JPH02167823A - Composition having dielectric or piezoelectric property - Google Patents

Abstract

PURPOSE:To obtain a dielectric or piezoelectric resin composition having excellent processability, mechanical strength, etc., by compounding a binder to a metal titanate whisker. CONSTITUTION:The objective resin composition having dielectric or piezoelectric property can be produced by compounding a binder such as thermosetting resin, thermoplastic resin, etc., to a metal titanate whisker expressed by the general formula MO.n(Ti,X)O2 (M is single or plural bivalent ions of metallic elements; X is none or Zr; n is integer) and having a fiber length of 1-1,000mum (preferably 2-50mum), a fiber diameter of 0.01-10mum (preferably 0.1-2mum) and a length/diameter ratio of 20-100. The representative metal titanate whiskers are barium titanate, lead titanate, strontium titanate, etc., for dielectric whisker and lead titanate zirconate, etc., for piezoelectric whisker.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a dielectric or piezoelectric composition comprising a metal titanate whisker and a binder, and a molded product thereof, and more particularly to a metal titanate whisker and a cured composition. A curable composition having dielectric or piezoelectric properties comprising a binder, a metal titanate whisker, and a coating composition having dielectric or piezoelectric properties comprising a binder capable of forming a coating, and a metal titanate whisker. The present invention relates to a dielectric or piezoelectric composite sheet made of a dielectric or piezoelectric material.

BACKGROUND OF THE INVENTION In recent years, along with the development of the electronic industry, dielectric materials and piezoelectric materials have made remarkable progress. Various materials are known that have dielectric or piezoelectric properties. For ceramics, crystal, Rochelle salt (NaKC4HO6・4H20
), BaTiO3 system, PZT system (PbTiO3PbZ
r03), CdS, ZnO, etc. are known. Industrially, dielectric porcelain and piezoelectric porcelain made by sintering BaTiO3-based or PZT-based materials are widely used. However, polymer dielectric materials and polymer piezoelectric materials have been developed due to problems such as not being energy efficient due to sintering at high temperatures and lack of remarkable formability. Polymer dielectrics and polymer piezoelectrics have the following features. In other words, ■ It must be flexible ■ It can be made into products of various shapes ■ It must have good mechanical compatibility with the human body, water, etc. ■ It must be possible to cover a large area ■ It must be possible to make thin films ■ It must have dielectric and piezoelectric properties on the film It has characteristics not found in ceramics, such as being able to provide a designed distribution of .

There are two main types of polymer dielectric materials and polymer piezoelectric materials.
There are two types of polymers, one of which is a group in which the polymer itself has dielectric or piezoelectric properties. Specific examples thereof include polyvinylidene fluoride, cyanoethylated polyol, polyvinylphosphabenzene, polyvinylquinoline, vinylidene cyanide/vinyl acetate copolymer, and vinylidene fluoride/trifluoroethylene copolymer. However, when comparing polyvinylidene fluoride, a typical example of these polymeric dielectric and piezoelectric materials, to the ceramic PZT type, the dielectric constant is 13 and 1200.
The problem was that the dielectric constant was low.

Therefore, efforts are being made to develop materials that combine the characteristics of polymeric dielectric and piezoelectric materials with those of ceramic dielectric and piezoelectric materials.

Another example of the polymeric dielectric/piezoelectric material is the above-mentioned composite dielectric/piezoelectric material. Composite dielectric/piezoelectric materials take advantage of both the processability and flexibility of ceramic-based ferroelectric/piezoelectric powders and polymers. Conventionally known ceramic materials include BaTiO3 and P.
Typical examples of conventionally known polymers include polyvinylidene fluoride-related polymers with high dielectric constants, rubber, and thermoplastic resins.

Generally, the dielectric constant, piezoelectric constant, etc. of a composite in which fine ceramic powder is dispersed in a polymer matrix increase in proportion to the amount of ceramic mixed. Therefore, when trying to obtain a high dielectric constant or piezoelectric constant, the polymer/ceramic ratio becomes extremely small to b:15, resulting in the disadvantage that the composite dielectric/piezoelectric material loses its characteristics as a polymer composition. technology remained unsolved.

Means for Solving the Problems The present invention is based on the general formula MO-n (T i , X) 02
A dielectric or piezoelectric composition comprising a metal titanate whisker represented by the formula (wherein M is a single or multiple divalent ion metal element, X is zero or zirconium, and n is an integer) and a binder. According to the present invention,
It has become clear that a dielectric or piezoelectric resin composition with excellent processability and mechanical strength can be obtained.

The present invention replaces the conventional ferroelectric ceramic fine powder with
Adoption of metal titanate whiskers represented by the general formula MO-n (Ti, This made it possible to solve the conventional problems.

The metal titanate whisker of the present invention is made of metal titanate, which is a conventionally known ferroelectric ceramic fine powder, in the form of a whisker, that is, a single crystal fiber, and its shape has a ratio of fiber length to fiber diameter. The fiber length and fiber diameter are not specified and vary depending on the purpose of use, but the fiber length is usually 1 to 1000 μm, preferably 2 to 50 μm, and the fiber diameter is usually 0.01 to 10 μm, preferably 0.1 ~2μm, and the fiber length/fiber diameter ratio is 2
A value of about 0 to 100 is preferable.

In particular, long Na gel-like whiskers have a much better sleeve strength effect, but they have a large porosity when packed closely and it is difficult to obtain a homogeneous resin composition. (ratio) is preferred, but most of the currently available fibers have a fiber diameter of 0.1 to 2 .mu.m and a fiber length of 1 to 20 .mu.m, and these can be fully applied in the present invention.

By employing such metal titanate whiskers as a ferroelectric material, the desired dielectric and piezoelectric properties can be obtained even if the amount added is smaller than that of conventional ferroelectric fine powder.

In addition, the dielectric or piezoelectric resin composition of the present invention has good processability and the resulting molded product has high mechanical properties, which is a completely new feature achieved for the first time by the present invention.

In the metal titanate whisker represented by the above general formula in the present invention, specific examples of the metal element represented by M include Ba5Ca and S rSMg.

Examples include one or a combination of two or more selected from the group consisting of Zn, Co, N15BeSCd, and pb. Therefore, typical compounds of the metal titanate whiskers of the present invention include ferroelectric metal titanate whiskers such as magnesium titanate, barium titanate, strontium titanate, and lead titanate. Examples include lead zirconate titanate.

In the present invention, it is also possible to use the various ferroelectric or piezoelectric whiskers mentioned above to which one divalent ion metal element is added as a dopant. Furthermore, these ferroelectric whiskers or piezoelectric whiskers can be used alone or in combination.

Representative examples of the method for synthesizing metal titanate whiskers represented by the above general formula employed in the present invention will be described.

1) Synthesis side of barium titanate whiskers JP-A-55-
This is a synthesis method disclosed in Japanese Patent No. 113623, in which water is added to powdered titanium dioxide and anhydrous potassium carbonate, the mixture is thoroughly kneaded, dried, and calcined at 1000°C for 24 hours. After cooling, it is poured into water and the fibrous material is defibrated using an agitator. This is filtered and dried to obtain potassium titanate hydrate whiskers.

Next, the thus obtained potassium titanate hydrate whiskers, barium hydroxide, and water were charged into an autoclave and kept at 500° C. for 20 hours. After the reaction, the rapidly cooled sample was taken out, filtered, washed with water, and dried at 80°C day and night to obtain barium titanate whiskers. The ratio of fiber length to fiber diameter of the obtained barium titanate whiskers was at least 10 or more.

2) Synthesis example of lead zirconate titanate whiskers Since lead zirconate titanate is a cubic crystal, pbo and T L 02
It has been found that, although only equiaxed particles can be synthesized by the reaction of TiZrO2 and ZrO2, acicular particles can be obtained by synthesizing TiZrO4 in a flux. This acicular TiZr04 and P
Lead zirconate titanate whiskers were obtained by dry mixing bO and firing at 800 to 900° C. for about 1 hour. S.E.
When observed using an M photograph, the ratio of fiber length to fiber diameter was at least 10 or more.

In the first aspect of the invention, the general formula MO◆n (Ti,
X) 02 (In the formula, MSX and n are the same as above)
A curable resin composition having desired dielectric and piezoelectric properties is obtained by bonding metal titanate whiskers represented by the formula with a curable binder.

Such a curable binder is one that binds the metal titanate whisker and other components added as necessary to impart moldability and/or binds to the support, and the presence of a catalyst, or in the absence of a chemical reaction, the molecular weight increases or crosslinks to become an insoluble and infusible binder, and it is generally activated by various external energies such as heat, light, and electron beams. However, even at room temperature or below, there are some that are activated under special atmospheres such as the presence of moisture in the atmosphere and the presence or absence of oxygen.

Note that organic curable resins are usually suitable as the curable binder of the present invention, but inorganic curable binders may also be used as long as they have processability and bonding strength.

Therefore, the binder of the present invention generally has a crosslinking point that causes a chemical reaction with heat, light, an electron beam, a catalyst, etc. and becomes a macromolecule, and a reactive group exhibiting reaction activity exists as a crosslinking point. do. Typical of these reactive groups are:
Unsaturated groups such as hydroxyl group, alkoxy group, carboxyl group, amino group, nitrile group, epoxy group, vinyl group, acetyl group and their derivatives, substituted organic groups in organometallic compounds, etc., and are usually one type of these reactive groups. Or two or more types coexist.

Therefore, the curable binder of the present invention is not particularly limited as long as it can be cured by reaction at the reaction active site, but representative examples include 1) amino resin, 2> phenol resin,
3) Alkyd resin, 4) Epoxy resin, 5) Urethane resin, 6) Polyamide resin, 7) Polyester resin, 8)
Vinyl resin, 9) Polyimide resin, 10) Polymercapto resin, 11) Silicone resin, 12) Fluorine resin) 15.1
3) Boron resin, 14) Organic titanium resin, 15) One or more mixtures of inorganic hardening substances such as silicates, phosphates, borates, etc., and their precursors, which are resistant to heat, light, etc. Examples include those that become insoluble and infusible binders by curing with electron beams, catalysts, etc.

The curable binder of the present invention is generally provided as a precursor before being made insoluble and infusible for ease of processability, and usually does not contain a solid powder, a liquid, a solution containing a solvent, or a dispersion medium. Dispersions or emulsions, and more particularly, may be provided or used as gases. In addition, some of these are unstable at room temperature or in a natural atmosphere and cure immediately by reaction, some cure by mixing two or more times, some cure by adding a catalyst, etc. There are some substances that react without applying external energy, and for such highly reactive substances, an environment that suppresses the reaction, such as an inert gas atmosphere, storage in a cool and dark place, addition of a reaction inhibitor, catalyst or more than one press. Although it is necessary to store the reaction components separately, even in such a case, it is sufficient that the metal titanate whiskers of the present invention are bonded and cured.

Furthermore, in the present invention, various commonly used additives such as colorants, dispersants, catalysts, co-catalysts, plasticizers, antioxidants, anti-aging agents, reaction inhibitors, reinforcing fillers, non-reinforcing fillers, etc. They may be used in combination, and reinforcing and/or non-reinforcing ferroelectric materials may be used in addition to the metal titanate whiskers of the present invention.

The present invention obtains a curable composition having dielectric or piezoelectric properties by bonding metal titanate whiskers with a curable binder, and the blending ratio of the metal titanate whiskers and the curable binder is determined by Although it cannot be determined due to the purpose of use, the combination of metal titanate whiskers and curable binder, if there are too few metal titanate whiskers, properties such as dielectric constant and piezoelectric properties cannot be expected to be exhibited, and conversely, the curable bond If the amount of the agent is too small, the bonding force will be insufficient and the strength of the molded product will be insufficient. Therefore, for every 100 parts by weight of the general binder (hereinafter referred to as parts by weight), 10 to 2 parts by weight of the metal titanate whisker are used.
000 parts, preferably 50 to 1000 parts is practical. However, the titanate metal salt whiskers of the present invention exhibit a strong hue and are excellent as reinforcing fillers, so these reinforcing properties and/or hues are utilized, and electrical properties are not substantially utilized. Curable compositions, even those that rely on other filling materials for dielectric or piezoelectric properties,
It is included in the resin composition of the present invention.

Furthermore, even if thermoplastic resins that are compatible with or phase-separate from the curable binder are used in υF in addition to the curable binder, if the curable binder is an essential component of the composition, these A thermoplastic resin may also be used in combination.

The method for producing the dielectric or piezoelectric resin composition of the present invention varies depending on the purpose of use and the type of curable binder, and although it cannot be specified, the curable binder can be used under stable and workable conditions and atmospheres. The metal titanate whiskers and the curable binder are mixed or dispersed using a commonly used mixer or disperser, and then treated under curing conditions. If necessary, commonly used catalysts, solvents, dispersion media, and various other additives can be added.

In addition, some curable binders or their precursors are generally unstable, and when two or more curable binders are mixed together, metal titanate whiskers and other substances may be present. When mixing additives, catalysts, etc., some of them harden at room temperature and in a natural atmosphere, so in such cases, they should be separated and stored until just before use, and then mixed immediately before use.

The curable composition of the present invention can be cured by heating if the curable adhesive is thermosetting, by ultraviolet light or electron beam if it is photocurable, or by UV rays or electron beams if the curable adhesive is thermosetting, or if it is cured in a special atmosphere such as moisture curable or anaerobic curable. A suitable dielectric or piezoelectric curable composition can be obtained by processing in each atmosphere, but the curing may also be carried out under reduced pressure or increased pressure. Furthermore, the curable composition having dielectric or piezoelectric properties of the present invention has
Not only can it be used as a composite of one or more of them, but it can also be used as a composite fixed to the surface of a support layer, and generally any of the commonly used molding methods such as painting, coating, and printing can be applied. Furthermore, when producing the resin composition of the present invention that exhibits dielectric or piezoelectric properties, it is also important to convert the resin composition into an electret by applying an electric field or the like to the molded product.

The dielectric or piezoelectric resin composition of the present invention is
It has excellent heat resistance, chemical resistance, surface smoothness of molded products, strength, and durability, and can be used as a substitute for ceramics as a dielectric or piezoelectric material, as well as as a substitute for conventionally known polymer dielectrics and piezoelectrics.
It is possible to improve the performance of piezoelectric materials and has extremely high industrial applicability.

A second aspect of the present invention is a dielectric or piezoelectric coating composition comprising metal titanate whiskers and a binder (hereinafter referred to as "substrate") that provides coating formation ability.

These substrates according to the present invention include soft substrates that form a soft coating layer and hard substrates that form a hard coating layer, depending on the intended use of the coating composition.

The soft substrate of the present invention refers to 1) amorphous or low-melting hydrocarbon compounds such as vaseline, lanolin, petrolatum, and bituminous compounds, or derivatives thereof; 2) fats and oils such as fatty acids and glycerin esters of fatty acids; 3) ) ethylene oxide,
Polyalkylene oxide consisting of a homopolymer or copolymer of alkylene oxide such as propylene oxide, 4
) Fatty acids and alkyl polyalkylene oxides added with glycerin oxide and alkylene oxide of fatty acids, or derivatives thereof; 5); Polyethylene, liquid polybrene, liquid acrylic resin, tributyl phosphate, etc. The following compounds are exemplified, and these compounds are used in combination or as a mixture of two or more thereof.

The hard substrate of the present invention has a film-forming ability of H under the atmospheric conditions in which it is used, and adhesives generally used in paints, inks, adhesives, sealants, molding materials, etc. can be used as they are. can. Examples of the hard substrates of the present invention include higher fatty acids and derivatives thereof, polyolefin resins, alkyd resins, acrylic resins, vinyl resins, vinylidene resins, polyether resins, vinyl formal resins, vinyl acetal resins, cellulose resins, and epoxy resins. , urethane resin, polyamide resin, polyimide resin, polyamideimide resin, polyester resin, polyacetal resin,
Examples include at least one hard binder selected from the group consisting of polyolefin resins, polyphenylene sulfide resins, liquid crystal polymers, polyimidazole, polyoxazoline resins, fluororesins, silicone resins, and the like.

In the present invention, the volume fi additives such as catalysts, curing agents, curing aids, and modifiers commonly used for these substrates are added to O.
May be used for F. Also, depending on the usage, a soft substrate, a rubber elastomer, and a hard substrate may be used in common.

The blending ratio of the metal titanate whiskers and the substrate of the present invention is the same as that of the above-mentioned curable composition, and specifically, the substrate 10
0 parts to 10 to 2000 parts of titanate metal salt whiskers
parts, preferably in the range of 50 to 1000 parts is practical. If there are too few titanate metal salt whiskers, properties such as dielectricity and piezoelectricity cannot be expected to be exhibited, and on the other hand, if there are too few substrates, the bonding strength will be insufficient and the coating performance of the molded object will deteriorate and cracks will occur. It is undesirable because it is weak or its strength is not sufficient.

The substrate itself preferably has a high dielectric constant, such as polyvinylidene fluoride, cyanoethylated polyol, polyvinylphosphabenzene, vinylidene fluoride, etc.
Trifluoroethylene copolymer, vinylidene cyanide,
Preferred examples include vinyl acetate copolymers.

As a method for incorporating the metal titanate whiskers of the present invention into a substrate, any commonly used dispersing machine, mixer, kneading machine, etc. can be used. This can be carried out in any atmosphere such as a specific gas replacement atmosphere. In the present invention, the substrate can be used in combination with a solvent or a dispersion solvent, and can be used as a solution or as an emulsion, colloid, or other dispersion, and further includes a process of incorporating the metal titanate whiskers of the present invention into the substrate and/or After containing, before and after using the coating composition, solutions, solvents, dispersion aids, silane coupling agents, viscosity modifiers, preservatives and preservatives are added to improve workability during preparation and/or use of the coating composition. Commonly used additives such as pasting agents, colorants, plasticizers, anti-settling agents, and flame retardant aids can be used in combination.

Furthermore, in order to exhibit the performance of the composition of the present invention, an electric field or the like can be applied to the coating composition to form an electret before preparing and/or using the coating composition.

The present invention is a coating composition having dielectric or piezoelectric properties, which is characterized by containing metal titanate whiskers. Metal titanate whiskers are generally single crystal fibers and therefore have excellent dielectric or piezoelectric properties. It has extremely high industrial applicability because it not only provides anisotropy but also exhibits a reinforcing effect.

In a third aspect of the invention, metal titanate whiskers are bonded by a binder to obtain a composite sheet having the desired form of dielectric or piezoelectric properties.

The dielectric or piezoelectric composite sheet of the present invention is applicable to electrical and electronic components such as capacitors and wire coatings, as well as electrical and electronic devices that utilize temperature changes in dielectric constant, piezoelectric effect, residual polarization, etc. Sheets and films consisting only of dielectric or piezoelectric parts, and composites consisting of two or more layers, each consisting of a dielectric or piezoelectric layer and a simple general insulating layer. Sheets and films with a layered structure, sheets and films with a multilayer structure consisting of two or more dielectric layers and/or two or more dielectric layers of different dielectric or piezoelectric properties, a piezoelectric layer and a general insulating layer; - Sheets and films in which the piezoelectric layer and/or the general insulating layer are partially missing due to a desired design, and at least one layer of the dielectric/piezoelectric layer in these sheets and films is a composite sheet containing titanate metal salt whiskers. It is constructed.

In the present invention, the binder is a substance that imparts sheet shapeability by combining metal titanate whiskers and other forces added as necessary, and/or a substance that binds to a support. There are no restrictions, and water-soluble polymers or hydrophobic polymers that are thermoplastic or thermosetting can be freely used, and should be selected depending on the purpose of use. Incidentally, organic binders are usually suitable as the binder of the present invention, but inorganic binders may also be used as long as they have sheet-forming ability and binding strength. Specific examples of the binder of the present invention include 1) amorphous or low-melting hydrocarbon compounds such as vaseline, lanolin, vetrotatum, and bituminous compounds, or derivatives thereof; 2) fatty acids and combinations of fatty acids and polyhydric alcohols; Condensates, as well as their polymers and derivatives; 3) homopolymers or copolymers of alkylene oxides such as ethylene oxide and propylene oxide; 4) natural resins and their derivatives such as rosin, maleated rosin, and ester gum; 5) ) Olefin resin, 6) Natural or synthetic rubber, 7) Alkyd resin, 8) Acrylic resin, 9> Vinyl resin, 10) Vinylidene resin, 11) Vinyl ether resin, 12) Polyether resin, 13) Vinyl acecool resin, 14) Cellulose resin, 15) Epoxy resin, 16) Urethane resin, 17) Polyamide resin, 18) Polyacetal resin,
19) polyester resin, 20) polymercapto resin,
20 polysulfide resin, 22) polyimidazole resin, 23) polyoxazoline, polyoxasilane resin, 24) silicone resin, 25) polymercapto resin, 2
6) Metal-containing corrosion compounds such as organosilicon compounds, organotitanium compounds, organophosphorus compounds, and organoboron compounds; 27) Natural or synthetic compounds such as inorganic binders such as silicates, phosphates, and borates. and a mixture of two or more of these. These include not only those whose molecular weight has already been made high, but also those whose molecular weight is increased by using one or a mixture of two or more raw materials whose molecular weight becomes high during processing under the presence of light, heat, catalysts, etc. to develop bonding strength. You can choose arbitrarily if
Furthermore, the binder is not limited to the above-mentioned examples.

The present invention uses metal titanate whiskers and a binder to form a sheet or film to obtain a composite sheet having dielectric or piezoelectric properties.The blending ratio of metal titanate whiskers and binder is determined by Although it cannot be specified due to the purpose, metal titanate whisker, and type of binder,
If the amount of metal titanate whiskers is too small, dielectric and piezoelectric properties cannot be expected. Conversely, if the amount of the binder is too small, the bonding force is insufficient and the strength of the sheet or film cannot be expected. Therefore, it is usually practical to use 50 to 2,000 parts of the metal titanate whisker, preferably 100 to 1,000 parts, per 100 parts of the binder.

The method for incorporating the metal titanate whiskers into the binder includes the metal titanate whiskers and the binder component (binder or the raw material of the binder), or a dispersion, emulsion, solution, or powder of the binder component. , paste, etc., and if necessary, various commonly used additives such as diluents, catalysts, colorants, silane coupling agents, dispersants, plasticizers, anti-aging agents, fillers, etc. A mixture or dispersion is obtained by mixing or dispersing.

Such a mixture or dispersion is used to form a sheet using a conventional method, such as applying or spreading two mixtures or dispersions on a surface that has mold releasability to form a sheet. Molding methods, sheet-forming methods by coating or spreading on the surface of sheet-like support layers such as paper, fabrics made of organic or inorganic fibers, resin films, etc., calendering methods, extrusion molding methods, and composite structures thereof, etc. Various methods can be used, and blow molding etc. can also be used if the processing technology is in place. Further, in order to bring out the performance of the composite sheet of the present invention, it is possible to apply an electric field or the like during or after sheet creation to make it into an electret.

The composite sheet of the present invention may contain a commonly used sheet modifier in addition to the metal titanate whiskers and the binder. Although it is possible to impart dielectricity or piezoelectricity only with the titanate metal salt whiskers of the present invention, it is also possible to use commonly used powdered dielectric ceramic powder, piezoelectric ceramic powder, or inorganic dielectric/piezoelectric compound powder in combination. This does not preclude doing so.

The dielectric or piezoelectric composite sheet of the present invention is
Metal titanate whiskers have excellent reinforcing properties, can be oriented as necessary, and anisotropy can be adjusted, and physical and chemical changes such as oxidation are unlikely to occur under normal usage environments. Since it also has excellent heat resistance, a composite sheet with stable dielectric or piezoelectric properties can be obtained, and has extremely high industrial applicability.

Furthermore, a composite sheet consisting of an elastic body as an antagonist and lead zirconate titanate whiskers as a metal titanate whisker had particularly excellent piezoelectricity.

Throughout the present invention, there is no mention of electric property; however, if metal titanate whiskers with good pyroelectric properties, such as lead titanate whiskers, are used, a composition with pyroelectric properties is expected. can.

EXAMPLES Next, examples will be given to illustrate the features of the present invention in more detail.

Example 1 Polypropylene resin (Sumitomo Noblen H3O1, manufactured by Sumitomo Chemical Co., Ltd.) and barium titanate whiskers (manufactured by Otsuka Chemical Co., Ltd., average w4 fiber length 14.27 zm, fiber diameter 0.3 to 0.51 trn) were each used at 65% /
After weighing to obtain a ratio of 35.60/40.40/60.30/70 and thoroughly drying at 110°C, melt the polypropylene resin for 5 minutes using Labo Plasto Mill (manufactured by Toyo Seiki Co., Ltd.). Kneading for 5 minutes at 175℃ each
The resulting compound was molded using a compression molding machine (
■ Loaded into a tank (manufactured by Shinto Metal Industry Co., Ltd.) at 190°C, gauge pressure 50
kgf/an? A flat plate sample was created by hot pressing, and the dielectric constant of each was measured.

The dielectric constant (ε) was measured using an LCR meter compliant with JIS K 6911E under conditions of a measurement frequency of IKHz and an inter-sample voltage of IV. The difference with the comparative example described later was obvious, with a difference in the induction rate of about 2 times or more (1st
figure).

Comparative Example 1 A similar flat plate was prepared in the same manner as in Example 1, except that commercially available powdered barium titanate (BT303, manufactured by Fuji Titanium Co., Ltd.) was used instead of the barium titanate whiskers in Example 1. Samples were prepared, and the dielectric constant of each was determined to be /1111.

It can be clearly seen from FIG. 1 that the composition of the present invention has excellent dielectric properties.

Example 2 Polyacetal resin (manufactured by Polyplastics ■, Duracon) and NBR (manufactured by Rohon Synthetic Rubber ■, JSRPN30A)
, CN content 35%) were mixed little by little at a temperature of 190°C using a heated roll to adjust the weight ratio to 60/40, and kneaded without applying stress. After mixing well, titanium Acid zirconate lead whiskers (manufactured by Ohita Kagaku ■, average fiber length 12 μm, fiber diameter 0.5-0.
6 μm) was added little by little to the above polymer alloy so that the weight ratio was polymer alloy/whisker = 35/65 and mixed uniformly, and then this was formed into a film with a thickness of 50 μm using a hot press. .

In order to impart piezoelectricity to this film, the molded product was
Piezoelectric constant (d 31) of a piezoelectric material obtained by applying a DC electric field with an electric field strength of 200 KV/cm from the front and back of the molded product for one hour while heating it to 0°C, and then rapidly cooling it to make it into a thermoelectret. is 1B0.5X10
'(CGS esu). As a reference, lead zirconate titanate (reagent grade 1, manufactured by Hirai Chemicals), which is known as a general piezoelectric ceramic powder, was used instead of lead zirconate titanate whiskers, and a film with a thickness of 50 μm was similarly formed using a hot press. After converting into an electret, its piezoelectric constant (d31) is 50.2X10-" (C
It can be clearly seen that the composition of the present invention exhibits excellent piezoelectric properties. Incidentally, a silver vapor-deposited film vacuum-deposited on both sides of the film was used as an electrode during electret formation and piezoelectric constant measurement.

Example 113 Butadiene was polymerized using hydrogen peroxide as a catalyst to obtain a liquid polybutadiene polyol with an average molecular weight of 2800, 285 meq/g of OHHO, 21% of 1.2 bonds, and 79% of 1,4 bonds. 100 parts of butadiene polyol, 600 parts of dried barium titanate whiskers, and 0.1 part of dibutyltin dilaurate were mixed using a three-roll paint roll. For 100 parts of this mixture, 1. Add 2 parts and heat at 120°C for 1 hour.
In-press hardening was performed. The electrical properties of the cured product thus obtained were measured in accordance with JIS K 6911, and the dielectric constant was 24 (IKHz, 20'C).
22 (IKHz, 120°C), dielectric loss tangent (tanδ)
were 0.013 and 0.003. A cured product was obtained in the same manner as in Example 3 except that the same amount of commercially available barium titanate powder (manufactured by Fuji Titanium ■, BT303) was added instead of barium titanate whiskers as a reference. Rate is 12 (IKHz, 20℃), 1
0 (IKHz, 120°C), and the dielectric loss tangent (tanδ
) were 0.02 and 0.005.

Effects of the Invention In the dielectric or piezoelectric composition of the present invention, the titanate metal salt whisker has excellent reinforcing properties, and exhibits highly anisotropic dielectric and piezoelectric properties by orienting it as necessary. Therefore, it has extremely high industrial applicability and can be used in place of conventional polymer dielectric/piezoelectric materials and polymer composite dielectric/piezoelectric materials.

[Brief explanation of the drawing]

FIG. 1 shows the relationship between the added amounts of barium titanate whiskers and barium titanate powder and the dielectric constant of molded products (flat plates) obtained in Example 1 and Comparative Example 1, respectively. (that's all)

Claims (11)

[Claims] (1) Metal titanate represented by the general formula MO・n(Ti, A dielectric or piezoelectric composition consisting of whiskers and a binder. (2) Metal titanate represented by the general formula MO・n(Ti, A dielectric or piezoelectric composition obtained by converting a composition consisting of whiskers and a binder into an electret. (3) The composition according to claim 1 or 2, wherein the metal titanate whisker is a barium titanate whisker or a doped barium titanate whisker. (4) The composition according to claim 1 or 2, wherein the metal titanate whiskers are lead zirconate titanate whiskers. (5) The binder is a curable resin, thermoplastic resin, hydrocarbon compound or derivative thereof, fatty acid and polycondensate of fatty acid and polyhydric alcohol, homopolymer or copolymer of alkylene oxide, natural resin and its derivative , an inorganic binder, and a metal-containing organic compound. (6) Claim (1) or (1) wherein the binder is a curable resin having at least one active reactive group selected from a hydroxyl group, an alkoxy group, a carboxyl group, an amino group, a nitrile group, an epoxy group, and an acetyl group. 2) The composition described. (7) Claim (1) or (7) comprising the metal titanate whiskers and a binder having coating forming ability or injection molding ability.
2) The composition described. (8) Amorphous or low-melting-point hydrocarbon compounds and derivatives thereof, fatty acids and polycondensates of fatty acids and polyhydric alcohols, polyalkylene oxides, alkyl polyalkylene oxides and derivatives thereof, liquids in which the binding agent capable of forming a coating is amorphous or has a low melting point. The composition according to claim 7, which is at least one selected from the group consisting of polyethylene, liquid polyprene, liquid polyacrylic resin, and tributyl phosphate. (9) The binder having coating forming ability or injection molding ability is higher fatty acid and its derivatives, polyolefin resin, alkyd resin, acrylic resin, vinyl resin, vinylidene resin, polyether resin, vinyl formal resin, vinyl acetal resin, cellulose. based resin, epoxy resin, urethane resin, polyamide resin, polyimide resin, polyamideimide resin, polyester resin, polyacetal resin,
The composition according to claim 7, which is at least one hard binder selected from the group consisting of polysulfone resin, polyphenylene sulfide resin, liquid crystal polymer, polyimidazole, polyoxazoline resin, fluororesin, and silicone resin. (10) General formula MO・n(Ti,X)O_2 (wherein, M
A dielectric or piezoelectric composite sheet comprising titanate metal salt whiskers represented by one or more divalent ion metal elements, X is zero or zirconium, and n is a real number) and a binder. (11) The composite sheet according to claim (10), comprising the metal titanate whiskers and a binder, and further comprising a support layer.