JP2905556B2 - Electrorheological fluid composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an electrorheological fluid composition. More specifically, an electrorheological fluid composition that generates a large shear stress by applying a relatively weak electric field, has a small current density flowing at that time, and has excellent stability over time of the generated shear stress and current density. It is about.

(Prior art) An electrorheological fluid is, for example, a fluid obtained by dispersing and suspending solid particles in an insulating dispersion medium. The rheological or flow properties of the electrorheological fluid is changed by applying an electric field change to a viscoplastic type fluid. It is a fluid that changes its properties. Generally, when an external electric field is applied, its viscosity rises significantly and induces a large shear stress. It is known as a fluid exhibiting the so-called Winslow effect. Since the Winslow effect has a characteristic of quick response, application of the electrorheological fluid to clutches, dampers, brakes, shock absorbers, actuators and the like has been attempted.

Conventionally, as an electrorheological fluid composition, in an insulating oil such as silicone oil, diphenyl chloride, and trans oil, cellulose, starch, soybean casein, silica gel, polystyrene ion exchange resin, solid particles such as crosslinked polyacrylate, etc. Are known.

However, the electrorheological fluid composition using cellulose, starch or soybean casein as a dispersed phase has a problem that the shear stress obtained when an electric field is applied is small, and a crosslinked polyacrylate is used as the dispersed phase. The electrorheological fluid composition has a problem that only a relatively weak electric field is not applied to induce a practically sufficient shear stress.

In addition, an electrorheological fluid composition using an alkali metal salt of polystyrene sulfonic acid, one of the polystyrene-based ion-exchange resins, as the dispersed phase generates a large shear stress even when a relatively weak electric field is applied. However, there was a problem that the current density flowing at that time was large, and the generated shear stress and current density were poor in stability over time.

On the other hand, it is also conceivable to use particles of a sulfonated polymer obtained by sulfonating a polymer crosslinked product mainly composed of styrene and divinylbenzene with a sulfonating agent using sulfuric acid as a dispersed phase of an electrorheological fluid composition. However, even if such an electrorheological fluid composition generates a large shear stress by applying a relatively weak electric field, the current density flowing at that time is large, and the generated shear stress and the current density have poor temporal stability. There was a problem.

(Problems to be Solved by the Invention) The present invention is to solve the above-mentioned problems of the conventional electrorheological fluid composition.

Accordingly, an object of the present invention is to provide an electrorheological device that generates a large shear stress even when a relatively weak electric field is applied, and has a small current density flowing at that time, and also has excellent stability over time of the generated shear stress and the current density. It is to provide a fluid composition.

(Means and Actions for Solving the Problems) The present invention provides a composition obtained by dispersing dispersed phase particles comprising a sulfonated polymer having an aromatic ring substituted with a sulfonic acid group in an insulating dispersion medium. In addition, the sulfonated polymer is a polymer crosslinked product of a monomer mixture (A) containing a vinyl aromatic compound (a) and a polyvinyl compound (b) as main components and optionally adding another vinyl compound (c) ( The present invention relates to an electrorheological fluid composition obtained by sulfonating I) with 500 parts by weight or more of chlorosulfuric acid with respect to 100 parts by weight of a polymer crosslinked product (I).

The average particle diameter of the dispersed phase particles used in the present invention is 0.1 to 1
It is preferably in the range of 00 μm. In the electrorheological fluid composition of the present invention, the shear stress obtained when an electric field is applied to the prepared electrorheological fluid composition tends to decrease as the particle size of the dispersed phase decreases, If the average particle size is less than 0.1 μm, there may be a problem that a large shear stress cannot be obtained when an electric field is applied to the prepared electrorheological fluid composition.
When the average particle diameter of the dispersed phase particles exceeds 100 μm, the shear stress value obtained when a certain electric field is applied to the prepared electrorheological fluid composition becomes irregular,
The problem that stability is difficult sometimes occurs.

The sulfonic acid group referred to in the present invention is a substance which releases a cation in the presence of a polar solvent such as water and turns itself into a sulfonic acid ion, and particularly a cation released in the presence of a polar solvent such as water. No restrictions.

The sulfonated polymer constituting the dispersed phase particles used in the present invention is a monomer mixture containing a vinyl aromatic compound (a) and a polyvinyl compound (b) as main components and optionally adding another vinyl compound (c). It is obtained by sulfonating the polymerized crosslinked product (I) of (A), but it is necessary to use a specific amount of chlorosulfuric acid as a sulfonating agent. By using chlorosulfuric acid as the sulfonating agent, it is possible to obtain a sulfonated polymer suitable for the dispersed phase particles that provides the above-described electrorheological fluid composition having excellent various properties. When a conventionally used sulfonating agent such as sulfuric acid alone is used alone, the prepared electrorheological fluid composition generates a large shear stress when a relatively weak electric field is applied. However, there arises a problem that the current density flowing through the wire is large and the generated shear stress and the current density have poor stability over time. It is necessary to use chlorosulfuric acid in a proportion of 500 parts by weight or more based on 100 parts by weight of the polymer crosslinked product (I), and it is particularly preferable to use chlorosulfuric acid in a proportion of 650 parts by weight or more. If the amount of chlorosulfuric acid used is less than 500 parts by weight, the reactivity of the sulfonating agent in the reaction mixture decreases with the progress of sulfonation, and the dispersed phase provides an electrorheological fluid composition having the above-mentioned various properties. A suitable sulfonated polymer for the particles cannot be obtained.

In the present invention, when sulfonating the polymer crosslinked product (I), as long as chlorosulfuric acid is used as a sulfonating agent in a ratio of 500 parts by weight or more based on 100 parts by weight of the polymer crosslinked product (I), Other sulfonating agents may be used in combination with chlorosulfuric acid.

When another sulfonating agent is used in combination, the ratio of chlorosulfuric acid to the total amount of the sulfonating agent is preferably 50% by weight or more. When the ratio of chlorosulfuric acid to the total amount of the sulfonating agent is less than 50% by weight, the prepared electrorheological fluid composition generates a large shear stress by applying a relatively weak electric field, but flows at that time. There may be a problem that the current density is large and the generated shear stress and the current density have poor stability over time.

Other sulfonating agents that can be used in the present invention may be selected from conventionally known sulfonating agents, such as sulfuric acid, sulfur trioxide and fuming sulfuric acid. More than one species can be used.

Monomer mixture (A) that can be used in the present invention
Is a vinyl aromatic compound (a) of 50.0 to 99.9.
Mol%, the content of the polyvinyl compound (b) is preferably in the range of 0.1 to 50.0 mol%. Vinyl aromatic compound (a)
Is less than 50.0 mol% and the composition ratio of the polyvinyl compound (b) exceeds 50.0 mol%, sulfonation does not easily proceed, or an electric field is applied to the electrorheological fluid composition using the obtained particles. May cause a problem that a large shear stress cannot be obtained when is applied. The composition ratio of the vinyl aromatic compound (a) was 99.9 mol%.
When the ratio is more than 0.1 and the constituent ratio of the polyvinyl compound (b) is less than 0.1 mol%, a problem may occur that particles adhere to each other when the crosslinked polymer obtained by polymerization is sulfonated.

Examples of the vinyl aromatic compound (a) that can be used in the present invention include styrene, vinyl naphthalene,
Vinyl aromatic hydrocarbons such as vinyl anthracene and vinyl phenanthrene; methyl styrene, ethyl styrene,
Monoalkylstyrene compounds such as propylstyrene, butylstyrene, pentylstyrene, hexylstyrene; dimethylstyrene, diethylstyrene, dipropylstyrene, methylethylstyrene, methylpropylstyrene, methylhexylstyrene, ethylbutylstyrene, ethylpropylstyrene, ethylhexylstyrene , Dialkylstyrene compounds such as propylbutylstyrene; trimethylstyrene, triethylstyrene, tripropylstyrene, methyldiethylstyrene, dimethylethylstyrene, methylethylpropylstyrene, methyldipropylstyrene, dimethylpropylstyrene,
Trialkylstyrene compounds such as ethyldipropylstyrene and diethylpropylstyrene; vinylmonoalkylnaphthalene compounds such as vinylmethylnaphthalene, vinylethylnaphthalene and vinylpropylnaphthalene; vinyldimethylnaphthalene, vinyldiethylnaphthalene, vinyldipropylnaphthalene and vinylmethyl Vinyl dialkyl naphthalene compounds such as ethyl naphthalene; vinyl trialkyl naphthalene compounds such as vinyl trimethyl naphthalene, vinyl triethyl naphthalene, vinyl tripropyl naphthalene, vinyl methyl diethyl naphthalene, vinyl dimethyl ethyl naphthalene, vinyl methyl ethyl propyl naphthalene; chlorostyrene, bromostyrene , Fluorostyrene, chloromethylstyrene, chloroethylstyrene , Chloropropyl styrene,
Halogenated vinyl aromatic compounds such as chlorodimethylstyrene, bromomethylstyrene, bromoethylstyrene, fluoromethylstyrene, fluoroethylstyrene, vinylchloronaphthalene, and vinylbromonaphthalene; methoxystyrene, dimethoxystyrene, trimethoxystyrene, ethoxystyrene, Ethoxystyrene, triethoxystyrene, propyloxystyrene, dipropyloxystyrene, tripropyloxystyrene, phenoxystyrene, methoxymethylstyrene, methoxyethylstyrene, methoxypropylstyrene, ethoxymethylstyrene, ethoxyethylstyrene, propyloxymethylstyrene, propyl Oxyethylstyrene, phenoxymethylstyrene, phenoxyethylstyrene,
Methoxydimethylstyrene, methoxydiethylstyrene, phenoxydimethylstyrene, phenoxydiethylstyrene, methoxychlorostyrene, methoxybromostyrene, vinylmethoxynaphthalene, vinyldimethoxynaphthalene, vinylethoxynaphthalene, vinyldiethoxynaphthalene, vinylmethoxymethylnaphthalene, vinylmethoxydimethylnaphthalene , Vinyldimethoxymethylnaphthalene, vinylmethoxyethylnaphthalene, vinylmethoxydiethylnaphthalene, vinyldimethoxyethylnaphthalene, vinylmethoxychloronaphthalene, and alkoxylated or aryloxylated vinyl aromatic compounds such as vinyldimethoxychloronaphthalene. One or more of them can be used.

Examples of the polyvinyl compound (b) that can be used in the present invention include divinylbenzene, divinyltoluene, divinylxylene, divinylethylbenzene,
Polyvinyl aromatic hydrocarbons such as divinyldiethylbenzene, divinylpropylbenzene, divinylnaphthalene, trivinylbenzene, trivinyltoluene, trivinylxylene, and trivinylnaphthalene; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylol Examples thereof include polyvinyl aliphatic compounds such as propane tri (meth) acrylate, N, N'-methylenebisacrylamide, diallyl maleate, and diallyl adipate, and one or more of these can be used.

In the monomer mixture (A) in the present invention, a vinyl compound (c) other than the vinyl aromatic compound (a) or the polyvinyl compound (b) can be blended as necessary, and the constituent ratio is 50 mol% or less. Is preferable. Examples of such other vinyl compounds (c) include olefinic hydrocarbons such as ethylene, propylene, isoprene, butadiene, vinyl chloride, and chloroprene or halogen-substituted products thereof; methyl (meth) acrylate, ethyl (meth) Ester compounds of unsaturated carboxylic acids such as acrylates; vinyl ester compounds of monovalent carboxylic acids such as vinyl acetate and vinyl propionate;
(Meth) acrylamide, diacetone acrylamide,
Unsaturated amide compounds such as methylolated (meth) acrylamide or derivatives thereof; unsaturated cyanide compounds such as (meth) acrylonitrile and crotonnitrile; unsaturated alcohol compounds such as (meth) allyl alcohol and croton alcohol; (meth) acrylic acid Unsaturated monobasic acids such as maleic acid, fumaric acid and itaconic acid; monoesters of monohydric alcohols such as maleic acid monomethyl ester and maleic acid monoallyl ester with unsaturated dibasic acids Compounds and the like can be mentioned, and one or more of these can be used.

The shape of the dispersed phase particles used in the present invention is preferably spherical or elliptical spherical. In the case where the shape of the dispersed phase particles is other than spherical or elliptical spherical, the problem that a large shear stress cannot be obtained when an electric field is applied to the prepared electrorheological fluid composition or the electric field was continuously applied. There may be a problem that the stability over time in the state is poor.

In the present invention, the method for producing the polymer crosslinked product (I) used as an intermediate in obtaining the sulfonated polymer is not particularly limited, and a known polymerization method may be employed. Examples of the polymerization method include a suspension polymerization method, an emulsion polymerization method, a dispersion polymerization method, a solution polymerization method, a bulk polymerization method, and the like, and a spherical or oval spherical particle suitable as a dispersed phase particle can be easily obtained. Thus, a suspension polymerization method or an emulsion polymerization method is preferable.

When a suspension polymerization method is used for producing the polymer crosslinked product (I) used in the present invention, the conditions for the polymerization are not particularly limited.

Water or the like is usually used as a dispersion medium for suspension polymerization.

As a dispersant for the suspension polymerization, known dispersants such as polyvinyl alcohol, carboxymethylcellulose, ammonium salts of styrene-maleic anhydride copolymer, bentonite, sodium poly (meth) acrylate, and poly (diallylmethylammonium chloride) are usually used. Things can be used.

Examples of the polymerization initiator for suspension polymerization include peroxides such as benzoyl peroxide, tertiary butyl hydroxy peroxide, cumene peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, tertiary butyl perphthalate, and caproyl peroxide. Oxides: azobisisobutyronitrile,
Azobisisobutylamide, 2,2'-azobis (2,4-dimethylmaleronitrile), azobis (α-dimethylvaleronitrile), azobis (α-methylbutyronitrile)
And the like, and one or more of these may be used.

In suspension polymerization, if necessary, a known emulsion polymerization inhibitor can be used to suppress the generation of fine particles.

Suspension polymerization is usually carried out at a temperature in the range of 50-100 ° C.
It takes about 30 hours.

As an operation of suspension polymerization, for example, water and a dispersant are charged, a mixture of monomers in which a polymerization initiator is dissolved is added under stirring, and the particle diameter is regulated using a dispersing machine or a stirring device. The reaction is carried out at a predetermined temperature in a suspended state.

When the emulsion polymerization method is used for producing the polymer crosslinked product (I) used in the present invention, the conditions for the polymerization are not particularly limited.

Water or the like is usually used as a solvent for emulsion polymerization.

As the emulsifier for emulsion polymerization, a known emulsifier such as a surfactant such as sodium lauryl sulfonate and polyoxyethyllenstearate can be used.

As the polymerization initiator for the emulsion polymerization, generally known ones such as sodium persulfate and ammonium persulfate can be used.

Emulsion polymerization is usually carried out at a temperature in the range of 50-100 ° C.
It takes about 40 hours.

As the operation of emulsion polymerization, a known method such as a sheet polymerization method, a temporary charging polymerization method, a monomer addition polymerization method, and an emulsion addition polymerization method can be used.

In order to carry out the seed polymerization method, usually, first, seed particles, water, an emulsifier, and the like are charged into a reaction vessel, and the mixture is uniformly dispersed with stirring, and then a part or all of the monomer mixture is added as necessary. Next, after heating to a predetermined temperature, a polymerization initiator is added to start the reaction. Furthermore, the remainder of the monomer mixture is added continuously or intermittently, and the emulsification is carried out at a predetermined temperature.

The polymer crosslinked product (I) in the present invention may be a substantially non-porous polymer crosslinked product called a gel type, or a known porous forming agent that imparts porosity to the polymer crosslinked product, such as a swellable polymer. Or a non-swellable organic solvent, a linear polymer soluble in a monomer, or a crosslinked porous polymer obtained by polymerizing a monomer mixture in the presence of a mixture thereof.

The sulfonated polymer constituting the dispersed phase particles used in the present invention is obtained by sulfonating the polymerized crosslinked product (I) with the above-mentioned specific sulfonating agent and pulverizing or granulating the polymer to an appropriate particle size. When the polymer crosslinked product (I) used is a particulate product obtained by a suspension polymerization method or an emulsion polymerization method, sulfonated polymer particles suitable as dispersed phase particles in the present invention can be obtained by sulfonation. It is preferable because it is possible.

The sulfonation reaction can be performed in the presence of a non-swelling or swelling solvent for the polymer crosslinked product (I),
Further, the reaction can be carried out without using any solvent.

Examples of the solvent that is non-swellable with respect to the polymer crosslinked product (I) include:
Any solvent may be used as long as it does not swell the polymer crosslinked product (I) and is inert to the sulfonating agent, and examples thereof include aliphatic hydrocarbons such as hexane, heptane, cyclohexane, and ligroin.

The solvent which swells with respect to the polymerized crosslinked product (I) may be any solvent which swells the polymerized crosslinked product (I) and is inactive with respect to the sulfonating agent. For example, dichloroethane, trichloroethylene, tetrachloroethane, propylene Examples include halogenated hydrocarbons such as dichloride and carbon tetrachloride; and aromatic hydrocarbons such as nitrobenzene and xylene.

The use amount of these solvents is preferably selected within the range of 1000 parts by weight or less based on 100 parts by weight of the polymer crosslinked product (I).

In the sulfonation reaction, for example, mercury sulfate,
A catalyst for the sulfonation reaction such as silver sulfate or a dehydrating agent such as phosphorus pentoxide can be used in combination with the sulfonating agent.

The sulfonation reaction is carried out at a temperature in the range of -20 to 250 ° C.
The sulfonation is carried out for about 0.3 to 100 hours. Preferred conditions for the sulfonation are those in which the polymer cross-linked product (I) is kept at 70 ° C. or more in the presence of chlorosulfuric acid for 30 minutes or longer, and the polymer cross-linked product (I) Is maintained in the presence of chlorosulfuric acid at a temperature in the range of -20 ° C to less than 70 ° C for 0.3 to 30 hours, and further held at a temperature of 70 ° C or more for 30 minutes or more. Among them, a method in which the control of the sulfonation reaction is easily considered is preferable.

The particles of the sulfonated polymer obtained by sulfonating the polymerized crosslinked product (I) are separated from the sulfonating agent and then sufficiently removed with a large amount of water in order to remove the acid and the like remaining in the particles. It is good to wash. Then, if necessary, the cation of the sulfonic acid group can be changed from a proton to a suitable cation species by a method such as neutralization or ion exchange.

As the cation of the sulfonic acid group present in the sulfonated polymer constituting the dispersed phase particles used in the present invention,
There is no particular limitation, for example, hydrogen; lithium, sodium,
Alkali metals such as potassium; alkaline earth metals such as magnesium and calcium; Group IIIA metals such as aluminum; Group IVA metals such as tin and lead; cationic species such as transition metals such as zinc and iron; or ammonium, organic Examples thereof include quaternary ammonium, pyridinium, and guadinium, and one or more of these can be used.

The dispersed phase particles used in the present invention preferably contain 10 parts by weight or less of water based on 100 parts by weight of the sulfonated polymer constituting the particles. In the electrorheological fluid composition of the present invention, since a small amount of water is contained in the dispersed phase particles, a large shear stress is induced when an electric field is applied. However, when the content of water in the sulfonated polymer particles exceeds 10 parts by weight, the dispersed phase particles adhere to each other or the insulating property of the prepared electrorheological fluid composition decreases, so that the electric field is reduced. When applied, a large current flows, which is not preferable.

 As an insulating dispersion medium that can be used in the present invention
Is not particularly limited, for example, polydimethylsiloxane,
Silicone oils such as polyphenylmethylsiloxane;
Liquid paraffin, decane, dodecane, methylnaphthale
Dimethylnaphthalene, ethylnaphthalene, biphenyl
, Decalin, partially hydrogenated triphenyl, etc.
Hydrogen; ether compounds such as diphenyl ether;
Lobenzene, dichlorobenzene, trichlorobenzene,
Bromobenzene, dibromobenzene, chloronaphthale
, Dichloronaphthalene, bromonaphthalene, chlorobi
Phenyl, dichlorobiphenyl, trichlorobiphenyl
, Bromobiphenyl, chlorodiphenylmethane, dic
Lorodiphenylmethane, trichlorodiphenylmethane,
Bromodiphenylmethane, chlorodecane, dichlorodeca
, Trichlorodecane, bromodecane, chlorododeca
, Dichlorododecane and bromododecane
Hydrocarbons: chlorodiphenyl ether, dichlorodiph
Phenyl ether, trichlorodiphenyl ether, bro
Halogenated diphenyl ethers such as modiphenyl ether
Ter compound; Daifoil (Daikin Industries, Ltd.
Made), Demnum (Made by Daikin Industries, Ltd.)
Compounds: dioctyl phthalate, trioctyl trimellitate
And ester compounds such as dibutyl sebacate.
One or more of these can be used
Can be

The electrorheological fluid composition of the present invention is obtained by dispersing the above-mentioned dispersed phase particles in an insulating dispersion medium, and the ratio between the dispersed phase particles and the insulating dispersion medium in the composition is based on 100 parts by weight of the former. The latter is preferably in the range of 50 to 500 parts by weight. When the amount of the dispersion medium exceeds 500 parts by weight, the shear stress obtained when an electric field is applied to the prepared electrorheological fluid composition may not be sufficiently large. When the amount of the dispersion medium is less than 50 parts by weight, the fluidity of the prepared composition itself is reduced, and it may be difficult to use the composition as an electrorheological fluid.

In the present invention, for example, a surfactant, a polymer dispersant, a polymer thickener, etc., in order to improve the dispersibility of the dispersed phase particles in the dispersion medium or to adjust the viscosity of the electrorheological fluid composition or the shear stress. Can be added to the composition.

(Effect of the Invention) The electrorheological fluid composition of the present invention generates a large shear stress even when a relatively weak electric field is applied, and has an excellent current characteristic that a current density flowing at that time is small, and the generated shear stress is low. Since it has excellent stability over time of stress and current density, it can be effectively used for clutches, dampers, brakes, shock absorbers, actuators and the like.

(Examples) Hereinafter, the present invention will be described with reference to examples, but the scope of the present invention is not limited to only these examples.

Example 1 4 l 3 l port equipped with stirrer, reflux condenser and thermometer
Charge 1.2 l of water into a separable flask and add Kuraray Povar
PVA-205 (Kuraray Co., Ltd. polyvinyl alcohol)
After adding and dissolving 16.0 g, styrene 250 g
Industrial divinyl benzene (manufactured by Wako Pure Chemical Industries, Ltd.,
Mixture of 55% by weight of benzene and 35% by weight of ethylstyrene
Product) 50 g and 4 g of azobisisobutyronitrile
The mixture was added. Then, the flask was stirred at 600 rpm.
The contents therein were dispersed and polymerized at 80 ° C. for 8 hours. Obtained
Separate the solids and wash thoroughly with water, then use a hot air dryer.
And dried at 80 ° C for 12 hours.
This is called a polymer crosslinked product (1). ｝ 286 g was obtained.

50 g of the crosslinked polymer (1) and 200 g of tetrachloroethane were charged into a 2-liter four-neck separable flask equipped with a stirrer, a thermometer and a dropping funnel, and cooled to 0 ° C. with stirring using an ice bath. Then, 350 g of chlorosulfuric acid was added from the dropping funnel over 2 hours to obtain a uniform dispersion. Next, the reaction mixture was removed from the ice bath and stirred at room temperature (20 ° C.) for 24 hours. Then, the temperature of the reaction mixture was further raised to 80 ° C., and the mixture was heated and stirred at the same temperature for 2 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., separated, and washed with water and acetone.

The obtained solid is treated with a 10% by weight aqueous sodium hydroxide solution 20
After neutralization with 0 ml, the mixture was thoroughly washed with water. Next, it is dried at 80 ° C. for 10 hours using a vacuum drier, and the dispersed phase particles composed of 94 g of a spherical sulfonated polymer are hereinafter referred to as dispersed phase particles (1). I got｝.

 The average particle diameter of the obtained dispersed phase particles (1) was measured by particle size distribution measurement.
Using a measuring device (SALD-1000, manufactured by Shimadzu Corporation).
As a result, it was 50 μm. Dispersed phase particles (1)
On-exchange capacity determined by neutralization titration and elemental analysis
As a result, the neutralization titration method was 5.0 mg equivalent / g, and the elemental analysis method.
Was 4.9 mg equivalent / g. Water content in dispersed phase particles (1)
The amount is measured by Karl Fischer moisture meter (Kyoto Electronics Industry Co., Ltd.,
MPS-3P), it was 2.5 parts by weight.
Was. (Average particle diameter in the following Examples and Comparative Examples,
Measurement of ion exchange capacity and water content was performed in the same manner as in this example.
went. ) 30 g of the obtained dispersed phase particles (1) was
Le KF96-20CS (Dimmel Silicon manufactured by Shin-Etsu Chemical Co., Ltd.)
Oil) mixed and dispersed in 70 g
Fluid composition {hereinafter, referred to as fluid composition (1). ｝
I got

Example 2 A 2-liter four-neck separable flask equipped with a stirrer, a thermometer, and a dropping funnel was charged with 50 g of the polymer crosslinked product (1) obtained in Example 1, and stirred at 0 ° C using an ice bath. And cooled. Next, 500 g of chlorosulfuric acid was added through the dropping funnel.
It was added over time to obtain a uniform dispersion. Then, after removing from the ice bath and stirring at room temperature (20 ° C.) for 12 hours, the temperature of the reaction mixture was further raised to 90 ° C. and heated at the same temperature for 3 hours.
The mixture was stirred to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., separated, and washed with water and acetone.

The obtained solid material is a 10% by weight aqueous solution of potassium hydroxide 330 m
After neutralization with l, the mixture was thoroughly washed with water. Next, it is dried at 80 ° C. for 10 hours using a vacuum drier, and the dispersed phase particles composed of 115 g of a spherical sulfonated polymer are hereinafter referred to as dispersed phase particles (2). I got｝.

When the average particle size of the obtained dispersed phase particles (2) was measured using a particle size distribution analyzer, it was 50 μm. When the ion exchange capacity of the dispersed phase particles (2) was quantified by a neutralization titration method and an elemental analysis method, it was 5.2 mg equivalent / g by the neutralization titration method and 5.0 mg equivalent / g by the elemental analysis method. The water content in the dispersed phase particles (2) was measured using a Karl Fischer moisture meter, and was 2.4 parts by weight.

 30 g of the obtained dispersed phase particles (2) 900 (new
70 g of partially hydrogenated triphenyl manufactured by Nippon Steel Chemical Co., Ltd.
Mixed and dispersed in the electrorheological fluid composition of the present invention.
Below, this is called fluid composition (2). I got｝.

Example 3 4 l 3 l equipped with stirrer, reflux condenser and thermometer
Charge 1.2 l of water into a separable flask and add Kuraray Povar
PVA-205 (Kuraray Co., Ltd. polyvinyl alcohol)
After adding and dissolving 16.0 g, a further 200 g of styrene and
Rostyrene 70 g, same industrial divinyl as used in Example 1
Mixture consisting of 30 g of benzene and 5 g of benzoyl peroxide
Things were added. Then at 400rpm stirring speed inside the flask
The contents were dispersed and polymerized at 80 ° C. for 9 hours. The solid obtained
Separate the items and wash them thoroughly with water.
At 12 ° C for 12 hours.
It is called a cross-linked product (2). ｝ 290 g was obtained.

A 2-liter four-neck separable flask equipped with a stirrer, thermometer and dropping funnel was charged with 50 g of the crosslinked polymer (2) and 250 g of 98% by weight concentrated sulfuric acid.
Cooled to ° C. Then, 350 g of chlorosulfuric acid was added from the dropping funnel over 2 hours to obtain a uniform dispersion. Then
Remove from the ice bath, stir at room temperature (20 ° C) for 5 hours,
Further, the temperature of the reaction mixture was raised to 80 ° C., and the mixture was heated and stirred at the same temperature for 13 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., separated, and washed with water and acetone.

The obtained solid material is a 10% by weight aqueous solution of lithium hydroxide 120 m
After neutralization with l, the mixture was thoroughly washed with water. Next, it is dried at 80 ° C. for 10 hours using a vacuum drier, and the dispersed phase particles composed of 84 g of a spherical sulfonated polymer are hereinafter referred to as dispersed phase particles (3). I got｝.

When the average particle diameter of the obtained dispersed phase particles (3) was measured using a particle size distribution analyzer, it was 66 μm. When the ion exchange capacity of the dispersed phase particles (3) was quantified by neutralization titration and elemental analysis, it was 5.3 mg equivalent / g by neutralization titration and 5.3 mg equivalent / g by elemental analysis. The water content in the dispersed phase particles (3) was measured using a Karl Fischer moisture meter, and was 2.8 parts by weight.

30 g of the obtained dispersed phase particles (3) are mixed and dispersed in 70 g of bromobenzene, and this is referred to as an electrorheological fluid composition (hereinafter referred to as a fluid composition (3)) of the present invention. I got｝.

Example 4 Three-liter four-neck equipped with stirrer, reflux condenser and thermometer
Charge 1.2 l of water into a separable flask and add Kuraray Povar
PVA-205 (Kuraray Co., Ltd. polyvinyl alcohol)
After adding and dissolving 16.0 g, further add 140 g of styrene and
130 g of toxic styrene, the same industrial grade as used in Example 1
30 g of vinylbenzene and 5 g of azobisisobutyronitrile
Was added. After that, the dispersion machine (rotation speed: 500
0 rpm) to disperse the contents in the flask,
Polymerized for 12 hours. Separate the resulting solid and wash thoroughly with water
After drying at 80 ° C for 12 hours using a hot air drier,
This is hereinafter referred to as a polymer crosslinked product (3).
U. ｝ 291 g was obtained.

50 g of the crosslinked polymer (3) and 200 g of dichloroethane were charged into a 2-liter four-neck separable flask equipped with a stirrer, a thermometer, and a dropping funnel.
Cooled to ° C. Next, 400 g of chlorosulfuric acid was added from the dropping funnel over 2 hours to obtain a uniform dispersion. Then
After removing from the ice bath and stirring at room temperature (20 ° C) for 6 hours,
Further, the temperature of the reaction mixture was raised to 80 ° C., and the mixture was heated and stirred at the same temperature for 7 hours to carry out a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., separated, and washed with water and acetone.

The obtained solid is added to a 10% by weight aqueous sodium hydroxide solution 25
After neutralization with 0 ml, the mixture was thoroughly washed with water. Next, it is dried at 80 ° C. for 10 hours using a vacuum drier, and the dispersed phase particles composed of 109 g of a spherical sulfonated polymer are hereinafter referred to as dispersed phase particles (4). I got｝.

When the average particle diameter of the obtained dispersed phase particles (4) was measured using a particle size distribution analyzer, it was 12 μm. When the ion exchange capacity of the dispersed phase particles (4) was determined by a neutralization titration method and an elemental analysis method, it was 5.5 mg equivalent / g by the neutralization titration method and 5.6 mg equivalent / g by the elemental analysis method. The water content in the dispersed phase particles (4) was measured using a Karl Fischer moisture meter, and was 2.6 parts by weight.

30 g of the obtained dispersed phase particles (4) are mixed and dispersed in 70 g of 1,2,4-tetrachlorobenzene, and the electrorheological fluid composition of the present invention (hereinafter referred to as fluid composition (4)). I got｝.

Example 5 50 g of the polymer crosslinked product (3) obtained in Example 4 was charged into a 2 l four-neck separable flask equipped with a stirrer, a thermometer and a dropping funnel, and stirred at 0 ° C. using an ice bath. And cooled. Next, 500 g of chlorosulfuric acid was added through the dropping funnel.
It was added over time to obtain a uniform dispersion. Then, after removing from the ice bath and stirring at room temperature (20 ° C.) for 24 hours, the temperature of the reaction mixture is further raised to 90 ° C. and heated at the same temperature for 45 minutes.
The mixture was stirred to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., separated, and washed with water and acetone.

The obtained solid is treated with a 10% by weight aqueous sodium hydroxide solution 26
After neutralization with 0 ml, the mixture was thoroughly washed with water. Next, it is dried at 80 ° C. for 10 hours using a vacuum dryer, and 108 g of dispersed phase particles composed of a spherical sulfonated polymer (hereinafter referred to as dispersed phase particles (5)). I got｝.

When the average particle diameter of the obtained dispersed phase particles (5) was measured using a particle size distribution analyzer, it was 12 μm. The ion exchange capacity of the dispersed phase particles (5) was determined by a neutralization titration method and an elemental analysis method. As a result, it was 5.6 mg equivalent / g by the neutralization titration method and 5.6 mg equivalent / g by the elemental analysis method. When the water content in the dispersed phase particles (5) was measured using a Karl Fischer moisture meter, it was 2.5 parts by weight.

 30 g of the obtained dispersed phase particles (5) 300 (new
Biphenyl and diphenyl ether manufactured by Nippon Steel Chemical Co., Ltd.
Mixture) dispersed and dispersed in 70 g of the electrorheological flow of the present invention.
Body composition ｛Hereinafter, this is referred to as a fluid composition (5). ｝
Obtained.

Example 6 After charging 50 ml of water, 0.4 g of sodium lauryl sulfonate and 1.0 g of dodecane into a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, the mixture was emulsified using a disperser. I let it. Further, 50 ml of water, 0.2 g of sodium persulfate, 30 g of styrene, 15 g of methylstyrene and 15 g of the same industrial divinylbenzene used in Example 1
Was added thereto, followed by heating at 50 ° C. for 8 hours with stirring to carry out polymerization to obtain 160 ml of an emulsion of seed particles.

Then, 1.2 l of water was charged into a 3 l four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, and 160 ml of an emulsion of seed particles prepared above and 2.8 g of sodium lauryl sulfonate were added. Thereafter, the mixture was uniformly dispersed with stirring. Then, while maintaining the rotation speed of the stirrer at 250 rpm, 70
2 g of sodium persulfate dissolved in 10 ml of water
Was added. Then, styrene 120g, methyl styrene 60
g and 60 g of the same industrial divinylbenzene used in Example 1 were added dropwise over 18 hours. Furthermore,
After reacting at the same temperature for 5 hours, the temperature was raised to 90 ° C., and the reaction was terminated after 3 hours. The solid content of the obtained dispersion was separated and dried at 80 ° C. for 12 hours using a hot-air drier to obtain 267 g of a spherical polymer crosslinked product (hereinafter referred to as a polymer crosslinked product (4)).

In a 2 l four-neck separable flask equipped with a stirrer, thermometer and dropping funnel, 50 g of the polymerized crosslinked product (4), 98% by weight
170 g of concentrated sulfuric acid and 200 g of dichloroethane were charged and cooled to 0 ° C. using an ice bath with stirring. Next, 330 g of chlorosulfuric acid was added from the dropping funnel over 2 hours to obtain a uniform dispersion. Then remove from the ice bath, room temperature (20 ° C)
After stirring for 24 hours, the temperature of the reaction mixture was further raised to 90 ° C., and the mixture was heated and stirred at the same temperature for 1 hour to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., separated, and washed with water and acetone.

The obtained solid is treated with a 10% by weight aqueous sodium hydroxide solution 20
After neutralization with 0 ml, the mixture was thoroughly washed with water. Next, it is dried at 80 ° C. for 10 hours using a vacuum drier, and the dispersed phase particles composed of 93 g of a spherical sulfonated polymer are hereinafter referred to as dispersed phase particles (6). I got｝.

When the average particle diameter of the obtained dispersed phase particles (6) was measured using a particle size distribution analyzer, it was 5 μm. When the ion exchange capacity of the dispersed phase particles (6) was determined by a neutralization titration method and an elemental analysis method, it was 5.0 mg equivalent / g by the neutralization titration method and 4.9 mg equivalent / g by the element distribution method. When the water content in the dispersed phase particles (6) was measured using a Karl Fischer moisture meter, it was 2.7 parts by weight.

 30 g of the obtained dispersed phase particles (6) were transferred to Shin-Etsu Silicon Oil
KF96-100CS (Shin-Etsu Chemical Co., Ltd.
Con oil) mixed and dispersed in 70 g of
Fluid composition (hereinafter referred to as fluid composition (6))
U. I got｝.

Example 7 Three-liter four-neck equipped with stirrer, reflux condenser and thermometer
Charge 1.2 l of water into a separable flask and add Kuraray Povar
PVA-205 (Kuraray Co., Ltd. polyvinyl alcohol)
After adding and dissolving 16.0 g, 130 g of styrene and
Xystyrene 60g, chlorostyrene 30g, used in Example 1
80 g of industrial divinylbenzene and azobisui
A mixture consisting of 5 g of sobutyronitrile was added. afterwards,
Contents in the flask using a disperser (rotational speed: 10000 rpm)
The product was dispersed and polymerized at 80 ° C. for 14 hours. The solid obtained
After washing thoroughly with water, use a hot air drier at 80 ° C.
And dried for 12 hours.
It is called a crosslinked product (5). ｝ 287 g was obtained.

50 g of the polymer crosslinked product (5) and 250 g of nitrobenzene were charged into a 2-liter four-neck separable flask equipped with a stirrer, a thermometer and a dropping funnel, and stirred with an ice bath.
Cooled to ° C. Next, 500 g of chlorosulfuric acid was added from the dropping funnel over 2 hours to obtain a uniform dispersion. Then
Remove from the ice bath, stir at room temperature (20 ° C) for 24 hours,
Further, the temperature of the reaction mixture was raised to 100 ° C., and the mixture was heated and stirred at the same temperature for 2 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., separated, and washed with water and acetone.

The obtained solid was neutralized with 45 g of pyridine, and then sufficiently washed with water. Next, it is dried at 80 ° C. for 10 hours using a vacuum drier, and is referred to as dispersed phase particles (7), hereinafter as 128 g of dispersed spherical particles of a spherical sulfonated polymer. I got｝.

When the average particle diameter of the obtained dispersed phase particles (7) was measured using a particle size distribution analyzer, it was 6 μm. When the ion exchange capacity of the dispersed phase particles (7) was determined by a neutralization titration method and an elemental analysis method, it was 3.9 mg equivalent / g by the neutralization titration method and 4.0 mg equivalent / g by the elemental analysis method. The water content in the dispersed phase particles (7) was measured using a Karl Fischer moisture meter, and was 2.6 parts by weight.

 30 g of the obtained dispersed phase particles (7) 900 (new
70 g of partially hydrogenated triphenyl manufactured by Nippon Steel Chemical Co., Ltd.
Mixed and dispersed in the electrorheological fluid composition of the present invention.
Below, this is called fluid composition (7). I got｝.

Comparative Example 1 50 g of the polymerized crosslinked product (1) obtained in Example 1 and 200 g of tetrachloroethane were charged into a 2 liter four-neck separable flask equipped with a stirrer, a thermometer, and a dropping funnel. And cooled to 0 ° C. Next, 350 g of 98% by weight concentrated sulfuric acid was added from the dropping funnel over 2 hours,
A uniform dispersion was obtained. Then, after removing from the ice bath and stirring at room temperature (20 ° C.) for 24 hours, the temperature of the reaction mixture is further increased.
The temperature was raised to 80 ° C., and the mixture was heated and stirred at the same temperature for 2 hours to carry out a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., separated, and washed with water and acetone.

The obtained solid is treated with a 10% by weight aqueous solution of sodium hydroxide 80
After neutralization with ml, the mixture was sufficiently washed with water. Next, the dispersion was dried at 80 ° C. for 10 hours using a vacuum dryer, and 63 g of spherical dispersed sulfonated polymer particles for comparison, hereinafter referred to as comparative dispersed phase particles (1). I got｝.

When the average particle diameter of the obtained comparative dispersed phase particles (1) was measured using a particle size distribution analyzer, it was 50 μm.
The ion exchange capacity of the comparative dispersed phase particles (1) was determined by neutralization titration and elemental analysis.
It was 2.7 mg equivalent / g and 2.7 mg equivalent / g by elemental analysis. The water content in the comparative dispersed phase particles (1) was measured using a Karl Fischer moisture meter, and was 2.7 parts by weight.

 30 g of the obtained comparative dispersed phase particles (1) was
oil KF96-20CS (dimethyl manufactured by Shin-Etsu Chemical Co., Ltd.)
Mix and disperse in 70 g of silicone oil)
Viscous fluid composition (hereinafter referred to as comparative fluid composition (1))
That. I got｝.

Comparative Example 2 50 g of the polymer crosslinked product (1) obtained in Example 1 and 200 g of tetrachloroethane were charged into a 2-liter four-neck separable flask equipped with a stirrer, a thermometer, and a dropping funnel, and the ice bath was stirred. And cooled to 0 ° C. Next, 350 g of 98% by weight concentrated sulfuric acid was added from the dropping funnel over 2 hours,
A uniform dispersion was obtained. Then, after removing from the ice bath and stirring at room temperature (20 ° C.) for 24 hours, the temperature of the reaction mixture is further increased.
The temperature was raised to 80 ° C., and the mixture was heated and stirred at the same temperature for 24 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., separated, and washed with water and acetone.

The obtained solid substance was added to a 10% by weight aqueous sodium hydroxide solution 17
After neutralization with 0 ml, the mixture was thoroughly washed with water. Next, the dispersion was dried at 80 ° C. for 10 hours using a vacuum drier, and 87 g of spherical dispersed sulfonated polymer particles for comparison, hereinafter referred to as comparative dispersed phase particles (2). I got｝.

When the average particle size of the obtained comparative dispersed phase particles (2) was measured using a particle size distribution analyzer, it was 50 μm.
The ion exchange capacity of the comparative dispersed phase particles (2) was determined by neutralization titration and elemental analysis.
4.6 mg equivalent / g, and 4.5 mg equivalent / g by elemental analysis. The water content in the comparative dispersed phase particles (2) was measured using a Karl Fischer moisture meter, and was 2.8 parts by weight.

 30g of the obtained comparative dispersed phase particles (2) was
oil KF96-20CS (dimethyl manufactured by Shin-Etsu Chemical Co., Ltd.)
Mix and disperse in 70 g of silicone oil)
Viscous fluid composition (hereinafter referred to as comparative fluid composition (2))
That. I got｝.

Comparative Example 3 50 g of the crosslinked polymer (1) and 350 g of tetrachloroethane were charged into a 2-liter four-neck separable flask equipped with a stirrer, a thermometer, and a dropping funnel, and cooled to 0 ° C. using an ice bath while stirring. . Then, 240 g of chlorosulfuric acid was added from the dropping funnel over 2 hours to obtain a uniform dispersion. Next, the reaction mixture was removed from the ice bath and stirred at room temperature (20 ° C.) for 24 hours. Then, the temperature of the reaction mixture was further raised to 80 ° C., and the mixture was heated and stirred at the same temperature for 2 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., separated, and washed with water and acetone.

The obtained solid substance was added to a 10% by weight aqueous sodium hydroxide solution 17
After neutralization with 0 ml, the mixture was thoroughly washed with water. Next, the dispersion was dried at 80 ° C. for 10 hours using a vacuum drier. Comparative dispersed phase particles composed of 88 g of a spherical sulfonated polymer were hereinafter referred to as comparative dispersed phase particles (3). I got｝.

When the average particle diameter of the obtained comparative dispersed phase particles (3) was measured using a particle size distribution analyzer, it was 50 μm.
The ion exchange capacity of the comparative dispersed phase particles (3) was determined by neutralization titration and elemental analysis.
It was 4.6 mg equivalent / g and 4.6 mg equivalent / g by elemental analysis. The water content in the comparative dispersed phase particles (3) was measured using a Karl Fischer moisture meter, and was 2.6 parts by weight.

 30 g of the obtained comparative dispersed phase particles (3) was
oil KF96-20CS (dimethyl manufactured by Shin-Etsu Chemical Co., Ltd.)
Mix and disperse in 70 g of silicone oil)
Viscous fluid composition (hereinafter referred to as Comparative fluid composition (3))
That. I got｝.

Example 8 Fluid compositions (1) to (7) and comparative fluid compositions (1) obtained in Examples 1 to 7 and Comparative Examples 1 to 3
Each of (3) was placed in a double cylindrical rotary viscometer with a coaxial electric field, the gap between the inner and outer cylinders was 1.0 mm, the shear rate was 400 S ^-1 , and the temperature was 25 ° C.
The shear stress value (initial value) when an AC external electric field of 4000 V / mm (frequency: 60 Hz) was applied under the above conditions and the current density flowing at that time (initial value) were measured.

In addition, a shear stress value (value after 7 days) and a current density (value after 7 days) after continuously operating the viscometer at 25 ° C. for 7 days while applying an external electric field of 4000 V / mm were measured. The stability over time of the fluid composition was investigated.

The results are shown in Table 1. Note that the dispersed phase particles (1) to (7) and the comparative dispersed phase particles (1) to (7) contained in the fluid compositions (1) to (7) and the comparative fluid compositions (1) to (3), respectively. The average particle diameter of (3) is the first
It is also shown in the table.

An electrorheological fluid is preferably a material having excellent shear stress characteristics such that a shear stress value obtained when a relatively weak electric field is applied is excellent, and a material having excellent current characteristics such that the electric field density flowing at that time is small is preferable. Those having both excellent stress characteristics and current characteristics are particularly preferable. Therefore,
As a parameter for judging the superiority of an electrorheological fluid composition by simultaneously evaluating the shear stress characteristics and the current characteristics, a ratio of a shear stress value obtained when a constant electric field is applied to a current density flowing at that time, that is, (shear stress (Value) / (current density) ｛Hereinafter, this value is referred to as a Z value. ｝ Is effective. That is, an electrorheological fluid composition having both excellent shear stress characteristics and current characteristics has a large Z value.

Each of the fluid compositions (1) to (7) and the comparative fluid compositions (1) to (3) obtained from a shear stress value and a current density observed when an electric field of 4000 V / mm was applied to each of them. Table 1 shows the initial value and the value after 7 days of the Z value of the fluid composition.

As is clear from Table 1, the fluid compositions (1) to (7) obtained by the present invention are excellent in shear stress characteristics that generate a large shear stress even when a relatively weak electric field is applied, At that time, the current density was small, and the current characteristics were excellent, and the generated shear stress and the current density were very excellent in stability over time. Further, the fluid compositions (1) to (7) obtained in the present invention may have an initial Z value of 1.5 or more, and may be an electrorheological fluid composition having a good balance between shear stress characteristics and current characteristics. all right. Further, the fluid compositions (1) to (7) obtained by the present invention have an electrorheological fluid having a Z value of 1.5 or more even after 7 days, and also having excellent stability over time of the balance between shear stress characteristics and current characteristics. It was found to be a composition.

On the other hand, in the comparative fluid composition (1), a large shear stress was not obtained by applying a relatively weak electric field, the current density flowing at that time was larger than that of the fluid composition of the present invention, and the generated shear stress and current Poor density stability over time 3
It became unmeasurable after days. The Z value of the comparative fluid composition (1) was 0.6 even in the initial stage, and the balance between the shear stress characteristics and the current characteristics was worse than that of the fluid composition of the present invention.

Further, the comparative fluid composition (2) and the comparative fluid composition (3)
Was obtained by the sulfonation of the same polymerized crosslinked product (1) and compared with the fluid composition (1) or the fluid composition (2) of the present invention, which is composed of dispersed phase particles having the same average particle size. The shear stress was small, the current density was large, and the stability of the generated shear stress and current density with time was poor, and both became unmeasurable after 6 days. The Z values of the comparative fluid composition (2) and the comparative fluid composition (3) were both 0.7 even at the initial stage, and the balance between the shear stress characteristics and the current characteristics was worse than the fluid composition of the present invention. .

────────────────────────────────────────────────── ─── front page of the continuation (72) inventor Minoru Kobayashi, Tsukuba City, Ibaraki Prefecture Kan'nondai 1-chome 25 address 12 Nippon Shokubai Kagaku Kogyo Co., Ltd. Tsukuba research Laboratories in the examiner Eriko Suzuki (58) investigated the field (Int.Cl. ⁶ , DB name) C10M 151/02 C10M 157/06 C10N 20:06 C10N 40:14 C10N 70:00 WPI / L (QUESTEL) CA (STN)

Claims (7)

(57) [Claims] 1. A composition obtained by dispersing dispersed phase particles comprising a sulfonated polymer having an aromatic ring substituted with a sulfonic acid group in an insulating dispersion medium, wherein the sulfonated polymer is vinyl. A polymerized crosslinked product (I) of a monomer mixture (A) containing an aromatic compound (a) and a polyvinyl compound (b) as main components and optionally other vinyl compounds (c) added to the polymerized crosslinked product (I) 100 An electrorheological fluid composition obtained by sulfonating with at least 500 parts by weight of chlorosulfuric acid based on parts by weight. 2. The electrorheological fluid composition according to claim 1, wherein the sulfonation is carried out by holding the polymerized crosslinked product (I) in the presence of chlorosulfuric acid at a temperature of 70 ° C. or more for 30 minutes or more. 3. The sulfonation is carried out in the presence of chlorosulfuric acid in the presence of chlorosulfuric acid at a temperature in the range of -20.degree.
2. The electrorheological fluid composition according to claim 1, wherein the composition is kept at a temperature of 70 ° C. or more for 30 minutes or more after holding for 0 hours. 4. The composition of the monomer mixture (A) is from 50.0 to 50.0%.
2. The composition according to claim 1, comprising 99.9 mol% of the vinyl aromatic compound (a) and 0.1 to 50.0 mol% of the polyvinyl compound (b).
4. The electrorheological fluid composition according to any one of items 1 to 3. 5. The method according to claim 1, wherein the dispersed phase particles contain 10 parts by weight or less of water based on 100 parts by weight of the sulfonated polymer.
An electrorheological fluid composition according to any one of the above. 6. The electrorheological fluid composition according to claim 1, wherein the average particle size of the dispersed phase particles is in the range of 0.1 to 100 μm. 7. The ratio between the dispersed phase particles and the insulating dispersion medium is preferably the former.
The electrorheological fluid composition according to any one of claims 1 to 6, wherein the latter is in the range of 50 to 500 parts by weight per 100 parts by weight.