JP2011012196A - Emulsion and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsion for improving water resistance of a conventional emulsion using a tackifier resin, a plasticizer, a softener, an antioxidant, an ultraviolet absorber, a crosslinking agent, a pigment or the like and the blending effect of a chloroprene-based polymer (CR), a styrene-butadiene-based polymer (SBR), an acrylic polymer (ACM) or the like to the emulsion, and to provide a method for producing the same.SOLUTION: The emulsion contains 3 wt.% conventional emulsifier and a hydrophobic material emulsified and stabilized by a hydrophilic group-containing polymer and has 10-200 nm average particle diameter. The method for producing the emulsion is provided.

Description

  The present invention relates to an emulsion having an average particle diameter of 10 to 200 nm in which a hydrophobic substance is emulsified and stabilized by a hydrophilic group-containing polymer, and a method for producing the emulsion.

  A so-called emulsion obtained by forcibly emulsifying a water-insoluble hydrophobic substance such as a resin, a plasticizer, a softener, an antioxidant, an ultraviolet absorber, a crosslinking agent, and an organic pigment in water using an emulsifier is an adhesive, It is used in a wide range of applications such as adhesives, primers, paints, coatings, binders, textile processing, paper processing, leather finishing, gloves, finger sack, balloons, floor polish, toner and ink. In addition, these dispersions obtained by dispersing inorganic fine particles such as titanium oxide, zinc oxide, zinc sulfide, and magnetic particles in water using an emulsifier or the like are also used in various applications.

  For example, emulsions of the above-mentioned tackifying resin, plasticizer, and softener include chloroprene polymer (hereinafter abbreviated as CR) emulsion adhesive, styrene butadiene polymer (hereinafter abbreviated as SBR) emulsion. Adhesive, acrylic polymer (hereinafter abbreviated as ACM) emulsion adhesive, ACM emulsion paint, ethylene / vinyl acetate polymer (hereinafter abbreviated as EVA) emulsion adhesive, polyolefin resin emulsion coating agent The epoxy resin emulsion adhesive is blended for the purpose of imparting tackiness, flexibility, film-forming property, polyolefin adhesiveness, and the like.

  The above-mentioned emulsion of antioxidants and UV absorbers is an aging of the above-mentioned emulsion adhesives, emulsion pressure-sensitive adhesives, emulsion paints, emulsion coating agents, etc. (hereinafter these may be abbreviated as emulsion adhesives etc.) It mixes for the purpose of prevention and coloring.

  The above-mentioned emulsion of the crosslinking agent (for example, blocked isocyanate or the like) is blended for the purpose of improving the strength and heat resistance of the emulsion adhesive or the like.

  The emulsion of the above pigment is blended for the purpose of coloring the emulsion adhesive or the like, and is itself used as a water-based ink.

  Conventional tackifier resins, plasticizers, softeners, antioxidants, UV absorbers, cross-linking agents, and pigment emulsions can be obtained by using common water-soluble emulsifiers or water-soluble polymers, and tackifier resins or plasticizers. Is forcibly emulsified and dispersed in water. Since these emulsions contain almost no organic solvent, they have merit in terms of safety and the environment, but because they contain a large amount of emulsifier, the adhesiveness, adhesion, etc. of the above-mentioned aqueous adhesives, adhesives, coating agents, paints, etc. The water resistance was not always satisfactory. Also, for example, most conventional emulsions have an average particle size of about 300 nm, and conventionally used solvent-based CR adhesives using organic solvents, SBR adhesives, ACM pressure-sensitive adhesives, ACMs Compared with paints, polyolefin coating agents, etc., the uniformity is much lower, so there is a problem that the compounding effect of tackifier resins, plasticizers, antioxidants, ultraviolet absorbers, crosslinking agents, pigments and the like is small.

  Therefore, instead of blending the tackifier resin emulsion into the ACM emulsion, an attempt is made to combine (add internally) the tackifier resin into the ACM emulsion particles when producing an ACM emulsion by emulsion polymerization of an acrylic monomer. It has been broken. For example, a method is disclosed in which an acrylic monomer in which a tackifying resin is dissolved in advance is emulsified in water using an emulsifier, and a radical initiator is added to perform emulsion polymerization (Patent Document 1).

  However, it is described that the tackifying resin is likely to precipitate, and finally the acrylic polymer and the tackifying resin form independent particles. In addition, since a large amount of general water-soluble emulsifiers are used, the effects of these emulsifiers on adhesion, adhesion, and water resistance have not been eliminated.

  Also, instead of a general emulsifier, an acrylic oligomer is used to forcibly emulsify an acid-modified tackifier resin (Patent Document 2), and a methacrylate polymer containing an organic acid in the molecule is used. A method for forcibly emulsifying a tackifying resin (Patent Document 3) and a method for forcibly emulsifying a tackifying resin using a styrene sulfonic acid / methacrylic acid ester random copolymer (Patent Document 4) are disclosed. Has been.

  However, since the emulsion obtained in Patent Document 2 has a large particle size, the compounding effect of the tackifying resin emulsion is still small, and since the tackifying resin has an acidic group, CR emulsion, SBR emulsion, ACM emulsion, epoxy resin There are limitations on compatibility with base emulsion polymers such as emulsions and polyolefin resin emulsions. Patent Documents 3 and 4 do not mention the particle size, but in the case of a polymer having a hydrophilic group in the molecule instead of the polymer end, the amount of the hydrophilic group-containing polymer necessary for stabilizing the emulsion is increased. There is a limit to reducing the particle size of emulsions. Moreover, since patent document 4 uses a polymer soluble in pure water, such as a styrene sulfonic acid / methacrylic acid ester random copolymer, instead of a general emulsifier, water resistance is not necessarily satisfactory.

Japanese Patent No. 3964264 JP 2005-330436 A Japanese Patent No. 3953796 Japanese Patent Publication No.7-24747

  As described above, emulsions of tackifier resins, plasticizers, softeners, antioxidants, ultraviolet absorbers, crosslinking agents, pigments, and the like having a small content of conventional emulsifiers and a small particle size are desired. It was.

  As a result of intensive studies to solve the above problems, the present inventors have used a specific hydrophilic group-containing polymer instead of the conventional emulsifier, and in the presence of a hydrophilic solvent, such as a tackifier resin and a plasticizer. By compulsorily emulsifying hydrophobic substances, emulsions such as tackifier resins and plasticizers having an average particle size of 10 to 200 nm and containing no conventional emulsifiers or a greatly reduced content of conventional emulsifiers are obtained. Thus, the present inventors have found that the conventional problems can be solved, and have completed the present invention. That is, the present invention is an emulsion containing a conventional emulsifier of 3 wt% or less, in which a hydrophobic substance is emulsified and stabilized by a hydrophilic group-containing polymer, and has an average particle size of 10 to 200 nm, and a method for producing the emulsion.

  Hereinafter, the present invention will be described in detail.

  The emulsion of the present invention contains a conventional emulsifier of 3 wt% or less. The content of the conventional emulsifier of 3 wt% or less means that the conventional emulsifier used in the conventional emulsion is not included or the content of the conventional emulsifier is remarkably reduced. What does not contain a conventional emulsifier means that the content of the conventional emulsifier is 0 wt%, and this is most preferable in view of the effects of the present invention. The content of the conventional emulsifier is remarkably reduced means that the content of the conventional emulsifier exceeds 0 wt% and is 3 wt% or less. From the viewpoint of adhesiveness, adhesion, and water resistance, 0 wt% is used. Exceeding 2 wt% or less is preferable. When the conventional emulsifier exceeds 3 wt%, adhesion of CR emulsion adhesive, SBR emulsion adhesive, ACM emulsion pressure sensitive adhesive, ACM emulsion paint, EVA emulsion adhesive, polyolefin resin emulsion coating agent, etc., formed by blending these emulsions And water resistance decrease significantly. Examples of conventional emulsifiers include conventionally used water-soluble anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers. Examples of anionic emulsifiers include rosinates and fatty acids. Salt, alkenyl succinate, alkyl ether carboxylate, alkyl diphenyl ether disulfonate, alkane sulfonate, alkyl succinate sulfonate, polyoxyethylene polycyclic phenyl ether sulfate, α-olefin sulfonate, Alkylbenzene sulfonate, naphthalene sulfonate formalin condensate, polystyrene sulfonate, polystyrene sulfonic acid methacrylic acid copolymer salt, polystyrene sulfonic acid acrylic acid copolymer salt, polystyrene sulfonic acid acrylic acid ester copolymer salt, Livinyl sulfonic acid copolymer salt, polyisoprene sulfonic acid copolymer salt, polyacrylic acid ester acrylic acid copolymer salt, polymethacrylic acid ester methacrylic acid copolymer salt, polyacrylamide acrylic acid copolymer, polymethacrylic acid Amide methacrylic acid copolymer, polyvinyl pyrrolidone, alkyl sulfosuccinate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate ester salt, higher fatty acid amide sulfonate, higher Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyalkylene alkyl amine, and alkyl alkanoic acid. Uramide, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, alkyl polyglucoxide, sucrose fatty acid ester, polyoxyethylene polyoxypropylene glycol, Examples of the cationic emulsifier include alkylamine salts, alkyl-type quaternary ammonium salts, fatty acid amide amine salts, and alkyl amino acid salts. Examples of amphoteric emulsifiers include alkyldimethylaminoacetic acid betaine, Examples thereof include alkyldimethylaminosulfobetaine and alkylsulfobetaine. Moreover, the above-mentioned types of anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers having a radically polymerizable unsaturated bond such as a propenyl group, an aryl group, and a methacryloyl group.

  In the emulsion of the present invention, a hydrophobic substance is emulsion-stabilized by a hydrophilic group-containing polymer. Emulsion stabilization means a state in which the hydrophobic substance is stably dispersed in water by adsorbing the hydrophilic group-containing polymer onto the surface of the fine particles of the hydrophobic substance. A hydrophilic group-containing polymer is a polymer based on CR or acrylic polymer, which is used as a substitute for an emulsifier, and includes a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an amine group, a hydroxyl group, a sulfuric acid group, and a carboxylic acid. Although it will not specifically limit if it contains the hydrophilic group selected from a salt, a sulfonate, a phosphate, an amine salt, a sulfate, or a polyalkylene oxide, For example, (A) following general formula (1) ) Chloroprene block copolymer or chloroprene graft copolymer (hereinafter abbreviated as amphiphilic CR block copolymer, amphiphilic CR graft copolymer), (B) carboxylic acid group, A hydrophilic group selected from a sulfonic acid group, a phosphoric acid group, an amine group, a hydroxyl group, a carboxylate, a sulfonate, a phosphate, an amine salt or a polyalkylene oxide; Hydrophilic group-containing chloroprene random copolymer (hereinafter abbreviated as hydrophilic group-containing CR random copolymer) having a structure randomly distributed in the limer, (C) terminal hydrophilicity represented by the following general formula (2) Examples thereof include one or more polymers selected from the group consisting of a group-containing chloroprene polymer, a terminal hydrophilic group-containing acrylate polymer, and a terminal hydrophilic group-containing methacrylic ester polymer.

（式中、水溶性ポリマー又は水溶性オリゴマーは、カルボン酸基、スルホン酸基、リン酸基、アミン基、水酸基、カルボン酸塩、スルホン酸塩、リン酸塩、アミン塩又はポリアルキレンオキサイドから選択される親水基を有する水溶性ポリマー又は水溶性オリゴマーを表す。）

(In the formula, the water-soluble polymer or water-soluble oligomer is selected from carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, hydroxyl group, carboxylate, sulfonate, phosphate, amine salt or polyalkylene oxide. Represents a water-soluble polymer or water-soluble oligomer having a hydrophilic group.)

（式中、Ｐはクロロプレン系ポリマー、アクリル酸エステル系ポリマー、又はメタクリル酸エステル系ポリマーを表し、Ｘはカルボン酸基、スルホン酸基、リン酸基、アミン基、硫酸基、カルボン酸塩、スルホン酸塩、リン酸塩、アミン塩、硫酸塩又はポリアルキレンオキサイドを表し、Ｒはアルキル基、アリール基、置換アルキル基又は置換アリール基を表し、ｎは１〜３の整数を表す。）
親水基含有ポリマーのゲル浸透クロマトグラフィー（ＧＰＣ）で測定した数平均分子量は特に制限するものではないが、乳化能を維持したり、ラテックス粘度の上昇を抑制するためには、５００〜１０００００が好ましく、１０００〜１００００がさらに好ましい。

(In the formula, P represents a chloroprene polymer, an acrylate polymer, or a methacrylate polymer, and X represents a carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, sulfuric acid group, carboxylate salt, sulfone. Represents an acid salt, a phosphate, an amine salt, a sulfate or a polyalkylene oxide, R represents an alkyl group, an aryl group, a substituted alkyl group or a substituted aryl group, and n represents an integer of 1 to 3.)
The number average molecular weight of the hydrophilic group-containing polymer measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 500 to 100,000 in order to maintain the emulsifying ability and suppress the increase in latex viscosity. 1000 to 10,000 is more preferable.

  The hydrophobic substance that is emulsion-stabilized by the hydrophilic group-containing polymer is not particularly limited as long as it is soluble in an organic solvent used during emulsification or is in a liquid state at an emulsification temperature. For example, a tackifier resin , Plasticizers, softeners, antioxidants, ultraviolet absorbers, crosslinking agents, pigments, resins, rubbers, thermoplastic elastomers, etc., among these, because they are relatively low molecular weight and easy to emulsify, A plasticizer, a softener, an antioxidant, an ultraviolet absorber, a crosslinking agent, and a pigment are preferable.

  The tackifying resin, which is a hydrophobic substance, is compatible with CR, SBR, ACM, EVA, epoxy resin, polyolefin, etc., and imparts tackiness, flexibility, adhesiveness, and adhesion depending on these uses and purposes. It is not particularly limited as long as it is, for example, aliphatic petroleum resin, aromatic petroleum resin, aliphatic-aromatic copolymer petroleum resin, terpene resin, phenol-modified terpene resin, aromatic-modified terpene resin, Examples include rosin acid ester resins, coumarone resins, coumarone-indene resins, hydrogenated products of these resins, and acid-modified products of these resins.

  The plasticizer which is a hydrophobic substance is particularly limited as long as it is compatible with CR, SBR, ACM, EVA, epoxy resin, polyolefin, etc., and provides tackiness and flexibility according to these uses and purposes. For example, phthalic acid such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di (2-ethylhexyl) phthalate, diisopropyl phthalate, dicyclohexyl phthalate, diamyl phthalate, dicapryl phthalate, diundecyl phthalate Esters, fumarates such as dibutyl fumarate and diisobutyl fumarate, phosphate esters such as tributyl phosphate, trioctyl phosphate, tricresyl phosphate, triphenyl phosphate, trimethyl citrate, triethyl citrate, citric acid Tributyl, acetyltriethyl citrate Citrates such as trihexyl citrate, tributyl-2,2,4-trimethyl-1,3-pentanediol diisobutyrate citrate, dioctyl adipate, diethyl adipate, di (2-methylethyl adipate) ), Adipic acid diesters such as dihexyl adipate, tartrate diesters such as diethyl tartrate and dibutyl tartrate, sebacate diesters such as diethyl sebacate, dipropyl sebacate and dinonyl sebacate, diethyl succinate, dibutyl succinate, etc. Succinic acid diester, glycerol diacetate, glycerol triacetate (triacetin), glycerol monoacetate glycerol, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, ethylene glycol diacetate, ethyl butyrate Glycolic acid diesters such as glycol, triethylene glycol diacetate, triethylene glycol dibutyrate, triethylene glycol dipropionate, and other polyalkyl esters of aromatic or aliphatic polycarboxylic acids, N, N-dicyclohexylbenzothiazyl -2-sulfenamide (DCHBSA), N-cyclohexylbenzothiazyl-2-sulfenamide (CBS), N-tert-butylbenzothiazyl-2-sulfenamide (BBS), N-oxydiethylenebenzothia Examples include dil-2-sulfenamide (OBS), N, N-diisopropylbenzothiazyl-2-sulfenamide (DPBS), and the like.

  The softening agent which is a hydrophobic substance is not particularly limited as long as it is compatible with rubber and resin and softens them. For example, paraffinic process oil, naphthenic process oil, aromatic process oil And mineral oil such as chlorinated paraffin, rapeseed oil, epoxidized soybean oil, castor oil, vegetable oil such as linseed oil and coconut oil, ethylene-α-olefin copolymer oligomer, and the like.

  The antioxidant, which is a hydrophobic substance, is not particularly limited as long as it prevents the oxidation of rubber or resin. For example, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert) -Butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate], 2,4-bis- (normal octylthio) -6- (4-hydroxy-3, -Di-tert-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′- Hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tri -(3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 2,4-bis [(octylthio) methyl] -ortho-cresol, isooctyl-3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate, tetrakis [methylene 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- [3- (3-tert Phenolic antioxidants such as -butyl-4-hydroxy-5-methylphenyl) -propionoxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane 2,2-hydroxy-5-methylphenyl-benzotriazole, 4,4'-bis- (2,2-dimethylbenzyl) diphenyla Amine, bis (1,2,2,6,6-pentamethyl-4-piperidyldecanedionate and other amine antioxidants, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thio Such as dipropionate, distearyl-3,3′-thiodipropionate, pentaerythrityl-tetrakis (3-laurylthiopropionate) ditridecyl-3,3′-thiodipropionate, 2-mercaptobenzimidazole, etc. Phosphorus antioxidants such as sulfur antioxidants, trisnonylphenyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, 2,2,6,6-tetramethyl And stable radical antioxidants such as piperidine-1-oxyl.

  The ultraviolet absorbent that is a hydrophobic substance is not particularly limited as long as it has ultraviolet absorbing ability and suppresses deterioration of rubber or resin. For example, salicylic acid derivatives, benzophenone derivatives, benzotriazole derivatives, oxalic acid anilides Derivatives, hindered amines and the like.

  The crosslinking agent that is a hydrophobic substance is not particularly limited as long as it acts as a crosslinking agent or crosslinking accelerator for rubber or resin. For example, polyisocyanate, blocked polyisocyanate, amino resin, aziridine compound, Examples include methylolated melamine, polymer polysulfide, polyamine, oximes, and alkylphenol resins.

  The pigment which is a hydrophobic substance is particularly limited as long as it can be used for CR, SBR, ACM, EVA, epoxy resin, polyolefin depending on the purpose and purpose, or can be used as ink by itself. However, in order to obtain an emulsion having a small particle size, those soluble in an organic solvent are preferable. I. Pigment yellow 74, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 16, C.I. I. Pigment Yellow 17 and other azo pigments, copper phthalocyanine blue or derivatives thereof (CI Pigment Blue 15: 3, CI Pigment Blue 15: 4), phthalocyanine pigments such as aluminum phthalocyanine, C.I. I. Pigment orange 48, C.I. I. Pigment orange 49, C.I. I. Pigment red 122, C.I. I. Pigment red 192, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment violet 19, C.I. I. In addition to quinacridone pigments such as Pigment Violet 42, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, quinophthalones, indanthrene pigments, diketopyrrolopyrrole pigments, aniline black pigments, And heterocyclic yellow pigments.

  The hydrophobic substance may be one kind or a combination of two or more kinds.

  The average particle size of the emulsion of the present invention is 10 to 200 nm. When the average particle size is less than 10 nm, the viscosity of the emulsion increases and the solid content cannot be increased. When the average particle diameter exceeds 200 nm, the effect of blending the tackifier resin or the plasticizer emulsion becomes remarkable. Considering the viscosity of the emulsion, 10 to 150 nm is preferable.

  In the present invention, when an emulsion of a hydrophobic substance such as a tackifier resin or a plasticizer is produced, a conventional emulsifier of 3 wt% or less, a hydrophilic group-containing polymer (for example, an amphiphilic CR block copolymer, an amphiphilic substance) CR graft copolymer, hydrophilic group-containing CR random copolymer, or a specific terminal hydrophilic group-containing chloroprene polymer, terminal hydrophilic group-containing acrylate polymer, and terminal hydrophilic group-containing methacrylate polymer One or more kinds of polymers) are used.

  As a method for producing the emulsion of the present invention, a hydrophilic group-containing polymer and a hydrophobic substance are dissolved in a hydrophilic solvent, and water is added to the resulting mixed solution with stirring to perform phase inversion emulsification.

  First, an amphiphilic CR block copolymer, an amphiphilic CR graft copolymer, and a method for producing an emulsion of a hydrophobic substance such as a tackifier resin and a plasticizer using the same will be described.

  An amphiphilic CR block copolymer is a hydrophobic chloroprene polymer or a chloroprene oligomer chain having a water-soluble oligomer or water-soluble polymer bonded to the end of the chain, and an amphiphilic CR graft copolymer Is a hydrophobic chloroprene polymer or chloroprene oligomer backbone with a water-soluble oligomer or water-soluble polymer branch bonded (grafted) in the presence of an appropriate amount of a hydrophilic solvent, This refers to a polymer having the ability to emulsify hydrophobic substances such as agents, softeners, antioxidants, ultraviolet absorbers, crosslinking agents, pigments, etc. in water, that is, a polymer having surface activity, which is represented by the following general formula (1). is there.

（式中、水溶性ポリマー又は水溶性オリゴマーは、カルボン酸基、スルホン酸基、リン酸基、アミン基、水酸基、カルボン酸塩、スルホン酸塩、リン酸塩、アミン塩又はポリアルキレンオキサイドから選択される親水基を有する水溶性ポリマー又は水溶性オリゴマーを表す。）
上記一般式（１）中の水溶性ポリマー又は水溶性オリゴマーとしては、例えば、ポリメタクリル酸、ポリアクリル酸、ポリ（無水）マレイン酸、ポリスチレンスルホン酸、ポリビニルスルホン酸、ポリアルキレンオキサイド等があげられる。

(In the formula, the water-soluble polymer or water-soluble oligomer is selected from carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, hydroxyl group, carboxylate, sulfonate, phosphate, amine salt or polyalkylene oxide. Represents a water-soluble polymer or water-soluble oligomer having a hydrophilic group.)
Examples of the water-soluble polymer or water-soluble oligomer in the general formula (1) include polymethacrylic acid, polyacrylic acid, poly (anhydride) maleic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, and polyalkylene oxide. .

  Examples of the amphiphilic CR block copolymer represented by the general formula (1) include polymethacrylic acid-CR diblock copolymer, polyacrylic acid-CR diblock copolymer, and benzoic acid. Vinyl / styrene copolymer-CR diblock copolymer, maleic anhydride / styrene copolymer-CR diblock copolymer, maleic anhydride / p-methoxystyrene copolymer-CR diblock copolymer, anhydrous Maleic acid / isobutylene copolymer-CR diblock copolymer, maleic anhydride / chloroprene copolymer-CR diblock copolymer, maleic acid / styrene copolymer-CR diblock copolymer, maleic acid / chloroprene Copolymer-CR diblock copolymer, maleic anhydride / 2,3-dichlorobutadiene / chloroprene copolymer-CR diblock copolymer Polymer, Polymethacrylic acid methoxyethylene glycol-CR block copolymer, Polymethacrylic acid polyalkylene glycol-CR block copolymer, Polymethacrylic acid 2- (dimethylamino) ethyl-CR block copolymer, Polystyrenesulfonic acid-CR Examples thereof include a block copolymer, a polyisoprenesulfonic acid (co) polymer-CR block copolymer, a poly 2- (methacryloyloxy) ethyl phosphate (co) polymer-CR block copolymer, and the like. Examples of the amphiphilic CR graft copolymer represented by the general formula (1) include polymethacrylic acid graft CR, polystyrene sulfonic acid graft CR, polystyrene / maleic acid copolymer graft CR, and polymethacrylic acid. And polyalkylene glycol graft CR.

  The content of the hydrophilic polymer block or hydrophilic oligomer block in the amphiphilic CR block copolymer and the amphiphilic CR graft copolymer is not particularly limited, but a tackifier resin, a plasticizer, etc. In order to maintain sufficiently high water resistance (e.g., the block copolymer itself is water-insoluble and basically does not dissolve in pure water), 1 to 50 wt% is preferable. 1 to 40 wt% is more preferable.

  As a method for producing the amphiphilic CR block copolymer, a hydrophilic monomer is polymerized by living polymerization, followed by block copolymerization of chloroprene, an azo compound having a hydrophilic polymer block or a hydrophilic oligomer block (so-called Although there is a method of radical polymerization of chloroprene or the like using a water-soluble macroazo initiator) as a radical initiator, particularly in living polymerization, it is possible to efficiently introduce a hydrophilic polymer block or a hydrophilic oligomer block into CR. The living radical polymerization method should be used. As the living radical polymerization method, for example, a so-called iniferter acting as an initiator / chain transfer agent / termination agent such as a dithiocarbamate ester compound or a xanthate ester compound is used as a polymerization controller, and a carbon-sulfur bond is irradiated under ultraviolet irradiation. Iniferter polymerization method in which a monomer is radically polymerized while repeating cleavage and recombination (for the iniferter polymerization method, Polymer Preprints, Japan (Proceedings of the Society of Polymer Science) Vol. 31, No. 6 (1982), 1289 to 1292 Page, Polymer Preprints, Japan (Proceedings of Polymer Society) Vol. 32, No. 6 (1983), pages 1047 to 1050), dithiocarboxylic acid ester compounds, dithiocarbamic acid ester compounds, The so-called RAFT (reversible addition), in which xanthate ester compounds, organic tellurium compounds, organic selenium compounds, etc. are used as polymerization control agents, and the radicals of monomers and polymers grow into these compounds while repeating reversible addition-cleavage transfer reactions. (Cleavage transfer) polymerization method (for RAFT polymerization, WO 98/01478 (Ezio Rizzardo et al.), WO 98/58974, WO 99/35178 (Charmot Dominique et al.), Polymer Journal, Vol. 64, No. 6, 329, 2007 ( Are described in detail in Shigeru Yamako et al.), TEMPO method using stable nitroxyl radical, iodine transfer polymerization method using iodine compound, radical polymerization of hydrophilic monomer in the presence of diphenylethylenes, and radical polymerization of chloroprene. Ah These can be used to synthesize amphiphilic CR block copolymers.

  As a method for producing an amphiphilic CR graft copolymer, a method of graft polymerizing a hydrophilic monomer to CR using an organic peroxide such as benzoyl peroxide in an organic solvent, and starting with allyl chloride contained in a small amount in CR There is a method of atom transfer polymerization (ATRP) of a hydrophilic monomer as an agent. The ATRP method includes an organic halide as an initiator, a metal complex such as cuprous chloride, cuprous bromide, iron complex, ruthenium complex as a catalyst, and bipyridine, polyamine as a ligand for activating the catalyst. Is a method of living radical polymerization of a radically polymerizable monomer using a nitrogen compound such as 1, if the hydrophilic monomer is ATRP polymerized using 1,2-bond-derived allyl chloride usually contained in CR as an initiator An amphiphilic CR-based graft polymer can be obtained. For the ATRP method, see Chemical Reviews, vol. 101, 2921-2990, 2001 (K. Matyjazewski et al.), Chemical Reviews, vol. 101, 3689-3745, 2001 (M. Sawamoto et al.), And these catalyst systems can also be used in the present invention.

  The main component of the amphiphilic CR block copolymer and amphiphilic CR graft copolymer used in place of the conventional emulsifier is chloroprene, but the characteristics of CR and the action as an emulsifier are not impaired. Thus, a monomer copolymerizable with chloroprene may be copolymerized so long as it does not dissolve in pure water and does not substantially impair properties insoluble in pure water. Examples of monomers copolymerizable with chloroprene include 2,3-dichloro-1,3-butadiene, 2-cyano-1,3-butadiene, 1-chloro-1,3-butadiene, 1,3-butadiene, Isoprene, 2- (N-piperidylmethyl) -1,3-butadiene, 2-triethoxymethyl-1,3-butadiene, 2- (N, N-dimethylamino) -1,3-butadiene, N- (2 -Methylene-3-butenoyl) morpholine, 1,3-butadienes such as diethyl 2-methylene-3-butenylphosphonate, styrene, α-methylstyrene, p-chloromethylstyrene, p-cyanostyrene, p-acetoxystyrene, P-styrenesulfonyl chloride, ethyl p-styrenesulfonyl, p-butoxystyrene, 4-vinylbenzoic acid, 3-isopropenyl Styrenes such as -α, α'-dimethylbenzyl isocyanate, styrene sulfonic acid, methyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate, i-butyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, Boronyl methacrylate, benzyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, methoxyethylene glycol methacrylate, ethyl carbitol methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid 4-hydroxybutyl, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, 3- (dimethylamino) propyl methacrylate, methacrylate 2- (isocyanato) ethyl phosphate, 2,4,6-tribromophenyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, methacrylic acid Methacrylic acid esters such as 2,2,3,3,3-pentafluoropropyl, 2,2,3,4,4,4-hexafluorobutyl methacrylate, butyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethylhexyl, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, cyclohexyl acrylate, bornyl acrylate, benzyl acrylate, phenyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 2,2,3 acrylate , 3-tetrafluoropropyl, 2,2,2-trifluoroethyl acrylate, acrylic acid 2 2,3,3,3-pentafluoropropyl, acrylic acid esters such as 2,2,3,4,4,4-hexafluorobutyl, etc., acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, α-cyanoethyl acrylate, maleic anhydride, maleic acid, citraconic anhydride, vinyl acetic acid, maleic acid ester, fumaric acid ester, crotonic acid, itaconic acid, fumaric acid, mono 2- (methacryloyloxy) ethyl phthalate, mono 2- ( Methacryloyloxy) ethyl succinate, mono 2- (acryloyloxy) ethyl succinate, methacryloxypropyltrimethoxysilane, methacryloxypropyldimethoxysilane, methacrylic acid, acrylic acid, acrolein, diacetone acrylamide, vinyl Tyl ketone, vinyl ethyl ketone, diacetone methacrylate, vinyl sulfonic acid, isoprene sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-acrylamido-1-methylsulfonic acid, 2-methacrylamide-2- Examples thereof include methylpropane sulfonic acid and dehydroalanine. Among these, in terms of relatively high radical copolymerization with chloroprene, 2,3-dichloro-1,3-butadiene, 2-cyano-1,3-butadiene, 1-chloro-1,3-butadiene, styrene, Methyl methacrylate, methacrylic acid, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, α-cyanoethyl acrylate, maleic anhydride, and maleic acid are preferred. 2,3-dichloro-1,3-butadiene, which has the highest copolymerizability with chloroprene, is more preferred.

  The emulsion of the hydrophobic substance such as the tackifier resin and the plasticizer of the present invention, when emulsifying and dispersing these hydrophobic substances, amphiphilic CR block copolymer or amphiphilic CR graft copolymer, and appropriate It is characterized in that it is produced using an amount of a hydrophilic solvent.

  As the method, an amphiphilic CR block copolymer, or an amphiphilic CR graft copolymer, a hydrophobic substance such as a tackifier resin or a plasticizer, and a conventional emulsifier that is soluble in an organic solvent as necessary. Is dissolved in a hydrophilic solvent (or an organic solvent containing at least a hydrophilic solvent). At this time, if the hydrophilic group is an acidic group, a basic compound is added to neutralize in advance. The basic compound is not particularly limited as long as it is soluble in the solution. For example, triethylamine, diethylamine, triethanolamine, diethanolamine, ethanolamine, propanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, morpholine, N-methylmorpholine, piperazine, 2-amino-2-methyl-1-propanol, 2-dimethylamino-2-methyl-1-propanol, N-methyldiethanolamine, N-ethyldiethanolamine, Examples include amines such as monoisopanolamine. Under stirring, water or water containing a conventional emulsifier is gradually added and phase-inverted emulsified to obtain an amphiphilic CR block copolymer or an amphiphilic CR graft copolymer. Emulsions of hydrophobic substances such as tackifying resins and plasticizers that have been stabilized are produced. Thereafter, the organic solvent is distilled off under reduced pressure to obtain an emulsion of a hydrophobic substance such as a tackifier resin or a plasticizer of the present invention.

  As another method, an amphiphilic CR block copolymer, or an amphiphilic CR graft copolymer and a tackifier resin, a hydrophobic material such as a plasticizer, and if necessary, soluble in an organic solvent. A conventional emulsifier is dissolved in a hydrophilic solvent (or an organic solvent containing at least a hydrophilic solvent). Under stirring, water containing a basic compound or water containing a basic compound and a conventional emulsifier is gradually added, and phase-inversion emulsification results in an amphiphilic CR block copolymer, Alternatively, an emulsion of a hydrophobic substance such as a tackifier resin or a plasticizer that is emulsion-stabilized with an amphiphilic CR graft copolymer is formed. Thereafter, the organic solvent is distilled off under reduced pressure to obtain an emulsion of a hydrophobic substance such as a tackifier resin and a plasticizer of the present invention. The basic compound used here is an inorganic base such as ammonia soluble in water, tetramethylammonium hydroxide, tetraethylammonium hydroxide, sodium hydroxide or potassium hydroxide in addition to the above amines. As the hydrophilic solvent, tetrahydrofuran, dioxane, methyl ethyl ketone, methyl isobutyl ketone, acetone, isopropanol, ethanol, methoxyethanol, dimethoxyethane, butyl cellosolve, ethyl cellosolve, butanol, methanol, etc. can be used, and these can be used alone or in combination of two or more. You may do it. Moreover, what contains a hydrophilic solvent in organic solvents, such as ethyl acetate, butyl acetate, isopropyl acetate, and toluene, may be used.

  Here, the amount of the amphiphilic CR block copolymer or the amphiphilic CR graft copolymer used is not particularly limited as long as it can stably emulsify hydrophobic substances such as tackifier resins and plasticizers. In order to sufficiently bring out the effects of a resin, a plasticizer, etc., the amount is preferably 30 parts by weight or less with respect to a hydrophobic substance such as a tackifier resin or a plasticizer, and more preferably 20 parts by weight or less in consideration of cost.

  Next, a method for producing a hydrophilic group-containing CR random copolymer, and an emulsion of a hydrophobic substance such as a tackifier resin and a plasticizer using these will be described.

  The hydrophilic group-containing CR random copolymer is a hydrophilic group selected from carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, sulfuric acid group, carboxylic acid group or polyalkylene oxide in the main chain of the chloroprene polymer. It is a polymer having a structure in which groups are randomly distributed, and serves as a substitute for an emulsifier and has the ability to emulsify and stabilize hydrophobic substances such as tackifier resins and plasticizers in the presence of a hydrophilic solvent.

  Examples of the hydrophilic group-containing CR random copolymer include chloroprene / maleic anhydride copolymer, chloroprene / maleic acid copolymer, chloroprene / citraconic anhydride copolymer, chloroprene / methacrylic acid copolymer, chloroprene / vinyl. Acetic acid copolymer, chloroprene / isoprene sulfonic acid copolymer, chloroprene / p-acetoxystyrene random copolymer, chloroprene / vinyl benzoic acid copolymer, chloroprene / 2,3-dichloro-1,3-butadiene / maleic anhydride Acid copolymer, chloroprene / p-styrene sulfonic acid ethyl ester random copolymer, chloroprene / styrene sulfonic acid random copolymer, chloroprene / vinyl sulfonic acid random copolymer, chloroprene / 2-acrylamido-2-methylpropane sulfone Acid random copolymer, chloroprene / 2-acrylamido-1-methylsulfonic acid random copolymer, chloroprene / 2-methacrylamide-2-methylpropanesulfonic acid random copolymer, chloroprene / 2- (N-piperidylmethyl) -1,3-butadiene random copolymer, chloroprene / 2- (N, N-dimethylamino) -1,3-butadiene random copolymer, chloroprene / N- (2-methylene-3-butenoyl) morpholine random copolymer Polymer, chloroprene / dehydroalanine random copolymer, chloroprene / methacrylic acid 2- (dimethylamino) ethyl random copolymer, chloroprene / methacrylic acid methoxyethylene glycol random copolymer, chloroprene / 2- (methacryloyloxy) ethylphos Faye Copolymers, chloroprene / methacrylic acid polyethylene oxide random copolymer.

  The hydrophilic group of the hydrophilic group-containing CR random copolymer is not particularly limited as long as it is a water-soluble group. For example, an acidic functional group (sulfonic acid group, carboxylic acid group, phosphoric acid group, amine group) Carboxylate, sulfonate, phosphate, amine salt), hydroxyl group, polyalkylene oxide and the like. Of these, acidic functional groups and polyalkylene oxide groups are more preferable in that the hydrophobic substance can be emulsified in a smaller amount. The content of the hydrophilic group in the hydrophilic group-containing CR random copolymer is not particularly limited, but is preferably 1 to 40 wt% in order to obtain sufficient emulsifying power and maintain water resistance. -20 wt% is more preferable.

  The main component of the hydrophilic group-containing CR random copolymer used in place of the conventional emulsifier is chloroprene, but it is copolymerized with a monomer that can be copolymerized with chloroprene within a range that does not impair CR characteristics and water insolubility. You may do it. The monomer copolymerizable with chloroprene is the same as that described in the amphiphilic CR block copolymer and the amphiphilic CR graft copolymer.

  Examples of the hydrophilic group-containing radical polymerizable monomer used in the production of the hydrophilic group-containing CR random copolymer include styrene sulfonic acid, 4- (methacryloyloxy) butyl sulfonic acid, and methallyl sulfonic acid. Vinyl sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-acrylamido-1-methyl sulfonic acid, 2-methacrylamido-2-methylpropane sulfonic acid, and salts thereof. Examples of phosphoric acid group-containing monomers include 2- (methacryloyloxy) ethyl phosphate and salts thereof, and examples of carboxyl group-containing monomers include methacrylic acid, acrylic acid, vinyl benzoic acid, vinyl acetic acid, maleic anhydride, maleic acid. Acid, maleate, fumar Ester, crotonic acid, itaconic acid, fumaric acid, citraconic anhydride, mono 2- (methacryloyloxy) ethyl phthalate, mono 2- (methacryloyloxy) ethyl succinate, mono 2- (acryloyloxy) ethyl succinate, salts thereof Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and the like. Examples of the polyalkylene oxide-containing monomer include polyethylene glycol methacrylate and polyethylene glycol acrylate, and examples of the amino group-containing monomer include dimethyl Minoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, dehydroalanine, 2- (N-piperidylmethyl) -1,3-butadiene, 2- (N, N-dimethylamino) -1,3- Examples thereof include butadiene, N- (2-methylene-3-butenoyl) morpholine, N-butyl-N-methyl-2-methylene-3-butenamide, and the quaternary ammonium salt-containing monomer includes [(2-methacryloyloxy ) Ethyl] trimethylammonium chloride, [(2-acryloyloxy) ethyl] trimethylammonium chloride, and the like. Among these, maleic acid, maleic anhydride, maleic acid ester, citraconic anhydride, fumaric acid, fumaric acid ester, methacrylic acid, acrylic acid, relatively high solubility in organic solvents and copolymerization with chloroprene, Styrene sulfonic acid, vinyl benzoic acid, vinyl acetic acid, polyethylene glycol methacrylate, polyethylene glycol acrylate, dehydroalanine, 2- (N-piperidylmethyl) -1,3-butadiene, 2- (N, N-dimethylamino) -1, A monomer selected from 3-butadiene, N- (2-methylene-3-butenoyl) morpholine, N-butyl-N-methyl-2-methylene-3-butenamide and the like is preferable. In addition, as a method for producing the hydrophilic group-containing CR random copolymer, chloroprene and a monomer containing a functional group that can be converted into a hydrophilic group are radically copolymerized and then converted into a hydrophilic group by a reaction such as hydrolysis. For example, examples of the monomer having a functional group that can be converted into sulfonic acid include p-styrenesulfonic acid alkyl ester, p-chlorosulfonylstyrene, and the like, which have a functional group that can be converted into a carboxyl group. As monomers, t-butyl methacrylate, t-butyl acrylate, benzyl methacrylate, benzyl acrylate, dehydroalanine, 2- (N-piperidylmethyl) -1,3-butadiene, 2- (N, N-dimethylamino) -1 , 3-butadiene, N- (2-methylene-3-butenoyl) morpholine, - butyl -N- methyl-2-methylene-3-butenamide, etc. Examples of the monomer having a transformable functional group to a hydroxyl group, glycidyl methacrylate, glycidyl acrylate, and the like.

  When the emulsion of the present invention is used for adhesives, primers, and sealants that require water resistance to moisture from the outside, among the above-mentioned hydrophilic groups, sulfonic acid that can exhibit latex stability with a smaller hydrophilic group content It is preferable to use an acidic group such as a group, a phosphoric acid group, or a carboxylic acid group, or a functional group that can be converted into these acidic groups. Further, in consideration of the solubility of the hydrophilic group-containing monomer, radical initiator and chain transfer agent in the polymerization solvent, it is preferable to use a carboxyl group-containing monomer or a polyalkylene oxide-containing monomer. Maleic acid, citraconic anhydride, maleic acid, maleic acid monoester, vinyl acetic acid, methacrylic acid and acrylic acid are particularly preferred.

  As a method for producing a hydrophilic group-containing CR random copolymer, radical copolymerization of chloroprene or the like with a monomer containing a hydrophilic group or a monomer containing a functional group that can be converted into a hydrophilic group, a reactive emulsifier and chloroprene as a radical There is a method of copolymerization, but as a method that can easily control the amount of hydrophilic group introduced into the CR skeleton, a monomer containing chloroprene and the like and a hydrophilic group or a monomer containing a functional group that can be converted into a hydrophilic group is used as a radical. A method of copolymerization is preferred. The radical copolymerization method here is a conventional traditional radical polymerization method, which is converted into a monomer or hydrophilic group containing chloroprene and a hydrophilic group in the presence of a radical initiator and a molecular weight regulator in the absence of a solvent or solvent. This is a radical copolymerization of monomers containing possible functional groups. As radical initiators, benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, paramentane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, succinic peroxide, hydrogen peroxide, potassium persulfate, Peroxide compounds such as ammonium persulfate, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methyl Ethyl) azo] formamide, dimethyl 2,2′-azobis (2- Tilpropionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis {2-methyl-N -[1,1′-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2 ′ -Azobis {2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl) propane ]} Dihydrochloride, 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2′-azobis (2-methylpropyl) Pion'amijin) dihydrochloride, 2,2'-azobis [N-(2-carboxyethyl) -2-methylpropionamidine] can be used tetrahydrate azo compounds such like. Examples of the molecular weight regulator include diisopropyl xanthogen disulfide, diethyl xanthogen disulfide, diethyl thiuram disulfide, 2,2′-dithiodipropionic acid, 3,3′-dithiodipropionic acid, 4,4′-dithiodibutanoic acid, 2,2 Disulfides such as' -dithiobisbenzoic acid, n-dodecyl mercaptan, octyl mercaptan, t-butyl mercaptan, thioglycolic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, 3-mercaptobenzoic acid 4-mercaptobenzoic acid, thiomalonic acid, dithiosuccinic acid, thiomaleic acid, thiomaleic anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homocysteine, 5-mercaptotetrazole acetic acid, 3-mer Mercaptans such as pto-1-propanesulfonic acid, halogenated hydrocarbons such as iodoform, diphenylethylene, p-chlorodiphenylethylene, p-cyanodiphenylethylene, α-methylstyrene dimer, benzyldithiobenzoate, 2-cyanoprop-2 -Ildithiobenzoate, organic tellurium compound, sulfur, etc. can be used, but in terms of more excellent latex stability, carboxyl groups-containing mercaptans such as disulfides such as xanthogen disulfide, thioglycolic acid, thiomalic acid, and thiosalicylic acid, polyethylene Glycol thiol is particularly preferred.

  A method for producing an emulsion of a hydrophobic substance such as a tackifier resin and a plasticizer using the hydrophilic group-containing CR random copolymer includes the amphiphilic CR block copolymer and the amphiphilic CR graft copolymer. It is the same as the case where it uses.

  Next, terminal hydrophilic group-containing chloroprene polymer, terminal hydrophilic group-containing acrylate ester polymer, terminal hydrophilic group-containing methacrylic ester polymer, and emulsions of hydrophobic substances such as tackifier resins and plasticizers using these polymers A manufacturing method will be described.

  A terminal hydrophilic group-containing chloroprene polymer, a terminal hydrophilic group-containing acrylate polymer, or a terminal hydrophilic group-containing methacrylic ester polymer is based on a conjugated diene polymer, an acrylate polymer, or a methacrylate polymer. At the end of the polymer skeleton, such as carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, sulfuric acid group, carboxylate, sulfonate, phosphate, amine salt, sulfate or polyalkylene glycol It is a polymer having the ability to emulsify and stabilize hydrophobic substances such as tackifier resins and plasticizers in the presence of hydrophilic solvents in the presence of hydrophilic solvents, by introducing a hydrophilic group of It is represented by the following general formula (2).

（式中、Ｐはクロロプレン系ポリマー、アクリル酸エステル系ポリマー、又はメタクリル酸エステル系ポリマーを表し、Ｘはカルボン酸基、スルホン酸基、リン酸基、アミン基、硫酸基、カルボン酸塩、スルホン酸塩、リン酸塩、アミン塩、硫酸塩又はポリアルキレンオキサイドを表し、Ｒはアルキル基、アリール基、置換アルキル基又は置換アリール基を表し、ｎは１〜３の整数を表す。）
末端親水基含有クロロプレン系ポリマーは、２−クロロ−１，３−ブタジエンモノマー単位を必須成分とするポリマーである。

(In the formula, P represents a chloroprene polymer, an acrylate polymer, or a methacrylate polymer, and X represents a carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, sulfuric acid group, carboxylate salt, sulfone. Represents an acid salt, a phosphate, an amine salt, a sulfate or a polyalkylene oxide, R represents an alkyl group, an aryl group, a substituted alkyl group or a substituted aryl group, and n represents an integer of 1 to 3.)
The terminal hydrophilic group-containing chloroprene polymer is a polymer having a 2-chloro-1,3-butadiene monomer unit as an essential component.

  The terminal hydrophilic group-containing chloroprene polymer is, for example, a hydrophilic group-containing thiol compound represented by the following general formula (3), a hydrophilic group-containing disulfide compound represented by the following general formula (4), or the following general formula (3 In the presence of the hydrophilic group-containing thiol compound represented by formula (4) and the hydrophilic group-containing disulfide compound represented by the following general formula (4), 2-chloro-1,3-butadiene and a monomer copolymerizable therewith are radicals. Although it is a polymer obtained by polymerization, the hydrophilic group is preferably a carboxylic acid group or a polyalkylene glycol group in terms of solubility in a polymerization solvent, and more preferably a carboxylic acid group in terms of availability. .

（式中、Ｘはカルボン酸基、スルホン酸基、リン酸基、アミン基、硫酸基、カルボン酸塩、スルホン酸塩、リン酸塩、アミン塩、硫酸塩又はポリアルキレンオキサイドを表し、Ｒ’はアルキル基、アリール基、置換アルキル基又は置換アリール基を表し、ｎは１〜３の整数を表す。）

(Wherein X represents a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an amine group, a sulfuric acid group, a carboxylate salt, a sulfonate salt, a phosphate salt, an amine salt, a sulfate salt or a polyalkylene oxide; Represents an alkyl group, an aryl group, a substituted alkyl group or a substituted aryl group, and n represents an integer of 1 to 3.)

（式中、Ｘはカルボン酸基、スルホン酸基、リン酸基、アミン基、硫酸基、カルボン酸塩、スルホン酸塩、リン酸塩、アミン塩、硫酸塩又はポリアルキレンオキサイドを表し、Ｒ’はアルキル基、アリール基、置換アルキル基又は置換アリール基を表し、ｎは０〜３の整数を表す。）
上記親水基含有チオール化合物としては、例えば、チオグリコール酸、チオリンゴ酸、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、チオサリチル酸、３−メルカプト安息香酸、４−メルカプト安息香酸、チオマロン酸、ジチオコハク酸、チオマレイン酸、チオマレイン酸無水物、ジチオマレイン酸、チオグルタール酸、システイン、ホモシステイン、５−メルカプトテトラゾール酢酸、３−メルカプト−１−プロパンスルホン酸、ポリエチレンオキサイドチオール等があげられ、親水基含有ジスルフィド化合物としては、例えば、２，２’−ジチオジプロピオン酸、３，３’−ジチオジプロピオン酸、４，４’−ジチオジブタン酸、２，２’−ジチオビス安息香酸、６，６’−ジチオジニコチン酸等があげられる。

(Wherein X represents a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an amine group, a sulfuric acid group, a carboxylate salt, a sulfonate salt, a phosphate salt, an amine salt, a sulfate salt or a polyalkylene oxide; Represents an alkyl group, an aryl group, a substituted alkyl group or a substituted aryl group, and n represents an integer of 0 to 3.)
Examples of the hydrophilic group-containing thiol compound include thioglycolic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, 3-mercaptobenzoic acid, 4-mercaptobenzoic acid, thiomalonic acid, and dithiosuccinic acid. Thiomaleic acid, thiomaleic anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homocysteine, 5-mercaptotetrazole acetic acid, 3-mercapto-1-propanesulfonic acid, polyethylene oxide thiol, etc., and hydrophilic group-containing disulfide compounds For example, 2,2′-dithiodipropionic acid, 3,3′-dithiodipropionic acid, 4,4′-dithiodibutanoic acid, 2,2′-dithiobisbenzoic acid, 6,6′-dithiodinicotine Examples include acids.

  In addition to the above, the terminal hydrophilic group chloroprene polymer includes potassium persulfate, ammonium persulfate, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-methyl-N- (1, 1-bis (hydroxymethyl) -2-hydroxyethyl) propionamide), 2,2′-azobis (2- (2-imidazolin-2-yl) propane) dihydrochloride, 2,2′-azobis (2-amidino) 2-chloro-1,3-butadiene is radically polymerized using a large amount of a hydrophilic group-containing radical initiator such as propane) dihydrochloride and macroazo initiator (manufactured by Wako Pure Chemical Industries, Ltd., VPE-0201). A method of introducing a hydrophilic group into a polymer terminal, or after anionic polymerization of 2-chloro-1,3-butadiene, anionic growth terminal is treated with maleic acid After capped with ester, it can be produced also terminal ester groups by methods such as hydrolyzed.

  The main component of the terminal hydrophilic group-containing chloroprene polymer used in place of the conventional emulsifier is a 2-chloro-1,3-butadiene monomer unit, but the properties of the chloroprene polymer and the action as an emulsifier are not impaired. A monomer copolymerizable with 2-chloro-1,3-butadiene may be copolymerized as long as it does not dissolve in pure water and does not impair properties substantially insoluble in pure water, such as an emulsifier. The monomer copolymerizable with 2-chloro-1,3-butadiene is the same as that described in the amphiphilic CR block copolymer and the amphiphilic CR graft copolymer.

  One to three hydrophilic groups in the terminal hydrophilic group-containing chloroprene polymer are present at the polymer terminal depending on the type of thiol compound, disulfide compound, radical initiator, or coupling agent used.

  The terminal hydrophilic group-containing chloroprene polymer can be produced by a conventional traditional radical polymerization method. For example, radical polymerization of chloroprene or the like in the presence of a radical initiator such as a peroxide or an azo compound, or a molecular weight regulator (chain transfer agent) such as a thiol compound or a disulfide compound in an appropriate solvent or without a solvent. It is. At this time, if a hydrophilic group-containing thiol compound or a hydrophilic group-containing disulfide compound is used, a terminal hydrophilic group-containing chloroprene polymer is produced by a chain transfer reaction of chloroprene radicals thereto. A method of synthesizing a terminal functional polymer (including a hydrophilic group such as an acidic group) using a chain transfer reaction to the above compound is a method in which a growth radical or an initiator radical is a functional group-containing thiol compound or a functional group-containing disulfide. The polymerization of the monomer is restarted by the functional group-containing sulfur radical generated by chain transfer to the compound, whereby the functional group derived from the thiol compound is introduced into the polymer terminal. This method is described in Advanced Polymer Materials Series 1 High Performance Liquid Polymer Material (Maruzen Co., Ltd., 1990, pages 13 and 32).

  Examples of the radical initiator include benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, paramentane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, cyclohexane peroxide, succinic acid peroxide, persulfate Peroxide compounds such as potassium, ammonium persulfate, hydrogen peroxide, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1 -Cyano-1-methylethyl) azo] forma Dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis {2-methyl-N- [1,1′-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2- (2-imidazoline-2- Yl) propane] dihydrochloride, 2,2′-azobis {2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis {2- [1- (2-hydroxy Ethyl) -2-imidazolin-2-yl) propane]} dihydrochloride, 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochlora 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, macroazo initiator (sum An azo compound such as VPE-0201 manufactured by Kojunkaku Kogyo Co., Ltd. can be used.

  Examples of the solvent for synthesizing the terminal hydrophilic group-containing chloroprene polymer include ethers such as tetrahydrofuran, dioxane and dimethoxyethane, aromatics such as toluene, benzene and chlorobenzene, dichloromethane, 1,1,2-trichloroethane, and the like. , Halogenated hydrocarbons such as dichloroethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl Alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, 3-methoxy-3-methylbutanol, 3-methoxybutanol, Alcohols such as acetone alcohol, methoxybutanol, methoxyethanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone, acetone, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate , Esters such as isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, dimethyl carbonate, ethyl acetoacetate, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, etc. It can be selected according to the solubility of the disulfide compound. If these compounds are dissolved in chloroprene and monomers copolymerized therewith, it may be solventless.

  The above-mentioned amphiphilic CR block copolymer and amphiphilic CR graft copolymer are used for the production method of emulsions of hydrophobic substances such as tackifier resins and plasticizers using the above-mentioned terminal hydrophilic group-containing chloroprene polymer. It is the same as if there was.

  The terminal hydrophilic group-containing acrylate polymer is a group of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, bornyl acrylate It is a polymer having at least one monomer unit selected from as an essential component, and is produced by the same method as the above-mentioned terminal hydrophilic group-containing chloroprene polymer. The terminal hydrophilic group-containing acrylate ester polymer does not impair the properties of the acrylate ester polymer and the action as an emulsifier, does not dissolve in pure water like conventional emulsifiers, and is substantially insoluble in pure water. Monomers that can be copolymerized with these acrylic acid ester monomers may be copolymerized within a range that does not impair the properties, and are appropriately adjusted according to the type of hydrophobic substance such as tackifier resin and plasticizer to be emulsified, and applications. Just do it. Examples of the monomer copolymerizable with the acrylate ester include 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 2,3-dichloro-1,3. -Butadiene, 2-cyano-1,3-butadiene, 1-chloro-1,3-butadiene, 2- (N-piperidylmethyl) -1,3-butadiene, 2-triethoxymethyl-1,3-butadiene, 1,3-butadienes such as 2- (N, N-dimethylamino) -1,3-butadiene, N- (2-methylene-3-butenoyl) morpholine, diethyl 2-methylene-3-butenylphosphonate, styrene, α-methylstyrene, p-chloromethylstyrene, p-cyanostyrene, p-acetoxystyrene, p-styrenesulfonyl chloride, ethyl p-styrenesulfone , P-butoxystyrene, 4-vinylbenzoic acid, 3-isopropenyl-α, α′-dimethylbenzyl isocyanate, styrenes such as styrene sulfonic acid, methyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate , I-butyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, bornyl methacrylate, benzyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, methoxyethylene methacrylate Glycol, ethyl carbitol methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2- (dimethylamino) ethyl methacrylate, 2- (diethylacetate) E) ethyl, 3- (dimethylamino) propyl methacrylate, 2- (isocyanato) ethyl methacrylate, 2,4,6-tribromophenyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, Methacrylic acid esters such as 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate and 2,2,3,4,4,4-hexafluorobutyl methacrylate , 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,2-triacrylate Fluoroethyl, acrylic acid 2,2,3,3,3-pentafluoropropyl, acrylic acid 2,2,3,4,4,4-hexafluorolob Acrylic esters such as chill, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, α-cyanoethyl acrylate, maleic anhydride, maleic acid, citraconic anhydride, vinyl acetic acid, maleic ester, fumaric ester, crotonic acid , Itaconic acid, fumaric acid, mono 2- (methacryloyloxy) ethyl phthalate, mono 2- (methacryloyloxy) ethyl succinate, mono 2- (acryloyloxy) ethyl succinate, methacryloxypropyltrimethoxysilane, methacryloxypropyldimethoxy Silane, methacrylic acid, acrylic acid, acrolein, diacetone acrylamide, vinyl methyl ketone, vinyl ethyl ketone, diacetone methacrylate, vinyl sulfonic acid, isoprene Sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-1-methyl sulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, dehydroalanine, and the like.

  The method for producing an emulsion of a hydrophobic substance such as a tackifier resin and a plasticizer using the terminal hydrophilic group-containing acrylate ester polymer is the above-mentioned amphiphilic CR block copolymer, amphiphilic CR graft copolymer. It is the same as the case where is used.

  The terminal hydrophilic group-containing methacrylate polymer is at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and bornyl methacrylate. This monomer unit is an essential component and is produced by the same method as the terminal hydrophilic group-containing acrylate ester polymer. The terminal hydrophilic group-containing methacrylic acid ester polymer does not impair the properties of the methacrylic acid ester polymer and the action as an emulsifier, does not dissolve in pure water like a conventional emulsifier, and is substantially insoluble in pure water. Monomers that can be copolymerized with these methacrylic acid ester monomers may be copolymerized within a range that does not impair the properties, and are adjusted as appropriate according to the type of hydrophobic substance such as tackifier resin and plasticizer to be emulsified, and applications. Just do it. Monomers that can be copolymerized with the acrylic ester include 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 2,3-dichloro-1,3-butadiene. 2-cyano-1,3-butadiene, 1-chloro-1,3-butadiene, 2- (N-piperidylmethyl) -1,3-butadiene, 2-triethoxymethyl-1,3-butadiene, 2- 1,3-butadienes such as (N, N-dimethylamino) -1,3-butadiene, N- (2-methylene-3-butenoyl) morpholine, diethyl 2-methylene-3-butenylphosphonate, styrene, α- Methylstyrene, p-chloromethylstyrene, p-cyanostyrene, p-acetoxystyrene, p-styrenesulfonyl chloride, ethyl p-styrenesulfonyl, p Butoxystyrene, 4-vinylbenzoic acid, 3-isopropenyl-α, α'-dimethylbenzyl isocyanate, styrenes such as styrenesulfonic acid, methyl acrylate, t-butyl acrylate, sec-butyl acrylate, acrylic acid i-butyl, i-propyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, bornyl acrylate, benzyl acrylate, phenyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, acrylic Methoxyethylene glycol acid, ethyl carbitol acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate 3- (dimethylamino) propyl acrylate, 2- (isocyanato) ethyl acrylate, 2,4,6-tribromophenyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2, acrylate 2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2-ethoxyethyl acrylate, acrylic 2-butoxyethyl acid, 3- (trimethoxysilyl) propyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3 acrylate , 3,3-pentafluoropropyl, acrylic acid esters such as 2,2,3,4,4,4-hexafluorobutyl, acrylamide, Tacrylamide, acrylonitrile, methacrylonitrile, α-cyanoethyl acrylate, maleic anhydride, maleic acid, citraconic anhydride, vinyl acetic acid, maleic acid ester, fumaric acid ester, crotonic acid, itaconic acid, fumaric acid, mono 2- (methacryloyloxy) ) Ethyl phthalate, mono 2- (methacryloyloxy) ethyl succinate, mono 2- (acryloyloxy) ethyl succinate, methacryloxypropyltrimethoxysilane, methacryloxypropyldimethoxysilane, methacrylic acid, acrylic acid, acrolein, diacetone acrylamide , Vinyl methyl ketone, vinyl ethyl ketone, diacetone methacrylate, vinyl sulfonic acid, isoprene sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methyl Propanesulfonic acid, 2-acrylamido-1-methyl sulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, dehydroalanine, and the like.

  A method for producing an emulsion of a hydrophobic substance such as a tackifier resin and a plasticizer using the terminal hydrophilic group-containing methacrylic acid ester polymer includes the amphiphilic CR block copolymer and the amphiphilic CR graft copolymer. It is the same as the case where is used.

  The emulsion of the present invention includes CR emulsion adhesive, SBR emulsion adhesive, ACM emulsion adhesive, ACM emulsion paint, EVA emulsion adhesive, polyolefin resin emulsion coating agent, polyolefin resin emulsion primer, epoxy resin emulsion adhesive, etc. Can be added for the purpose of imparting tackiness, flexibility, film-forming property, polyolefin adhesiveness, anti-aging, anti-coloring, colorability, curability and the like. Further, it can be used alone as a raw material for toner, electrode binder or water-based ink. At this time, the emulsion of the present invention, acid acceptor such as zinc oxide, hydrotalcite, epoxy resin, pH adjuster such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, phosphoric acid, carboxylate, PH buffering agents such as phosphates, carbonates, ammonium salts, wetting agents, antifoaming agents, antifreezing agents, hydrophobized cellulose, polyacrylic acid copolymers, polymethacrylic acid copolymers, associative nonionic surfactants , Thickeners such as polyalkylene oxide, polyvinyl alcohol, and clay may be blended.

  The emulsion of the present invention is significantly improved in water resistance and the effect of blending with emulsions such as CR, SBR, ACM and the like with respect to conventional emulsions.

  In order to describe the present invention more specifically, examples are shown below, but the present invention is not limited to these examples.

  The number average molecular weight Mn, the weight average molecular weight Mw, and the molecular weight distribution Mw / Mn of the hydrophilic group-containing polymer of the present invention were measured under the following conditions using GPC8220 manufactured by Tosoh Corporation (eluent = tetrahydrofuran, flow rate = 1. 0 ml / min, column temperature = 40 ° C., peak detection = differential refractometer, packed column = TSK-gel (registered trademark) G7000Hxl / GMHxl / GMHxl / G3000Hxl / guard column HL, molecular weight calculation = polystyrene conversion). The number average molecular weight Mn, weight average molecular weight Mw and molecular weight distribution Mw / Mn of the CR latex polymer were measured under the following conditions using GPC8220 manufactured by Tosoh Corporation (eluent = tetrahydrofuran, flow rate = 1.0 ml / min, column temperature). = 40 ° C, peak detection = differential refractometer, packed column = TSK-gel (registered trademark) G7000Hxl / GMHxl / GMHxl / guard column HL, molecular weight calculation = polystyrene conversion).

  The monomer conversion during polymerization was calculated using Shimadzu Gas Chromatograph GC-17A (GL Sciences capillary column NEUTRABOND-5, flame ionization detector) using benzene as a standard substance.

  The particle sizes of the CR latex and emulsion were measured using a laser diffraction / scattering particle size distribution meter Microtrac UPA (manufactured by Nikkiso Co., Ltd.).

  The mechanical stability of the CR latex was evaluated from the rubber precipitation rate by the Marlon test method.

  The amount of carboxyl groups in the water-insoluble polymer containing hydrophilic groups was measured by neutralization titration with potassium hydroxide.

  The amount of chlorine in the water-insoluble polymer containing a hydrophilic group and the latex polymer was measured by the oxygen flask combustion-ion chromatography method under the following conditions. After precisely weighing 20 mg of the polymer sample, it was burned by a flask combustion method and absorbed in an absorbing solution consisting of 10 ml of an N / 100 sodium hydroxide aqueous solution to which 100 μl of 30% hydrogen peroxide solution was added. The absorption solution was made up to 50 ml with pure water, and chloride ions in the absorption solution were quantified by ion chromatography. The measurement conditions of ion chromatography are ion chromatograph manufactured by Tosoh Corporation, column = TSKgel (registered trademark) IC-Anion-PWXL PEEK, eluent = 1.3 mM potassium gluconate, 1.3 mM borax, 30 mM boric acid. 10 volume% acetonitrile, 0.5 volume% glycerol aqueous solution, column temperature = 40 ° C., flow rate = 1.2 ml / min, detector = electric conductivity detector.

  The performance evaluation of the emulsion as an adhesive compounding agent was performed by the following method. CR latex synthesized in the following Synthesis Example 7 on two No. 10 cotton canvases (based on 100 parts by weight of CR latex, 40 parts by weight of emulsion, zinc oxide emulsion manufactured by Osaki Kogyo, 1 part by weight of AZ-SW, Shin Chemical) After applying an industrial wetting agent, 1 part by weight of Orphine EXP.4036), apply with a brush and dry in an oven at 70 ° C. for 3 minutes (repeating the above application-drying operations twice), then brush again After applying, taking an open time (leaving for a fixed time) at room temperature, it was crimped with a hand roller. Immediately after the pressure bonding, the film was cut into a width of 25 mm, and a 180 ° T-type peel test was performed using a Tensilon-type tensile tester under the condition of a tensile speed of 100 mm / min. Further, after the test piece was cured at room temperature for 5 days, a peel test was similarly conducted. Adhesiveness was evaluated from changes in peel strength and peel state due to open time. That is, when the adhesiveness is sufficient, the decrease in peel strength is small even when a long open time is taken, but when it is insufficient, the peeling (so-called glue separation) at the adhesive interface becomes remarkable and the peel strength decreases. Increase. The water resistance was evaluated by performing a 180 ° T-type peel test in the same manner as described above in the wet state after immersing the test piece after curing for 5 days in tap water at room temperature for 3 days.

Synthesis Example 1 (Synthesis of hydrophilic group-containing polymer (amphiphilic CR block copolymer))
In a 1000 ml Pyrex (registered trademark) glass flask equipped with a nitrogen gas introduction tube and a reflux condenser, xanthate ester represented by the following general formula (5) 7.50 g (35.0 mmol), represented by the following general formula (6) After adding 4.25 g (17.5 mmol) of xanthate disulfide, 25.00 g (290.7 mmol) of methacrylic acid, and 50.00 g of methyl ethyl ketone, the mixture was sufficiently degassed by repeating freeze-degas-thaw three times. While stirring in a nitrogen atmosphere, polymerization was carried out for 12 hours while irradiating with ultraviolet rays (UM452 (450 W) manufactured by Ushio Electric Co., Ltd.) from a distance of 80 mm in a thermostat at 30 ° C. At this time, the polymerization conversion rate of methacrylic acid was 80%. Subsequently, 125.00 g (1.41 mol) of simple distilled chloroprene and 300 ml of methyl ethyl ketone were added, and ultraviolet irradiation was performed at 30 ° C. for 14 hours with sufficient stirring in a nitrogen atmosphere. The chloroprene conversion was 51% and the total conversion of methacrylic acid was 86%. The polymer was isolated by pouring the contents into 3000 ml of methanol and dried. The number average molecular weight Mn of the polymer measured by GPC was 2600, the weight average molecular weight Mw was 5200, the molecular weight distribution Mw / Mn was 2.0, the chlorine content of the polymer was 27.3 wt%, and the sulfur content was 2.5 wt%. . In the infrared absorption spectrum, peaks derived from carboxylic acid in methacrylic acid and unsaturated bond in CR were observed, and the resulting polymer did not dissolve in toluene and chloroform, which are good solvents for CR. Dissolved in some acetone. Moreover, the acetone solution of the produced polymer was dissolved in an aqueous triethylamine solution. From the above results, it was judged that a polymethacrylic acid-CR diblock body (carboxyl group content = 2.67 mmol / g) having a methacrylic acid content of 23 wt% was produced.

合成例２（親水基含有ポリマー（両親媒性ＣＲグラフト共重合体）の合成）
還流冷却管、三方コックを備えた１０００ｍｌ褐色ガラスフラスコに、ｎ−ドデシルメルカプタン３．００ｇ、２，２’−アゾビス（２，４−ジメチルバレロニトリル）４．００ｇ、及びトルエン３００．０ｇを仕込んで溶解後、クロロプレン１６０．０ｇを添加し、凍結−脱気−融解を２回繰返して十分脱気した後、窒素雰囲気下、マグネチックスターラーで攪拌しながら、５０℃のオイルバスで７４時間加熱しながら重合し、ＣＲのトルエン溶液を得た。７４時間後のクロロプレンの重合転化率は９８．５％だった。ここへメタクリル酸５０．００ｇ、ベンゾイルパーオキサイド０．５０ｇを添加し、窒素雰囲気下、９０℃で５時間加熱しながら重合した。内容物を２０００ｍｌのメタノールへ投入してポリマーを分離し、乾燥した。ＧＰＣにより測定した生成ポリマーの数平均分子量Ｍｎは９５００、重量平均分子量Ｍｗは１９８００であった。ポリマーの塩素含量は３１．２ｗｔ％、赤外吸収スペクトルには、メタクリル酸中のカルボン酸及びＣＲ中の不飽和結合由来のピークが観測された。以上の結果からメタクリル酸含量２２ｗｔ％のポリメタクリル酸−ＣＲグラフト共重合体（カルボキシル基量＝２．５６ミリモル／ｇ）が生成したと判断した。

Synthesis Example 2 (Synthesis of hydrophilic group-containing polymer (amphiphilic CR graft copolymer))
A 1000 ml brown glass flask equipped with a reflux condenser and a three-way cock was charged with 3.00 g of n-dodecyl mercaptan, 4.00 g of 2,2′-azobis (2,4-dimethylvaleronitrile), and 300.0 g of toluene. After dissolution, 160.0 g of chloroprene is added, and freeze-degas-thaw is repeated twice, and after sufficient degassing, the mixture is heated in a 50 ° C oil bath for 74 hours while stirring with a magnetic stirrer in a nitrogen atmosphere. Polymerization was performed to obtain a toluene solution of CR. The polymerization conversion rate of chloroprene after 74 hours was 98.5%. Methacrylic acid 50.00g and benzoyl peroxide 0.50g were added here, and it superposed | polymerized, heating at 90 degreeC for 5 hours by nitrogen atmosphere. The contents were poured into 2000 ml of methanol to separate the polymer and dried. The number average molecular weight Mn of the produced polymer measured by GPC was 9500, and the weight average molecular weight Mw was 19,800. The polymer had a chlorine content of 31.2 wt%, and in the infrared absorption spectrum, a peak derived from a carboxylic acid in methacrylic acid and an unsaturated bond in CR was observed. From the above results, it was determined that a polymethacrylic acid-CR graft copolymer (carboxyl group content = 2.56 mmol / g) having a methacrylic acid content of 22 wt% was produced.

Synthesis Example 3 (Synthesis of hydrophilic group-containing polymer (hydrophilic group-containing CR random copolymer))
In a 500 ml glass flask equipped with a nitrogen gas inlet tube and a reflux condenser, tetrahydrofuran (92.52 g), dithiobis (thioformic acid) O, O-diisopropyl 3.00 g, 4,4′-azobis (4-cyanopentanoic acid) 0.80 g Then, 22.08 g of maleic acid was charged and dissolved, then 33.55 g of chloroprene was added, and after freeze-degas-thaw was repeated twice and sufficiently degassed, the mixture was stirred with a magnetic stirrer under a nitrogen atmosphere. Polymerization was performed for 92 hours while heating in an oil bath at 50 ° C. After cooling to room temperature, 0.33 g of phenothiazine was added as a stabilizer. At this time, the polymerization conversion rate of chloroprene was 76.5%. The contents were poured into 2000 ml of pure water to precipitate a polymer and dried under reduced pressure to obtain a chloroprene-maleic acid random copolymer. The weight of the dry polymer was 25.12 g, the number average molecular weight Mn of the resulting polymer measured by GPC was 7900, and the weight average molecular weight Mw was 13500. The content of carboxylic acid groups in the resulting polymer measured by neutralization titration was 7.0 wt% (carboxyl group content = 1.56 mmol / g).

Synthesis Example 4 (Synthesis of hydrophilic group-containing polymer (terminal hydrophilic group-containing chloroprene polymer))
In a 1000 ml brown glass flask equipped with a three-way cock, under a nitrogen atmosphere, 43.00 g of thiomalic acid, 9.60 g of 2,2′-azobis (2,4-dimethylvaleronitrile), 330.00 g of chloroprene, and 215.00 g of acetone The solution is heated and polymerized in an oil bath at 50 ° C. for 70 hours while stirring with a magnetic stirrer, and an acetone solution of a terminal hydrophilic group-containing chloroprene polymer (chloroprene polymer-thiomalic acid) (carboxyl group in the solution). Amount = 1.09 mmol / g). The polymerization conversion rate of chloroprene after 70 hours was 98.5%.

  The number average molecular weight Mn of the produced polymer measured by GPC was 2200, and the weight average molecular weight Mw was 4800.

Synthesis Example 5 (Synthesis of hydrophilic group-containing polymer (terminal hydrophilic group-containing acrylate ester polymer))
A 200 ml glass flask equipped with a three-way cock was charged with 5.28 g of thiomalic acid, 0.69 g of 4,4′-azobis (4-cyanopentanoic acid), and 50.00 g of tetrahydrofuran, and then dissolved, 25.00 g of methyl methacrylate. Then, 10.00 g of butyl acrylate was added, and after freezing-degassing-thawing was repeated twice and sufficiently degassing, the mixture was heated and polymerized in a 60 ° C. oil bath for 24 hours while stirring with a magnetic stirrer in a nitrogen atmosphere. Thus, a tetrahydrofuran solution of a terminal hydrophilic group-containing polymethyl methacrylate / butyl acrylate copolymer was obtained (the amount of carboxyl groups in the solution = 0.83 mmol / g). The polymerization conversions of methyl methacrylate and butyl acrylate after 24 hours were 91.0% and 98.5%.

  The number average molecular weight Mn of the produced polymer measured by GPC was 1800, and the weight average molecular weight Mw was 3700.

Synthesis Example 6 (Synthesis of hydrophilic group-containing polymer (terminal hydrophilic group-containing methacrylate ester polymer))
A 200 ml glass flask equipped with a three-way cock was charged with 5.28 g of thiomalic acid, 0.35 g of 2,2′-azobisisobutyronitrile, and 50.00 g of acetone, and then added with 35.37 g of methyl methacrylate. Then, after freezing-degassing-thawing twice repeatedly and sufficiently degassing, it was polymerized by heating in an oil bath at 60 ° C. for 27 hours while stirring with a magnetic stirrer under a nitrogen atmosphere. An acetone solution of methyl methacrylate (the amount of carboxyl groups in the solution = 0.80 mmol / g) was obtained. The polymerization conversion rate of methyl methacrylate after 27 hours was 89.3%.

  The number average molecular weight Mn of the produced polymer measured by GPC was 1500, and the weight average molecular weight Mw was 2800.

Synthesis Example 7 (Synthesis of CR latex)
A 2000 ml separable flask was charged with 4.51 g of potassium hydroxide, 0.83 g of sodium hydroxide, 1.01 g of sodium salt of formalin naphthalenesulfonic acid formalin and 320.00 g of pure water, dissolved, and heated to 50 ° C. did. Separately, 35.00 g of an acetone solution of a terminal hydrophilic group-containing chloroprene polymer synthesized in Synthesis Example 4, 50.00 g of acetone, and 1.80 g of a nonionic emulsifier (Nippon Emulsifier, New Coal N-714) were mixed and dissolved. The obtained solution was added to the above separable flask under stirring to prepare a seed dispersion of the terminal hydrophilic group-containing chloroprene polymer. The monomer was emulsified by charging 0.80 g of n-dodecyl mercaptan and 400.00 g of chloroprene. After degassing the system by flowing nitrogen at a flow rate of 0.8 L / min for 20 minutes, 0.25 g of erythorbic acid and 0.05 g of sodium hydrosulfite were added as reducing agents, and potassium persulfate as an initiator. Polymerization was carried out at 15 ° C. while feeding a mixed solution of 0.60 wt% and sodium anthraquinone sulfonate 0.02 wt% at a rate of 7 ml / h. As a result, emulsion polymerization proceeded without generating scale. After the polymerization for 8 hours, 7.00 g of an 8.6 wt% chloroprene solution of a phenolic antioxidant (manufactured by Kawaguchi Chemical, Antage W-500) was added as a polymerization terminator to terminate the polymerization. The polymerization conversion rate of chloroprene was 91.2%. Unreacted monomers, acetone and water were distilled off by a rotary evaporator to obtain CR latex (solid content 51 wt%, average particle size 110 nm).

Example 1
1.00 g of polymethacrylic acid-CR diblock body obtained in Synthesis Example 1 (carboxyl group amount = 2.67 mmol), terpene phenol resin (Arakawa Chemical, Tamanol 803L) 10.00 g (carboxyl group amount = 8.9) Mmol), 1.20 g of triethylamine, and 12.00 g of acetone were weighed into a 100 ml glass beaker and completely dissolved. To this acetone solution, 12.00 g of pure water was slowly added dropwise with stirring with a magnetic stirrer. Thereafter, acetone and water were distilled off by a rotary evaporator to obtain an emulsion A (solid content 52 wt%, average particle size 160 nm).

  An adhesive composition was prepared using the obtained emulsion-A, and the adhesive performance was evaluated. The results are shown in Table 1. Compared with the emulsion of the comparative example, there is little decrease in peel strength due to open time and decrease in peel strength after water immersion, and it is clear that contact adhesion and water resistance are remarkably improved as compared with conventional latex.

実施例２
合成例２で得たポリメタクリル酸−ＣＲグラフト共重合体１．００ｇ（カルボキシル基量＝２．５６ミリモル）、テルペンフェノール樹脂（荒川化学製、タマノール８０３Ｌ）１０．００ｇ（カルボキシル基量＝８．９ミリモル）、トリエチルアミン１．２０ｇ、及びアセトン１２．００ｇを１００ｍｌのガラスビーカーに秤量し、完全に溶解した。このアセトン溶液に、マグネチックスターラー攪拌下、１２．００ｇの純水をゆっくり滴下した。その後、ロータリーエバポレーターでアセトンと水分を留去し、エマルション−Ｂを得た（固形分５２ｗｔ％、平均粒径１７０ｎｍ）。

Example 2
1.00 g of polymethacrylic acid-CR graft copolymer obtained in Synthesis Example 2 (carboxyl group content = 2.56 mmol), terpene phenol resin (Arakawa Chemical, Tamanol 803L) 10.00 g (carboxyl group content = 8. 9 mmol), 1.20 g of triethylamine, and 12.00 g of acetone were weighed into a 100 ml glass beaker and completely dissolved. To this acetone solution, 12.00 g of pure water was slowly added dropwise with stirring with a magnetic stirrer. Thereafter, acetone and water were distilled off by a rotary evaporator to obtain an emulsion B (solid content: 52 wt%, average particle size: 170 nm).

  Adhesive composition was prepared using the obtained emulsion-B, and adhesive performance was evaluated. The results are shown in Table 1. Compared with the emulsion of the comparative example, there is little decrease in peel strength due to open time and decrease in peel strength after water immersion, and it is clear that contact adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 3
2.0 g of chloroprene-maleic acid random copolymer obtained in Synthesis Example 3 (carboxyl group amount = 3.11 mmol), terpene phenol resin (Arakawa Chemical Co., Ltd., Tamanol 803L) 10.00 g (carboxyl group amount = 8.9) Mmol), 1.80 g of N, N′-diethylaminoethanol, and 12.00 g of acetone were weighed into a 100 ml glass beaker and completely dissolved. To this acetone solution, 12.00 g of pure water was slowly added dropwise with stirring with a magnetic stirrer. Thereafter, acetone and water were distilled off with a rotary evaporator to obtain Emulsion-C (solid content 52 wt%, average particle size 195 nm).

  An adhesive composition was prepared using the obtained emulsion-C, and the adhesive performance was evaluated. The results are shown in Table 1. Compared with the emulsion of the comparative example, there is little decrease in peel strength due to open time and decrease in peel strength after water immersion, and it is clear that contact adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 4
2.85 g of chloroprene-based polymer-thiomalic acid acetone solution obtained in Synthesis Example 4 (carboxyl group amount = 3.11 mmol), 0.10 g of nonionic emulsifier (manufactured by Lion, Esomin T-25), terpene phenol resin (Arakawa Chemical) 10.00 g (manufactured by Tamanol 803L) (carboxyl group amount = 8.9 mmol), 1.75 g of N, N′-diethylaminoethanol, and 12.00 g of acetone were weighed in a 100 ml glass beaker and completely dissolved. To this acetone solution, 12.00 g of pure water was slowly added dropwise with stirring with a magnetic stirrer. Thereafter, acetone and water were distilled off with a rotary evaporator to obtain Emulsion-D (solid content 52 wt%, average particle size 165 nm, conventional emulsifier 0.73 wt% in the emulsion solid content).

  An adhesive composition was prepared using the obtained emulsion-D, and the adhesive performance was evaluated. The results are shown in Table 1. Compared with the emulsion of the comparative example, there is little decrease in peel strength due to open time and decrease in peel strength after water immersion, and it is clear that contact adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 5
Tetrahydrophilic group-containing polymethyl methacrylate / butyl acrylate copolymer tetrahydrofuran solution obtained in Synthesis Example 5. 4.47 g (carboxyl group amount = 3.71 mmol), nonionic emulsifier (manufactured by Lion, Esomine T-25) 0 .10 g, 10.00 g of terpene phenol resin (manufactured by Arakawa Chemical, Tamanol 803 L) (carboxyl group amount = 8.9 mmol), 1.85 g of N, N′-diethylaminoethanol, and 12.00 g of tetrahydrofuran in a 100 ml glass beaker Weighed and dissolved completely. To this tetrahydrofuran solution, 12.00 g of pure water was slowly added dropwise under magnetic stirring. Thereafter, tetrahydrofuran and water were distilled off by a rotary evaporator to obtain Emulsion-E (solid content 52 wt%, average particle size 190 nm, conventional emulsifier 0.73 wt% in the emulsion solid content).

  An adhesive composition was prepared using the obtained Emulsion-E, and the adhesive performance was evaluated. The results are shown in Table 1. Compared with the emulsion of the comparative example, there is little decrease in peel strength due to open time and decrease in peel strength after water immersion, and it is clear that contact adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 6
4.78 g (carboxyl group amount = 3.82 mmol) of acetone solution of terminal methyl group-containing polymethyl methacrylate obtained in Synthesis Example 6, 0.10 g of nonionic emulsifier (Ao 320, manufactured by Kao), terpene phenol resin (Arakawa Chemical) Manufactured by Tamanol 803L), 10.00 g (carboxyl group amount = 8.9 mmol), 1.30 g of triethylamine, and 12.00 g of acetone were weighed in a 100 ml glass beaker and completely dissolved. To this acetone solution, 12.00 g of pure water was slowly added dropwise with stirring with a magnetic stirrer. Thereafter, acetone and water were distilled off with a rotary evaporator to obtain Emulsion-F (solid content 52 wt%, average particle size 185 nm, conventional emulsifier 0.75 wt% in the emulsion solid content).

  An adhesive composition was prepared using the obtained emulsion-F, and the adhesive performance was evaluated. The results are shown in Table 1. Compared with the emulsion of the comparative example, there is little decrease in peel strength due to open time and decrease in peel strength after water immersion, and it is clear that contact adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 7
2.85 g of chloroprene polymer-thiomalic acid acetone solution obtained in Synthesis Example 4 (carboxyl group amount = 3.11 mmol), nonionic emulsifier (manufactured by Kao, Amit 320) 0.15 g, terpene phenol resin (manufactured by Arakawa Chemical, (Tamanol 803L) 10.00 g (carboxyl group amount = 8.9 mmol), phenolic antioxidant W-500 (manufactured by Kawaguchi Chemical) 0.15 g, N, N′-diethylaminoethanol 1.75 g, and acetone 12.50 g Was weighed into a 100 ml glass beaker and completely dissolved. To this acetone solution, 12.00 g of pure water was slowly added dropwise with stirring with a magnetic stirrer. Thereafter, acetone and water were distilled off by a rotary evaporator to obtain an emulsion-G (solid content: 52 wt%, average particle size: 155 nm, conventional emulsifier in emulsion solid content: 1.10 wt%).

  Adhesive composition was prepared using the obtained emulsion-G, and adhesive performance was evaluated. The results are shown in Table 1. Compared with the emulsion of the comparative example, there is little decrease in peel strength due to open time and decrease in peel strength after water immersion, and it is clear that contact adhesion and water resistance are remarkably improved as compared with conventional latex.

Comparative Example 1
An adhesive composition was prepared using a commercially available emulsion (E-200NT, manufactured by Arakawa Chemical Industries), and the adhesive performance was evaluated. The results are shown in Table 1. It is clear that the peel strength reduction due to open time and the peel strength reduction after water immersion are large compared to the emulsions of the examples.

Comparative Example 2
2.85 g of chloroprene polymer-thiomalic acid acetone solution obtained in Synthesis Example 4 (carboxyl group amount = 3.11 mmol), terpene phenol resin (manufactured by Arakawa Chemical, Tamanol 803L) 10.00 g (carboxyl group amount = 8. 9 mmol), 1.75 g of N, N′-diethylaminoethanol, and 12.00 g of acetone were weighed into a 100 ml glass beaker and completely dissolved. An aqueous solution obtained by dissolving 1.00 g of an anionic emulsifier (manufactured by Kao, Perex SSH, active ingredient 50 wt%) in 12.00 pure water was slowly added dropwise to this acetone solution while stirring with a magnetic stirrer. Thereafter, acetone and water were distilled off with a rotary evaporator to obtain Emulsion-H (solid content 52 wt%, average particle size 180 nm, conventional emulsifier in emulsion solid content 3.56 wt%).

  An adhesive composition was prepared using the obtained emulsion-H, and the adhesive performance was evaluated. The results are shown in Table 1. It is clear that the peel strength reduction due to open time and the peel strength reduction after water immersion are large compared to the emulsions of the examples.

Comparative Example 3
2.85 g of chloroprene polymer-thiomalic acid acetone solution obtained in Synthesis Example 4 (carboxyl group amount = 3.11 mmol), nonionic emulsifier (Lion, Esomine T-25) 0.05 g, terpene phenol resin (Arakawa Chemical) (Manufactured by Tamanol 803L) 15.00 g (carboxyl group amount = 13.35 mmol), N, N′-diethylaminoethanol 1.90 g, and acetone 12.00 g were weighed in a 100 ml glass beaker and completely dissolved. To this acetone solution, 12.00 g of pure water was slowly added dropwise with stirring with a magnetic stirrer. Thereafter, acetone and water were distilled off by a rotary evaporator to obtain Emulsion-I (solid content 52 wt%, average particle size 330 nm).

  An adhesive composition was prepared using the obtained emulsion-I, and the adhesive performance was evaluated. The results are shown in Table 1. The results are shown in Table 1. It is clear that the peel strength reduction due to open time and the peel strength reduction after water immersion are slightly greater than the emulsions of the examples. In addition, precipitation was observed during storage of the composition at room temperature.

Claims (17)

An emulsion comprising 3 wt% or less of a conventional emulsifier, wherein a hydrophobic substance is emulsified and stabilized by a hydrophilic group-containing polymer, and has an average particle size of 10 to 200 nm. The hydrophobic substance is one or more substances selected from the group consisting of a tackifier resin, a plasticizer, a softener, an antioxidant, an ultraviolet absorber, a crosslinking agent, and a pigment. Emulsion. The emulsion according to claim 1 or 2, wherein the hydrophilic group-containing polymer is a chloroprene block copolymer or a chloroprene graft copolymer represented by the following general formula (1).

(In the formula, the water-soluble polymer or water-soluble oligomer is selected from carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, hydroxyl group, carboxylate, sulfonate, phosphate, amine salt or polyalkylene oxide. Represents a water-soluble polymer or water-soluble oligomer having a hydrophilic group.) The hydrophilic group-containing polymer is selected from carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, hydroxyl group, carboxylate, sulfonate, phosphate, amine salt or polyalkylene oxide. The emulsion according to claim 1 or 2, which is a hydrophilic group-containing chloroprene random copolymer having a structure randomly distributed therein. The hydrophilic group-containing polymer is one selected from the group consisting of a terminal hydrophilic group-containing chloroprene polymer, a terminal hydrophilic group-containing acrylate polymer, and a terminal hydrophilic group-containing methacrylate polymer represented by the following general formula (2) The emulsion according to claim 1, wherein the emulsion is the above polymer.

(In the formula, P represents a chloroprene polymer, an acrylate polymer, or a methacrylate polymer, and X represents a carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, sulfuric acid group, carboxylate salt, sulfone. Represents an acid salt, a phosphate, an amine salt, a sulfate or a polyalkylene oxide, R represents an alkyl group, an aryl group, a substituted alkyl group or a substituted aryl group, and n represents an integer of 1 to 3.) A terminal hydrophilic group-containing acrylate polymer is a group of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and bornyl acrylate The emulsion according to claim 5, which is a polymer having at least one monomer unit selected from The terminal hydrophilic group-containing methacrylate polymer is at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and bornyl methacrylate. The emulsion according to claim 5, which is a polymer having the monomer unit as an essential component. The emulsion according to any one of claims 1 to 7, wherein the number average molecular weight determined by gel permeation chromatography (GPC) of the hydrophilic group-containing polymer is 500 to 100,000. The hydrophilic group-containing polymer and the hydrophobic substance are dissolved in a hydrophilic solvent, and water is added to the obtained mixed solution with stirring to perform phase inversion emulsification. The method for producing an emulsion according to the item. The hydrophobic substance is one or more substances selected from the group consisting of a tackifier resin, a plasticizer, a softener, an antioxidant, an ultraviolet absorber, a crosslinking agent, and a pigment. Emulsion manufacturing method. The method for producing an emulsion according to claim 9 or 10, wherein the hydrophilic group-containing polymer is a chloroprene block copolymer or a chloroprene graft copolymer represented by the following general formula (1). .

(In the formula, the water-soluble polymer or water-soluble oligomer is selected from carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, hydroxyl group, carboxylate, sulfonate, phosphate, amine salt or polyalkylene oxide. Represents a water-soluble polymer or water-soluble oligomer having a hydrophilic group.) The hydrophilic group-containing polymer is selected from carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, hydroxyl group, carboxylate, sulfonate, phosphate, amine salt or polyalkylene oxide. The method for producing an emulsion according to claim 9 or 10, wherein the emulsion is a hydrophilic group-containing chloroprene random copolymer having a structure randomly distributed therein. The hydrophilic group-containing polymer is one selected from the group consisting of a terminal hydrophilic group-containing chloroprene polymer, a terminal hydrophilic group-containing acrylate polymer, and a terminal hydrophilic group-containing methacrylate polymer represented by the following general formula (2) It is the above polymer, The manufacturing method of the emulsion of Claim 9 or Claim 10 characterized by the above-mentioned.

(In the formula, P represents a chloroprene polymer, an acrylate polymer, or a methacrylate polymer, and X represents a carboxylic acid group, sulfonic acid group, phosphoric acid group, amine group, sulfuric acid group, carboxylate salt, sulfone. Represents an acid salt, a phosphate, an amine salt, a sulfate or a polyalkylene oxide, R represents an alkyl group, an aryl group, a substituted alkyl group or a substituted aryl group, and n represents an integer of 1 to 3.) A terminal hydrophilic group-containing acrylate polymer is a group of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and bornyl acrylate 14. The method for producing an emulsion according to claim 13, wherein the polymer comprises one or more monomer units selected from the above as essential components. The terminal hydrophilic group-containing methacrylate polymer is at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and bornyl methacrylate. The method for producing an emulsion according to claim 13, wherein the polymer comprises a monomer unit as an essential component. The hydrophilic solvent is one or more solvents selected from tetrahydrofuran, dioxane, methyl ethyl ketone, methyl isobutyl ketone, acetone, isopropanol, ethanol, methoxyethanol, dimethoxyethane, butyl cellosolve, ethyl cellosolve, butanol and methanol. The method for producing an emulsion according to any one of claims 9 to 15. An adhesive, a pressure-sensitive adhesive, a primer, a paint, a coating agent, a binder, a toner or an ink comprising the emulsion according to any one of claims 1 to 8.