JP2003253135A - Anionic emulsified dispersion of thermoplastic elastomer and its preparation process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain anionic emulsified dispersion which can be utilized in many applications, can impart suitable properties to emulsions conventionally used in those applications when it is mixed with the emulsions before use, or can be used as an asphalt modifier that can be mixed with or dissolved in, for example, hot asphalt or asphalt emulsion by a simple and easy method, that can improve the flow resistance, toughness and low-temperature flexibility and that is excellent in long-term stability and mechanical stability. <P>SOLUTION: The anionic emulsified dispersion of a thermoplastic elastomer and its preparation process are obtained by emulsifying and dispersing a thermoplastic elastomer by using three kinds of different anion surface active agents in an amount less than those of a nonionic, a cationic and the anionic surface active agent. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an anionic emulsion dispersion of a thermoplastic elastomer and a method for producing the same.

More specifically, as a surfactant used for emulsifying / dispersing a thermoplastic elastomer, a nonionic surfactant, an anionic surfactant and a heteroionic surfactant of a cationic surfactant in an amount smaller than that of the anionic surfactant are used. By using 3 types of agents, the emulsifying property is improved,
Improved aging stability and mechanical stability, for asphalt modification, coated paper, foam rubber, tire cord, coating (cans, plastics, inorganic materials, wood, etc.), paint, floor polish For adhesives (water-based adhesives, polymer cement, mortar adhesives, etc.), adhesives, removable labels, direct mail, and textile processing for carpets, car seats, mats, etc.
The present invention relates to an anionic emulsion dispersion of a thermoplastic elastomer capable of imparting suitable properties when used as an emulsion for a waterproof material or when mixed with an emulsion used for these applications, and a method for producing the same.

[0003]

2. Description of the Related Art For example, one application of a block copolymer latex which can be used in many applications is asphalt,
Rubber, resin (including thermoplastic elastomer, the same applies below)
Asphalt (modified asphalt) with improved viscosity at 60 ℃, toughness, tenacity, temperature sensitivity, etc. was developed by adding modifiers made of polymer materials such as It has been used for the purpose of improving wear resistance.

As the above-mentioned modifier, a thermoplastic elastomer is dissolved in an organic solvent, and then 10% by weight (hereinafter referred to as "%") or less of the polyalkylene oxide group-containing anionic surfactant is contained as a main component with respect to the elastomer. If necessary, an emulsifying dispersant in which a nonionic surfactant is used is added, and then warm water is added to emulsify and disperse, and the organic solvent is removed to obtain an asphalt modifier for an aqueous emulsified dispersion having an average particle size of 5 μm or less. It is disclosed to use (JP-A-2-292368).

Specific examples of the polyalkylene oxide group-containing anionic surfactant and the nonionic surfactant used as necessary include polyoxyethylene nonylphenol ether sulfate soda salt (ethylene oxide 4 mol adduct) and polyoxy, respectively. Ethylene dodecyl ether sodium acetate (Ethylene oxide 3
Mole adduct), and polyoxyethylene nonylphenol ether (ethylene oxide 4 mole adduct).

Further, as a block copolymer latex which can be used for many purposes, general formulas: ABA, (AB) n, B- (AB) n, (A-
B) n-A or AB- (BA) n (In the formula, A is an inelastic polymer block having a second-order transition temperature of 25 ° C or higher, and B has a second-order transition temperature of 10 ° C or lower. (A) a rosin acid salt or disproportionated rosin acid salt, and (b) a general formula:

[0007]

[Chemical 1]

(Wherein R ¹ is an alkylphenyl group having an alkyl group having 8 to 18 carbon atoms or an alkyl group having 8 to 12 carbon atoms, R ² is an alkylene group having 2 to 5 carbon atoms, and m is 3 to 50). Block copolymer latex emulsified using a compound represented by the formula (1) and optionally a thickener (methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, casein, polyacrylic acid or a derivative thereof). Japanese Patent Publication Sho 52-22
651).

Further, as a technique similar to the block copolymer latex, a styrene-butadiene random copolymer obtained by a solution polymerization method or a styrene-butadiene copolymer latex which can be used in many applications is obtained. A styrene-butadiene binary block copolymer or a mixture thereof is used as an emulsifier (a) a higher fatty acid, rosin acid or disproportionated rosin acid, and (b) a general formula:

[0010]

[Chemical 2]

(In the formula, R ¹ is an alkyl group having 8 to 18 carbon atoms or an alkylphenyl group having 8 to 12 carbon atoms, R ² is an alkylene group having 2 to 5 carbon atoms, and n is 3 to 5
An integer of 0) is dissolved in the polymer solution,
A styrene-butadiene copolymer latex obtained by mixing and emulsifying this with an alkaline aqueous solution is disclosed (Japanese Patent Publication No. Sho 5).
2-15100, JP-A-51-13847).

However, both the block copolymer latex and the styrene-butadiene copolymer latex have a problem that they are not always sufficient in stability over time or mechanical stability.

In order to solve the above problems, the present inventors have
As an emulsifier for emulsifying and dispersing a thermoplastic elastomer, a styrenated phenol polyalkylene oxide adduct, a polyalkylene polyamine polyalkylene oxide adduct, a polyhydric alcohol fatty acid ester, a polyhydric alcohol fatty acid ester polyalkylene oxide adduct, and a benzylated phenol poly It is an aqueous emulsification dispersion type asphalt modifier using one or more of alkylene oxide adducts and an anionic surfactant, which can be mixed and dissolved in hot asphalt by a simple method and impairs workability. We are developing an aqueous emulsified dispersion type asphalt modifier with improved stability over time and mechanical stability, which can improve the flow resistance, toughness and low temperature flexibility of asphalt without any damage ( JP-A-2001-59053).

The aqueous emulsion-dispersion asphalt modifier described in JP 2001-59053 A is superior to conventional asphalt modifiers, but still has problems in storage stability and mechanical stability. There is room for improvement.

[0015]

The present invention is disclosed in Japanese Patent Laid-Open No. 2001-2001.
It was made in order to solve the problem that the storage stability and mechanical stability in the aqueous emulsion dispersion described in JP-A-59053 do not always have sufficient performance.

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, by partially forming a complex of a cationic surfactant and an anionic surfactant, the complex has an anionic surfactant activity. By having a structure partially similar to the anionic surfactant, the affinity with anionic surfactants is improved, the emulsifying and dispersing power of anionic surfactants is increased, and the stability of the emulsion over time and mechanical stability The present invention has been completed and the present invention has been completed, and it was found that foaming due to an anionic surfactant in the solvent distillation step can be suppressed.

That is, in the present invention, a thermoplastic elastomer is emulsified and dispersed by using a nonionic surfactant, an anionic surfactant and three kinds of different ionic surfactants of a cationic surfactant which are smaller than the amount of the anionic surfactant. The anionic emulsion dispersion of a thermoplastic elastomer (claim 1) characterized in that the cationic surfactant is 0.1 to 50.0 with respect to 100 parts by weight (hereinafter referred to as "part") of the anionic surfactant. 3. The anionic emulsion dispersion according to claim 1 (claim 2), wherein the nonionic surfactant is a styrenated phenol polyalkylene oxide adduct, and the anionic emulsion dispersion according to claim 1 or 2. 3), the styrenated phenol polyalkylene oxide adduct is a monostyrenated phenol polyalkylene oxide adduct: di Styrene phenol polyalkylene oxide adduct of styrenated above triphenol polyalkylene oxide adduct = 10 to 20: 40 to 5
The anionic emulsion dispersion according to claim 3 (claim 4), wherein the nonionic surfactant is benzylated phenol polyalkylene oxide addition, wherein the total amount is 100 at a ratio of 5:30 to 45 (weight ratio). The anionic emulsified dispersion according to claim 1 or 2 (claim 5), wherein the benzylated phenol polyalkylene oxide adduct is
Monobenzylated phenol polyalkylene oxide adduct: Dibenzylated phenol polyalkylene oxide adduct: Tri or higher benzylated phenol polyalkylene oxide adduct = 10 to 20:40 to 55:30 to 45
The anionic emulsion dispersion according to claim 5, wherein the total amount is 100 at a ratio of (weight ratio) (claim 6),
Furthermore, a nonionic interface is added to a solution containing a cellulose derivative as a thickening agent, the solution comprising the anionic emulsion dispersion according to claim 1 (claim 7), a thermoplastic elastomer and an organic solvent. It is characterized in that after preparing a solution in which an active agent, an anionic surfactant and a cationic surfactant in an amount smaller than that of the anionic surfactant are dissolved, they are mixed with water to emulsify and then the organic solvent is distilled off. In the method for producing the anionic emulsion dispersion according to claim 1, 2, 3, 4, 5 or 6, (claim 8) and the method for producing the anionic emulsion dispersion according to claim 8, after the organic solvent is distilled off. The method for producing an anionic emulsion dispersion according to claim 7 (claim 9), further comprising adding and dissolving a thickener.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION When the thermoplastic elastomer used in the present invention is used as an aqueous pressure-sensitive adhesive, for example, by mixing it with an acrylic water-based pressure-sensitive adhesive, its holding power at high temperature can be improved. When used as an improving component or as an asphalt modifier, it has good compatibility with asphalt.For example, when added to asphalt, the softening point, viscoelasticity, toughness, high temperature viscosity and low temperature flexibility of asphalt. As a component capable of improving the chipping resistance and the like, when added to SBR latex for water-based chipping-resistant paint, etc., it has good compatibility with SBR and can improve the chipping resistance and adhesion. Is what is used.

The thermoplastic elastomer may be used without particular limitation as long as it has been conventionally used for the above purpose. For example,
For example, the general formulas used as hot melt adhesives: A-B-A, (A-B) n, B- (A-B) n and (A-B) n-A, where A is 25 And a block copolymer represented by an elastic polymer block having a second-order transition temperature of 10 ° C. or lower, and an integer of 2 or more).

The non-elastic polymer block is, for example, a homopolymer block of a monomer selected from monovinyl aromatic hydrocarbons such as styrene and α-methylstyrene, or a copolymer block composed of two or more kinds, monovinyl. Examples include taper-type copolymer blocks of aromatic hydrocarbons and aliphatic conjugated diene compounds of the following B block component, random copolymer blocks of monovinyl aromatic hydrocarbons and aliphatic conjugated diene compounds of the following B block component, and the like. To be Specific examples of the block include a styrene polymer, a copolymer of styrene and α-methylstyrene, a tapered copolymer of styrene and butadiene or isoprene, and a random copolymer of styrene and butadiene or isoprene. Examples of the block include those having a molecular weight of 1,000 to 200,000, more preferably 10,000 to 50,000.

As the elastic polymer block,
For example, a homopolymer block of a monomer selected from aliphatic conjugated diene compounds such as butadiene and isoprene, a copolymer block of two or more of the above monomers, an aliphatic conjugated diene compound and a monovinyl aromatic compound. And the taper type copolymer block, a random copolymer block of an aliphatic conjugated diene compound and a monovinyl aromatic compound, and a polymer block obtained by hydrogenating these polymer blocks. Specific examples of the block include a butadiene polymer, an isoprene polymer, a copolymer of butadiene and isoprene, a tapered copolymer of styrene and butadiene or isoprene, a random copolymer of styrene and butadiene or isoprene, and hydrogenated. Examples of the block include butadiene polymers and hydrogenated styrene / butadiene copolymers, and the molecular weight thereof is generally 5,0.
00-500,000, and even 100,000-35
The one of 000 is used.

The content of the non-elastic polymer block in the block copolymer is 10 to 70 based on the total polymer.
%, And more preferably 20 to 40%. When the content is out of the above range, the characteristics of the thermoplastic elastomer are not easily exhibited.

The molecular weight of the block copolymer is
10,000-700,000, and even 100,000
It is preferably 0 to 500,000. If the molecular weight is too small, the mechanical strength of the film obtained from the latex tends to be insufficient, and if it is too large, the viscosity during emulsification becomes too high and the emulsification becomes incomplete or difficult. , Tend to adversely affect the performance of the resulting latex.

Specific examples of the block copolymer include:
Examples include SBS block copolymers, SIS block copolymers, hydrogenated SBS block copolymers and the like.
These may be used alone or in combination of two or more.

The block copolymer may be obtained by a method of sequentially polymerizing the monomers block by block in the presence of a living polymerization initiator, or by simultaneously charging two or more monomers having different reactivities, and polymerizing the monomers. It can be obtained by a method of obtaining a block copolymer, a method of coupling a living block copolymer with the above initiator, or the like.

As the polymer solution for producing the block copolymer latex from the block polymer, the polymerization solution may be used as it is, or the solid matter of the block copolymer may be benzene, toluene, xylene, cyclohexane, It may be used by dissolving it in a solvent such as cyclooctane, chloroform, carbon tetrachloride, trichlene, dichloromethane. The polymer solution is preferably used usually in the concentration range of 5 to 30%.

In the present invention, in order to emulsify / disperse the thermoplastic elastomer, three kinds of nonionic surfactants, anionic surfactants and three kinds of different ionic surfactants of cationic surfactants less than the anionic surfactant are used. Is used. To emulsify / disperse the thermoplastic elastomer, three kinds of nonionic surfactants, anionic surfactants, and three kinds of different ionic surfactants of cationic surfactants less than the anionic surfactant are used. A complex with an anionic surfactant is partially formed, and since the complex has a structure partially similar to the anionic surfactant, the affinity with the anionic surfactant is improved, and the anionic surfactant is further improved. The emulsifying / dispersing power can be increased, and thus the daily stability and mechanical stability of the emulsion can be improved. Also,
Since a complex (usually water-insoluble) of an anion-cationic surfactant is formed, water resistance is improved, and foaming due to the anionic surfactant in the solvent distillation step can be suppressed. Further, since the amount of the cationic surfactant is smaller than the amount of the anionic surfactant, the resulting emulsion dispersion of the thermoplastic elastomer becomes an anionic emulsion dispersion, which is used for modifying anionic water-based paints and water-based adhesives. Alternatively, it can be used as an asphalt modifier. Furthermore, since a nonionic surfactant that does not affect the ionicity is used in addition to the anionic surfactant and the cationic surfactant, an anionic emulsion dispersion having good emulsification dispersibility can be obtained.

The complex of the anionic surfactant and the cationic surfactant is partially formed means that the anionic surfactant is used in a larger amount than the cationic surfactant, so that even if the complex is formed, the anionic surfactant is It means that the drug is not all complex.

Specific examples of the nonionic surfactants include styrenated phenol polyalkylene oxide adducts, polyalkylene polyamine polyalkylene oxide adducts, polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid ester polyalkylene oxide adducts, and One or more of the benzylated phenol polyalkylene oxide adducts (hereinafter, also referred to as a specific emulsifier) and other conventional nonionic surfactants may be mentioned. These may be used alone or in combination of two or more.

When the above-mentioned specific emulsifier is used as the above nonionic surfactant, the anionic emulsion dispersion produced, and the stability and mechanical properties of the respective modifiers using the anionic emulsion dispersion over time. Stability can be improved. Further, by suppressing foaming when removing under reduced pressure the organic solvent used in the production of the thermoplastic elastomer solution during emulsification / dispersion of the thermoplastic elastomer (for example, toluene, xylene, benzene, cyclohexane, cyclooctane, etc.), Desolvation can be easily performed in a short time, and an aqueous dispersion that is stable in storage can be produced.

The styrenated phenol polyalkylene oxide adduct is one or more of monostyrenated phenol, distyrenated phenol and tri or more styrenated phenol, and an alkylene oxide having 2 to 4 carbon atoms (for example, ethylene oxide, propylene). Oxide, butylene oxide).
For example, a distyrenated phenol polyethylene oxide adduct is represented by the following formula.

[0032]

[Chemical 3]

The above tri- or more styrenated phenol means that a tri- or more styrenated phenol may be mixed with a small amount of tetra or more styrenated phenol.

Preferred specific examples of the styrenated phenol polyalkylene oxide adduct include, for example, a monostyrenated phenol polyalkylene oxide adduct having an average ethylene oxide addition mole number of 20 moles: a distyrenated phenol polyalkylene oxide adduct: tri or more. Styrenated phenol polyalkylene oxide adduct of 10 to 20:40 to 55:30 to 45 (weight ratio)
And the like are included so that the total amount becomes 100.

As the styrenated phenol polyalkylene oxide adduct, a monostyrenated phenol polyalkylene oxide adduct, a distyrenated phenol polyalkylene oxide adduct, and a tri- or more styrenated phenol polyalkylene oxide adduct are used alone. However, since it is better that the emulsifiability has a distribution, it is preferable to use a mixture thereof.

The polyalkylene polyamine polyalkylene oxide adduct is, for example, a polyalkylene polyamine such as polyethyleneimine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine, which is addition-polymerized with an alkylene oxide having 2 to 4 carbon atoms. (For example, block- or random addition-polymerization of ethylene oxide and propylene oxide or butylene oxide).

As a preferred specific example of the polyalkylene polyamine polyalkylene oxide adduct, for example, a polyfunctional nitrogen-based polyamine obtained by randomly or block-adding ethylene oxide and propylene oxide to polyethyleneimine (for example, having a molecular weight of 1200 or 1800). Examples include ether compounds.

The polyhydric alcohol fatty acid ester is
For example, sucrose is composed of a polyhydric alcohol having 3 to 8 valences and a saturated or unsaturated fatty acid having 8 to 22 carbon atoms, and sorbitan has an average of 2 to 3 hydroxyl groups remaining per molecule. For example, the average number of hydroxyl groups per molecule is 5-7.
It is the one that remains.

Specific examples of the polyhydric alcohol include glycerin, dixerine, sorbitol, sorbide, the above-mentioned sorbitan, and sucrose.

Specific examples of the saturated or unsaturated fatty acid include saturated fatty acids such as lauric acid, palmitic acid, stearic acid, behenic acid, and straight chain or branched synthetic saturated fatty acids having 8 to 22 carbon atoms. Unsaturated fatty acids such as oleic acid, linoleic acid, and linoleic acid.

Specific preferred examples of the polyhydric alcohol fatty acid ester include, for example, sorbitan oleic acid ester (having a distribution of mono-, di-, tri-, and tetra-esters and having an average of 2 to 3 hydroxyl groups per molecule). Can be given.

The polyhydric alcohol fatty acid ester polyalkylene oxide adduct is composed of, for example, a polyhydric alcohol having a valence of 3 to 8 and a saturated or unsaturated fatty acid having 8 to 22 carbon atoms. Taking, for example, a polyhydric alcohol fatty acid ester or sucrose remaining 2-3 per molecule, hydroxyl groups average 5 to 7 per molecule.
It is a polyhydric alcohol fatty acid ester that remains by addition-polymerizing an alkylene oxide having 2 to 4 carbon atoms (for example, ethylene oxide, propylene oxide, butylene oxide).

As the polyhydric alcohol and the saturated or unsaturated fatty acid, the same ones as those used in the production of the polyhydric alcohol fatty acid ester are used.

Preferred specific examples of the polyhydric alcohol fatty acid ester polyalkylene oxide adduct include, for example, Tween 60 and Tween 80 manufactured by Atlas Co., Ltd.
Tween85, Sorgen TW- from Daiichi Kogyo Seiyaku Co., Ltd.
20, Sorgen TW-60, Sorgen TW-80 and the like.

The benzylated phenol polyalkylene oxide adduct is one or more selected from monobenzylated phenol, dibenzylated phenol, and tri- or more benzylated phenol, and an alkylene oxide having 2 to 4 carbon atoms (for example, ethylene oxide, Propylene oxide,
Butylene oxide). For example, a dibenzylated phenol polyethylene oxide adduct is represented by the following formula.

[0046]

[Chemical 4]

The above-mentioned tri or higher benzylated phenol means that a small amount of tetra or higher benzylated phenol may be mixed in the tribenzylated phenol.

Preferred specific examples of the benzylated phenol polyalkylene oxide adduct include, for example, monobenzylated phenol ethylene oxide adduct having an average ethylene oxide addition mole number of 20 moles: dibenzylated phenol ethylene oxide adduct: tri or more benzylated phenols. Ethylene oxide adduct = 10-20:
40-55: 30-45 (weight ratio) with a total amount of 1
Examples include those included so as to become 00.

As the benzylated phenol polyalkylene oxide adduct, a monobenzylated phenol polyalkylene oxide adduct, a dibenzylated phenol polyalkylene oxide adduct, and a tri- or higher benzylated phenol polyalkylene oxide adduct are used alone. However, since it is better that the emulsifiability has a distribution, it is preferable to use a mixture thereof.

The above specific emulsifiers may be used alone or in combination of two or more, and among these, a styrenated phenol polyalkylene oxide adduct and a benzylated phenol polyalkylene oxide adduct are added. The product has a high polydispersity (having a wide distribution of both hydrophobic groups and hydrophilic groups), and a high polydispersity of the thermoplastic elastomer to be emulsified, which is preferable because the emulsification performance is good and the foaming trouble is reduced. .

Examples of ordinary nonionic surfactants other than the above specific nonionic surfactants include, for example, alkyl polyoxyethylene ethers (wherein the alkyl group has 8 to 2 carbon atoms).
2), alkylphenol polyoxyethylene ether (the carbon number of the alkyl group is 8 to 12), alkyl polyoxyethylene polyoxypropylene ether (the carbon number of the alkyl group is 8 to 22, which of the blocks of polyoxyethylene and polyoxypropylene is It may be added first, or may be added randomly, fatty acid polyoxyethylene ester (fatty acid is a saturated or unsaturated fatty acid having 8 to 22 carbon atoms), polyoxyethylene (cured)
Castor oil, alkyl polyoxyethylene amine (alkyl group having 8 to 18 carbon atoms), alkyl polyoxyethylene amide (alkyl group having 8 to 18 carbon atoms) and the like can be mentioned.

As the nonionic surfactant, only the specific emulsifier may be used as the nonionic surfactant, or only a normal nonionic surfactant other than the specific emulsifier may be used as the nonionic surfactant. Further, these may be used in combination. When the specific emulsifier and a normal nonionic surfactant other than the specific emulsifier are used in combination, the use ratio may be appropriately determined and used according to the purpose.

The anionic surfactant used in the present invention can be used without particular limitation as long as it can be used in the production of the aqueous emulsion dispersion of the thermoplastic elastomer.

Examples of the anionic surfactants include carboxylic acid type anionic surfactants, sulfate ester type anionic surfactants, sulfonic acid type anionic surfactants,
Examples thereof include phosphate ester type anionic surfactants. These may be used alone or in combination of two or more.

Specific examples of the carboxylic acid type anionic surfactant include, for example, the general formula: RCOOM (wherein R is a C _7-21 saturated or unsaturated hydrocarbon group,
M is a fatty acid salt represented by Na, K, NH ₄ , a cation such as alkanolamine · H), a salt of a resin acid obtained by extraction of pine trees, etc., and the main component is an abietic acid salt (eg,

[0056]

[Chemical 5]

A rosinate, which is a salt of a carboxylic acid contained in petroleum, represented by the general formula:

[0058]

[Chemical 6]

(Wherein M is a cation such as Na, K or an alkanolamine.H, n is 1 or more), a naphthenate having a structure represented by the general formula: R (OC ₂ H ₄ ) _n OCH ₂ COOM (wherein R is a C _10-18 alkyl group, alkylphenyl group, M is a cation such as Na or K, and n is 2 or more), a general formula:

[0060]

[Chemical 7]

(Wherein R is a C _8-18 unsaturated hydrocarbon group, M is a cation such as Na), an alkenyl succinate represented by the general formula: RCON (CH ₃ ) CH ₂ COOM (wherein , R is a C _11-18 saturated or unsaturated hydrocarbon group,
M is a cation such as Na) and is represented by the general formula:

[0062]

[Chemical 8]

(Wherein R is a C _11-18 saturated or unsaturated hydrocarbon group, M is a cation such as Na or an alkanolamine.H), and the like are N-acylglutamates. These may be used alone or in combination of two or more.

Specific examples of the sulfate ester type anionic surfactant include the general formula: ROSO ₃ M (wherein R is a C _8-18 saturated or unsaturated hydrocarbon group,
M is a cation such as Na, K, NH ₄ or alkanolamine · H), and is a primary alkyl sulfate salt represented by the general formula:

[0065]

[Chemical 9]

(In the formula, RR ¹ CH— is a secondary alcohol having a C _12-16 straight-chain or branched-chain alkyl group, and
A secondary alkyl sulfate salt represented by a group excluding H group, M is a cation such as Na, and a general formula: R (OC ₂ H ₄ ) _n OSO ₃ M (wherein R is a saturated C _12-18 ). Or an unsaturated hydrocarbon group,
M is a cation such as Na, K, NH ₄ or alkanolamine · H, n is 2 or more), and an alkyl polyoxyethylene sulfate is represented by the general formula:

[0067]

[Chemical 10]

(Wherein R is a C _8-12 alkyl group, M is a cation such as Na, and n is 2 or more), and is represented by the general formula: RCOOCH ₂ CH (OH) CH ₂ OSO ₃ M (wherein R is a C _11-17 saturated or unsaturated hydrocarbon group,
M is a cation such as Na), and is represented by the general formula: RCONHC ₂ H ₄ OSO ₃ M (wherein R is a C _11-17 saturated or unsaturated hydrocarbon group,
M is a cation such as Na), an acylaminosulfate salt, olive oil, castor oil, cottonseed oil, rapeseed oil, beef tallow, etc. Sulfated oil, oleic acid, ricinoleic acid, etc., double bonds, hydroxyl group-containing fatty acid propyl, butyl ester, etc. can give. These may be used alone or in combination of two or more.

Specific examples of the sulfonic acid type anionic surfactant include, for example, a sulfonated product of C _14-19 α-olefin, which is generally RCH═CHCH ₂ SO ₃ M (alkenyl compound) and

[0070]

[Chemical 11]

Α-Olefin sulfonic acid (AOS) obtained as a mixture of (M is a cation such as Na or K)
Salt, to the n- paraffins C _{8 to 20} SO _2, Cl ₂ in a sulfoxy compound or second alkane sulfonates obtained by neutralizing the Suruhokuroru product with an alkali, methyl fatty acid C _{12 to 18,} isopropyl ester, etc. Α-sulfonated salt of α-sulfofatty acid ester salt of the general formula: RCOOC ₂ H ₄ SO ₃ M (wherein R is a C _11-17 saturated or unsaturated hydrocarbon group,
M, a cation such as Na), an acyl isethionate represented by the general formula: RCON (CH ₃ ) C ₂ H ₄ SO ₃ M (wherein R is a C _11-17 saturated or unsaturated hydrocarbon group, M is a cation such as Na) N-acyl-N-methyltauric acid represented by the general formula:

[0072]

[Chemical 12]

(Wherein R is a C _2-20 straight or branched chain alkyl group, M is a cation such as Na), and is represented by the general formula:

[0074]

[Chemical 13]

(Wherein RR ¹ CH- is a C _9-13 linear or branched alkyl group, M is a cation such as Na or K), and alkylbenzene sulfonate (ABS, L
AS), general formula:

[0076]

[Chemical 14]

(Wherein R is a C _3-5 straight-chain or branched-chain alkyl group, M is a cation such as Na), and is represented by the general formula:

[0078]

[Chemical 15]

(Wherein R is a C ₁₂ alkyl group, M is Na
Cations such as) alkyl diphenyl ether disulfonate, petroleum sulfonate, lignin sulfonate, and the like. These may be used alone or in combination of two or more.

Specific examples of the phosphate ester type anionic surfactant include, for example, the general formula:

[0081]

[Chemical 16]

(Wherein R is a C _8-18 alkyl group, M is a cation such as H, Na, K, NH ₄ or alkanolamine.H) and the alkyl phosphate salt ((1) phosphoric acid) Monoester salt, (2) Diester salt, (3) (1)
And (2) as a mixture), the general formula:

[0083]

[Chemical 17]

(Wherein R is a C _12-18 alkyl group, M is a cation such as H, Na, K, or alkanolamine.H, n is 2 or more), and an alkyl polyoxyethylene phosphate ( Usually present as a mixture with a diester salt), the general formula:

[0085]

[Chemical 18]

(In the formula, R is a C _8-12 alkyl group, M is a cation such as H, Na, K, and alkanolamine.H, n is 2 or more), and an alkyl polyoxyethylene phosphate ( It is usually present as a mixture of a monoester salt and a diester salt).

In addition, the sulfate ester salt (Na salt, K salt, etc.) of the styrenated phenol polyalkylene oxide adduct, the sulfate ester salt (Na salt, K salt, etc.) of the benzylated phenol polyalkylene oxide adduct, etc. can give. These may be used alone or in combination of two or more.

Raw materials used for the anionic surfactant
Specific examples of the alcohol include
Xanol, n-octanol, decanol, dodecano
, Tetradecanol, hexadecanol, octade
Synthetic first-class compounds such as kanol, alfol and dobanol
Alcohol, Targitol S, Softanol, Oxoa
Synthetic secondary alcohols such as rucor, benzylalco
And octylphenol, phenol as phenol
C such as nylphenol and dodecylphenol _{8 ~ 22}of
, Styrenated phenol, benzylated phenol
However, specific examples of the amine include laurylamine and lauryl.
Higher amines such as rumethylamine and dioleylamine,
Specific examples of the carboxylic acid include lauric acid and myristin
Acid, palmitic acid, oleic acid, stearic acid, beheni
Examples thereof include acid and rosin acid.

The anionic surfactants may be used alone or in combination of two or more. Among these, the sulfate ester salt (Na salt, K salt, etc.) of the styrenated phenol polyalkylene oxide adduct and the sulfate ester salt (Na salt, K salt, etc.) of the benzylated phenol polyalkylene oxide adduct are the above. A carboxylic acid type surfactant is preferable from the viewpoint of good compatibility with a specific nonionic surfactant, and also from the viewpoint of good adsorbability of the complex formed with the cationic surfactant to the emulsion.

The cationic surfactant used in the present invention can be used without particular limitation as long as it can be used in the production of the aqueous emulsion dispersion of the thermoplastic elastomer.

Examples of the cationic surfactants include alkylamine salt type cationic surfactants, acylamine salt type cationic surfactants, quaternary ammonium salt type cationic surfactants, amide bond-containing ammonium salt type cationic surfactants. , An ester bond- or ether bond-containing ammonium salt type cationic surfactant, an imidazoline or imidazolium salt type cationic surfactant, and the like. These may be used alone or in combination of two or more.

The above-mentioned alkylamine salt type cationic surfactant
Specific examples of agents and acylamine salt-type cationic surfactants
For example, C_12-18Primary alkyl having an alkyl group of
Min salts (hydrochloride, acetate, etc.), C₁₇The alkyl group of
Is an acylaminoethyldiethyl group having an alkenyl group
Min salts (hydrochloride, formate, acetate, lactate, etc.), C
_12-18N-alkyl polyalkyl having alkyl groups of
Polyamine salt (hydrochloride, acetate, C number of alkylene group)
Is 2 to 3, the number of repeating alkyleneamine groups is 1 to 3),
C₁₇Fatty acid groups containing alkyl or alkenyl groups of
Polyethylene polyamide salt (hydrochloride, ethyleneamine group
The number of repetitions is 2), C₁₇Diethyl group having an alkyl group of
Minoethylamide salt (hydrochloride, acetate, lactate, etc.)
I can give you something. These may be used alone or in combination of two or more.
You may use in combination.

Specific examples of the quaternary ammonium salt type cationic surfactant and the amide bond-containing ammonium salt type cationic surfactant include, for example, alkyl or alkenyl having a C _12-18 alkyl group or a C ₁₈ alkenyl group. Trimethylammonium salt (the anion is C
l ⁻ , Br ⁻ , CH ₃ SO ₄ ^—, etc., a dialkyl or dialkenyldimethylammonium salt having a C _12-18 alkyl group or a C ₁₈ alkenyl group (the anion is Cl
_{^{-, Br -, CH 3 SO}} 4 -), alkyl or alkenyl dimethyl benzyl ammonium salt (anion having an alkyl or alkenyl group of C ₁₈ of C _{12 to 18} C
l ^-), alkylpyridinium salts (anions having an alkyl group of C _{12 to 18} is Cl ^-, Br ^-), an alkyl group or an acyl amino ethylmethyl diethyl ammonium salt having an alkenyl group of C ₁₇ of C ₁₇ (yin Ion is CH ₃ SO ₄
^- ), An acylaminopropyldimethylbenzylammonium salt having a C ₁₃ alkyl group (the anion is C
l ^-), acyl aminopropyl dimethyl hydroxyethyl ammonium salts (anions ClO ₄ having an alkyl group of C ₁₇ ^-), Cl acyl aminoethyl pyridinium salt (anion having an alkyl group of C ₁₁ ^-), C ₁₇ Diacylaminoethyldimethylammonium salt having a C ₁₇ alkyl group or a C ₁₇ alkenyl group (the anion is C
l ⁻ , and one of the methyl groups may be a hydroxyethyl group). Further, a compound in which a tertiary amine such as trialkyl or alkenyldialkylamine is cationized with a quaternizing agent such as xylenyl dichloride can also be used. These may be used alone or in combination of two or more.

[0094] Examples of the ester bond or an ether bond-containing ammonium salt type cationic surfactants, for example, Zia siloxy ethyl methyl hydroxyethyl ammonium salt (anion having an alkyl or alkenyl group of C ₁₇ of C ₁₇ is CH ₃ SO ₄ ⁻ ), an alkyloxymethylpyridinium salt having a C ₁₆ alkyl group (the anion is Cl ⁻ ), and the like. These may be used alone or in combination of two or more.

Specific examples of the imidazoline or imidazolium salt type cationic surfactant include, for example, C
Alkyl or alkenyl imidazolines having _{11 to 17} alkyl groups or C ₁₇ alkenyl groups (including acetates, carbonates and quaternary compounds), C _{11 to 17} alkyl groups or C
1-Hydroxyethyl 2-alkyl or alkenyl imidazoline having ₁₇ alkenyl groups (also quaternary compounds), 1 having C ₁₇ alkyl or alkenyl groups
- acylaminoethyl-2-alkyl imidazolium salt ^{_{(anion, CH 3 SO 4 -, C}} 2 H 5 SO 4 -, 2 -position an alkyl group is methyl group or ethyl group) and the like. These may be used alone or in combination of two or more.

The above cationic surfactants may be used alone or in combination of two or more. Among these, the quaternary ammonium salt type cationic surfactant is preferable from the viewpoint of the ability to form a complex with the anionic surfactant.

The ratio of the nonionic surfactant, the anionic surfactant and the cationic surfactant used is such that the total amount is 100 parts, preferably the nonionic surfactant containing a specific nonionic surfactant. 10 to 90 parts, more preferably 30 to 70 parts, especially 4
0-60 parts are used, and the total amount of anionic surfactant and cationic surfactant is 10-90 parts, and further 30-70.
Parts, particularly 40 to 60 parts, are used for emulsifying the mixture of the thermoplastic elastomer and the solvent during the production of the thermoplastic elastomer aqueous dispersion, preventing foaming in the solvent distilling step, and It is preferable from the viewpoint of storage stability of the anionic emulsion dispersion (hereinafter, also referred to as a thermoplastic elastomer emulsion dispersion). When the amount of the nonionic surfactant, especially the nonionic surfactant containing a specific emulsifier, is less than 10 parts, the effect of improving the emulsification dispersibility due to the use of the nonionic surfactant tends to be hardly obtained. , 90 parts by weight, it is possible to sufficiently improve the emulsifying property of the mixture of the thermoplastic elastomer and the solvent during the production of the thermoplastic elastomer emulsified dispersion by using the anionic surfactant and the cationic surfactant. It tends to be difficult. Further, since the amount of the complex of the anionic surfactant and the cationic surfactant produced is small, it tends to be difficult to obtain the effect of preventing foaming in the solvent distillation step. It is preferable to use a complex of an anionic surfactant and a cationic surfactant and a specific emulsifier or a nonionic surfactant containing the same in order to obtain a synergistic foam suppressing effect.

The mixing ratio of the cationic surfactant to the anionic surfactant varies depending on the type and amount of the nonionic surfactant used in combination and is therefore difficult to unambiguously define. Agent 100
0.1 to 50.0 parts, more 0.5 to 4 parts
It is preferably 0.0 parts, especially 1.0 to 30.0 parts. If the mixing ratio of the cationic surfactant is too low, the effect of forming a complex of cationic surfactant-anionic surfactant is not sufficiently expressed,
If the amount is too large, the thermoplastic elastomer emulsion dispersion produced does not exhibit sufficient anionic properties. However, it is essential for adjusting the number of cationic groups of the cationic surfactant to be used within 50% with respect to the number of anionic groups of the anionic surfactant used in order to bring out the effect of the present invention. is there.

Specific examples of the combination of the anionic surfactant and the cationic surfactant include, for example, a sodium salt (styrene salt of a compound obtained by adding 13 mol of ethylene oxide to phenol having an average of 2 styrene groups added thereto and further sulfating the phenol. Phenol EOA Na Sulfate) 100
Part with lauryl dimethyl benzyl ammonium chloride (LDMBAC) 3 to 20 parts, rosin K
(Natural anion compound potassium salt) 100 parts and lauryl dimethyl benzyl ammonium chloride (LDM
BAC) in combination with 3 to 30 parts, 13 parts of ethylene oxide is added to phenol having an average of 2 styrene groups added, and further 100 parts of sodium salt of a compound (styrenated phenol EOA Na Na sulfate) and lauryl dimethyl ammonium ethyl are added. Sulfate (LDME
AS) in combination with 1 to 30 parts, 100 parts of rosin K (potassium salt of a natural anion compound) and lauryl dimethyl ammonium ethyl sulfate (LDMEAS) 1
~ 30 parts and the like can be mentioned. Among them, the combination of styrenated phenol EOA Na sulfate or rosin K / LDMBAC has good compatibility with the nonionic surfactant, and the adsorption of the complex of the anionic surfactant and the cationic surfactant onto the emulsion. It is preferable because it has good properties.

The anionic emulsion dispersion of the thermoplastic elastomer used in the various modifiers of the present invention comprises a nonionic surfactant, preferably a nonionic surfactant and an anionic surfactant containing a specific emulsifier, and further an anion. It is produced by emulsion-dispersing the thermoplastic elastomer in the presence of a cationic surfactant in an amount smaller than that of the surfactant to give an anionic emulsion dispersion.

The amount of the nonionic surfactant, the anionic surfactant and the cationic surfactant (hereinafter, also referred to as total surfactant) used relative to 100 parts of the thermoplastic elastomer is 1 to 15 parts, more preferably 5 to 13 parts. Is preferred. When the amount of all the surfactants used is too small, the emulsifying ability of the mixture of the thermoplastic elastomer and the solvent during the production of the anionic emulsion dispersion is not good, and when the amount is too large, the solvent distillation step is performed. In this case, foaming trouble occurs, and the time required for distilling off the solvent is significantly increased, which is a problem in production.

The ratio of the thermoplastic elastomer and the total surfactant contained in the anionic emulsion dispersion is 40.
It is preferably from 65% to 65%, more preferably from 45% to 60% from the viewpoint of storage stability of the anionic emulsion dispersion and viscosity that facilitates pumping when used as each modifier. .

The anionic emulsion dispersion is produced by, for example, mixing a molten mixture of a thermoplastic elastomer in an organic solvent and a total surfactant with hot water in a line mixer. After emulsifying / dispersing the molten mixture by adding hot water to the molten mixture, the organic solvent is added, for example, at 60 ° C, 7 ° C.
20-640 mmHg (about 96.0-85.3 kPa)
It can be carried out by removing with.

At the time of removing the organic solvent, Japanese Patent Laid-Open No. 2001-5
In the case of the conventional thermoplastic elastomer aqueous dispersions other than the aqueous emulsion dispersion described in the 9053 publication, foaming is prominent, and it takes a long time to remove the solvent, but in the present invention, the anionic surfactant and the cationic surfactant are not used. Foaming can be reduced because a complex is formed, and an anionic emulsion dispersion of a thermoplastic elastomer can be easily produced. When a specific emulsifier is used as the nonionic surfactant, a synergistic effect that foaming can be further reduced can be expected.

The particle size of the produced anionic emulsified dispersion varies depending on the emulsification method, the amount of emulsifier used, the concentration of the emulsified dispersion, etc., but is usually 5 μm or less, further 0.6 to 3 μm. In particular, it is 0.8 to 2 μm. If the particle size is too large, the stability tends to be insufficient, and conversely if the particle size is too small, the viscosity tends to be high, and it tends to be difficult to manufacture and problems in pumping tend to occur.

The anionic emulsified dispersion liquid of the present invention produced in this manner partially forms a complex of an anionic surfactant and a cationic surfactant, and the complex has an affinity with the anionic surfactant. Since it is good, the emulsifying property with an anionic surfactant becomes better,
Good temporal stability and mechanical stability. There is little foaming during the production of the anionic emulsion dispersion, and when used as an aqueous pressure-sensitive adhesive, for example, by mixing with an aqueous pressure-sensitive adhesive, the holding power at high temperature is improved, or When added to SBR latex for chipping resistant paint, etc., it has good compatibility with SBR and improves chipping resistance and adhesion, and when added to asphalt, softening point, viscoelasticity of asphalt, Toughness,
High temperature viscosity, low temperature flexibility and the like can be improved.

A thickener may be added during the production of the anionic emulsion dispersion of the present invention. When a thickener is added, an aqueous emulsion dispersion containing a thickener having good storage stability in which water and the thermoplastic elastomer are less likely to separate even when stored for a long period of time.

Specific examples of the thickener include bentonite, aluminosilicate, sodium carboxymethyl cellulose which is a cellulose derivative, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl ethyl cellulose and hydroxyethyl ethyl cellulose. Can be given. In addition, natural polysaccharide polymers such as xanthan gum and rhamzan gum are also included. These may be used alone or in combination of two or more. Among these, sodium carboxymethyl cellulose which is a cellulose derivative, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl ethyl cellulose, hydroxyethyl ethyl cellulose and the like, and also natural polysaccharide polymers such as xanthan gum and rhamsan gum. preferable. In particular, among the cellulose derivatives, hydroxyalkyl cellulose such as hydroxyethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose are preferable, and natural polysaccharide polymers such as xanthan gum and rhamsan gum are preferable.

When the above thickener is added, the solid content is 0.1 to 3.0 parts with respect to 100 parts of the thermoplastic elastomer,
Furthermore, it is preferable to add 0.1 to 1.8 parts. When the thickener is a cellulose derivative or a natural polysaccharide polymer, the addition amount is preferably 0.1 to 2.0 parts, more preferably 0.1 to 1.0 part. If the added amount is too small, the effect of using the thickener cannot be sufficiently obtained, and if the added amount is too large, the viscosity increases too much, and it becomes difficult to carry out pumping, and each reforming performance is A tendency to decrease occurs.

The anionic emulsion dispersion of the present invention as described above generally has a solid content concentration of 40 to 65%, further 45 to 60%, and a viscosity (25 ° C., measured by a B-type viscometer).
Is 100 to 700 mPa · s, and further 150 to 500
mPa · s, and by adding a thickener, the solid content concentration is generally 40 to 65%, further 45 to 60%, and the viscosity (25 ° C., measured by a B-type viscometer) is 2
00-6000 mPa · s, further 350-4000
It will be something like mPa · s.

When the anionic emulsified dispersion liquid of the present invention is used as a modifier, it is usually 0.5 to 50%, more preferably 1.0 to 30% in terms of solid content relative to the substance to be modified (solid content). Is added. If the addition amount is too small, the modifying effect is not sufficiently obtained, and if the addition amount is too large, the viscosity of the modified product becomes too high to be practical. In addition, the modified product becomes expensive.

When the anionic aqueous dispersion of the present invention is used, if necessary, an antioxidant, an ultraviolet absorber, an antiseptic / antifungal agent, an antifoaming agent, a dispersion stabilizer, a plasticizer, a pigment, etc. may be added. May be used. In addition, paraffin type, aroma type,
Oil such as naphthenic oil may be added. Furthermore, SB
R latex, chloroprene latex, polybutadiene latex, rubber latex such as ethylene propylene rubber latex, acrylic emulsion, vinyl acetate emulsion, EVA emulsion, urethane emulsion and the like may be mixed with a polymer compound emulsion or used separately. You may use together. Since the anionic aqueous dispersion of the present invention contains a nonionic surfactant as an emulsifier, it is less likely to cause an aggregation phenomenon when mixed with a cationic emulsion than a normal anionic emulsion, but when mixed with a cationic emulsion or the like. In addition, it is preferable that the workability is not impaired.
Further, it may be used in combination with water-reactive compounds such as cement, lime and isocyanate compounds.

The method of adding the oil may be a method of making an oil-extended thermoplastic elastomer into an aqueous emulsion dispersion, or dissolving the thermoplastic elastomer in the solvent and dissolving the oil at the same time as a polymer solution. Examples thereof include a method of adding and a method of mixing a nonionic and / or anionic emulsion of oil with the anionic emulsion dispersion of the present invention. The amount of oil added is preferably 5 to 300 parts per 100 parts of the thermoplastic elastomer. The oil may be any of paraffinic, aromatic and naphthenic oils, but is preferably naphthenic oil.

The use of oil can be expected to have the effects of, for example, improving crack resistance, facilitating regeneration of deteriorated asphalt, and imparting flexibility.

When the anionic emulsified dispersion of the present invention is used, it is generally filled in a container such as a drum or a container and conveyed, and then charged into a coating machine or a mixing facility with another emulsion using a pump. The method of doing is adopted. In this case, when the thermoplastic elastomer and the dispersion medium, water, are separated (water separation phenomenon of emulsion) in the container during storage / transportation and the concentration becomes non-uniform, the coating amount and the addition amount to other emulsions become inconsistent. It becomes uniform, and problems such as a constant coating film thickness and a constant modification effect cannot be obtained. Therefore, it is important to improve the emulsification dispersibility and thus the storage stability. In addition, when the emulsified dispersion liquid is added by a pump, the emulsified / dispersed state is destroyed by the shearing force of the pump, and the thermoplastic elastomer separates from the water that is the dispersion medium, causing problems (pump clogging, reduced capacity, unusable ) Cause. Also for this prevention measure, it is important to improve the emulsification performance and the mechanical stability.

Next, the anionic emulsion dispersion of the present invention is added to a solution containing a thermoplastic elastomer and an organic solvent.
A nonionic surfactant, an anionic surfactant, and a solution of three kinds of different ionic surfactants of a cationic surfactant in an amount smaller than that of the anionic surfactant are prepared, and then mixed with water to emulsify the mixture. A method for producing by emulsifying the organic solvent and a method for producing an emulsified dispersion by adding and dissolving a thickening agent to the produced emulsified dispersion will be described.

First, one example in the case of emulsifying a thermoplastic elastomer with three kinds of nonionic surfactants, anionic surfactants and three kinds of different ionic surfactants of cationic surfactants less than the amount of anionic surfactants explain.

A solution prepared by dissolving 100 parts of a thermoplastic elastomer in 100 to 1000 parts of an organic solvent (the ratio of the two is different depending on the solubility of the elastomer in the organic solvent) was prepared, and then a nonionic surfactant and an anionic interface were prepared. Dissolve a given amount of activator and cationic surfactant.

The temperature and time for dissolving the thermoplastic elastomer in the organic solvent are not particularly limited, but 30
Dissolve uniformly at ~ 80 ° C (usually requires 2-3 hours)
Is preferred. As the dissolving solvent, for example, toluene, xylene, cyclohexane, etc. are preferably used.

A thermoplastic elastomer organic solvent solution containing the obtained emulsifier is added at 30 to 80 ° C., further 40 to 60 ° C.
After adjusting to 30 to 80 ℃, 40 to 60 ℃
80-600 parts of water adjusted to 100-400
An emulsion is manufactured by mixing and emulsifying with a part.
The amount of water used is determined according to the physical properties of the emulsion such as the desired particle size.

The thermoplastic elastomer organic solvent solution containing the emulsifier may be mixed with water by adding the thermoplastic elastomer organic solvent solution containing the emulsifier to the water, but water may be added to the thermoplastic elastomer organic solvent solution containing the emulsifier. It is preferable to add them, since an emulsion having a uniform particle size can be produced.

The mixing / emulsifying method is not particularly limited, but an optimum emulsifying / dispersing machine according to the purpose and specifications, for example, continuous emulsification and transfer of emulsified products are available from Tokushu Kika Kogyo Co., Ltd. A line mixer manufactured by Eurotech or Cavitron manufactured by Eurotech will also be used as a batch manufacturing system, but examples include Combimix manufactured by Tokushu Kika Kogyo Co., Ltd., which is equipped with anchors, dispers and mixers, but is not limited to these. It is not something that will be done.

The emulsified dispersion liquid containing the organic solvent produced in this manner is 25 to 60 ° C. and 720 to 640 mmHg.
The organic solvent is distilled off under reduced pressure (about 96.0 to 85.3 kPa) (usually 0.3% or less, preferably 0.2% or less, more preferably 0.1% or less). The anionic emulsion dispersion of the invention is produced.

At the time of distilling off the organic solvent, water, an antifoaming agent or the like for adjusting the concentration is added if necessary, and nitrogen gas is flown.

The temperature of the water is preferably the same as the temperature of the emulsion dispersion containing the organic solvent. Examples of the defoaming agent include silicone-based defoaming agents, low molecular weight propylene oxide compounds, and the like.
The addition amount is usually about 0.1 to 2 parts with respect to 100 parts of the thermoplastic elastomer emulsion.

The emulsified dispersion liquid after the organic solvent is distilled off separates when stored for a long period of time (emulsion water separation phenomenon).
In some cases, a thickener is added if necessary. The addition amount of the thickener is determined from the viewpoints of the storage stability of the obtained emulsion dispersion and the ease of use and the like.

Further, if necessary, a preservative and the like are added.

The anionic emulsified dispersion liquid of the present invention thus produced is preferably used as the emulsifying component used for emulsifying / dispersing the thermoplastic elastomer, preferably a specific nonionic surfactant and other optional nonionic surfactants. A thermoplastic elastomer was emulsified using a surfactant, an anionic surfactant-cationic surfactant complex consisting of a part of an anionic surfactant and a cationic surfactant, and the rest of the anionic surfactant. In addition, by using a thickener, if necessary, the emulsion dispersion performance is improved and the storage stability and mechanical stability are improved.

The anionic emulsion dispersion of the present invention thus produced is for coated paper, foam rubber, tire cord, coating (can, plastic, inorganic material, wood, etc.), paint, Floor polishes, adhesives (water-based adhesives, polymer cement, mortar adhesives, etc.), adhesives, removable labels, direct mail and textiles for carpets, automobile seats, mats, etc., waterproof materials, etc. Can be used as an emulsion. Further, it can be used as a mixture with an emulsion which has been conventionally used for these purposes. When used for these purposes, properties and functions peculiar to elastomers such as improvement of strength and adhesion / adhesiveness or imparting of flexibility can be added to the object to be treated.

However, since the anionic emulsion dispersion of the present invention contains a nonionic surfactant as an emulsifier, it is less likely to cause an agglomeration phenomenon when mixed with a cationic emulsion as compared with a normal anionic emulsion. When mixed with a hydrophilic emulsion or the like, it is preferably within a range that does not impair workability. It is also useful as an asphalt modifier.

When the anionic emulsion dispersion of the present invention is used as a mixture with an emulsion conventionally used for the above-mentioned uses, the anionic emulsion dispersion 1 of the present invention 1 is used.
The amount (solid content) of the emulsion conventionally used with respect to 00 parts (solid content) is 1 to 20000 parts, and further 10 to 10000 parts. Without hindering
Moreover, the advantages of the anionic emulsion dispersion of the present invention can be added, which is preferable. For example, when the anionic emulsion dispersion of the present invention is used as a mixture with a conventionally used asphalt modifier, it is conventionally used for 100 parts (solid content) of the anionic emulsion dispersion of the present invention. The use amount (solid content) of the asphalt modifier (emulsion) is preferably 1 to 200 parts, more preferably 10 to 100 parts from the viewpoint that suitable performance can be imparted to the asphalt. When the anionic emulsion dispersion of the present invention is used as a mixture with a conventionally used emulsion for an aqueous pressure-sensitive adhesive, the anionic emulsion dispersion 1 of the present invention 1
The amount (solid content) of the emulsion that has been conventionally used is 100 to 2000 relative to 00 parts (solid content).
Parts, and more preferably 200 to 1000 parts, is preferable from the viewpoint that the holding power can be improved without impairing the performance of conventionally used emulsions.

As an example, the case of using the anionic emulsion dispersion of the present invention as an asphalt modifier will be described in detail below.

The asphalt to which the anionic emulsion dispersion of the present invention is added is not particularly limited, and examples thereof include petroleum asphalt, natural asphalt, blown asphalt, semi-blown asphalt, decolorized asphalt (petroleum resin) and goose asphalt. Added.

The following cases may be mentioned as examples of modifying the asphalt with the anionic emulsion dispersion of the present invention.

(1) Modification of hot asphalt The above anionic emulsified dispersion is added directly to hot asphalt sufficiently melted to a stirrable viscosity while stirring, and water is evaporated to make the thermoplastic elastomer almost asphalt. Stir until dissolved and dispersed.

(2) Modification of hot asphalt mixture After mixing the aggregate and the hot asphalt, the anionic emulsified dispersion is added to the mixture while stirring and water is evaporated to make the thermoplastic elastomer almost evenly asphalt. Stir until dissolved and dispersed. When used in a recycled asphalt mixture, the recycled material is further added before the addition of the anionic emulsion dispersion of the present invention (the generated material which is a waste of the asphalt mixture generated when excavated for repairing a paved road is pulverized. Then, it is mixed with the new asphalt mixture so that it can be used again).

(3) Modification of Asphalt Emulsion (a) An asphalt emulsion was prepared by mixing an asphalt with an anionic emulsifier or a nonionic emulsifier or an emulsifier having a combination of these as an aqueous emulsified dispersion, and the anionic emulsified dispersion. And stir until uniform.

(B) The above anionic emulsion dispersion was added to heated asphalt, the water was evaporated, and the mixture was stirred until the thermoplastic elastomer was dissolved and dispersed in the asphalt almost uniformly. Then, this was mixed with an emulsifier and water. To obtain an aqueous emulsified dispersion of modified asphalt.

(C) An emulsifier which is anionic, nonionic or a combination thereof is added to the anionic emulsion dispersion and heated asphalt is mixed to obtain an aqueous emulsion dispersion.

(4) Modification of normal temperature asphalt mixture A mixture of the asphalt emulsion of the above (3) and the anionic emulsified dispersion or a modified asphalt emulsion is sprinkled on an aggregate and mixed, or the asphalt emulsion and the anion are mixed. The emulsified dispersion liquid is separately sprinkled on the aggregate and mixed, and stirred until almost uniform. When used in a recycled asphalt mix, it will also be mixed with recycled materials (however,
When the anionic emulsified dispersion liquid (asphalt modifier) and the cationic asphalt emulsion are mixed, they are mixed within a range where workability is obtained).

When using a type of asphalt modifier such as the anionic emulsified dispersion, generally, a method of filling and transporting it in a container such as a drum can or a container and introducing it into the asphalt using a pump is used. Has been taken.
In this case, if the thermoplastic elastomer and the dispersion medium, water, separate in the container during storage / transportation and the concentration becomes non-uniform, the addition amount as an asphalt modifier becomes non-uniform, resulting in a constant modification. There are problems that the effect is not obtained and that the separated thermoplastic elastomer in the added asphalt modifier is difficult to dissolve in asphalt. Therefore, the storage stability of the thermoplastic elastomer in the asphalt modifier is important. When the asphalt modifier is added by a pump, the emulsified / dispersed state is destroyed by the shearing force of the pump, and even if the thermoplastic elastomer is separated from the water that is the dispersion medium, the thermoplastic elastomer does not dissolve well in the asphalt. In addition, the pump itself may be clogged with the thermoplastic elastomer, which may reduce the performance of the pump or even render it unusable, and the mechanical stability of the asphalt modifier is important.

The asphalt modifier is a heated asphalt mixture, a regenerated heated asphalt mixture, an asphalt mixture such as foam door asphalt mixture, a room temperature asphalt mixture and a regenerated room temperature asphalt emulsion for asphalt mixture, and a tack coat, It is preferably used for reforming asphalt of coating materials such as seal coat and armor coat, and is used for roads, airports, ports, railways, rail freight yards, premises,
It can be used for paving parking lots, sidewalks, bicycle paths, sports facilities, racetracks, tennis courts, oil tank foundations, irrigation structures, waste treatment plants, etc. In addition, civil engineering,
It can be used to improve asphalt for rooftops, roofs, etc., floor soundproofing materials for houses, flooring materials, asphalt for construction such as coating steel pipes, and other asphalt for electrical insulation compound, tunnel insulation, etc.

[0143]

EXAMPLES Next, the anionic emulsion dispersion of the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

The evaluation methods used in the examples and the like will be summarized below.

(Foaming) A solution obtained by diluting the thermoplastic elastomer aqueous dispersion two-fold with water was placed in a 100 ml Nessler tube.
After adding the solution to the flask and stirring the solution 30 times by hand by inverting it and allowing it to stand, the amount of bubbles is measured with time.

(Viscosity) Brookfield type rotational viscometer, BL type manufactured by Toki Sangyo Co., Ltd. is used.

A single cylindrical rotor is rotated in a sample at 25 ° C., and the viscosity is determined from the shear rate and shear stress at that time.

(Particle Diameter of Thermoplastic Elastomer Aqueous Dispersion) The thermoplastic elastomer aqueous dispersion collected after the toluene was distilled off during the production of the emulsion was evaluated by a light diffraction method using SALD2000 manufactured by Shimadzu Corporation.

(Storage Stability) Using a Hitachi desktop centrifuge (CT5DL type manufactured by Hitachi, Ltd.), a sample and a container (2
7φ × 90 mm) A sample (thermoplastic elastomer aqueous dispersion) was sampled so that the total weight of the tare was 135 g (sample: about 45 g).

The conditions for centrifugation are 3000 rpm (17
61 g) x 30 minutes, and after the centrifugation, about 1 g of the thermoplastic elastomer aqueous dispersion in the lower layer of the container was taken with a straw and weighed with a precision balance.
The weight after evaporating and drying for 15 minutes was obtained, and the total solid content concentration was obtained from the following formula.

[0151]

[Equation 1]

(Mechanical stability) JIS 6387 [Reference-
Mechanical Stability], a sample amount of 50 g was used under the conditions of a load of 10 kg, a time of 5 minutes, a rotation speed of 1000 rpm, and a temperature of 60 ° C. in accordance with the “Marron stability test method”.

The solidification rate was calculated from the following formula. The smaller the value, the better the mechanical stability.

[0154]

[Equation 2]

(Initial Adhesion) A tilting ball tack test was conducted according to JIS Z0237. 30 degree tilt angle,
The measurement temperature was 25 ° C., and the initial tackiness was evaluated by the ball number held on the tacky part.

(Adhesiveness) 1 according to JIS Z0237
An 80 degree peel test was performed. Stainless steel plate (size: 50 mm × 150 mm × 1.5) as a test plate (subject)
mm) was used and the measurement temperature was 25 ° C.

(Holding power) 4 according to JIS Z0237
The holding power was measured under the atmosphere of 0 ° C and 100 ° C. 1
The holding force was evaluated by the fall time when a load of 00 g was applied.

(Adhesiveness in high temperature environment) An adhesive tape having a length of 60 mm and a width of 25 mm was attached to the peripheral surface of a glass rod having a diameter of 2 cm, and cured at room temperature for 24 hours. Then, after leaving it in an atmosphere of 150 ° C. for 1 hour, the sticking state of the adhesive tape was visually observed and evaluated according to the following criteria. ◯: No change from the sticking state before leaving. Δ: Exfoliation is recognized at the end of the adhesive tape. Poor: Exfoliation is observed in more than half of the adhesive tape.

(Chipping resistance) 6 with a gravure tester
500 g of No. crushed stone was injected 5 times at a pressure of 5 kg / cm ² (about 0.49 MPa), the state of the test piece was visually observed, and evaluated according to the following criteria. ○: There is no scratch. Δ: Delamination occurs. X: There is interfacial peeling.

(Soundproofing) A steel ball having a diameter of 10 mm was dropped from a height of 1 m on the coating surface of the test piece, and the collision sound generated at that time was measured 5 times by an indicating sound level meter to obtain an average value. The smaller the value, the higher the soundproofing effect.

(Adhesion) The test piece was measured 3 times by the tape peeling method (2 mm cross cut) according to JIS K5400, and the average value was obtained. The larger the value, the better the adhesion.

The method for evaluating the anionic emulsion dispersion of the present invention as an asphalt modifier will be described below.

(Physical properties of asphalt) Straight asphalt (60 to 80, manufactured by Cosmo Oil Co., Ltd. (hereinafter referred to as Cosmo 60 to 80)) was heated to 170 ° C. and rotated by a stirrer equipped with a 4-blade stirring blade. Number 400-500rp
The anionic emulsion dispersion of the present invention was mixed under the condition of m.

The blending ratio of the anionic emulsion dispersion of the present invention is 10% straight asphalt (Cosmo 60-80).
It was 6 parts in terms of solid content with respect to 0 part.

The physical property test of asphalt was evaluated according to the method described in "Pavement Test Method Handbook" (published by Japan Road Association on November 10, 1988).

(Physical properties of evaporation residue of asphalt emulsion) Commercially available asphalt emulsion (PK-4, manufactured by Toho Rika Co., Ltd.) 10
Anionic emulsion dispersion 6 of the present invention in 0 part (solid content)
Part (solid content) was added, and the anionic emulsion dispersion of the present invention was mixed for 10 minutes at a rotation speed of 400 to 500 rpm with a stirrer equipped with a 4-blade stirring blade, and then 90 to 95 while continuing stirring. After heating to ℃ to evaporate most of the water, the temperature is further raised to 130 to 140 ℃ to completely evaporate the water to obtain an asphalt emulsion evaporation residue, and the physical properties (penetration, softening point, elongation Degree, toughness, tenacity).

The evaluation of the physical properties of the obtained evaporation residue of the asphalt emulsion was carried out according to the method described in "Handbook of Pavement Test Methods".

Next, the contents and abbreviations of the main raw materials used in Examples and the like will be described below.

Thermoplastic elastomer SBS: TR-2631 manufactured by JSR Co., Ltd.
C, molecular weight about 140,000

Surfactant Styrenated phenol EOA: Phenol having an average of 2 styrene groups added and 20 mol of ethylene oxide added (monostyrenated phenol polyalkylene oxide adduct: distyrenated phenol polyalkylene oxide adduct: tri or more Styrenated phenol polyalkylene oxide adduct of 18:48:34 (weight ratio)) Benzylated phenol EOA: 20 moles of ethylene oxide added to phenol having an average of 2 benzyl groups (monobenzylated phenol polyalkylene oxide) Adduct: Dibenzylated phenol polyalkylene oxide adduct: Tri or higher benzylated phenol polyalkylene oxide adduct = 16: 47: 37 (weight ratio)) Lauryl alcohol EOA: Lauryl al 20 moles of ethylene oxide added to the polymer LDMBAC: Lauryl dimethyl benzyl ammonium chloride LDMEAS: Lauryl dimethyl ammonium ethyl sulfate Styrenated phenol EOA Sulfate Na: Phenol with an average of 2 styrene groups added (mono: di: tri Compound rosin K obtained by adding 13 moles of ethylene oxide to the above-mentioned styrenated phenol EOA and further sulfated: potassium salt of natural anion compound

Thickener HEC: hydroxyethyl cellulose (MR250HR, manufactured by Hercules)

Example 1 Emulsifier equipped with a disper, a mixer and an anchor (TK Combimix 3M-5, manufactured by Tokushu Kika Kogyo Co., Ltd.)
Type), SBS 100 parts (600 g), toluene 300
(1800 g) was charged and the temperature was raised to 55 ° C. to dissolve SBS.

After dissolution, the styrenated phenol EOA was used as an activator (the amount of the activator described below is calculated as solid content).
4.7 parts (28.2 g), styrenated phenol EOA
Na sulfate 3 parts (18.0 g) and LDMBAC 0.3
(1.8g), and the peripheral speed of the mixer is 12.8m /
s, the peripheral speed of the disper was 9.6 m / s, and the number of revolutions of the anchor was 60 rpm, followed by stirring and mixing for 10 minutes.

After that, 250 parts of warm water at 55 ° C. (15
00g) was added over 30 minutes. After the addition, the mixture was stirred for 10 minutes to obtain an SBS emulsion dispersion.

After that, 60 ° C., 720 to 640 mmH
Toluene was distilled off at g (about 96.0 to 85.3 kPa), the residual amount of toluene was adjusted to 0.05% or less, and the solid content was adjusted to 5%.
An anionic emulsion dispersion liquid adjusted to 0% was obtained.

The foaming of the obtained SBS anionic emulsion dispersion was 20 ml immediately after, 1 ml after 1 minute, and 3 ml after 5 minutes.

The viscosity, particle size, storage stability and mechanical stability of the obtained SBS anionic emulsion dispersion (solid content 50%) were measured. The results are shown in Table 1.

Further, the physical properties of asphalt when used as an asphalt modifier and the physical properties of evaporation residue of asphalt emulsion were measured. The results are shown in Table 1.

Example 2 An SBS anionic emulsion dispersion was prepared and evaluated in the same manner as in Example 1 except that the LDMBAC used in Example 1 was replaced with LDMEAS. The results are shown in Table 1.

Examples 3 to 8 and Comparative Examples 1 to 5 SBS anionic emulsion dispersions were produced and evaluated in the same manner as in Example 1 except that the raw materials shown in Table 1 were used in the proportions shown in Table 1. The results are shown in Table 1.

Incidentally, Examples 6 to 8 and Comparative Examples 3 to 4
Is the SBS obtained in Examples 1-2 and 4 and Comparative Examples 1-2.
To the emulsified dispersion liquid (solid content 55%), for example, in the case of Example 6, 0.2 part (1.2 g) of HEC, which is a thickener, was added as a powder, and water was added so that the solid content was 50%. And add
It was prepared by stirring (2000 rpm) and then leaving it for 12 hours to dissolve HEC. Example 7-
8 and Comparative Examples 3 to 4 were also prepared by using the thickeners shown in Table 1 in the amounts shown in Table 1 and performing the same operation.

Examples 9 to 10 Emulsion polymerization was carried out using 80 parts of the SBS anionic emulsion dispersion having a solid content of 50% obtained in Examples 1 and 6 and an anionic surfactant, glass transition temperature 60 ° C., Mooney viscosity. A mixture of (ML1 + 4) 50 and 20 parts of SBR latex having a solid content of 50% (JSR0678, manufactured by JSR Co., Ltd.) was evaluated. The results are shown in Table 1.

Example 11 60 parts of SBS anionic emulsion dispersion having a solid content of 50% obtained in Example 1 and a naphthenic oil having a solid content of 50% emulsified with styrenated phenol EOA (Idemitsu Kosan Co., Ltd.)
Manufactured by NM-280) was mixed and evaluated. The results are shown in Table 1.

[0184]

[Table 1]

The anionic emulsion dispersion of the present invention is described in JP-A-2
Compared to the emulsion dispersion in which the nonionic activator and the anionic activator described in 001-59053 are used together, the coagulation rate measurement result of the Marron stability test shows a value of 1/10 or less, and storage stability of several%. It can be seen that the emulsifiability is significantly improved, since the stability is improved on the order.

When it is mixed with SBR latex, the effect of improving the elongation and improving the crack resistance can be expected.

When mixed with a naphthenic oil, the flexibility is improved, and a useful effect for regenerating deteriorated asphalt can be expected.

When such an anionic emulsion dispersion of the present invention is used as an asphalt modifier, for example,
It is easy to mix and dissolve in asphalt, and it is possible to improve the softening point, viscoelastic properties, toughness, high temperature viscosity, etc. of asphalt, improving the flow resistance, abrasion resistance, and toughness of pavement. It is possible to extend the life of pavement.
Further, since it is possible to easily modify the asphalt emulsion, which has been difficult with the conventional solid thermoplastic elastomer, it is also effective for modifying the room temperature paving compound and the coating material. Further, since the low temperature flexibility of the hot asphalt can be improved, it is also effective for reforming waterproof materials and the like.

Examples 12 to 15 and Comparative Examples 6 to 8 The deteriorated asphalt was mixed with the SBS anionic emulsion dispersions obtained in Examples 1 and 11 in the proportions shown in Table 2, and the regeneration effect was obtained. evaluated. The results are shown in Table 2.

Deteriorated asphalt is from Cosmo 60-
80 was used as a 1 mm thin film which was oxidized and deteriorated by a hot air dryer at 85 ° C. for 48 hours.

[0191]

[Table 2]

When the SBS anionic emulsion dispersion of the present invention is mixed with deteriorated asphalt, the softening point, the elongation, the toughness and the tenacity are remarkably improved, and the regeneration and modification effects of the deteriorated asphalt are sufficiently observed.

Examples 16 to 18 and Comparative Example 9 Acrylic emulsion AE200 having a solid content of 51% emulsion-polymerized with an anionic surfactant and a glass transition temperature of 45 ° C.
(Manufactured by JSR Co., Ltd.) and the SBS anionic emulsion dispersion obtained in Example 2 were mixed in the proportions shown in Table 3. After adjusting the pH to 8 by adding 0.1 part of 25% aqueous ammonia to 100 parts (solid content) of the obtained mixture, a polycarboxylic acid emulsion type thickener (manufactured by Nippon Acrylic Industry Co., Ltd., By adding 0.1 part of Primal ASE-60), the viscosity becomes about 10,000 mPa · s.
A (BM type) water-based pressure-sensitive adhesive was prepared.

The resulting water-based pressure-sensitive adhesive was applied to the surface of a substrate made of polyester film (thickness: 25 μm) using an applicator having a gap of 15 / 10,000 inches,
By drying the coating film at 110 ° C. for 1 minute, an adhesive tape having an adhesive layer (20 to 25 g / m ² ) formed on the surface of the base material was manufactured.

The obtained tape was used to evaluate the items shown in Table 3. The results are shown in Table 3.

[0196]

[Table 3]

The SBS anionic emulsion dispersion of the present invention comprises
It can be suitably used as a modifier for an aqueous pressure-sensitive adhesive.

The water-based pressure-sensitive adhesive using the SBS anionic emulsified dispersion of the present invention has good adhesiveness to an adherend and also has suitable adhesiveness even in a high temperature environment, and has a high heat resistance. It has excellent sex.

Examples 19 to 20 and Comparative Example 10 100 parts (solid content) of the SBS anionic emulsion dispersion obtained in Examples 3 and 4 or 54% solid content obtained by emulsion polymerization with an anionic surfactant, glass transition. SB of temperature 30 ℃
R Latex JSR0545 (JSR Corporation)
100 parts (solid content) with a dispersant (Aron Kasei Co., Ltd.)
Manufactured by Aron A-20) 0.2 parts, calcium carbonate 150
Part, talc 50 parts, and water to obtain a total solid content of 70
%, And 0.2 parts of a polyether polyurethane thickener (DK Thickener SCT-275, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added so that the viscosity would be 30,000 mPa · s. .

The obtained paint was applied to a 0.8 mm thick steel plate by airless spraying so that the coating thickness would be 1.6 mm. After that, it was dried at 90 ° C. for 10 minutes and at room temperature for 1 day.

The obtained test pieces were evaluated for the evaluation items shown in Table 4. The results are shown in Table 4.

[0202]

[Table 4]

The SBS anionic emulsion dispersion of the present invention is excellent in chipping resistance, soundproofing and adhesion, and is also useful as a water-based chipping resistant coating.

Examples 21 to 23 and Comparative Example 11 100 parts of Cosmo 60 to 80 (manufactured by Cosmo Oil Co., Ltd.) were added to the SBS anionic emulsion dispersions obtained in Examples 3 and 4, and anions. SBR latex JSR Rhodex (manufactured by JRS Co., Ltd.) having a solid content of 50% emulsion-polymerized with a surface-active agent, a glass transition temperature of 50 ° C., and a Mooney viscosity (ML1 + 4) of 50 was mixed at a ratio shown in Table 5. (Solid content conversion) was added in an amount of 10 parts by solid content and mixed uniformly.

The strength and elongation of the obtained asphalt waterproof material were measured in accordance with JIS A6021 using Autograph AG-500A manufactured by Shimadzu Corporation.

For comparison, a commercial asphalt waterproof material, blown asphalt (manufactured by Cosmo Oil Co., Ltd.) was evaluated.
The results are shown in Table 5.

[0207]

[Table 5]

The SBS anionic emulsion dispersion of the present invention comprises:
When used as a modifier for asphalt waterproofing materials,
It can be seen that it has excellent balance of strength and elongation and exhibits suitable performance.

[0209]

INDUSTRIAL APPLICABILITY The anionic emulsion dispersion of the present invention has improved emulsifiability as compared with the one described in JP 2001-59053 A, and thus has improved storage (aging) stability and mechanical stability. It is an improved one.

The anionic emulsion dispersion of the present invention is useful as an asphalt modifier, and also as an emulsion that can be used in water-based pressure-sensitive adhesives or water-based chipping resistant coatings. Suitable properties can be imparted when used by mixing with the emulsion used.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/00 C08K 5/00 (72) Inventor Yukihiro Okubo 2-11-24 Tsukiji, Chuo-ku, Tokyo J S-R Co., Ltd. (72) Inventor Etsuo Ito 22-101 Okuinji Temple Taikoyama, Nagaokakyo-shi, Kyoto (72) Inventor Masayo Kuze 1492-3 F Boterm, Kodai-cho Koga-gun, Shiga Prefecture 4D077 AA03 AA05 AC01 DD03Y DD29Y DE04Y DE08Y 4F070 AA11 AC42 AC50 AC72 AC84 AE13 AE14 CA16 CB02 4G065 AA01 AB10Y AB38Y BA03 BA04 BA06 BA07 BB06 CA02 DA03 DA06 DA07 FA01 4J002 AB033 AB053 BP011 CH022 DJ007DJ037 EN136 EU1061370

Claims (9)

[Claims] 1. A thermoplastic elastomer is emulsified and dispersed using a nonionic surfactant, an anionic surfactant and three different ionic surfactants of a cationic surfactant in an amount smaller than that of the anionic surfactant. An anionic emulsion dispersion of a characteristic thermoplastic elastomer. 2. The anionic emulsion dispersion according to claim 1, wherein 0.1 to 50.0 parts by weight of a cationic surfactant is mixed with 100 parts by weight of an anionic surfactant. 3. The anionic emulsion dispersion according to claim 1, wherein the nonionic surfactant is a styrenated phenol polyalkylene oxide adduct. 4. The styrenated phenol polyalkylene oxide adduct is monostyrenated phenol polyalkylene oxide adduct: distyrenated phenol polyalkylene oxide adduct: tri or more styrenated phenol polyalkylene oxide adduct = 10 to 20. : 4
The total amount is 10 at a ratio of 0 to 55:30 to 45 (weight ratio).
The anionic emulsion dispersion according to claim 3, wherein the anionic emulsion dispersion is contained so as to be 0. 5. The anionic emulsion dispersion according to claim 1, wherein the nonionic surfactant is a benzylated phenol polyalkylene oxide adduct. 6. The benzylated phenol polyalkylene oxide adduct is a monobenzylated phenol polyalkylene oxide adduct: dibenzylated phenol polyalkylene oxide adduct: tri or more benzylated phenol polyalkylene oxide adduct = 10 to 20. : 4
The total amount is 10 at a ratio of 0 to 55:30 to 45 (weight ratio).
The anionic emulsion dispersion according to claim 5, wherein the anionic emulsion dispersion is contained so as to be 0. 7. The anionic emulsion dispersion according to claim 1, further comprising a cellulose derivative as a thickener. 8. A solution containing a nonionic surfactant, an anionic surfactant and a cationic surfactant in an amount smaller than that of the anionic surfactant is prepared in a solution comprising a thermoplastic elastomer and an organic solvent, and then a solution of water is prepared. The method for producing an anionic emulsified dispersion according to claim 1, 2, 3, 4, 5 or 6, which comprises mixing and emulsifying and then distilling off the organic solvent. 9. The method for producing an anionic emulsion dispersion according to claim 8, wherein the organic solvent is distilled off, and then a thickener is further added and dissolved. How to make a dispersion.