JP2018030910A - Polymer emulsion and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer emulsion which is improved in water resistance and adhesiveness of an emulsion coating film by further reducing an emulsifier without deteriorating emulsion stability and to provide a method for producing the same.SOLUTION: There is provided a polymer emulsion which is dispersion-stabilized in water or an aqueous solvent with 3 pts.wt. of an emulsifier based on 100 pts.wt. of a polymer containing a (meth)acrylate repeating structural unit (A), an aromatic monovinyl repeating structural unit (B) and a divinyl sulfonic acid salt repeating structural unit (C). There is provided a method for producing a polymer emulsion by emulsifying 99.9-1.0 mol% of (meth)acrylic acid esters providing the structural unit (A), 99.9 mol% or less of styrenes providing the structural unit (B), 0.1-5.0 mol% of di-vinylbenzene sulfonic acid or a salt thereof providing the structural unit (C), 20.0 mol% or less of a monomer having a radically polymerizable double bond, with an emulsifier in water or an aqueous solvent and then performing emulsion polymerization by adding a radical polymerization initiator.SELECTED DRAWING: None

Description

  The present invention relates to a polymer emulsion in which water-soluble components such as an emulsifier contained in an emulsion are reduced and the water resistance and adhesion of an emulsion coating film are remarkably improved, and a method for producing the polymer emulsion.

  Polymer fine particles are used in a wide range of industrial fields such as emulsion paints, adhesives, binders, fiber treatment agents, inks, paper coating agents, information display materials, recording materials, and medical diagnostic materials. Known methods for producing polymer fine particles include suspension polymerization, dispersion polymerization, emulsion polymerization, microemulsion polymerization, soap-free emulsion polymerization, and the like. Among these, emulsion polymerization is capable of producing a high molecular weight polymer at a high speed and is easy to control the temperature, and thus has been used for a long time as an industrial production method for emulsion paints and adhesives (for example, non-patent documents). 1).

  In the emulsion polymerization, an emulsifier for emulsifying the monomer is indispensable, and a low molecular weight anionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, or a high molecular weight polymer emulsifier (dispersant) is used. These emulsifiers contribute to stabilization of dispersion of emulsion particles by physical adsorption on the surface of the emulsion particles. However, these emulsifiers are chemically stimulated when hard water is used as the polymerization medium or when various additives such as fillers, pigments, solvents, and pH adjusters are added to the emulsion, or during compounding and coating. May be desorbed by the mechanical shearing force of the emulsion and cause destabilization of the emulsion. Moreover, the emulsifier desorbed in the process of applying an emulsion paint or an adhesive to a substrate and drying it causes a decrease in adhesion and adhesion, and whitening of the coating film due to moisture absorption (see Non-Patent Document 2, for example). ).

  As a method for solving the above-mentioned problems of emulsifiers, soap-free emulsion polymerization is known. For example, an attempt has been made to use an emulsifier having a water-soluble monomer or a polymerizable vinyl group (also referred to as a reactive emulsifier) instead of the emulsifier (see, for example, Non-Patent Document 3). For example, sodium styrenesulfonate, which is a water-soluble radically polymerizable monomer, is industrially used for the purpose of enhancing the stability of emulsions in the production of polymer emulsions by emulsion polymerization. However, the surface activity of water-soluble monomers represented by sodium styrenesulfonate is inferior to that of the above-mentioned (conventional) emulsifiers. It is difficult to obtain the properties, that is, there is a limit to the reduction of the emulsifier. On the other hand, so-called reactive emulsifiers in which polymerizable vinyl groups are introduced into the molecules of the emulsifiers are known and used industrially, but there are still problems with polymerization reactivity and adhesiveness of emulsions. Therefore, in order to further improve the emulsion stability, the water resistance of the coating film, and the adhesiveness, a method capable of further reducing the emulsifier has been strongly demanded (see, for example, Patent Document 1).

Japanese Patent No. 5332141

Journal of the Japan Society of Color Material, 2007, 80, 11, 462-476 Journal of the Imaging Society of Japan, 2005, 44, 5, 369-374 Journal of the Adhesion Society of Japan, 1982, Vol. 18, No. 12, 530-535

  The present invention has been made in view of the above problems, and its object is to improve the water resistance and adhesiveness of emulsion coating films by reducing the emulsifier without reducing emulsion stability. It is in providing an emulsion and its manufacturing method.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have found that divinylbenzenesulfonic acid or a salt thereof which is a water-soluble monomer (hereinafter, divinylbenzenesulfonic acid or a salt thereof is referred to as “DVBS”). It has been found that it has excellent surface activity, and by using DVBS instead of an emulsifier, it has been found that the stability of the polymer emulsion and the water resistance and adhesiveness of the emulsion coating film can be improved, and the present invention has been completed.

  That is, the present invention provides a polymer emulsion dispersed and stabilized in water or an aqueous medium with 3 parts by weight or less of an emulsifier with respect to 100 parts by weight of a polymer containing the following repeating structural units (A), (B) and (C). Concerning.

[In the repeating structural unit (A), R ₁ represents hydrogen, a methyl group or an ethyl group, and R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with a hetero atom. Represent,
In the repeating structural unit (B), R ₃ represents hydrogen or a methyl group, R ₄ represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with hydrogen or a hetero atom,
In the repeating structural unit (C), M represents a proton, sodium ion, potassium ion, lithium ion, ammonium ion or quaternary ammonium ion.
Where x is the number of repeating structural units (A) contained in the polymer, y is the number of repeating structural units (B) contained in the polymer, and z is the number of repeating structural units (C) contained in the polymer. 1.0 ≦ 100x / (x + y + z) ≦ 99.9, 100y / (x + y + z) ≦ 99.9, 0.1 ≦ 100z / (x + y + z) ≦ 5.0. ]
Moreover, this invention concerns on the said polymer emulsion which contains the following repeating structural unit (D) further in the said structural unit (A), (B) and (C).

[In the repeating structural unit (D), R _5, R ₆ and R ₇ are each independently a linear or branched group having 1 to 10 carbon atoms which may be substituted with hydrogen, halogen, cyano group or hetero atom. Represents an alkyl group. ]
The present invention also provides a radical polymerizable monomer in water or 3 parts by weight of an emulsifier with respect to 100 parts by weight of the radical polymerizable monomer containing the following (e), (f), (g) and (h). The present invention relates to a method for producing a polymer emulsion, which is emulsified in an aqueous medium and subjected to emulsion polymerization by adding a radical polymerization initiator.
(E) 99.9-1.0 mol% of acrylic acid esters and / or methacrylic acid esters represented by the following formula (E),
(F) 99.9 mol% or less of styrene (F) represented by the following formula (F),
(G) 0.1 to 5.0 mol% of divinylbenzenesulfonic acid represented by the following formula (G) or a salt thereof, and (h) represented by the following formula (H), wherein the formulas (E) and (F ) And 20.0 mol% or less of a radically polymerizable monomer copolymerizable with the compound represented by formula (G)

[In formula (E), R ₁ represents hydrogen, a methyl group or an ethyl group, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with a hetero atom,
In Formula (F), R ₃ represents hydrogen or a methyl group, R ₄ represents hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms that may be substituted with a hetero atom,
In the formula (G), M represents a proton, sodium ion, potassium ion, lithium ion, ammonium ion or quaternary ammonium ion,
In formula (H), R _5, R ₆ and R ₇ are each independently a straight chain or branched chain having 1 to 10 carbon atoms which may be substituted with hydrogen, a halogen group, a cyano group or a hetero atom. Represents an alkyl group. ]

  Furthermore, the present invention provides one or more selected from the group consisting of paints, coating agents, adhesives, primers, binders, fiber treatment agents, toners, information display materials and medical diagnostic materials, using the polymer emulsion. Related to use in combination.

  The polymer emulsion of the present invention is obtained by significantly improving the stability of the emulsion and the water resistance of the coating film by using divinylbenzenesulfonic acid or a salt thereof instead of the emulsifier. When used as an adhesive or primer, the suppression of aggregates and the improvement in durability of the coating film and the adhesive layer can be expected. In addition, it can be expected to be used in a wide range of industrial fields such as various binders such as fiber treatment agents and battery electrode materials, inks, toners, information display materials, and medical diagnostic materials.

As described in Reference Example 1, sodium styrene sulfonate (hereinafter, sodium styrene sulfonate may be abbreviated as “SS” and displayed in FIG. 1) and an aqueous solution of sodium divinylbenzene sulfonate (hereinafter, sodium divinylbenzene sulfonate). It is abbreviated as “DVBS” (shown in FIG. 1) and is a result of measuring the surface tension of an aqueous solution. Here, the horizontal axis represents the concentration of the aqueous solution (wt% (wt%)), and the vertical axis represents the surface tension (dyn / cm) of the aqueous solution. It is a measurement result of the polymerization rate of sodium styrenesulfonate (displayed as “SS” in FIG. 2) and sodium divinylbenzenesulfonate (displayed as “DVBS” in FIG. 2) described in Reference Example 2. The horizontal axis represents the monomer solution heating time (h (hours)), and the vertical axis represents the monomer polymerization conversion (%).

The present invention will be described in detail below.
The present invention relates to methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2,2,2-tolufluoroethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate. Acrylate monomers such as butyl acrylate, 2-ethylhexyl acrylate, 2,2,2-trifluoroethyl acrylate, styrene, chlorostyrene, bromostyrene, cyanostyrene, aminostyrene, methoxystyrene, ptoxystyrene In producing a polymer emulsion by emulsion polymerization of a radically polymerizable monomer such as a styrenic monomer such as acetoxystyrene, it is characterized in that divinylbenzenesulfonic acid or a salt thereof is used instead of the emulsifier. That is, by using DVBS, the emulsifier used in the conventional emulsion is not contained or the content thereof is remarkably reduced.

What the content of the emulsifier is remarkably reduced means that 3 parts by weight or less of the emulsifier is contained with respect to 100 parts by weight of the polymer derived from the above-mentioned radical polymerizable monomer. When it exceeds 3 parts by weight, the water resistance and adhesiveness of the emulsion may be significantly lowered.
Emulsifiers can be classified, for example, into the following three types. The first category includes higher fatty acid salts, alkenyl succinates, rosinates, sodium alkyl sulfates, higher alcohol sulfate sodium esters, alkyl benzene sulfonates, alkyl diphenyl ether disulfonates, sulfonates of higher fatty acid amides, The most common anionic emulsifiers such as higher fatty acid alkylolamide sulfates, alkyl sulfobetaines, polyoxyethylene alkyl ethers, polyoxyethylene styrenated phenyl ethers, polyoxyethylene sorbitan fatty acid esters, higher fatty acid alkanolamides, polyvinyl alcohol The most common nonionic emulsifier, alkylamine salt, quaternary ammonium salt, alkyl ether type quaternary ammonium salt etc. The most common cationic emulsifier, alkyl Tyne, alkyl sulfobetaines, the most common amphoteric emulsifiers such as alkylamine oxide. These emulsifiers stabilize the emulsion by physical adsorption to the surface of the emulsion particles, and the emulsifying power of the monomer is high, but as described above (especially low molecular weight type emulsifiers) are chemically There is a drawback that it is easily detached by stimulation or mechanical shearing force. On the other hand, polymer-type emulsifiers such as polyvinyl alcohol give excellent emulsion stability, but have problems in water resistance and adhesiveness.

  Examples of the second classification include commercially available reactive emulsifiers such as latemuru (manufactured by Kao), eleminol (manufactured by Sanyo Kasei Kogyo), and aquaron (manufactured by Daiichi Kogyo Seiyaku). These emulsifiers are those in which radically polymerizable vinyl groups are introduced into the emulsifier molecules in order to compensate for the disadvantages of the first class of emulsifiers, and the emulsifying power is excellent but the copolymerizability is not sufficient. There are drawbacks such as the tendency to hinder the adhesion of the film.

  The third category is styrene sulfonate, vinyl sulfonic acid, 2-acrylamido-2-methyl-1-propane sulfonic acid, methallyl sulfonic acid, 2-sulfoethyl methacrylate, isoprene sulfonic acid, acrylic acid, methacrylic acid. Water-soluble monomers such as vinyl benzoate, N-methylol methacrylamide, 2-hydroxyethyl methacrylate, and poly (oxyethylene) methacrylate. Compared with the above-mentioned first and second class of emulsifiers, these do not contain large hydrophobic groups and have a small molecular size, so if they can be efficiently introduced into emulsion particles, not only the stability of the emulsion, but also the water resistance and adhesion of the coating film. Although it is expected that the properties can be greatly improved, the combined use with the above-mentioned first and second types of emulsifiers is avoided because the monomer emulsifying power (surface activity) is insufficient or the aqueous phase is easily homopolymerized. I can't.

The present inventors have found that the surface activity of DVBS, which is a water-soluble monomer, is far higher than the surface activity of conventional water-soluble monomers, leading to the present invention.
That is, the present invention relates to a polymer emulsion dispersed and stabilized in water or an aqueous medium with 3 parts by weight or less of an emulsifier with respect to 100 parts by weight of a polymer containing repeating structural units (A), (B) and (C). .

[In the repeating structural unit (A), R ₁ represents hydrogen, a methyl group or an ethyl group, and R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with a hetero atom. In the repeating structural unit (B), R ₃ represents hydrogen or a methyl group, and R ₄ represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with hydrogen or a hetero atom. In the repeating structural unit (C), M represents a proton, sodium ion, potassium ion, lithium ion, ammonium ion or quaternary ammonium ion.
Where x is the number of repeating structural units (A) contained in the polymer, y is the number of repeating structural units (B) contained in the polymer, and z is the number of repeating structural units (C) contained in the polymer. 1.0 ≦ 100x / (x + y + z) ≦ 99.9, 100y / (x + y + z) ≦ 99.9, 0.1 ≦ 100z / (x + y + z) ≦ 5.0. ]

  Moreover, this invention is the said polymer emulsion which contains the following repeating structural unit (D) further in the said structural unit (A), (B) and (C).

[In the repeating structural unit (D), R _5, R ₆ and R ₇ are each independently a linear or branched group having 1 to 10 carbon atoms which may be substituted with hydrogen, halogen, cyano group or hetero atom. Represents an alkyl group. ]
The present invention also provides a radical polymerizable monomer in water or 3 parts by weight of an emulsifier with respect to 100 parts by weight of the radical polymerizable monomer containing the following (e), (f), (g) and (h). The present invention relates to a method for producing a polymer emulsion, which is emulsified in an aqueous medium and subjected to emulsion polymerization by adding a radical polymerization initiator.
(E) 99.9-1.0 mol% of acrylic acid esters and / or methacrylic acid esters represented by the following formula (E),
(F) 99.9 mol or less of styrenes (F) represented by the following formula (F),
(G) 0.1 to 5.0 mol% of divinylbenzenesulfonic acid represented by the following formula (G) or a salt thereof, and (h) represented by the following formula (H), wherein the formulas (E) and (F ) And 20.0 mol% or less of a radically polymerizable monomer copolymerizable with the compound represented by formula (G)

[In formula (E), R ₁ represents hydrogen, a methyl group or an ethyl group, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with a hetero atom,
In Formula (F), R ₃ represents hydrogen or a methyl group, R ₄ represents hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms that may be substituted with a hetero atom,
In the formula (G), M represents a proton, sodium ion, potassium ion, lithium ion, ammonium ion or quaternary ammonium ion,
In formula (H), R _5, R ₆ and R ₇ are each independently a straight chain or branched chain having 1 to 10 carbon atoms which may be substituted with hydrogen, a halogen group, a cyano group or a hetero atom. Represents an alkyl group. ]

  By the way, it is known from JP-A-58-76662 that emulsion polymerization of a radically polymerizable monomer having a phenyl group such as styrene in water using DVBS and an emulsifier. This document describes that styrene is emulsion-polymerized using a monomer having a sulfonated phenyl group and a small amount of an emulsifier in order to produce a latex (polymer emulsion) having appropriate stability. Examples of the monomer having a converted phenyl group include DVBS and styrene sulfonate. However, there is no mention of differences in the polymerizability and surface activity between DVBS and styrene sulfonate. Moreover, as a radically polymerizable monomer, it is limited to the radically polymerizable monomer which has a phenyl group, and there is no description regarding an acrylic ester or a methacrylic ester.

  The production method of the polymer emulsion of the present invention is basically the same as the emulsion polymerization, microemulsion polymerization, miniemulsion polymerization, dispersion polymerization, suspension polymerization, reverse phase emulsion polymerization and the like described in the above non-patent literature except that DVBS is used. Are the same. For example, as described in Non-Patent Document 3 (Journal of the Adhesion Society of Japan, 1982, Vol. 18, No. 12, 530-535), the reactor is charged with ion-exchanged water, a predetermined amount of radically polymerizable monomer, excess Emulsion polymerization can be carried out by heating and stirring in a nitrogen atmosphere after charging a polymerization initiator such as potassium sulfate and, if necessary, an emulsifier such as sodium dodecylbenzenesulfonate or Emulgen 920 (manufactured by Kao Corporation). In addition, as described in Non-Patent Document 2 (Journal of Imaging Society of Japan, 2005, Vol. 44, No. 5, pp. 369-374), after adding a radical polymerizable monomer to an emulsifier aqueous solution, After the monomer oil droplets are subdivided by shearing force, a mini-emulsion polymerization can be carried out by adding a polymerization initiator, heating and stirring in a nitrogen atmosphere. Alternatively, microemulsion polymerization can be performed by adding an appropriate oil to the emulsifier aqueous solution and the radical polymerizable monomer and further miniaturizing the monomer oil droplets. Although the matrix (continuous phase) in the above-described polymerization method is water, as described in Non-Patent Document 1 (Journal of the Japan Society of Color Material, 2007, Vol. 80, No. 11, pages 462-476), instead of water. Further, by using hexane or cyclohexane as a matrix and using a surfactant having a low HLB (hydrophilic and hydrophobic balance) as an emulsifier, reverse phase emulsion polymerization can also be performed.

Hereinafter, the most common production method by emulsion polymerization will be described.
For example, the monomer emulsification is performed by first mixing (h) the radically polymerizable monomer (shown in the formula (H)) with DVBS or an aqueous solution containing DVBS and an emulsifier, followed by stirring or homogenizer treatment to emulsify. Prepare the solution. What is necessary is just to superpose | polymerize at predetermined temperature, adding a polymerization initiator, after charging the said monomer emulsion into a reactor and deaerating. At this time, in order to avoid sudden heat generation, a part of the monomer emulsion may be charged into the reactor to start polymerization, and polymerization may be performed while continuously adding the remaining monomer emulsion. Or you may superpose | polymerize, adding a radically polymerizable monomer continuously to the solution containing an emulsifier.

  Further, when the amount of DVBS added is increased, emulsion polymerization may be carried out by adding a molecular weight modifier (chain transfer agent) to the radical polymerizable monomer in order to adjust the film forming property of the polymer emulsion. The polymerization is continued until the polymerization conversion rate of the monomer reaches about 100%, or when the target monomer conversion rate is reached, a polymerization inhibitor is added to terminate the polymerization. Then, a polymer emulsion is obtained by removing the unreacted monomer under reduced pressure.

  In the case of producing polymer fine particles, the fine particles separated by filtration may be washed with a suitable solvent to remove unnecessary emulsifiers and unreacted monomers.

  The radical polymerizable monomer is the above-mentioned (e) acrylic acid ester and / or methacrylic acid ester, ethacrylic acid ester, (f) styrene, (g) DVBS, and a glass transition temperature required for each use. The monomer composition may be adjusted according to physical properties such as heat distortion temperature, hardness, solvent resistance, specific gravity, and coefficient of thermal expansion.

  The radical polymerizable monomer (h) represented by the formula (H) and copolymerizable with the compounds represented by the formula (E), the formula (F) and the formula (G) is not particularly limited. For example, vinyl ethers such as isobutyl vinyl ether, ethyl vinyl ether, 2-phenyl vinyl alkyl ether, nitrophenyl vinyl ether, cyanophenyl vinyl ether, chlorophenyl vinyl ether, chloroethyl vinyl ether, decyl acrylate, lauryl acrylate, octyl acrylate, dodecyl acrylate, Stearyl acrylate, cyclohexyl acrylate, bornyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, methoxyethylene glycol acrylate, ethyl carbitol acrylate , 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3- (trimethoxy acrylate) Ril) propyl, polyethylene glycol acrylate, glycidyl acrylate, 2- (acryloyloxy) ethyl phosphate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3,3-pentafluoroacrylate Propyl, acrylic esters such as 2,2,3,4,4,4-hexafluorobutyl, decyl methacrylate, lauryl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, Boronyl methacrylate, benzyl methacrylate, phenyl methacrylate, glycidyl methacrylate, polyethylene glycol methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, methoxyethyl methacrylate Glycol, ethyl carbitol methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2- (methacryloyloxy) ethyl phosphate, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate 3- (dimethylamino) propyl methacrylate, 2- (isocyanato) ethyl methacrylate, 2,4,6-tribromophenyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, methacrylic acid 2 , 2,3,3,3-pentafluoropropyl, methacrylic acid esters such as 2,2,3,4,4,4-hexafluorobutyl, diacetone methacrylate, methyl 2-ethyl acrylate, 2- Ethyl ethyl acrylate, 2-ethyl acrylic Ethacrylic acid esters such as ethacrylic acid ester monomers such as propyl acid and butyl 2-acrylate, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2, 3-dichloro-1,3-butadiene, 2-cyano-1,3-butadiene, 1-chloro-1,3-butadiene, 2- (N-piperidylmethyl) -1,3-butadiene, 2-triethoxymethyl 1,1,3-butadiene, 2- (N, N-dimethylamino) -1,3-butadiene, N- (2-methylene-3-butenoyl) morpholine, 1,2-methylene-3-butenylphosphonate diethyl, etc. 3-butadienes, N-phenylmaleimide, N- (chlorophenyl) maleimide, N- (methylphenyl) maleimide, N- (isopropylphenyl) Reimide, N- (sulfophenyl) maleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N- (nitro Phenyl) maleimide, N-benzylmaleimide, N- (4-acetoxy-1-naphthyl) maleimide, N- (4-oxy-1-naphthyl) maleimide, N- (3-fluoranthyl) maleimide, N- (5-fluoresceinyl) ) Maleimide, N- (1-pyrenyl) maleimide, N- (2,3-xylyl) maleimide, N- (2,4-xylyl) maleimide, N- (2,6-xylyl) maleimide, N- (aminophenyl) ) Maleimide, N- (tribromophenyl) maleimide N- [4- (2-Benzimidazolyl) phenyl] maleimide, N- (3,5-dinitrophenyl) maleimide, N- (9-acridinyl) maleimide, maleimide, N- (sulfophenyl) maleimide, N-cyclohexylmaleimide , Maleimides such as N-methylmaleimide, N-ethylmaleimide, N-methoxyphenylmaleimide, fumarate such as dibutyl fumarate, dipropyl fumarate, diethyl fumarate, dicyclohexyl fumarate, bis-2-ethylhexyl fumarate, dodecyl fumarate Acid diesters, fumaric acid monoesters such as butyl fumarate, propyl fumarate and ethyl fumarate, maleic acid diesters such as dibutyl maleate, dipropyl maleate and diethyl maleate, butyl maleate and maleate Maleic acid monoesters such as pill, ethyl maleate, dicyclohexyl maleate, acid anhydrides such as maleic anhydride, citraconic anhydride, acrylamide, N-methylacrylamide, N-ethylacrylamide, 2-hydroxyethylacrylamide, N, N-diethylacrylamide, acryloylmorpholine, N, N-dimethylaminopropylacrylamide, isopropylacrylamide, N-methylolacrylimide, sulfophenylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-1-methylsulfone Acrylamides such as acid, diacetone acrylamide, acrylamide alkyl trialkyl ammonium chloride, methacrylamide, N-methyl methacrylamide N-ethylmethacrylamide, 2-hydroxyethylmethacrylamide, N, N-diethylmethacrylamide, N, N-dimethylmethacrylamide, N-methylolmethacrylamide, methacryloylmorpholine, N, N-dimethylaminopropylmethacrylamide, isopropyl Methacrylamide such as methacrylamide, 2-methacrylamide-2-methylpropane sulfonic acid, methacrylamide alkyltrialkylammonium chloride, others, vinylpyrrolidone, sulfophenylitaconimide, acrylonitrile, methacrylonitrile, fumaronitrile, α-cyanoethyl Acrylate, citraconic acid, citraconic anhydride, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versamic acid, crotonic acid, Taconic acid, fumaric acid, maleic acid, mono 2- (methacryloyloxy) ethyl phthalate, mono 2- (methacryloyloxy) ethyl succinate, mono 2- (acryloyloxy) ethyl succinate, methacryloxypropyltrimethoxysilane, methacryloxy Propyldimethoxysilane, acrolein, vinylmethylketone, N-vinylacetamide, N-vinylformamide, vinylethylketone, vinylsulfonic acid, allylsulfonic acid, dehydroalanine, sulfur dioxide, isobutene, N-vinylcarbazole, vinylidene dicyanide, Paraquinodimethane, chlorotrifluoroethylene, tetrafluoroethylene, norbornene, N-vinylcarbazole, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, styrenes Examples thereof include sulfonic acid and styrene sulfonate.

  The radical polymerizable monomer (h) represented by the formula (H) and copolymerizable with the compounds represented by the formula (E), formula (F) and formula (G) has the above-mentioned glass transition temperature, heat In addition to deformation temperature, hardness, solvent resistance, specific gravity, and coefficient of thermal expansion, it may be used for the purpose of imparting hydrophilicity, water repellency, curability, temperature sensitivity, etc. to the emulsion polymer.

  Polymerization of the monomers listed above results in various residues derived from the monomers, which are repeating structural units contained in the polymer.

  The emulsifier is not particularly limited, but examples of the anionic emulsifier include rosin acid salt, fatty acid salt, alkenyl succinate, alkyl ether carboxylate, alkyl diphenyl ether disulfonate, alkane sulfonate, alkyl succinate. Nate sulfonate, polyoxyethylene polycyclic phenyl ether sulfate ester, α-olefin sulfonate, alkylbenzene sulfonate, naphthalene sulfonate formalin condensate, taurine derivative, polystyrene sulfonate, polystyrene sulfonate styrene copolymer Polymer, polystyrene sulfonic acid N-vinyl pyrrolide copolymer, polystyrene sulfonic acid N-substituted maleimide copolymer, polystyrene sulfonic acid methacrylic acid copolymer, polystyrene sulfonic acid acrylic acid copolymer, polymer Styrene sulfonic acid acrylic acid ester copolymer, styrene sulfonic acid maleic acid copolymer, styrene sulfonic acid acrylamide copolymer, styrene sulfonic acid methacrylamide copolymer, styrene sulfonic acid 2-hydroxyethyl methacrylate copolymer, polyvinyl phosphone Acid copolymer, polyvinyl sulfonic acid copolymer, polyisoprene sulfonic acid copolymer, polyacrylic acid ester acrylic acid copolymer, polymethacrylic acid ester methacrylic acid copolymer, polyacrylamide acrylic acid copolymer, polymethacrylic acid Amide methacrylic acid copolymer, alkyl sulfosuccinate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, sulfate salt of alkyl propenylphenol polyethylene oxide adduct, allyl alkyl phosphate Nonionic emulsifiers such as sulfates of enol polyethylene oxide adducts, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, sulfonates of higher fatty acid amides, sulfates of higher fatty acid alkylolamides, etc. As, for example, polyoxyalkylene alkylamine, alkyl alkanolamide, amine oxide nonionic emulsifier, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyalkylene polycyclic phenyl ether, alkyl propenyl phenol polyethylene oxide adduct , Allyl alkylphenol polyethylene oxide adduct, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, soy Vitan fatty acid ester, glycerin fatty acid ester, alkyl polyglucoxide, sucrose fatty acid ester, polyoxyethylene polyoxypropylene glycol, polyvinyl alcohol, carboxymethylcellulose, polyvinylpyrrolidone, hydroxyethylcellulose, polyacrylamide, polymethacrylamide, polydimethylaminoethyl methacrylate , Polydimethylaminoethyl acrylate, polydiethylaminoethyl methacrylate, polydiethylaminoethyl acrylate, poly-t-butylethylaminoethyl methacrylate, poly-t-butylaminoethyl acrylate, polydimethylaminoethyl methacrylate / methyl methacrylate copolymer, polydimethylaminoethyl Both acrylate / methyl methacrylate Examples include amphoteric emulsifiers such as alkyldimethylaminoacetic acid betaine, alkyldimethylaminosulfobetaine, alkyl, and the like, and polydimethylaminoethyl methacrylate / butyl acrylate copolymer, polydimethylaminoethyl acrylate / ethyl acrylate copolymer. Examples include sulfobetaine. Further, as the conventional emulsifier, the above-mentioned commercially available reactive emulsifiers and water-soluble monomers can be mentioned.

  In addition, it is preferable that the usage-amount of DVBS shall be 0.1-5.0 mol% in 100 mol% of all radically polymerizable monomers. If the amount is less than 0.1 mol%, it may be difficult to sufficiently stabilize the emulsion. If the amount exceeds 5.0 mol%, the water resistance and adhesion of the emulsion coating film may increase due to an increase in sulfonic acid groups and the degree of crosslinking. And film forming properties may be deteriorated.

  Moreover, it is good for the usage-amount of an above-described emulsifier to be 3 weight part or less with respect to 100 weight part of all radically polymerizable monomers. If it exceeds 3 parts by weight, the water resistance and adhesiveness of the emulsion coating will be reduced.

  Examples of the radical polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide. 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t -Butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, cumylperoxyoct Ate, persulfate , Peroxides such as 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] formamide, 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] propion Mido}, 2,2′-azobis {2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis {2- (2-imidazolin-2-yl) propane] disulfate disulfide Hydrate, 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] Tetrahydrate, 1,1′-azobis (1-acetoxy-1-phenylmethane), 4,4′-diazendiylbis (4-cyano) And azo compounds such as pentanoic acid) .alpha.-hydro-.omega.-hydroxypoly (oxyethylene) polycondensates. If necessary, reduction of these polymerization initiators and ascorbic acid, erythorbic acid, aniline, tertiary amine, longalite, hydrosulfite, sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium hypophosphite, etc. An agent may be used in combination.

  The usage-amount of a radical polymerization initiator is 0.1-10 weight part normally with respect to 100 weight part of all the monomers.

  The molecular weight regulator is not particularly limited, but is diisopropylxanthogen disulfide, diethylxanthogen disulfide, diethylthiuram disulfide, 2,2′-dithiodipropionic acid, 3,3′-dithiodipropionic acid, 4,4 ′. -Disulfides such as dithiodibutanoic acid, 2,2'-dithiobisbenzoic acid, n-dodecyl mercaptan, octyl mercaptan, t-butyl mercaptan, thioglycolic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thio Salicylic acid, 3-mercaptobenzoic acid, 4-mercaptobenzoic acid, thiomalonic acid, dithiosuccinic acid, thiomaleic acid, thiomaleic anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homocysteine, 5-mercaptote Razole acetic acid, 3-mercapto-1-propanesulfonic acid, 3-mercaptopropane-1,2-diol, mercaptoethanol, 1,2-dimethylmercaptoethane, 2-mercaptoethylamine hydrochloride, 6-mercapto-1-hexanol, Mercaptans such as 2-mercapto-1-imidazole, 3-mercapto-1,2,4-triazole, cysteine, N-acylcysteine, glutathione, N-butylaminoethanethiol, N, N-diethylaminoethanethiol, iodoform, etc. Halogenated hydrocarbons, diphenylethylene, p-chlorodiphenylethylene, p-cyanodiphenylethylene, α-methylstyrene dimer, benzyldithiobenzoate, 2-cyanoprop-2-yldithiobenzoate, organic telluride Compound, sulfur, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium pyrosulfite, potassium pyrosulfite, sodium hypophosphite and the like. The amount of the molecular weight regulator used is usually 10 parts by weight or less with respect to 100 parts by weight of the total monomers.

  The above-mentioned polymerization inhibitor is not necessarily required when the monomer is polymerized to almost 100%, but phenothiazine, 2,6-di-t-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-t-butylphenol), 2-mercaptobenzimidazole, hydroquinone, N, N-diethylhydroxylamine, sodium nitrite, lithium nitrite, stable nitroxyl radical, hydroquinone, hydroquinone monomethyl ether, etc. can be used. .

In addition to the polymerization initiator, reducing agent, and molecular weight regulator described above, pH buffering agents such as sodium carbonate, sodium hydrogen carbonate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate may be added.
The polymerization conditions are not particularly limited, but may be heated at 10 to 100 ° C. for 2 to 12 hours in an inert gas atmosphere, and may be appropriately adjusted depending on the monomer and emulsifier composition and the polymerization initiator species.

  In addition to the general emulsion polymerization method described above, for example, DVBS and a radically polymerizable monomer copolymerizable with DVBS are copolymerized in water or an aqueous solvent to obtain a polymer having surface activity (polymer type emulsifier). After the first formation, a radical polymerizable monomer that is a main component of the polymer emulsion may be added to carry out emulsion polymerization (so-called in situ polymerization).

  The polymer emulsion of the present invention is an emulsion emulsion, coating film, adhesive, primer, fiber treatment agent, battery electrode material, as well as emulsion stability, coating film water resistance and adhesion. Such as various binders, inks, and toners are extremely useful in the industry.

  The following examples further illustrate the present invention, but the present invention is not limited to these examples.

<Purity measurement of sodium parastyrene sulfonate>
The active double bond was quantified by the oxidation-reduction titration method to obtain the sodium styrenesulfonate content in the sample.
(1) Instrument and device 1) Weighing bottle: diameter 50 mm, depth 70 mm
2) 500 ml, 1000 ml volumetric flask 3) 500 ml Erlenmeyer flask with a stopper 4) Electrochemical balance (2) Reagent 1) Bromine solution: 22.00 g of potassium bromide (KBr), 3.00 g of potassium bromate (KBrO ₃ ) The whole was dissolved in pure water to make 1000 ml.
2) Aqueous sulfuric acid solution (concentrated sulfuric acid / pure water volume ratio = 1/1)
3) Potassium iodide aqueous solution (200 g / L)
4) 0.1 mol / L sodium thiosulfate aqueous solution 5) Starch aqueous solution: 6.00 g of starch was dissolved in pure water to make 1000 ml as a whole.
(3) Operation 1) Weigh 20 g of sample to the order of 0.1 mg in a weighing bottle.
2) Rinse into a 500 ml volumetric flask with pure water to make the liquid volume about 400 ml.
3) Put a magnetic rotor and stir to dissolve the sample.
4) Take out the rotor, align the mark with pure water and shake to make the test solution.
5) Add 25 ml of bromine solution to a 500 ml conical stoppered flask containing 200 ml of pure water.
6) Add 5 ml of the test solution, add 10 ml of sulfuric acid aqueous solution, seal tightly and leave for 20 minutes.
7) Add 10 ml of potassium iodide aqueous solution quickly and leave for 10 minutes.
8) Titrate with an aqueous sodium thiosulfate solution, and after the solution becomes light yellow, add 1 ml of starch solution as an indicator, and titrate until the blue color of the resulting iodine starch disappears.
9) Separately, as a blank test, add 200 ml of pure water, add 25 ml of bromine solution to a conical flask with a stopper, quickly add 10 ml of potassium iodide aqueous solution and 10 ml of sulfuric acid aqueous solution, and perform the operation of 8).
(4) Calculation The sodium styrenesulfonate content is calculated by the following formula.

A = 100 × [0.01031 × (ab) × f] / (S × 5/500)
A: Sodium styrenesulfonate content (%)
a: Sodium thiosulfate aqueous solution (ml) required for the blank test
b: Sodium thiosulfate aqueous solution (ml) required for this test
f: Potency of sodium thiosulfate aqueous solution S: Sample amount (g)

<Purity measurement of divinylbenzene sulfonate>
Purity was measured by nuclear magnetic resonance spectrum.
(1) Preparation of sample 0.02 g of sample and 0.01 g of triethylamine or methyl isobutyl ketone as an internal standard substance are weighed in a weighing bottle (50 mmφ × 70 mm) to the order of 0.1 mg, and a total amount of heavy water or heavy acetone is 0.6 g. The sample was added until dissolved to prepare an NMR measurement sample.
(2) Measuring equipment Model = Bruker AV-400M
Integration count = 16
(3) Calculation of purity The purity of the product was calculated by the following formula.

Purity (wt%) = (B / M _b ) × (a / a _H ) / (b / b _H ) × M _a / S × 100
a: integral value of any of the object peak b: integral value of any of the internal standard substance a _H: number of hydrogens of any product peak selected in _a b _H: any number of hydrogens of product peaks selected in _b M _a : Molecular weight of target substance M _b : Molecular weight of internal standard substance B: Amount of collected internal standard (g)
S: Amount of sample collected (g)

<Measurement of styrene, methacrylate ester and acrylonitrile polymerization conversion>
About 50 g of isopropanol is precisely weighed into a glass flask with a stopcock, and 0.1 to 0.5 g of the emulsion polymerization solution is precisely weighed and shaken well, and then the supernatant is gas chromatographed (G-17A, Shimadzu Corporation). (Column = NEUTRA BOND-5, flame ionization detector manufactured by GL Science). The polymerization conversion rate was calculated from the peak area of the monomer with respect to 2-ethoxyethanol added as an internal standard during emulsion polymerization.

<Analysis of Polymerizability of DVBS and SS>
Apparatus: Bruker Biospin, AV-400M
Preparation method of measurement sample: a predetermined amount of sodium divinylbenzenesulfonate (DVBS) or sodium styrenesulfonate (SS) in 10 g of heavy water (99.5%) containing about 0.05% tetramethylammonium bromide as an internal standard substance After the polymerization initiator was dissolved, the solution was collected in a glass tube for NMR measurement, deaerated by a nitrogen flow, sealed, and then the polymerization was started by immersing the glass tube in a 57 ° C. hot water bath. The tube was taken out every predetermined time, and the NMR spectrum was measured, and the signal intensity derived from the double bond contained in DVBS and SS was traced.

<Measurement of particle size of polymer emulsion>
The particle size distribution was measured using Nanotrac 150 (manufactured by Nikkiso).

<Measurement of aggregation rate after polymerization>
After cooling the emulsion to room temperature, the aggregate was filtered off using a 200-mesh stainless steel wire mesh, vacuum dried (100 ° C. × 3 hours) together with the wire mesh, and the aggregation rate was calculated from the following equation.

  Aggregation rate (wt%) = 100 × [dry weight of (wire mesh + aggregate) −original wire mesh weight] / (charged monomer weight)

<Water resistance evaluation of polymer emulsion>
After applying a polymer emulsion adjusted to a solid content of about 45 wt% to a thickness of about 0.25 mm using a doctor blade on a black ABS (acrylonitrile / butadiene / styrene resin) plate, left at room temperature for about 2 hours, Dry in an oven at 90 ° C. for 10 minutes. This test piece was immersed in water at 40 ° C. for 2 days, and then judged from the state of the emulsion polymer coating film as follows.

○: Almost no whitening or blistering of the coating film is observed.
Δ: Some whitening or blistering of the coating film is observed.
X: Whitening or blistering of the coating film is remarkable.

<Adhesive evaluation of polymer emulsion>
After applying a polymer emulsion adjusted to a solid content of about 45 wt% to a thickness of about 0.25 mm using a doctor blade on a black ABS (acrylonitrile / butadiene / styrene resin) plate, left at room temperature for about 2 hours, It was dried in an oven at 80 ° C. for 20 minutes. After leaving this test piece at room temperature for 2 days, make 100 grids that reach the substrate at 2 mm intervals on the coated surface with a cutter knife, put cellophane adhesive tape on it and pull it in a 180 ° direction. The adhesiveness was evaluated from the ratio (%) of the coating film remaining after peeling.

Reference Example 1 Surface activity of sodium divinylbenzenesulfonate Sodium styrenesulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., purity 88.0 wt%, hereinafter sometimes referred to as sodium styrenesulfonate “SS”) and sodium divinylbenzenesulfonate (Tosoh Organic Chemical Co., Ltd., purity 84.0 wt%) is dissolved in ion-exchanged water to prepare an aqueous solution with a predetermined concentration (in terms of pure content), and the Wilhelmy method using a platinum plate (ESB-IV type manufactured by Kyowa Kagaku, The surface tension was measured in a thermostatic chamber at 25 ° C. with an automatic equilibrium electro surface tension meter.

  As shown in FIG. 1, the present inventors have found that DVBS exhibits a clearly lower surface tension (higher surface activity) than SS. That is, DVBS was expected to exhibit a monomer emulsifying power superior to SS.

Reference Example 2 Polymerization of sodium divinylbenzenesulfonate Sodium styrenesulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., purity 88.0 wt%) 1.09 mmol, sodium divinylbenzenesulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., purity 84.0 wt) %) 2.17 mmol and 0.09 mmol of water-soluble azo initiator V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 10.00 g of heavy water and collected in an NMR glass tube. The solution was degassed by bubbling nitrogen, and after sealing, heating was started in a hot water bath at 57 ° C. The polymerization conversion was calculated from the decrease in the signal integration value derived from the double bond. As shown in FIG. 2, it was found that DVBS exhibits radical polymerizability equal to or higher than SS. From the results of Reference Examples 1 and 2, DVBS was expected to be used as a reactive emulsifier.

Reference Example 3 (examined at 1 mol% DVBS)
A 200 ml glass flask reactor equipped with a reflux condenser and a nitrogen inlet tube was charged with 80.00 g of ion exchange water, 1.0700 g of sodium divinylbenzenesulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., purity 84.0%), potassium persulfate ( Wako Pure Chemical Industries, Ltd., first grade) 0.1304g, sodium dodecylbenzenesulfonate (Tokyo Chemical Industry Co., Ltd.) 0.0820g, and 2-ethoxyethanol 0.10g, aspirator suction / nitrogen introduction Degassing was repeated 5 times. Here, 40.00 g of styrene (manufactured by Wako Pure Chemical Industries, Ltd., special grade) was added and stirred using a football type PTFE stirrer (φ10 mm × 25 mm) (manufactured by Koike Seimitsu Seisakusho, HERACLES-20G, high range, (7 scales), nitrogen gas (0.1 L / min) was allowed to flow for 10 minutes for deaeration. Thereafter, the reactor was immersed in an oil bath at 65 ° C. and polymerized for 5 hours under the above stirring conditions. DVBS in all radical polymerizable monomers is 1.01 mol%, and the amount of sodium dodecylbenzenesulfonate added is 0.21 parts by weight.

  As shown in Table 1, it is clear that the aggregates are overwhelmingly smaller and the polymerization rate is extremely high as compared with Reference Example 4 in which no water-soluble monomer was added. Also, compared with Reference Example 5 using equimolar SS instead of DVBS, the aggregation rate is low, the emulsion particle size is small and the polymerization rate is high, so DVBS is more effective as a reactive emulsifier than SS. Can be expected.

Reference Example 4 (Study without the water-soluble monomer of Reference Example 3)
Styrene emulsion polymerization was carried out under the same conditions as in Reference Example 3 except that sodium divinylbenzenesulfonate was not used.

As shown in Table 1, compared with Reference Example 3, there were many aggregates and the polymerization rate was greatly inferior.
Reference Example 5 (Study at 1 mol% SS)
In addition to sodium divinylbenzenesulfonate, 0.9110 g of sodium styrenesulfonate (purity 88.0%, manufactured by Tosoh Organic Chemical Co., Ltd.) (1.0 mol% added in all radical polymerizable monomers) was used. Were all subjected to emulsion polymerization of styrene under the same conditions as in Reference Example 3.

  As shown in Table 1, compared with Reference Example 3, since there were many aggregates, the emulsion particle size was large and the polymerization conversion rate was low, SS was less effective as a reactive emulsifier than DVBS. Conceivable.

Example 1 (implemented with 1 mol% DVBS)
A 200 ml glass flask reactor equipped with a reflux condenser and a nitrogen inlet tube was charged with 80.00 g of ion exchange water, 1.0700 g of sodium divinylbenzenesulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., purity 84.0%), potassium persulfate ( Wako Pure Chemical Industries, Ltd., first grade) 0.1320 g, sodium dodecylbenzenesulfonate (Tokyo Chemical Industry Co., Ltd.) 0.0820 g, and 2-ethoxyethanol 0.10 g, aspirator suction / nitrogen introduction Degassing was repeated 5 times. To this, 20.00 g of styrene (made by Wako Pure Chemical Industries, Ltd., special grade) and 24.60 g of n-butyl acrylate (made by Tokyo Chemical Industry Co., Ltd., first grade) were added, and a football type PTFE stirrer (φ10 mm × 25 mm) ) Was used for deaeration by flowing nitrogen gas (0.1 L / min) for 10 minutes while stirring (made by Koike Seimitsu Seisakusho, HERACLES-20G, high range, 7 scale). Thereafter, the reactor was immersed in an oil bath at 65 ° C. and polymerized for 10 hours under the above stirring conditions. DVBS in all radical polymerizable monomers is 1.01 mol%, and the amount of sodium dodecylbenzenesulfonate added is 0.18 parts by weight.

  As shown in Table 2, it is clear that the aggregates are overwhelmingly less and the polymerization rate is extremely high as compared with Comparative Example 1 in which DVBS is not added. Further, it is clear that the aggregation rate is low and the polymerization rate is high even when compared with Comparative Example 2 using equimolar SS instead of DVBS. Moreover, since emulsion particle size is smaller than Comparative Example 2 and adhesiveness is excellent, it is considered that DVBS was introduced into emulsion particles more efficiently than SS. Although it is difficult to measure the polymerization conversion rate of DVBS, it is estimated that almost 100% was polymerized from the result of Reference Example 2 and the formation of a stable emulsion.

Example 2 (composition change of Example 1)
All except that the sodium divinylbenzenesulfonate was increased to 2.1400 g, the sodium dodecylbenzenesulfonate was decreased to 0.0400 g, and 0.15 g of 1-dodecanethiol (Tokyo Chemical Industry Co., Ltd., first grade) was added. Under the same conditions as in Example 1, styrene and n-butyl acrylate were subjected to emulsion polymerization. DVBS in all radical polymerizable monomers is 2.00 mol%, and the amount of sodium dodecylbenzenesulfonate added is 0.09 parts by weight.

  As shown in Table 2, there are slightly more aggregates and a slightly larger emulsion particle size than in Example 1, but there are fewer aggregates and excellent adhesion and water resistance than in Comparative Examples. It is clear. Although it is difficult to measure the polymerization conversion rate of DVBS, it is estimated that almost 100% was polymerized from the result of Reference Example 2 and the formation of a stable emulsion.

Example 3 (composition change of Example 1)
Sodium divinylbenzenesulfonate was increased to 1.5000 g, styrene was reduced to 17.00 g, and 3.00 g of 2,2,2-trifluoroethyl methacrylate (Tokyo Chemical Industry Co., Ltd., first grade) was added instead. In all other cases, emulsion polymerization of styrene, n-butyl acrylate and 2,2,2-trifluoroethyl methacrylate was carried out under the same conditions as in Example 1. DVBS in all radical polymerizable monomers is 1.45 mol%, and the amount of sodium dodecylbenzenesulfonate added is 0.08 parts by weight.

  As shown in Table 2, it is clear that there are fewer aggregates and the adhesiveness and water resistance are superior compared to the comparative example. Although it is difficult to measure the polymerization conversion rate of DVBS, it is estimated that almost 100% was polymerized from the result of Reference Example 2 and the formation of a stable emulsion.

Example 4 (composition change of Example 1)
Emulsification of styrene, n-butyl acrylate and acrylonitrile under the same conditions as in Example 1 except that styrene was reduced to 18.00 g and 2.00 g of acrylonitrile (special grade, manufactured by Tokyo Chemical Industry Co., Ltd.) was added instead. Polymerization was performed. DVBS in all radical polymerizable monomers is 0.99 mol%, and the amount of sodium dodecylbenzenesulfonate added is 0.11 parts by weight.

  As shown in Table 2, it is clear that there are fewer aggregates and the adhesiveness and water resistance are superior compared to the comparative example. Although it is difficult to measure the polymerization conversion rate of DVBS, it is estimated that almost 100% was polymerized from the result of Reference Example 2 and the formation of a stable emulsion.

Comparative Example 1
Except that sodium divinylbenzenesulfonate was not used, emulsion polymerization of styrene and n-butyl acrylate was carried out under the same conditions as in Example 1. The addition amount of sodium dodecylbenzenesulfonate with respect to 100 weight parts of styrene and n-butyl acrylate is 0.18 parts by weight.

  As shown in Table 2, compared with Examples 1 and 2, there were many aggregates and the polymerization rate was greatly inferior.

Comparative Example 2 (examined at 1 mol% SS)
Styrene and n-butyl acrylate were all used under the same conditions as in Example 1, except that 0.9110 g of sodium styrenesulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., purity 88.0%) was used instead of sodium divinylbenzenesulfonate. The emulsion polymerization of was carried out. SS in all radical polymerizable monomers is 1.01 mol%, and the amount of sodium dodecylbenzenesulfonate added is 0.18 parts by weight.

  As shown in Table 2, compared with Examples 1 and 2, there were many aggregates, and adhesiveness and water resistance were inferior.

Comparative Example 3 (no water-soluble monomer, double conventional emulsifier)
Emulsion polymerization of styrene and n-butyl acrylate was carried out under the same conditions as in Example 1 except that sodium divinylbenzenesulfonate was not used and sodium dodecylbenzenesulfonate was increased to 1.5680 g. The amount of sodium dodecylbenzenesulfonate added to 100 parts by weight of all radical polymerizable monomers is 5.74 parts by weight.

  As shown in Table 2, although there were few aggregates and the polymerization rate was high, compared with Examples 1-4, adhesiveness and water resistance were large and inferior.

Comparative Example 4 (examined with excessive DVBS)
Emulsion polymerization of styrene and n-butyl acrylate was carried out under the same conditions as in Example 1 except that the amount of sodium divinylbenzenesulfonate was increased to 6.5000 g. DVBS in all radical polymerizable monomers is 5.83 mol%, and the amount of sodium dodecylbenzenesulfonate added is 0.18 parts by weight.

  As shown in Table 2, although there were few aggregates and the polymerization rate was high, compared with Examples 1 and 2, water resistance and adhesiveness were greatly inferior. This is thought to be due to the sulfonic acid groups in the emulsion polymer and the increased degree of crosslinking.

  The polymer emulsion of the present invention is an emulsion emulsion, coating film, adhesive, primer, fiber treatment agent, battery electrode material, as well as emulsion stability, coating film water resistance and adhesion. Such as various binders, inks, toners, information display materials, medical diagnostic materials, etc. are extremely useful in the industry.

Claims (5)

A polymer emulsion dispersed and stabilized in water or an aqueous medium with 3 parts by weight or less of an emulsifier with respect to 100 parts by weight of a polymer containing the following repeating structural units (A), (B) and (C).

[In the repeating structural unit (A), R ₁ represents hydrogen, a methyl group or an ethyl group, and R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with a hetero atom. In the repeating structural unit (B), R ₃ represents hydrogen or a methyl group, and R ₄ represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with hydrogen or a hetero atom. In the repeating structural unit (C), M represents a proton, sodium ion, potassium ion, lithium ion, ammonium ion or quaternary ammonium ion.
Where x is the number of repeating structural units (A) contained in the polymer, y is the number of repeating structural units (B) contained in the polymer, and z is the number of repeating structural units (C) contained in the polymer. 1.0 ≦ 100x / (x + y + z) ≦ 99.9, 100y / (x + y + z) ≦ 99.9, 0.1 ≦ 100z / (x + y + z) ≦ 5.0. ] The polymer emulsion according to claim 1, wherein the emulsion polymer further comprises the following repeating structural unit (D) in the structural units (A), (B), and (C).

[In the repeating structural unit (D), R _5, R ₆ and R ₇ are each independently a linear or branched group having 1 to 10 carbon atoms which may be substituted with hydrogen, halogen, cyano group or hetero atom. Represents an alkyl group. ]   The repeating structural unit (A) is an n-butyl acrylate polymer residue, an ethyl acrylate polymer residue, a propyl acrylate polymer residue, a 2-ethylhexyl acrylate polymer residue, a methyl methacrylate polymer residue, an ethyl methacrylate. One or a combination of two or more selected from the group consisting of a polymerization residue, a propyl methacrylate polymerization residue, a n-butyl methacrylate polymerization residue, and a 2,2,2-trifluoroethyl methacrylate polymerization residue The polymer emulsion according to claim 1 or 2, wherein the polymer emulsion is a monomer polymerization residue and the repeating structural unit (B) is a styrene polymerization residue. Radical polymerizable monomer is emulsified in water or an aqueous medium using an emulsifier of 3 parts by weight or less of 100 parts by weight of radically polymerizable monomer containing the following (e), (f), (g) and (h), and radical The manufacturing method of the polymer emulsion of any one of Claims 1-3 which adds a polymerization initiator and emulsion-polymerizes.
(E) 99.9-1.0 mol% of acrylic acid esters and / or methacrylic acid esters represented by the following formula (E),
(F) 99.9 mol or less of styrenes (F) represented by the following formula (F),
(G) 0.1 to 5.0 mol% of divinylbenzenesulfonic acid represented by the following formula (G) or a salt thereof, and (h) represented by the following formula (H), wherein the formulas (E) and (F ) And 20.0 mol% or less of a radically polymerizable monomer copolymerizable with the compound represented by formula (G)

[In formula (E), R ₁ represents hydrogen, a methyl group or an ethyl group, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with a hetero atom,
In Formula (F), R ₃ represents hydrogen or a methyl group, R ₄ represents hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms that may be substituted with a hetero atom,
In the formula (G), M represents a proton, sodium ion, potassium ion, lithium ion, ammonium ion or quaternary ammonium ion,
In formula (H), R _5, R ₆ and R ₇ are each independently a straight chain or branched chain having 1 to 10 carbon atoms which may be substituted with hydrogen, a halogen group, a cyano group or a hetero atom. Represents an alkyl group. ]   The polymer emulsion according to claim 1 or 2 selected from the group consisting of paint, coating agent, adhesive, primer, binder, fiber treatment agent, toner, information display material and medical diagnostic material. Use for combination.

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