oven at 3000 W for 30 seconds.
In addition, each water-based adhesive C1 shown in Table 6 was replaced with a bar coater No. 75 was applied to M-EVA (weight application amount after drying: about 30 g / m ² ), and the obtained M-EVA was placed in a microwave oven and subjected to electromagnetic wave treatment at 5000 W for 170 seconds.
A water-based adhesive C2 was applied to each of the obtained cotton canvas and M-EVA (cotton canvas application amount: weight after drying: about 70 g / m ² , M-EVA application amount: weight after drying: about 30 g / m ² ) These cotton canvases were placed in a hot air oven at 80 ° C. for about 15 minutes, and M-EVA was placed in a hot air oven at 80 ° C. for about 10 minutes, and the coated surfaces of the aqueous adhesive were bonded together while hot.
The obtained cotton / adhesive layer / M-EVA laminated structure was again put into a hot air dryer, heat-treated at 80 ° C. for 10 minutes, taken out from the dryer, and then pressure-bonded by hand.
The obtained laminated structure was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was evaluated by the same method and evaluation criteria as described above. The results are shown in Table 6.

<Test Example H: Evaluation 7 for Adhesion to M-EVA / Synthetic Leather>
In each emulsion (non-volatile content ratio) obtained in the examples, Adecanol UH-756VF (manufactured by ADEKA) as a thickener and Nopco Wet 50 (manufactured by San Nopco) as a dispersant are contained in the amounts shown in Table 7 (Non-volatile content ratio, unit: parts by weight) was added, and the mixture was prepared with water so that the non-volatile content of the formulation was 40%, and stirred with a three-one motor to obtain an aqueous adhesive H1 and an aqueous adhesive H2.
The obtained water-based adhesive H1 of Table 7 was used as a bar coater No. 75 was applied to M-EVA (weight application amount after drying: about 30 g / m ² ), and the obtained M-EVA was placed in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 110 seconds.
Aqueous adhesives H1 and H2 were applied to each of the obtained M-EVA and synthetic leather (amount of H-2 applied to synthetic leather: about 30 g / m ² after drying, H-1 applied to M-EVA) The weight was about 30 g / m ² after drying, and the obtained synthetic leather and M-EVA were placed in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 15 seconds.
Subsequently, the coated surfaces of the synthetic leather and the aqueous adhesive of M-EVA were bonded together and pressure-bonded.
The synthetic leather / adhesive layer / M-EVA laminated structure thus obtained was again placed in a microwave oven and subjected to electromagnetic wave treatment at 3900 W for 120 seconds. Immediately removed from the microwave and crimped by hand.
The obtained laminated structure was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was evaluated by the same method and evaluation criteria as described above. The results are shown in Table 7.

<Examples 36 to 52>
Using the copolymers and surfactants shown in Tables 8 and 9 in the weight ratios shown in Tables 8 and 9, an aqueous emulsion (E-36) substantially in the same manner as in <Production Example 1 of aqueous emulsion> To (E-52).
The copolymers and surfactants in the table are as follows.
Copolymer P1: C ₂ (ethylene) / EVA (ethylene / vinyl acetate copolymer) / MAH (maleic anhydride) copolymer (OREVAC T9314, manufactured by ARKEMA)
Copolymer P2: C ₂ / EVA / MAH copolymer (OREVAC T9318, manufactured by ARKEMA)
Copolymer Q1: MAH-modified EVA (OREVAC G18211, manufactured by ARKEMA)
Copolymer R1: EVA part saponified product (Mersen H6051, manufactured by Tosoh Corporation)
Copolymer R2: EVA part saponification product (Mersen H6410M, manufactured by Tosoh Corporation)
Copolymer R3: EVA partly saponified product (Mersen H6820, manufactured by Tosoh Corporation)
Copolymer R4: EVA part saponification product (Mersen H6822X, manufactured by Tosoh Corporation)
Copolymer R5: EVA partly saponified product (Mersen H6960, manufactured by Tosoh Corporation)
Copolymer S1: EVA (EVATEATE KA-40, manufactured by Sumitomo Chemical Co., Ltd.)
Copolymer T1: heat-degraded polyethylene (UMX2000, manufactured by Sanyo Chemical Industries, Ltd.)
Copolymer U1: Ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE HX8290, manufactured by ARKEMA)
Copolymer U2: ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE LX4110, manufactured by ARKEMA)
Surfactant 1: Compound represented by the above formula (A) (Latemul E-1000A, 30% aqueous solution, manufactured by Kao Corporation)
Surfactant 2: Compound represented by the above formula (B) (Neugen EA-177, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

<Test Example D: Evaluation 4 of Adhesiveness to M-EVA>
Table 10 shows 100 parts by weight of each aqueous emulsion (non-volatile content) obtained in Examples, Adecanol UH-420 (manufactured by ADEKA) as a thickener, and Nopco Wet 50 (manufactured by San Nopco) as a dispersant. The stated amount (nonvolatile content ratio, unit: parts by weight) was added, and the mixture was prepared with water so that the nonvolatile content of the formulation was 40%, and stirred with a three-one motor to obtain an aqueous adhesive D.
The obtained water-based adhesive D in Table 10 was applied to a canvas of 100% cotton using a glass rod (coating amount: weight about 130 g / m ² after drying) and air-dried for 1 hour.
Also, the same water-based adhesive D applied to cotton was applied to the bar coater No. 75 was applied to M-EVA (foamed ethylene / vinyl acetate copolymer) (weight application amount after drying: about 30 g / m ² ), and the obtained M-EVA was naturally dried for 1 hour. Then, apply to cotton canvas and M-EVA using a glass rod (cotton canvas: weight after drying about 70 g / m ² , M-EVA coating amount: weight after drying about 30 g / m ² ), put in a microwave oven, Electromagnetic wave treatment was performed at 750 W for 30 seconds.
Subsequently, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA were bonded together and pressure-bonded.
The cotton / adhesive layer / M-EVA laminated structure thus obtained was again placed in a microwave oven and subjected to electromagnetic wave treatment at 750 W for 110 seconds. After removing from the dryer, it was crimped by hand. Thereby, a laminated structure composed of cotton / adhesive layer / M-EVA was obtained.
The obtained laminated structure was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was evaluated by the same method and evaluation criteria as described above. The results are shown in Table 10.

<Test example: Appearance observation>
All of the aqueous emulsions (E-15) to (E-52) are homogeneously dispersed by visual observation, and do not cause aggregation, precipitation, phase separation, or the like even during long-term storage. Stable.

  According to the aqueous emulsion of the present invention, an aqueous emulsion excellent in emulsification dispersibility and stability can be provided.

Claims (7)

An aqueous emulsion containing the following (A), (B) and (C).
(A) Two or more kinds of surfactants represented by the following formula (I)

(In the formula, X represents a hydrogen atom or —SO ₃ M (M is a hydrogen atom, NH ₄ or an alkali metal). N represents an integer of 1 to _3. m represents an integer of 1 to 100.)
(B) Thermoplastic resin (C) Water 2. The aqueous emulsion according to claim 1, wherein the surfactant (A) contains two or more of a surfactant in which X is a hydrogen atom and a surfactant in which X is —SO ₃ M. ₃ . _3. The aqueous emulsion according to claim 1, wherein the surfactant (A) contains two or more of a surfactant in which X is a hydrogen atom and a surfactant in which X is —SO ₃ NH ₄ .   The aqueous emulsion according to any one of claims 1 to 3, wherein the thermoplastic resin (B) is a polymer including one or more structural units derived from an α-olefin having 2 to 20 carbon atoms.   The water-based emulsion as described in any one of Claims 1-4 containing the dispersoid of a particle size (number basis) 0.01-1.0 micrometer.   A method for forming a coating film, wherein the aqueous emulsion according to any one of claims 1 to 5 is coated on a substrate and dried.   The coating film obtained by the method of Claim 6.