JP2007297502A - Soapless polychloroprene-based latex and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a soapless polychloroprene-based latex improving adhesion and water resistance of a conventional polychloroprene-based latex adhesive. <P>SOLUTION: The invention relates to the soapless polychloroprene-based latex characterized by comprising 2 wt.% or less of an emulsifier and an amphiphilic chloroprene-based copolymer where a hydrophilic oligomer or polymer having an acidic functional group is attached to a hydrophobic chloroprene-based polymer, and to the method for producing the soapless polychloroprene-based latex characterized by using the amphiphilic chloroprene-based copolymer where a hydrophilic oligomer or polymer having an acidic functional group is attached to a hydrophobic chloroprene-based polymer in producing the soapless chloroprene-based latex by emulsion polymerization of chloroprene or chloroprene and a monomer copolymerizable with the chloroprene monomer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a soapless polychloroprene-based latex in which the emulsifier in the latex is reduced and the adhesion and water resistance are remarkably improved, and a method for producing the same.

  Adhesives and primers based on polychloroprene (hereinafter may be abbreviated as CR) are applications that make full use of the characteristics of CR such as polarity, cohesive strength, and flexibility. Mainly used in a wide range of fields such as building materials, woodwork, shoes making, and vehicle manufacturing. Conventional CR adhesives were mainly used in which CR, tackifier resin, zinc oxide, antioxidant, etc. were dissolved in organic solvents such as toluene, hexane, ethyl acetate, cyclohexane, etc. The demand for solventization is increasing year by year. Although CR latex has been attracting attention as a response to this requirement, conventional CR latex has insufficient adhesiveness and water resistance, and has not yet replaced solvent-based CR adhesives.

  Conventional CR latexes emulsified chloroprene monomer in water using emulsifiers such as potassium rosinate, sodium alkyl sulfate, higher alcohol sulfate ester sodium, polyoxyethylene alkyl ether, alkylamine salt, quaternary ammonium salt, polyvinyl alcohol and the like. Thereafter, it is produced by a method in which chloroprene is polymerized by adding a radical initiator such as potassium persulfate, and then unreacted monomers are removed by a method such as steam stripping. The latex contains about 1 to 6 wt% of the above-mentioned emulsifier with respect to CR, and this is considered to be a main factor that hinders the development of adhesiveness and water resistance of conventional CR latex adhesives. That is, in the process of applying an adhesive based on a conventional CR latex to an adherend and drying, the emulsifier desorbed from the surface of the CR latex particles and the emulsifier dissolved in water are not adhered to the surface of the adhesive film or the surface. It is considered that the original adhesiveness of CR is inhibited by the segregation of the emulsifier on the adherend interface. Therefore, an attempt was made to produce a so-called soapless CR latex that does not contain these emulsifiers. For example, after radical copolymerization of styrene and acrylic acid in water, neutralization with ammonia, followed by addition of chloroprene and emulsion polymerization to obtain a soapless CR latex (Patent Document 1), in the presence of an amine in water A method (Patent Document 2) for obtaining a soapless CR latex by radical copolymerization of chloroprene and an active chlorine-containing monomer is disclosed.

  However, since any hydrophilic group-containing copolymer used for emulsification of chloroprene is a random copolymer, the balance between hydrophilicity and hydrophobicity is poor, and the adsorptivity to the surface of CR latex particles is not sufficient. It was difficult to maintain sufficient sex.

  On the other hand, a radically polymerizable monomer such as an acrylate ester is emulsified in water using a salt of an amphiphilic acrylate ester copolymer comprising a hydrophobic acrylate polymer block and a hydrophilic acrylic acid oligomer or polymer block as an emulsifier. Although a method for obtaining a soapless latex by polymerization is disclosed, there is no description on chloroprene (Patent Documents 3 and 4).

JP 58-89602 A Japanese Patent Publication No. 52-32987 Special table 2004-530751 gazette JP 2005-513252 A

  As described above, a novel CR latex in which the adhesion and water resistance of the conventional CR latex adhesive are improved has been desired.

  As a result of intensive studies to solve the above problems, the present inventor has found that an amphiphilic CR copolymer in which a hydrophilic oligomer or a hydrophilic polymer is linked to a CR polymer (hereinafter abbreviated as amphiphilic CR). ) Was used to emulsion-polymerize chloroprene or a monomer copolymerizable with chloroprene and chloroprene, and a stable soap press CR latex was obtained, and it was found that the conventional problems could be solved, and the present invention was completed. is there.

  That is, the present invention contains an emulsifier in an amount of 2 wt% or less and an amphiphilic chloroprene copolymer in which a hydrophobic oligomer or hydrophilic polymer having an acidic functional group is linked to a hydrophobic chloroprene polymer. A featured pressless CR latex and a method for producing the same.

  Hereinafter, the present invention will be described in detail.

  The soapless CR-based latex of the present invention has a significantly reduced emulsifier and contains 2 wt% or less of emulsifier with respect to CR. When the emulsifier exceeds 2 wt%, the adhesiveness and water resistance of the CR-based latex are significantly reduced. Here, the emulsifier is not particularly limited as long as it is a commonly used emulsifier, and examples thereof include an anionic emulsifier, a nonionic emulsifier, and a cationic emulsifier. Examples of the anionic emulsifier include potassium rosinate. , Fatty acid salt, alkenyl succinate, sodium alkyl sulfate, sodium higher alcohol sulfate, alkyl benzene sulfonate, alkyl diphenyl ether disulfonate, sulfonate of higher fatty acid amide, sulfate of higher fatty acid alkylol amide, alkyl sulfo Betaine and the like, nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyvinyl alcohol and the like, and cationic emulsifiers include alkylamine salts, Grade ammonium salt, and the like.

  The soapless CR latex of the present invention contains an amphiphilic chloroprene copolymer in which a hydrophilic oligomer or hydrophilic polymer having an acidic functional group is linked to a hydrophobic chloroprene polymer. By containing the amphiphilic chloroprene copolymer, the amount of conventional emulsifier used can be significantly reduced. The content of the amphiphilic chloroprene copolymer in the soapless CR-based latex is not particularly limited, but in order not to impair the water resistance of the latex, with respect to the polymer contained in the final latex, The content of the hydrophilic monomer polymerization residue contained in the amphiphilic chloroprene copolymer is preferably 10 wt% or less, and more preferably 5 wt% or less.

  The hydrophobic chloroprene polymer in the amphiphilic chloroprene copolymer refers to a polymer having chloroprene as a main polymerization unit, and examples thereof include a chloroprene homopolymer and a chloroprene copolymer. As monomers capable of radical copolymerization with chloroprene constituting the chloroprene copolymer, 2,3-dichloro-1,3-butadiene, 2-cyano-1,3-butadiene, 1-chloro-1,3-butadiene, etc. 1,3-butadienes, styrene, α-methylstyrene, p-chloromethylstyrene, p-cyanostyrene, p-acetoxystyrene, p-styrenesulfonyl chloride, ethyl p-styrenesulfonyl, p-butoxystyrene, 4- Styrenes such as vinyl benzoic acid and 3-isopropenyl-α, α'-dimethylbenzyl isocyanate, methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate , Methacrylic acid 2- (dimethylamino) Ethyl, 2- (diethylamino) ethyl methacrylate, 3- (dimethylamino) propyl methacrylate, 2- (isocyanato) ethyl methacrylate, 2,4,6-tribromophenyl methacrylate, 2,2,3 methacrylate , 3-tetrafluoropropyl, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,4,4,4-hexamethacrylate Methacrylic acid esters such as fluorobutyl, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, cyclohexyl acrylate, 3- (trimethoxysilyl) acrylate Propyl, acrylic acid 2,2,3,3-tetrafluoropropyl, acrylic acid , 2,2-trifluoroethyl, acrylic acid esters such as 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, and others , Acrylonitrile, methacrylonitrile, α-cyanoethyl acrylate, maleic anhydride, methacrylic acid, acrylic acid and the like. 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, and α-cyanoethyl acrylate are preferred. 2,3-dichloro-1,3-butadiene, which has the highest copolymerizability with chloroprene, is more preferred.

  The hydrophilic oligomer or hydrophilic polymer having an acidic functional group in the amphiphilic chloroprene copolymer refers to an oligomer or polymer that is soluble in water or an alkaline aqueous solution, such as polystyrene sulfonic acid, polyvinyl sulfonic acid, Phosphoric acid group-containing polyacrylic acid ester, polymethacrylic acid, polyacrylic acid, vinyl benzoate / styrene copolymer, maleic anhydride / styrene copolymer, maleic anhydride / p-methoxystyrene copolymer, maleic anhydride / Isobutylene copolymer, maleic anhydride / chloroprene copolymer, maleic anhydride / 2,3-dichlorobutadiene / chloroprene copolymer, maleic acid / chloroprene copolymer, and the like.

  These hydrophilic oligomers or hydrophilic polymers are indispensable components for stably dispersing CR latex particles in water, and are sulfonic acid groups, phosphoric acid groups, carboxyl groups, and salts thereof, hydroxyl groups, polyalkylene oxides, It can be obtained by radical polymerization of a monomer containing a hydrophilic group such as an amino group or a quaternary ammonium salt. However, copolymerization of a hydrophilic group-containing monomer and a copolymerizable monomer is possible as long as the hydrophilicity is not impaired. Combined may be used. Alternatively, it can also be obtained by radical polymerization of a hydrophobic monomer having a functional group such as an ester group and then converting the functional group to a hydrophilic group by a hydrolysis reaction with an acid or an alkali. Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, 4- (methacryloyloxy) butyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, and salts thereof, which have a functional group that can be converted into sulfonic acid. Examples of the monomer include p-styrene sulfonic acid alkyl ester and p-chlorosulfonyl styrene. Examples of the phosphoric acid group-containing monomer include 2- (methacryloyloxy) ethyl phosphate and salts thereof. Examples of the carboxyl group-containing monomer include methacrylic acid, acrylic acid, vinyl benzoic acid, maleic anhydride, maleic acid, crotonic acid, itaconic acid, fumaric acid, citraconic acid, mono 2- (methacryloyloxy) ethyl phthalate, mono 2- ( (Methacryloyloxy) ethyl succinate, mono 2- (acryloyloxy) ethyl succinate, and salts thereof, and the like, and monomers having a functional group convertible to a carboxyl group include t-butyl methacrylate and t-butyl acrylate. Benzyl methacrylate, benzyl acrylate and the like. 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 monomer having a convertible functional group include glycidyl methacrylate and glycidyl acrylate. Examples of the polyalkylene oxide-containing monomer include polyethylene glycol methacrylate and polyethylene glycol acrylate. Examples of the amino group-containing monomer include dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, and diethylaminoethyl acrylate. Examples of the quaternary ammonium salt-containing monomer include [(2-methacryloyloxy) ethyl] trimethylammonium chloride, [(2-acryloyloxy) ethyl] trimethylammonium chloride, and the like.

  Hydrophilic chloroprene copolymer in which a hydrophilic oligomer or hydrophilic polymer having an acidic functional group is linked to a hydrophobic chloroprene polymer is composed of a lipophilic polymer block and a hydrophilic polymer block, such as chloroprene. Ability to emulsify monomers in water, that is, a polymer having surface activity.For example, a hydrophobic chloroprene polymer linked to a water-soluble polymer such as polystyrene sulfonic acid or polyalkylene oxide, or a hydrophobic chloroprene polymer. Examples thereof include a chloroprene block copolymer represented by the following general formula (1) to which a hydrophilic oligomer block or a hydrophilic polymer block is linked.

（式中、Ｕは水素、メチル基又はシアノ基を表し、Ｖはメチル基、カルボキシル基、カルボキシル基含有アルキル基又はカルボキシル基含有アリール基を表し、Ａはクロロプレン、２，３−ジクロロ−１，３−ブタジエン、スチレン、ｐ−メトキシスチレン又はイソブチレンの重合残基を表し、Ｑは無水マレイン酸、シトラコン酸、マレイン酸又はフマル酸の重合残基を表し、ｋ、ｍ及びｎは０以上の整数を表し、ｐは１以上の整数を表す。）
これらのうち、クロロプレン等のモノマーを水中に十分乳化させることができ、かつ安定なＣＲラテックスを得るために、疎水性のクロロプレン系ポリマーに親水性オリゴマーブロック又は親水性ポリマーブロックが連結している上記一般式（１）で表されるクロロプレン系ブロック共重合体であることが好ましい。ここに、上記一般式（１）で表されるクロロプレン系ブロック共重合体としては、例えば、ポリメタクリル酸−ＣＲジブロック共重合体、ポリアクリル酸−ＣＲジブロック共重合体、安息香酸ビニル／スチレン共重合体−ＣＲジブロック共重合体、無水マレイン酸／スチレン共重合体−ＣＲジブロック共重合体、無水マレイン酸／ｐ−メトキシスチレン共重合体−ＣＲジブロック共重合体、無水マレイン酸／イソブチレン共重合体−ＣＲジブロック共重合体、無水マレイン酸／クロロプレン共重合体−ＣＲジブロック共重合体、無水マレイン酸／スチレン共重合体−ＣＲジブロック共重合体、マレイン酸／クロロプレン共重合体−ＣＲジブロック共重合体、無水マレイン酸／２，３−ジクロロブタジエン／クロロプレン共重合体−ＣＲジブロック共重合体等があげられる。

(In the formula, U represents hydrogen, a methyl group or a cyano group, V represents a methyl group, a carboxyl group, a carboxyl group-containing alkyl group or a carboxyl group-containing aryl group, A represents chloroprene, 2,3-dichloro-1, Represents a polymerized residue of 3-butadiene, styrene, p-methoxystyrene or isobutylene, Q represents a polymerized residue of maleic anhydride, citraconic acid, maleic acid or fumaric acid, and k, m and n are integers of 0 or more And p represents an integer of 1 or more.)
Among these, a monomer such as chloroprene can be sufficiently emulsified in water and a hydrophilic oligomer block or a hydrophilic polymer block is linked to a hydrophobic chloroprene polymer in order to obtain a stable CR latex. A chloroprene block copolymer represented by the general formula (1) is preferable. Examples of the chloroprene block copolymer represented by the general formula (1) include polymethacrylic acid-CR diblock copolymer, polyacrylic acid-CR diblock copolymer, vinyl benzoate / Styrene copolymer-CR diblock copolymer, maleic anhydride / styrene copolymer-CR diblock copolymer, maleic anhydride / p-methoxystyrene copolymer-CR diblock copolymer, maleic anhydride / Isobutylene copolymer-CR diblock copolymer, maleic anhydride / chloroprene copolymer-CR diblock copolymer, maleic anhydride / styrene copolymer-CR diblock copolymer, maleic acid / chloroprene copolymer Polymer-CR diblock copolymer, maleic anhydride / 2,3-dichlorobutadiene / chloroprene copolymer-CR dibro Click copolymer.

  When the soapless CR latex of the present invention is used for adhesives, primers, and sealants that require water resistance to moisture from the outside, the latex is stable with less hydrophilic oligomer or polymer content among the above-mentioned monomers. Use of a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, a carboxylic acid group-containing monomer, or a monomer having a functional group that can be converted into sulfonic acid, phosphoric acid, or carboxylic acid is preferable. Furthermore, it is preferable to use a carboxyl group-containing monomer in consideration of the solubility of the monomer in the polymerization solvent, and in consideration of the monomer price and polymerization rate, methacrylic acid, acrylic acid, or maleic anhydride and styrene, isobutylene, chloroprene, etc. The combination (alternating copolymerization) is particularly preferred. That is, when a hydrophilic oligomer or polymer block is synthesized using a monomer that easily undergoes radical polymerization alone, such as methacrylic acid or acrylic acid, there may be no monomers corresponding to Q and A in the general formula (1). . On the other hand, a hydrophilic oligomer block or hydrophilic using maleic anhydride, citraconic acid, maleic acid, fumaric acid (also referred to as 1,2-disubstituted monomer, corresponding to Q in the general formula (1)) that is not radically polymerized alone. When synthesizing a functional polymer block, an electron donating monomer (general formula (1)) such as styrene, chloroprene and isobutylene which promotes the polymerization of these monomers, that is, has alternating copolymerization properties with 1,2-disubstituted monomers. May be used in combination with a 1,2-disubstituted monomer. In general, monomers having a cyclic structure such as maleic anhydride and citraconic acid have high alternating copolymerization properties with electron donating monomers, and monomers having a non-cyclic structure such as maleic acid and fumaric acid have low alternating copolymerization properties. It has been known. However, it has been found that the living radical mechanism increases the alternating copolymerization of 1,2-disubstituted monomers having no cyclic structure and can be sufficiently utilized for the synthesis of amphiphilic chloroprene copolymers even with maleic acid.

  The saw press CR latex of the present invention can also be used for applications such as secondary batteries and capacitor electrode binders. When used in a closed system that is blocked from the outside, that is, when there is no contact with external moisture, a hydroxyl group, an alkylene oxide, an amino group-containing monomer or a hydroxyl group, and a functional group that can be converted to an amino group. You may use the monomer which has.

  The content of the hydrophilic oligomer block or hydrophilic polymer block in the amphiphilic chloroprene-based copolymer is not particularly limited, but in order to obtain sufficient monomer emulsifying power and maintain water resistance 1 to 50 wt% is preferable, and 1 to 40 wt% is more preferable.

  As a method for producing the amphiphilic chloroprene copolymer, a growing polymer radical (active species) is converted into a covalently-bonded species (resting species) that can be reversibly radically cleaved by the action of light, heat, or a catalyst. A method in which hydrophilic monomers are polymerized by so-called living radical polymerization in which radical polymerization is carried out while suppressing growth radical deactivation by recombination of growth radicals and disproportionation by conversion, followed by block copolymerization of chloroprene , An azo compound having a hydrophilic oligomer block or a hydrophilic polymer block (so-called water-soluble macroazo initiator), a method of radical polymerization of chloroprene using a carboxyl group-containing azo compound as a radical initiator, a hydroxyl group, a carboxyl group, etc. Radical polymerization of chloroprene, etc. using mercaptans as chain transfer agents Method, radical polymerization of chloroprene in the presence of radical initiators such as potassium persulfate and ammonium persulfate to introduce a hydrophilic group at the end of the chloroprene polymer, using an organic peroxide such as benzoyl peroxide in an organic solvent There are methods such as graft polymerization of hydrophilic monomers to CR, radical copolymerization of reactive emulsifiers and chloroprene, radical polymerization of hydrophilic monomers in the presence of diphenylethylenes, and radical polymerization of chloroprene. It is preferable to use a living radical polymerization method in that a hydrophilic oligomer or a polymer block can be efficiently introduced into the polymer. 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 the Society of Polymer Science) Vol. 32, No. 6 (1983), pages 1047 to 1050), dithiocarboxylic acid ester compounds, dithiocarbamic acid ester compounds, key compounds. A so-called RAFT (reversible addition-fragmentation transfer) polymerization method (RAFT polymerization) is used in which a radical polymerization is performed by repeating a reversible addition-cleavage transfer reaction of monomers and polymers to these compounds using a tomato acid ester compound or the like as a polymerization control agent. Are described in detail in WO 98/01478 (Ezio Rizzardo et al.), WO 98/58974, WO 99/35178 (Charmot Dominique et al.), And the TEMPO method using stable nitroxyl radicals. A solvable CR block copolymer can be synthesized. As another living radical polymerization method, there is a method of atom transfer polymerization (ATRP) of a hydrophilic monomer using allyl chlorine contained in a small amount in CR as an initiator. 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.

  Among the above production methods, the iniferter polymerization method and the RAFT polymerization method are most preferable in that the hydrophilic monomer and chloroprene can be polymerized at a lower temperature.

  The soapless CR-based latex of the present invention is a hydrophilic oligomer having an acidic functional group in a hydrophobic chloroprene-based polymer when emulsion-polymerizing chloroprene or a monomer copolymerizable with chloroprene and chloroprene to produce a CR-based latex. Alternatively, an amphiphilic chloroprene copolymer to which a hydrophilic polymer is linked is used. In particular, in order to stably emulsify a monomer such as chloroprene in water and obtain a stable latex, a hydrophilic oligomer block or a hydrophilic polymer block is linked to a hydrophobic chloroprene polymer in the following general formula (1). It is preferable to use an amphiphilic chloroprene copolymer represented.

（式中、Ｕは水素、メチル基又はシアノ基を表し、Ｖはメチル基、カルボキシル基、カルボキシル基含有アルキル基又はカルボキシル基含有アリール基を表し、Ａはクロロプレン、２，３−ジクロロ−１，３−ブタジエン、スチレン、ｐ−メトキシスチレン又はイソブチレンの重合残基を表し、Ｑは無水マレイン酸、シトラコン酸、マレイン酸又はフマル酸の重合残基を表し、ｋ、ｍ及びｎは０以上の整数を表し、ｐは１以上の整数を表す。）
上記の疎水性のクロロプレン系ポリマー、酸性官能基を有する親水性オリゴマー又は親水性ポリマー、両親媒性クロロプレン系共重合体、親水性オリゴマーブロック又は親水性ポリマーブロックについては、前に説明したのと同じである。

(In the formula, U represents hydrogen, a methyl group or a cyano group, V represents a methyl group, a carboxyl group, a carboxyl group-containing alkyl group or a carboxyl group-containing aryl group, A represents chloroprene, 2,3-dichloro-1, Represents a polymerized residue of 3-butadiene, styrene, p-methoxystyrene or isobutylene, Q represents a polymerized residue of maleic anhydride, citraconic acid, maleic acid or fumaric acid, and k, m and n are integers of 0 or more And p represents an integer of 1 or more.)
The above-mentioned hydrophobic chloroprene polymer, hydrophilic oligomer or hydrophilic polymer having an acidic functional group, amphiphilic chloroprene copolymer, hydrophilic oligomer block or hydrophilic polymer block are the same as described above. It is.

  The amount of the amphiphilic chloroprene copolymer used in the emulsion polymerization is not particularly limited as long as the monomer can be sufficiently emulsified and sufficient stability of the produced latex can be maintained, but an increase in the viscosity of the latex is considered. Then, it is preferable that it is 30 wt% or less of all the preparation monomers, and it is further more preferable that it is 20 wt% or less when the adhesiveness and water resistance of the latex finally obtained are considered.

  In the method of emulsion polymerization of chloroprene or chloroprene and a monomer copolymerizable therewith in the production of the soapless CR latex of the present invention, a hydrophilic oligomer or hydrophilic polymer having an acidic functional group is linked to the chloroprene polymer. Other than using an amphiphilic chloroprene copolymer, it is the same as conventional emulsion polymerization.

  Examples from the production of the amphiphilic chloroprene copolymer to the production of saw press CR latex using the amphiphilic chloroprene copolymer will be described below.

  First, in a solvent such as tetrahydrofuran or dioxane, by radical polymerization of a hydrophilic monomer using the above-described iniferter polymerization method or RAFT polymerization method with a dithiocarbamate ester, a xanthate ester compound or a dithiocarboxylate ester compound as a polymerization controller, After synthesizing a hydrophilic oligomer or polymer having a dithiocarbamate ester, xanthate ester or dithiocarboxylate ester end, and subsequently adding chloroprene to radical block copolymerization, the end of the hydrophilic oligomer block or hydrophilic polymer block is obtained. Amphiphilic CR having a structure in which CR is linked can be synthesized. This polymer solution was triethylamine, diethylamine, triethanolamine, diethanolamine, ethanolamine, propanolamine, N, N-dimethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-methyl-1-propanol, ammonia, water An amphiphilic aqueous CR solution is prepared by adding to an aqueous solution of a basic compound such as sodium oxide or potassium hydroxide. As the basic compound, low molecular weight amines such as triethylamine and ethanolamine, and ammonia are preferable in consideration of adhesion and water resistance of soapless CR latex. A monomer such as chloroprene and, if necessary, a molecular weight regulator such as mercaptan are added to the aqueous solution to emulsify the monomer, and then polymerization is performed by adding a radical initiator and a reducing agent as necessary. In order to prevent the increase in the amount of 1,2-bond and isomerized 1,2-bond in CR and maintain the stability of CR, the polymerization temperature is preferably 70 ° C. or lower. In order to further ensure the stability of CR, 60 ° C. or lower is preferable. When the target monomer conversion is reached, a polymerization inhibitor is added to stop the polymerization. Thereafter, the unreacted monomer is distilled off under reduced pressure to obtain a soapless CR latex. Moreover, you may add a general emulsifier and a dispersing agent for the purpose of the stability improvement of latex, viscosity reduction, surface tension reduction, etc. during or after superposition | polymerization. However, the addition amount of these emulsifiers is 2 wt% or less with respect to the CR polymer. If it exceeds 2 wt%, the adhesiveness and water resistance of the CR latex adhesive due to the emulsifier will be significantly reduced. In order to suppress adhesion inhibition by the emulsifier, the emulsifier contained in the latex is more preferably 1 wt% or less.

  Examples of the molecular weight regulator include mercaptans such as n-dodecyl mercaptan, octyl mercaptan, t-butyl mercaptan, thioglycolic acid, thiomalic acid, sulfides such as diisopropylxanthogen disulfide, diethylxanthogen disulfide, diethylthiuram disulfide, and benzyldithiobenzoate. , 2-cyanopropyldithiobenzoate, 3-chloro-2-butenyldithiobenzoate, S- (thiobenzoyl) thioglycolic acid, dithiocarboxylic acid esters such as cumyldithiobenzoate, halogenated hydrocarbons such as iodoform, diphenyl Ethylene, p-chlorodiphenylethylene, p-cyanodiphenylethylene, α-methylstyrene dimer, sulfur and the like can be used. Examples of the radical initiator include benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, paramentane hydroperoxide, dicumyl peroxide, potassium persulfate, peroxide compounds such as ammonium persulfate, and 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] formamide, dimethyl 2,2'-azobis (2-methylpropionate), 4,4′-azobis (4-cyanovaleric acid) 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-methylpropionamidine) dihydrochloride, 2,2'-azobis [N (2-carboxyethyl) -2-methylpropionamidine] can be used azo compounds of tetra-hydrate and the like. As a reducing agent for promoting the decomposition of the peroxide, hydrosulfite, longalite, sodium sulfite, sodium thiosulfate, ferrous sulfate, ascorbic acid, aniline and the like can be used. Examples of the polymerization inhibitor include phenothiazine, 2,6-di-tert-butyl-4-methylphenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), tris (nonylphenyl) phosphite, 4,4′-thiobis (3-methyl-6-tert-butylphenol), N-phenyl-1-naphthylamine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, Hydroquinone, N, N-diethylhydroxylamine and the like can be used.

  The soapless CR latex of the present invention is an inorganic filler such as rosin ester resin, terpene phenol resin, petroleum resin, coumarone indene resin, alkylphenol resin, silica, clay, aluminum paste, titanium oxide, calcium carbonate, etc. Materials, hydrophobic cellulose, polycarboxylates, associative nonionic surfactants, polyalkylene oxides, clay thickeners, polyisocyanate compounds, epoxy resins, oxazoline compounds, carbodiimide compound hardeners, zinc oxide, plastics An agent, a wetting agent, an antifreezing agent, a film-forming aid, and the like can be blended and used as an aqueous adhesive, an aqueous primer, or a sealing agent.

  The soap-press CR latex obtained in the present invention can significantly reduce the amount of emulsifier contained in the conventional CR latex, so that the CR latex adhesive, primer, sealant, capacitor with significantly improved adhesion and water resistance Enables production of electrode binders.

  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 polymer of the present invention were measured under the following conditions by GPC8120 manufactured by Tosoh Corporation (eluent = tetrahydrofuran, flow rate = 1.5 ml / m). min, column temperature = 40 ° C., peak detection = differential refractometer, packed column = TSK-gel (registered trademark, the same applies hereinafter) G7000Hxl / GMHxl / GMHxl / G3000Hxl / guard column HL, molecular weight calculation = polystyrene conversion). The amount of chlorine and sulfur in the polymer was measured by oxygen flask combustion-ion chromatography, and the infrared absorption spectrum of the polymer was measured using Spectrum 2000 manufactured by Perkin Elmer. The monomer conversion during the polymerization was calculated by using Shimadzu Gas Chromatograph GC-17A (GL Sciences capillary column NEUTRABOND-5, flame ionization detector) with benzene as an internal standard.

  The performance evaluation of the saw press CR latex as an adhesive was performed by the following method. CR latex adhesive composition was applied to two No. 9 cotton canvases with a brush, dried in an oven at 80 ° C. for 5 minutes (the above coating and drying operations were repeated three times), and then open time at room temperature (constant) After being left for a long time, it was pressure-bonded with a hand roller. After curing at room temperature for 1 day, it 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 50 mm / min. 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 is evaluated by performing a 180 ° T-type peel test in the same manner as described above after a test piece cured at room temperature for 1 day after being crimped at an open time of 3 hours, immersed in pure water for 3 hours at room temperature, and then wet. did.

Synthesis example 1
In a 100 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 (2) 1.50 g (7.0 mmol), represented by the following general formula (3) After adding 0.85 g (3.5 mmol) of xanthogenic acid disulfide, 5.00 g (58.14 mmol) of methacrylic acid, and 10.00 g of methyl ethyl ketone, the mixture was sufficiently degassed by repeating freeze-deaeration-thawing three times. While stirring in a nitrogen atmosphere, polymerization was carried out for 10 hours while irradiating with ultraviolet rays (UM452 (450 W) manufactured by Ushio Electric Co., Ltd.) from a distance of 80 mm in a constant temperature bath at 30 ° C. At this time, the polymerization conversion rate of methacrylic acid was 80%. Subsequently, 25.00 g (282 mmol) of simple distilled chloroprene and 60 ml of methyl ethyl ketone were added, and after irradiating with ultraviolet rays at 30 ° C. for 12 hours with sufficient stirring under a nitrogen atmosphere, 2,6-di- t-Butylhydroxytoluene was added. The chloroprene conversion was 51% and the total conversion of methacrylic acid was 86%. The number average molecular weight Mn of the produced polymer measured by GPC was 2600, the weight average molecular weight Mw was 5200, and the molecular weight distribution Mw / Mn was 2.0. The chlorine content of the dried polymer is 27.3 wt%, the sulfur content is 2.5 wt%, and the infrared absorption spectrum shown in FIG. 1 shows peaks derived from carboxylic acid in methacrylic acid and unsaturated bonds in CR. Observed. Further, the produced polymer did not dissolve in toluene and chloroform, which are good solvents for CR, but dissolved in acetone, which is a non-solvent. 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 (amphiphilic CR block copolymer-A) having a composition having a methacrylic acid content of about 24 wt% was produced.

合成例２
下記一般式（４）で表されるキサントゲン酸エステル１．５０ｇ（７．６ｍｍｏｌ）、一般式（３）で表されるキサントゲン酸ジスルフィド０．８０ｇ（３．３ｍｍｏｌ）、アクリル酸５．００ｇ（６９．４ｍｍｏｌ）、メチルエチルケトン１１．００ｇを１００ｍｌパイレックス（登録商標）ガラスフラスコに仕込み、合成例１と同じ方法で、３０℃で５時間紫外線照射しながら重合を行った。この時点でのアクリル酸の重合転化率は８０％だった。続いて、単蒸留したクロロプレン２５．００ｇ（２８２ｍｍｏｌ）、メチルエチルケトン６０ｍｌを添加し、窒素雰囲気下、十分攪拌しながら、３０℃で１２時間紫外線照射を行った後、安定剤として２，６−ジ−ｔ−ブチルヒドロキシトルエンを添加した。クロロプレン転化率は５２％、アクリル酸のトータル転化率は８８％だった。ＧＰＣにより測定した生成ポリマーの数平均分子量Ｍｎは２５００、重量平均分子量Ｍｗは５５００及び分子量分布Ｍｗ／Ｍｎは２．２０であった。乾燥ポリマーの塩素含量は２７．３ｗｔ％、イオウ含量は２．２ｗｔ％であり、ＣＲの良溶剤であるトルエン、クロロホルムに溶解しなかったが、非溶媒であるアセトンに溶解した。また、生成ポリマーのアセトン溶液は、トリエチルアミン水溶液に溶解した。以上の結果から、アクリル酸含量約２６ｗｔ％の組成を有するポリアクリル酸−ＣＲジブロック体（両親媒性ＣＲブロック共重合体−Ｂ）が生成したと判断できた。

Synthesis example 2
1.50 g (7.6 mmol) of xanthate represented by the following general formula (4), 0.80 g (3.3 mmol) of xanthate disulfide represented by the general formula (3), 5.00 g of acrylic acid (69 4 mmol), 11.00 g of methyl ethyl ketone was charged into a 100 ml Pyrex (registered trademark) glass flask, and polymerization was carried out in the same manner as in Synthesis Example 1 while irradiating with ultraviolet rays at 30 ° C. for 5 hours. At this time, the polymerization conversion of acrylic acid was 80%. Subsequently, 25.00 g (282 mmol) of simple distilled chloroprene and 60 ml of methyl ethyl ketone were added, and after irradiating with ultraviolet rays at 30 ° C. for 12 hours with sufficient stirring under a nitrogen atmosphere, 2,6-di- t-Butylhydroxytoluene was added. The chloroprene conversion was 52% and the total conversion of acrylic acid was 88%. The number average molecular weight Mn of the produced polymer measured by GPC was 2500, the weight average molecular weight Mw was 5500, and the molecular weight distribution Mw / Mn was 2.20. The dry polymer had a chlorine content of 27.3 wt% and a sulfur content of 2.2 wt%, and did not dissolve in toluene and chloroform, which are good solvents for CR, but dissolved in acetone, which is a non-solvent. Moreover, the acetone solution of the produced polymer was dissolved in an aqueous triethylamine solution. From the above results, it was judged that a polyacrylic acid-CR diblock body (amphiphilic CR block copolymer-B) having a composition having an acrylic acid content of about 26 wt% was produced.

合成例３
下記一般式（５）で表されるカルバミン酸エステル１．５０ｇ（６．３ｍｍｏｌ）、下記一般式（６）で表されるカルバミン酸ジスルフィド０．８０ｇ（２．７ｍｍｏｌ）、メタクリル酸５．００ｇ（５８．１ｍｍｏｌ）、メチルエチルケトン１１．００ｇを１００ｍｌパイレックス（登録商標）ガラスフラスコに仕込み、合成例１と同じ方法で、３０℃で１０時間紫外線照射しながら重合を行った。この時点でのメタクリル酸の重合転化率は８３％だった。続いて、単蒸留したクロロプレン２５．００ｇ（２８２ｍｍｏｌ）、メチルエチルケトン６０ｍｌを添加し、以下、合成例１と同様に重合を行った。クロロプレン転化率は５０％、メタクリル酸のトータル転化率は８６％だった。ＧＰＣにより測定した生成ポリマーの数平均分子量Ｍｎは２８００、重量平均分子量Ｍｗは５８００及び分子量分布Ｍｗ／Ｍｎは２．１０であった。乾燥ポリマーの塩素含量は２７．３ｗｔ％、イオウ含量は２．２ｗｔ％であり、ＣＲの良溶剤であるトルエン、クロロホルムに溶解しなかったが、非溶媒であるアセトンに溶解した。また、生成ポリマーのアセトン溶液は、トリエチルアミン水溶液に溶解した。以上の結果から、メタクリル酸含量約２６ｗｔ％の組成を有するポリメタクリル酸−ＣＲジブロック体（両親媒性ＣＲブロック共重合体−Ｃ）が生成したと判断できた。

Synthesis example 3
1.50 g (6.3 mmol) of carbamic acid ester represented by the following general formula (5), 0.80 g (2.7 mmol) of carbamic acid disulfide represented by the following general formula (6), 5.00 g of methacrylic acid ( 58.1 mmol) and 11.00 g of methyl ethyl ketone were charged into a 100 ml Pyrex (registered trademark) glass flask, and polymerization was carried out in the same manner as in Synthesis Example 1 while irradiating with ultraviolet rays at 30 ° C. for 10 hours. At this point, the polymerization conversion rate of methacrylic acid was 83%. Subsequently, 25.00 g (282 mmol) of simply distilled chloroprene and 60 ml of methyl ethyl ketone were added, and polymerization was performed in the same manner as in Synthesis Example 1 below. The chloroprene conversion was 50% and the total conversion of methacrylic acid was 86%. The number average molecular weight Mn of the produced polymer measured by GPC was 2800, the weight average molecular weight Mw was 5800, and the molecular weight distribution Mw / Mn was 2.10. The dry polymer had a chlorine content of 27.3 wt% and a sulfur content of 2.2 wt%, and did not dissolve in toluene and chloroform, which are good solvents for CR, but dissolved in acetone, which is a non-solvent. 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 (amphiphilic CR block copolymer-C) having a composition having a methacrylic acid content of about 26 wt% was produced.

合成例４
合成例２において、アクリル酸及びメチルエチルケトンの代わりに、クロロプレン５．００ｇ（５６．５ｍｍｏｌ）、無水マレイン酸５．５０ｇ（５６．１ｍｍｏｌ）及びベンゼン２０．００ｇを仕込んだ他は全て合成例２と同じ仕込処方で、３０℃で１２時間紫外線照射しながら重合を行った。この時点でのクロロプレン及び無水マレイン酸の重合転化率は７０％だった。続いて、単蒸留したクロロプレン２０．００ｇ（２２６ｍｍｏｌ）、ベンゼン２０ｍｌを添加し、３０℃で１２時間紫外線照射しながら重合を行った。クロロプレンのトータル転化率は５０％、メタクリル酸のトータル転化率は８５％だった。ＧＰＣにより測定した生成ポリマーの数平均分子量Ｍｎは２２００、重量平均分子量Ｍｗは５０００及び分子量分布Ｍｗ／Ｍｎは２．２７であった。乾燥ポリマーの塩素含量は２９．９ｗｔ％、イオウ含量は２．９ｗｔ％であり、ポリマーのアセトン溶液は、トリエチルアミン水溶液に溶解したことから、無水マレイン酸含量約２１ｗｔ％の組成を有するポリ（クロロプレン／無水マレイン酸共重合体）−ＣＲジブロック体（両親媒性ＣＲブロック共重合体−Ｄ）が生成したと判断できた。

Synthesis example 4
Synthetic Example 2 was the same as Synthetic Example 2 except that 5.00 g (56.5 mmol) of chloroprene, 5.50 g (56.1 mmol) of maleic anhydride and 20.00 g of benzene were used instead of acrylic acid and methyl ethyl ketone. Polymerization was carried out while irradiating with ultraviolet rays at 30 ° C. for 12 hours in a charged formulation. At this time, the polymerization conversion of chloroprene and maleic anhydride was 70%. Subsequently, 20.00 g (226 mmol) of simply distilled chloroprene and 20 ml of benzene were added, and polymerization was performed while irradiating with ultraviolet rays at 30 ° C. for 12 hours. The total conversion of chloroprene was 50% and the total conversion of methacrylic acid was 85%. The number average molecular weight Mn of the produced polymer measured by GPC was 2200, the weight average molecular weight Mw was 5000, and the molecular weight distribution Mw / Mn was 2.27. The chlorine content of the dried polymer was 29.9 wt%, the sulfur content was 2.9 wt%, and the acetone solution of the polymer was dissolved in an aqueous triethylamine solution, so that poly (chloroprene / It was judged that a maleic anhydride copolymer) -CR diblock body (amphiphilic CR block copolymer-D) was produced.

Synthesis example 5
In Synthesis Example 2, the same formulation as in Synthesis Example 2 except that 5.00 g (56.5 mmol) of chloroprene and 6.50 g (56.1 mmol) of maleic acid were used instead of 5.00 g of acrylic acid. The polymerization was carried out with ultraviolet irradiation for 12 hours. At this point, the polymerization conversions of chloroprene and maleic acid were 50% and 40%. Subsequently, 25.00 g (282 mmol) of simple distilled chloroprene and 40 ml of methyl ethyl ketone were added, and polymerization was performed while irradiating with ultraviolet rays at 30 ° C. for 12 hours. The total conversion of chloroprene was 55%, and the total conversion of maleic acid was 65%. The number average molecular weight Mn of the produced polymer measured by GPC was 2800, the weight average molecular weight Mw was 5900, and the molecular weight distribution Mw / Mn was 2.11. The chlorine content of the dried polymer was 28.2 wt%, the sulfur content was 2.5 wt%, and the acetone solution of the polymer was dissolved in an aqueous triethylamine solution, so that poly (chloroprene / maleic acid) having a composition with a maleic acid content of about 21 wt% was obtained. It was judged that an acid copolymer) -CR diblock body (amphiphilic CR block copolymer-E) was produced.

Synthesis Example 6
In a 200 ml brown flask equipped with a nitrogen gas inlet tube and a reflux condenser, 1.14 g (5.00 mmol) of a dithiocarboxylic acid ester represented by the following general formula (7), 5.01 g (58.19 mmol) of methacrylic acid, 2 , 2′-azobis (2-methylpropionitrile) 0.026 g (0.16 mmol) and dioxane 11.35 g were charged into a 100 ml eggplant-shaped flask, and freeze-degas-thaw was repeated three times to sufficiently degas. Then, the mixture was heated in an oil bath at 80 ° C. while stirring with a magnetic stirrer in a nitrogen atmosphere. After heating for 4 hours, it was cooled to room temperature. At this time, the polymerization conversion rate of methacrylic acid was 78%. Subsequently, 24.52 g (277 mmol) of simple distilled chloroprene, 60 ml of tetrahydrofuran, 0.17 g (0.71 mmol) of 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2,4 -Dimethylvaleronitrile) 0.14 g (15.46 mmol) was added, and after freeze-degas-thaw was repeated three times and thoroughly degassed, an oil at 50 ° C. was stirred with a magnetic stirrer in a nitrogen atmosphere. Heated in the bath. After heating for 32 hours, 2,6-di-t-butylhydroxytoluene was added to terminate the polymerization. The chloroprene conversion was 61% and the total conversion of methacrylic acid was 91%. The polymerization solution was poured into a large amount of pure water to precipitate a polymer. The number average molecular weight Mn measured by GPC was 4600, the weight average molecular weight Mw was 6200, and the molecular weight distribution Mw / Mn was 1.4. The chlorine content of the dried polymer was 28.7 wt%, and the sulfur content was 1.5 wt%. The resulting polymer did not dissolve in toluene and chloroform, which are good solvents for CR, but dissolved in acetone, which is a non-solvent. 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 (amphiphilic CR block copolymer-F) having a composition having a methacrylic acid content of 23.04 wt% was produced.

合成例７
窒素ガス導入管及び還流冷却管を備えた２００ｍｌ褐色フラスコに下記一般式（８）で表されるジチオカルボン酸エステル２．５０ｇ（１１．７８ｍｍｏｌ）、アクリル酸５．００ｇ（６９．３９ｍｍｏｌ）、２，２’−アゾビス（２−メチルプロピオニトリル）０．０２５ｇ（０．１３ｍｍｏｌ）、ジオキサン５．３ｇ、テトラヒドロフラン５．０ｇを仕込んだ後、凍結−脱気−融解を３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、８０℃のオイルバスで４時間加熱後、室温まで冷却した。この時点でのアクリル酸の重合転化率は９１％だった。続いて、単蒸留したクロロプレン６０．００ｇ（６７７．９７ｍｍｏｌ）、テトラヒドロフラン９０ｍｌ、２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．２ｇ（０．８１ｍｍｏｌ）を添加し、凍結−脱気−融解を３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℃で加熱した。４２時間加熱後、２，６−ジ−ｔ−ブチルヒドロキシルトルエンを添加し、重合を停止した。クロロプレン転化率は６８％、アクリル酸のトータル転化率は９６％だった。重合溶液を多量の純水に注ぎ、ポリマーを析出させた。ＧＰＣにより測定した数平均分子量Ｍｎは５１００、重量平均分子量Ｍｗは７９００及び分子量分布Ｍｗ／Ｍｎは１．５５であった。乾燥ポリマー中の塩素含量は３３．７ｗｔ％、イオウ含量は１．６ｗｔ％であった。生成ポリマーのテトラヒドロフラン溶液は、トリエチルアミン水溶液に溶解したことから、ポリアクリル酸−ＣＲジブロック体（両親媒性ＣＲブロック共重合体−Ｇ）が生成したと判断した。

Synthesis example 7
In a 200 ml brown flask equipped with a nitrogen gas inlet tube and a reflux condenser, 2.50 g (11.78 mmol) of dithiocarboxylic acid ester represented by the following general formula (8), 5.00 g (69.39 mmol) of acrylic acid, 2 , 2′-azobis (2-methylpropionitrile) 0.025 g (0.13 mmol), dioxane 5.3 g, and tetrahydrofuran 5.0 g were added, and freeze-degas-thaw was repeated three times to sufficiently degas. Then, while stirring with a magnetic stirrer in a nitrogen atmosphere, the mixture was heated in an oil bath at 80 ° C. for 4 hours and then cooled to room temperature. At this time, the polymerization conversion of acrylic acid was 91%. Subsequently, 60.00 g (677.97 mmol) of simple distilled chloroprene, 90 ml of tetrahydrofuran and 0.2 g (0.81 mmol) of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, followed by freeze-deaeration. -After repeating the melting three times and sufficiently degassing, the mixture was heated at 50 ° C while stirring with a magnetic stirrer in a nitrogen atmosphere. After heating for 42 hours, 2,6-di-t-butylhydroxyl toluene was added to terminate the polymerization. The chloroprene conversion was 68% and the total conversion of acrylic acid was 96%. The polymerization solution was poured into a large amount of pure water to precipitate a polymer. The number average molecular weight Mn measured by GPC was 5100, the weight average molecular weight Mw was 7900, and the molecular weight distribution Mw / Mn was 1.55. The chlorine content in the dried polymer was 33.7 wt% and the sulfur content was 1.6 wt%. Since the tetrahydrofuran solution of the produced polymer was dissolved in an aqueous triethylamine solution, it was judged that a polyacrylic acid-CR diblock body (amphiphilic CR block copolymer-G) was produced.

合成例８
窒素ガス導入管及び還流冷却管を備えた２００ｍｌ褐色フラスコに下記一般式（９）で表されるジチオカルボン酸エステル１．００ｇ（４．５６ｍｍｏｌ）、メタクリル酸４．８０ｇ（５５．７６ｍｍｏｌ）、２，２’−アゾビス（２−メチルプロピオニトリル）０．０２０ｇ（０．１２ｍｍｏｌ）、ジオキサン１１．００ｇを１００ｍｌナス型フラスコに仕込んだ後、凍結−脱気−融解を３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、８０℃のオイルバスで加熱した。４時間加熱後、室温まで冷却した。この時点でのメタクリル酸の重合転化率は７４％だった。続いて、単蒸留したクロロプレン２０．００ｇ（２２６．０ｍｍｏｌ）、２，３−ジクロロ−１，３−ブタジエン５．００ｇ（４０．７ｍｍｏｌ）、テトラヒドロフラン６０ｍｌ、２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．２０ｇ（０．８１ｍｍｏｌ）を添加し、凍結−脱気−融解を３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℃のオイルバスで加熱した。３２時間加熱後、２，６−ジ−ｔ−ブチルヒドロキシトルエンを添加し、重合を停止した。クロロプレン転化率は６５％、２，３−ジクロロ−１，３−ブタジエン転化率は８７％、メタクリル酸のトータル転化率は９２％だった。重合溶液を多量の純水に注ぎ、ポリマーを析出させた。ＧＰＣにより測定した数平均分子量Ｍｎは５３００、重量平均分子量Ｍｗは８５００及び分子量分布Ｍｗ／Ｍｎは１．６であった。乾燥ポリマーの塩素含量は３５．３ｗｔ％、イオウ含量は１．３ｗｔ％であり、生成ポリマーのテトラヒドロフラン溶液は、トリエチルアミン水溶液に溶解したことから、メタクリル酸含量２０．４ｗｔ％の組成を有するポリメタクリル酸−ＣＲジブロック体（両親媒性ＣＲブロック共重合体−Ｈ）が生成したと判断できた。

Synthesis example 8
In a 200 ml brown flask equipped with a nitrogen gas inlet tube and a reflux condenser, a dithiocarboxylic acid ester 1.00 g (4.56 mmol) represented by the following general formula (9), methacrylic acid 4.80 g (55.76 mmol), 2 , 2′-azobis (2-methylpropionitrile) 0.020 g (0.12 mmol) and dioxane 11.00 g were charged into a 100 ml eggplant type flask, and then freeze-degas-thaw was repeated three times to sufficiently degas. Then, the mixture was heated in an oil bath at 80 ° C. while stirring with a magnetic stirrer in a nitrogen atmosphere. After heating for 4 hours, it was cooled to room temperature. At this time, the polymerization conversion rate of methacrylic acid was 74%. Subsequently, 20.00 g (226.0 mmol) of chloroprene obtained by simple distillation, 5.00 g (40.7 mmol) of 2,3-dichloro-1,3-butadiene, 60 ml of tetrahydrofuran, 2,2′-azobis (2,4- Dimethylvaleronitrile) 0.20 g (0.81 mmol) was added, freeze-degassing-thaw was repeated three times, and after sufficient degassing, an oil bath at 50 ° C. was stirred with a magnetic stirrer in a nitrogen atmosphere. And heated. After heating for 32 hours, 2,6-di-t-butylhydroxytoluene was added to terminate the polymerization. The chloroprene conversion was 65%, the 2,3-dichloro-1,3-butadiene conversion was 87%, and the total conversion of methacrylic acid was 92%. The polymerization solution was poured into a large amount of pure water to precipitate a polymer. The number average molecular weight Mn measured by GPC was 5300, the weight average molecular weight Mw was 8500, and the molecular weight distribution Mw / Mn was 1.6. The dry polymer had a chlorine content of 35.3 wt% and a sulfur content of 1.3 wt%. Since the tetrahydrofuran solution of the resulting polymer was dissolved in an aqueous triethylamine solution, polymethacrylic acid having a composition with a methacrylic acid content of 20.4 wt% was obtained. It was judged that a -CR diblock body (amphiphilic CR block copolymer-H) was produced.

合成例９
窒素ガス導入管及び還流冷却管を備えた２００ｍｌ褐色フラスコに一般式（９）で表されるジチオカルボン酸エステル１．５０ｇ（５．００ｍｍｏｌ）、無水マレイン酸２．００ｇ（２０．４０ｍｍｏｌ）、スチレン２．５５ｇ（２４．４８ｍｍｏｌ）、４，４’−アゾビス（４−シアノペンタン酸）６５．０ｍｇ（０．２３ｍｍｏｌ）、ジオキサン１０．００ｇを１００ｍｌナス型フラスコに仕込んだ後、凍結−脱気−融解を３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、８０℃のオイルバスで加熱した。１０時間加熱後、室温まで冷却した。この時点でのスチレン、無水マレイン酸の重合転化率は７２％だった。続いて、単蒸留したクロロプレン２６．００ｇ（２９４ｍｍｏｌ）、テトラヒドロフラン６０ｍｌ、２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．１０ｇ（１０．３３ｍｍｏｌ）を添加し、凍結−脱気−融解を３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℃のオイルバスで加熱した。３２時間加熱後、２，６−ジ−ｔ−ブチルヒドロキシトルエンを添加し、重合を停止した。クロロプレン転化率は５８％だった。重合溶液を多量の純水に注ぎ、ポリマーを析出させた。ＧＰＣにより測定した数平均分子量Ｍｎは４６００、重量平均分子量Ｍｗは６２００及び分子量分布Ｍｗ／Ｍｎは１．４であった。乾燥ポリマーの塩素含量は３２．８ｗｔ％、イオウ含量は１．７ｗｔ％であり、生成ポリマーは、ＣＲの良溶剤であるトルエン、クロロホルムに溶解しなかったが、非溶媒であるアセトンに溶解した。また、生成ポリマーのアセトン溶液は、トリエチルアミン水溶液に溶解した。以上の結果から、無水マレイン酸／スチレン交互共重合体−ＣＲジブロック体（両親媒性ＣＲブロック共重合体−Ｉ）が生成したと判断できた。

Synthesis Example 9
In a 200 ml brown flask equipped with a nitrogen gas introduction tube and a reflux condenser, 1.50 g (5.00 mmol) of dithiocarboxylic acid ester represented by the general formula (9), 2.00 g (20.40 mmol) of maleic anhydride, styrene 2.55 g (24.48 mmol), 4,4′-azobis (4-cyanopentanoic acid) 65.0 mg (0.23 mmol), and dioxane 10.00 g were charged into a 100 ml eggplant-shaped flask, and then freeze-deaerated— After thorough degassing by repeating the melting three times, the mixture was heated in an oil bath at 80 ° C. while stirring with a magnetic stirrer under a nitrogen atmosphere. After heating for 10 hours, it was cooled to room temperature. At this time, the polymerization conversion of styrene and maleic anhydride was 72%. Subsequently, 26.00 g (294 mmol) of simple distilled chloroprene, 60 ml of tetrahydrofuran, and 0.10 g (10.33 mmol) of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, followed by freeze-deaeration-thawing. After repeating the above three times for sufficient deaeration, the mixture was heated in a 50 ° C. oil bath while stirring with a magnetic stirrer under a nitrogen atmosphere. After heating for 32 hours, 2,6-di-t-butylhydroxytoluene was added to terminate the polymerization. The chloroprene conversion was 58%. The polymerization solution was poured into a large amount of pure water to precipitate a polymer. The number average molecular weight Mn measured by GPC was 4600, the weight average molecular weight Mw was 6200, and the molecular weight distribution Mw / Mn was 1.4. The chlorine content of the dried polymer was 32.8 wt%, the sulfur content was 1.7 wt%, and the product polymer was not dissolved in toluene and chloroform, which are good solvents for CR, but dissolved in acetone, which is a non-solvent. Moreover, the acetone solution of the produced polymer was dissolved in an aqueous triethylamine solution. From the above results, it was judged that a maleic anhydride / styrene alternating copolymer-CR diblock body (amphiphilic CR block copolymer-I) was produced.

Synthesis Example 10
In a 200 ml brown flask equipped with a nitrogen gas inlet tube and a reflux condenser, 3.19 g (13.40 mmol) of dithiocarboxylic acid ester represented by the general formula (9), 5.00 g (48.00 mmol) of chloroprene, maleic anhydride 4.65 g (47.40 mmol), 4,4′-azobis (4-cyanopentanoic acid) 0.14 g (0.50 mmol), and dioxane 22.00 g were charged into a 100 ml eggplant type flask, and then freeze-deaerated— After thorough degassing by repeating the melting three times, the mixture was heated in an oil bath at 60 ° C. while stirring with a magnetic stirrer in a nitrogen atmosphere. After heating for 10 hours, it was cooled to room temperature. At this time, the polymerization conversion rates of chloroprene and maleic anhydride were 74% and 79%. Subsequently, 25.00 g (282.5 mmol) of simply distilled chloroprene, 60 ml of tetrahydrofuran and 0.20 g (0.81 mmol) of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, followed by freeze-deaeration. -Thawing was repeated three times, and after sufficient deaeration, the mixture was heated in a 50 ° C oil bath while stirring with a magnetic stirrer under a nitrogen atmosphere. After heating for 32 hours, 2,6-di-t-butylhydroxytoluene was added to terminate the polymerization. The chloroprene conversion was 65% and the total conversion of maleic anhydride was 100%. The polymerization solution was poured into a large amount of pure water to precipitate a polymer. The number average molecular weight Mn measured by GPC was 2300, the weight average molecular weight Mw was 3300, and the molecular weight distribution Mw / Mn was 1.4. Since the dry polymer had a chlorine content of 33.6 wt% and a sulfur content of 2.5 wt%, and the tetrahydrofuran solution of the resulting polymer was dissolved in an aqueous triethylamine solution, a chloroprene / maleic anhydride copolymer-CR diblock ( It was judged that an amphiphilic CR block copolymer-J) was produced.

Synthesis Example 11
In a 200 ml brown flask equipped with a nitrogen gas inlet tube and a reflux condenser, 1.50 g (5.00 mmol) of dithiocarboxylic acid ester represented by the general formula (9), 1.00 g (10.20 mmol) of maleic anhydride, styrene 1.28 g (12.24 mmol), methacrylic acid 1.05 g (12.24 mmol), 4,4′-azobis (4-cyanopentanoic acid) 65.0 mg (0.23 mmol), dioxane 10.00 g 100 ml eggplant type After charging the flask, freeze-deaeration-thaw was repeated three times and sufficiently deaerated, and then heated in an oil bath at 80 ° C. while stirring with a magnetic stirrer under a nitrogen atmosphere. After heating for 10 hours, it was cooled to room temperature. At this time, the polymerization conversion of styrene and maleic anhydride was 76%, and the polymerization conversion of methacrylic acid was 71%. Subsequently, 26.00 g (294 mmol) of simple distilled chloroprene, 60 ml of tetrahydrofuran, and 0.10 g (10.33 mmol) of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, followed by freeze-deaeration-thawing. After repeating the above three times for sufficient deaeration, the mixture was heated in a 50 ° C. oil bath while stirring with a magnetic stirrer under a nitrogen atmosphere. After heating for 32 hours, 2,6-di-t-butylhydroxytoluene was added to terminate the polymerization. The chloroprene conversion was 59%. The polymerization solution was poured into a large amount of pure water to precipitate a polymer. The number average molecular weight Mn measured by GPC was 4,800, the weight average molecular weight Mw was 8,200, and the molecular weight distribution Mw / Mn was 1.7. The chlorine content of the dried polymer was 34.0 wt% and the sulfur content was 1.7 wt%. The produced polymer was not dissolved in toluene and chloroform, which are good solvents for CR, but dissolved in acetone as a non-solvent. Moreover, the acetone solution of the produced polymer was dissolved in an aqueous triethylamine solution. From the above results, it was judged that a maleic anhydride / styrene / methacrylic acid copolymer-CR diblock body (amphiphilic CR block copolymer-K) was produced.

Synthesis Example 12
In a 200 ml brown flask equipped with a nitrogen gas inlet tube and a reflux condenser, 1.68 g (7.60 mmol) of dithiocarboxylic acid ester represented by the general formula (7), 5.00 g (56.5 mmol) of chloroprene, and maleic acid 6 .50 g (56.1 mmol), 4,4′-azobis (4-cyanopentanoic acid) 195.0 mg (0.69 mmol) and dioxane 30.00 g were charged, and then freeze-degas-thaw was repeated three times. After sufficiently deaerated, the mixture was heated in an oil bath at 50 ° C. while stirring with a magnetic stirrer in a nitrogen atmosphere. After heating for 48 hours, it was cooled to room temperature. At this time, the polymerization conversion of chloroprene was 71%, and the polymerization conversion of maleic acid was 45%. Subsequently, 26.00 g (294 mmol) of simple distilled chloroprene, 60 ml of tetrahydrofuran, and 0.10 g (10.33 mmol) of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, followed by freeze-deaeration-thawing. After repeating the above three times for sufficient deaeration, the mixture was heated in a 50 ° C. oil bath while stirring with a magnetic stirrer under a nitrogen atmosphere. After heating for 32 hours, 2,6-di-t-butylhydroxytoluene was added to terminate the polymerization. The total conversion of chloroprene was 65% and the total conversion of maleic acid was 70%. The polymerization solution was poured into a large amount of pure water to precipitate a polymer. The number average molecular weight Mn measured by GPC was 3900, the weight average molecular weight Mw was 5300, and the molecular weight distribution Mw / Mn was 1.35. The chlorine content of the dried polymer was 33.0 wt%, the sulfur content was 1.9 wt%, and the resulting polymer was not dissolved in toluene and chloroform, which are good solvents for CR, but dissolved in acetone, which is a non-solvent. Moreover, the acetone solution of the produced polymer was dissolved in an aqueous triethylamine solution. From the above results, it was judged that a chloroprene / maleic acid copolymer-CR diblock body (amphiphilic CR block copolymer-L) having a maleic acid content of about 18 wt% was produced.

Example 1
In a 200 ml flask equipped with a nitrogen gas introduction tube, a reflux condenser, and a stirrer, 3.60 g of the amphiphilic CR block copolymer-A obtained in Synthesis Example 1 (methacrylic acid content: 9.3 mmol, all charged monomers) 12 wt%) and 7.00 g of acetone were added to dissolve the polymer, and then 1.19 g (11.80 mmol) of triethylamine and 42.00 g of pure water were added. After distilling off acetone under reduced pressure with an aspirator, 30.00 g (339 mmol) of chloroprene, 1.01 g (5 mmol) of n-dodecyl mercaptan, 30 mg of 2,2′-azobis (2-methylpropionitrile) (0 .18 mmol, added as a benzene solution), and after degassing the system sufficiently while flowing a small amount of nitrogen under stirring, polymerization was carried out in a nitrogen atmosphere at 50 ° C., resulting in emulsification without causing scaling. Polymerization proceeded. After heating for 3 hours, 0.05 g of 2,6-t-butyl-4-methylphenol was added to terminate the polymerization. The polymerization conversion rate of chloroprene was 80%. Unreacted monomers and water were distilled off using a rotary evaporator to obtain CR Latex-A (solid content: 37 wt%, methacrylic acid content for all polymers: about 3.0 wt%, emulsifier content: 0 wt% for chloroprene polymer) . Even when 5 times the amount of methanol was added to the obtained latex, no polymer was precipitated and the latex was extremely stable. Therefore, it was judged that a soapless CR latex was obtained.

  Using the obtained CR latex-A, an adhesive composition was prepared with the formulation shown in Table 1, and the adhesive performance was evaluated. The results are shown in Table 1. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

実施例２
実施例１において、合成例１で得た両親媒性ＣＲブロック共重合体−Ａの代わりに合成例２で得た両親媒性ＣＲブロック共重合体−Ｂ３．００ｇ（アクリル酸含量〜１０．６ｍｍｏｌ、全仕込モノマーの１０ｗｔ％）を用い、トリエチルアミンを１．２９ｇ（１２．８ｍｍｏｌ）添加した他は全て実施例１と同じ条件でクロロプレンの乳化重合を行った。ロータリーエバポレーターで未反応モノマー及び水分を留去しＣＲラテックス−Ｂを得た（固形分３７ｗｔ％、全ポリマーに対するアクリル酸含量は約３ｗｔ％、乳化剤含量はクロロプレン系ポリマーに対して０ｗｔ％）。得られたラテックスに５倍量のメタノールを添加してもポリマーは全く析出せず、ラテックスは極めて安定だったことから、ソープレスＣＲラテックスが得られたと判断した。

Example 2
In Example 1, instead of the amphiphilic CR block copolymer-A obtained in Synthesis Example 1, amphiphilic CR block copolymer-B 3.00 g obtained in Synthesis Example 2 (acrylic acid content ˜10.6 mmol) The emulsion polymerization of chloroprene was carried out under the same conditions as in Example 1, except that 1.29 g (12.8 mmol) of triethylamine was added. Unreacted monomers and water were distilled off using a rotary evaporator to obtain CR Latex-B (solid content: 37 wt%, acrylic acid content for all polymers: about 3 wt%, and emulsifier content: 0 wt% for chloroprene polymer). Even when 5 times the amount of methanol was added to the obtained latex, no polymer was precipitated and the latex was extremely stable. Therefore, it was judged that a soapless CR latex was obtained.

  Using the obtained CR latex-B, an adhesive composition was prepared with the formulation shown in Table 1, and the adhesive performance was evaluated. The results are shown in Table 1. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 3
In Example 1, instead of the amphiphilic CR block copolymer-A obtained in Synthesis Example 1, amphiphilic CR block copolymer-C 3.20 g obtained in Synthesis Example 3 (methacrylic acid content: 9.5 mmol) The emulsion polymerization of chloroprene was carried out under the same conditions as in Example 1 except that 1.15 g (11.4 mmol) of triethylamine was added. Unreacted monomers and water were distilled off using a rotary evaporator to obtain CR Latex-C (solid content 37 wt%, methacrylic acid content with respect to all polymers was about 3 wt%, and emulsifier content was 0 wt% with respect to chloroprene polymer). Even when 5 times the amount of methanol was added to the obtained latex, no polymer was precipitated and the latex was extremely stable. Therefore, it was judged that a soapless CR latex was obtained.

  Using the obtained CR latex-C, an adhesive composition was prepared with the formulation shown in Table 1, and the adhesive performance was evaluated. The results are shown in Table 1. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 4
In a 200 ml flask equipped with a nitrogen gas inlet tube, a reflux condenser and a stirrer, 2.00 g of amphiphilic CR block copolymer-D obtained in Synthesis Example 4 (maleic anhydride content ˜5.6 mmol, all charged monomers) 6.7 wt%) and 6.00 g of acetone were added to dissolve the polymer, and then 1.36 g (13.5 mmol) of triethylamine and 42.00 g of pure water were added. After distilling off acetone under reduced pressure with an aspirator, 25.00 g (282 mmol) of chloroprene, 5.00 g (40.7 mmol) of 2,3-dichloro-1,3-butadiene, and 1.00 g of n-dodecyl mercaptan ( 5 mmol), 2,2′-azobis (2-methylpropionitrile) 30 mg (0.18 mmol, added as a benzene solution) was added, and the emulsion polymerization was carried out in the same manner as in Example 1; Emulsion polymerization proceeded without generation. After heating for 3 hours, 0.05 g of 2,6-t-butyl-4-methylphenol was added to terminate the polymerization. The polymerization conversion rates of chloroprene and 2,3-dichloro-1,3-butadiene were 74% and 86%, respectively. Unreacted monomers and water were distilled off using a rotary evaporator to obtain CR Latex-D (solid content: 37 wt%, maleic anhydride content with respect to all polymers: about 3 wt%, emulsifier content: 0 wt% with respect to chloroprene polymer). Since the latex was extremely stable, it was judged that soapless CR latex was obtained.

  Using the obtained CR latex-D, an adhesive composition was prepared with the formulation shown in Table 1, and the adhesive performance was evaluated. The results are shown in Table 1. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 5
In Example 4, instead of the amphiphilic CR block copolymer-D obtained in Synthesis Example 4, the amphiphilic CR block copolymer-E 2.5 g obtained in Synthesis Example 5 (maleic acid content to 5.1 mmol) 8.3 wt% of all charged monomers), and all the same amounts of chloroprene and 2,3-dichloro-1,3-butadiene were used in the same manner as in Example 4 except that 1.13 g (12.15 mmol) of triethylamine was charged. Emulsion copolymerization was performed. As a result, the emulsion polymerization proceeded without causing scaling, and after heating for 3 hours, 0.05 g of 2,6-t-butyl-4-methylphenol was added to terminate the polymerization. The polymerization conversion rates of chloroprene and 2,3-dichloro-1,3-butadiene were 75% and 89%, respectively. Unreacted monomer and water were distilled off using a rotary evaporator to obtain CR Latex-E (solid content 37 wt%, maleic acid content with respect to the total polymer was about 2.3 wt%, and the emulsifier content was 0 wt% with respect to the chloroprene polymer). . Since the latex was extremely stable, it was judged that soapless CR latex was obtained.

  Using the obtained CR latex-E, an adhesive composition was prepared with the formulation shown in Table 1, and the adhesive performance was evaluated. The results are shown in Table 1. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 6
In a 200 ml flask equipped with a nitrogen gas inlet tube, a reflux condenser, and a stirrer, 3.57 g of the amphiphilic CR block copolymer-F obtained in Synthesis Example 6 (methacrylic acid content: 8.7 mmol, total charged monomers: 12 wt%) and 7.05 g of acetone were added to dissolve the polymer, and then 1.07 g (10.62 mmol) of triethylamine and 41.38 g of pure water were added. After distilling off acetone under reduced pressure with an aspirator, 30.05 g (339.6 mmol) of chloroprene, 1.01 g (5 mmol) of n-dodecyl mercaptan, 2,2′-azobis (2-methylpropionitrile) 32 .84 mg (0.20 mmol, added as a benzene solution) was added, the system was thoroughly degassed while flowing a small amount of nitrogen under stirring, and then polymerization was performed at 50 ° C. in a nitrogen atmosphere, resulting in scaling. Emulsion polymerization proceeded without. After heating for 3 hours, 0.05 g of 2,6-t-butyl-4-methylphenol was added to terminate the polymerization. The polymerization conversion rate of chloroprene was 80%. Unreacted monomers and water were distilled off using a rotary evaporator to obtain CR Latex-F (solid content: 37 wt%, methacrylic acid content for all polymers: about 3.0 wt%, emulsifier content: 0 wt% for chloroprene polymer) . Even when 5 times the amount of methanol was added to the obtained latex, no polymer was precipitated and the latex was extremely stable. Therefore, it was judged that a soapless CR latex was obtained.

  Using the resulting CR latex-F, an adhesive composition was prepared with the formulation shown in Table 2, and the adhesive performance was evaluated. The results are shown in Table 2. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

実施例７
クロロプレン３０．０５ｇの代わりにクロロプレン２５．５５ｇ（２８８．７ｍｍｏｌ）、２，３−ジクロロ−１，３−ブタジエン４．５ｇ（３６．６ｍｍｏｌ）を用いた他は全て実施例６と同じ方法で重合を行った。その結果、スケーリングが発生することなく乳化重合が進行し、３時間重合後のクロロプレン及び２，３−ジクロロ−１，３−ブタジエンの重合転化率は８１％及び９８％だった。ロータリーエバポレーターで未反応モノマー及び水分を留去したところ、実施例１と同様、安定なソープレスＣＲラテックス−Ｇが得られた（固形分４０％、全ポリマーに対するメタクリル酸含量は約３ｗｔ％、乳化剤含量はクロロプレン系ポリマーに対して０ｗｔ％）。

Example 7
Polymerization was carried out in the same manner as in Example 6 except that 25.55 g (288.7 mmol) of chloroprene and 4.5 g (36.6 mmol) of 2,3-dichloro-1,3-butadiene were used instead of 30.05 g of chloroprene. Went. As a result, emulsion polymerization proceeded without causing scaling, and the polymerization conversion rates of chloroprene and 2,3-dichloro-1,3-butadiene after polymerization for 3 hours were 81% and 98%. When unreacted monomers and water were distilled off using a rotary evaporator, a stable soap press CR latex-G was obtained in the same manner as in Example 1 (solid content 40%, methacrylic acid content with respect to the total polymer was about 3 wt%, emulsifier The content is 0 wt% with respect to the chloroprene polymer).

  Using the obtained CR latex-G, an adhesive composition was prepared with the formulation shown in Table 2, and the adhesive performance was evaluated. The results are shown in Table 2. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 8
Polymerization was carried out in the same manner as in Example 6 except that 27.0 g (305.1 mmol) of chloroprene and 2.05 g (20.81 mmol) of 2-hydroxypropyl methacrylate were used instead of 30.05 g of chloroprene. Emulsion polymerization proceeded without scaling, and the polymerization conversion rates of chloroprene and 2-hydroxypropyl methacrylate after 3 hours of polymerization were 83% and 25%. When unreacted monomers and water were distilled off using a rotary evaporator, a stable soap-press CR latex-H was obtained in the same manner as in Example 6 (solid content 38 wt%, methacrylic acid content with respect to the total polymer was about 3 wt%, emulsifier The content is 0 wt% with respect to the chloroprene polymer).

  Using the obtained CR latex-H, an adhesive composition was prepared with the formulation shown in Table 2, and the adhesive performance was evaluated. The results are shown in Table 2. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 9
In a 200 ml flask equipped with a nitrogen gas inlet tube, a reflux condenser, and a stirrer, 4.00 g of amphiphilic CR block copolymer-G obtained in Synthesis Example 7 (acrylic acid content ˜4.8 mmol, all charged monomers) 13 wt%) and 7.00 g of tetrahydrofuran were added to dissolve the polymer, and then 0.60 g (4.94 mmol) of triethylamine and 40.00 g of pure water were added. To this was added 31.02 g (mmol) of chloroprene that had been simply distilled, 1.00 g (mmol) of n-dodecyl mercaptan, and 60 mg of potassium persulfate, and the system was sufficiently deaerated while flowing a small amount of nitrogen under stirring. As a result of polymerization at 40 ° C. in a nitrogen atmosphere, emulsion polymerization proceeded without causing scaling. After heating for 8 hours, 0.05 g of 2,6-t-butyl-4-methylphenol was added to terminate the polymerization. The polymerization conversion of chloroprene was 72%. When unreacted monomers and water were distilled off using a rotary evaporator, a stable soap-press CR latex-I was obtained (solid content 39 wt%, acrylic acid content of all polymers about 1.5 wt%, emulsifier content chloroprene-based) 0 wt% relative to polymer).

  Using the obtained CR latex-I, an adhesive composition was prepared with the formulation shown in Table 2, and the adhesive performance was evaluated. The results are shown in Table 2. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 10
Example except that amphiphilic CR block copolymer-4.03 g (13 wt% of all charged monomers) obtained in Synthesis Example 8 was used instead of amphiphilic CR block copolymer-F 3.57 g. Polymerization was carried out in the same manner as in 7. As a result, emulsion polymerization proceeded without causing scaling, and the polymerization conversion rates of chloroprene and 2,3-dichloro-1,3-butadiene after polymerization for 3 hours were 80% and 97%. When unreacted monomers and water were distilled off with a rotary evaporator, a stable soap press CR latex-J was obtained in the same manner as in Example 7 (solid content 39%, methacrylic acid content with respect to the total polymer was about 3 wt%, emulsifier The content is 0 wt% with respect to the chloroprene polymer).

  Using the obtained CR latex-J, an adhesive composition was prepared with the formulation shown in Table 2, and the adhesive performance was evaluated. The results are shown in Table 2. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 11
Example except that amphiphilic CR block copolymer-I 6.00 g (20 wt% of all charged monomers) obtained in Synthesis Example 9 was used instead of amphiphilic CR block copolymer-F 3.57 g. Polymerization was carried out in the same manner as in 7. As a result, emulsion polymerization proceeded without causing scaling, and the polymerization conversion rates of chloroprene and 2,3-dichloro-1,3-butadiene after polymerization for 3 hours were 79% and 97%. When unreacted monomers and water were distilled off using a rotary evaporator, a stable soap-press CR latex-K was obtained in the same manner as in Example 7 (solid content 39%, maleic anhydride content with respect to the total polymer was about 2.0 wt. %, The emulsifier content is 0 wt% with respect to the chloroprene polymer).

  Using the obtained CR latex-K, an adhesive composition was prepared with the formulation shown in Table 2, and the adhesive performance was evaluated. The results are shown in Table 2. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 12
Instead of amphiphilic CR block copolymer-F3.57 g, amphiphilic CR block copolymer-J5.00 g obtained in Synthesis Example 10 (17 wt% of all charged monomers) and sodium dodecylbenzenesulfonate 0. Polymerization was carried out in the same manner as in Example 7 except that 15 g was used. As a result, emulsion polymerization proceeded without causing scaling, and the polymerization conversion rates of chloroprene and 2,3-dichloro-1,3-butadiene after polymerization for 3 hours were 79% and 97%. When unreacted monomers and water were distilled off using a rotary evaporator, a stable soap-press CR latex-L was obtained in the same manner as in Example 7 (solid content 39%, maleic anhydride content relative to the total polymer was about 3.5 wt. %, The anionic emulsifier content is 0.5 wt% with respect to the chloroprene polymer).

  Using the obtained CR latex-L, an adhesive composition was prepared with the formulation shown in Table 2, and the adhesive performance was evaluated. The results are shown in Table 2. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 13
Example except that amphiphilic CR block copolymer-K3.50 g (20 wt% of all charged monomers) obtained in Synthesis Example 11 was used instead of amphiphilic CR block copolymer-F3.57 g. Polymerization was carried out in the same manner as in 7. As a result, emulsion polymerization proceeded without causing scaling, and the polymerization conversion rates of chloroprene and 2,3-dichloro-1,3-butadiene after polymerization for 3 hours were 78% and 96%. When unreacted monomers and water were distilled off using a rotary evaporator, a stable soap press CR latex-M was obtained in the same manner as in Example 7 (solid content: 39%, maleic anhydride and methacrylic acid content relative to the total polymer was about 2.0 wt%, the emulsifier content is 0 wt% with respect to the chloroprene polymer).

  Using the obtained CR latex-M, an adhesive composition was prepared with the formulation shown in Table 2, and the adhesive performance was evaluated. The results are shown in Table 2. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Example 14
Examples except that amphiphilic CR block copolymer-L6.00 g (20 wt% of all charged monomers) obtained in Synthesis Example 12 was used instead of amphiphilic CR block copolymer-F3.57 g. Polymerization was carried out in the same manner as in 7. As a result, the emulsion polymerization proceeded without causing scaling, and the polymerization conversion rates of chloroprene and 2,3-dichloro-1,3-butadiene after polymerization for 3 hours were 77% and 95%. When unreacted monomers and water were distilled off using a rotary evaporator, a stable soap-press CR latex-N was obtained in the same manner as in Example 7 (solid content 39%, maleic acid content relative to the total polymer was about wt%, emulsifier The content is 0 wt% with respect to the chloroprene polymer).

  Using the obtained CR latex-N, an adhesive composition was prepared with the formulation shown in Table 2, and the adhesive performance was evaluated. The results are shown in Table 2. Compared with the CR latex 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 adhesion and water resistance are remarkably improved as compared with conventional latex.

Comparative Example 1
In a 500 ml flask equipped with a nitrogen gas inlet tube, a reflux condenser and a stirrer, 98.5 g of chloroprene, 1.5 g of methacrylic acid, 0.3 g of n-dodecyl mercaptan, 5 g of sodium alkyldiphenyl ether disulfonate (manufactured by Kao, Plex SSH) Solid content conversion), Naphthalenesulfonic acid formalin condensate sodium salt (Kao, demole N) 0.5g, Triethanolamine 0.2g, 100g of pure water were charged. I was degassed. Sodium hydrosulfite (0.01 g) was added, and 0.1 wt% potassium persulfate aqueous solution was continuously added dropwise at 40 ° C. in a nitrogen atmosphere to carry out emulsion polymerization of chloroprene. The polymerization was terminated by adding 0.05 g of 2,6-tert-butyl-4-methylphenol at a conversion rate of 85%. Unreacted monomers and water were removed by a rotary evaporator to obtain a stable conventional CR latex-O (solid content: 40 wt%, emulsifier content: 5.5 wt% based on chloroprene polymer).

  Using the obtained CR latex-O, an adhesive composition was prepared with the formulation shown in Table 3, and the adhesive performance was evaluated. The results are shown in Table 3. Compared with the Examples, it is clear that the peel strength decrease due to open time and the peel strength decrease after water immersion are large.

比較例２
アルキルジフェニルエーテルジスルホン酸ナトリウムの代わりにドデシルベンゼンスルホン酸ナトリウム３．０ｇを用いた他は全て比較例１と同じ方法でクロロプレンの乳化重合を行い、安定な従来型のＣＲラテックス−Ｐを得た（固形分４０ｗｔ％、乳化剤含量はクロロプレン系ポリマーに対して３．４ｗｔ％）。得られたＣＲラテックス−Ｐを用いて表３に示した配合で接着剤組成物を調製し、接着性能を評価した。結果を表３に示す。実施例と比較して、オープンタイムによる剥離強度低下及び水浸漬後の剥離強度低下が大きいことが明らかである。

Comparative Example 2
The emulsion polymerization of chloroprene was carried out in the same manner as in Comparative Example 1 except that 3.0 g of sodium dodecylbenzenesulfonate was used instead of sodium alkyldiphenyl ether disulfonate to obtain a stable conventional CR latex-P (solid 40% by weight and the emulsifier content is 3.4% by weight with respect to the chloroprene polymer). Using the obtained CR latex-P, an adhesive composition was prepared with the formulation shown in Table 3, and the adhesive performance was evaluated. The results are shown in Table 3. Compared with the Examples, it is clear that the peel strength decrease due to open time and the peel strength decrease after water immersion are large.

Comparative Example 3
In Example 1, when chloroprene was subjected to emulsion polymerization, polymerization was performed in the same manner as in Example 1 except that 0.7 g of sodium dodecylbenzenesulfonate was added in addition to the amphiphilic CR block copolymer-A. It was. The polymerization conversion rate of chloroprene after polymerization for 3 hours was 82%. Unreacted monomer and water were distilled off using a rotary evaporator to obtain a stable CR latex-Q (solid content: 39 wt%, emulsifier content: about 2.4 wt% based on chloroprene polymer).

  Using the obtained CR latex-Q, an adhesive composition was prepared with the formulation shown in Table 3, and the adhesive performance was evaluated. The results are shown in Table 3. Compared with the Examples, it is clear that the peel strength decrease due to open time and the peel strength decrease after water immersion are large.

Comparative Example 4
In Example 6, when chloroprene was subjected to emulsion polymerization, polymerization was performed in the same manner as in Example 6 except that 0.7 g of sodium dodecylbenzenesulfonate was added in addition to the amphiphilic CR block copolymer-F. It was. The polymerization conversion of chloroprene after polymerization for 3 hours was 84%. Unreacted monomers and water were distilled off with a rotary evaporator to obtain CR Latex-R (solid content 39 wt%, emulsifier content about 2.4 wt% with respect to chloroprene polymer).

  Using the obtained CR latex-R, an adhesive composition was prepared with the formulation shown in Table 3, and the adhesive performance was evaluated. The results are shown in Table 3. Compared with the Examples, it is clear that the peel strength decrease due to open time and the peel strength decrease after water immersion are large.

The infrared absorption spectrum of the methacrylic acid-chloroprene block copolymer obtained in Synthesis Example 1 is shown.

Claims (6)

A soapless poly containing 2 wt% or less of an emulsifier and an amphiphilic chloroprene copolymer in which a hydrophilic oligomer having an acidic functional group or a hydrophilic polymer is linked to a hydrophobic chloroprene polymer Chloroprene latex. The soapless polychloroprene latex according to claim 1, wherein the amphiphilic chloroprene copolymer according to claim 1 is a chloroprene block copolymer represented by the following general formula (1): .

(In the formula, U represents hydrogen, a methyl group or a cyano group, V represents a methyl group, a carboxyl group, a carboxyl group-containing alkyl group or a carboxyl group-containing aryl group, A represents chloroprene, 2,3-dichloro-1, Represents a polymerized residue of 3-butadiene, styrene, p-methoxystyrene or isobutylene, Q represents a polymerized residue of maleic anhydride, citraconic acid, maleic acid or fumaric acid, and k, m and n are integers of 0 or more And p represents an integer of 1 or more.) The hydrophilic oligomer or hydrophilic polymer having an acidic functional group contains a polymerized residue of a monomer selected from methacrylic acid, acrylic acid, maleic anhydride, maleic acid, and fumaric acid. The soapless polychloroprene-based latex according to claim 2. In producing soapless polychloroprene latex by emulsion polymerization of chloroprene or chloroprene and a monomer copolymerizable with chloroprene, a hydrophilic oligomer or hydrophilic polymer having an acidic functional group is linked to a hydrophobic chloroprene polymer. The method for producing a soapless polychloroprene latex according to any one of claims 1 to 3, wherein an amphiphilic chloroprene copolymer is used. The pressless polychloroprene latex according to claim 4, wherein the amphiphilic chloroprene copolymer according to claim 4 is a chloroprene block copolymer represented by the following general formula (1): Manufacturing method.

(In the formula, U represents hydrogen, a methyl group or a cyano group, V represents a methyl group, a carboxyl group, a carboxyl group-containing alkyl group or a carboxyl group-containing aryl group, A represents chloroprene, 2,3-dichloro-1, Represents a polymerized residue of 3-butadiene, styrene, p-methoxystyrene or isobutylene, Q represents a polymerized residue of maleic anhydride, citraconic acid, maleic acid or fumaric acid, and k, m and n are integers of 0 or more And p represents an integer of 1 or more.) An adhesive comprising the saw pressed polychloroprene latex according to any one of claims 1 to 3.

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