JP2001261757A - Cross-linked particle, method for producing the same and composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a cross-linked particle capable of imparting hydrophilicty, water absorption, antifogging properties, ion exchangeability, ionic conductivity, ion scavenging properties, etc., by surface treatment of an organic material or an inorganic material with the cross-linked particle, incorporation, etc., thereof into the organic material or organic material and its composition. SOLUTION: This cross-linked particle is characterized in that the particle comprises (a) a block copolymer having a hydrophilic polymer block and a hydrophobic polymer block and (b) a polymerization cross-linked material of a radical-polymerizable monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to imparting hydrophilicity, water absorption, anti-fogging property, ion exchange property, ionic conductivity, ion trapping property, etc. by surface treatment or kneading of an organic or inorganic material. Crosslinked particles and compositions thereof.

[0002]

2. Description of the Related Art Hitherto, polymers having a polar group such as a sulfonic acid group, a carboxylic acid group and a phosphoric acid group have been known, and have been used in various applications such as surfactants, emulsifiers and dispersants. It is used. On the other hand, in recent years, such properties as the dispersibility of the polar group, hydrophilicity, ion-capturing property, ionic conductivity, and adhesion to the base material are utilized to make the binder resin, the coating material, the antistatic agent, the surface treatment agent, Application to battery materials is being studied. In particular, the sulfonic acid group-containing polymer easily exhibits the above characteristics due to the strong ionicity of the sulfonic acid group, and its application has attracted attention. For example, substrates made of metals such as stainless steel, aluminum and copper, inorganic materials such as concrete and slate, and organic materials such as plastic, wood and paper are used for building materials, electric appliances, electronic materials, optics, precision materials, automobiles, and communication equipment. It is widely used in measuring instruments, battery materials, office equipment, medical materials, general household products, and the like. These substrate surfaces are often used after being coated with various coating materials for the purpose of surface protection and surface modification.
In general, urethane resin, phenol resin, acrylic resin, polyester resin, polyamide resin, polyether, styrene resin, polyesteramide, polycarbonate, polyvinyl chloride, silicone resin, and the like are known as coating materials.

[0003] These coating materials are rather hydrophobic coating materials, and are often mainly intended to protect the surface of the base material. Polar group-containing polymers are used to impart a surface modification function such as making the substrate surface hydrophilic or hygroscopic, preventing adhesion of dirt, or capturing ionic substances floating in water and air. ing. However, polar group-containing polymers known so far, when used for coating on the surface of a substrate, kneading into various materials, etc., are inherently polar groups, such as hydrophilicity, hygroscopicity, and ion-trapping properties. There is a problem that the characteristics possessed cannot be sufficiently exhibited.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above various problems by dispersibility, hydrophilicity, water absorption,
It is an object of the present invention to provide crosslinked particles and a composition thereof that can provide high effects in ion capturing properties, ion conductivity, and the like.

[0005]

The present invention comprises (a) a block copolymer having a hydrophilic polymer block and a hydrophobic polymer block and (b) a crosslinked product of a radical polymerizable monomer polymer. , A crosslinked particle comprising a hydrophilic group / g or more, a method for producing the same, and a composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION A block copolymer having a hydrophilic polymer block and a hydrophobic polymer block (hereinafter, referred to as "block copolymer") used in the present invention will be described. Here, as the hydrophobic polymer block, a polymer or a copolymer containing a hydrocarbon monomer as a main component is exemplified. Examples of the polymer or copolymer mainly containing a hydrocarbon monomer include (co) polymers mainly containing diene monomers and olefin monomers such as aromatic vinyl compounds and olefins. Preferred are (co) polymers as main components or (co) polymers obtained by hydrogenating them. In the present invention, the diene monomer is preferably a diene monomer having 4 to 12 carbon atoms, more preferably a diene monomer having 4 to 8 carbon atoms, and particularly preferably a diene monomer having 4 to 6 carbon atoms. is there. Specific examples of these diene monomers include, for example, 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene,
3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene,
1,4-hexadiene, 1,5-hexadiene, 2,3
-Hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,2-heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1 , 5-heptadiene,
1,6-heptadiene, 2,3-heptadiene, 2,5
-Heptadiene, 3,4-heptadiene, 3,5-heptadiene, cyclopentadiene, dicyclopentadiene, ethylidene norbornene, and various aliphatic or alicyclic diene having 4 to 7 carbon atoms. These can be used alone or in combination of two or more. Of these, particularly preferred are
1,3-butadiene and isoprene.

[0007] Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, and vinylnaphthalene. Examples of the olefin include ethylene and propylene. These monomers may be used alone or in combination of two or more. Of these, aromatic vinyl compounds are preferred, and styrene is particularly preferred.

In addition to the above-mentioned diene monomers, olefin monomers such as aromatic vinyl compounds and olefins,
Other monomers can be used in combination. Other monomers include, for example, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid, crotonic acid, and maleic acid. Mono- or dicarboxylic acid or anhydride of dicarboxylic acid such as acid, fumaric acid, itaconic acid, vinyl cyanide compound such as (meth) acrylonitrile, vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone, vinyl acetate, (meth) acrylamide, (meth) Unsaturated compounds such as glycidyl acrylate; These other monomers can be used alone or in combination of two or more.

The polymer block mainly composed of a diene monomer may be copolymerized with the above-mentioned aromatic vinyl compound or olefin as another monomer in an inferior amount. The polymer block mainly composed of an aromatic vinyl compound may be copolymerized with the diene monomer or the olefin in an inferior amount. Further, the polymer block mainly composed of an olefin may be copolymerized with the diene-based monomer or the aromatic vinyl compound in an inferior amount as another monomer. When these other monomers are used in combination, the amount used in the polymer block is usually 60% or less, preferably 50% by weight or less, more preferably 30% by weight or less, and particularly preferably 20% by weight or less. is there.

As a method for introducing a hydrophilic group such as a sulfonic acid group into a hydrophobic polymer block, a base polymer composed of two kinds of hydrophobic polymer blocks is produced, and one block of the obtained base polymer is prepared. Examples include a method of sulfonation and a method of copolymerizing a monomer containing a hydrophilic group such as a sulfonic acid group during polymerization of a polymer block. Examples of the hydrophilic group include a sulfonic acid (salt) group, a carboxylic acid (salt) group (carboxyl group), a phosphoric acid (salt) group, an amine group, an amide group, a hydroxyl group, an alkyl ester group, and an acid anhydride group. Can be Among these, a sulfonic acid (salt) group, a carboxylic acid (salt) group (carboxyl group), a phosphoric acid (salt) group, an amine group, an amide group, and a hydroxyl group are preferable, and a sulfonic acid group and a carboxylic acid group are more preferable. (Carboxyl groups), particularly preferred are sulfonic acid groups. In the present invention, when the hydrophilic group is a sulfonic acid group, the sulfonic acid content is 0.2 mmol / g or more, preferably 0.5 mmol / g, more preferably 1.0 mmol / g or more. When the amount of the sulfonic acid group is less than 0.2 mmol / g, the effect of the hydrophilic group such as hydrophilicity is not sufficiently exhibited, which is not preferable. In the present invention, the sulfonic acid group content was obtained by elemental analysis of the sulfur content of the crosslinked particles of the present invention, and the sulfonic acid content (mmol / g) of the crosslinked particles was obtained by converting sulfur atoms to sulfonic acid groups. .

In the present invention, the block copolymer can be produced by copolymerizing monomers constituting each block using an initiator and, if necessary, a solvent. Examples of such an initiator include a radical polymerization initiator such as hydrogen peroxide, benzoyl peroxide, and azobisisobutyronitrile, and an anionic polymerization initiator such as n-butyllithium, sodium naphthalene, and metallic sodium. Further, the polymerization temperature is usually -100 to 150C, preferably 0 to 130C. As the polymerization method, anionic polymerization is particularly preferably used from the viewpoint of obtaining a block copolymer.

The above block copolymer may be used by hydrogenating (hydrogenating) a part or all of the remaining double bond based on the diene monomer. In this case, a known hydrogenation catalyst can be used.
Examples of the catalyst and the method are described in JP-A-222115. After hydrogenation of the above-mentioned block copolymer as a base polymer, a hydrophilic group can be introduced by a method described later, but after introducing a hydrophilic group into the copolymer, hydrogenation may be carried out.

Preferred base polymers used in the present invention are a block A (hereinafter referred to as "block A") obtained by polymerizing a monomer containing at least a weight% of a diene monomer and an olefin monomer. % Is a block copolymer containing a block B (hereinafter, referred to as “block B”) obtained by polymerizing a monomer containing at least 10% by weight. The preferred structure of the block copolymer is AB type or A type.
(BA) n-type or B (AB) n-type or (AB)
n-type (where n is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably 1). In the block copolymer, the ratio A / B of the block A and the block B is preferably 5 to 95/95 to 5, more preferably 10 to 90/90 to 10, and particularly preferably 20 to 80/80. 20. The polymerization degree of the blocks A and B is preferably such that A is 5 or more and B
Is 5 or more, more preferably A is 10 or more, and B is 10 or more, and particularly preferably A is 50 or more, and B is 5 or more.
0 or more.

Among these, AB type and A type are preferable.
BA-type and BAB-type block copolymers. Specific preferred base polymers include, for example, isoprene-styrene block copolymer, styrene-isoprene-styrene triblock copolymer, isoprene-styrene-isoprene triblock copolymer, butadiene-styrene block copolymer , Styrene-butadiene-
Examples include a styrene triblock copolymer, a butadiene-styrenebutadiene triblock copolymer, and hydrogenated products of these block copolymers. In the block A, the aromatic monomer or another monomer may be partially copolymerized, and in the block B, the diene-based monomer or another monomer may be partially copolymerized.

The weight average molecular weight (hereinafter referred to as "Mw") of these base polymers or hydrogenated products thereof in terms of polystyrene is preferably 500 to 1,000,000, more preferably 1,000 to 500,000, and particularly preferably. Is from 2,000 to 200,000. Mw is 50
If it is less than 0, characteristics such as hydrophilicity of the hydrophilic group may not be sufficiently exhibited. On the other hand, if it exceeds 1,000,000, problems such as gelation when introducing the hydrophilic group may occur. May occur.

A known method can be used as a method for adding a hydrophilic group to the base polymer by a method such as addition. For example, when a sulfone group is introduced, it can be produced, for example, by sulfonation according to the method described in Japanese Society of Science, New Experiment Lecture (Vol. 14, III, p. 1773) or JP-A-2-227403. it can.

According to this method, either the double bond portion or the aromatic portion based on the diene monomer in the base polymer is preferentially sulfonated using a sulfonating agent. Can be manufactured. In the case of sulfonation, the following method is preferable. (1) When using a non-hydrogenated base polymer or a base polymer in which block A is partially hydrogenated, it is preferable to preferentially sulfonate block A, while (2) block A In a fully hydrogenated base polymer, it is preferred that block B be preferentially sulfonated. When the block A is preferentially sulfonated as in (1) above, the sulfonating agent may be a complex of sulfuric anhydride and an electron-donating compound or a bisulfite (Na salt, K salt, Li salt). And acetylsulfuric acid. Also,
As described in (2), in order to preferentially sulfonate the block B, as the sulfonating agent, in addition to the above-mentioned complex, sulfuric anhydride, chlorosulfonic acid, fuming sulfuric acid, concentrated sulfuric acid, acetyl sulfate, or the like is used. Is preferred.

Here, as the electron donating compound, N,
Ethers such as N-dimethylformamide, dioxane, dibutyl ether, tetrahydrofuran, diethyl ether; pyridine, piperazine, trimethylamine,
Amines such as triethylamine and tributylamine;
Sulfides such as dimethyl sulfide and diethyl sulfide; nitrile compounds such as acetonitrile, ethyl nitrile and propyl nitrile; and the like, of which N, N-dimethylformamide and dioxane are preferable.

When a non-hydrogenated base polymer or a partially hydrogenated base polymer is used, the amount of the sulfonating agent is at least 0.2 mol based on 1 mol of the block A in the base polymer. If it is 1.2 mol or less, preferably 0.5 mol or more and 1.1 mol or less, if less than 0.2 mol, sufficient hydrophilicity may not be obtained. It is not preferable because the sulfonating agent remains as an impurity. When a hydrogenated base polymer is used, the amount of the sulfonating agent is usually from 0.2 mol to 1.2 mol, preferably from 1 mol to 1 mol of the block B in the base polymer.
0.5 mol or more and 1.1 mol or less, if less than 0.2 mol, sufficient hydrophilicity may not be obtained.
If it exceeds, the unreacted sulfonating agent remains as impurities, which is not preferable.

In the sulfonation, a solvent inert to a sulfonating agent such as sulfuric anhydride or sulfuric acid may be used. Examples of the solvent include halogens such as chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene and dichloromethane. Nitro compounds such as nitromethane and nitrobenzene; aliphatic hydrocarbons such as liquid sulfur dioxide, propane, butane, pentane, hexane, and cyclohexane; ether solvents such as dioxane and tetrahydrofuran; and water. These solvents may be used as a mixture of two or more. The reaction temperature of this sulfonation is usually-
70 to 200 ° C, preferably -30 to 50 ° C,
If the temperature is lower than 70 ° C., the sulfonation reaction is slow, which is not economical.

The sulfonated product of the block copolymer used in the present invention is preferably obtained by reacting the sulfonated product with water or a basic compound. Examples of the basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide,
Alkali metal alkoxides such as sodium-t-butoxide and potassium-t-butoxide; sodium carbonate,
Carbonates such as potassium carbonate and lithium carbonate; methyllithium, ethyllithium, n-butyllithium, sec-
Organometallic compounds such as butyllithium, amyllithium, propylsodium, methylmagnesium chloride, ethylmagnesium bromide, propylmagnesium iodide, diethylmagnesium, diethylzinc, triethylaluminum, triisobutylaluminum; aqueous ammonia, trimethylamine, triethylamine, tripropylamine And amines such as tributylamine, pyridine, aniline and piperazine; and metal compounds such as sodium, lithium, potassium, calcium and zinc. These basic compounds can be used alone or in combination of two or more. Among these basic compounds, alkali metal hydroxides and aqueous ammonia are preferable, and sodium hydroxide, lithium hydroxide and potassium hydroxide are particularly preferable.

The amount of the basic compound used is preferably 1.5 mol or less, more preferably 1.2 mol or less, based on 1 mol of the sulfonating agent used. And the purity of the product decreases. In this reaction, the basic compound can be used in the form of an aqueous solution, or can be used by dissolving it in an organic solvent inert to the basic compound. Examples of the organic solvent include the above-mentioned various organic solvents, aromatic hydrocarbon compounds such as benzene, toluene, and xylene; and alcohols such as methanol, ethanol, propanol, isopropanol, and ethylene glycol. These solvents may be used as a mixture of two or more.

When the basic compound is used as an aqueous solution or an organic solvent solution, the basic compound concentration is usually
It is about 1 to 70% by weight, preferably about 10 to 50% by weight. The reaction temperature is usually -30 to 150 ° C,
Preferably it is 0-120 degreeC, More preferably, it is + 50-1.
It is carried out at 00 ° C. and can be carried out under normal pressure, reduced pressure or increased pressure. Further, the reaction time is generally 0.1 to 24 hours, preferably 0.5 to 5 hours. When a hydrophilic group other than a sulfonic acid group is introduced, it can be produced by appropriately performing a method such as carboxylation, phosphorylation, amination, amidation, or hydroxylation.

When a monomer containing a hydrophilic group is copolymerized, for example, a monomer containing a sulfonic acid group,
It can be produced by appropriately copolymerizing a monomer containing a carboxylic acid group (carboxyl group), an amino group, an amide group, a phosphoric acid group or a hydroxyl group. Preferred examples of the monomer having a sulfonic acid group include those obtained by adding a sulfonic acid (salt) group to the diene-based monomer or the olefin-based monomer. Specific examples thereof include butadiene containing a sulfonic acid (salt) group, isoprene containing a sulfonic acid (salt) group, styrene containing a sulfonic acid (salt) group, ethylene containing a sulfonic acid (salt) group, and sulfonic acid (salt) group containing Propylene and the like. Of these, preferred are sulfonic acid (salt) group-containing isoprene,
Styrene containing sulfonic acid (salt) groups. In addition, monomers having a hydrophilic group other than a sulfonic acid group include (meth)
Mono or dicarboxylic acid or anhydride of dicarboxylic acid such as acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, (meth) acrylic phosphate, amino (meth) acrylate, (meth) acrylamide, hydroxyalkyl (meth) It can be produced by copolymerizing acrylate or the like.

In the present invention, the content of the hydrophilic group in the block copolymer is not particularly limited, but usually, the number of the monomer units having a hydrophilic group is 50 (mol)% of the constituent monomer units in the block. Or more, more preferably 70% or more. When the content is 50% or more, expected characteristics such as hydrophilicity of the crosslinked particles described later are improved, which is preferable. Although the hydrophobic polymer block may contain a hydrophilic group, the number of monomer units containing a hydrophilic group may be one of the constituent monomer units in the hydrophobic polymer block.
It is preferably at most 0 (mol)%, more preferably at most 5%.

In the present invention, the block copolymer is usually used for producing crosslinked particles in a state of being dissolved in a medium such as water or a state of being emulsified and dispersed in a medium such as water. The method for emulsifying and dispersing the block copolymer is not particularly limited, but is preferably a method described in JP-A-10-30625.
The method can be carried out by mixing a block copolymer solution in an organic solvent with water, emulsifying the solution, and then removing the organic solvent while leaving water by the method described in No. 0 or the like.

The thus obtained block copolymer emulsion of the present invention usually has a particle size of 0.1 to 500 nm,
Preferably from 0.5 to 300 nm, more preferably from 1 to 300 nm.
２００200 nm. The solid content of the obtained polymer emulsion is usually 5 to 50% by weight, preferably 10 to 50% by weight.
To 40% by weight, which can be appropriately selected depending on use conditions, storage conditions, and the like.

The crosslinked particles of the present invention can be produced by polymerizing a radical polymerizable monomer containing a crosslinkable monomer in the presence of the block copolymer. Examples of the crosslinkable monomer include hydrocarbon monomers such as divinylbenzene, divinyltoluene, divinylxylene, divinylethylbenzene, divinylnaphthalene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol diene. (Meta)
Acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate,
Tetramethylolpropane tri (meth) acrylate,
(Meth) acrylic acid ester derivatives such as tetramethylolmethane tri (meth) acrylate, acrylamide derivatives such as methylenebis (meth) acrylamide, and other monomers having two or more polymerizable double bonds in one molecule Can be Examples of the other monomer include the above-described diene-based monomer, aromatic vinyl monomer, olefin-based monomer, and other monomers. As a method for producing crosslinked particles by polymerizing monomers containing these crosslinkable monomers in the presence of the block copolymer, an aqueous solution or emulsified dispersion of the block copolymer and a crosslinkable monomer are used. It is preferable to mix the monomer and the polymerization initiator to carry out thermal polymerization.

Examples of the polymerization initiator include, in addition to the radical polymerization initiator, known water-soluble initiators such as persulfate and hydroperoxide, and known redox polymerization initiators obtained by combining these initiators with a reducing agent. Can be used. The block copolymer, the monomer, and the initiator may be polymerized by batch addition, or may be polymerized by adding each component as needed. The solvent to be used is usually water, but the water-soluble or water-insoluble organic solvent can be used in combination to adjust the particle size of the crosslinked particles, the pore size within the particle size, and the like. The solid content concentration of the monomer containing the crosslinkable monomer at the time of polymerization is usually from 1 to 70% by weight, preferably from 10 to 50% by weight. It is possible to control the diameter. The polymerization temperature is usually 20 to
The temperature is 150 ° C, preferably 40 to 120 ° C, particularly preferably 60 to 110 ° C.

The proportion of the block copolymer and the monomer containing a crosslinkable monomer is usually 90/10 to 2/9 by weight.
8, preferably 70/30 to 10/90, particularly preferably 50/50 to 20/80. If the amount of the block copolymer is more than 90% by weight, the crosslinking of the crosslinked particles may not proceed sufficiently, which is not preferable. On the other hand, if the amount is less than 2% by weight, expected properties such as hydrophilicity are not sufficiently exhibited, which is not preferable. The particle size of the crosslinked particles of the present invention is usually from 0.1 nm to
It is 10 μm, and can be appropriately selected according to the purpose of use.

The crosslinked particles of the present invention can be used alone depending on the application, but can be used in combination with a polymer having a binding property for the purpose of coating or the like. As the polymer having binding properties, an aqueous emulsion polymer is preferable, and an emulsion of a known polymer is used. Preferred emulsions include urethane emulsions,
Acrylic emulsion, epoxy emulsion, polyester emulsion, polystyrene emulsion, polyolefin emulsion, ethylene / (meth) acrylic acid copolymer emulsion, aliphatic diene / aromatic monomer copolymer sulfonated emulsion, and the like.
These may be used alone or in combination of two or more.

The ratio of the polymer having a binding property is usually 90% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less in the total composition in terms of solid content. If it exceeds 90% by weight, the expected properties such as hydrophilicity of the crosslinked particles are not exhibited, which is not preferable. Further, additives such as a lubricant, a coating improver, a thickener, an antioxidant, and an ultraviolet absorber can be added to the crosslinked particles of the present invention and the composition thereof, if necessary.

One application of the crosslinked particles and the composition of the present invention is a coating material, but there is no particular limitation on the substrate that can be used. As the base material, for example, a polymer material such as a polycarbonate resin, an acrylic resin, an ABS resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, and polyamide; a non-ferrous metal such as aluminum, copper, and duralumin; and a steel plate such as stainless steel and iron , Glass, wood,
Examples thereof include paper, gypsum, alumina, and inorganic cured products. There is no particular limitation on the shape of the base material, even in a flat type,
A porous material such as a fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric may be used.

The coating method for coating the crosslinked particles and the composition of the present invention is not particularly limited, and brush coating, spraying, roll coater, flow coater, bar coater, dipping treatment and the like may be used. it can. The thickness of the applied film varies depending on the application, but it is usually 0.01 to 1000 μm, preferably 0.1 to 100 μm as a dry film thickness. The drying conditions are not particularly limited, but the drying is carried out, for example, at 50 to 150 ° C, preferably 70 to 130 ° C.

The crosslinked particles and the composition of the present invention are particularly effective for modifying the surface of a substrate. In particular, by coating on a hydrophobic surface, it becomes possible to develop or maintain hydrophilicity and hygroscopicity. It is also effective in preventing adhesion of dirt and dust due to static electricity and the like. In addition, when coated on a porous material such as a nonwoven fabric, for example, it exhibits a function of capturing a weak base such as ammonia or amine present in the air or water, or an ionic substance. Also, by coating the surface of the battery separator,
It is expected that the affinity with the battery electrolyte is improved, which leads to an improvement in battery characteristics such as cycle characteristics and self-discharge characteristics. Furthermore, it has the excellent characteristics that it has high adhesion to various substrates, prevents the coating film from peeling off from the substrates, and can maintain stable performance for a long period of time.

The crosslinked particles and the composition of the present invention can be applied to various uses. For example, dyeing aids for fibers,
Water-absorbent non-woven fabric, non-woven fabric for wet tissue, non-woven fabric for sealing material, anti-fouling material for (non) woven fabric, ion-exchange fiber, hydrophilizing agent for battery separator, air purifying filter, water purifying filter, etc., deodorant Fiber, deodorant paint, deodorant paper, antibacterial material, antifogging agent, recording medium for inkjet, anti-condensation material, antistatic agent, paint or coating material with anti-staining function, floor polish, masking material, water-absorbing resin , Paper sizing materials, paper strength enhancing materials, adhesives, and photographic materials such as silver halide photographic light-sensitive materials. Further, as a coating material for surface protection, for example, it is possible to apply to metals such as stainless steel, aluminum and copper, inorganic substances such as concrete and slate, polymer materials such as polyethylene terephthalate, wood, paper and the like. In addition, as applications other than the above, fillers for liquid chromatography, electrorheological fluids, organic pigments, spacers, separation materials, biochemical carriers, virus concentration reagents, fillers for cosmetics, hydrophilic materials for printing plates, various types Additives, compounding agents and the like can be mentioned.

[0037]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. In the examples, parts and% are by weight unless otherwise specified. Various evaluations and measurements in the examples were performed by the following methods. (1) Particle size of crosslinked particles LPA-3100 LASER P manufactured by Otsuka Electronics Co., Ltd.
The average particle size of the emulsion was measured using ARTICLE ANALYZER. (2) Weight average molecular weight (Mw) The weight average molecular weight (Mw) of the base polymer was measured by gel permeation chromatography (GPC) using polystyrene as a standard sample.

Reference Example 1 (1) 500 g of dioxane was placed in a glass reaction vessel,
50 g of sulfuric anhydride was added thereto while maintaining the internal temperature at 25 ° C., and the mixture was stirred for 2 hours to obtain a sulfuric anhydride-dioxane complex. (2) In another glass reaction vessel, put a polyisoprene-polystyrene AB type block copolymer (styrene / isoprene = 50/50 (weight ratio), weight average molecular weight 10,000) 85
g was dissolved in 400 g of tetrahydrofuran. The whole amount of the complex obtained above was added thereto while maintaining the internal temperature at 25 ° C., and stirring was further continued for 2 hours to obtain a sulfonated polymer in which almost only the polyisoprene block was sulfonated. (3) Another flask was charged with 500 g of water and 26 g of sodium hydroxide. To this solution, the entire amount of the sulfonated solution was added with stirring while maintaining the internal temperature at 50 ° C. After stirring for 1 hour after the addition, 1000 g of water was added, and all the solvent and a part of the water were removed by azeotropic distillation to obtain an emulsion. The solid content concentration of this emulsion is 20
%Met. This emulsion is referred to as emulsion X1.

Reference Example 2 In Example 1, polybutadiene-polystyrene was used instead of 85 g of the polyisoprene-polystyrene AB type block copolymer (styrene / isoprene = 50/50 (weight ratio), weight average molecular weight 10,000). AB type block copolymer (styrene / butadiene = 8
The procedure was carried out in the same manner except that 169 g of 0/20 (weight ratio), weight average molecular weight 10,000) was used to obtain a sulfonated polymer emulsion in which only the polybutadiene block was sulfonated. The solid concentration of this emulsion was 20%. This emulsion is referred to as emulsion X2. (Reference Example 3) In Reference Example 1, a polyisoprene-polystyrene AB type block copolymer (styrene / isoprene = 50/50 (weight ratio), weight average molecular weight 10,000) 85
g of polyisoprene-polystyrene-polyisoprene ABA type block copolymer (isoprene / styrene / isoprene = 35/30/35 (weight ratio), weight average molecular weight 5000) in place of g. Thus, a sulfonated polymer emulsion in which only the polyisoprene block was sulfonated was obtained. This solid content concentration was 20%. This product is called Emulsion X3. Reference Example 4 (1) 1,2-Dichloroethane 50 was added to a glass reaction vessel.
0 g was added, and 50 g of sulfuric anhydride was added thereto while maintaining the internal temperature at 25 ° C. In another glass reaction vessel, a hydrogenated product of a polybutadiene-polystyrene AB type block copolymer (butadiene / styrene = 50/50 (weight ratio), a weight average molecular weight of 20,000, and a hydrogenation ratio of the polybutadiene block: 9)
(9%) 130 g was dissolved in 800 g of 1,2-dichloroethane. The whole amount of the complex obtained above was added thereto while maintaining the internal temperature at 25 ° C., and stirring was further continued for 2 hours to obtain a sulfonated polymer in which almost only the polystyrene block was sulfonated. (3) Another flask was charged with 500 g of water and 26 g of sodium hydroxide. To this solution, the entire amount of the sulfonated solution was added with stirring while maintaining the internal temperature at 50 ° C. After stirring for 1 hour after the addition, 1000 g of water was added, and all the solvent and a part of the water were removed by azeotropic distillation to obtain an emulsion. The solid content concentration of this emulsion is 20
%Met. This emulsion is referred to as emulsion X4.

Example 1 10 ml of the emulsion X1 was placed in a 500 cc flask purged with nitrogen.
0 g, divinylbenzene 20 g, water 250 g, and sodium persulfate 0.2 g were added, and the mixture was stirred at 2000 rpm for 10 minutes. Thereafter, polymerization was carried out at 80 ° C. for 5 hours to obtain crosslinked particles Y1. The particle size of Y1 was 20 nm, and the sulfonic acid content was 1.9 mmol / g. Example 2 Emulsion X2 was placed in a 500 cc flask purged with nitrogen.
0 g, trimethylolpropane triacrylate 10
g, 10 g of styrene, 250 g of water, and 0.2 g of sodium persulfate, and the mixture was stirred at 2000 rpm for 10 minutes.
Thereafter, polymerization was carried out at 80 ° C. for 5 hours, and the crosslinked particles Y2
I got The particle size of Y2 is 25 nm, and the sulfonic acid content is 1.
It was 2 mmol / g. Example 3 Emulsion X3 was placed in a 500 cc flask purged with nitrogen.
0 g, divinylbenzene 5 g, 2-ethylhexyl acrylate 15 g, water 250 g, sodium persulfate 0.2
g and stirred at 2000 rpm for 10 minutes. Thereafter, polymerization was carried out at 80 ° C. for 5 hours to obtain crosslinked particles Y3. Y3 has a particle size of 15 nm and a sulfonic acid content of 2.3 m.
mol / g. Example 4 10 emulsions X4 were placed in a 500 cc flask purged with nitrogen.
0 g, trimethylolpropane triacrylate 5 g,
Styrene 5 g, 2-ethylhexyl acrylate 10
g, 300 g of water and 0.2 g of sodium persulfate.
The mixture was stirred at 000 rpm for 10 minutes. Thereafter, polymerization was carried out at 80 ° C. for 5 hours to obtain crosslinked particles Y4. The particle size of Y4 was 20 nm, and the sulfonic acid content was 1.3 mmol / g. Example 5 Emulsion X1 was placed in a 500 cc flask purged with nitrogen.
0 g, divinylbenzene 20 g, water 60 g, and sodium persulfate 0.2 g were added, and the mixture was stirred at 2000 rpm for 10 minutes. Thereafter, polymerization was carried out at 80 ° C. for 5 hours to obtain crosslinked particles Y5. The particle size of Y5 was 180 nm, and the sulfonic acid content was 1.9 mmol / g.

Test Example Using the obtained crosslinked particles (Y1 to Y5), the following performance evaluation was carried out. Table 1 shows the results. a) Antistatic Property 15 g (in terms of solid content) of crosslinked particles, 5 g (in terms of solid content) of a binder and water shown in Table 1 of the present invention were mixed to prepare an emulsified dispersion having a solid content of 10%. This emulsified dispersion was applied to the PET surface using a bar coater. After application,
After drying at 105 ° C. for 15 minutes, a PET film coated with crosslinked particles and a binder was obtained. This film was left overnight in an atmosphere of 23 ° C. and 50% humidity. Hewlett-Packard's concentric electrodes 1
Using 6008A and 4329A which is a high resistance meter of the company, a voltage of 100V was applied under an atmosphere of 23 ° C. and 50% humidity, and the surface specific resistance of the film was measured.

B) Wetting with water and aqueous alkali solution
Water or 30 drops with a dropper on the PET film coated with the crosslinked particles and the binder prepared in the property a).
1% aqueous solution of potassium hydroxide was dropped. The degree of penetration of the water droplets and the like was evaluated as ○ for good, × for poor, and × for intermediate. As shown in Table 1,
Since the crosslinked particles and the composition thereof of the present invention are excellent in antistatic property or water wettability, it is understood that the polar group easily emerges on the surface and easily exhibits various characteristics possessed by the polar group.

[0043]

[Table 1] 1 Binder type: A; polystyrene / polyisoprene / polystyrene (1
0/80 / 10wt, Mw 50,000) Block copolymer sulfonate Emulsion of polyisoprene block obtained by sulfonating 10% of polyisoprene block B: acrylic emulsion (AE343, JSR Corporation)
C) Styrene-butadiene rubber emulsion (JSR0
561, manufactured by JSR Corporation) D; Ethylene- (meth) acrylic acid copolymer emulsion (Chemipearl S-650, manufactured by Mitsui Chemicals, Inc.)

[0044]

The crosslinked particles of the present invention and the composition thereof are
Because of its excellent antistatic properties and water wettability, polar groups are easily exposed on the surface, and various properties such as dispersibility, hydrophilicity, water absorption, ion trapping properties, and ion conductivity of polar groups are easily exhibited. , Excellent crosslinked particles and compositions.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Makoto Okegami 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F term (reference) 4J002 BB001 BB071 BC031 BG001 BN212 CD001 CF001 CK021 GH00 HA07 4J026 AA16 AA17 AA66 AA69 AC16 AC26 BA04 BA28 BA38 DB14 DB15 DB16 FA03 FA09 GA08 GA09 HD05 HD06 HD13 HE01 HE02 4J100 BA56H CA31 EA05 HA61 HB50 HB52 HB54

Claims (7)

[Claims] 1. Crosslinked particles comprising (a) a block copolymer having a hydrophilic polymer block and a hydrophobic polymer block, and (b) a polymerized crosslinked product of a radical polymerizable monomer. 2. The crosslinked particle according to claim 1, wherein the hydrophilic group is a sulfonic acid group or a sulfonic acid salt group. 3. The crosslinked particles according to claim 2, wherein the sulfonic acid content is 0.2 mmol / g or more. 4. A block copolymer having a hydrophilic polymer block and a hydrophobic polymer block, wherein the block copolymer is mainly composed of a polymer block of a monomer mainly composed of a diene monomer and an aromatic vinyl compound. A block copolymer having a polymer block of a monomer or a hydrogenated product thereof, wherein one of the hydrophilic polymer block and the hydrophobic polymer block in the block copolymer has a hydrophilic group. The crosslinked particles according to claim 1, characterized in that: 5. The crosslinked particle according to claim 1, wherein the particle size is 0.1 nm to 10 μm. 6. A method for producing a crosslinked particle, comprising polymerizing a radical polymerizable monomer containing a crosslinkable monomer in the presence of a block copolymer having a hydrophilic polymer block and a hydrophobic polymer block. Production method. 7. A composition comprising the crosslinked particles according to claim 1 and a polymer having a binding property.