JP2873541B2 - Resin composition for molding antenna substrate material of high frequency communication equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition for electronic parts. More specifically, the present invention relates to a resin composition which has both good dielectric properties and excellent physical properties and is useful as a material for electronic / electric parts used in a high frequency band, particularly as an antenna substrate material for a high frequency communication device.

[0002]

2. Description of the Related Art With the remarkable spread of mobile communication devices such as portable telephones, cordless phones, and automobile telephones and the remarkable development of satellite communication devices, the frequency of communication signals has been increased and the communication devices have been further improved. There is a demand for miniaturization.

[0003] By the way, two kinds of dielectric characteristics, that is, relative dielectric constant (ε) and dielectric loss tangent (tan δ) of an antenna board incorporated in a communication device are greatly involved in increasing the signal frequency and reducing the size of the communication device. . Relative permittivity is a parameter indicating the degree of polarization in a dielectric.The higher the relative permittivity of an antenna substrate, the shorter the wavelength of a signal propagating through a circuit formed on the substrate, and the higher the frequency of the signal. . Therefore, if the relative permittivity of the substrate can be set high, it is possible to achieve a higher frequency, a shorter circuit, and a smaller communication device. The dielectric loss tangent is a parameter that represents the amount of a signal propagating in a dielectric that is converted into heat and lost.The lower this value is, the smaller the signal loss is, the lower the energy consumption is, and the smaller the battery can be. This allows the machine itself to be miniaturized, and in addition allows long-term continuous use.

[0004] Conventionally, the antenna board of a communication device mainly includes:
(B) an insulating layer made of a thermosetting resin such as bisphenoltriazine or thermosetting polyphenylene ether;
Alumino borosilicate glass (CaO-Al ₂ O ₃ -B
A copper-clad laminate is used in which a plurality of prepreg layers impregnated with the thermosetting resin are alternately pressure-laminated on a fiber cloth of ₂ O ₃ —SiO ₂ ), and copper foils are adhered on both surfaces thereof. I have.
The laminate has a dielectric loss tangent of 0.1 MHz at 25 ° C. of 0.
Although it is as low as about 003, the relative dielectric constant is about 6.7, which is insufficient for high frequencies ranging from several hundred MHz to GHz. Further, the relative permittivity of the insulating layer and the prepreg layer is different, and the relative permittivity of the laminate itself changes greatly depending on the number of layers to be laminated, so that it is difficult to set the frequency. Since the insulating layer and the prepreg layer also have different coefficients of thermal expansion, a long-term use may cause a shift at the lamination interface, change the relative dielectric constant, and cause communication failure. Further, alternately laminating a very thin insulating layer and a prepreg layer requires an extremely complicated operation.

Further, a copper-clad laminate obtained by laminating a prepreg layer obtained by impregnating a thermosetting resin in a fiber cloth of high dielectric titania-silicate glass (SiO ₂ —BaO ₂ —TiO ₂ ) and an insulating layer, Are known. This laminate has a dielectric loss tangent value equivalent to that of a conventional one and a relative dielectric constant as high as about 11 to 12, and is suitable for high frequency use. The problems inherent in the laminate, such as the occurrence of trouble and the complexity of manufacturing, have not been solved.

On the other hand, a synthetic resin has a
It is used as a component material for general electronic and electrical equipment such as home appliances. Further, in order to improve the heat resistance, mechanical strength, dimensional stability and the like of the synthetic resin, a fibrous inorganic filler has been added.

For example, JP-A-3-35585 discloses a resin composition reinforced by a fibrous filler such as glass fiber or fibrous potassium titanate. The composition comprises:
It is intended to be applied to general electronic and electrical components such as switches, tape guides, and gears, and exhibits undesired properties due to the fibrous inorganic filler in the high frequency band. Cannot be used.
Glass fibers increase the dielectric loss tangent and reduce the signal transmission. In addition, even if the glass fiber is small, the fiber diameter is 5-1.
Since it has a fiber length of about 5 μm and a fiber length of about 100 μm or more, when mixed with a synthetic resin and molded, the mixture emerges on the surface of the molded product, and irregularities which hinder signal transmission in a high frequency band are generated. The fibrous potassium titanate has a fiber diameter of 0.05 to 2
It is a microfiber having a length of about μm and a fiber length of about 2 to 50 μm, which is effective for strengthening the synthetic resin, but significantly increases the dielectric loss tangent, thereby lowering the signal transmission rate. In addition, alkali components such as potassium contained in the fibers corrode electrodes and wirings of electronic components, cause disconnection, current leakage, and the like.

Japanese Unexamined Patent Publication (Kokai) No. 3-281574 discloses a high dielectric resin composition containing fibrous barium titanate. However, this composition is used for a capacitor which is used for a purpose different from an antenna substrate or the like. It is used as a material. In addition, the composition is generally unsuitable for high frequency applications because of its slightly higher dielectric loss tangent. The publication does not suggest that the use of fibrous barium titanate having a specific shape and dielectric properties significantly improves the high frequency suitability of the resin composition.

Further, it is conceivable to use a granular dielectric inorganic filler such as granular barium titanate, but the granular dielectric filler has a constant relative dielectric constant even when the amount added to the resin is increased. The value does not exceed the value, and the desired relative permittivity cannot be obtained. A resin composition to which a particulate filler is added is insufficient in dimensional stability, heat resistance, mechanical strength, and the like, and is not preferable as a material for electronic / electric parts.

As described above, conventionally, the above-mentioned copper-clad laminate is exclusively used for a high-frequency antenna substrate, and it is impossible to apply a synthetic resin reinforced with a fibrous inorganic filler to such an application. , Not done.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems of the prior art, and as a result, as an inorganic filler, a fibrous material having a specific size and dielectric properties has been synthesized. By blending it in, it has a high dielectric constant and a low dielectric loss tangent equal to or higher than that of conventional copper-clad laminates, has excellent surface smoothness, dimensional stability, heat resistance, etc., high mechanical strength, and high frequency The present inventors have found that a resin composition useful as a material for electronic and electric components used in a band, particularly a material for an antenna substrate of a high-frequency communication device, has been obtained, and the present invention has been completed.

That is, according to the present invention, the synthetic resin matrix has a fiber diameter of 3 μm or less, a fiber length of 5 μm or less, a relative dielectric constant of 50 or more and a dielectric loss tangent of 0.1 or less in a high frequency band of 1 GHz or more. The present invention relates to a resin composition for electronic components, which comprises a fibrous inorganic filler.

In the present invention, the relative dielectric constant and the dielectric loss tangent in the MHz band were measured according to JIS K-6911. The relative permittivity and the dielectric loss tangent in the GHz band were measured using a network analyzer (trade name: 8510C,
HEWLET PACKARD Co., Ltd.).

In the present invention, the synthetic resin serving as the matrix is not particularly limited, and known resins can be used. Specifically, for example, polyethylene, polypropylene, chlorinated polyolefin, 5-methylpentene resin,
Cyclic polyolefin, polystyrene, modified polystyrene, syndiotactic polystyrene, polyphenylene ether, ABS resin, polyamide, acrylic resin, methacrylic resin, polyacetal, polycarbonate, thermoplastic polyimide, polyetherimide, polyamideimide, ionomer resin, polyetherketone, poly Ether nitrile, polyphenylene sulfide, polysulfone, polyester, aromatic polyester, liquid crystal polyester, polyethylene terephthalate, polybutylene terephthalate, thermoplastic resin such as hot-melt fluororesin, phenolic resin, urea resin, melamine resin, guanamine resin, amino resin, Unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicone resin, urethane resin, thermosetting Sex polyphenylene ether,
Triazine resins, thermosetting resins such as polyimides and the like can be mentioned, as the thermoplastic resin, cyclic polyolefin, polyetherimide, liquid crystal polyester, polyphenylene ether, modified polystyrene, heat-fusible fluororesin, polyphenylene sulfide, heat Plastic polyimide, 5-methylpentene resin, syndiotactic polystyrene and the like are preferable, and as the thermosetting resin,
Epoxy resin, thermosetting polyphenylene ether, triazine resin, polyimide and the like are preferable. Among them, the dielectric loss tangent in the high frequency band of 1 GHz or more is 10
^-2 or less are particularly preferable, and specific examples thereof include a cyclic polyolefin, polyetherimide, polyphenylene ether, syndiotactic polystyrene, 5-methylpentene resin, polyphenylene sulfide, liquid crystal polyester, and a heat-meltable fluororesin. be able to.

One type of synthetic resin can be used alone or two or more types can be used in combination.

In the present invention, a fibrous inorganic filler having specific dimensions and dielectric properties is used.
By using such a specific fibrous inorganic filler,
High relative dielectric constant and low dielectric loss tangent are given to synthetic resin, surface smoothness, dimensional stability, heat resistance are improved, mechanical strength is high, signal transmission efficiency in high frequency band is good, and long-term use There is no change in relative dielectric constant. Further, it has been found that the resin composition containing the fibrous inorganic filler has a remarkable increase in the relative dielectric constant in a higher frequency band, and the signal transmission efficiency is further improved. The reason why such a remarkable effect is obtained is not sufficiently clear at present, but since the fibrous material has a specific size and dielectric properties, polarization is likely to occur, and it is presumed that this is involved. .

The size of the fibrous inorganic filler is 3 μm in fiber diameter.
Or less and a fiber length of 5 μm or more. If the fiber diameter exceeds 3 μm, irregularities occur on the surface of the molded product, which hinders signal reception in a high-frequency band of 1 GHz or more (particularly, a frequency band of about 12 GHz or more), resulting in poor signal transmission efficiency.
When the fiber length is less than 5 μm, the effect of improving the mechanical strength and heat resistance becomes insufficient. Further, among the fibrous inorganic fillers having the above-mentioned shape, those having an aspect ratio of 3 or more can be preferably used.

The dielectric properties of the fibrous inorganic filler are 1 GHz
The relative dielectric constant in the above high frequency band is 50 or more, preferably 100 or more, and the dielectric loss tangent is 0.1 or less, preferably 0.05 or less. When the relative permittivity is less than 50, it becomes difficult to reduce the size of the antenna when used as an antenna substrate, for example. If the dielectric loss tangent exceeds 0.1, the signal transmission efficiency deteriorates.

The method for measuring the dielectric properties of the fibrous inorganic filler is as follows. Filling the press mold with the fibrous inorganic filler, applying a pressure of 500 kg to ² t / cm ² ,
Obtain a temporary molded body. The temporary compact is taken out of the mold and fired at 1000 to 1400 ° C. in a muffle furnace. The specific gravity of the obtained sintered body is measured, the porosity is calculated, and the dielectric properties of the sintered body are also measured, and the dielectric properties of the fibrous inorganic filler itself are determined by the logarithmic mixing rule.

The fibrous inorganic filler which can be used in the present invention is not particularly limited as long as it has the above-mentioned specific dimensions and dielectric properties, and examples thereof include fibrous metal titanate. Specific examples of the fibrous metal titanate include, for example, fibrous barium titanate, fibrous calcium titanate, fibrous magnesium titanate, fibrous strontium titanate, fibrous barium strontium titanate, fibrous barium titanate Calcium, fibrous barium magnesium titanate, fibrous alkaline earth metal salts such as fibrous calcium magnesium titanate,
Fibrous metal titanate salts in which some of the alkaline earth metal atoms are replaced with other metals, such as fibrous barium bismuth titanate and fibrous barium neodymium titanate, fibrous lead zirconate titanate, and lead niobate titanate Examples thereof include fibrous metal titanates in which a part of titanic acid such as magnesium is substituted by another metal, and one kind can be used alone or two or more kinds can be used in combination.

Among the above fibrous metal titanates, fibrous alkali metal titanates are preferable, and furthermore, fibrous strontium titanate, fibrous barium strontium, fibrous barium calcium titanate, and fibrous titanate are preferred. Those containing two or more alkaline earth metals such as barium magnesium and fibrous calcium magnesium titanate are particularly preferred.

In the above specific examples, fibrous barium strontium titanate, fibrous barium calcium titanate,
Fibrous barium magnesium titanate, fibrous calcium magnesium titanate and the like are novel fibrous substances, and are disclosed in JP-A-3-281574 or Japanese Patent Application No. 5-91781.
It can be manufactured according to the method described in (1). For example, in water, preferably under weakly alkaline pH 8-10,
(C) fibrous titania compound and (d) Ba source compound, S
At least one of an r source compound, a Ca source compound, and a Mg source compound is mixed, and an aqueous solution of a carbonate such as ammonium carbonate is added thereto.
After depositing at least one of the carbonates of r, Ca and Mg, it can be produced by fractionating and heat-treating it at about 700 to 1100 ° C. As the Ba source compound, the Sr source compound, the Ca source compound and the Mg source compound, known compounds can be used, and examples thereof include acetates and chlorides.

The fibrous inorganic filler may be treated with a surface treating agent for the purpose of further improving the dispersibility of the filler in the synthetic resin. Known surface treatment agents can be used, and examples thereof include coupling agents such as a silane coupling agent and a titanate coupling agent. The amount of the surface treatment agent is not particularly limited,
Usually, it may be in a range that does not impair the dielectric properties and physical properties of the composition of the present invention.

The amount of the fibrous inorganic filler is not particularly limited, and can be appropriately selected from a wide range according to the set value of the relative dielectric constant and the dielectric loss tangent, the use of the composition, and the like. It may be about 95% by weight, preferably about 30 to 75% by weight.

Known additives for resins may be added to the composition of the present invention as long as the dielectric properties and physical properties are not impaired. Specific examples of the additive include, for example, an ultraviolet absorber, an antistatic agent, a surface treatment agent, a compatibilizer, a heat conduction improver, a lubricity improver, a colorant, a dye, an antioxidant, a plasticizer, and an interface. Examples include an activator, a flame retardant, and a plating property improving agent.

The composition of the present invention can be produced by mixing the above synthetic resin and a fibrous inorganic filler according to a known method.

In the composition of the present invention, the desired relative dielectric constant and dielectric loss tangent can be set, for example, by appropriately changing the amount of the fibrous inorganic filler, but usually the ratio in a high frequency band of 1 GHz or more is high. It is preferable that the dielectric constant is 7.0 or more and the dielectric loss tangent is 10 ⁻² or less. By setting such dielectric properties, the signal propagation speed in the high frequency band of the obtained composition is further increased,
Alternatively, the signal loss is reduced, and the signal transmission efficiency is significantly improved.

When the composition of the present invention is applied to applications requiring heat resistance, the deflection temperature under a load of 18.5 kg / cm ² is preferably set to 130 ° C. or higher. This setting can also be easily performed by adjusting the amount of the fibrous inorganic filler to be added.

The composition of the present invention can be formed into a molded article having a desired shape by a known method such as injection molding, extrusion molding, compression molding, cast molding and the like.

For producing a wiring board such as an antenna substrate using the composition of the present invention, a known method can be employed.
For example, after a molded article of the composition of the present invention is etched as required, a metal film such as copper may be formed on the entire surface or a part thereof as necessary, and then wiring may be printed. The formation of the metal film can be performed by a known method such as sputtering, ion plating, and vacuum deposition.
Further, the metal foil may be bonded or pressed with an appropriate adhesive.

[0031]

The composition of the present invention has good dielectric properties such as a high relative dielectric constant and a low dielectric loss tangent, is excellent in surface smoothness, dimensional stability, heat resistance and the like, and has high mechanical strength.

The composition of the present invention has good signal transmission efficiency in a high frequency band, and the higher the frequency, the more the transmission efficiency is improved.

Since the composition of the present invention has excellent surface smoothness, if it is used, for example, as a material for an antenna substrate, it can exhibit extremely good reflection characteristics and further improve the signal transmission efficiency. Is also very easy to print.

The composition of the present invention is excellent in dimensional stability and heat resistance, has high mechanical strength, and has a uniform dispersion of the fibrous inorganic filler and partial deviation of the dielectric properties such as a copper-clad laminate. Therefore, even if the device is used for a relatively high temperature for a long period of time, the dielectric characteristics do not change, and the signal transmission efficiency does not decrease.

In the composition of the present invention, since the dielectric properties are correlated with the amount of the fibrous inorganic filler, the frequency can be easily set by adjusting the amount.

Since the composition of the present invention can be integrally molded by a known molding method, the production of a molded article is very simple.

Since the composition of the present invention has the above-mentioned excellent properties, it can be used in high-frequency bands such as antenna boards of communication devices, printed wiring boards of electronic and electric equipment other than communication devices, and radio wave filters. It can be used very suitably as a material for electrical components. Here, examples of the electronic / electric device other than the communication device include a computer and its terminal, office equipment, measurement and control equipment, video equipment, transportation equipment such as an automobile and an airplane, audio, a television, and a camera.

[0038]

EXAMPLES Reference examples, examples and comparative examples are given below.
The invention will be made clearer. The load deflection temperature (18.5 kgf / cm ² load) shown here is based on JIS K-
6911, tensile strength was measured according to JIS K-7113, bending strength and flexural modulus were measured according to JIS K-7203, and Izod impact strength (with notch) was measured according to JIS K-7110.

Reference Example 1 (Production of fibrous barium strontium titanate) 20.0 g of fibrous titania hydrate (TiO ₂ １ ／ H ₂ O, average fiber length 15 μm, average fiber diameter 0.3 μm)
(0.244 mol) was dispersed in 1 liter of deionized water, and 10 ml of 25% aqueous ammonia was added dropwise with stirring to adjust the pH to 9, and then 153 g of a 20.0% by weight aqueous barium acetate solution (0.120 mol) was added. ) And 127 g (0.123 mol) of a 20.0% by weight aqueous strontium acetate solution were simultaneously added dropwise. The dropping was performed over 30 minutes while stirring at room temperature (20 ° C.). Then, 15% by weight
200 g of an aqueous ammonium carbonate solution was added dropwise with stirring over 60 minutes. After further stirring for 30 minutes, the solid was collected by filtration, washed with water and dried, and 61 g of a white fibrous material was obtained.
I got 30 g of the fibrous material was placed in an alumina crucible and heat-treated at 970 ° C. for 3 hours in an air atmosphere.
4.5 g of fibrous barium strontium titanate were obtained.

The fibrous barium strontium titanate had an average fiber diameter of 0.3 μm, an average fiber length of 8 μm, and an aspect ratio of 27.

A press mold was filled with 8.0 g of fibrous barium strontium titanate, and a pressure of 1 t / cm ² was applied to obtain a temporary molded body. The molded body was taken out and fired in a muffle furnace at 1350 ° C. for 2 hours to obtain a sintered body. The specific gravity of the obtained sintered body was determined, and the porosity was calculated to be 3.2%. The relative dielectric constant of the sintered body at 1 GHz was measured to be 1110, and the relative dielectric constant of fibrous barium strontium titanate itself was calculated to be 1400 by the logarithmic mixing rule. The dielectric loss tangent is 0.
01. Hereinafter, it is referred to as “BSTW”.

Reference Example 2 (Production of fibrous barium titanate) 20.0 g of fibrous titania hydrate (TiO ₂ １ ／ H ₂ O, average fiber length 15 μm, average fiber diameter 0.3 μm)
(0.244 mol) was dispersed in 1 liter of deionized water, and 10 ml of 25% aqueous ammonia was added dropwise with stirring to adjust the pH to 9. Then, 312 g (0.244 mol) of a 20% by weight aqueous barium acetate solution was added. Each was dropped. The dropping was performed over 30 minutes while stirring at room temperature (20 ° C.). Thereafter, a 15% by weight aqueous solution of ammonium carbonate 20
0 g was added dropwise with stirring over 60 minutes. 30 more
After stirring was continued for minutes, the solid was collected by filtration, washed with water and dried to obtain 68 g of a white fibrous material.

30 g of this fibrous material was placed in an alumina crucible and heated at 980 ° C. for 2 hours in an air atmosphere.
24.3 g of a white fibrous barium titanate was obtained.

The fibrous barium titanate has an average fiber diameter of 1 μm, an average fiber length of 10 μm, and an average aspect ratio of 10 μm.
Met. Its relative dielectric constant at 1 GHz is 10
00 and the dielectric loss tangent was 0.02. BTW (A)
That.

Comparative Reference Example 1 The procedure of Reference Example 1 was repeated, except that the heat treatment temperature was changed to 1050 ° C., to obtain a fibrous barium titanate having an average fiber diameter of 1 μm, an average fiber length of 2 μm, and an average aspect ratio of 2. . The dielectric constant at 1 GHz was 850 and the dielectric loss tangent was 0.03. Hereinafter, it is referred to as BTW (B).

Reference Example 3 (Production of Fibrous Calcium Magnesium Titanate) Instead of barium acetate aqueous solution and strontium acetate aqueous solution, 67.7 g of 20% by weight calcium chloride aqueous solution and 58.1 g of 20% by weight magnesium chloride solution were used. , The amount of the aqueous ammonium carbonate solution to be 204 g,
Except that the heat treatment temperature was 980 ° C., the same operation as in Reference Example 1 was performed to obtain fibrous calcium magnesium titanate.

The fibrous calcium magnesium titanate had an average fiber diameter of 0.2 μm, an average fiber length of 8 μm, and an average aspect ratio of 40. The dielectric constant at 1 GHz was 1100 and the dielectric loss tangent was 0.008.
Hereinafter, it is referred to as “CMWT”.

Example 1 A cyclic polyolefin resin (trade name: ZEONEX 280, manufactured by Nippon Zeon Co., Ltd.) at the mixing ratio (% by weight) shown in Table 1
1.30, relative dielectric constant at 1 GHz, dielectric loss tangent
3 × 10 ⁻⁴ ) and fibrous barium titanate (B in Reference Example 2)
TW (A)) to obtain pellets of the present composition.

For mixing, a twin screw extruder (trade name: PCM4)
5, Ikekai Iron Works Co., Ltd.) and cylinder temperature 300
After melting the cyclic polyolefin resin at ℃, adopt a side feed method of adding barium titanate fiber,
After mixing, strand cutting was performed to obtain pellets of the present composition.

Using the pellets obtained, J
The IS specimen was injection molded and the dielectric properties and physical strength were measured. Table 1 shows the results.

Injection molding machine: trade name: FS-150, manufactured by Nissei Plastics Co., Ltd. Cylinder temperature 290 ° C., mold temperature 130 ° C., injection pressure 800 kg / cm ² Comparative Example 1 Fibrous titanium as fibrous filler Barium acid (BTW (B) of Comparative Reference Example 1) or fibrous potassium titanate (trade name: Tismo D, manufactured by Otsuka Chemical Co., Ltd., average fiber diameter 0.4 μm, average fiber length 15 μm, average aspect ratio:
38, relative dielectric constant at 1 GHz: 17, dielectric loss tangent:
0.13, referred to as "PTW (A)")
Test pieces were obtained in the same manner as in Example 1, and physical properties were measured.
Table 1 shows the results.

BTW (B) is a fibrous material whose dielectric properties are within the scope of the present invention but whose dimensions are not within the scope of the present invention.

PTW (A) is a fibrous material whose dimensions are within the scope of the present invention, but whose dielectric properties are not within the scope of the present invention.

[0054]

[Table 1]

As can be seen from Table 1, the resin composition of the present invention containing BTW (A) (Example 1) has a high relative dielectric constant and a low dielectric loss tangent, and is also excellent in overall physical properties.

On the other hand, the resin composition containing BTW (B) (Comparative Example 1, Nos. 2, 3) is as excellent as the composition of the present invention in terms of relative dielectric constant and dielectric loss tangent. However, the heat deformation temperature and flexural modulus are inferior, and it is clear that they are unsuitable for use in electronic components.

The resin composition containing PTW (A) (Comparative Example 1, No. 4) is excellent in overall physical strength, but is not sufficiently high in relative dielectric constant and has a dielectric loss tangent. Is considerably high, so that it is not suitable for a high frequency antenna substrate.

Example 2 A polyetherimide resin (trade name: Ultem [1010-1000, manufactured by Nippon GE Plastics Co., Ltd.]) was used as a matrix resin, and the fibrous barium strontium titanate of Reference Example 2 was used as a fibrous filler. Reference example 2
In the same manner as in Example 1 except that the cylinder temperature was set to 340 ° C. to obtain pellets of the present composition.

Using the obtained pellets, J
The IS specimen was injection molded and the dielectric properties and physical strength were measured. Table 2 shows the results.

Injection molding machine (trade name: FS-150, manufactured by Nissei Plastic Industry Co., Ltd.) Cylinder temperature: 370 ° C., mold temperature: 120 ° C., injection pressure: 700 kg / cm ² Comparative Example 2 Particulate titanium as inorganic filler Barium strontium acid (average particle size 0.8 μm, manufactured by Kyoritsu Ceramics Co., Ltd., “BS
T ") or fibrous potassium titanate (trade name: Tismo N, manufactured by Otsuka Chemical Co., Ltd., average fiber diameter 0.4 μm,
Average fiber length 15 μm, average aspect ratio: 38, 1GH
relative permittivity at z: 18, dielectric tangent: 0.11, "P
TW (B) ”), a test piece was obtained and physical properties were measured in the same manner as in Example 2. Table 2 shows the results.

The PTW (A) is a fibrous material whose dimensions are within the scope of the present invention, but whose dielectric properties are not within the scope of the present invention.

[0062]

[Table 2]

From Table 2, it can be seen that the resin composition of the present invention containing BSTW (Example 2) has a high relative dielectric constant and a low dielectric loss tangent, has excellent physical properties, and has a high frequency band. It is apparent that the lower the dielectric loss tangent is, the higher the relative dielectric constant is, and the higher the signal transmission efficiency is.

On the other hand, the resin composition containing the granular BST (Comparative Example 2, Nos. 2 and 3) has the same relative dielectric constant and dielectric constant at 1 MHz as the composition of the present invention, but 3 GHz. No improvement in the relative permittivity was observed even in the high-frequency band, and the physical properties such as flexural strength, flexural modulus, and deflection temperature under load were remarkably inferior.

The resin composition containing PTW (B) (Comparative Example 2, No. 4) has physical properties similar to those of the present invention, but has a high dielectric loss tangent and is not preferred.

Example 3 Thermotropic liquid crystal polyester resin (trade name: Vectra C950, manufactured by Polyplastics Co., Ltd.) was used as the matrix resin, and the fibrous calcium magnesium titanate of Reference Example 1 (Reference Example 3) was used as the fibrous filler. CMT
W) was further performed using calcium pyrophosphate (average particle size of about 10 μm, manufactured by Taihei Chemical Industry Co., Ltd.) as an etching aid at the compounding ratio (% by weight) shown in Table 3 and a cylinder temperature of 310 ° C. In the same manner as in Example 1, pellets of the present composition were obtained.

Using the obtained pellets, JIS test pieces were injection molded in the same manner as in Example 1 except that the following conditions were employed, and the dielectric properties and physical strength were measured. Table 3 shows the results.

Cylinder temperature 330 ° C., mold temperature 120
° C, injection pressure 800 kg / cm ² Comparative Example 3 A molded product was obtained in the same manner as in Example 3 except that fibrous potassium titanate (Tismo N, PTW (B)) was used as the fibrous inorganic filler. A measurement was made. Table 3 shows the results
Shown in

[0069]

[Table 3]

From Table 3, it can be seen that the resin composition of the present invention containing CMTW (Example 3) shows PTW in physical properties.
Resin composition containing (B) (Comparative Example 3, No. 2,
Although it is almost the same as 3), it can be seen that the relative dielectric constant is high and the dielectric loss tangent is extremely low. It is also found that the relative dielectric constant increases in the high frequency band, as in the case of the BSTW of Example 2.
In addition, it can be confirmed that the calcium pyrophosphate powder blended as an etching aid has almost no effect of improving the dielectric properties.

Example 4 As a matrix resin, a polyetherimide resin (Ultem [1010-1000]) and a PPE resin (trade name:
PPE P101L, manufactured by Asahi Kasei Corporation, 2,6-dimethylphenylene ether homopolymer) and epoxy-modified styrene-styrene graft copolymer (trade name:
RESEDA GP-500, Toa Gosei Chemical Industry Co., Ltd.
) As a fibrous filler in the proportion (% by weight) shown in Table 4 of fibrous barium titanate (BTW (A) of Reference Example 2) or fibrous barium strontium titanate (BSTW of Reference Example 3). Use, cylinder temperature 340 ℃
A pellet of the present composition was obtained in the same manner as in Example 1 except for the above.

Using the obtained pellets, JIS test pieces were injection molded in the same manner as in Example 1 except that the following conditions were employed, and the dielectric properties and physical strength were measured. Table 4 shows the results.

Injection molding machine ... Product name: Minimat 26/1
5B, Sumitomo Heavy Industries, Ltd. Cylinder temperature 340 ° C, mold temperature 80 ° C, injection pressure 1
400 kg / cm ² Comparative Example 4 As an inorganic filler, particulate barium titanate (average particle size: 0.5 μm, manufactured by Fuji Titanium Co., Ltd., “BT”) or fibrous potassium titanate (Tismo N, PT
Except for using W (B)), a test piece was obtained and physical properties were measured in the same manner as in Example 4. Table 4 shows the results.

[0074]

[Table 4]

From Table 4, it can be seen that the resin composition of the present invention containing BTW (A) or BSTW has a high relative dielectric constant and a low dielectric loss tangent, and is also excellent in mechanical properties and heat resistance (heat distortion temperature). You can see that Further, in the high frequency band of 3 GHz, a remarkable improvement in the relative permittivity is recognized.

On the other hand, the resin composition containing the granular BT (Comparative Example 4, No. 2) has the same relative dielectric constant and dielectric loss tangent at 1 MHz as the composition of the present invention. The properties are inferior and the mechanical strength is also extremely low. Further, it can be seen that PTW has a high physical reinforcing effect, but cannot provide satisfactory dielectric properties (especially, dielectric loss tangent) (Comparative Examples 4, Nos. 3, 4).

Example 5 A fluororesin (trade name: Neoflon PFA AP-210, Daikin Industries, Ltd.) was used as the matrix resin, and fibrous barium strontium titanate (BSTW of Reference Example 3) was used as the fibrous filler. And a pellet of the composition of the present invention was obtained in the same manner as in Example 1 except that the cylinder temperature was 390 ° C.

Using the obtained pellets, JIS test pieces were injection molded in the same manner as in Example 1 except that the following conditions were employed, and the dielectric properties and physical strength were measured. Table 4 shows the results.

Cylinder temperature 380 ° C., mold temperature 200
C., injection pressure 500 kg / cm ² Comparative Example 5 As an inorganic filler, barium strontium titanate (BST) or E glass short fiber (diameter 13 μm, length 1.5 mm, aspect ratio about 115, Nippon Electric Glass Fiber ( A test piece was obtained and the physical properties were measured in the same manner as in Example 5 except for using). Table 5 shows the results.

[0080]

[Table 5]

From Table 5, it can be seen that the resin composition of the present invention containing BSTW has a high relative dielectric constant and a low dielectric loss tangent, and is also excellent in mechanical properties and heat resistance (thermal deformation temperature). . Further, in the high frequency band of 3 GHz or more, a remarkable improvement in the relative permittivity is recognized.

On the other hand, the resin composition containing BST in a granular form (Comparative Example 4, No. 2) has the same relative dielectric constant and dielectric loss tangent at 1 MHz as the composition of the present invention, but 3 GHz.
In the above, all the characteristics are remarkably inferior and the mechanical strength is remarkably low. Further, the resin composition containing glass fiber (Comparative Example 5, No. 3) has a small effect of imparting dielectric properties (particularly, a dielectric loss tangent), and also has an insufficient effect of reinforcing mechanical properties.

Example 6 A phenol type epoxy resin (trade name: EPCLON850, manufactured by Dainippon Ink and Chemicals, Inc.) was used as a matrix resin, and fibrous barium titanate (BTW (A) of Reference Example 2) was used as a fibrous filler. ) Or fibrous barium strontium titanate (BSTW of Reference Example 3), respectively, and sufficiently mixed at the blending ratio (% by weight) in Table 6. To this, 15 phr R
(15 parts by weight with respect to 100 parts by weight of the epoxy resin) was added, mixed well and dispersed, and then degassed under vacuum to obtain the present composition.

A spacer having a thickness of 3 mm was placed around the Teflon sheet, and the composition was cast and allowed to stand at room temperature for 3 hours. The composition was cured by heating at 130 ° C. for 3 hours. 18.5 kgf / cm ² load) was measured. The surface roughness (center average roughness Ra) was measured using Surfcom 300B (trade name, manufactured by Tokyo Seimitsu Co., Ltd.). Table 6 shows the results.

Comparative Example 6 As a fibrous filler, E glass short fibers (diameter 13 μm,
The same operation as in Example 6 was performed except that 1.5 mm in length, an aspect ratio of about 115, manufactured by Nippon Electric Glass Fiber Co., Ltd. or fibrous potassium titanate (Tismo D, PTW (A)) was used. , Bending strength, load deflection temperature and surface roughness were measured. Table 6 shows the results.

[0086]

[Table 6]

From Table 6, it can be seen that the reinforcing effect of the mechanical strength is the same in any case, but the resin composition containing BTW (A) or BSTW (Example 6) is made of glass fiber or PT.
Compared with the resin composition containing W (Comparative Example 6), it is found that the dielectric loss tangent is particularly low and the dielectric properties are excellent. Furthermore,
It is found that when glass fibers are contained, the surface smoothness of the composition is remarkably reduced, and the composition cannot be used as a high-frequency electronic component.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ayumi Kuromoto 463 Kagasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture Inside the Tokushima Research Laboratory, Otsuka Chemical Co., Ltd. No. 27 Otsuka Chemical Co., Ltd. (58) Field surveyed (Int. Cl. ⁶ , DB name) C08K 7/00-7/14 H01B 3/00-3/48 H01Q 1/38

Claims (3)

(57) [Claims] 1. A fiber having a fiber diameter of 3 μm in a synthetic resin matrix.
m, a fiber length of 5 μm or more, an aspect ratio of 3 or more, and a fibrous material of an alkaline earth metal titanate salt having a relative dielectric constant of 50 or more and a dielectric loss tangent of 0.1 or less in a high frequency region of 1 GHz or more of 0.1 or less. An antenna substrate for a high-frequency communication device, characterized in that the resin composition has a relative permittivity of 7.0 or more and a dielectric loss tangent of 10 ^-2 or less in a high-frequency range of 1 GHz or more of the resin composition. A resin composition for material molding. 2. A fibrous material alkaline earth metal titanate is fibrous material strontium titanate, fibrous materials barium strontium titanate, fibrous material barium calcium titanate, fibrous barium titanate magnesium
The resin composition according to claim 1, wherein the resin composition is at least one selected from the group consisting of a product and a barium magnesium titanate fibrous material. 3. A resin composition according to claim 1 fibrous material alkaline earth metal titanate is a fibrous material barium strontium titanate.