JP2598828B2 - Electrorheological fluid composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an electrorheological fluid composition. More specifically, a large shear stress is generated even when a relatively weak electric field is applied, and the current density flowing at that time is excellent in current characteristics that the current density is small, and the generated shear stress and the current density are excellent in stability over time. It relates to an electrorheological fluid composition.

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

Conventionally, as an electrorheological fluid composition, in an insulating oil such as silicone oil, diphenyl chloride, trans oil, etc., solid particles such as cellulose, starch, soybean casein, silica gel, polystyrene-based ion exchange resin, 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 type ion exchange resin of polystyrene sulfonic acid, which is one of polystyrene ion exchange resins, as a disperse phase can obtain 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.

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

Therefore, an object of the present invention is to generate a large shear stress by applying a relatively weak electric field, and to provide an excellent current characteristic that a current density flowing at that time is small, and to stabilize the generated shear stress and the current density with time. It is to provide an electroviscous fluid composition excellent in the above.

(Means and Action for Solving the Problems) The present invention relates to 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. The present invention relates to an electrorheological fluid composition characterized in that the number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles exceeds the number of aromatic rings present in the sulfonated polymer.

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, When the average particle diameter 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 sulfonic acid group which releases a cation in the presence of a polar solvent such as water and becomes itself a sulfonic acid ion, and is particularly a cation released in the presence of a polar solvent such as water. No restrictions. The number of sulfonic acid groups referred to in the present invention is the total number of sulfonic acid groups contained in a sulfone compound constituting the dispersed phase particles.

The number of sulfonic acid groups present in the sulfonated polymer constituting the dispersed phase particles used in the present invention needs to be larger than the number of aromatic rings present in the sulfonated polymer,
In particular, the number of sulfonic acid groups is preferably in the range of 105 to 200 with respect to 100 aromatic rings in the sulfonated polymer. When the number of sulfonic acid groups in the sulfonated polymer is larger than the number of aromatic rings, compared with the case where the number of sulfonic acid groups is equal to or less than the number of aromatic rings, when an electric field is applied to the prepared electrorheological fluid composition, The obtained shear stress greatly increases, the current density flowing at that time is small, the current characteristics are excellent, and the stability of the generated shear stress and current density over time is significantly improved.

As a method for obtaining a sulfonated polymer constituting the dispersed phase particles which can be used in the present invention, for example, the vinyl aromatic compound (a) and the polyvinyl compound (b) are used as essential components and other vinyl A method of sulfonating an aromatic ring present in the polymerized crosslinked product (I) of the monomer mixture (A) to which the compound (c) is added can be given.

Examples of the vinyl aromatic compound (a) that can be used in the present invention include methoxystyrene, dimethoxystyrene, trimethoxystyrene, ethoxystyrene,
Diethoxystyrene, triethoxystyrene, propyloxystyrene, dipropyloxystyrene, tripropyloxystyrene, methoxymethylstyrene, methoxyethylstyrene, methoxypropylstyrene, ethoxymethylstyrene, ethoxyethylstyrene, propyloxymethylstyrene, propyloxyethylene Styrene, methoxydimethylstyrene, methoxydiethylstyrene, vinylmethoxynaphthalene, vinyldimethoxynaphthalene, vinylethoxynaphthalene, vinyldiethoxynaphthalene, vinylmethoxymethylnaphthalene, vinylmethoxydimethylnaphthalene, vinyldimethoxymethylnaphthalene, vinylmethoxyethylnaphthalene, vinylimimethoxy Such as diethylnaphthalene and vinyldimethoxyethylnaphthalene Vinyl aromatic compounds having at least one alkoxy group in the aromatic ring; methyl styrene,
Ethyl styrene, propyl styrene, butyl styrene,
Pentylstyrene, hexylstyrene, dimethylstyrene, diethylstyrene, dipropylstyrene, methylethylstyrene, methylpropylstyrene, methylhexylstyrene, ethylbutylstyrene, ethylpropylstyrene, ethylhexylstyrene, propylbutylstyrene, trimethylstyrene, triethylstyrene, triethylstyrene Propylstyrene, methyldiethylstyrene, dimethylethylstyrene, methylethylpropylstyrene, methyldipropylstyrene, dimethylpropylstyrene, ethyldipropylstyrene, diethylpropylstyrene,
Vinyl methyl naphthalene, vinyl ethyl naphthalene, vinyl propyl naphthalene, vinyl dimethyl naphthalene,
At least one aromatic ring such as vinyl diethyl naphthalene, vinyl dipropyl naphthalene, vinyl methyl ethyl naphthalene, vinyl trimethyl naphthalene, vinyl triethyl naphthalene, vinyl tripropyl naphthalene, vinyl methyl diethyl naphthalene, vinyl dimethyl ethyl naphthalene, vinyl methyl ethyl propyl naphthalene;
Aromatic compound having at least one aryloxy group on an aromatic ring such as phenoxystyrene, phenoxymethylstyrene, phenoxyethylstyrene, phenoxydimethylstyrene, phenoxydiethylstyrene; amino Vinyl aromatic compounds having at least one amino group on an aromatic ring such as styrene, N-methylaminostyrene, N, N-dimethylaminostyrene, aminomethylstyrene, aminoethylstyrene, N, N-dimethylaminomethylstyrene Vinyl aromatic hydrocarbons such as styrene, vinyl naphthalene, vinyl anthracene, vinyl phenanthrene; chlorostyrene, bromostyrene, fluorostyrene, chloromethylstyrene, chloroethylstyrene, chloropropylstyrene Vinyl aromatic compounds having at least one halogen group on an aromatic ring such as chlorodimethylstyrene, bromomethylstyrene, bromoethylstyrene, fluoromethylstyrene, fluoroethylstyrene, vinylchloronaphthalene, and vinylbromonaphthalene. And one or more of these can be used.

In order to make the number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles used in the present invention larger than the number of aromatic rings in the sulfonated polymer, it is necessary that at least the sulfonic acid group is present in the above-mentioned polymerized crosslinked product (I). It is necessary to introduce two or more sulfonic acid groups for at least one of the aromatic rings to be formed. However, since such a large amount of sulfonic acid groups are introduced into the aromatic ring, the vinyl aromatic compound (a) Preferably contains a vinyl aromatic compound having at least one electron donating group in the aromatic ring.

Examples of the electron donating group include an alkoxy group, an alkyl group,
Although a phenoxy group or an amino group can be mentioned, among these, an alkoxy group is particularly preferred.

The vinyl aromatic compound having at least one electron-donating group in the aromatic ring is a vinyl aromatic compound (a) in a proportion of at least 5.0 mol% in the monomer mixture (A).
It is preferable to use it by containing it. Particularly preferably, a vinyl aromatic compound having at least one alkoxy group in the aromatic ring is used so that the ratio in the monomer mixture (A) is 5.0 mol% or more. By using the vinyl aromatic compound having at least one alkoxy group in the aromatic ring at a specific ratio, even under mild sulfonation conditions of, for example, 80 ° C. or less, the sulfonated polymer in the obtained sulfonated polymer can be obtained. It is possible to sulfonate to an amount in which the number of acid groups exceeds the aromatic ring present in the sulfonated polymer. On the other hand, a crosslinked polymer using styrene as the vinyl aromatic compound (a) ′ is
It is difficult to introduce sulfonic acid groups in an amount exceeding the number of aromatic rings in the polymerized crosslinked product, not only under mild sulfonation conditions of 80 ° C. or less but also under severe conditions of high temperature and long time.

In the present invention, the polyvinyl compound (b) is preferably used in the monomer mixture (A) in the range of 0.5 to 50.0 mol%. When the proportion of the polyvinyl compound (b) exceeds 50 mol%, sulfonation hardly proceeds, and a large shear stress cannot be obtained when an electric field is applied to an electrorheological fluid composition using the obtained particles. May occur, and the ratio of the polyvinyl compound (b) is
When the amount is less than 0.5 mol%, a problem may occur that particles adhere to each other when a polymerized crosslinked product obtained by polymerization is sulfonated.

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, diethyl glycol di (meth) acrylate, trivinyl Examples thereof include polyvinyl aliphatic compounds such as methylosepropane tri (meth) acrylate, N, N'-methylenebisacrylamide, diallyl maleate, and diacetyl adipate. One or more of these may be used. Can be.

When a sulfonated polymer is obtained in the present invention, the monomer mixture (A), which is a raw material of the polymerized crosslinked product (I) suitably used as an intermediate thereof, is a vinyl aromatic compound (a)
And the polyvinyl compound (b) as an essential component. The total amount of the compound (a) and the compound (b) is at least 50.0 mol% in the monomer mixture (A) as a main component of the monomer mixture (A). It is preferred to use them in such a ratio.

Further, the blending ratio of the vinyl aromatic compound (a) and the polyvinyl compound (b) in the monomer mixture (A) is preferably in the range of 50 to 99 mol% of the former and 50 to 1 mol% of the latter.

The monomer mixture (A) in the present invention may optionally contain a vinyl compound (c) other than the vinyl aromatic compound (a) or the polyvinyl compound (b). 50.0 mol%)
Preferably it is: Such other vinyl compounds (c) include, for example, ethylene, propylene,
Olefinic hydrocarbons such as isoprene, butadiene, vinyl chloride, and chloroprene or halogen-substituted products thereof; unsaturated carboxylic acid ester compounds such as methyl (meth) acrylate and ethyl (meth) acrylate; vinyl acetate, vinyl propionate and the like Vinyl ester compounds of monovalent carboxylic acids; unsaturated amide compounds such as (meth) acrylamide, diacetacrylamide, methylolated (meth) acrylamide and derivatives thereof;
Unsaturated cyanide compounds such as (meth) acrylonitrile and crotonnitrile; unsaturated alcohol compounds such as (meth) allyl alcohol and croton alcohol; unsaturated monobasic acids such as (meth) acrylic acid; maleic acid, fumaricin, itaconic acid Unsaturated dibasic acids; monoester compounds of a monohydric alcohol such as maleic acid monomethyl ester and maleic acid monoallyl ester with an unsaturated dibasic acid; and one or more of these. Can be used.

The shape of the dispersed phase particles used in the present invention is preferably a shape or an elliptical sphere. In the case where the shape of the dispersed phase particles is other than spherical or elliptical spherical, the problem that large shear stress cannot be obtained when an electric field is applied to the adjusted electrorheological fluid composition and the application of the electric field were continued. There is a problem that the stability with time in the state becomes poor. As a method for producing the polymer crosslinked product (I) suitably used as an intermediate in obtaining a sulfonated polymer in the present invention, There is no particular limitation, and known polymerization methods such as suspension polymerization, emulsion polymerization, dispersion polymerization, solution polymerization, and bulk polymerization can be used. A suspension polymerization method or an emulsion polymerization method is preferred because I) can be easily obtained.

When a suspension polymerization method is used as the polymerization method in producing the polymer crosslinked product (I) 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 the 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. Azobisisobutyronitrile, azobisisobutylamide, 2,2'-azobis (2,4-dimethylmaleronitrile), azobis (α-dimethylvaleronitrile), azobis (α-methylbutyronitrile), etc. Azo compounds and the like can be mentioned, and one or more of these can 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) in the present invention, the polymerization conditions are not particularly limited.

Water or the like is usually used as the emulsion polymerization solution.

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

As the polymerization initiator for the emulsion polymerization, generally, a known initiator 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, for example, known methods such as a seed 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. Further, the remaining monomer mixture is continuously or intermittently added, and the emulsification is carried out at a predetermined temperature.

The polymer crosslinked product (I) in the present invention may be a substantially nonporous polymer crosslinked product called a gel type, or a known porous material that imparts porosity to the polymer crosslinked product obtained at the time of polymerization. Porosity forming agent, for example, a swelling organic solvent, a non-swelling organic solvent, a linear polymer soluble in a monomer, or a porous polymer crosslinked product obtained by polymerizing a monomer mixture in the presence of a mixture thereof. There may be.

When the sulfonated polymer constituting the dispersed phase particles used in the present invention is obtained by a method of passing the polymer crosslinked product (I) of the monomer mixture (A) as an intermediate, the sulfonated polymer particles are polymerized crosslinked product It is obtained by sulfonating (I) and pulverizing or granulating 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 in the absence of a 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, cyclohexane, and ligroin.

The solvent which is swellable with respect to the polymerized crosslinked product (I) may be any solvent which swells the polymerized crosslinked product (I) and is inert to the sulfonating agent. For example, dichloroethane, trichloroethylene, tetrachloroethane, Halogenated hydrocarbons such as propylene 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).

The sulfonating agent may be selected from conventionally known sulfonating agents, and examples thereof include chlorosulfuric acid, sulfuric acid, fuming sulfuric acid, and sulfur trioxide, and one or more of these can be used. it can. Among them, 80
Use of chlorosulfuric acid or fuming sulfuric acid because sulfonation can easily proceed until the number of sulfonic acid groups in the resulting sulfonated polymer reaches an amount exceeding the number of aromatic rings even at a mild reaction temperature of not more than ℃. Is preferred.

The sulfonation reaction is carried out at a temperature in the range of -20 to 250 ° C.
It takes about 0.3 to 100 hours. However, in the present invention, a monomer mixture (A) having a ratio of 5.0 mol% or more in the monomer mixture (A) of a vinyl aromatic compound having at least one electron-donating group in an aromatic ring is used. It is particularly preferable to use a vinyl aromatic compound having at least one alkoxy group on an aromatic ring in a proportion of at least 5.0 mol% in the monomer mixture (A), thereby limiting the material of the reactor. The polymerized crosslinked product (I) can be sulfonated at a temperature of 80 ° C. or lower, which is advantageous from industrial practicality, and the sulfonated polymer constituting the dispersed phase particles used in the present invention can be easily obtained.

5.0 mol% of a vinyl aromatic compound having at least one alkoxy group in an aromatic ring in the monomer mixture (A)
The sulfonation conditions for sulfonating the polymer crosslinked product (I) obtained by using the above proportions include, for example,
Method of sulfonating in a temperature range of 50 to 80 ° C for 0.3 to 48 hours, sulfonation in a temperature range of -20 to 50 ° C for 0.3 to 10 hours, and further sulfonation in a temperature range of 50 to 80 ° C for 0.3 to 48 hours However, a method considering the ease of controlling the sulfonation reaction is more 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 to remove acids 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 and organic quaternary Examples thereof include 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 when an electric field is applied, It is not preferable because a large current flows.

 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; chloro
Benzene, dichlorobenzene, trichlorobenzene,
Lomobenzene, dibromobenzene, chloronaphthalene,
Dichloronaphthalene, bromonaphthalene, chlorobiphe
Nil, dichlorobiphenyl, trichlorobiphenyl, butyl
Lomobiphenyl, chlorodiphenylmethane, dichlorolo
Diphenylmethane, trichlorodiphenylmethane, bro
Modiphenylmethane, chlorodecane, dichlorodecane,
Trichlorodecane, bromodecane, chlorododecane, di
Halogenated carbonization of chlorododecane, bromododecane, etc.
Hydrogen; chlorodiphenyl ether, dichlorodiphenyl
Ether, trichlorodiphenyl ether, bromodiph
Halogenated diphenyl etherification such as phenyl ether
Compound; Daifoil (Manufactured by Daikin Industries, Ltd.), Dem
Nam (For example, Daikin Industries, Ltd.); lid
Dioctyl luate, Trioctyl trimellitate, SEBASHI
Ester compounds such as dibutyl acid
One or more of these can be used
Wear.

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, in order to improve the dispersibility of the dispersed phase particles in the dispersion medium or to adjust the viscosity or the shear stress of the electrorheological fluid composition, for example, a surfactant, a polymer dispersant, a polymer thickener, etc. Various additives 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. Because of its excellent stability over time in 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.

Reference Example 1 Three of four equipped with a stirrer, reflux condenser and thermometer
Charge water 1.2 into a mouth-separable flask and add polyvinyl
Alcohol (Kuraray Co., Ltd., Kuraray Povar) PVA-2
05) After adding and dissolving 16.0 g, add methoxy
300g of len, industrial divinylbenzene (Wako Pure Chemical Industries
55% by weight of divinylbenzene, ethyl styrene
30 g of a mixture such as 35% by weight) and azobisisobutyroni
A mixture consisting of 4 g of toril was added. Then, stir at 650 rpm
Disperse the contents in the flask at a stirring speed, at 70 ° C for 13 hours
Polymerized. The solid obtained was filtered off and washed thoroughly with water.
After that, it was dried at 80 ° C for 12 hours using a hot air drier,
Combined crosslinked product (hereinafter referred to as "polymerized crosslinked product (1)"). ｝
305 g were obtained.

REFERENCE EXAMPLE 2 Four of three equipped with a stirrer, reflux condenser and thermometer
Charge water 1.2 into a mouth-separable flask and add polyvinyl
Alcohol (Kuraray Co., Ltd., Kuraray Povar) PVA-2
05) After adding and dissolving 10.0 g, further add
Re 200g, Styrene 50g, same industry as used in Reference Example 1
Benzene 30g and azobisisobutyronite
A mixture consisting of 4 g of ril was added. Then, stirring at 500rpm
Disperse the contents of the flask at a speed
I combined. After filtering the obtained solid matter and washing sufficiently with water,
Dry at 80 ° C for 12 hours using a hot air dryer to obtain a spherical polymer.
Crosslinked product (hereinafter referred to as "polymerized crosslinked product (2)"). ｝ 255g
I got

Reference Example 3 Four with a stirrer, reflux condenser and thermometer
Charge water 1.2 into a mouth-separable flask and add polyvinyl
Alcohol (Kuraray Co., Ltd., Kuraray Povar) PVA-2
05) After adding and dissolving 16.0, add methoxystyrene
30 g, styrene 130 g, methylstyrene 80 g, in Reference Example 1
The same industrial divinylbenzene as used 60 g, isooctane
300 g of tan and 12 g of azobisisobutyronitrile
Was added. After that, dispersing machine (rotation speed: 5000rpm)
Disperse the contents of the flask using a, 11 hours at 70 ℃
Polymerized. The resulting solid is filtered off and thoroughly mixed with acetone.
After washing with water, dry at 80 ° C for 12 hours using a hot air dryer
And a spherical polymer crosslinked product (hereinafter referred to as a polymer crosslinked product)
It is called (3). I got $ 280.

Reference Example 4 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 dispersed using a disperser. Emulsified. Furthermore, water 50 ml, sodium persulfate 0.2 g, methoxystyrene 30 g, styrene 15 g
After adding 15 g of the same industrial divinylbenzene as used in Reference Example 1, the mixture was heated at 50 ° C. for 8 hours with stirring to carry out polymerization to obtain 160 ml of an emulsion of seed particles.

Then, water 1.2 was charged into a three-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel,
After 160 ml of the seed particle emulsion prepared above and 2.8 g of sodium lauryl sulfonate were added, they were uniformly dispersed with stirring. Thereafter, the mixture was heated to 70 ° C. while keeping the number of rotations of the stirrer at 250, and 2 g of sodium persulfate dissolved in 10 ml of water was added. Next, a mixture consisting of 120 g of methoxystyrene, 60 g of styrene and 60 g of the same industrial divinylbenzene used in Reference Example 1 was added dropwise over 18 hours. Further, after reacting at 70 ° C. for 5 hours, the temperature was raised to 90 ° C.
After hours, the reaction was terminated.

The solid content of the obtained latex was separated by filtration and dried at 80 ° C. for 12 hours using a hot air drier to obtain a spherical polymer crosslinked product (hereinafter referred to as polymer crosslinked product (4)). ｝ 265 g was obtained.

Reference Example 5 Four equipped with a stirrer, reflux condenser and thermometer
Charge water 1.2 into a mouth-separable flask and add polyvinyl
Alcohol (Kuraray Co., Ltd., Kuraray Povar) PVA-2
05) After adding and dissolving 16.0 g, add methoxy
90 g of ren, 90 g of styrene, same industrial one used in Reference Example 1
120 g of divinylbenzene and azobisisobutyronitrile
A mixture consisting of 4 g of toluene was added. Then, stirring speed of 400rpm
Disperse the contents in the flask at a temperature and polymerize at 70 ° C for 12 hours
did. The solid obtained is filtered off, washed thoroughly with water and then heated.
Dry at 80 ° C for 12 hours using an air dryer, and use a spherical polymer
Bridge product. Hereinafter, this is referred to as a polymer crosslinked product (5). ｝ 282g
Obtained.

Reference Example 6 Four of 3 equipped with a stirrer, reflux condenser and thermometer
Charge water 1.2 into a mouth-separable flask and add polyvinyl
Alcohol (Kuraray Co., Ltd., Kuraray Povar) PVA-2
05) After adding and dissolving 16.0 g, add dimethoxys
Tylene 50g, Styrene 150g, Methylstyrene 60g, Reference example
40 g of the same industrial divinyl benzene as used in 1 and
Add a mixture consisting of 4 g of azohisisobutyronitrile
Was. Then, the contents in the flask were stirred at a stirring speed of 670 rpm.
It was dispersed and polymerized at 70 ° C. for 14 hours. The solid obtained is filtered.
Separately, after thoroughly washing with water, use a hot air drier at 80 ° C for 12
After drying for a time, the spherical polymer crosslinked product
Bridge (6). ｝ 291 g was obtained.

Reference Example 7 Four of three equipped with a stirrer, reflux condenser and thermometer
Charge water 1.2 into a mouth-separable flask and add polyvinyl
Alcohol (Kuraray Co., Ltd., Kuraray Povar) PVA-2
05) After adding and dissolving 16.0g, add ethoxy
150 g of len, 70 g of styrene, 50 g of chlorostyrene, Reference Example 1
30 g of the same industrial divinylbenzene used in
A mixture consisting of 4 g of zobisisobutyronitrile was added.
Then, use a dispersing machine (rotation speed: 10,000 rpm)
The contents therein were dispersed and polymerized at 70 ° C. for 13 hours. Obtained
The solids are filtered off, washed thoroughly with water and then dried with a hot air drier.
And dried at 80 ° C. for 12 hours.
This is called a polymer crosslinked product (7). ｝ 287 g was obtained.

Reference Example 8 3-4 equipped with a stirrer, a reflux cooling device and a thermometer
Water 1.2 into a one-neck separable flask,
Alcohol (Kuraray Co., Ltd., Kuraray Povar) PVA
-205) After adding and dissolving 16.0 g, further add
170 g of styrene and 100 g of styrene used in Reference Example 1
Same industrial divinyl benzene 30g, polystyrene (Japanese
30 g of Kojun Pharmaceutical Co., Ltd., degree of polymerization: 1600-1800)
A mixture consisting of 4 g of zobisisobutyronitrile was added.
After that, use a dispersing machine (rotation speed: 8,000 rpm)
The contents therein were dispersed and polymerized at 70 ° C. for 13 hours. Obtained
The solids obtained were filtered off and washed thoroughly with acetone and water.
Dry at 80 ° C for 12 hours using a hot air dryer to obtain a spherical polymer.
Crosslinked product (hereinafter referred to as "polymerized crosslinked product (8)"). ｝ 289g
I got

Comparative Reference Example 1 Three of four equipped with a stirrer, reflux condenser and thermometer
Charge water 1.2 into a mouth-separable flask and add polyvinyl
Alcohol (Kuraray Co., Ltd., Kuraray Povar) PVA-2
05) After adding and dissolving 16.0 g, styrene 300
g, the same industrial divinylbenzene 3 used in Reference Example 1
Mix consisting of 0 g and 4 g of azobisisobutyronitrile
Things were added. Then, at a stirring speed of 670 rpm,
The contents were dispersed and polymerized at 80 ° C. for 7 hours. Obtained solid
After filtering off the shape and washing thoroughly with water, use a hot air drier
After drying at 80 ° C for 12 hours, a spherical comparative polymer crosslinked product
Hereinafter, this is referred to as comparative polymer crosslinked product (1). ｝ 305g
Was.

Example 1 50 g of the polymerized crosslinked product (1) obtained in Reference Example 1 and 250 g of tetrachloroethane were charged into a two-necked separable flask equipped with a stirrer, a thermometer and a dropping funnel, and an ice bath was stirred. And cooled to 0 ° C. Next, 250 g of chlorosulfuric acid was added from the dropping funnel over 2 hours to obtain a uniform dispersion. Then remove from the ice bath and allow to reach room temperature (20
After stirring at 5 ° C.) for 5 hours, the contents in the flask were heated to 70 ° C., and heated and stirred at the same temperature for 12 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., filtered, 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 107 g of dispersed phase particles composed of a spherical sulfonated polymer is hereinafter referred to as dispersed phase particles (1). I got｝.

The average particle diameter of the obtained dispersed phase particles (1) was measured using a particle size distribution analyzer (manufactured by Shimadzu Corporation, SALD-1000) and found to be 45 μm.

When the number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles (1) was determined by a neutralization titration method and an elemental analysis method, the number of aromatic rings in the sulfonated polymer was 100 in the neutralization titration method. In 172 elemental analysis, the water content in the dispersed phase particles (1), which was 169 for 100 aromatic rings, was measured using a Karl Fischer moisture meter (MPS-3P, manufactured by Kyoto Electronics Industry Co., Ltd.). As a result, it was 2.8 parts by weight.

 30 g of the obtained dispersed phase particles (1) was
Le KF9620CS (dimethylsilicon 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 50 g of the crosslinked polymer (1) obtained in Reference Example 1 was charged into a two-necked separable flask equipped with a stirrer and a thermometer, and cooled to 0 ° C using an ice bath. Next, 300 g of chlorosulfuric acid was added from the dropping funnel over 2 hours with stirring to obtain a uniform dispersion. Then remove from the ice bath,
After stirring at room temperature (20 ° C.) for 5 hours, the content in the flask was heated to 70 ° C., and heated and stirred at the same temperature for 10 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., filtered, and washed with water.

The obtained solid is 390 m of 10% by weight aqueous potassium hydroxide solution.
After neutralization with l, the mixture was thoroughly washed with water. Next, it is dried at 80 ° C. for 10 hours using a vacuum dryer, and 125 g of dispersed phase particles composed of a spherical sulfonated polymer is hereinafter referred to as dispersed phase particles (2). I got｝.

When the average particle diameter of the obtained dispersed phase particles (2) was measured using a particle size distribution analyzer, it was 45 μm.

When the number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles (2) was quantified by a neutralization titration method and an elemental analysis method, the neutralization titration method was based on 100 aromatic rings in the sulfonated polymer. According to the 186 elemental analysis method, it was 182 for 100 aromatic rings.

The water content in the dispersed phase particles (2) was measured using a Karl Fischer moisture meter, and was 2.7 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 2 50 g of the polymer crosslinked product (2) obtained in Reference Example 2 and 300 g of dichloroethane were charged into a two-necked separable flask equipped with a stirrer, a thermometer and a dropping funnel, and the mixture was stirred in an ice bath. And cooled to 0 ° C. Then, chlorosulfuric acid 250 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 5 hours, the content in the flask was heated to 70 ° C., and heated and stirred at the same temperature for 14 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., filtered, and washed with water and acetone.

The obtained solid material is treated with a 10% by weight aqueous solution of lithium hydroxide 150 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 99 g of a spherical sulfonated polymer are hereinafter referred to as dispersed phase particles (3). I got｝.

When the average particle size of the obtained dispersed phase particles (3) was measured using a particle size distribution analyzer, it was 55 μm.

When the number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles (3) was quantified by neutralization titration and elemental analysis, the number of aromatic rings in the sulfonated polymer was determined to be 100 in the neutralization titration. In the 162 elemental analysis method, it was 160 for 100 aromatic rings.

The water content in the dispersed phase particles (3) was measured using a Karl Fischer moisture meter, and was 2.6 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 A two-necked separable flask equipped with a stirrer and a thermometer was charged with 200 g of 30% by weight fuming sulfuric acid and 300 g of tetrachloroethane, and cooled to 0 ° C. using an ice bath with stirring. Then, the crosslinked polymer (2) obtained in Reference Example 2
Was added over 1 hour to obtain a uniform dispersion. Then
Remove from the ice bath, stir at room temperature (20 ° C) for 4 hours,
The contents in the flask were heated to 60 ° C., and heated and stirred at the same temperature for 18 hours to carry out a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., filtered, and washed with water and acetone.

The obtained solid was treated with a 10% by weight aqueous sodium hydroxide solution 21
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 is referred to as dispersed phase particles (4) hereinafter. I got｝.

When the average particle diameter of the obtained dispersed phase particles (4) was measured using a particle size distribution analyzer, it was 55 μm.

The number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles (4) was quantified by neutralization titration and elemental analysis. In the neutralization titration, the number of aromatic rings in the sulfonated polymer was 100. According to 131 elemental analysis, it was 132 for 100 aromatic rings.

When the water content in the dispersed phase particles (4) was measured using a Karl Fischer moisture meter, it was 2.5 parts by weight.

 30 g of the obtained dispersed phase particles (4) was
Le KF96-100CS (Shin-Etsu Chemical Co., Ltd.
Recon oil) mixed and dispersed in 70 g
Viscous fluid composition (hereinafter referred to as fluid composition (4))
U. I got｝.

Example 5 50 g of the crosslinked polymer (3) obtained in Reference Example 3 and 250 g of nitrobenzene were charged into a two four-neck separable flask equipped with a stirrer, a thermometer, and a dropping funnel. And cooled to 0 ° C. Next, 300 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 5 hours, the content in the flask was heated to 70 ° C., and heated and stirred at the same temperature for 18 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., filtered, and washed with water and acetone.

The obtained solid substance is 250 m aqueous solution of 10% by weight potassium hydroxide.
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 97 g of a spherical sulfonated polymer are 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 10 μm.

When the number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles (5) was determined by a neutralization titration method and an elemental analysis method, the number of aromatic rings in the sulfonated polymer was 100 in the neutralization titration method. According to the 109 elemental analysis method, it was 106 for 100 aromatic rings.

The water content in the dispersed phase particles (5) was measured using a Karl Fischer moisture meter, and was 3.0 parts by weight.

30 g of the obtained dispersed phase particles (5) are mixed and dispersed in 70 g of 1,2,4-trichlorobenzene, and the electrorheological fluid composition of the present invention (hereinafter referred to as fluid composition (5)). I got｝.

Example 6 50 g of the polymerized crosslinked product (4) obtained in Reference Example 4 and heptane 300 were charged into a four-neck separable flask equipped with a stirrer, a thermometer and a dropping funnel, and the mixture was stirred and cooled with an ice bath. And cooled to 0 ° C. Next, 300 g of chlorosulfuric acid was added from the dropping funnel over 2 hours to obtain a uniform dispersion. Next, after removing from the ice bath and stirring at room temperature (20 ° C.) for 5 hours, the content in the flask was heated to 70 ° C., and 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., filtered, and washed with water and acetone.

The obtained solid substance was added to a 10% by weight aqueous sodium hydroxide solution 22
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 100 g of 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 number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles (6) was determined by a neutralization titration method and an elemental analysis method, the number of aromatic rings in the sulfonated polymer was 100 in the neutralization titration method. In 142 elemental analysis, it was 139 for 100 aromatic rings.

The water content in the dispersed phase particles (6) was measured using a Karl Fischer moisture meter, and was 2.9 parts by weight.

 30 g of the obtained dispersed phase particles (6) 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 (6). I got｝.

Example 7 50 g of the polymerized crosslinked product (5) obtained in Reference Example 5 and 300 g of cycloloethane were charged into a two four-neck separable flask equipped with a stirrer, a thermometer, and a dropping funnel, and an ice bath was stirred. And cooled to 0 ° C. Next, 250 g of chlorosulfuric acid was added from the picking funnel over 2 hours to obtain a uniform dispersion. Then remove from the ice bath, room temperature (20 ° C)
After stirring for 5 hours, the content in the flask was heated to 70 ° C., and heated and stirred at the same temperature for 16 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., filtered, and washed with water and acetone.

The obtained solid was neutralized with 40 g of pyridine, and then sufficiently washed with water. Then, using a vacuum dryer, at 80 ℃ 10
After drying for 123 hours, dispersed phase particles composed of 123 g of a spherical sulfonated polymer (hereinafter referred to as dispersed phase particles (7)). I got｝.

When the average particle diameter of the obtained dispersed phase particles (7) was measured using a particle size distribution analyzer, it was 75 μm.

When the number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles (7) was determined by a neutralization titration method and an elemental analysis method, the number of aromatic rings in the sulfonated polymer was 100 in the neutralization titration method. In the 122 elemental analysis method, it was 120 for 100 aromatic rings.

The water content in the dispersed phase particles (7) was measured using a Karl Fischer moisture meter, and was 3.1 parts by weight.

30 g of the obtained dispersed phase particles (7) are mixed and dispersed in 70 g of liquid paraffin, and this is referred to as an electrorheological fluid composition (hereinafter referred to as a fluid composition (7)) of the present invention. I got｝.

Example 8 250 g of 30% by weight fuming sulfuric acid and dichloroethane were placed in a two four-neck separable flask equipped with a stirrer and a thermometer.
250 g was charged and cooled to 0 ° C. using an ice bath with stirring. Next, the polymer crosslinked product (6) obtained in Reference Example 6 was treated with 1
It was added over time to obtain a uniform dispersion. Next, after removing from the ice bath and stirring at room temperature (20 ° C.) for 4 hours, the content in the flask was heated to 60 ° C., and heated and stirred at the same temperature for 15 hours to perform a sulfonation reaction. Thereafter, the reaction compound was poured into water at 0 ° C., filtered, and washed with water and acetone.

The obtained solid is treated with a 10% by weight aqueous sodium hydroxide solution 18
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 89 g of spherical sulfonated polymer are hereinafter referred to as dispersed phase particles (8). I got｝.

When the average particle diameter of the obtained dispersed phase particles (8) was measured using a particle size distribution analyzer, it was 40 μm.

When the number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles (8) was determined by a neutralization titration method and an elemental analysis method, the number of aromatic rings in the sulfonated polymer was 100 in the neutralization titration method. According to the 109 elemental analysis method, it was 106 for 100 aromatic rings.

The water content in the dispersed phase particles (8) was measured using a Karl Fischer moisture meter, and was 2.6 parts by weight.

 30 g of the obtained dispersed phase particles (8) was
Le KF96-50CS (Dimethylsilicone manufactured by Shin-Etsu Chemical Co., Ltd.)
Con oil) mixed and dispersed in 70 g of
Fluid composition (hereinafter referred to as fluid composition (8))
U. I got｝.

Example 9 50 g of the polymer crosslinked product (7) obtained in Reference Example 7 was charged into a two four-neck separable flask equipped with a stirrer and a thermometer, and cooled to 0 ° C using an ice bath. Next, 300 g of chlorosulfuric acid was added from the dropping funnel over 2 hours with stirring to obtain a uniform dispersion. Then remove from the ice bath,
After stirring at room temperature (20 ° C.) for 5 hours, the contents in the flask were heated to 70 ° C., and 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., filtered, and washed with water.

The obtained solid was treated with a 10% by weight aqueous sodium hydroxide solution 21
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 97 g of a spherical sulfonated polymer are hereinafter referred to as dispersed phase particles (9). I got｝.

When the average particle size of the obtained dispersed phase particles (9) was measured using a particle size distribution analyzer, it was 5 μm.

The number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles (9) was quantified by neutralization titration and elemental analysis. In the neutralization titration, the number of aromatic rings in the sulfonated polymer was 100. In 144 elemental analysis, the ratio was 141 for 100 aromatic rings.

The water content in the dispersed phase particles (9) was measured using a Karl Fischer moisture meter, and was 2.8 parts by weight.

 30 g of the obtained dispersed phase particles (9) 300 (new
Biphenyl and diphenyl ether manufactured by Nippon Steel Chemical Co., Ltd.
Of the present invention)
Fluid composition {hereinafter, referred to as fluid composition (9). ｝
I got

Example 10 50 g of the polymerized crosslinked product (8) obtained in Reference Example 8 and 300 g of tetrachloroethane were charged into a two-necked separable flask equipped with a stirrer, a thermometer, and a dropping funnel, and the mixture was stirred in an ice bath. And cooled to 0 ° C. Next, 250 g of chlorosulfuric acid was added from the dropping funnel over 2 hours to obtain a uniform dispersion. Then remove from the ice bath and allow to reach room temperature (20
After stirring at 5 ° C.) for 5 hours, the contents in the flask were heated to 70 ° C., and heated and stirred at the same temperature for 15 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., filtered, and washed with water and acetone.

The obtained solid substance was added to a 10% by weight aqueous sodium hydroxide solution 22
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 is referred to as a dispersed phase particle (10), which is composed of 100 g of a spherical sulfonated polymer. I got｝.

When the average particle diameter of the obtained dispersed phase particles (10) was measured using a particle size distribution analyzer, it was 8 μm.

When the number of sulfonic acid groups in the sulfonated polymer constituting the dispersed phase particles (10) was determined by neutralization titration and elemental analysis, the number of aromatic rings in the sulfonated polymer was 100 By 147 elemental analysis, the ratio was 144 for 100 aromatic rings.

The water content in the dispersed phase particles (10) was measured using a Karl Fischer moisture meter, and was 2.7 parts by weight.

 30 g of the obtained dispersed phase four particles (10) 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 (10). I got｝.

Comparative Example 1 50 g of the comparative polymer crosslinked product (1) obtained in Comparative Reference Example 1 and 250 g of tetrachloroethane were charged into a two four-neck separable flask equipped with a stirrer, a thermometer, and a dropping funnel. Cooled to 0 ° C. using a bath. Next, 250 g of chlorosulfuric acid was added from the dropping funnel over 2 hours to obtain a uniform dispersion. Then remove from the ice bath,
After stirring at room temperature (20 ° C.) for 5 hours, the content in the flask was heated to 70 ° C., and heated and stirred at the same temperature for 12 hours to perform a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., filtered, and washed with water and acetone.

The obtained solid is treated with a 10% by weight aqueous sodium hydroxide solution 18
After neutralization with 0 ml, it was thoroughly washed. Next, the dispersion was dried at 80 ° C. for 10 hours using a vacuum drier, and 89 g of comparative dispersed phase particles composed of spherical sulfonated polymer (hereinafter referred to as comparative dispersed phase particles (1)). I got｝.

The average particle size of the obtained comparative dispersed phase particles (1) was measured using a particle size distribution analyzer and found to be 45 μm.

When the number of sulfonic acid groups in the sulfonated polymer constituting the comparative dispersed phase particles (1) was determined by a neutralization titration method and an elemental analysis method, the neutralization titration method reduced the number of aromatic rings in the sulfonated polymer to 100. In contrast, the number of aromatic rings is 100 in 90 elemental analysis
Was 87.

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 Reference Example 1 and 250 g of tetrolachloroethane were charged into a two-necked separable flask equipped with a stirrer, a thermometer, and a dropping funnel.
It was cooled to 0 ° C. using an ice bath with stirring. Next, 250 g of chlorosulfuric acid was added from the dropping funnel over 2 hours to obtain a uniform dispersion. Next, the mixture was removed from the ice bath and stirred at room temperature (20 ° C.) for 17 hours to carry out a sulfonation reaction. Thereafter, the reaction mixture was poured into water at 0 ° C., filtered, and washed with water and acetone.

The obtained solid is added to a 10% by weight aqueous sodium hydroxide solution 15
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 81 g of a comparative dispersed phase particle composed of a spherical sulfonated polymer (hereinafter referred to as comparative dispersed phase particle (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 45 μm.

When the number of sulfonic acid groups in the sulfonated polymer constituting the comparative dispersed phase particles (2) was determined by a neutralization titration method and an elemental analysis method, the neutralization titration method reduced the number of aromatic rings in the sulfonated polymer to 100. In contrast, the number of aromatic rings is 100 in 96 elemental analysis.
Was 94.

The water content in the comparative dispersed phase particles (2) was measured using a Karl Fischer moisture meter, and was 3.0 parts by weight.

 30 g of the obtained comparative dispersed phase particles (2) was
Oil KF96-20CS (Shin-Etsu Chemical Co., Ltd.
(Silicone oil) mixed and dispersed in 70g for comparison
Electro-rheological fluid composition ｛Comparative fluid composition
It is called (2). I got｝.

Example 11 Fluid compositions (1) to (10) and comparative fluid compositions (1) to (2) obtained in Examples 1 to 10 and Comparative examples 1 and 2
Are placed in a double-cylindrical rotational viscometer with a coaxial electric field.
The shear stress value (initial value) and the current density flowing when an external external electric field of 4000 V / mm (frequency: 60 Hz) is applied under the conditions of an outer cylinder gap of 1.0 mm, a shear rate of 400 s ^-1 and a temperature of 25 ° C. It was 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 (10) and the comparative dispersed phase particles (1) to (10) contained in the fluid compositions (1) to (10) and the comparative fluid compositions (1) and (2), respectively. The average particle diameter of (2) is the first
The table is also shown.

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 a current 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 valid. 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 (10) and the comparative fluid compositions (1) to (2) obtained from the shear stress value and the 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 (10) 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. The fluid compositions (1) to (10) obtained by the present invention have an initial Z value.
It was found to be 1.0 or more, indicating that the composition was an electrorheological fluid having a good balance between shear stress characteristics and current characteristics. Further, the fluid compositions (1) to (10) obtained by the present invention are:
Even after days, the Z value was 1.0 or more, indicating that the composition was an electrorheological fluid having excellent stability over time in the balance between shear stress characteristics and current characteristics.

On the other hand, in the comparative fluid composition (1), a large shear stress was obtained by applying a relatively weak electric field, but 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 The current density was poor in stability over time, and became unmeasurable after 6 days. The Z value of the comparative fluid composition (1) was 0.7 at 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.

In addition, the comparative fluid composition inner product (2) is a fluid composition (1) or a fluid composition (2) of the present invention obtained from the same polymerized crosslinked product (1) and composed of dispersed phase particles having the same average particle size. ), The obtained shear stress value was small, the current density was large, and the current characteristics were inferior. The Z value of the comparative fluid composition (2) was 0.9 at 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. Furthermore, the comparative fluid composition (2) had a Z value of 0.6 after seven days, which was smaller than the initial value, and the temporal stability of the balance between the shear stress characteristics and the current characteristics was worse than that of the fluid composition of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location (C10M 161/00 151: 02 125: 14) C10N 10:02 20:00 30:04 40:14 70:00

Claims (11)

(57) [Claims] 1. A composition comprising dispersed particles of a sulfonated polymer having an aromatic ring substituted with a sulfonic acid group in an insulating dispersion medium, wherein the composition comprises An electrorheological fluid composition characterized in that the number of sulfonic acid groups in the sulfonated polymer exceeds the number of aromatic rings present in the sulfonated polymer. 2. A polymerization crosslinking of a monomer mixture (A) in which a sulfonated polymer contains a vinyl aromatic compound (a) and a polyvinyl compound (b) as main components, and optionally adds another vinyl compound (c). The electrorheological fluid composition according to claim 1, which is obtained by sulfonating an aromatic ring present in the body (I). 3. The electrorheological fluid composition according to claim 2, wherein the blending ratio of the vinyl aromatic compound (a) and the polyvinyl compound (b) is in the range of 50 to 99 mol% of the former and 50 to 1 mol% of the latter. 4. The vinyl aromatic compound (a) comprises a vinyl aromatic compound having at least one electron donating group on an aromatic ring, and at least one electron donating group on an aromatic ring. The electrorheological fluid composition according to claim 2 or 3, wherein the proportion of the vinyl aromatic compound having the following in the monomer mixture (A) is 5.0 mol% or more. 5. The electrorheological fluid composition according to claim 4, wherein the electro-donating group is an alkoxy group. 6. The sulfonated polymer is a polymerized crosslinked product (I)
3. A compound obtained by sulfonation in a temperature range of 50 to 80 DEG C.
An electrorheological fluid composition as described. 7. The sulfonated polymer, after sulfonating the crosslinked polymer (I) at a temperature in the range of -20 to 50 ° C.,
The electrorheological fluid composition according to claim 2, which is obtained by sulfonating in a temperature range of ° C. 8. The electrorheological fluid composition according to claim 6, wherein the sulfonation is carried out using chlorosulfuric acid or fuming sulfuric acid as the sulfonating agent. 9. 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. 10. The dispersed phase particles have an average particle size of 0.1 to 100 μm.
The electrorheological fluid composition according to any one of claims 1 to 9, wherein 11. The electrorheological fluid composition according to claim 1, wherein the ratio of the dispersed phase particles to the insulating dispersion medium is in the range of 50 to 500 parts by weight with respect to 100 parts by weight of the former. Stuff.