JPH0657274A - Electrically responsive composition - Google Patents

Abstract

PURPOSE:To obtain the compsn. which has optical properties and viscosity changing when voltage is applied by compounding a specific fluorine compd. and an electrical insulating medium which dissolves the compd. when voltage is applied. CONSTITUTION:The compsn. comprises a fluorine compd. of formula I or II and an electrical insulating medium which dissolves the compd. when voltage is applied. In formula I, R1 is H, F, Cl, Br, or I; n is an integer of 3-30; m is an integer of 0-2; and R2 is CH2OH, COOH, COOM (wherein M is an alkali metal or a primary to quaternary ammonium salt), or CH2SH. In formula II, Rf is C3xF6x-1 (wherein x is an integer of 2-4); and y is an integer of 1-3. If the compsn. is sandwiched between electrodes and voltage is applied between the electrodes, the transparency of the compsn. increases and, in some cases, the viscosity also increases.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrosensitive composition, and more particularly to an electrosensitive composition capable of changing physical properties such as optical characteristics and viscosity by applying a voltage.

[0002]

2. Description of the Related Art Heretofore, electrorheological fluid compositions (hereinafter referred to as ER fluid compositions) and liquid crystal compositions have been known as electrosensitive compositions. The ER fluid composition is, for example, a fluid obtained by dispersing solid particles in an electrically insulating medium, and has a property of increasing its viscosity when a voltage is applied to it, a so-called electrorheological effect (hereinafter referred to as ER effect). ). Such ER effect is known as the Winslow effect, and when a composition is inserted between electrodes and a voltage is applied, the solid particles dispersed in the composition are polarized by the action of an electric field generated between the electrodes. Furthermore, it is manifested as a result of resisting external shear flow by being coordinately connected to each other in the direction of electric field by electrostatic attraction based on polarization. Since the ER fluid composition has the ER effect as described above, a clutch, a damper, a shock absorber, a valve, an actuator, a vibrator,
It is expected to be applied to power transmission or braking of a printer or a device by electric control such as a vibration element.

Specific examples of conventionally known ER fluid compositions are, for example, silica gel, cellulose, in an electrically insulating oil such as silicone oil, diphenyl chloride, or trans oil.
It is a dispersion of solid particles having water adsorbed and retained on the surface of the particles, such as starch, soybean casein, and polystyrene-based ion exchange resin. Further, for example, those using inorganic solid particles having a low electric conductivity containing a semiconductor as solid particles (Japanese Patent Laid-Open No. 2-91194), hydroxides of polyvalent metals, hydrotalcites, acidity of polyvalent metals. Also known are those using inorganic ion-exchanger particles composed of salts, hydroxyapatite, Nasicon-type compounds, clay minerals, potassium titanates, heteropolyacid salts or insoluble ferrocyanides (JP-A-3-200897). There is.

On the other hand, the liquid crystal composition is a composition capable of changing the crystal arrangement in the liquid phase by the application of a voltage, whereby the optical characteristics are changed. Due to this property, it is mainly used as a liquid crystal display device.

[0005]

Since the conventional ER fluid composition is a heterogeneous system (dispersion system) in which solid particles are dispersed in an electrically insulating medium as described above, it cannot be used or stored. , Solid particles can be aggregated by mutual attraction between particles,
There was a problem with storage stability, such as precipitation and sticking to electrodes and vessel walls, making it impractical.

In recent years, attempts have been made to use the ER fluid composition as a lubricating oil for automobile engines and the like.
This is because with normal lubricating oil, the viscosity decreases with increasing temperature, but the ER fluid composition similarly decreases with increasing temperature in the state of no voltage application. It is based on the idea that when a voltage is applied, the effect of increasing the viscosity due to this cancels out the decrease in viscosity due to temperature, whereby a constant viscosity can be maintained regardless of temperature. However, even in this case, since the conventional ER fluid composition is a heterogeneous system containing solid particles, the problem of wear when used as a lubricating oil cannot be overcome and it cannot be put to practical use.

Therefore, there has been a demand for a fluid composition which is a homogeneous system containing no solid particles and whose viscosity can be changed in response to the application of a voltage.

On the other hand, although the conventional liquid crystal composition can change its optical characteristics by the application of a voltage, it is disposed between special electrodes which are arranged with extremely thin gaps and whose surfaces are oriented. However, it is expensive because it requires a complicated configuration in combination with a polarizing plate and a retardation plate to visualize its optical changes. Is limited to. Therefore, without the need for such a complicated configuration,
There has been a demand for a composition whose optical characteristics can be changed by applying a voltage.

The present invention has been achieved as a result of research in view of these circumstances, and an object thereof is to provide a composition whose physical properties such as optical properties and viscosity properties can be changed by applying a voltage. Especially.

[0010]

SUMMARY OF THE INVENTION The above problems have 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 primary to quaternary ammonium). Salt) or CH
₂ SH) or formula (II),

[0011]

[Chemical 2]

(Wherein R _f is C _3x F _6x-1 , where x is an integer of 2 to 4 and y is an integer of 1 to 3);
The problem can be solved by providing an electrosensitive composition comprising an electrically insulating medium capable of dissolving the fluorine compound when a voltage is applied.

As described above, the electrosensitive composition of the present invention comprises a fluorine compound represented by the formula (I) or (II) and an electrically insulating medium capable of dissolving the fluorine compound when a voltage is applied. The composition comprises:

The compound of formula (I) is generally known as a fluorine-containing aliphatic compound. The compound is essentially composed of a fluorine-substituted alkyl chain and an end group having a dissociative polar functional group. In particular, in the compound of formula (I) used in the electrosensitive composition of the present invention, the fluorine-substituted alkyl chain has 3 to 30, preferably 3 to 20 continuous CF ₂ groups. Contains.
The terminal group having a dissociative polar functional group is a hydroxymethyl group, a carboxyl group, an alkali metal salt of a carboxyl group, a primary to quaternary ammonium salt, or a mercaptomethyl group.

Examples of such compounds include, for example, F (CF ₂ ) ₈ CH ₂ CH ₂ 0H; 2- (perfluorooctyl) ethanol F (CF ₂ ) ₁₀ CH ₂ CH ₂ 0H; 2- (perfluoro). Decyl) ethanol F (CF ₂ ) _2a CH ₂ CH ₂ 0H; Cm manufactured by Asahi Glass Co., Ltd.
Alcohol (a is a mixture of 3 to 8) F (CF ₂ ) ₉ CH ₂ 0H; perfluorononylmethanol H (CF ₂ ) ₈ CH ₂ 0H; 1H, 1H, 9H-hexadecafluorononanol H (CF ₂ ) ₈ CO0H; 9H-hexadecafluorononanoic acid F (CF ₂ ) ₇ CO0H; perfluorooctanoic acid F (CF ₂ ) ₁₇ C00H; perfluorostearic acid and the like. These compounds can be produced by known methods, and some of them are commercially available, and thus can be easily obtained.

The compounds of formula (II) are generally known as perfluoroalkylenooxy aromatic acids. In particular,
In the compound of formula (II) used in the electrosensitive composition of the present invention, the perfluoroalkylenooxy side chain has 6, 9 or 12 straight carbon atoms. Also, 1 to 3 carboxyl groups are bonded to the aromatic ring.

Examples of such compounds include, for example:

[0018]

[Chemical 3]

[0019]

[Chemical 4]

And so on. These compounds can be produced by known methods, and some of them are commercially available, and thus can be easily obtained.

The electrically insulative medium used in the present invention is an electrically insulative medium which can dissolve the above-mentioned fluorine compound when a voltage is applied. Such a medium has a property of solvating a polarized fluorine compound when a voltage is applied.
As a typical electrically insulating medium having a solvation effect,
Examples thereof include those having a group capable of being solvated by a hydrogen bond such as a methyl group or a methylene group.
The solvation effect is not limited to hydrogen bonding.

Examples of the electrically insulating medium which can be used in the present invention include silicone oil, sebacic acid esters, trimellitic acid esters, partially hydrogenated triphenyl, phosphazene oil, adipic acid esters and phthalic acid. Esters, aliphatic carboxylic acid esters such as vegetable oils, aliphatic hydrocarbons such as refined kerosene, alkyl-substituted aromatic hydrocarbons, halogen-substituted aliphatic or aromatic hydrocarbons, ethers, phosphazenes And the like, and each can be used alone or in admixture of two or more.

Among such electrically insulating media, for example, a mixture with a fluorine compound represented by the above formula (I) or formula (II) is solvated and becomes transparent in the state before voltage application. In this case, the electrically insulating medium used in the present invention can be obtained by mixing an electrically insulating medium having a low solvating power and adjusting the solvating force of the mixed medium.

Of these, particularly silicone oil is a preferable electric insulating medium from the viewpoints of electric insulating property, thermal stability, storage stability, non-hygroscopic property, non-corrosive property and easy availability.

The compounding ratio of the compound of formula (I) or formula (II) to the electrically insulating medium is not particularly limited, as long as the fluorine compound can be stably solubilized in the medium when a voltage is applied. It can be selected according to the degree of change in physical properties such as desired viscosity change and optical change. The compounding ratio of the compound of formula (I) or formula (II) to the electrically insulating medium is, for example, 0.1 to 35% by weight. Particularly, about 1 to 15% is preferable.

To prepare the electrosensitive composition of the present invention using the above-described electrically insulating medium and the compound of formula (I) or formula (II), simply mix the two and stir at room temperature. Good. In addition, in the electrosensitive composition of the present invention, a suitable stabilizer other than the fluorine compound and the electrically insulating medium,
Additives such as a dispersant, an antioxidant, a flame retardant, a heat stabilizer, an ultraviolet absorber, an antifoaming agent, an antifungal agent, and a coloring agent can also be mixed.

The composition of the present invention is homogeneous and cloudy when no voltage is applied. That is, in the composition in this state, the fluorine compound is uniformly dispersed in the electrically insulating medium to form a cloudy composition. The present inventors have found that when a voltage is applied to this composition, the composition becomes a homogeneous system containing no solid particles and changes to transparent, and some of them also increase its viscosity. Found and arrived at the present invention.

It is considered that this change is caused by the following mechanism, but the present invention is not restricted by such a theory. That is, in the state where no voltage is applied, the above-mentioned fluorine compound is dispersed as insoluble particles in the composition in the electrically insulating medium, so that it is light dispersible and the composition has low viscosity. When a voltage is applied to the composition, polarization of the fluorine compound is promoted by the action of an electric field generated between the electrodes, and the electrically insulating medium has a group capable of solvating the polarized fluorine compound in its molecule (for example, methyl group or methylene group). Group), the fluorine compound is solvated, becomes soluble in the electrically insulating medium, and the composition becomes transparent. In addition, they are coordinated with each other in the direction of the electric field by electrostatic attraction based on the polarization of the fluorine compound, or a solvation of the electrically insulating medium causes a network-like intermolecular force bond to resist external shear flow. Therefore, it is considered that the viscosity increases.

Therefore, when the electrosensitive composition of the present invention is inserted between the electrodes and a DC voltage is applied to the electrodes, its transparency and, in some cases, its viscosity change. This change is a change in which the transparency is improved by applying a voltage, and the viscosity is a change in which the viscosity is increased by applying a voltage. The applied voltage is not particularly limited, but is, for example, 0.1 to 10 KV / m.
m. Usually, application of 0.5 to 3 KV / mm is appropriate.

Some of the electrosensitive compositions of the present invention maintain their transparent state when the voltage is cut off in the transparent state by applying a voltage, for example, about 10 minutes to about 2 minutes.
Some of them return to a cloudy state after being left for 4 hours. Further, when the voltage is cut off in a transparent state by applying a voltage, when a shearing force is applied to the voltage, the cloudy state is immediately returned. These state changes depend on the type and blending ratio of the fluorine compound and the electrically insulating medium. Therefore, the electrosensitive composition of the present invention can be effectively used in various industrial fields depending on their selection.

The electro-sensitive composition of the present invention having the above-mentioned characteristics and containing no solid particles when a voltage is applied is, for example, an engine lubricating oil, a clutch fluid or a damper whose viscosity can be adjusted by applying a voltage. Material, shock absorber filling fluid, valve lubricating oil, actuator fluid, vibrator filling material, mechanical lubricating oil, printer ink, or for power transmission of equipment by electric control such as vibration element, for braking, or for lubricating oil etc. Expected to be used or applied. In addition, since the electrosensitive composition of the present invention can change the transparency by application of voltage or shearing force, it can be used as an optical shutter, an optical sensor, an optical switch, a light shielding material, a pressure sensor, a display, or the like. You can

[0032]

EXAMPLES Examples of the present invention will be described below. (Example 1) Silicone oil having a viscosity of 0.1 Pa · S at room temperature (TSF451-1 manufactured by Toshiba Silicone Co., Ltd.)
00) in F (CF ₂ ) ₈ CH ₂ CH ₂ OH (manufactured by Daikin Fine Chemicals Co., Ltd., A-1820, 2- (p
erfluorooctyl) ethanol) was evenly dispersed so that the content thereof was 5% by weight to obtain an electrosensitive composition of Example 1. This composition was cloudy. This composition was put in a double cylinder type rotational viscometer, and a DC voltage of 2 KV / mm was applied between the inner and outer cylinders at 25 ° C., a rotating force was applied to the inner cylinder electrode, and the transparency was visually observed while stirring the composition. It was measured. Further, by changing the rotational force of the inner cylinder electrode, the shear stress (Pa) at each shear rate (sec ^-1 ) and the current value (μA / cm ² ) between the inner and outer cylinders at the time of measuring the shear stress.
Was measured. The measurement results are shown in Table 1.

[0033]

[Table 1]

Example 2 F (C used in Example 1
F (CF ₂ ) ₇ COO instead of F ₂ ) ₈ CH ₂ CH ₂ OH
H (manufactured by Daikin Fine Chemicals Co., Ltd., C-
An electrosensitive composition of Example 2 was obtained in the same manner as in Example 1 except that 1700 perfluoroctanoic acid) was used. This composition was cloudy. The transparency of this composition when a voltage was applied, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 2.

[0035]

[Table 2]

Example 3 F (C used in Example 1
F ₂ ) ₈ CH ₂ CH ₂ OH instead of the formula,

[0037]

[Chemical 5]

An electrosensitive composition of Example 3 was obtained in the same manner as in Example 1 except that the compound (perfluoroalkylmonocarboxylic acid PFNA manufactured by Neos Co., Ltd.) was used. This composition was cloudy. 0.5 to this composition
KV / mm, 1.0KV / mm, 1.5KV / mm,
2. A DC voltage of OKV / mm was applied, and the transparency at that time, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 3.

[0039]

[Table 3]

Example 4 Instead of the silicone oil used in Example 3, dioctyl sebacate (R-00C (CH
_{2) 8 C00-R, R} = H (CH 2) 4 CH (C 2 H 5) CH
_2- , Kyowa Hakko Kogyo Co., Ltd., D0S bis (2-ethylhexyl sebacate)) was used in the same manner as in Example 3 to obtain an electrosensitive composition of Example 4. This composition was cloudy. 2.0 KV / mm of this composition
The transparency at the time of applying a DC voltage, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 4.

[0041]

[Table 4]

Example 5 F (C used in Example 1
F ₂ ) ₈ CH ₂ CH ₂ OH instead of the formula,

[0043]

[Chemical 6]

An electrosensitive composition of Example 5 was obtained in the same manner as in Example 1 except that the compound (perfluoroalkyldicarboxylic acid PFIP manufactured by Neos Co., Ltd.) was used. This composition was cloudy. 0.5K for this composition
V / mm, 1.0 KV / mm, 1.5 KV / mm, 2.
A DC voltage of 0 KV / mm was applied, and the transparency at that time, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 5.

[0045]

[Table 5]

Example 6 The F (C used in Example 1 was used.
F (CF ₂ ) ₉ CH ₂ instead of F ₂ ) ₈ CH ₂ CH ₂ OH
An electrosensitive composition of Example 6 was obtained in the same manner as in Example 1 except that OH (manufactured by Idemitsu Petrochemical Co., Ltd.) was used.
This composition was cloudy. The transparency of this composition when a voltage was applied, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 6.

[0047]

[Table 6]

Example 7 The F (C used in Example 1 was used.
F (CF ₂ ) ₁₇ CO instead of F ₂ ) ₈ CH ₂ CH ₂ OH
An electrosensitive composition of Example 7 was obtained in the same manner as in Example 1 except that OH (manufactured by Idemitsu Petrochemical Co., Ltd.) was used.
This composition was cloudy. The transparency of this composition when a voltage was applied, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 7.

[0049]

[Table 7]

Example 8 Instead of the silicone oil used in Example 7, dioctyl sebacate (R-00C (CH
_{2) 8 C00-R, R} = H (CH 2) 4 CH (C 2 H 5) CH
_2- , Kyowa Hakko Kogyo Co., Ltd., D0S bis (2-ethylhexyl sebacate)) was used in the same manner as in Example 7 to obtain the electrosensitive composition of Example 8. This composition was cloudy. 2.0 KV / mm of this composition
The transparency at the time of applying a DC voltage, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 8.

[0051]

[Table 8]

Example 9 F (C used in Example 1
F (CF ₂ ) ₁₀ CH ₂ instead of F ₂ ) ₈ CH ₂ CH ₂ OH
An electrosensitive composition of Example 9 was obtained in the same manner as in Example 1 except that CH ₂ OH (A-2020 2- (perfluorodecyl) ethanol manufactured by Daikin Fine Chemical Laboratory Co., Ltd.) was used. This composition was cloudy. The transparency of this composition when a voltage was applied, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 9.

[0053]

[Table 9]

Example 10 Instead of the silicone oil used in Example 9, phosphazene oil (manufactured by Otsuka Chemical Co., Ltd.,
An electrosensitive composition of Example 10 was obtained in the same manner as in Example 9 except that Ootsukaphosphalol NF-46) was used. This composition was cloudy. 2. of this composition
The transparency at the time of applying a 0 KV / mm DC voltage, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 10.

[0055]

[Table 10]

(Example 11) Instead of the silicone oil used in Example 9, dioctyl sebacate (R-00C (C
_{H 2) 8 C00-R,} R = H (CH 2) 4 CH (C 2 H 5) C
H ₂ -, Kyowa Hakko Kogyo Co., except for using D0S sebacic acid bis (2-ethylhexyl)) Example 9
An electrosensitive composition of Example 11 was obtained in the same manner as in.
This composition was cloudy. 2.0 KV / of this composition
In the same manner as in Example 1, the transparency at the time of applying a DC voltage, the shear stress at each shear rate, and the current value were measured. The results are shown in Table 1.
Shown in 1.

[0057]

[Table 11]

(Example 12) F (CF) used in Example l
₂ ) F (CF ₂ ) _2a CH ₂ C instead of ₈ CH ₂ CH ₂ OH
An electrosensitive composition of Example 12 was obtained in the same manner as in Example 1 except that H ₂ 0H (a is a mixture of an integer of 3 to 8 and Cm alcohol manufactured by Asahi Glass Co., Ltd.) was used. This composition was cloudy. The transparency of this composition when a voltage was applied, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 12.

[0059]

[Table 12]

Example 13 The F (CF) used in Example 1 was used.
₂ ) ₈ CH ₂ CH ₂ OH instead of H (CF ₂ ) ₈ CH ₂ 0
H (manufactured by Daikin Fine Chemicals Co., Ltd., A-
5810 1H, 1H, 9H-Hexadecafluorononanol) was used, and in the same manner as in Example 1, an electrosensitive composition of Example 13 was obtained. This composition was cloudy. The transparency of this composition when a voltage was applied, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 13.

[0061]

[Table 13]

Example 14 The F (CF) used in Example 1 was used.
₂ ) H (CF ₂ ) ₈ CO0H instead of ₈ CH ₂ CH ₂ OH
(C-5 manufactured by Daikin Fine Chemicals Co., Ltd.
The electrosensitive composition of Example 14 was obtained in the same manner as in Example 1 except that 800 9H-Hexadecafluorononanoic acid) was used. This composition was cloudy. The transparency of this composition when a voltage was applied, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 14.

[0063]

[Table 14]

Example 15 The same as Example 9 except that partially hydrogenated triphenyl oil (Therm S-900 manufactured by Nippon Steel Chemical Co., Ltd.) was used in place of the silicone oil used in Example 9. Thus, an electrosensitive composition of Example 15 was obtained. This composition was cloudy. 2. of this composition
The transparency at the time of applying a 0 KV / mm DC voltage, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 15.

[0065]

[Table 15]

Example 16 The same as Example 9 except that a completely fluorinated inert liquid (Sumitomo 3M, Fluorinert FC-43) was used in place of the silicone oil used in Example 9. Thus, the electrosensitive composition of Example 16 was obtained. This composition was cloudy. The transparency of this composition when a DC voltage of 2.0 KV / mm was applied, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 16.

[0067]

[Table 16]

Example 17 As Example 9 except that trimellitic acid ester oil (manufactured by Dainippon Ink and Chemicals, Inc., Monosizer W-700) was used in place of the silicone oil used in Example 9. Similarly, an electrosensitive composition of Example 17 was obtained. This composition was cloudy. The transparency of this composition when a DC voltage of 2.0 KV / mm was applied, the shear stress at each shear rate, and the current value were measured in the same manner as in Example 1. The results are shown in Table 17.

[0069]

[Table 17]

Example 18 5 parts by weight of dioctyl sebacate used in Example 4 and 95 parts by weight of phosphazene oil used in Example 10 were mixed to obtain a mixed electrically insulating medium.
F (CF ₂ ) ₇ CO0 used in Example 2 was added to this mixed medium.
H was uniformly dispersed so that the content of H was 5% by weight to obtain an electrosensitive composition of Example 18. Although this composition was translucent, it was cloudy. 1.5 of this composition
The composition was changed to a transparent state when it was placed between electrodes spaced by mm and a DC voltage of 2.0 KV / mm was applied and the transparency was visually observed.

(Comparative Example 1) F (C) used in Example 1
F (CF ₂ ) ₂ CH ₂ instead of F ₂ ) ₈ CH ₂ CH ₂ OH
OH (manufactured by Daikin Fine Chemicals Co., Ltd., A
-1210 2,2,3,3,3-Pentafluoropropanol) was used to obtain a composition of Comparative Example 1 in the same manner as in Example 1. _{F (CF 2) 2 CH 2} 0H is dissolved in the medium, the composition was clear. Transparency of this composition when a voltage is applied,
The shear stress and current value at each shear rate were measured in the same manner as in Example 1. The results are shown in Table 18.

[0072]

[Table 18]

From the above results, it is clear that the electrosensitive compositions of the present invention shown in Examples 1 to 18 change their optical characteristics and viscosity by the application of voltage. On the other hand, in the composition using the fluorine compound which is not included in the scope of the present invention as shown in Comparative Example 1, both are transparent before and after the voltage application and the transparency does not change, and the ER effect Was not recognized.

[0074]

The electrosensitive composition of the present invention has the formula (I)
Alternatively, since it comprises a fluorine compound represented by the formula (II) and an electrically insulating medium capable of dissolving the fluorine compound when a voltage is applied, it is a homogeneous system containing no solid particles when a voltage is applied, and There is an effect that optical characteristics and viscosity characteristics can be changed.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 7, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

Therefore, there has been a demand for a fluid composition which is a homogeneous system and whose viscosity can be changed in response to the application of a voltage.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

As described above, the electrosensitive composition of the present invention comprises a fluorine compound represented by the formula (I) or (II) and an electrically insulating medium capable of dissolving the fluorine compound when a voltage is applied. The composition comprises:
Here, “capable of being dissolved” means that the amount of the fluorine compound is small.
Even if part of it dissolves in the above electrically insulating medium when voltage is applied
Is possible, for example, when applying voltage
Part of the fluorine compound is highly concentrated around the electrode due to movement.
Including the case where it is gradually dissolved and locally insoluble
is there.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

The electrically insulative medium used in the present invention is electrically insulative and contains the above-mentioned fluorine compound when a voltage is applied.
It is a medium that can be dissolved at least in part . Such a medium has a property of solvating a polarized fluorine compound when a voltage is applied. Representative electrically insulating media having a solvating effect include those having a group capable of being solvated by a hydrogen bond , such as a methyl group or a methylene group. The sum effect is not limited to hydrogen bonding.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

The compounding ratio of the compound of formula (I) or formula (II) to the electrically insulating medium is not particularly limited, and the fluorine compound may be contained in the medium in a small amount when a voltage is applied.
As long as it can be partially dissolved, it can be selected depending on the desired degree of change in physical properties such as viscosity change and optical change. The compounding ratio of the compound of formula (I) or formula (II) to the electrically insulating medium is, for example, 0.1 to 35% by weight.
Is. Particularly, about 1 to 15% is preferable.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

The composition of the present invention is homogeneous and cloudy when no voltage is applied. That is, in the composition in this state, the fluorine compound is uniformly dispersed in the electrically insulating medium to form a cloudy composition. The present inventors have found that when a voltage is applied to this composition, the composition is at least partially
The present invention has been accomplished by finding that some of them change to be transparent and increase their viscosity.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

It is considered that this change is caused by the following mechanism, but the present invention is not restricted by such a theory. That is, in the state where no voltage is applied, the above-mentioned fluorine compound is dispersed as insoluble particles in the composition in the electrically insulating medium, so that it is light dispersible and the composition has low viscosity. When a voltage is applied to the composition, polarization of the fluorine compound is promoted by the action of an electric field generated between the electrodes, and the electrically insulating medium has a group capable of solvating the polarized fluorine compound in its molecule (for example, methyl group or methylene group). Group), the fluorine compound is solvated to increase the solubility in an electrically insulating medium,
The product is more transparent. Also , they are coordinated and aligned with each other in the electric field direction by electrostatic attraction due to polarization of the fluorine compound.
It is considered that the viscosity increases due to resistance to external shear flow due to the above.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

It has the above-mentioned characteristics and when a voltage is applied.
The electro-sensitive composition of the present invention having an increased viscosity is, for example, an engine lubricating oil, a clutch fluid, a damper material, a shock absorber filling fluid, a valve lubricating oil, an actuator fluid, a vibrator filling, the viscosity of which can be adjusted by applying a voltage. For power transmission of equipment by electric control such as material, mechanical lubricating oil, printer ink, or vibration element,
It is expected to be used or applied for braking or as a lubricating oil. In addition, since the electrosensitive composition of the present invention can change the transparency by application of voltage or shearing force, it can be used as an optical shutter, an optical sensor, an optical switch, a light shielding material, a pressure sensor, a display, or the like. You can

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0074

[Correction method] Change

[Correction content]

[0074]

The electrosensitive composition of the present invention has the formula (I)
Alternatively, since it is composed of a fluorine compound represented by the formula (II) and an electrically insulating medium capable of at least partially dissolving the fluorine compound when a voltage is applied,
There is an effect that optical characteristics and viscosity characteristics can be changed.

Claims (1)

[Claims] 1. Formula (I), R ₁ — (CF ₂ ) _n — (CH ₂ ) _m —R ₂ (wherein R ₁ is H, F, Cl, Br or I, and n is 3 to Is an integer of 30, m is an integer of 0 to 2, R ₂ is CH ₂ OH, COOH, COOM (M is an alkali metal or a primary to quaternary ammonium salt), or CH
₂ SH) or formula (II): (In the formula, R _f is C _3x F _6x-1 , where 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 the fluorine compound when a voltage is applied.