JPH03281574A - Highly dielectric resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition capable of injection molding, high in mechanical strength, thus useful for electrical and electronic parts and mechanical parts, comprising a synthetic resin capable of injection molding and specific alkaline earth metal titanate. CONSTITUTION:The objective composition can be obtained by incorporating (A) a synthetic resin capable of injection molding (e.g. phenolic resin, polybutylene terephthalate) with (B) 25-70vol.%, based on the whole volume of the final composition, of fibrous alkaline earth metal titanate, pref. fibrous barium titanate ((n)=1) of the formula (M is one alkaline earth metal or a combination of two or more kinds of such metal; (n) is 1-12) 3-100mum in fiber length, 0.1-10mum in fiber diameter and pref. >=10 in aspect ratio, prepared by deposition of an alkaline earth metal carbonate, through solution reaction, on the surface of a fibrous titania compound followed by treatment under heating at 500-1300 deg.C.

Description

[Detailed description of the invention] (Industrial application field) TECHNICAL FIELD The present invention relates to a light dielectric composition.

(Traditional American technology) As a new material, fine ceramic products have unique and excellent properties and functions that metal materials and polymer materials do not have, and are used in all industrial fields and are attracting attention. - Highly dielectric porcelain has grown significantly in the electronics-related industry field, and its dielectric materials are generally various materials made of alkaline earth metal titanates such as barium titanate. This alkaline earth metal titanate salt is usually synthesized from a compound that becomes titanium oxide when heated and a compound that becomes an alkaline earth metal oxide when heated, and has the general formula MO·nT io 2 (in the formula, Isomers with an elemental ratio of M/Ti of 1 or more are known, where M is an alkaline earth metal and n is a real number from 1 to 12. When trying to mold these into 3-electric porcelain, there is a relatively large amount of meat, a lot of force, a large piece of wood, a few days, and a lot of time! The two types of irregularly shaped sheets are pressure-formed using a dry press, etc., and the green sheet is made by extrusion molding or roll rolling, etc., and then punched into a predetermined shape using a punching press, etc. After that, these next molded products are fired at 1000-1400℃ to obtain the final product, but for products with complex shapes, after cooling, further cutting processing is performed for finishing, etc. The process to obtain it is extremely laborious and time-consuming, making it unsuitable for mass production.

In order to solve these problems, we have developed a highly dielectric resin molding made by injection molding using a resin composition made by kneading an injection moldable synthetic resin and a powdered material whose main component is an alkaline earth metal titanate. Various products are proposed. By doing this, complicated machining is simplified and J! However, in order to obtain the desired high dielectric constant, it is necessary to use a powder material whose main component is alkaline earth metal titanate, which is a dielectric. It is necessary to increase the amount of addition to the resin, and increasing the amount impairs the injection moldability of the resin composition and results in a molded product with extremely low mechanical strength, which cannot be used as a commercial product in practical terms. do not have. Therefore, various studies have been conducted on fibrous alkaline earth metal titanates by devising the shape of alkaline earth metal titanates.

In order to obtain a resin composition that is injection moldable, has high mechanical strength, and has high dielectric properties, it is necessary to use fibrous titanium 11, which itself has a high dielectric constant and mechanical strength. is necessary. Alkaline earth metal titanate has the general formula M
O・nTio2 (where M is an alkaline earth metal, n is 1
The elemental ratio of M/T i, which is represented by ~12 real numbers), is 1
The above isomers are known. In industry, the most well-known and used powder is alkaline earth metal titanate powder with n=1 or powder containing this as the main component, but as mentioned earlier, these powdered dielectric In the case of a resin composition obtained by kneading a material and a synthetic resin, in order to stably obtain the desired high dielectric property, it is necessary to increase the amount of powdered dielectric material added to the resin, and therefore the resin composition What if the injection moldability of the product is impaired? j! The range of use has been limited due to the significant decrease in mechanical strength.

It is thought that these causes are due to the shape of the material, which is powdery, and several reports have been made in which research has been conducted in the direction of changing the shape to a fibrous shape. However, in these production methods, it is not possible to obtain a fibrous alkaline earth metal salt with n=1, and conversely, under conditions to achieve n=1, the salt has not only a fibrous shape but also a granular or other shape. A product containing a mixture of substances is obtained, and the advantages such as improved mechanical strength due to fibrous formation cannot be fully demonstrated.

The present inventors have conducted long-term research on titanic acid compounds,
Various new titanic acid compounds, manufacturing methods, and their uses have been announced.As a result of extensive research into the reaction characteristics of titanic acid compounds, the present invention has revealed that alkaline earth metals are preliminarily applied to the surface of a fibrous titania compound by a solution reaction. It was discovered that by attaching a metal carbonate and heat-treating at 500 to 1300°C, a fibrous alkaline earth metal titanate with n=1 can be obtained without any loss in the fiber shape of the original titania compound. A patent application is pending for this manufacturing method (Japanese Patent Application No. 1-149206). The fibrous titania compound mentioned here is easily obtained by the reaction of a fibrous alkali metal salt.

(Problems to be Solved by the Invention!) An object of the present invention is to provide a resin composition that can be injection molded, has high mechanical strength, and has high dielectric properties.

(Means for solving the ff problem) The present invention involves depositing an alkaline earth metal carbonate on the surface of (a) an injection moldable synthetic resin and (b) a fibrous titania compound by a solution reaction at a temperature of 500 to 1300°C. The general formula MO-nT io obtained by heat treatment with (
In the formula, M is one kind or a combination of two or more kinds of alkaline earth metals, and n is a real number from 1 to 12)'1'
The present invention relates to a highly dielectric resin composition having Vf consisting of the fibrous alkaline earth metal titanate shown below.

The high electrical conductivity resin of the present invention differs from the conventionally known MH resin compositions in that it has injection molding DJ performance, high mechanical strength, and -) high dielectric constant. 4. In the present invention, the injection moldable synthetic resin may be either thermoplastic or thermosetting resin, and is not particularly limited, such as Phenolic resin, area resin, melamine resin, Gu? Namin resin, Ami 7 fat, unsaturated polyester resin, No? Lil 7 tallate fallen fat, epoxy resin,
Silicone resin, urethane resin, a-rotrifluoroethylene resin, tetrafluoroethylene-hexylfluoropropylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl heptadide resin, ethylene-tetrafluoroesalene copolymer , ethylene-chlorine copolymer, ethylene chloride copolymer, L'nyl chloride resin, vinylidene chloride resin, polyethylene, polypropylene, chlorinated polyolefin, ethylene-vinyl adiadate pyropolymer, ethylene ethyl acrylate copolymer, 1 bottle , polystyrene, ABSPj4 fat, poly? Methacrylic resin, polyayatar, polycarbonate, cellulose resin, bolibi, alcohol, polyethylene urethane elastomer, polyimide,
Poly1-tylimide, polyamideimide, ionone ~
Hatred? 1. Tri-7-ethylene-ocindo, methyl-pentene polymer, polyallyl sulfone, polyallyl ether, vol-tylketone, poly-7-ethyl-ketone, poly-7-ethyl-pentene polymer, polyallyl sulfone, polyallyl ether, vol. Examples include polymer alloys and blends of keyaki hydride, polysulfone, aromatic volume 1, polyethylene terephthalate, polybutylene 1/7 talate, thermoplastic poly-containing chill J, last 7 and other molecular substances.

Next, the fibrous alkaline earth metal titanate in the present invention is a specific 1 ffl dark blue fluoro titanate Lt, I metal. Both are required. That is, in the present invention, the crystallinity is ^<
, aia strength 11. It is necessary to use highly fibrous alkaline earth metal titanates.

The fibrous alkaline earth metal titanate used in the present invention is prepared by depositing a carbonate of the alkaline earth metal titanate on the surface of the fibrous titanium compound by solution reaction.
Heat treatment at 1300°C - and IJ rise, general y~M
O・nT io = (in the formula, llnia4*1JJr,
1 gold gr, n is natural enemy from 1 to 12).

Examples of the remains of M [, then, Be, M') H, Ca, S
r, 113 a, a monomer or a mixture of two or more elements of Ra]
Further, the shape of the fibrous alkaline earth titanate-k14 of the present invention includes fiber length 3 100
0μ age, fiber a diameter o, 1=ioμ mackerel, preferably 7
The fiber length ratio (#ffl fiber length/fiber diameter ratio) is 1O or less.

Particularly preferred are those having a uniform fiber length of 10-20μ and an average fiber diameter of 0.2-1μ. Heating temperature is 500
Below 'C, the carbonate remains as it is, and 1:(00tej
If it exceeds, the weave shape will be destroyed due to melting etc.e,')Ll
, in either case I:6 the desired fibrous alkaline earth metal titanate cannot be obtained. If an aspect ratio of less than 10 is used, the mechanical strength of the composition of the present invention cannot be expected, and the desired IT ratio cannot be achieved.

Furthermore, in the present invention 1-, Moekikai Seiki! ! In addition to ff and fibrous alkaline earth titanate & maple, other additives such as surface treatment agents, compatibilizers, heat conduction improvers, Lubricant tendency! - It is also possible to add shavings, coloring agents, etc. These synthetic resins, [compounding ratio 1 when 1-form alkaline earth metal titanate and appropriately added additives, etc. are being blended, wl, ll-form alkali zatanate IJ, f: similar metals make up the entire composition. For capacity, 2
It is preferably in the range of 5 to 70% by volume, preferably 40 = 65% by volume. The reason why the blending ratio is expressed in terms of volume ratio is that the difference in specific gravity is too small in terms of weight ratio, and it is impossible to limit the numerical value that proves the inventive step of the present invention. The reason for limiting the blending ratio of acid-alkaline soil is 21] Volume % powder vortex addition amount:! #
This is because the electrical properties are not sufficient and molding becomes difficult if the amount added exceeds 70% by volume.

The dielectric resin composition of the present invention can be used, for example, in various capacitors. By using a molded product of the composition in, for example, a feedthrough capacitor, a single-plate capacitor, or a multilayer capacitor, it becomes possible to produce a capacitor with high dielectric properties and excellent voltage resistance. In particular, when thermoplastic resin is used, through-type high-voltage capacitors, which previously required complicated processes, can be easily manufactured by injection molding, significantly shortening the work process and reducing costs. In conclusion, particularly preferred synthetic resins include polyethylene terephthalate (P ET ), polypropylene (P P >,
Polyethylene (PE), polycarbonate (PC), polyacrylate, polyamide, polybutylene terephthalate (PBT), polyvinylidene heptadide, polysulfone, polyphenylene sulfide (PPS), liquid crystal polymers or polymers of these synthetic resins Examples include alloys. Furthermore, when a resin composition is formed by adding additives in shapes other than fibrous, specifically plate-like, granular, etc., to the fibrous alkaline earth metal titanate for various purposes, the high dielectric property The characteristics of the fibrous material are fully exhibited.

(Example) EXAMPLES The present invention will be specifically explained in detail with reference to Examples below.

Actual total 1 Fibrous titania hydrate (Ti(')2・I/2H2('
), uniform fiber I# length 15μ, average fiber diameter 0.2μ brass) 1
08 homogeneously dispersed in 233 g of a 10@t% barium chloride aqueous solution, 70 g of a 20-1% ammonium carbonate aqueous solution was added dropwise at room temperature over 30 minutes with stirring.
After stirring for another 30 minutes, the mixture was separated in a furnace, washed with water, and dried to obtain 32 g of a white fibrous substance. This thing is X
Linear diffraction, infrared spectrum (hereinafter abbreviated as IR), and scanning electron microscopy observation revealed that the raw material titania hydrate retains its fibrous shape, barium carbonate is homogeneously deposited on its surface, and B a COs / T. iO2=1. / 1
(% Le ratio). 10 liters of the product obtained by this method was transferred to an alumina crucible and heat treated in a Matsufuru furnace at 950°C for 2 hours to yield 8.1 g.
A white fibrous material was obtained. In IR analysis of this product, the yield of barium carbonate completely disappeared, and even when folded with χIg, BaO-
No diffraction peaks other than TiO2 were observed, and observation using a scanning electron microscope (hereinafter abbreviated as SEM) confirmed that the raw material tILII shape was maintained.
Fibrous BaO.T i O2 could be synthesized with a yield of over 30%. FIG. 1 is a SEM photograph of fibrous BaO.T io 2 (barium titanate).

The method for synthesizing the fibrous B&0-TiO□ in Example 1 is hereinafter referred to as a solution method.

Next, the obtained fibrous Ba0-Tie was kneaded with a synthetic resin to examine its properties as a resin composition. First, polybutylene tele 7 tarley) (PBT), PBT 53vo1% and the fibrous material 47vo1% are heated to softening of the resin, α, sufficiently kneaded, and then injection molded into a disc. Shape and JIS
Sample preparation and measurement were performed according to the dielectric constant measurement method specified in K6911.

Dielectric constant 36, dielectric loss tangent 0, 0+9 (both IMHz, 25
℃). In addition, the tensile strength was measured according to the JIS method, and the result was 5QQkgF/cm2.

Example 2 Using the fibrous BgO-TiO7 obtained in Example 1, polyphenylene salt 7 fluid (PP
The properties of the resin composition obtained in the same manner as in Example 1 were measured using PPS (S) at a ratio of 53v01% of PPS and 1% of the fibrous material 47vo. The result is a dielectric constant of 32
, dielectric loss tangent 0.025, tensile strength 770kgf/el1
It was 2.

Example 3 Same method as Example 2 "cP P S 40vo1%,
The properties of the resin composition obtained with the fibrous material at a ratio of 60 VOI% were measured. The result is a dielectric constant of 42 and a dielectric loss tangent of 0.0.
22, tensile strength was 550 kgf/cm''.

Example 4 Using the fibrous B11O-T102 obtained in Example 1, polyvinyritine septate (PVDF) was used as the resin.
The characteristics of the #I fat composition obtained in the same manner as in Example 1 were measured using a method similar to Example 1 at a ratio of 57 vol % of P V D F and 1 % of the fibrous material 43 vol. The result is a dielectric constant of 65
, dielectric loss tangent Q, 118, tensile strength 460kgr/cm
It was z.

Example 5 Fibrous BILo-TO obtained on top side 1! In addition, commercially available powdered barium titanate KYOR-X BT-8 (manufactured by Kyoritsu Ceramic Materials Co., Ltd.) was
Powdered material (average particle size 1 μm) that is pulverized after being baked for a period of time
We conducted an investigation using Specifically, the same method as in Example 1 was carried out using PBT as the resin.
The characteristics of the resin composition obtained at a ratio of 1%, the fibrous Ba0-TO, 30vol.1%, and the powdered barium titanate 10vol.1% were measured. The results are dielectric constant 20, dielectric voltage 4'IO,018, tensile strength 470kgF/el1
It was 2.

Example 6 Using the fibrous BaO-TiO2 obtained in Example 1, a 7 ether resin (Bell Pearl S 97) was used as the resin.
The properties of a resin composition obtained in the same manner as in Example 1 were measured using 0) at a ratio of 50 vol % of the 7-engine 7-l resin and 50 vol % of the fibrous material.

The results are dielectric constant 38, dielectric loss tangent 0.038, and tensile strength 69.
It was 0 kgf/cm2.

Example 7 Resin PBT 75vo1%, the fibrous BaO.
The properties of the resin composition obtained in the same manner as in Example 1 were measured using TiO, 25vol%. The results are dielectric constant 18, dielectric loss tangent 0.0+2, tensile strength 790kgf, 7
cm”.

Comparative Example 1 Resin PBT 80vo1%, the fibrous BaO-T
The properties of the resin composition obtained in the same manner as in Example 1 were measured at a ratio of i0220vo1%. The result is a dielectric constant of 1
1. Dielectric loss tangent 0.022, tensile strength 810kgf/c
It was "m".

Comparative Example 2 10% of the fibrous titania hydrate used in Example 1 was added to a powder (average particle size 0.8 μm) obtained by thoroughly pulverizing 25 g of Palitum carbonate (special grade reagent) in a mortar. A homogeneous dry mixture was placed in an alumina crucible in the same manner as in Example 1, and the
By baking at 50° C. for 2 hours, 8.2 g of white powder was obtained. In IR analysis of this product, barium carbonate had disappeared, but in X-ray diffraction, it was found that in addition to Bao-TlO2, it was a six-pointed aggregate with a miscellaneous composition such as Tio2 (rutile) and Ba0.3TiO. In the SEM image shown in Figure #42, the shape of the raw material fibers was partially broken, damaged, melted, granular, or a powdery mixture.

The method used in Comparative Example 2 is called the firing method,
This method was carried out with reference to a known method for synthesizing fibrous alkaline earth metals. The thus obtained product was treated in the same manner as in Example 1, with resin PBT53vo1% and the product 4
A resin composition was obtained at a ratio of 7vol% and its properties were measured. The results were a dielectric constant of 14, a dielectric loss tangent of 0.019, and a tensile strength of 280 kgf/cm'.

Comparative Example 3 Using the powdered barium titanate (average particle size 1 μm) used in Example 5, resin P B was prepared in the same manner as in Example 1.
The characteristics of the resin composition obtained at a ratio of 53 vol. 1% T and 47 vol. 1% powdery material were measured. The result is dielectric constant +2
．． The dielectric loss tangent was 0.021, and the tensile strength was 280 kgf/cJ.

Comparative Example 4 Resin PBT was molded in the same manner as in Top Side 1, and its dielectric properties were measured. The results are a dielectric constant of 3.1 and a dielectric loss tangent of 0.
It was 003.

Comparative Example 5 A PPS resin was molded in the same manner as in Comparative Example 4, and its dielectric properties were measured. The result is a dielectric constant of 4.6 and a dielectric loss tangent of 0.
,002.

Comparative Example 6 Using the same method as in Comparative Example 4, PVDF was molded and its dielectric properties were measured. The results were a dielectric constant of 12 and a dielectric loss tangent of 0.150.

(Effects of the Invention) The highly dielectric resin composition of the present invention has high dielectric properties, can be molded into complex shapes by injection molding, and has high mechanical strength, so it can be used for electrical and electronic parts. , it can be widely applied to mechanical parts, etc.

[Brief explanation of drawings]

FIG. 1 shows fibrous Bao obtained according to Example 1 of the present invention.
FIG. 2 is a scanning electron micrograph showing the product obtained in Comparative Example 2 of the present invention. (Above) Applicant Otsuka Chemical Co., Ltd. Representative Patent Attorney 1) Iwao Mura Figure 14

Claims (4)

[Claims] (1) General formula obtained by depositing alkaline earth metal carbonate on the surface of (a) injection moldable synthetic resin and (b) fibrous titania compound by solution reaction and heat treatment at 500 to 1300°C It is composed of a fibrous alkaline earth metal titanate represented by MO・nTiO_2 (where M is one or a combination of two or more alkaline earth metals, and n is a real number from 1 to 12). Characteristic highly dielectric resin composition. (2) The highly dielectric resin composition according to claim 1, wherein the fibrous alkaline earth metal titanate accounts for 25 to 70% by volume of the total volume of the resin composition. (3) The fibrous alkaline earth metal titanate represented by the general formula MO・nTiO_2 is a fibrous barium titanate (n=
1) The highly dielectric resin composition according to claim 1. (4) The highly dielectric resin composition according to claim 1, wherein the aspect ratio (ratio of fiber length/fiber diameter) of the fibrous alkaline earth metal titanate is 10 or more.