JP2002100238A - Sheet-like molding and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet-like molding provided with high-frequency properties and electrical insulation properties such as low permittivity and suited to the use wherein its thickness is regulated. SOLUTION: A resin composition is formed by combining a filler characterized as follows: the maximum particle size is 50 μm or less, particle density is 1.0 g/cm3 or less, the particle size gradient expressed by (d10-d90)/d50 in oversize cumulative distribution based on volume is 2.0 or less, d50 is 20 μm or less, and the total amount of elution of boron, alkali metal and alkali earth metal is 500 ppm or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet-like molded product and a laminated product, and more particularly, to an excellent high-frequency characteristic capable of realizing a low dielectric constant and a low dielectric loss tangent which is optimal for an electronic device equipped with a high-frequency circuit. The present invention relates to a sheet-shaped molded article and a laminate having excellent electrical insulation properties. More specifically, a sheet-shaped molded product and a laminate that can be suitably used for applications in which the thickness is regulated in an insulating material, a resin sealing material, a laminated plate, and the like in electronic / electric parts and semiconductor fields, etc. About.

[0002]

2. Description of the Related Art Innovations in electronic technology have been remarkable, and electronic devices have not been reduced in size. Factors that have brought about this include higher density of packaging technology, higher integration of semiconductors, and miniaturization of semiconductor packages. Highly integrated devices are inevitably speeding up, and high speeds themselves have become demands of the times, so clock frequencies for computers, their peripheral devices, digital communication devices, etc. are already several dominant for consumer use. Has become.

[0003] In addition, the advanced information society is promoting the consumer use of communication satellites as a high-density medium of diversified media.
Miniaturized electronic devices are creating new demand for mobile communications and mobile phones. These new media have been assigned higher frequencies to avoid existing spectrum allocations and to secure more channels for mobile radiotelephones. Against this background, electronic devices equipped with a high-frequency circuit are increasing rapidly.

[0004] In view of the above background, there is a demand for a material having a high dielectric constant and a low dielectric loss tangent that can be used in high-speed and high-frequency circuits. Conventionally, as a method that can be used for such a purpose, there is generally a method of introducing air and other inert gas into a resin.
As the introduction method in this case, chemical foaming, gas foaming, and the like are known.

[0005] This technique is difficult to form closed cells,
There are drawbacks such as that the temperature at the time of molding is extremely strict and that large-scale equipment is required. In particular, it is difficult to satisfy the requirements as a sheet-shaped molded product for applications such as electronic devices in which the thickness is regulated and surface smoothness is required. That is, it is difficult to adjust the bubble diameter, and holes may be formed on the surface due to the bubbles, and in some cases, the sheet may penetrate, thereby impairing the smoothness of the surface or impairing the function as an insulating layer. Was.

On the other hand, in order to solve such problems, the present inventors have developed a sheet-like molding in which a resin composed of a fine hollow glass sphere having a specific particle size, particle density and particle size gradient is mixed with a resin. The body and the laminate have been previously proposed, but as the development of applications progresses, more excellent electrical insulation is required, and as a result of further investigation, the present invention has been achieved.

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to a sheet-like molded product having high-frequency characteristics and electrical insulation characteristics that provide a low-dielectric-constant effect and a low-dielectric-tangent effect, and suitable for uses whose thickness is regulated. It is intended to provide a laminate.

[0008]

According to the present invention, the maximum particle size is 50 μm or less, the particle density is 1.0 g / cm ³ or less, (d
_The particle size gradient represented by ₁₀ −d ₉₀ ) / d ₅₀ is 2.0 or less, d ₅₀ is 20 μm or less, and the total amount of boron, alkali metal and alkaline earth metal eluted measured by the following method is the sample. A filler consisting of a fine hollow glass sphere having a mass of 500 ppm or less is added in an amount of 5
The present invention provides a sheet-like molded product obtained by molding a resin composition containing 60% by mass.

The maximum particle size is 50 μm or less, the particle density is 1.0 g / cm ³ or less, the particle size gradient represented by (d ₁₀ −d ₉₀ ) / d ₅₀ is 2.0 or less, and the d ₅₀ is 20 μm or less. ,
In addition, the sum of the elution amounts of boron, alkali metal and alkaline earth metal measured by the following method is 5% of the sample mass.
Provided is a sheet-like molded product obtained by impregnating a porous base material with a resin composition containing 5 to 60% by mass of a filler composed of a minute hollow glass sphere having a content of 00 ppm or less in a total amount with a resin. Further, there is provided a laminate obtained by laminating the above-mentioned sheet-like molded body on a substrate.

However, d ₁₀ , d ₅₀ , and d ₉₀ are particle diameters at which the values of the integrated distribution on a volume-based sieve measured using a laser scattering type particle size analyzer are 10%, 50%, and 90%, respectively. is there.

(Measurement Method of Elution Amount of Boron, Alkali Metal and Alkaline Earth Metal) To a sample (12.5 g) was added 200 cm ³ of distilled water, and the mixture was treated at 97 ° C. for 24 hours with stirring. After the treatment, the solid is filtered, the amounts of boron, alkali metal and alkaline earth metal dissolved in the filtrate are quantified, and the total elution amount of these is expressed as a ratio to the sample mass.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a filler made of a fine hollow glass sphere has a function of firstly lowering the dielectric constant and the dielectric loss tangent of a sheet-like molded product and a laminate. If d ₅₀ of hollow glass microspheres is more than 20 [mu] m, or, if the maximum particle size exceeds 50 [mu] m, in applications where such are used as an electrical insulating layer constituting the multilayer printed circuit board, the thickness is regulated In addition, the minute hollow glass spheres cannot completely fit within the layer thickness, and the possibility of occurrence of surface defects and reduction of the product yield is increased, which is not satisfactory as a sheet-shaped molded body.

When the particle size gradient of the fine hollow glass spheres is more than 2.0, generally when the particle size distribution is wide, the particle density of each particle is likely to be distributed, and the particle density is relatively low. Large particles are not preferred because they cause excessive stress in the processing step and are liable to be crushed, which increases the possibility that the effect of lowering the dielectric constant and the effect of reducing the dielectric loss tangent sufficient for the purpose of use will not be exhibited. More preferably, the particle size gradient is 1.8 or less.

On the other hand, if the particle density exceeds 1.0 g / cm ³ , the effect of lowering the dielectric constant and the effect of lowering the dielectric loss tangent cannot be obtained sufficiently. A more preferred particle density is 0.5 g / cm ³ or less. In the present invention, d ₁₀ , d ₅₀ and d ₉₀ are:
The particle density is measured by a laser scattering particle size analyzer, and the particle density is measured by a dry automatic densitometer.

Further, the filler made of the fine hollow glass spheres of the present invention has a total elution amount of boron, alkali metal and alkaline earth metal of 500 pp of the sample mass.
m or less. When the content exceeds 500 ppm, the possibility of causing a decrease in the electrical insulation of the sheet-like molded body due to elution of soluble components and formation of ions increases. More preferred boron,
Elution amount of alkali metal and alkaline earth metal is 300
ppm or less.

In the present invention, boron, alkali metal and
The method for measuring the elution amount of alkaline earth metals is as follows.
You. That is, 200 ml of distilled water was added to the sample (12.5 g).
cm ^ThreeAt a temperature of 97 ° C. while stirring.
Perform time processing. After the treatment, the solid is filtered and dissolved in the filtrate.
Boron, alkali and alkaline earth metals present
And elute these total elution volumes with respect to the sample mass.
Display as a percentage.

The fine hollow glass sphere used in the present invention is preferably produced by the following method. First, the glass blending raw material is vitrified by heating, and is generally blended at a ratio such that a plurality of different raw materials have a target glass composition. Glass raw materials include quartz sand, shirasu, perlite, pine stone, obsidian, silica gel, zeolite, bentonite, soda ash, borax,
Examples thereof include boric acid, zinc white, lime, calcium phosphate, sodium sulfate, and alumina.

The glass blending material contains a foaming agent. The foaming agent has a function of generating gas when the glass-mixed raw material is vitrified by heating to form a sphere, thereby making the vitrified molten glass hollow. Specific examples include sulfates, carbonates, nitrates, acetates of sodium, potassium, lithium, calcium, magnesium, barium, aluminum and zinc, and crystallization water contained in various raw materials.

Adjustment of the content of the blowing agent is extremely important for obtaining the particle size and particle density of the present invention. For example, in the case of carbonate, 1 to 15 in terms of CO ₂ in the glass raw material is required.
It is preferred that the content be contained so as to be in mass%. When the content of the carbonate is less than 1% by mass, the particle density of the fine hollow glass sphere obtained by insufficient foaming is undesirably increased to more than 1 g / cm ³ . Conversely, when the content of the carbonate exceeds 15% by mass, the amount of the foaming gas is too large and is discharged to the outside without staying inside the particles. As a result, a fine hollow glass spherical body cannot be obtained, which is not preferable.

As a glass obtained from a glass blending raw material
Is borosilicate glass, aluminosilicate glass, stone
British glass is exemplified. Borosilicate glass is S
iO _Two-B_TwoO_Three-Na_TwoO-based glass,
Aluminosilicate glass is made of SiO_Two-Al_TwoO_Three-Na_Two
O or SiO_Two-Al_TwoO_Three-Gas containing CaO as a main component
And quartz glass is made of silicon dioxide (SiO 2)._Two)
Is a single-component glass consisting of
Both are suitably used as glass components of hollow glass spheres.
Used.

[0021] Such glass blended raw materials are then wet ground. Flammable liquids are used as liquids for wet grinding,
Of these, it is preferable to use the same liquid as the slurry liquid at the time of spray combustion because the manufacturing process is simplified. It is preferable to adjust the amount of the liquid so that the concentration of the glass-mixed raw material in the liquid in the wet pulverization process is the same as the concentration of the glass-mixed raw material in the slurry at the time of spraying, since the manufacturing process is simplified.

As the wet mill used, a medium stirring mill represented by a ball mill or a bead mill is more preferable than its fine grinding ability, but other wet mills can also be used. Since contamination from the material of the pulverizer causes a decrease in the yield of the fine hollow glass spheres, the material of the liquid contacting part should be a material with little wear such as alumina, zirconia, alumina / zirconia composite ceramics, or a raw material of glass mixture. It is desirable to select a material having the same composition as a part.

The average particle size of the glass preparation raw material after the wet pulverization is such that a fine hollow glass sphere having a target d ₅₀ and a particle size gradient can be efficiently obtained, and a fine hollow glass sphere having a uniform composition can be obtained. From the viewpoint of being obtained, the thickness is preferably 2 μm or less.

For dispersing and stabilizing the slurry, a dispersant and a dispersion stabilizer may be added. As the dispersant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a polymer surfactant, or the like can be used. Among them, high molecular anionic surfactants are particularly preferable. For example, an acid such as an acid-containing acrylic oligomer which is a copolymer of acrylic acid and an acrylic ester and has a large acid value of about 5 to 100 mgKOH / g. Oligomers and the like are preferred. Such a high molecular weight anionic surfactant contributes to the dispersion and dispersion stabilization of the slurry, and can advantageously suppress the viscosity of the slurry to a low level.

When the glass-mixed raw material thus obtained does not have a predetermined concentration as a slurry, an insufficient amount of liquid is added to adjust the glass-mixed raw material to a predetermined concentration. The concentration of the glass mixture raw material in the slurry is 5-5.
0% by mass is preferable, and 10 to 40% by mass is more preferable. If the concentration of the glass-mixed raw material in the slurry is less than 5% by mass, the basic unit of the flammable liquid forming the slurry is undesirably increased. Conversely, if it exceeds 50% by mass, the viscosity of the slurry increases and handling becomes inconvenient.
Further, it is not preferable because fine droplets during spraying are hindered.

Next, the slurry is sprayed using a two-fluid nozzle or by applying pressure to form droplets. The produced droplets contain a glass blending raw material. If the size of the droplet is too large, combustion by heating becomes unstable or large particles are generated, which is not preferable. On the other hand, if it is too small, the obtained glass composition becomes difficult to be uniform, and the yield of the fine hollow glass spheres is undesirably reduced. Preferred droplet sizes are in the range of 0.1 to 70 μm.

When the droplets are heated, the raw material for glass preparation is melted and vitrified, and the foaming component in the glass is gasified to form a fine hollow glass spherical body.
As the heating means, combustion, electric heating, or the like can be used.
The heating temperature depends on the temperature at which the glass mixture raw material is vitrified. Specifically, it is in the range of 300 to 1800 ° C.
In the present invention, since the liquid component of the slurry is a flammable liquid, it burns and generates heat, contributing to the melting of the glass.

The formed minute hollow glass spheres are recovered by a method using a cyclone, a bag filter, a scrubber, a packed tower, or the like. Next, when the unfoamed product in the recovered powder is removed and only the foamed product is recovered, the product is recovered by a flotation method using water. When sorting low-density foamed products, a method of flotation with alcohol having a low specific gravity is effective. Next, classification treatment is performed so as to have a maximum particle diameter of 50 μm or less. The classification process is not particularly limited,
A method using an air classifier, a sieving device, or the like is preferable.

Further, boron, alkali metals (sodium, potassium, lithium, etc.) and alkaline earth metals (calcium, magnesium, barium, strontium, etc.) are used as raw materials for melting and refining glass and for adjusting viscosity. In such a case, it is highly possible that a part thereof remains on the particle surface during the formation of the fine hollow glass sphere, and in the present invention, the total of the elution amounts of these boron, alkali metal and alkaline earth metal is 500 ppm or less. ,
More preferably, the treatment is performed so as to be 300 ppm or less.

Although there are various methods for this purpose, generally, it is most preferable to wash the obtained fine hollow glass spheres with water as a simple and effective means. The method of washing with water is not particularly limited, but from the viewpoint of increasing the washing efficiency, a method of using hot water at a temperature of 50 ° C. or higher and stirring while stirring is effective. Further, it is more effective to perform the water washing a plurality of times as necessary. The glass sphere may be a glass sphere having a surface on which an elution preventing film is formed, or a glass sphere made of a component having a small amount of elution may be used as it is.

The fine hollow glass sphere produced by the above method has a d ₅₀ measured by a laser scattering type particle size measuring apparatus.
Is 20 μm or less, the particle size gradient is 2.0 or less, and the particle density measured by a dry automatic densitometer is 1.0 g / cm.
³ or less, and has a sufficient hollowness to impart a low dielectric constant and a low dielectric loss tangent.
By excluding those having a particle diameter of more than μm, it is possible to collect those very suitable for applications requiring high surface smoothness or applications in which the thickness of the composite material is regulated. Further, the minute hollow glass sphere can be maintained at a high level without impairing the insulating properties of the sheet-shaped molded product and the laminate of the present invention. Further, as for the particle strength, for example, when used as a filler for a resin, a material having sufficient strength that does not break when formed into a sheet is obtained.

The fine hollow glass sphere obtained in this manner is most suitable as a filler for a resin composition of a sheet-like molded product. Further, in order to improve physical durability such as improvement in chemical durability and adhesion with a thermosetting resin or a thermoplastic resin, for example, perhydropolysilazane is applied to the surface of a fine hollow glass sphere to convert it to a silica film. In this case, it is also preferable to cover the surface of the fine hollow glass sphere with a silica layer, and to further perform a surface treatment with a silane coupling agent.

In the present invention, as the resin, any of a thermosetting resin and a thermoplastic resin can be used. Examples of the thermosetting resin include an epoxy resin, a phenol resin, a furan resin, an unsaturated polyester resin, a xylene resin, an alkyd resin, and a melamine resin.

As the thermoplastic resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride,
Polyvinyl acetate, polyimide resin, polyamide resin, polyamideimide resin, polycarbonate resin, methacrylic resin, ABS resin, polytetrafluoroethylene (P
Fluoropolymers such as TFE), tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and ethylene-tetrafluoroethylene copolymer (ETFE). Can be

In the present invention, the resin composition comprises, as an essential component, a filler comprising a resin and a fine hollow glass sphere.
A solvent, a curing assistant, a coupling agent, and the like are added as necessary. In addition, a fibrous reinforcing material, a filler, an additive, a stabilizer, and a flame retardant can be used alone or in combination with each other as long as the purpose is not impaired.

In the present invention, the compounding ratio of the filler in the resin composition must be 5 to 60% by mass in the total amount of the resin and the filler. If the amount is less than 5% by mass, a sufficient effect of reducing the dielectric constant and the effect of decreasing the dielectric loss tangent cannot be obtained. If the amount exceeds 60% by mass, it becomes difficult to obtain a resin composition having a uniform composition. A more preferable compounding ratio is 10
５０50% by mass.

The present invention is a sheet-shaped resin composition molded article and a laminated body containing a specified amount of such a specified filler. The molded article and the laminated body have excellent high-frequency characteristics and electrical insulation properties. I have. That is, they have a characteristic that enables a low dielectric constant, a low dielectric loss tangent, and excellent electrical insulation.

Specifically, first, as to the high-frequency characteristics, those obtained by using the resin composition containing the filler of the present invention have higher filler properties than those of the same sheet-shaped molded product or laminate. It is possible to easily lower the dielectric constant by 10% or more, preferably 20% or more, and more preferably also to reduce the dielectric loss tangent, as compared with those obtained by using a resin composition that is not blended.

That is, the dielectric constant and the dielectric loss tangent of the sheet-shaped molded product or the laminate of the present invention are 90% or less as compared with those of the sheet-shaped molded product or the laminate without the filler. It is possible to easily obtain a molded product or a laminated product having high frequency characteristics of preferably 80% or less. In the present invention, when the dielectric constant and the dielectric loss tangent are compared between a molded article or a laminated body containing a filler and a molded article or a laminated body not containing the filler, as the sheet-shaped molded articles, the molded articles are the same (the surface-treated articles are the same). The surface-treated products are compared with each other, and the laminate is a comparison between the laminates. The dielectric constant and the dielectric loss tangent are based on JIS K6911 and JIS C648.
1 is measured by the mutual induction bridge method (transformer bridge method).

Next, with regard to the electrical insulation properties, those obtained by using the resin composition containing the filler of the present invention do not contain the filler as compared with the same sheet-shaped molded product or laminated product. Electrical resistance of 110% or more, preferably 150% or more can be easily achieved as compared with that obtained by using the resin composition.

That is, the electric insulation resistance value of the sheet-shaped molded product or the laminate of the present invention is compared with the electric insulation resistance value of the sheet-shaped molded product or the laminated product not containing the filler.
It is possible to easily obtain a molded article or a laminate having an electrical insulating property of 110% or more, preferably 150% or more. In the present invention, when comparing the electrical insulation resistance values of a molded article or a laminated body containing a filler and a molded article or a laminated body not containing the filler, when the sheet-like molded articles are formed, the molded articles are the same as each other (the surface-treated articles have the same surface). In the case of treated products), and in the case of a laminate, a comparison between laminates is meant. Electrical insulation resistance value is JIS K691
1 and JIS C6481.

In the present invention, there is no particular limitation on the method for producing a sheet-shaped molded product from a resin composition containing a filler. Generally, it is preferable to sufficiently stir and mix the composition so as to obtain a uniform composition. Then, for the purpose of uniformly dispersing the fine hollow glass spherical filler in the resin composition, the resin is melted using a high-temperature kneader, a screw-type extrusion kneader, a co-directional twin-screw extruder or the like to form a sheet. It is preferred to mold.

When used as a laminate for a multilayer printed board, the resin composition may be made of glass fiber woven fabric, glass fiber non-woven fabric, polyamide fiber woven fabric, polyester fiber woven fabric, polyester fiber non-woven fabric, polytetrafluoroethylene A sheet-like porous substrate such as a nonwoven fabric or a mixed nonwoven fabric or a mixed woven fabric is impregnated into a sheet to be formed into a sheet. A sheet-shaped molded product may be formed by using a paper or a film as a base material and applying a coating of a predetermined resin composition to the surface thereof.

Further, one or more of these sheet-like molded bodies are laminated on another substrate to form a sheet-like laminate having excellent high-frequency characteristics. In this case, a metal, ceramic, glass, silicon, resin, or the like is suitable as the substrate. As the sheet-shaped molded product or the laminate of the present invention, generally, one having a thickness of 1.0 mm or less is particularly useful, but a thin one may be a film-like one having a thickness of 50 μm or less, and a thick one may be two or less. It may be a laminate of about 0.0 mm.

In addition, the sheet-like molded product and the laminate of the present invention have not only the effect of reducing the dielectric constant and the effect of reducing the dielectric loss tangent, but also the effect of reducing the weight, heat insulation, heat resistance, sound insulation, light scattering, and light resistance. Since it also has various functions of providing impact properties, it can be used as a sheet-like molded article having a wide range of uses that exhibits various composite effects according to the intended use of the resin composition.

[0046]

EXAMPLES Example 1 (Example) 85.0 Silicon Dioxide
g, calcium carbonate 22.5 g, boric acid 18.2 g, dibasic calcium phosphate 5.0 g, lithium carbonate 2.0 g,
After mixing 6.7 g of sodium sulfate, 14.2 g of borax, and 7.7 g of a dispersant (trade name: Homogenol L-1820, manufactured by Kao Corporation) in 600 g of kerosene, a medium stirring mill was used. And wet pulverization to obtain a slurry of the glass mixture raw material. The medium stirring mill used was
The internal volume is 1400 cm ³ , and the beads have an average particle size of 0.6
A zirconia material having a diameter of ⁵ mm was used in an amount of 1120 cm ³ . The operating conditions were 2500 rpm for 30 hours.
min.

The obtained slurry of the glass-mixed raw material was sprayed with a two-fluid nozzle, and fired by approaching a flame to perform spray combustion to produce a fine hollow glass spherical body. The obtained micro hollow glass spheres are collected with a bag filter, mixed with water, and centrifuged to collect only the water-floating product as a slurry. The solution was transferred to a container equipped with a stirrer and a reflux condenser, and washed at 60 ° C. for 3 hours with stirring. The solid was filtered with a reduced pressure filter, and the solid was further washed with 400 cm ³ of deionized water. After washing, filtration and drying at 120 ° C., water floating particles were obtained. Next, the surface of the floating particles was treated with perhydropolysilazane to form a silica layer on the surface of the particles. When the shape of the water-floating particles was observed with a scanning electron microscope, all of the particles were spherical. As a result of X-ray diffraction measurement, it was confirmed that these particles were glassy.

Next, the water floating particles were made of polyester 1
Classification was performed using a turbo screener (trade name: TS125 × 200, manufactured by Turbo Kogyo Co., Ltd.) in which a 7 μm net was set, and sieved products were collected. The particle size of the sieved product can be measured with a laser scattering particle size analyzer (Nikkiso Co., Ltd., trade name Microtrac HR)
A Model 9320-X100, the same applies hereinafter)
As a result, d ₅₀ was 9.5 μm, and in the integrated distribution on a volume-based sieve, d ₁₀ was 13.3 μm, d ₉₀ was 6.8 μm, and the particle size gradient was 0.684. The particle density of the sieved product measured by a dry automatic densitometer (trade name: Acupic 1330, manufactured by Shimadzu Corporation) was 0.39 g / cm ³ . The total elution amount of boron, alkali metal and alkaline earth metal measured by ICP-AES (inductively coupled high frequency plasma atomic emission spectrometry) was 160 ppm.

Next, Epicoat 1 was used as an epoxy resin.
52 (manufactured by Yuka Shell Co., epoxy equivalent: 175, the same applies to the following) dissolved in 85 parts by mass of tetrahydrophthalic anhydride and 1 part by mass of an imidazole-based curing agent, The resin composition was obtained by mixing 15 parts by mass of the filler. An epoxy resin cured product was prepared from this resin composition by a casting method, and a 20 cm square, 3 mm
20mm width, 40mm for thickness and insulation resistance measurement
A test piece was cut out into a sheet having a length of 3 mm.

A conductive silver paste was applied to both sides of the obtained sheet for measuring the relative dielectric constant and the dielectric loss tangent, and the dielectric constant and the dielectric loss tangent were measured in accordance with JIS K6911 (the same applies hereinafter). .8, dielectric loss tangent is 0.01
It was 2. In addition, a test piece for measuring insulation resistance was immersed in boiling distilled water for 48 hours, and the insulation resistance value was also measured according to JISK.
3. Measured according to 6911 (hereinafter the same).
It was 3 × 10 ¹³ Ω.

Example 2 (Comparative Example) A sheet-like molded body was obtained in the same manner as in Example 1 except that the water-washing treatment and the perhydropolysilazane treatment were not performed for the purpose of removing the soluble matter remaining on the particle surface. In addition, the ICP of the obtained fine hollow glass sphere was
-The total elution amount of boron, alkali metal and alkaline earth metal measured using AES was 3000 ppm. The obtained molded article has a dielectric constant of 2.9 and a dielectric loss tangent of 0.2.
012. Further, it was immersed in boiling distilled water for 48 hours, and the insulation resistance value was measured to be 3.6 × 10 ¹⁰ Ω.

Example 3 (Comparative Example) A sheet-like molded product was obtained in the same manner as in Example 1 except that the fine hollow glass sphere was not used. The dielectric constant of the obtained molded body was 3.2 and the dielectric loss tangent was 0.014. In addition, 4 boiling water
After immersion treatment for 8 hours, the insulation resistance value was measured to be 1.7.
× 10 ¹³ Ω.

Example 4 (Example) A glass cullet having an average particle size of about 10 μm (composition SiO ₂ : 59.5%, Al ₂ O ₃ : 17.6) obtained by previously melting and pulverizing the raw materials.
_{%, B 2 O 3: 8.3} %, MgO: 3.1%, CaO:
(3.7%, SrO: 7.8%) 139.6 g, magnesium sulfate 14.0 g, and a dispersant 7.7 g were mixed in 500 g of kerosene, and then wet-ground using a medium stirring mill to prepare a glass mixture. A slurry of the raw material was obtained. The internal volume of the medium stirring mill used was 1400 cm ³ , and the beads were 1120 c beads made of zirconia having an average diameter of 0.65 mmφ.
m ³ put to use. The operating conditions were a stirring rotation speed of 2500.
rpm and wet pulverization for 1 hour to obtain a slurry of the glass mixture raw material.

The kerosene slurry of the obtained glass blending raw material was formed into droplets by using a two-fluid nozzle, and a flame was brought close to the droplets to perform combustion, thereby vitrifying and producing a fine hollow glass spherical body. The resulting micro hollow glass spheres are collected with a bag filter, mixed with water and centrifuged to collect only the water-floating product as a slurry. The solution was transferred to a container equipped with a stirrer and a reflux condenser, and stirred while stirring.
After washing at 7 ° C. for 3 hours, the solid matter was filtered with a reduced pressure filter, and the solid matter was washed with 460 cm ³ of demineralized water, filtered, and then dried at 120 ° C. to obtain water floating particles. . Observing the shape of the water levitating particles with a scanning electron microscope,
All were spherical. As a result of X-ray diffraction measurement, it was confirmed that these particles were glassy.

When the particle size of the recovered powder was measured using a laser scattering particle size analyzer, d ₅₀ was 7.2 μm, d ₁₀ was 3.2 μm in the integrated distribution on a volume-based sieve, and d ₉₀ was 14 μm. At 0.8 μm, the particle size gradient was 1.61. The maximum particle size was about 18.5 μm. The particle density measured by a dry automatic densitometer was 0.54 g / cm ³ . Boron measured using ICP-AES;
The total elution amount of alkali metal and alkaline earth metal is 1
It was 10 ppm.

Then, in the same manner as in Example 1, 85 parts by mass of tetrahydrophthalic anhydride and 1 part by mass of an imidazole-based curing agent were dissolved in 100 parts by mass of Epicoat 152 as an epoxy resin. 35 parts by mass of the filler was mixed to obtain a resin composition. This resin composition was prepared as an epoxy resin cured product by a casting method, and a 20 cm square was used for measurement of relative dielectric constant and dielectric loss tangent.
3 mm thick, 20 mm wide for insulation resistance measurement, 4
A test piece was cut out into a sheet having a length of 0 mm and a thickness of 3 mm.

A conductive silver paste was applied to both sides of the obtained sheet for measuring the relative dielectric constant and the dielectric loss tangent, and the dielectric constant and the dielectric loss tangent were measured in the same manner as in Example 1. The dielectric constant was 2.8 and the dielectric loss tangent was 2.8. Was 0.011. Also, the test piece for insulation resistance measurement was immersed in boiling distilled water for 48 hours,
When the insulation resistance value was measured in the same manner as in Example 1, it was 5.0 ×
It was 10 ¹³ Ω.

[Example 5 (Comparative Example)] Particles after recovery of water-floating product
Except that the operation of removing the soluble residue on the surface was not performed
In the same manner as in Example 4, water floating particles were obtained. Of water levitated particles
When the shapes were observed with a scanning electron microscope, all were true.
It was spherical. As a result of the X-ray diffraction measurement,
It was confirmed to be glassy. Particle density of recovered powder
Is 0.55 g / cm ^ThreeMet. In addition, ICP-AES
Boron, alkali metal and alkaline earth measured using
The total elution amount of similar metals was 1500 ppm.

Next, in the same manner as in Example 1, 85 parts by mass of tetrahydrophthalic anhydride and 1 part by mass of an imidazole-based curing agent were dissolved in 100 parts by mass of Epicoat 152 as an epoxy resin. The resin composition was obtained by mixing 36 parts by mass of the filler. This resin composition was prepared as an epoxy resin cured product by a casting method, and a 20 cm square was used for measurement of relative dielectric constant and dielectric loss tangent.
3 mm thick, 20 mm wide for insulation resistance measurement, 4
A test piece was cut out into a sheet having a length of 0 mm and a thickness of 3 mm.

A conductive silver paste was applied to both sides of the obtained sheet for measuring the relative dielectric constant and the dielectric loss tangent, and the dielectric constant and the dielectric loss tangent were measured in the same manner as in Example 1. The dielectric constant was 2.8 and the dielectric loss tangent was 2.8. Was 0.012. The obtained test piece for insulation resistance measurement was immersed in boiling distilled water for 48 hours, and the insulation resistance value was measured in the same manner as in Example 1. The result was 1.5 × 10 ¹¹ Ω.

Example 6 (Example) Tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (Aflon PFA P-62X, trade name, manufactured by Asahi Glass Co., Ltd.) 1
To 00 parts by mass, 15 parts by mass of the filler composed of the fine hollow glass spheres of Example 1 were added, and a pellet was produced using a co-directional twin screw extruder under the conditions of a cylinder temperature of 350 ° C. and a pressure of 100 MPa. In addition, the pellet
It is compression molded into a 20 cm square, 1 mm thick sheet with a load of 0.5 MN at 0 ° C.
μm). The dielectric constant of this sheet-shaped molded product was 1.6 and the dielectric loss tangent was 0.0002.

Example 7 (Comparative Example) 20c was prepared in the same manner as in Example 6 except that the fine hollow glass spheres were not used.
A sheet-shaped molded body having an m-square and a 1 mm-thickness on which aluminum was deposited on both sides was obtained. The dielectric constant of the obtained sheet-like molded product was 2.
1. The dielectric loss tangent was 0.0003.

Example 8 (Example) Silicon dioxide 17.5
g, 4.5 g of calcium carbonate, 7.8 g of borax, 1.0 g of dibasic calcium phosphate, 0.6 g of sodium sulfate, 0.4 g of potassium carbonate, and 1.6 g of a dispersing agent to prepare a glass mixture raw material. It was wet-pulverized using a ball mill to obtain a slurry of the glass-mixed raw material. The ball mill used was a table-top ball mill with an internal volume of 500 cm ^3.
I put about ³ and used it. The glass blended raw material and 150 g of kerosene were put therein, and wet pulverized at 100 rpm for 8 hours to obtain a slurry of the glass blended raw material.

The obtained slurry of the glass-mixed raw material was sprayed with a two-fluid nozzle, ignited by approaching a flame, spray-burned, and vitrified to produce a fine hollow glass spherical body. The obtained micro hollow glass spheres are collected with a bag filter, mixed with water, and centrifuged to collect only the water-floating product as a slurry. The solution was transferred to a container equipped with a stirrer and
After washing at 0 ° C. for 6 hours, the solid was filtered with a reduced pressure filter, and the solid was washed with 100 cm ³ of demineralized water, filtered, and then dried at 120 ° C. to obtain water floating particles. . Next, the surface of the water floating particles was treated with perhydropolysilazane to form a silica layer on the surface of the particles. When the shape of the water-floating particles was observed with a scanning electron microscope, all of the particles were spherical. As a result of X-ray diffraction measurement, it was confirmed that these particles were glassy.

Next, the water floating particles were made of polyester 2
Classification was performed using the same turbo screener as in Example 1 in which a 4 μm net was set, and the sifted product was collected. When the particle size of the sieved product was measured with a laser scattering particle size analyzer, d ₅₀ was 10.5 μm, and in the integrated distribution on the volume-based sieve, d ₁₀ was 16.2 μm and d ₉₀ was 6.5 μm. The particle size gradient was 0.92. The particle density measured by a dry automatic densitometer was 0.38 g / cm ³ . The total elution amount of boron, alkali metal and alkaline earth metal measured by ICP-AES was 130 ppm. The breaking strength when the volume was reduced by 10% on a volume basis by hydrostatic pressure was 40 MPa.

A resin obtained by dissolving 3 parts by mass of dicyandiamide and 0.2 parts by mass of 2-ethyl-4-methylimidazole as a curing agent in 100 parts by mass of an epoxy resin (trade name: Epicoat 1001, manufactured by Yuka Shell Co., Ltd., epoxy equivalent: 480) Then, 40 parts by mass of a filler composed of the above-mentioned fine hollow glass spheres which had been previously treated with perhydropolysilazane and further subjected to surface treatment with a silane coupling agent were blended to obtain a resin composition. This resin composition was weighed at 70 g / m
Impregnating a ^second glass fiber fabric (manufactured by Asahi-Schwebel Co., Ltd.), to obtain a prepreg molded in resin amount 59 mass% of the sheet is dried.

This prepreg was prepared with a 20 mm width, 40 mm
The test piece was cut out into a sheet of length. The test piece for insulation resistance measurement was immersed in boiling distilled water for 48 hours, and the insulation resistance value was measured in the same manner as in Example 1.
0 ¹³ Ω.

Next, the 11 prepregs were stacked, and copper foil (thickness: 35 μm) was stacked above and below the prepreg.
Laminate molding at 0 ° C., pressure 8 MPa for 90 minutes, sheet thickness 1.6
mm copper-clad laminate was obtained. The obtained laminate had a dielectric constant of 3.6 and a dielectric loss tangent of 0.013.

Example 9 (Comparative Example) A resin composition, a prepreg, and a copper-clad laminate were obtained in the same manner as in Example 8, except that the fine hollow glass spheres were not used. The insulation resistance value of the obtained prepreg was 1.7 × 10 ¹³ Ω, the dielectric constant of the obtained laminate was 4.9, and the dielectric loss tangent was 0.026.
Met.

[0070]

Industrial Applicability The sheet-like molded product and laminate of the present invention are capable of reducing the dielectric constant and the dielectric loss tangent, have excellent insulating properties, and have a fine hollow spherical shape having a specific particle size, particle size distribution and density. It is made of a resin composition containing a specific amount of a filler made of a body, and can be used very suitably for applications such as high-speed and high-frequency circuits that require excellent high-frequency characteristics whose thickness is regulated. Further, the sheet-shaped molded body and the laminated body of the present invention are electronic and electric parts, insulating materials such as semiconductors,
It can also be suitably used in fields such as resin sealing materials and laminates.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08K 7/28 C08K 7/28 5G333 C08L 101/00 C08L 101/00 H01B 17/56 H01B 17/56 LF term (reference) ) 4F071 AA01 AA42 AB28 AC09 AC12 AD04 AE03 AE17 AH13 BA03 BB01 BC01 4F072 AA04 AA07 AB09 AB30 AD28 AE01 AF27 AG03 AH04 AH22 AJ04 AK05 AK14 AL12 AL13 4F100 AA04 AA07 AA08 A04A23A04 A04A04A04A04A04A01 JG05A YY00A 4J002 AA011 AA021 BB031 BB121 BD041 BD101 BD151 BD161 BG061 BN151 CC031 CC041 CC121 CC181 CD001 CF011 CF211 CG001 CL001 CM041 DL006 FA096 FD016 GF00 5G303 AA07 AB06 AB07 BA02 CA02 CB CB CB CB CB CB CB CB CB CB CB CB CB CB

Claims (6)

[Claims] (1) a maximum particle diameter of 50 μm or less, a particle density of 1.0 g / cm ³ or less, a particle size gradient represented by (d ₁₀ −d ₉₀ ) / d ₅₀ of 2.0 or less, and a d ₅₀ of 20 μm or less. And the sum of the amounts of boron, alkali metal and alkaline earth metal eluted measured by the following method is 500% of the sample mass.
A sheet-like molded product obtained by molding a resin composition containing 5 to 60% by mass of a filler composed of minute hollow glass spheres having a content of not more than 1 ppm in a total amount with a resin. Where d ₁₀ , d
_50, d _90, the value of cumulative distribution on a volume basis sieve was measured using a laser scattering type particle size measuring apparatus, each 10
%, 50%, and 90%. (Method for Measuring Elution Amount of Boron, Alkali Metal and Alkaline Earth Metal) A sample (12.5 g) was mixed with 200 ml of distilled water.
cm ³ was added and stirred at a temperature of 97 ° C. for 24 hours.
Perform time processing. After the treatment, the solid is filtered, the amounts of boron, alkali metal and alkaline earth metal dissolved in the filtrate are quantified, and the total elution amount of these is expressed as a ratio to the sample mass. 2. The maximum particle size is 50 μm or less, the particle density is 1.0 g / cm ³ or less, the particle size gradient (d ₁₀ −d ₉₀ ) / d ₅₀ is 2.0 or less, and the d ₅₀ is 20 μm or less. And the sum of the amounts of boron, alkali metal and alkaline earth metal eluted measured by the following method is 500% of the sample mass.
A sheet-like molded product obtained by impregnating a porous base material with a resin composition containing 5 to 60% by mass of a filler composed of a fine hollow glass sphere having a content of not more than 1 ppm in a total amount with a resin. However, d ₁₀ , d ₅₀ , and d ₉₀ are the particle diameters at which the values of the integrated distribution on a volume-based sieve measured using a laser scattering type particle size analyzer are 10%, 50%, and 90%, respectively. (Method for Measuring Elution Amount of Boron, Alkali Metal and Alkaline Earth Metal) A sample (12.5 g) was mixed with 200 ml of distilled water.
cm ³ was added and stirred at a temperature of 97 ° C. for 24 hours.
Perform time processing. After the treatment, the solid is filtered, the amounts of boron, alkali metal and alkaline earth metal dissolved in the filtrate are quantified, and the total elution amount of these is expressed as a ratio to the sample mass. 3. The sheet-shaped molded product according to claim 1, wherein the filler has a particle density of 0.5 g / cm ³ or less. 4. A laminate obtained by laminating the sheet-like molded product according to claim 1, 2 or 3 on a substrate. 5. The dielectric constant of the sheet-like molded product according to claim 1, 2 or 3 or the laminate of claim 4 is compared with the dielectric constant of the sheet-like molded product or laminate without the filler. And 90% or less. 6. The insulation resistance value of the sheet-like molded product according to claim 1, 2 or 3, or the insulation resistance value of the sheet-like molded product or laminate not containing the filler. A sheet-like molded product or a laminate that is 110% or more as compared with