JP2003282982A - Polyurethane elastomer actuator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane elastomer actuator wherein the amount of transformation is large in the case that a driving voltage is a low voltage of at most 1 kV. <P>SOLUTION: This polyurethane elastomer actuator has a characteristic wherein a polyurethane elastomer layer which can be transformed by orientation of an electric field is installed, and a fullerenol is introduced in a polyurethane elastomer constituting the polyurethane elastomer layer. By difference between film thicknesses of both electrode layers arranged on both sides of the polyurethane elastomer layer or difference between electrode metals constituting both of the electrodes, flexing displacement and its direction can be controlled. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low electric field drive actuator based on the electrostrictive effect of a fullerenol-introduced polyurethane elastomer.

[0002]

2. Description of the Related Art Conventionally, polyurethane elastomer actuators have been characterized not by a driving method in a solvent but by driving in the atmosphere by applying an electric field.
The drive voltage of an actuator made of ceramics or polymer materials requires a high voltage of about several tens of kV, whereas the polyurethane elastomer actuator has several kV.
It is also characterized by having a large bending displacement at a relatively low voltage of V.

However, from the viewpoint of practical use, the polyurethane elastomer actuator needs to be driven at a low voltage of 1 kV or less like a polymer gel actuator or a mechanochemical element using a conductive polymer. Becomes

[0004]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a polyurethane elastomer actuator having a large amount of deformation even when the driving voltage is a low voltage of 1 kV or less.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that polyurethane elastomers in which fullerenol is used as a curing agent are introduced into polyurethane elastomers that can be deformed by electric field orientation. The present invention has been completed by finding that the actuator can be effectively driven even at a low voltage of 1 kV or less.

That is, the present invention is a polyurethane elastomer actuator comprising a polyurethane elastomer layer which can be deformed by electric field orientation, wherein fullerenol is introduced into the polyurethane elastomer constituting the polyurethane elastomer layer. Is a polyurethane elastomer actuator.

The bending displacement and its direction can be controlled by the difference in the film thickness of the two electrode layers provided on both sides of the polyurethane elastomer layer or the difference in the electrode metal forming the two electrode layers.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION [Polyurethane Elastomer Actuator] The polyurethane elastomer actuator of the present invention comprises a polyurethane elastomer layer which is deformable by electric field orientation, and the polyurethane elastomer layer is polyurethane which is deformable by electric field orientation. It is formed of a fullerenol-introduced polyurethane elastomer in which fullerenol is introduced into the elastomer. Therefore, the polyurethane elastomer actuator has a large bending displacement and can be effectively and effectively driven even at a low voltage of 1 kV or less (preferably 800 V or less, more preferably 500 V or less). This is because the fullerenol has a hydroxyl group formed in a star shape, so that the polymer chains forming the polyurethane elastomer are sterically (three-dimensionally) crosslinked by the star hydroxyl group. It seems that the tensile strength is increased. Specifically, by introducing fullerenol into the polyurethane elastomer, the crosslinking of the polyurethane elastomer is promoted, the density of the three-dimensional network structure is increased, and the interaction between the molecular chains of the polyurethane elastomer is strengthened,
It is considered that the conformational change of the molecular chain with respect to the voltage becomes larger. This is because the star-like fullerenol restrains the molecular group of the dielectric polyol component or the polyol component having a relatively strong polar group (or dipole moment) that constitutes the strongly crosslinked polyurethane elastomer. It is considered that the application of an electric field leads to a large movement of the molecular chain and can drive even a low electric field.

Examples of polyurethane elastomers containing fullerenol include, for example, Japanese Patent No. 3026066.
JP-A-7-240544 and JP-A-8-3
35726, JP-A-2000-101159, JP-A-2000-101160, and JP-A-2000.
-49397 gazette etc. using polyisocyanate (especially organic polyisocyanate) as a raw material of a polyurethane elastomer, a polyol (especially high molecular weight polyol), and a chain extender as needed, and using fullerenol as a hardening agent. It can be prepared by Specifically, for the polyurethane elastomer, for example, a method in which a polyisocyanate and a polyol are reacted by a conventionally known method and then a chain extender or the like is reacted therewith, or the above-mentioned components (polyisocyanate, polyol, chain extension) are used. It can be prepared by preparing a urethane prepolymer by a so-called one-shot method in which agents and the like) are simultaneously reacted in a predetermined ratio, and then adding fullerenol to carry out a reaction (particularly a curing reaction).

In the urethane prepolymer, the ratio of polyisocyanate to polyol (NCO / OH) is
It is preferably in the range of 1.5 to 9 (molar ratio).

(Polyisocyanate) The polyisocyanate may be one having two or more isocyanate groups in the molecule, and examples thereof include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate and 2,4. , 4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,
3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6- Cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5
-Naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-
Toluidine diisocyanate, dianidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 1,3-xylylene diisocyanate, ω, ω′-
Diisocyanate-1,4-diethylbenzene, polymethylene polyfernyl polyisocyanate, and isocyanurate-modified products of these polyisocyanates,
Examples include carbodiimide-modified products and burette-modified products. The polyisocyanates may be used alone or in combination of two or more.

As the (polyol) polyol, polymer polyols such as polyester-based polyols, polyether-based polyols, polycarbonate-based polyols and polybutadiene-based polyols can be preferably used. The polyols may be used alone or in combination of two or more. In addition, as the polymer polyol,
It is also possible to use a polymer polyol obtained by appropriately blending these exemplified polymer polyols with a polyolefin polyol.
The polyols may be used alone or in combination of two or more.

The polyester-based polyol is, for example, a condensate of polycarboxylic acid and low-molecular polyol,
Some have a weight average molecular weight of 500 to 10,000. Specifically, poly (ethylene adipate) (“PEA”),
Poly (diethylene adipate) (“PDA”), Poly (propylene adipate) (“PPA”), Poly (tetramethylene adipate) (“PBA”), Poly (hexamethylene adipate) (“PHA”), Poly (neopene pliers) Renadipate) (“PNA”), 3-methyl-1,
Polyol consisting of 5-pentanediol and adipic acid, random copolymer of PEA and PDA, PEA and PP
A random copolymer of A, a random copolymer of PEA and PBA, a random copolymer of PHA and PNA, or a caprolactone polyol obtained by ring-opening polymerization of ε-caprolactone, β-methyl-δ-valerolactone is ethylene. Polyol and the like obtained by ring-opening with glycol (all of these have a weight average molecular weight of 500 to 100).
00 is preferable). Each component (polycarboxylic acid, low molecular weight polyol, etc.) for preparing the polyester-based polyol can be used alone or in combination. Further, examples of the polyester-based polyol include a copolymer of at least one acid component of the following acid components and at least one glycol component of the glycol components.

Acid component: terephthalic acid, isophthalic acid, phthalic anhydride, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid (mixture), paraoxybenzoic acid, trimellitic acid anhydride, ε-caprolactone , Β-methyl-δ valerolactone.

Glycol component: ethylene glycol, propylene glycol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 2,
2-dimethyl-1,3-propanediol, 1,9-nonanediol, methyloctanediol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, 1,4-cyclohexanedimethanol, pentaerythritol, 3-methyl-1. , 5-pentanediol.

As the polyether polyol, for example, an alkylene oxide (eg, ethylene oxide, propylene oxide, etc.) can be obtained by ring-opening addition polymerization using a polyhydric alcohol (eg, diethylene glycol) which is an active hydrogen compound as an initiator. it can. Specifically, polyether-based polyols include, for example, polytetramethylene glycol (“PTMG”), polypropylene glycol (“PPG”), polyethylene glycol (“PEG”), polyoxymethylene, propylene oxide and ethylene oxide. And copolymers thereof are included. Further, the polyether polyol may be one prepared by cationic polymerization of tetrahydrofuran and having a weight average molecular weight of 500 to 5,000.
Specifically, polytetramethylene ether glycol (“PTMG”), which is a homopolymer of tetrahydrofuran.
Examples of tetrahydrofuran include copolymers with alkylene oxides (for example, copolymers of tetrahydrofuran and propylene oxide, copolymers of tetrahydrofuran and ethylene oxide, etc.). The weight average molecular weight of each of these polyether polyols is preferably 500 to 10,000. Each component (such as alkylene oxide) for preparing the polyether polyol can be used alone or in combination.

As the polycarbonate-based polyol,
Conventionally known polyol (polyhydric alcohol) and phosgene,
Obtained by condensation with chloroformic acid ester, dialkyl carbonate or diallyl carbonate, various molecular weights are known. Particularly preferred as such a polycarbonate-based polyol is one using 1,6-hexanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, or 1,5-pentanediol as the polyol. And its weight average molecular weight is in the range of about 500 to 10,000. Examples of the polycarbonate-based polyol include poly (hexanediol carbonate),
Examples thereof include poly (nonane diol carbonate). Each component for preparing the polycarbonate-based polyol can be used alone or in combination.

As the polybutadiene-based polyol, a hydroxyl group-containing liquid diene-based polymer can be used. As the hydroxyl group-containing liquid diene polymer, weight average molecular weight: 600 to 3000, average number of hydroxyl groups (number of functional groups):
It is preferably 1.7 to 3.0, for example, having 4 to 4 carbon atoms.
Polymers or copolymers of 12 diene components, and further copolymers of these diene components (monomers) and copolymerizable monomers (for example, C2-22 itch-olefinic addition polymerizable monomers) The butadiene-based polymer may be modified to have a hydroxyl group at the terminal.
Specifically, as the polybutadiene-based polyol, butadiene homopolymer, isoprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, etc. Examples of the butadiene-based polymer of 1 are modified with a hydroxyl group at the terminal. Of these hydroxyl group-containing liquid diene polymers, the liquid diene polymer can be produced, for example, by reacting a conjugated diene monomer in a liquid reaction medium by heating in the presence of hydrogen peroxide.

As the polyol used as the raw material for the polyurethane elastomer, a polyolefin polyol obtained by hydrogenating the hydroxyl group-containing liquid diene polymer (saturated double bond) may be used.

(Chain extender) As a chain extender, any chain extender may be used, as long as it is generally used when the urethane prepolymer is chain extended. Examples of the chain extender include low molecular weight polyol compounds and polyamine compounds. The chain extender may be used alone or in combination of two or more. As the low molecular weight polyol compound as a chain extender, primary polyol, secondary polyol, 3
Any of the class polyols may be used, but the diols are preferred. Specifically, low molecular weight polyol compounds include trimethylolpropane (“TMP”), ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 2,5-hexane Diol, 2,4-hexanediol, 2-ethyl-
1,3-hexanediol, cyclohexanediol,
2-ethyl-2- (hydroxymethyl) -1,3-propanediol and the like can be mentioned. Further, as the polyamine compound, diamine, triamine, tetraamine, etc., 1
Any of primary amine, secondary amine, and tertiary amine can be used. Specifically, as the polyamine compound, an aliphatic amine such as hexamethylenediamine,
Alicyclic amines such as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis-2-chloroaniline, 2,2 ', 3,3'-tetrachloro-4,4 ′ -Diaminophenylmethane, 4,4′-
Examples include aromatic amines such as diaminodiphenyl, 2,4,6-tris (dimethylaminomethyl) phenol, and the like. As the chain extender, low molecular weight polyol compounds (particularly diols) are suitable.

In the present invention, as a method for mixing the urethane prepolymer and the chain extender to extend the chain of the urethane prepolymer, the mixing ratio of the chain extender to the urethane prepolymer, the reaction temperature, It can be carried out by a known method including the reaction time and the like.

(Fullerenol) Fullerenol
ol) is a fullerene (C ₆₀ ) into which a hydroxyl group has been introduced, and the hydroxyl group is usually introduced into the fullerene in a star-like form. The number of hydroxyl groups in fullerenol is not particularly limited, but is preferably 2 or more (for example, 2 to 20) per molecule. In the present invention, the fullerenol is 1
It preferably has 5 to 18 hydroxyl groups per molecule, and more preferably 8 to 15 (particularly 10 to 1).
It is preferable to have the hydroxyl group of 2).
The site in which the hydroxyl group is introduced in fullerene is not particularly limited.

The fullerenol can be used alone or in combination of two or more kinds.

Such fullerenol is obtained, for example, by adding sulfuric acid (especially fuming sulfuric acid) to fullerene to carry out a sulfonation reaction to obtain a sulfonated fullerene, and further hydrolyzing the sulfonated fullerene. It can be prepared. Specifically, in the sulfonation reaction, the ratio of fullerene to fuming sulfuric acid can be selected from the range of about 15 ml of fuming sulfuric acid to 1 g of fullerene. The sulfonation reaction time is 1
~ 4 weeks can be selected. On the other hand, the hydrolysis reaction time can be selected from the range of 1 to 3 days.

(Additive) The polyurethane elastomer is
It may contain various additives and the like. Examples of such additives include plasticizers, flame retardants, fillers, stabilizers,
Colorants and the like can be mentioned. As the plasticizer, a nonionic plasticizer is preferable. Specifically, examples of the plasticizer include dioctyl phthalate (“DOP”), dibutyl phthalate (“DBP”), dioctyl adipate (“DO”).
A "), triethylene glycol dibenzoate, tricresyl phosphate, dioctyl phthalate, fatty acid ester of pentaerythritol, dioctyl sebacate,
Diisooctyl azelate, dibutoxyethoxyethyl adipate and the like can be used.

[Fullerenol-Introduced Polyurethane Elastomer] In the present invention, it is sufficient that fullerenol is introduced into the polyurethane elastomer. For example, fullerenol can be introduced into the polyurethane elastomer by using it as a curing agent. That is, as described above, the urethane prepolymer can be reacted with fullerenol to prepare a fullerenol-introduced polyurethane elastomer. The proportion of fullerenol is 0.05 to 2% by weight (preferably 0.08 to 1% by weight, more preferably 0.1%) based on the total amount of urethane prepolymer (solid content).
˜0.5 wt%). Even if the proportion of fullerenol is less than 0.05% by weight based on the total amount of urethane prepolymer (solid content), it is 2
Even if it exceeds the weight%, the drivability at low voltage is lowered.

The fullerenol-introduced polyurethane elastomer can be used alone or in combination of two or more kinds.

The method for producing the fullerenol-introduced polyurethane elastomer by reacting the urethane prepolymer with fullerenol is not particularly limited, and for example, a mixture of the urethane prepolymer and fullerenol is heated to give the urethane prepolymer. And a fullerenol are reacted with each other. The reaction temperature is, for example, 80 to 150.
It can be selected from the range of about 0 ° C (preferably 85 to 100 ° C). The reaction time is, for example, 3
It can be selected from the range of about 0 minutes to 2 hours (preferably 1 hour 30 minutes to 2 hours).

In the present invention, as the curing agent, a curing agent known or commonly used as a curing agent for polyurethane or polyurethane elastomer can be used together with the fullerenol. As such a known or commonly used curing agent, a low molecular weight polyol compound, polyamine compound or the like exemplified in the section of the chain extender can be used.

[Method of Manufacturing Actuator] The polyurethane elastomer actuator of the present invention (that is,
As a method for producing a polyurethane elastomer actuator including a fullerenol-introduced polyurethane elastomer, for example, Japanese Patent No. 3026066, Japanese Patent Laid-Open No. 7-240544, Japanese Patent Laid-Open No. 8-335726, Japanese Patent Laid-Open No. 2000-101159, Open 200
The same method for producing a polyurethane elastomer / actuator as the “method for producing a polyurethane elastomer / actuator” described in JP-A No. 0-101160, JP-A No. 2000-49397, etc. can be adopted. Specifically, for example, the fullerenol-introduced polyurethane elastomer is formed into a film, a sheet (thickness: about 0.01 to 1 mm) or a thin film. In this molding method, when a release agent is used,
After molding, the release agent can be removed. It should be noted that removal of the mold release agent of the molded polyurethane elastomer is sufficient by removing it by usual wet cleaning, but for example, as surface modification for applying electrodes, ion treatment such as plasma treatment by glow discharge or corona discharge treatment is performed. -It is preferable to remove impurities such as a release agent using ozone, electrons or ultraviolet rays.

A polyurethane elastomer actuator can be produced by forming electrodes on both sides of the film-shaped, sheet-shaped or thin-film fullerenol-introduced polyurethane elastomer. The material of the electrode for shrinking the fullerenol-introduced polyurethane elastomer by electric field orientation is, for example, gold,
In addition to metal compounds such as metals and alloys of platinum, aluminum, metal indium, indium oxide, stannic oxide, ITO, silver, etc., conductive resins such as polyaniline and elastomer rubber, carbon, etc. can be used. Further, a conductive resin or conductive elastomer in which a metal compound such as gold or platinum is dispersed in a resin can also be used. As a method of forming the electrodes, for example, an ion plating method, a plasma CVD method, an ion sputter coating method, a vacuum vapor deposition method, a screen printing, an ion beam assist method, an ionization vapor deposition method, or the like can be adopted.

It is preferable that the rigidity and the expansion / contraction characteristics of the electrode itself are at a low level that does not affect the physical properties of the fullerenol-introduced polyurethane elastomer. The thickness of the electrode applied to the fullerenol-introduced polyurethane elastomer varies depending on the electrode material, the type of urethane elastomer or the film thickness (film thickness or sheet thickness) of the fullerenol-introduced polyurethane elastomer.
It is preferably about 0.05 to 10 μm.

In the present invention, the fullerenol-introduced polyurethane elastomer actuator can also function as a means for elastically restoring the electrode.
The pitch lines are shifted by making the thicknesses of both electrodes different. That is, since the bending displacement and the bending displacement can be expressed by the rigidity pitch line in the thickness direction of the fullerenol-introduced polyurethane elastomer being slightly displaced from the thickness center, the electrode thicknesses are controlled between each other in such a manner. is there. Simply, the pitch lines may be offset by coating or sheeting one side of the electrode with some elastomeric material. This elastomer material is preferably a material having good insulation and a low dielectric constant.

When the polyurethane elastomer actuator of the present invention (that is, the fullerenol-introduced polyurethane elastomer actuator) is laminated, the driving force at the time of expansion is expanded by the number of laminated layers. Thermoplastic materials are preferred as the elastomeric material.

Examples of the material of the elastic restoring layer include polyurethane, polyester, polyamide, acrylonitrile, butyl rubber, coumaroindene resin, epoxy resin,
Cyclized rubber, chloroprene rubber, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, silicone, styrene rubber, vinyl chloride copolymer resin, polyvinyl acetal and the like can be used. It may be a solution type such as a solvent or a water dispersion system, or a solid substance. Solvents and emulsions are preferable for reducing the film thickness.

The thickness of the elastic recovery layer formed on the polyurethane elastomer varies depending on the material thereof, the type of the urethane elastomer or the film thickness of the fullerenol-introduced polyurethane elastomer, but is preferably about 0.1 to 20 μm. Further, it is preferably about 0.1 to 100% of the thickness of the main body.

In the fullerenol-introduced polyurethane elastomer actuator of the present invention, the bending displacement and the contracting displacement occur continuously and linearly by the electric field, and the generated force and the amount of deformation can be linearly controlled by the electric field. In particular, even if the driving voltage is a low voltage of 1 kV or less, the amount of deformation is large (in particular, larger than that of the conventional polyurethane elastomer actuator), and it is possible to drive at a low voltage of 1 kV or less.

[0038]

According to the polyurethane elastomer actuator of the present invention, the amount of deformation is large even when the driving voltage is a low voltage of 1 kV or less. Therefore, it is extremely useful as an actuator.

[0039]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(Preparation Example 1 of Fullerenol) Fullerene 3
g and 45 ml of fuming sulfuric acid are mixed and stirred at 67 ° C. for 1 to 4 weeks to carry out a sulfonation reaction, and then distilled water is added and stirred at 85 ° C. for 3 days to carry out a hydrolysis reaction. The number of hydroxyl groups introduced into the molecule differs depending on
A seed fullerenol was prepared. That is, fullerenol having a large number of hydroxyl groups (sometimes referred to as "OHrich fullerenol") and fullerenol having a small number of hydroxyl groups (sometimes referred to as "OHpoor fullerenol")
And were prepared.

(Example 1) Poly-3 methyl-1,5-pentane adipate polyol having an average molecular weight of 2,945 (PMPA, manufactured by Kuraray Co., Ltd., trade name "Kurapol P"
3010 "), and 10.8 parts by weight of paraphenylene diisocyanate (PPDI, manufactured by DuPont, trade name" HIREN ") to 100 parts by weight, and under a nitrogen stream,
The reaction was carried out at 5 ° C for 2 hours to obtain a urethane prepolymer having a terminal isocyanate group.

OHrich fullerenol obtained in Preparation Example 1 of the fullerenol was added to the urethane prepolymer in an amount of 0.1 to 0.5% by weight (specifically, 0% by weight) based on the total amount of the urethane prepolymer (solid content). .1% by weight,
0.15% by weight, 0.2% by weight, 0.25% by weight, 0.
7% (3% by weight, 0.4% by weight, 0.5% by weight), added and mixed, and then poured into a mold having a thickness of 0.2 mm and kept at 110 ° C in advance. , 110 ° C
The amount of OHrich fullerenol introduced varies depending on the curing reaction by leaving it in the oven for 24 hours.
Various types of fullerenol-introduced polyurethane elastomers were prepared. The fullerenol-introduced polyurethane elastomer may be collectively referred to as "fullerenol-introduced polyurethane elastomer A".

The above seven types of fullerenol-introduced polyurethane elastomers A were respectively cast by the casting method.
It was molded into a film having a thickness of 200 μm to prepare a film-like fullerenol-introduced polyurethane elastomer A. Then, a gold electrode layer (thickness: 0.
(1 to 0.5 μm) was subjected to discharge treatment on the film surface by a high frequency corona, and then formed by an ion assisted vapor deposition method to prepare a unimorph type fullerenol-introduced polyurethane elastomer actuator. In addition, this fullerenol-introduced polyurethane elastomer
The actuator may be collectively referred to as "fullerenol-introduced polyurethane elastomer actuator A".

(Example 2) OHr as fullerenol
In the same manner as in Example 1, except that OHpoor fullerenol was used in place of ich fullerenol, and the addition concentration of OHpoor fullerenol was 0.25% by weight based on the total amount of the urethane prepolymer, OHpoor fullerenol was used as the urethane prepolymer. 0.2 for the total amount
Fullerenol-introduced polyurethane elastomer introduced at a ratio of 5% by weight (may be referred to as "0.25% fullerenol-introduced polyurethane elastomer B")
Was produced. Then, in the same manner as in Example 1 except that the fullerenol-introduced polyurethane elastomer A was replaced by the fullerenol-introduced polyurethane elastomer B, a fullerenol-introduced polyurethane elastomer / actuator (when referred to as “fullerenol-introduced polyurethane elastomer / actuator B”) There is).

(Comparative Example 1) Poly-3 methyl-1,5-pentane adipate polyol having an average molecular weight of 2,945 (PMPA, manufactured by Kuraray Co., Ltd., trade name "Kurapol P"
3010 "), and 10.8 parts by weight of paraphenylene diisocyanate (PPDI, manufactured by DuPont, trade name" HIREN ") to 100 parts by weight, and under a nitrogen stream,
The reaction was carried out at 5 ° C for 2 hours to obtain a urethane prepolymer having a terminal isocyanate group. To 100 parts by weight of this urethane prepolymer, 1.0 part by weight of 1,2-propanediol (manufactured by Kanto Chemical Co., Ltd.) and 1.4 parts by weight of trimethylolpropane (manufactured by Kanto Chemical Co., Ltd.) were melted and mixed in advance. A polyurethane elastomer (sometimes referred to as "additive-free polyurethane elastomer C") is poured into a mold having a thickness of 0.2 mm which has been kept at 110 ° C and left in an oven at 110 ° C for 16 hours for curing reaction.
Was prepared.

Then, in place of the fullerenol-introduced polyurethane elastomer A, an additive-free polyurethane elastomer C was used, and in the same manner as in Example 1, a polyurethane elastomer actuator (hereinafter referred to as "additive-free polyurethane elastomer actuator C") was used. In some cases).

Comparative Example 2 A polyurethane elastomer in which fullerene is dispersed by mixing additive-free polyurethane elastomer C prepared in the same manner as in Comparative Example 1 with fullerene (referred to as "fullerene-dispersed polyurethane elastomer D"). In some cases). And
A polyurethane elastomer / actuator (which may be referred to as “fullerene-dispersed polyurethane elastomer / actuator D”) was obtained in the same manner as in Example 1 except that the fullerene-dispersed polyurethane elastomer A was used instead of the fullerenol-introduced polyurethane elastomer A. It was made.

(Evaluation of flexural displacement characteristics by introducing fullerenol) In Example 1, OHrich fullerenol was added in an amount of 0.25% by weight based on the total amount of the urethane prepolymer.
The fullerenol-introduced polyurethane elastomer actuator A ("0.25% fullerenol-introduced polyurethane elastomer A") prepared by adding the fullerenol-introduced polyurethane elastomer (may be referred to as "0.25% fullerenol-introduced polyurethane elastomer A") "Introduced polyurethane elastomer / actuator A"), additive-free polyurethane elastomer / actuator C prepared in Comparative Example 1, and Comparative Example 2
The flexural displacement characteristics of the fullerene-dispersed polyurethane elastomer / actuator D manufactured by the above were evaluated, and the measurement results are shown in FIG.

Specifically, the lower end of each polyurethane elastomer actuator was fixed, and when a voltage was applied to both electrodes, the amount of displacement that was curved in the vertical direction due to its own weight on the upper end side was measured. Then, a graph of the relationship between the electric field strength (kV / cm) of the applied voltage and the displacement amount (mm) is shown in FIG. In addition, it took about 0.5 seconds from the application of the electric field to the end of the extension, and when the application of the electric field was released, the original shape was quickly restored.

From the graph of the relationship between the electric field strength (kV / cm) and the amount of displacement (mm) shown in FIG. 1, the 0.25% fullerenol-introduced polyurethane elastomer actuator A is similar to the additive-free polyurethane elastomer actuator C. In addition, the amount of displacement increases in proportion to the square of the applied voltage, and the bending displacement is 0.25% fullerenol-introduced polyurethane elastomer actuator A.
Is larger under a low electric field. Further, the fullerene-dispersed polyurethane elastomer / actuator D in which the fullerene is simply dispersed in the polyurethane elastomer has a smaller bending displacement than the additive-free polyurethane elastomer / actuator C.

Therefore, by introducing fullerenol into the polyurethane elastomer, as shown in the graph of FIG. 1, the bending of the actuator (the 0.25% fullerenol-introduced polyurethane elastomer actuator A) by the polyurethane elastomer into which fullerenol has been introduced. The displacement occurs even at a low voltage of about 400 V, and the displacement occurs at a lower voltage than the actuator using a polyurethane elastomer in which fullerenol is not introduced into the polyurethane elastomer (non-added polyurethane elastomer / actuator C). This is because the introduction of fullerenol (particularly, fullerenol having a droxyl group introduced into a star) into the polyurethane elastomer promotes cross-linking between the molecular chains (polymer chains) of the polyurethane elastomer and increases the density of the three-dimensional network structure. It is considered that the conformation of the polyurethane elastomer molecular chain group is more likely to occur even at a low voltage due to the increase in the value, and the bending is shifted to the lower voltage side. This means that an actuator made of polyurethane elastomer in which fullerene is simply dispersed in polyurethane elastomer (fullerene-dispersed polyurethane elastomer / actuator D) is an actuator made of polyurethane elastomer in which fullerene is not introduced into polyurethane elastomer (additive-free polyurethane elastomer
It is also clear from the fact that the bending displacement is considerably smaller than that of the actuator C).

(Evaluation of flexural displacement characteristics by varying fullerenol concentration) The amount of fullerenol obtained in Example 1 was different (0.1 with respect to the total amount of urethane prepolymer).
0.5% by weight) For the fullerenol-introduced polyurethane elastomer A, the flexural displacement was measured when a voltage of 1 kV (electric field strength of 40 kV / cm) was applied, and the concentration of fullerenol when the applied voltage was kept constant at 1 kV. A graph showing the relationship between (wt%) and the displacement amount (mm) of the fullerenol-introduced polyurethane elastomer is shown in FIG.

From the graph of the relationship between the fullerenol concentration (% by weight) and the displacement amount (mm) of the fullerenol-introduced polyurethane elastomer when the applied voltage was kept constant at 1 kV, as shown in FIG. The displacement of the fullerenol-introduced polyurethane elastomer / actuator increases, and the fullerenol-introduced polyurethane elastomer / actuator (0.25% fullerenol-introduced polyurethane elastomer / actuator A) has the largest bending when the addition concentration of fullerenol is 0.25% by weight. It was confirmed that it showed displacement.

Therefore, it was confirmed that in the fullerenol-introduced polyurethane elastomer actuator by the fullerenol-introduced polyurethane elastomer, the actuation function can be arbitrarily controlled by the concentration of fullerenol added.

(Evaluation of flexural displacement characteristics based on the number of hydroxyl groups introduced into fullerenol) In Example 1, OHric
A fullerenol-introduced polyurethane elastomer prepared by using a fullerenol-introduced polyurethane elastomer (0.25% fullerenol-introduced polyurethane elastomer A) prepared by adding h fullerenol in a proportion of 0.25% by weight based on the total amount of the urethane prepolymer. Actuator A (0.25% fullerenol-introduced polyurethane elastomer / actuator A) and fullerenol-introduced polyurethane elastomer obtained in Example 2
Regarding the actuator B and the fullerene-dispersed polyurethane elastomer / actuator D obtained in Comparative Example 2, the bending displacement amount when a voltage was applied was measured to evaluate the bending displacement characteristics, and the electric field strength (kV / c) of the applied voltage was measured.
A graph of the relationship between m) and the amount of displacement (mm) is shown in FIG.

From the graph of the relationship between the electric field strength (kV / cm) and the displacement amount (mm) shown in FIG. 3, a fullerenol-introduced polyurethane elastomer (furrichenol) having a large number of hydroxyl groups in the molecule (OHrich fullerenol) is used. The 0.25% fullerenol-introduced polyurethane elastomer A) uses a fullerenol-introduced polyurethane elastomer (OHpoor fullerenol) having a smaller number of hydroxyl groups in the molecule (0.25%
It was confirmed that the displacement amount was larger at each applied voltage than in the fullerenol-introduced polyurethane elastomer B). Further, in the fullerene-dispersed polyurethane elastomer / actuator D in which the polyurethane elastomer in which the fullerene is simply dispersed is used, almost no flexural displacement occurs in a low electric field. Therefore, fullerenol having a hydroxyl group in a star shape is It is clear that it contributes to a large bending displacement by increasing the crosslink density between the molecular chains of the polyurethane elastomer.

(Evaluation of Actuator Generation Force) The thickness of the 0.25% fullerenol-introduced polyurethane elastomer A layer obtained in Example 1 was 200 μm 0.2.
5% fullerenol-introduced polyurethane elastomer actuator A, and the addition amount of fullerenol was 0.25% by weight and 0.2 with respect to the total amount of the urethane prepolymer.
A fullerenol-introduced polyurethane elastomer actuator using the 0.25 fullerenol-introduced polyurethane elastomer A obtained in the same manner as in Example 1 except that the thickness of the 5% fullerenol-introduced polyurethane elastomer A layer was 400 μm. Introduction Polyurethane Elastomer / Actuator A-
1 "), and the force generated by the actuator was evaluated. Specifically, a weight is attached to the tip of each actuator (0.25% fullerenol-introduced polyurethane elastomer / actuator A, 0.25% fullerenol-introduced polyurethane elastomer / actuator A-1) and each weight required for bending 5 mm ( mg)
To the electric field strength (kV / cm) was measured, and a graph of the relationship between the load (mg) and the electric field strength (kV / cm) is shown in FIG.

From the graph of the relationship between load (mg) and electric field strength (kV / cm) shown in FIG. 4, 0.25% fullerenol-introduced polyurethane elastomer actuator A and 0.25% fullerenol-introduced polyurethane elastomer actuator A For both -1 actuators, the load and the electric field strength are in a proportional relationship, and
The 0.25% fullerenol-introduced polyurethane elastomer A layer having a thickness of 200 μm is 0.25% fullerenol-introduced polyurethane elastomer / actuator A. It was confirmed that the thickness was larger than that of the 0.25% fullerenol-introduced polyurethane elastomer actuator A-1 having a thickness of 400 μm.

(Evaluation of Force Generated by Actuator under Constant Load) The thickness of the 0.25% fullerenol-introduced polyurethane elastomer A layer obtained in Example 1 was 200 μm.
m 0.25% fullerenol-introduced polyurethane elastomer actuator A, the addition amount of fullerenol is 0.25% by weight based on the total amount of urethane prepolymer, and the thickness of the 0.25% fullerenol-introduced polyurethane elastomer A layer is 400 μm. Except that the 0.25% fullerenol-introduced polyurethane elastomer A obtained in the same manner as in Example 1 was used.
25% fullerenol-introduced polyurethane elastomer / actuator A-1 "), and the amount of fullerenol added is 0.25% by weight based on the total amount of the urethane prepolymer and 0.25% fullerenol-introduced polyurethane elastomer A layer. Of 0.2 was obtained in the same manner as in Example 1 except that the thickness was 100 μm.
With respect to the fullerenol-introduced polyurethane elastomer actuator (may be referred to as "0.25% fullerenol-introduced polyurethane elastomer actuator A-2") using 5% fullerenol-introduced polyurethane elastomer A, the generation force of the actuator at a load of 200 mg was evaluated. Specifically, each actuator (0.25% fullerenol-introduced polyurethane elastomer / actuator A, 0.25% fullerenol-introduced polyurethane elastomer / actuator A-1,
A bending displacement characteristic was evaluated by measuring a bending displacement amount when a voltage of 200 mg was applied to the tip of a 0.25% fullerenol-introduced polyurethane elastomer / actuator A-2), and the bending displacement characteristics were evaluated. A graph of the relationship between the strength (kV / cm) and the displacement amount (mm) is shown in FIG.

From the graph of the relationship between the electric field strength (kV / cm) of the applied voltage and the displacement amount (mm) at a load of 200 mg shown in FIG. 5, the thickness of the 0.25% fullerenol-introduced polyurethane elastomer A layer is 200 μm. 0.
The generated force of the 25% fullerenol-introduced polyurethane elastomer / actuator A is the largest, and especially when the applied voltage is 400 V, the thickness of the 0.25% fullerenol-introduced polyurethane elastomer A layer is 400 μm.
0.25% compared to the 0.25% fullerenol-introduced polyurethane elastomer actuator A-1
It was confirmed that the fullerenol-introduced polyurethane elastomer / actuator A had a generating force about 10 times.

Therefore, the fullerenol-introduced polyurethane elastomer / actuator using the fullerenol-introduced polyurethane elastomer has a generating force suitable for various applications by controlling the film thickness of the fullerenol-introduced polyurethane elastomer constituting the actuator. Actuation mechanism devices can be developed.

[Brief description of drawings]

FIG. 1 is a diagram showing a graph of a relationship between an electric field strength (kV / cm) of an applied voltage and a displacement amount (mm) when a lower end of an actuator is fixed and a voltage is applied to both electrodes.

FIG. 2 is a graph showing the relationship between the concentration (wt%) of fullerenol and the displacement amount (mm) of the fullerenol-introduced polyurethane elastomer when the applied voltage is kept constant at 1 kV.

FIG. 3 is a graph showing the relationship between the electric field strength (kV / cm) of the applied voltage and the displacement amount (mm) when the lower end of the actuator is fixed and a voltage is applied to both electrodes.

FIG. 4 is a diagram showing a graph of a relationship between a load (mg) required for bending 5 mm and an electric field strength (kV / cm) with a weight attached to the tip of the actuator.

FIG. 5 is a graph showing a relationship between an electric field strength (kV / cm) of an applied voltage and a displacement amount (mm) when a weight of 200 mg is attached to the tip of the actuator.

Continued front page    F term (reference) 4J034 BA03 DA01 DB04 DF01 DF02                       DF12 DF16 DF20 DF21 DG03                       DG04 DG06 DG08 DG09 GA02                       GA03 GA06 GA33 HA01 HA06                       HA07 HC01 HC03 HC11 HC12                       HC13 HC17 HC22 HC45 HC46                       HC52 HC61 HC64 HC67 HC71                       HC73 LA06 LA32 LA33 RA11

Claims (2)

[Claims] 1. A polyurethane elastomer comprising a polyurethane elastomer layer capable of being deformed by electric field orientation.
A polyurethane elastomer actuator, wherein fullerenol is introduced into the polyurethane elastomer constituting the polyurethane elastomer layer. 2. The bending displacement and its direction are controlled by the difference in the film thickness of both electrode layers provided on both sides of the polyurethane elastomer layer or the difference in the electrode metal forming both electrode layers. Polyurethane elastomer
Actuator.