JPH1129508A - Electrically sensitive compound, electrically sensitive composition and use thereof - Google Patents

Abstract

(57) Abstract: The electrosensitive compound of the present invention is a compound represented by the formula [I], and in an electrosensitive composition, this compound is dispersed in an electrically insulating medium. Embedded image “Ph” represents a divalent aromatic group, p is 1 to 4q + 1,
q is 0, 1 or 2, r is 0 or 1, n is 2-2
0, m is 2n + 1 or 2n-1, X is H or F, A
Is mainly a monovalent group having no releasable hydrogen atom at the terminal. In the composition of the present invention, the rheological characteristics fluctuate due to the flow of the electrically insulating medium accompanying the movement of the electrosensitive compound due to the applied voltage.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electro-sensitive compound capable of changing a fluid characteristic while maintaining a liquid state by applying a voltage in a state of being dispersed in an electrically insulating medium. And a method for using the composition.

[0002]

2. Description of the Related Art Currently known electrorheological fluids are roughly classified into a particle dispersion system and a liquid crystal system. Particle-dispersed electrorheological fluids gel by an electric field,
Below the yield stress, it exhibits the behavior described as an elastic solid. This is because the particles are arranged in the direction of the electric field and form a chain structure between the electrodes. On the other hand, in a liquid crystal-based electrorheological fluid, molecules form a domain structure oriented in a certain direction, and an increase in interaction between domains due to an electric field causes an increase in viscosity. In a liquid crystal-based electrorheological fluid, non-Newtonian flow may sometimes appear due to the electric field strength, but it is generally considered that elasticity and yield stress do not appear and only viscosity increase occurs. Therefore, the liquid crystal-based electrorheological fluid has an advantage that it can be linearly controlled by an applied voltage, and the rheological characteristics are very easily controlled.
However, liquid crystal electrorheological fluids are very expensive, and their use is currently limited to small ones such as liquid crystal elements sandwiched between transparent substrates.

On the other hand, as an electrorheological fluid of a particle dispersion type, for example, water is adsorbed and retained on the surface of particles such as silica gel, cellulose, starch, soybean casein, and polyester ion exchange resin in an electrically insulating oil. Composition containing solid particles that can be used, composition containing inorganic solid particles with low electric conductivity, hydroxide of polyvalent metal, hydrotalcites, acid salt of polyvalent metal, hydroxyapatite, nasicon type Compounds, clay favorites,
Compositions and the like in which inorganic compounds such as potassium titanates, heteropolyacid salts or insoluble ferrocyanide compounds are blended are known (JP-A-2-91194, JP-A-3-2-2).
00897).

Many of such particle-dispersed electrorheological fluids are obtained by dispersing inorganic particles in an electrically insulating oil composed of an organic compound. Due to the difference in specific gravity between the two, the particles settle during storage, such as sedimentation during storage. There is a problem with sex. In addition, in such a particle-dispersed electrorheological fluid, when a voltage is applied, the dispersed particles form a chain-like structure and exhibit a rheological change that becomes an elastic solid below the yield stress. Difficult to control.

By the way, JP-A-6-57274 discloses that the formula (I) R _1- (CF ₂ ) _n- (CH ₂ ) _m -R ₂
Wherein R ₁ is H, F, Cl, Br or I;
n is an integer of 3 to 30, m is an integer of 0 to 2, R ₂ is CH ₂ OH, COOH, COOM (M is an alkali metal or a quaternary ammonium salt), or CH ₂ S
H) or formula (II) Rf-O-Ph- (COO
H) a fluorine compound represented by _y (where Rf is C _3x F _6x-1 , wherein x is an integer of 2 to 4 and y is an integer of 1 to 3); An electrosensitive composition comprising an electrically insulating medium capable of dissolving a compound upon application of a voltage is disclosed.

The compound represented by the formula (I) or the formula (II) is dissolved in an electrically insulating medium by the action of an electric field when a voltage is applied, so that the composition is homogeneous. It is described that the rheological performance fluctuates by becoming transparent and increasing the viscosity thereof. However, a phenomenon in which a substance is dissolved in an insoluble solvent by applying a voltage has not been found. Also,
When a voltage is applied to a composition in which the compound represented by the above formula is contained in an electrically insulating oil, an extremely slow rheological change may be observed, but the change is extremely slow and small. Not available.

[0007]

SUMMARY OF THE INVENTION The present invention forms an electro-sensitive composition in which the rheological properties fluctuate by applying a voltage based on a new rheological theory, and the fluctuation can be easily controlled. It is an object of the present invention to provide an electrosensitive compound which can be used.

Another object of the present invention is to provide a novel electrosensitive composition using the above electrosensitive compound and a method for using the electrosensitive composition.

[0009]

Means for Solving the Problems The present invention is an electrosensitive compound capable of exhibiting electrosensitivity represented by the following formula [I].

[0010]

Embedded image

In the above formula [I], “Ph” represents at least a divalent aromatic group which may have a substituent,
Is any of 1 to 4q + 1, and q is 0, 1 or 2
Wherein r is 0 or 1, and n is 2 to
An integer of 20, m is either 2n + 1 or 2n-1, X is H or F, and A is each independently a hydrogen atom, a monovalent organic group having 2 or more carbon atoms, or or a monovalent radical of less than 2 carbon atoms having no free hydrogen atoms at the terminal, _{or, - [(CH 2) s} O] t -
Wherein s is 2 to 5 and t is 1 to 5, and in this case, the number of Xs per carbon atom is 2n-2, and the divalent group is bond bonded to an oxygen atom of said radical -C _n X _2n-2 - are directly and carbon atoms constituting bonded to a form a cyclic structure.

Further, the electro-sensitive composition of the present invention comprises an electrically insulating medium, and the above-mentioned formula [I] dispersed in the electrically insulating medium.
And an electrosensitive compound represented by the formula: further,
The method for using the electrosensitive composition of the present invention includes applying a voltage to an electrosensitive composition comprising an electrically insulating medium and an electrosensitive compound represented by the above formula [I] dispersed in the electrically insulating medium. It is characterized by doing.

When a voltage is applied to the electrically insulating composition in which the compound represented by the above formula [I] is dispersed in an electrically insulating medium, at least a part of the compound represented by the above formula [I] is changed between the electrodes. Then, for example, a reciprocating motion or a convection motion forms a moving flow of the electrically insulating medium with the movement of the compound. The rheological properties of the electro-sensitive composition of the present invention are changed by the moving flow of the electrically insulating medium induced by the movement of the compound represented by the formula [I]. Since the rheological properties of the fluid are not changed by forming a chain structure like a fluid, the electrosensitive composition of the present invention maintains a liquid state even when a voltage is applied. Therefore,
For example, if a Newtonian fluid is used as the electrically insulating medium, it exhibits characteristics that it does not have a yield stress like a liquid crystal-based electrorheological fluid, so that linear control by an applied voltage becomes possible.

[0014]

Next, the electrosensitive compound, the electrosensitive composition and the method of using the electrosensitive composition of the present invention will be described in detail.

First, the electrosensitive compound of the present invention will be described. The electrosensitive compound of the present invention can be represented by the following formula [I].

[0016]

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In the above formula [I], “Ph” represents a substituent.
It is a divalent aromatic group which may have. This aromatic group
Examples of phenylene and naphthylene groups
Can be. Also, at least these aromatic rings are formed.
Also, one carbon atom is a hetero atom (eg, nitrogen atom, oxygen atom
Or a cyclic structure substituted with a sulfur atom)
Good. When this Ph is a phenylene group, the ortho position,
The next group in either the meta or para position
In the above formula [I], q is
And when p is 1, the group A is C_nX
_mIt is usually attached at the para-position to the (O)-group.
Similarly, when p is 2, the group A is C _nX
_mIt often bonds to the meta position with respect to the (O)-group.

In the above formula [I], X is a hydrogen atom (H)
Or a fluorine atom (F), usually C _n
All of X in the group represented by X _m- are a hydrogen atom or a fluorine atom, but a hydrogen atom and a fluorine atom may be mixed.

In the formula [I], n is an integer of 2 to 20, preferably 5 to 10, and m is 2n + 1 or 2n-1. When m is 2n + 1,
C _n X _m - group represented by is a saturated alkyl group or a saturated perfluoroalkyl group. Further, when m is _{2n-1, C n X m} - group represented by the one having a hydrocarbon group with a double bond, a fluoroalkenyl group having one double bond.

When m and n have a relationship of m = 2n + 1, a preferred example of the group represented by C _n X _m- is C ₈ H
_{17 -, C 10 H 21 -} , C 12 H 25 -, C 18 H 37 - a linear alkyl group or branched alkyl groups such as, C ₈ F ₁₇ -,
_{C 10 F 21 -, C 12} F 25 - and C ₁₈ F ₃₇ - linear perfluoroalkyl group, such _{as, CF 3 - (CF 2)} S -C (C
And a branched perfluoroalkyl group such as F ₃ ) _2- (s is an integer of 0 to 16).

When m and n have a relationship of m = 2n-1, the group represented by C _n X _m- is a group having a carbon-carbon double bond, and has the following formula [I-b ] Is preferable.

[0022]

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[0023] In the formula [Ib], R ^11, R ¹² and R ¹³ are each independently preferably an alkyl group or fluoroalkyl group, further the R ^11, R
It is preferred that ¹² and R ¹³ are each independently —C _j F _k . Here, j is an integer of 1 to 5, and k is 2
j + 1. Particularly, R ¹¹ is CF ₃ — or CF ₃
It is preferably one of, R ¹² and R _{^13, (CF 3) CF 2 -} - CF 2, (CF 3) 2 CF -, (CF
₃₎ is preferably ₃ C- either further (C
Particularly preferred is F ₃ ) ₂ CF—. Further, one of R ¹² and R ¹³ may be a divalent group such as — (CF ₃ ) ₂ C—, and in this case, a group A described later and the divalent group are To form a ring structure.

A preferred compound of the electrosensitive compound of the present invention having a group as described above can be represented by the following formula [Ia]. In the formula [I], r is 0 or 1, therefore, if r is 0, the C _n X _m - group represented by, preferably the group represented by the formula [Ib] Is directly bonded to the group Ph or the group A. When r is 1, the above C _n X _m
The group represented by-, preferably the group represented by the formula [Ib], is bonded to the group Ph or the group A via -O-.

In the above formula [I], a compound represented by the above formula [Ib] suitable as a group represented by C _n X _m -is represented by the following formula [I-
a].

[0026]

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In the formulas [I] and [Ia], q is 0, 1,
Or 2, when q is 1, the group defined by q is preferably a phenylene group, and when q is 2, the group defined by q is preferably a biphenyl group .

In the above formulas [I] and [Ia], the group A
Is a hydrogen atom or a monovalent organic group having 2 or more carbon atoms, or a monovalent group having less than 2 carbon atoms having no releasable hydrogen atom at the terminal.

That is, for example, when the compounds represented by the formulas [I] and [Ia] have one group A, this group A is a group having a releasable hydrogen atom at the terminal such as -COOH. Never be. Specific examples of this group A include:

[0030]

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Preferably, the group is selected from the group consisting of: In the above formula [II], B represents -CO-, -SO
₂ - and - (CH _{2) g} - (g is usually an integer of 1 to 5)
Any group selected from the group consisting of

A is independently 0, 1, 2
Or 3; a ′ is either 0 or 1; and h is 0, 1 or 2.
Further, c and c ′ are each independently 0 or 1, and have a relationship of c + c ′ = 1. That is, c and c ′
Do not become 0 at the same time and do not become 1 at the same time, and one of them is always 1. B is 0
Or any integer from 1 to 10.

When c = 1 and c ′ = 0, the group represented by the formula [II] is as follows.

[0034]

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When c = 0 and c ′ = 1, the group represented by the formula [II] is as follows.

[0036]

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In the formula [II], R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group and a propyl group. it can.

Further, in the formula [III], d is 0 or 1
E is 0 or 1, and f is 0
Or an integer of 1 to 5.

In the formula [III], R ² is independently an alkyl group having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group and a propyl group.

In the formulas [II] and [III], M
Is an atom capable of forming a monovalent anion or a group capable of forming a monovalent anion. Specific examples of, Cl ^{- -} This M, Br ^- and I ^- halogen ions such, C
_{^{H 3 COO -, BF 4 -}} , BPh 4 -, PO 4 W 12 0 36 - ( _{i.e., PO 4 · n (W0 3} ) -), CH 3 PhSO 3 -, CF 3 SO 3
_{^{-, CH 3 SO 3 -,}} PhSO 3 -, HPO 3 -, HSO 4 -, N
O ₃ ^- and OH ^- can be mentioned.

In the formula [IV], R ³ represents —NO ₂ ,
—CN, —OH, —PO ₃ H or a salt thereof, —SO ₃ H or a salt thereof, —COOH (q た だ し 0) or a salt thereof (q = 0, 1, 2), —N (X ⁰ ) ₂ or -N ⁺ (X
⁰ ) ₃ · M ⁻ (where X ⁰ is H or an alkyl group having 1 to 3 carbon atoms), and a halogen atom (eg, F, Br,
A phenyl group which may have at least one group or atom selected from the group consisting of I, Cl), -OH, -C
1 to 22 carbon atoms which may have a substituent such as OOH
And at least one group selected from the group consisting of alkylene groups having 1 to 22 carbon atoms, which may have a substituent such as —OH or —COOH.

Here, examples of the alkyl group include a methyl group, ethyl group, propyl group, octyl group, lauryl group and salicyl group. Examples of the substituted phenyl group include p-nitrophenyl. Groups, p-cyanophenyl, p-aminophenyl and p-bromophenyl groups.

In the formula [V], R ⁰ has 1 to 2 carbon atoms.
2 alkyl or alkenyl groups, or
It is a single bond. I is usually an integer of 1 to 30, preferably 1 to 10.

That is, when R ⁰ is a single bond, the group “A”
Is a divalent group, which is, for example,
Together with the group having the structure represented by [Ia], a cyclic structure is formed.

In this case, the group forming a cyclic structure is generally a divalent group represented by-[(CH ₂ ) _s O] _t- (s is 2
-5, and t is 1-5), preferably-(C
H ₂ CH ₂ 0) _i- (i is a divalent group usually represented by 1 to 30, preferably 1 to 10).

When the group “A” is a divalent group as described above, the group C _n X _m − which forms a cyclic structure in cooperation with the divalent group “A” can be represented by, for example, the following formula: Ic]

[0047]

Embedded image

And a bond of a group “A” described below is directly bonded to a carbon atom constituting the group —C _n X _2n-2 — represented by the formula [Ic]. To form an annular structure. Here, R ¹³ in the above formula [Ic] is -C _{j ′}
F _{2j '-} or -C _j' H _2j '- (provided that, j' is 1 to 5
Is an integer).

Then, for example, in the above formula [Ic],
r is 1, q is 0, p is 1, A is -C
When H ₂ CH ₂ O—, the compound having a cyclic structure has a structure represented by the following formula [Id], preferably a structure represented by [Ie].

[0050]

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[0051]

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In the above formula [I] or [Ia], q is 0, 1, or 2, and p has a relationship of 1 to 4q + 1. That is, a plurality of groups A can be bonded to the aromatic group represented by Ph.
In the case where a plurality of (p) groups A are bonded as described above, the p-1 groups A may be -COOH. In this case, the remaining group A is a monovalent group having no releasable hydrogen atom at the terminal.

When a plurality of groups A are bonded, these groups A may be the same or different. Specific examples of the electrosensitive compound represented by the above formula [I] include compounds 1 to 17 represented by the following formulas.

[0054]

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[0055]

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[0056]

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The above compounds can be synthesized by combining known methods. For example, the compound 1 can be synthesized as follows.

For example, first, p-perfluorononenylphenyl ether is dissolved in an organic solvent such as chloroform, and chlorosulfonic acid is added dropwise with stirring to produce perfluorononenyloxybenzenesulfonyl chloride. After removing the reaction solvent from the obtained reaction product, washed with water, 1,1,2-trifluoro-1,2,2
-White crystals of perfluorononenyloxybenzenesulfonyl chloride can be obtained by recrystallization from an organic solvent such as trichloroethane.

The white crystals thus obtained are dissolved in an ether solvent, and N, N-dimethyl-1,3-propanediamine and an aqueous solution of sodium hydroxide are added thereto with stirring to cause a reaction.
By removing the reaction solvent, a pale yellow paste-like substance (sulfoamide compound) can be obtained.

This sulfoamide compound is dissolved in an aprotic organic solvent such as acetonitrile, cooled on ice, methyl iodide is added dropwise with stirring, and the resulting solid is collected by filtration and recrystallized with alcohol. Compound 1 [N- [3-
White crystals of (p-perfluorononenyloxybenzenesulfonamido) propyl] -N, N, N-trimethylammonium iodide] can be obtained.

Compounds other than the above-mentioned compound 1 can be produced by applying the above-mentioned method. Most of the compounds represented by the above formula [I], particularly the above compounds 1 to 17, are usually powders, and can be easily and stably dispersed (floated) in an electrically insulating medium.

The compound represented by the formula [I] has electrosensitivity. That is, when these compounds are suspended (or evenly dispersed) in, for example, an electrically insulating medium and a voltage is applied to the electrically insulating medium, the above formula is obtained.
The compound represented by [I] moves between the electrodes, and can change the rheological properties of an electrically insulating medium (electrically sensitive composition) containing the compound.

The electro-sensitive composition of the present invention utilizes the properties of the electro-sensitive compound represented by the above formula [I], and comprises an electrically insulating medium and the above-mentioned electro-sensitive medium dispersed in the medium. And a compound represented by the formula [I].

The electrically insulative medium used here is an electrically insulative medium which is used when the electrically sensitive compound of the present invention is mixed with the electrically sensitive compound represented by the above formula [I]. In particular, liquids which can form heterogeneous dispersions at temperatures (i.e., temperatures) and elastic liquids can be used. In particular, in the present invention, since the rheological properties of the Newtonian fluid can be varied by blending the above-mentioned electrosensitive compound, a fluid exhibiting Newtonian flow at the operating temperature is preferably used as the electrically insulating medium. You. In addition, even in the case of a non-Newtonian fluid (for example, a liquid having elasticity), the rheological properties of the non-Newtonian fluid can be changed by adding the electrosensitive compound represented by the formula [I] to the non-Newtonian fluid.

As an example of such an electrically insulating medium,
Examples include silicone compounds, aliphatic hydrocarbon compounds, alicyclic hydrocarbon compounds, aromatic hydrocarbon compounds, animal and vegetable oils, esters, phosphazenes, and halogenated solvents. More specifically, silicone oil, silicone gel, refined mineral oil, synthetic oil (eg, alkylbenzene, alkylnaphthalene), sebacate ester compound, trimellitate ester, triphenylphosphazene oil, adipate esters, phthalate esters , Low molecular weight polyolefins, crosslinked low molecular weight polyolefins, crosslinked silicone compounds, fluorinated silicone oils and fluorinated oils. These can be used alone or in combination.

The electro-sensitive composition of the present invention may contain a coloring agent, an antioxidant, and the like as long as the electro-sensitivity is not impaired.
Preservatives, rust preventives, fungicides, viscosity modifiers, stabilizers and the like can also be added.

The electro-sensitive composition of the present invention comprises the above-mentioned electrically insulating medium and the electro-sensitive compound represented by the formula [I], and is represented by the formula [I] in the composition. The electrosensitive compound is usually contained in an amount of 0.1 to 30% by weight, preferably 1 to 15% by weight. By blending the electrosensitive compound in the above amount in the electrically insulating medium, the rheological properties of the composition can be arbitrarily varied when a voltage is applied to the composition.

In such an electrosensitive composition, the formula
Since the electrosensitive compound represented by [I] does not dissolve in the electrically insulating medium, it forms a heterogeneous dispersion in the state of particles dispersed in the electrically insulating medium.

The electrosensitive compound represented by the formula [I] is dispersed in the electrosensitive composition of the present invention into fine particles to form a heterogeneous dispersion system (fluid). The average particle size of the compound is usually 0.1 to 2000 μm.
m, preferably in the range of 5 to 1000 μm. An electrosensitive compound having such a particle size is stably dispersed in an electrically insulating medium. As a method of dispersing, for example, a uniform dispersion may be performed using a dispersant, high-speed stirring, ultrasonic irradiation, or the like.

When a voltage is applied to the electrosensitive composition of the present invention, the rheological properties of the composition change. For example, an electro-sensitive composition produced by adding 5% by weight of the compound 1 represented by the above formula to a silicone oil having a viscosity of 0.1 Pa · s at room temperature, which is a Newtonian fluid at room temperature, and uniformly dispersing the compound 1 When a voltage is applied to a product under the application of a shear stress by using a stress-controlled rheometer modified so that the voltage shown in FIG. 1 can be applied, the viscosity of the electro-sensitive composition becomes extremely short. Rise. That is, as shown in FIG. 1, two disks having a diameter of 35 mm are arranged so as to form a gap of 1 mm. A voltage can be applied between the upper disk and the lower disk. By placing the electro-sensitive composition in the gap between the upper disc and the lower disc and rotating the upper disc, a shear stress is applied to the electro-sensitive composition filled in the gap to increase the viscosity of the electro-sensitive working medium. Is measured.

Here, the viscosity of the electrically insulating medium is 0.1 Pa ·
Therefore, as shown in FIG. 2, the viscosity of the electrosensitive composition at this temperature is approximately 0.1 Pa · s. Next, when a voltage is applied so as to generate a potential difference between the upper disk and the lower disk, the viscosity of the electrosensitive composition rapidly increases as shown in FIG. Such a rise in viscosity does not occur even when a voltage is similarly applied using an electrically insulating medium containing no electrosensitizing compound. By closely observing the electro-sensitive composition when a voltage is applied to the stress control type rheometer, it can be confirmed that a part of the electro-sensitive compound in the composition moves between the electrodes. Then, such an electrosensitive compound moves so as to circulate or reciprocate mainly between the electrodes, and a moving flow or a circulating flow of the electrically insulating medium is formed along with the movement of the electrosensitive compound. The formation of a circulating flow of the electrically insulating medium accompanying the movement of the electrosensitive compound increases the viscosity of the electrosensitive composition of the present invention.

Then, as shown in FIG. 2, when the application of the voltage is stopped, the moving flow of the electrosensitive compound is stopped, so that the viscosity of the electrosensitive composition is the same as the viscosity when no voltage is applied. It returns to the viscosity (almost 0.1 Pa · s). The electrosensitive composition of the present invention has a very short time (response time) from when a voltage is applied to when the viscosity increases (in most cases, about 0.1 to 30 seconds) and reaches a high viscosity range. I do.

The change in viscosity at the time of voltage application is as follows.
It depends on the applied voltage. FIG. 3 shows that the voltage (E) applied to the electrosensitive composition was 0 KV, 1 KV, 2 KV, 3 KV,
The change in viscosity when changing to 4 KV is shown. When E = 0, the viscosity of the electro-sensitive composition is approximately 0.1 Pa · s, and by increasing the applied voltage to 1 KV, 2 KV, 3 KV, and 4 KV, The viscosity of the object increases.

The difference between the viscosity at E = 0 and the viscosity when a voltage is applied is the ER effect (Electrorheology effect). That is, when a voltage is applied to the electrically-sensitive composition of the present invention having the electrically-insulating medium and the insensitive electro-sensitive compound of the present invention in the medium, reciprocating motion and circulating motion of the electro-sensitive compound occur between the electrodes, It is considered that a convection of the electrosensitive compound is formed in the electrically insulating medium between the electrodes, and this convection becomes a resistance to the flow in a direction perpendicular to the installation position of the electrode, which indicates a change in rheological characteristics. Such a new configuration of the ER effect is inferred from the observation of the behavior of the electrosensitive compound in a voltage application experiment, and the effect of the present invention is not limited by the above mechanism.

Further, the electrosensitive composition of the present invention exhibits elasticity while being a liquid. FIG. 4 shows a strain (or displacement (St) when a stress at a shear rate of 0.5 Pa was applied to the above-described electrosensitive composition for 200 seconds and then the stress was instantaneously removed.
It is a figure which measured the time change of rain)). When the stress is continuously applied for 200 seconds, the electro-sensitive composition exhibits a creep behavior that is deformed by the applied stress. afterwards,
When the creep recovery (value at the circumference of the disk) is measured with the stress removed instantaneously, the creep recovery is observed immediately after the stress is removed. That is, the electrosensitive composition has elasticity while being a liquid. In this state, the electrosensitive composition of the present invention clearly behaves very similar to a liquid in this state, since the strain measured under stress changes almost linearly with time, but after the stress is removed, Although exhibiting elasticity, the electro-sensitive composition is still liquid in this state.

In the conventionally known particle-dispersed electrorheological fluid, the dispersed particles form a chain structure by applying a voltage, whereby the apparent viscosity increases, and the solid state having elasticity below the yield stress is obtained. Becomes Thus, a particle-dispersed electrorheological fluid is:
By forming the chain structure, when the external force is equal to or lower than the yield stress, it behaves as a solid state, and when the external force is equal to or higher than the yield stress, it indicates a liquid state in which the chain structure is broken. This means that a solid state and a liquid state appear depending on the magnitude of the external force, and it is impossible to linearly control the rheological change of the system by applying a voltage.

However, the electrosensitive composition of the present invention does not show a solid state when voltage is applied, and the composition remains in a liquid state like a liquid crystal electrorheological fluid.
The rheological properties of the composition change. This is optimal for the linear control method because only one state of the liquid state is shown regardless of the magnitude of the external force. The advantage of the linear control method is that complicated feedback control is not required.
The control is easy and the control equipment is inexpensive.

When the electrosensitive composition of the present invention is used, the applied voltage is usually 0.05 to 10 KV / mm, preferably 0.5 to 7 KV / mm. Usually 0.001 to 30 μA / cm ² , preferably
0.1 to 15 μA / cm ² . Because of such a small current, the electric power consumed to change the rheological properties of the electrosensitive composition of the present invention is extremely small, and therefore, the heat generated by the change in the rheological properties is almost ignored. It is so small that it can be done.

The rheological changes in the electro-sensitive composition of the present invention are as follows: engine lubricating oil, clutch fluid, damper material, shock absorber filling fluid, valve lubricating oil, actuator fluid, vibrator filling material, mechanical lubricating oil, printer ink, vibration It can be used in devices and the like. In particular, the electrosensitive composition of the present invention may be prepared by adding a small amount of the electrosensitive compound represented by the formula [I] to an electrically insulating medium having a certain conductivity or less, and various fluids can be used as the electrically insulating medium. By applying a voltage to such an electro-sensitive composition, the viscosity of the composition at the portion where the voltage is applied can be controlled. Therefore, when the composition is used as a hydraulic oil, quantitative and constant pressure control becomes easy.

[0080]

By using the electrosensitive compound of the present invention, an electrosensitive composition exhibiting an electrorheological effect based on a new mechanism can be obtained. That is, when a voltage is applied to the electrosensitive composition of the present invention in which the electrosensitive compound represented by the formula [I] is blended in an electrically insulating medium, the electrosensitive compound represented by the formula [I] is applied between the electrodes. Reciprocating movement occurs, and a moving flow of the electrically insulating medium is formed accompanying the movement of the electrosensitive compound. The movement of the electrosensitive compound and the formation of the moving flow of the electrically insulating medium formed by the movement of the compound change the rheological properties of the electrosensitive composition of the present invention. And
Variations in the rheological properties of the electrosensitive composition of the present invention include:
The rheological properties of the electro-sensitive composition of the present invention can be controlled by controlling the applied voltage because the electro-sensitive compound is induced by the movement of the electro-sensitive compound contained in the composition.

[0081]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples of the present invention, but the present invention should not be construed as being limited thereto.

[0082]

EXAMPLE 1 Synthesis first stage of compound 1 [p- perfluoro root oxy benzenesulfonyl _{chloride] (C 9 F 17 -0-} C 6 H 4 -SO 2 Cl) Synthesis p- perfluorophenyl root sulfonyl phenyl ether ( C ₉ F ₁₇ -0-C ₆ H
₅ ) 52.4 g (0.1 mol) were dissolved in 100 ml of chloroform and 35 g of chlorosulfonic acid were stirred at room temperature.
(0.3 mol) was added dropwise. After reacting for about 5 hours, the reaction product was washed with a large amount of water, the solvent was removed, and recrystallized with 1,1,2-trifluoro-1,2,2-trichloroethane to give a white color. 59.2 g of crystals were obtained. The analysis results of the obtained crystals are shown below.

Melting point: 62-64 ° C., result of elemental analysis; F:
51.90% (calculated value; 51.86%), IR spectrum analysis result; CF; 1064 to 1330 cm ^-1 , Ph-
H; 1493 cm ^-1 , 1594 cm ^-1 , -SO ₂ ; 1389 c
m ^-1 .

From the above analysis results, this white crystal was found to be p-perfluorononenyloxybenzenesulfonyl chloride (C
₉ F ₁₇ -0-C ₆ H ₄ -SO ₂ Cl). (yield;
95%) second stage [N- [3- (p- perfluoro root oxy benzenesulfonamide) propyl] -N, N, N- trimethylammonium _{iodide] (C 9 F 17 -0-} C 6 H 4 - SO ₂ -NH- (CH ₂ ) _3-
Synthesis of N ⁺ (CH ₃ ) ₃ .I) 12.5 g (0.02 mol) of p-perfluorononenyloxybenzenesulfonyl chloride synthesized in the first step above
Was dissolved in 100 ml of diethyl ether, and 2.2 g of N, N-dimethyl-1,3-propanediamine was stirred at room temperature.
(0.022 mol) and an aqueous solution of sodium hydroxide (aqueous solution prepared by dissolving 0.8 g (0.02 mol) of sodium hydroxide in a small amount of water) were added and reacted.

After reacting for about 2 hours, the reaction product was washed with a large amount of water, and the solvent was removed to obtain a pale yellow paste-like substance (sulfoamide compound). 13.1 g (0.02 mol) of the sulfamide compound thus obtained was dissolved in 100 ml of acetonitrile, and 5.7 g (0.04 mol) of methyl iodide was added dropwise with stirring under ice cooling.

The solid produced by the reaction for about 2 hours was collected by filtration. The filtrate was recrystallized from methanol to obtain 14.3 g of white crystals. The analysis results of the obtained crystals are shown below.

Melting point: 206-207 ° C., result of IR spectrum analysis; CF: 1060-1330 cm ⁻¹ , Ph-
^{H; 1590cm -1, N-H} ; 3152cm -1, -SO 2;
1340 cm ^-1 .

As a result of the above analysis, this white crystal was [N- [3-
(p-perfluorononenyloxybenzenesulfonamido) propyl] -N, N, N-trimethylammonium iodide] (Compound 1 above). (Yield 90%) Compound 1 [N- [3- (p-perfluorononenyl) in a silicone oil having a viscosity of 0.1 Pa · s at room temperature (trade name: TSF451-100, manufactured by Toshiba Silicone Co., Ltd.) Oxybenzenesulfonamido) propyl] -N, N, N-trimethylammonium iodo (C ₉ F ₁₇ -0-C ₆ H ₄ -SO ₂ -NH- (CH ₂ ) ₃ -N ⁺
(CH ₃ ) ₃ .I) was added to the above silicone oil in an amount of 5% by weight, and the mixture was sufficiently stirred to uniformly disperse Compound 1 in the silicone oil to produce an electrosensitive composition.

The viscosity (mPa · s) at each shear rate (s ⁻¹ ) and the current value (μA / c) when no voltage was applied and when a DC voltage was applied were applied to the obtained electrosensitive composition.
m ² ) was measured.

The above measurement was performed as follows using an improved stress control type rheometer (an improved type of Rheo-Stress RS-100, parallel plate type measurement sensor manufactured by Haake) shown in FIG.

Using a parallel plate type measuring sensor consisting of two disks having a diameter of 35 mm arranged with a gap of 1 mm in the container, the container was filled with the electrosensitive composition described in Table 1 below. did. A DC voltage was applied to this sensor.
The voltage applied to this sensor is controllable,
In addition, an ammeter is provided so that the current flowing between the electrodes can be measured.

FIG. 5 shows the viscosity at each shear rate.

[0093]

Example 2 In Example 1, compounds 2 to 17 shown in the following Table 1 were synthesized in place of the compound 1, and these were used to produce an electrosensitive composition according to the following table.

The viscosity (mPa · s) at each shear rate (s ⁻¹ ) and the current value (μA / c) when no voltage was applied and when a DC voltage was applied were applied to the obtained electrosensitive composition.
m ² ) was measured.

The viscosities at each shear rate are shown in FIGS.

[0096]

[Table 1]

[0097]

Example 3 The electrosensitive composition prepared in Example 1 was placed in the apparatus used in Example 1, and the voltage was set to 1 KV, 2 KV, and 3 KV.
V and 4 KV were applied, and the viscosity and current value of the composition under the same shear stress as in Example 1 were measured. The results are shown in FIG.

From FIG. 3, it is apparent that the electrosensitive composition exhibits Newtonian fluidity in a low shear rate region and a high shear rate region when a voltage is applied, and exhibits the properties of a viscoelastic liquid having no yield stress. It is.

[0099]

Example 4 The electrosensitive composition prepared in Example 1 was placed in the apparatus used in Example 1, and a 0.5 Pa stress was applied for 200 seconds while applying a DC current of 4 KV between the electrodes. The stress was removed instantaneously and the strain was measured.

FIG. 4 shows the results. From FIG. 4, it is clear that the electro-sensitive composition at the time of applying a voltage is an elastic liquid that exhibits a creep behavior that deforms in response to the application of a stress and shows a slight creep recovery after the stress is removed.

The electrosensitive composition of the present invention exhibits a creep behavior in which, when a shear stress is applied while a voltage is being applied, the composition is deformed in response to the application of the stress, which is clearly a normal liquid behavior. However, when the shear stress is instantaneously removed, the liquid state shows a slight creep recovery, and the normal liquid does not show such a creep recovery. However, even in the state showing the creep recovery, the electro-sensitive composition of the present invention maintains the liquid state.

It is known that a liquid crystal-based electrorheological fluid is in a liquid state showing a large creep recovery when a voltage is applied. However, it does not exhibit elasticity and always behaves as a liquid. Since the liquid crystal-based electrorheological fluid is in a liquid state even when a voltage is applied as described above, it has an advantage that it is easy to linearly control a change in viscosity due to a voltage. In contrast, a conventional particle-dispersion type electrorheological fluid exhibits creep recovery when a voltage is applied, and the behavior when a voltage is applied is accompanied by a change from a liquid to a solid. For this reason, it is difficult to linearly control the conventional particle-dispersion type electrorheological fluid.

The electro-sensitive composition of the present invention is, in appearance, a particle-dispersed electro-sensitive composition and is not a liquid crystal-based electrorheological fluid. And behaves similarly to liquid crystal-based electrorheological fluids. Therefore, the electrosensitive composition of the present invention has the property that linear control is possible while being an electrorheological fluid of a particle dispersion type, and the voltage controllability is similar to that of a liquid crystal type electrorheological fluid. ing.

[0104]

Example 5 The apparatus used in Example 1 was charged with the electrosensitive composition prepared in Example 1 and under a shear rate of 50 / s.
A DC voltage of 2 KV was applied and removed, and the electric field response of the electrosensitive composition was measured from the viscosity and the current value during the removal.

FIG. 2 shows the results. The viscosity of the electrosensitive composition produced in Example 1 rapidly increased immediately after voltage application, and reached a peak after 1 to 2 seconds, and was maintained when voltage was continuously applied. When the application of the voltage was stopped, the viscosity returned to the value before the application of the voltage within 10 seconds.

[0106]

Example 6 The electro-sensitive composition prepared in Example 1 was placed in the apparatus used in Example 1 and subjected to a vibrational strain having a strain amplitude of 3%, and a dynamic elastic modulus G ′ at each angular frequency was obtained. The loss modulus G ″ was measured.

The results are shown in FIGS. From FIGS. 22 and 23, the electrosensitive composition of the present invention exhibited substantially the same dynamic elastic modulus G ′ value (elastic property) and loss elastic modulus G ″ value (viscous property) at each voltage application. Fig. 22
From FIG. 23 and FIG. 23, it can be seen that the electrosensitive composition of the present invention has such a property that a change in viscosity and the appearance of elasticity occur upon application of a voltage, and the values of both appear almost to the same extent.

[0108]

EXAMPLE 7 The electrosensitive composition prepared in Example 1 was placed in the apparatus used in Example 1, and a vibration distortion of angular frequency 1 Hz was applied while applying a DC voltage of 3 KV to the measurement sensor. The dynamic elastic modulus G 'value and the loss elastic modulus G "value when the strain was gradually increased were measured.

FIG. 24 shows the results. As a result, Example 6
Similarly to the above, the electrosensitive composition of the present invention exhibited substantially the same dynamic elastic modulus G ′ value and loss elastic modulus G ″ value at each voltage application. It can be seen that has the property that the change in viscosity and the elasticity appear almost to the same degree when a voltage is applied.

[Brief description of the drawings]

FIG. 1 is a view schematically showing a parallel plate type measurement sensor used for measuring electrorheological characteristics in the present invention.

FIG. 2 is a graph showing a change in viscosity when a voltage is applied to and removed from an electrosensitive composition containing Compound 1.

FIG. 3 is a graph showing a change in viscosity when a voltage between 1 KV and 4 KV is applied to an electrosensitive composition containing Compound 1.

FIG. 4 is a graph showing the creep behavior when applying a voltage to the electrosensitive composition containing compound 1 while applying a voltage and the creep recovery when the stress is removed.

FIG. 5 is a graph showing a viscosity when no voltage is applied and a viscosity when a voltage is applied to the electrosensitive composition containing Compound 1.

FIG. 6 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing Compound 2.

FIG. 7 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing Compound 3.

FIG. 8 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing Compound 4.

FIG. 9 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing Compound 5.

FIG. 10 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing compound 6.

FIG. 11 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing Compound 7.

FIG. 12 is a graph showing the viscosity of the electrosensitive composition containing Compound 8 when no voltage is applied and the viscosity when a voltage is applied.

FIG. 13 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing compound 9.

FIG. 14 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing Compound 10.

FIG. 15 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing compound 11.

FIG. 16 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing Compound 12.

FIG. 17 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing compound 13;

FIG. 18 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing Compound 14.

FIG. 19 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing Compound 15.

FIG. 20 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing Compound 16;

FIG. 21 is a graph showing the viscosity when no voltage is applied and the viscosity when a voltage is applied to the electrosensitive composition containing compound 17;

FIG. 22 is a graph showing a change in a dynamic elastic modulus with respect to an angular frequency when an applied voltage of 1 to 4 KV is applied to the electrosensitive composition containing Compound 1.

FIG. 23 is a graph showing a change in a loss elastic modulus with respect to an angular frequency when an applied voltage of 1 to 4 KV is applied to an electrosensitive composition containing Compound 1.

FIG. 24 shows the strain amplitude dependence of the dynamic elastic modulus and the loss elastic modulus when applying an applied voltage of 3 KV to the electrosensitive composition containing Compound 1 and applying a vibration strain of angular frequency of 1 Hz. It is a graph shown.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI C07C 229/14 C07C 229/14 233/36 233/36 233/78 233/78 235/50 235/50 311/18 311/18 311/29 311/29 C07F 5/02 C07F 5/02 AB C09K 3/00 C09K 3/00 C // C10M 105/50 C10M 105/50 105/56 105/56 C10N 40:14 (72) Inventor Hiroyuki Fukube 1-1, Oike-cho, Kosai-cho, Koga-gun, Shiga Prefecture Inside the Neos Central Research Institute, Inc. 72) Inventor Kazuya Edamura 2-9-1-306 Higashishinkoiwa, Katsushika-ku, Tokyo

Claims (8)

[Claims] 1. An electro-sensitive compound capable of exhibiting electro-sensitivity represented by the following formula [I]: [In the above formula [I], “Ph” represents an at least divalent aromatic group which may have a substituent, and p is 1 to 4q
+1; q is 0, 1 or 2; r is 0 or 1; n is an integer of 2 to 20; m is 2n + 1 or 2n-1. X is H or F, and A is each independently a hydrogen atom, a monovalent organic group having 2 or more carbon atoms, or a monovalent having less than 2 carbon atoms having no releasable hydrogen atom at the terminal. or a group, _{or, - [(CH 2) s} O] t - represented by a divalent group (s is 2 to 5, t is 1 to 5), and in this case , The number of Xs per carbon atom is 2n−2
, And the bond attached to an oxygen atom of the divalent group, the group -C _n X _2n-2 - are directly and carbon atoms constituting a bond to form a cyclic structure. 2. In the above formula [I], A is each independently: Electrosensitive compound as in claim 1, wherein said that it is a group or a hydrogen atom selected from the group consisting of; [In the above formula, B is, -CO -, - SO ₂ - and - (CH _{2) g-} (g is an integer of 1 to 5) any group selected from the group consisting of: a is each independently 0, 1, 2 or 3; a ′ is 0 or 1, and h is
0, 1, or 2; c and c ′ are each independently 0 or 1, having a relationship of c + c ′ = 1, and b is any of 0 or 1 to 10 , D
Is an integer of 0 or 1 to 3, e is 0 or 1, f is any of 0 or 1 to 5, i is 1
R ⁰ is an alkyl group or alkenyl group having 1 to 22 carbon atoms, or a single bond, and when R ⁰ is a single bond, R ⁰ is a carbon atom in the formula [I]. the number of X with respect to is 2n-2, bond attached to an oxygen atom of the divalent group, the group -C _n X _2n-2 - to form a ring structure directly bonded to the carbon atoms constituting the R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms, and R ³ is —NO ₂ , —CN, —OH, —PO ₃ H or a salt thereof,
SO ₃ H or a salt thereof, —COOH (q ≠ 0) or a salt thereof (q = 0, 1, 2), —N (X ⁰ ) ₂ or —N ⁺ (X ⁰ ) ₃ .M ⁻ (here And X ⁰ is H or an alkyl group having 1 to 3 carbon atoms) and a phenyl group which may have at least one group or atom selected from the group consisting of halogen atoms, a substituent such as -OH, -COOH, etc. Is an at least one group selected from the group consisting of an alkyl group having 1 to 22 carbon atoms and an alkyl group having 1 to 22 carbon atoms, which may have a substituent such as -OH and -COOH. And M is an atom capable of forming a monovalent anion or a group capable of forming a monovalent anion. In the formula [I], when q is 1 and p is 2 or more, , P-1 A's may be -COOH. ]. 3. In the above formula [I], C _n X _m − is C ₉ F ₁₇
3. The electrosensitive compound according to claim 1, wherein the compound is any group selected from the group consisting of —, C ₆ F ₁₃ — and C ₈ H ₁₇ —. 4. 4. The electrosensitive compound represented by the formula [I],
The electrosensitive compound according to any one of claims 1 to 3, wherein the compound has a structure represented by the following formula [Ia]: [In the above formula [Ia], “Ph” represents an at least divalent phenylene group which may have a substituent, p is any one of 1 to 4q + 1, and q is any one of 0, 1 or 2. R ¹¹ , R ¹² and R ¹³ are each independently —C _j F _k , (j is an integer of 1 to 5, and k is
2j + 1), and A is each independently: A hydrogen atom or a group selected from the group consisting of: (However, in the above formula, B represents -CO-, -SO ₂
— And — (CH ₂ ) _g — (g is an integer of 1 to 5), and each group is independently any one of 0, 1, 2, or 3. , A ′ is either 0 or 1, and h is
0, 1, or 2; c and c ′ are each independently 0 or 1, having a relationship of c + c ′ = 1, and b is any of 0 or 1 to 10 , D
Is either 0 or 1-3, and e is 0 or 1.
And f is either 0 or 1 to 5, and i
Is an integer of 1 to 30; R ⁰ is an alkyl group or an alkenyl group having 1 to 22 carbon atoms, or a single bond, and when R ⁰ is a single bond, the formula [I-a R ^13] was adjusted, -C _{j 'F 2j'} - or -C _{j 'H 2j'} - a and (where, j 'is an integer of 1 to 5), the group _{- (CH 2 CH 2 O)} i The bond bonded to the oxygen of — is directly bonded to the carbon atom of the group represented by R ¹³ to form a cyclic structure, and R ¹ and R ² each independently have 1 to 3 carbon atoms. R ³ is —NO ₂ , —CN, —OH, —PO ₃ H or a salt thereof,
SO ₃ H or a salt thereof, —COOH (q ≠ 0) or a salt thereof (q = 0, 1, 2), —N (X ⁰ ) ₂ or —N ⁺ (X ⁰ ) ₃ .M ⁻ (here And X ⁰ is H or an alkyl group having 1 to 3 carbon atoms) and a phenyl group which may have at least one group or atom selected from the group consisting of halogen atoms, a substituent such as -OH, -COOH, etc. And at least one group selected from the group consisting of alkylene groups having 1 to 22 carbon atoms, which may have a substituent such as -OH, -COOH, or an alkyl group having 1 to 22 carbon atoms. M is an atom capable of forming a monovalent anion or a group capable of forming a monovalent anion, provided that, in the formula [I], q is 1 and p is 2 or more. Alternatively, p-1 A may be -COOH. )]. 5. An electrosensitive composition comprising an electrically insulating medium and the electrosensitive compound according to any one of claims 1 to 4, dispersed in the electrically insulating medium. 6. The electricity-sensitive composition according to claim 5, wherein said electro-sensitive composition forms a moving flow in said electro-sensitive composition in response to application of a voltage to said composition. Sensitive composition. 7. The electricity-sensitive composition according to claim 5, wherein the rheological properties of the composition vary with application of a voltage to the composition. Sensitive composition. 8. A method for using an electrosensitive composition comprising applying a voltage to the electrosensitive composition according to any one of claims 5 to 7.