KR101178785B1 - Laminate plate, use therefor, and production method thereof - Google Patents

Abstract

This invention is a laminated board provided with the nonwoven fabric layer containing a thermosetting resin composition, In the said thermosetting resin composition, an inorganic filler contains 80-400 volume parts with respect to 100 volume parts of thermosetting resins, The said inorganic filler is (A) Gibbsite type aluminum hydroxide particles having an average particle diameter (D ₅₀ ) of 2 to 15 µm. (B) 1.5 ~ 15 ㎛ a mean particle diameter (D ₅₀₎ for having boehmite (boehmite) particles, 1.5 ~ 15 ㎛ a mean particle diameter (D ₅₀₎ to have, a number determined by the glass starting temperature than 400 ℃ At least one inorganic component selected from the group consisting of inorganic particles containing or not containing crystal water and (C) a particulate component consisting of aluminum oxide particles having an average particle diameter (D ₅₀ ) of 1.5 µm or less. And the mixing ratio (volume ratio) of the gibbsite-type aluminum hydroxide particles (A), the inorganic component (B), and the fine particle component (C) is from 1: 0.1 to 3: 0.1 to 3. .

Description

Laminate, Metal Foil Clad Laminate, Printed Wiring Board, Circuit Board and LED Backlight Unit, LED Lighting Device, Manufacturing Method of Laminate {{LAMINATE PLATE, USE THEREFOR, AND PRODUCTION METHOD THEREOF}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to laminates for various electronic devices, metal foil clad laminates, printed wiring boards and circuit boards, LED backlight units, and methods for manufacturing the laminates, and particularly, for mounting heating components such as light emitting diodes (LEDs). It is related with the laminated board used.

Conventionally, the laminated board which laminated | stacked and integrated the surface material layer which contained the resin composition in the woven fabric base material on the surface of the nonwoven fabric layer which contained the resin composition in the nonwoven fabric base material is provided (for example, Japanese patent application publication number) 2006-272671). Such a laminated board is processed into the printed wiring board for mounting an electrical and electronic component by forming a conductor pattern on the surface, and is processed into a circuit board by forming an electrical circuit using this conductor pattern.

However, in recent years, since a large amount of heat generation is used as an electrical / electronic component mounted in a laminated board, or the mounting density of the electrical / electronic component which generate | occur | produces heats up, in order to respond to such a case, the laminated board with high heat dissipation is desired. there was. It is because when the laminated board with high heat dissipation is used, heat generated from the electrical and electronic components easily radiates through the laminated board, and the life of the electrical and electronic components can be extended.

Japanese Patent Application Publication No. 2006-272671

This invention is made | formed in view of the point mentioned above, and an object of this invention is to provide the laminated board with high heat dissipation, and its manufacturing method, without impairing heat resistance and a drill workability. Moreover, an object of this invention is to provide the metal foil clad laminated board, a printed wiring board, a circuit board, an LED backlight unit, and an LED illuminating device with high heat dissipation.

A laminated plate provided with a nonwoven fabric layer containing the thermosetting resin composition of the present invention, wherein the thermosetting resin composition contains 80 to 400 parts by volume with respect to 100 parts by volume of the thermosetting resin, and the inorganic filler comprises (A) 2 and gibbsite (gibbsite) type aluminum hydroxide particles having an average particle diameter (D ₅₀₎ of ~ 15 ㎛, (B) having an average particle diameter of 1.5 ~ 15 ㎛ (D ₅₀₎ for having boehmite (boehmite) particles, 1.5 At least one inorganic material selected from the group consisting of inorganic particles having a crystal starting water having a glass starting temperature of 400 ° C. or higher or containing no crystal water having an average particle diameter (D ₅₀ ) of ˜15 μm. component and, (C) 1.5㎛ than average particle diameter (D ₅₀₎ having a composition containing fine particles made of aluminum oxide particles, wherein the gibbsite-type aluminum hydroxide particles (a) and the inorganic components of (B) It is characterized in that from 0.1 to 3: mixing ratio (volume ratio) of the particulate component (C), 1: 0.1-3.

It is preferable that a woven fabric layer is formed on the surface of the nonwoven fabric layer.

It is preferable that the said thermosetting resin contains the epoxy resin.

It is preferable that the said thermosetting resin contains the phenol compound as a hardening | curing agent component of the said epoxy resin.

It is preferable that the said thermosetting resin contains an epoxy vinyl ester resin, a radically polymerizable unsaturated monomer, and a polymerization initiator.

It is preferable that the binder of the nonwoven fabric base material of the said nonwoven fabric layer is an epoxy compound.

It is preferable that the said woven fabric layer contains aluminum hydroxide.

The metal foil clad laminate of the present invention is characterized by forming a metal foil on at least one surface of the laminate.

The printed wiring board of the present invention is characterized by providing a conductor pattern on at least one surface of the laminate.

The circuit board of the present invention is characterized by forming a circuit on at least one surface of the laminate.

The LED backlight unit of the present invention is characterized in that the LED is mounted on at least one surface of the laminate.

The LED lighting apparatus of the present invention is characterized by mounting an LED on at least one surface of the laminate.

The manufacturing method of the laminated board of this invention impregnates the said nonwoven fabric base material with an inorganic filler continuously conveying a nonwoven fabric base material, laminates a woven fabric on both surfaces, conveying this nonwoven fabric base material continuously, As a manufacturing method of the laminated board which hardens the said thermosetting resin composition by pressing and heating this laminated body with a roller, and forms a nonwoven fabric layer and a woven fabric layer,

In the thermosetting resin composition, is contained unit 80-400 volume with respect to the portion thermosetting resin 100 by volume, the inorganic filler, (A) gibbsite type aluminum hydroxide particles having an average particle diameter (D ₅₀₎ of 2 ~ 15 ㎛ and, (B) containing water of crystallization less than 1.5 to 15 ㎛ a mean particle diameter (D ₅₀₎ for having boehmite particles and 1.5 to an average particle size of 15 ㎛ (D ₅₀₎ for having, a glass starting temperature 400 ℃ At least one inorganic component selected from the group consisting of inorganic particles containing no or no crystal water, and (C) a particulate component consisting of aluminum oxide particles having an average particle diameter (D ₅₀ ) of 1.5 µm or less, The mixing ratio (volume ratio) of the said gibbsite type aluminum hydroxide particle (A), the said inorganic component (B), and the said microparticles | fine-particles component (C) is 1: 0.1-3: 0.1-3, It is characterized by the above-mentioned.

In the laminated board of this invention, heat dissipation can be improved, without impairing heat resistance and a drill workability.

In the metal foil clad laminate, the printed wiring board, the circuit board, the LED backlight unit, and the LED lighting apparatus of the present invention, heat dissipation can be improved.

The manufacturing method of the laminated board of this invention can manufacture a laminated board continuously, and can improve productivity compared with a batch type.

(A) is sectional drawing which shows an example of embodiment of the laminated board of this invention, (b) is sectional drawing which shows an example of another embodiment.
It is a figure which shows schematically an example of embodiment of the manufacturing method of the laminated board of this invention.
3 is a diagram schematically showing an example of an embodiment of the LED backlight unit of the present invention.
4 shows another example of the embodiment of the LED backlight unit of the present invention, and (a) and (b) are schematic views.

Hereinafter, embodiments for carrying out the present invention will be described.

As shown to Fig.1 (a), the laminated board A of this invention is provided with the nonwoven fabric layer 1 containing a thermosetting resin composition. The nonwoven fabric layer 1 can be formed with the hardened | cured material of the prepreg etc. which contain a thermosetting resin composition in a nonwoven fabric base material.

As the nonwoven fabric base material, for example, any one selected from glass nonwoven fabric and glass paper, or synthetic resin nonwoven fabric and paper using synthetic resin fibers such as aramid fibers, polyester fibers, and polyamide fibers (nylon) can be used. Although the thickness of a nonwoven fabric base material can be 10-300 micrometers, it is not limited to this. It is preferable to use the epoxy compound excellent in thermal strength as a binder of a nonwoven fabric base material. A binder is a binder for bonding and solidifying the fiber which comprises a nonwoven fabric base material here. An epoxy silane etc. can be used as an epoxy compound of a binder. Moreover, it is preferable to mix | blend 5-25 mass parts of binders with respect to 100 mass parts of fibers which comprise a nonwoven fabric base material.

The thermosetting resin composition contains a thermosetting resin and an inorganic filler. As a thermosetting resin, liquid thermosetting resin can be used at normal temperature, for example. Moreover, as a thermosetting resin, the mixture of a resin component and a hardening | curing agent component can be used. As a resin component, radical polymerization type thermosetting resins, such as an epoxy resin, an unsaturated polyester resin, and a vinyl ester resin, etc. can be used.

As specific thermosetting resin, what used the epoxy resin as a resin component can be illustrated. In this case, at least one selected from the group consisting of bisphenol A type, bisphenol F type, cresol novolak type, phenol novolak type, biphenyl type, naphthalene type, fluorene type, xanthene type, dicyclopentadiene type and anthracene type One epoxy resin can be used. Moreover, although dicyandiamide and a phenolic compound can be used as a hardening | curing agent component of an epoxy resin, it is preferable to use a phenolic compound for the improvement of the heat resistance of a laminated board. As this phenolic compound, allylphenol, a phenol novolak, an alkyl phenol novolak, a triazine structure containing phenol novolak, bisphenol A novolak, a dicyclopentadiene structure containing phenol resin, a xyloxic phenol, terpene modified phenol, polyvinyl phenols , At least one selected from the group consisting of naphthalene structure-containing phenol-based curing agents and fluorene structure-containing phenol-based curing agents can be used. In addition, the hardening | curing agent component of a phenol compound can be mix | blended 30-120 mass parts with respect to 100 mass parts of epoxy resins.

As another example of specific thermosetting resin, epoxy vinyl ester resin can be used as a resin component, In this case, a radically polymerizable unsaturated monomer and a polymerization initiator can be used as a hardening | curing agent component.

The epoxy resin used to obtain the epoxy vinyl ester resin is not particularly limited in structure, and examples thereof include bisphenol type epoxy resins, novolac type epoxy resins, alicyclic epoxy resins, glycidyl esters, and glycidyl. Amines, heterocyclic epoxy resins, brominated epoxy resins, and the like. Examples of the bisphenol epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin and bisphenol S epoxy resin. As said novolak-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a bisphenol A novolak-type epoxy resin, a dicyclopentadiene novolak-type epoxy resin, etc. are mentioned. Examples of the alicyclic epoxy resins include 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo Hexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, etc. are mentioned. Phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester, etc. are mentioned as said glycidyl ester. Examples of the glycidylamines include tetraglycidyldiaminodiphenylmethane, triglycidyl P-aminophenol, N, N-diglycidylaniline, and the like. As said heterocyclic epoxy resin, 1, 3- diglycidyl-5, 5- dimethyl hydantoin, triglycidyl isocyanurate, etc. are mentioned, for example.

Examples of the brominated epoxy resins include tetrabromo bisphenol A type epoxy resins, tetrabromo bisphenol F type epoxy resins, brominated cresol novolac type epoxy resins, and brominated phenol novolac type epoxy resins.

It is preferable to use brominated epoxy resin among the said epoxy resins from the point which is especially excellent in flame retardance. Moreover, the epoxy resin which made the carboxyl group-containing rubbery polymer react with a part of epoxy groups of these epoxy resins can also be used. The epoxy resin which made such carboxyl group-containing rubbery polymer react is especially preferable at the point which improves impact resistance, punching workability, and interlayer adhesiveness of laminated boards, such as the copper clad laminated board obtained.

Examples of the carboxyl group-containing rubbery polymer include those in which a carboxyl group-containing monomer and a conjugated diene-based monomer are copolymerized with other monomers, or a copolymerized diene-based monomer and another monomer with a carboxyl group. . The carboxyl group may be located anywhere in the terminal and side chain of a molecule | numerator, and the quantity is preferably 1-5 in 1 molecule, and more preferably 1.5-3.

Examples of the conjugated diene monomer include butadiene, isoprene and chloroprene. In addition, other monomers used as needed include acrylonitrile, styrene, methyl styrene, halogenated styrene, etc., but acrylonitrile is added to the rubbery polymer in consideration of compatibility with the radically polymerizable unsaturated monomer of the reaction product obtained. It is preferable to copolymerize 10-40 weight%, and it is more preferable to copolymerize 15-30 weight%.

And in manufacturing an epoxy vinyl ester resin, you may make each component of an epoxy resin, a carboxyl group-containing rubbery polymer, and ethylenically unsaturated monobasic acid react simultaneously, and after making an epoxy resin and a carboxyl group-containing rubbery polymer react, You may make ethylenic unsaturated monobasic acid react. In this case, the reaction ratio of the epoxy resin used to obtain the epoxy vinyl ester resin, the carboxyl group-containing rubbery polymer and the ethylenically unsaturated monobasic acid is not particularly limited, but the carboxyl group-containing polymer is added per 1 equivalent of the epoxy group of the epoxy resin. It is preferable that the total carboxyl group of the free-form polymer and the ethylenically unsaturated monobasic acid is in the range of 0.8 to 1.1 equivalents, and in particular, it is preferable to be in the range of 0.9 to 1.0 equivalents in terms of obtaining a resin having excellent storage stability. .

In addition, in the manufacture of epoxy vinyl ester resin, as ethylenic unsaturated monobasic acid used for reaction with an epoxy resin, it is (meth) acrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethyl maleate, Monobutyl maleate, sorbic acid, and the like, among others, methacrylic acid is preferred.

The radically polymerizable unsaturated monomer has at least one radically polymerizable unsaturated group in one molecule. As such a radically polymerizable unsaturated monomer, for example, diallyl phthalate, styrene, methyl styrene, halogenated styrene, (meth) acrylic acid, methyl methacrylate, ethyl methacrylate, butyl acrylate, divinylbenzene, ethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate, among which 1 type, or 2 or more types are used.

And about the compounding quantity of a radically polymerizable unsaturated monomer, it is preferable to set it as the ratio of 25 mass parts or more and 45 mass parts or less with respect to 100 mass parts of total amounts of an epoxy vinyl ester resin and a radical polymerizable unsaturated monomer. When it is 25 mass parts or more, the impregnation with the nonwoven fabric base material and woven fabric base material of the thermosetting resin composition obtained becomes favorable, and when it is 45 mass parts or less, the laminated board obtained using this thermosetting resin composition is excellent in dimensional stability, This is because high heat resistance is also excellent.

As said polymerization initiator, ketone peroxides, such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, diacyl peroxides, such as benzoyl peroxide, isobutyl peroxide, cumene hydroperoxide, hydroperoxides such as tert-butyl hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-tert-butyl peroxide, 1,1-di-tert-butylperoxy-3,3, Peroxy ketals such as 5-trimethylcyclohexanone and 2,2-di (tert-butylperoxy) -butane, alkyls such as tert-butylperbenzoate and tert-butylperoxy-2-ethylhexanoate Organic peroxides such as peresters, bicarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate, tert-butylperoxyisobutyl carbonate, and the like; Species or two or more kinds are used. By using such an organic peroxide, a thermosetting resin composition is heat-hardened.

Although it does not restrict | limit especially about the compounding quantity of the polymerization initiator with respect to a thermosetting resin, It is preferable to set in about 0.5-5.0 mass parts with respect to 100 mass parts of total amounts of an epoxy vinyl ester resin and a radically polymerizable unsaturated monomer. It is more preferable to make it into the range of 0.9-2.0 mass parts especially in consideration of the varnish life and curability of a thermosetting resin composition.

Boehmite particles having an inorganic filler, 2 ~ 15 ㎛ a mean particle diameter (D ₅₀₎ for having gibbsite-type aluminum hydroxide particles (A) and 1.5 to an average particle size of 15 ㎛ (D _50), and from 1.5 to At least one inorganic component (B) having an average particle diameter (D ₅₀ ) of 15 μm and selected from the group consisting of inorganic particles containing crystal water having a glass starting temperature of 400 ° C. or higher or free of crystal water; , it uses a fine-particle component (C) consisting of aluminum oxide particles having an average particle diameter (D ₅₀₎ of less than 1.5㎛. In addition, in this specification, the average particle diameter of an inorganic filler calculates a cumulative curve using 100% of the total volume of the powder population obtained by measuring by the laser diffraction type particle size distribution measuring apparatus, and the cumulative curve is 50 It means the particle diameter of the point which becomes%.

The gibbsite type aluminum hydroxide particles (A) are aluminum compounds represented by Al (OH) ₃ or Al ₂ O _{3 to 3} H ₂ O, and are components which give the laminated plate A a good balance of thermal conductivity, flame retardancy, and drillability. to be. In addition, long is the average particle diameter (D ₅₀₎ of site-type aluminum hydroxide particles (A) is a 2 ~ 15 ㎛, and preferably 3 ~ 10 ㎛. When the average particle diameter (D ₅₀ ) of the gibbsite-type aluminum hydroxide particles (A) exceeds 15 µm, the drillability is lowered, and when it is less than 2 µm, the thermal conductivity is lowered and the productivity is lowered. Further, Gibb as site-type aluminum hydroxide particles (A), having an average particle diameter (D ₅₀₎ is 2 ~ 10 ㎛ the first gibbsite-type aluminum hydroxide with a mean particle size (D ₅₀₎ is 10 ~ 15 ㎛ second It is preferable to use a blend with a gibbsite type aluminum hydroxide in that the heat dissipation property is further improved as the filler is more densely packed.

The inorganic component (B) is at least one selected from the group consisting of boehmite particles and inorganic particles having a glass starting temperature of 400 ° C. or higher or containing no crystal water. Boehmite particles are aluminum compounds represented by (AlOOH) or (Al ₂ O _{3 to} H ₂ O), and are components that impart thermal conductivity and flame retardance without lowering the heat resistance of laminate A. The average particle diameter (D ₅₀ ) of the boehmite particles is 1.5 to 15 μm, preferably 3 to 10 μm. When the average particle diameter (D ₅₀ ) of the boehmite particles exceeds 15 µm, the drillability decreases, and when it is less than 1.5 µm, the thermal conductivity falls and the productivity decreases.

The inorganic particle which contains the crystal water whose glass start temperature is 400 degreeC or more, or does not have crystal water is a component which provides thermal conductivity and flame retardance, without reducing the heat resistance of a circuit board. Specific examples of such inorganic particles include inorganic oxides such as titanium oxide (no crystal water), magnesium oxide (no crystal water) and crystalline silica (no crystal water); Inorganic nitrides such as boron nitride (no crystal water), aluminum nitride (no crystal water), and silicon nitride (no crystal water); Inorganic carbides such as silicon carbide (no crystal water); And natural minerals, such as talc (glass start temperature 950 degreeC), kaolin (glass start temperature 500-1000 degreeC), etc. are mentioned. These may be used independently and may be used in combination of 2 or more type. Among these, crystalline silica, talc, kaolin, clay and the like are particularly preferable in terms of excellent thermal conductivity. And the glass start temperature of crystal water can be measured using thermogravimetric analysis (TGA) or differential scanning calorimetry (DSC). The average particle diameter of the inorganic particles (D ₅₀₎ is a 1.5 ~ 15 ㎛, and preferably 3 ~ 10 ㎛. When the average particle diameter of the inorganic particles (D ₅₀₎ is more than 15㎛, there is a fear that the drill machinability lowered. And the upper limit of glass start temperature is not specifically set, For example, it is 1000 degreeC.

In addition, as an inorganic component (B), in order to reduce the abrasion of the drill at the time of drilling, Mohs hardness needs to be smaller than Mohs hardness 12 of aluminum oxide, Preferably it is 7.5 or less, More preferably, it is 6.0 or less Most preferably, it is 5.0 or less. For example, the Mohs' Hardness of the said inorganic component (B) is 5.5-6.0 in titanium oxide (anatase type), 7.0-7.5 in titanium oxide (rutile), 2.5 in magnesium oxide, 7.0 in crystalline silica, and boron nitride. 2.0, aluminum nitride 7.0, silicon nitride 9.5, talc 1.0, calcined kaolin 2.0 and clay 2.0.

The fine particle component (C) is a component that provides high thermal conductivity to the laminate obtained. Aluminum oxide particles constituting the fine particle component (C) is less than the mean particle size (D ₅₀₎ 1.5㎛, preferably 0.4 ~ 0.8 ㎛. When the average particle diameter of a microparticles | fine-particles component (C) exceeds 1.5 micrometers, it is difficult to fill with the compounding quantity sufficient for laminated board A, and also drill property falls. Moreover, when the average particle diameter of a microparticle component (C) is too small, there exists a possibility that the thermal conductivity of the laminated board A may become inadequate. Further, the aluminum oxide particles, but the Mohs scale is hard to 12, since the average particle diameter (D ₅₀₎ is less than 1.5㎛, may not to damage the drill workability.

The compounding ratio (volume ratio) of the said gibbsite type aluminum hydroxide particle (A), the said inorganic component (B), and the said fine particle component (C) is 1: 0.1-3: 0.1-3, Preferably, it is 1: 0.1 ~ 2: 0.1-2, More preferably, it is 1: 0.1-1: 0.1-1. When the compounding quantity of an inorganic component (B) exceeds 3 with respect to the compounding quantity 1 of a gibbsite type aluminum hydroxide particle (A), the drill workability and heat dissipation property of the laminated board A obtained fall, and when it is less than 0.1, heat resistance falls do. Moreover, with respect to the compounding quantity 1 of the gibbsite type aluminum hydroxide particle (A), when the compounding quantity of a microparticles | fine-particles component (C) exceeds 3, drill workability falls and when it is less than 0.1, thermal conductivity falls, It is difficult to mix | blend high inorganic fillers, and there exists a possibility that moldability may deteriorate.

The mixing ratio of the inorganic filler with respect to 100 volume parts of thermosetting resins is 80-400 volume parts, Preferably it is 90-400 volume parts, More preferably, it is 100-400 volume parts. When the blending ratio of the inorganic filler is less than 80 volume parts, the thermal conductivity of the resulting laminated plate A is lowered, and when it exceeds 400 volume parts, the drill workability is lowered, and the manufacturability (resin impregnability, formability) of the laminated plate A is reduced. Also deteriorates. Moreover, especially when the mixing | blending ratio of a gibbsite type aluminum hydroxide particle (A) is too large, specifically, when it exceeds 100 volume part, it exists in the tendency for heat resistance to fall because many crystal water generate | occur | produces. And as an inorganic component (B), when boehmite particle | grains and the inorganic particle which contains crystal water whose glass start temperature is 400 degreeC or more, or does not have crystal water are mix | blended, the compounding ratio of an inorganic particle is It is preferable that it is 50 volume% or less, further 30 volume% or less, especially 20 volume% or less of the inorganic filler whole quantity.

The thermosetting resin composition mix | blends the above-mentioned gibbsite type | mold aluminum hydroxide particle (A), an inorganic component (B), and the inorganic filler containing fine particle component (C) with said thermosetting resin, such as a liquid, and a disper ( It is prepared by a well-known preparation method which disperse | distributes the particle | grains of each inorganic filler using a disper, a ball mill, a roller, etc. And various additives, such as a curing catalyst of a thermosetting resin, can be mix | blended with a thermosetting resin composition as needed. Moreover, in consideration of viscosity adjustment of a thermosetting resin composition, impregnation with a nonwoven fabric base material, etc., if necessary, processing aids, such as a solvent, such as an organic solvent, a viscosity reduction agent, and a coupling agent, can also be mix | blended. have.

The prepreg for forming the nonwoven fabric layer 1 is made by impregnating a thermosetting resin composition in the said nonwoven fabric base material, and then making the thermosetting resin composition impregnated in a nonwoven fabric base material into the semi-hardened state (B stage state) by heat drying etc. You can get it. In the prepreg for forming the nonwoven fabric layer 1, although content of a thermosetting resin composition can be 40-95 mass% with respect to the prepreg whole quantity, it is not limited to this.

And in manufacturing the laminated board A of this invention, after stacking one or several sheets of the prepreg for forming the nonwoven fabric layer 1, this thermosetting resin in a prepreg is hardened by heat-pressure molding. In addition, the metal foil clad laminate of the present invention is formed as a single-sided or double-sided metal foil clad laminate in which laminate A becomes an insulating layer by forming metal foil 3 such as copper foil or nickel foil on the surface of nonwoven fabric layer 1. can do. In this case, after stacking the prepreg and metal foil 3 for forming the nonwoven fabric layer 1, and heat-molding, the nonwoven fabric layer 1 and the metal foil 3 are laminated and integrated. Although the conditions of heat press molding at the time of manufacturing laminated board A and a metal foil clad laminated board can be set suitably according to the kind of thermosetting resin, etc., For example, temperature 80-250 degreeC, pressure 0.05-0.98 kPa (5-100 kgf) / m ² ), 20 to 300 minutes.

Moreover, the printed wiring board of this invention can be formed by forming a conductor pattern on the surface of the said laminated board A. FIG. In this case, it can process to a printed wiring board by performing a circuit processing process and through-hole process, such as an additive method and a subtractive method, to the said metal foil clad laminated board. In addition, the circuit board of the present invention can be formed by forming an electric and electronic circuit on the laminate A. FIG. In this case, an electric and electronic circuit can be formed using the conductor pattern of the printed wiring board formed by the said metal foil clad laminated board. In addition, the LED mounting circuit board of the present invention can be formed by forming the LED mounting electric and electronic circuit on the laminate A. In this case, the electric and electronic circuit of the said circuit board can be formed as an LED mounting electric and electronic circuit.

Another embodiment of the laminated plate A of the present invention is shown in Fig. 1B. This laminated board A is what is called a composite laminated board formed with the nonwoven fabric layer 1 containing a thermosetting resin composition, and the woven fabric layer 2 containing a thermosetting resin composition. In terms of heat dissipation, the composite laminate is inferior to the laminate in which the insulating layer is formed only by the nonwoven fabric layer 1 and no woven fabric is used. However, the composite laminate is inexpensive and excellent in dimensional stability and mechanical properties. As mentioned above, the nonwoven fabric layer 1 can be formed with the hardened | cured material of the prepreg etc. which contain a thermosetting resin composition in a nonwoven fabric base material. Moreover, the woven fabric layer 2 can be formed with the hardened | cured material of the prepreg etc. which contain a thermosetting resin composition in a woven fabric base material.

In the case of such a composite laminate, the nonwoven fabric layer 1 can be formed in the same manner as described above, but the mixing ratio of the inorganic filler to 100 parts by volume of the thermosetting resin is preferably 150 to 400 parts by volume. When the mixing ratio of the inorganic filler is less than 150 volume parts, there is a fear that the thermal conductivity of the laminated plate A to be obtained is lowered, and when it exceeds 400 volume parts, the drill workability is lowered or the manufacturability (resin impregnability and moldability of the laminated plate A) is reduced. ) May be lowered.

As a woven fabric base material for forming the woven fabric layer 2, it is chosen from synthetic resin cloth using synthetic resin fibers, such as glass cloth or aramid fiber, polyester fiber, and polyamide fiber (nylon), for example. Either one can be used. Although the thickness of a woven fabric base material can be 50-500 micrometers, it is not limited to this.

As the thermosetting resin composition for forming the woven fabric layer 2, it may be the same as the said thermosetting resin composition for forming the nonwoven fabric layer 1, may differ, and when it makes a difference, it is a thing of the thermosetting resin and inorganic filler to be used. The kind, content of an inorganic filler with respect to a thermosetting resin, etc. can be changed. In particular, what removes an inorganic filler from the said thermosetting resin composition for forming the nonwoven fabric layer 1, ie, the said thermosetting resin and the thing which consists of a solvent and an additive mix | blended as needed can be used. Thereby, the impregnation property of the thermosetting resin composition with respect to a woven fabric base material can be improved. In the case where the woven fabric layer 2 contains an inorganic filler, it is preferable to use aluminum hydroxide as the inorganic filler in order to improve the tracking resistance of the laminate. Thereby, it is thought that the crystal water of aluminum hydroxide inhibits the thermal decomposition and the carbonization of the surface of a laminated board, and the tracking resistance of a laminated board is improved. Moreover, in order to improve the tracking resistance of a laminated board, it is preferable that aluminum hydroxide with respect to 100 volume parts of thermosetting resins in the woven fabric layer 2 is 25-150 volume parts. In addition, the mean particle size (D ₅₀₎ is preferably used in an aluminum hydroxide 2 ~ 15 ㎛.

The prepreg for forming the woven fabric layer 2 is made by impregnating a thermosetting resin composition in the said woven fabric base material, and then making the thermosetting resin composition impregnated in a woven fabric base material into the semi-hardened state (B stage state) by heat drying etc. You can get it. In the prepreg for forming the woven fabric layer 2, although content of a thermosetting resin composition can be 40-95 mass% with respect to the prepreg whole quantity, it is not limited to this.

And in forming the composite laminated board as the laminated board A of this invention of FIG. 1 (b), after superposing the prepreg for forming the nonwoven fabric layer 1, and the prepreg for forming the woven fabric layer 2, By heat-press molding this, the thermosetting resin in each prepreg is hardened, the nonwoven fabric layer 1 and the woven fabric layer 2 are formed, and the nonwoven fabric layer 1 and the woven fabric layer 2 are hardened by hardening of these thermosetting resins. Is bonded and laminated to integrate. Here, the nonwoven fabric layer 1 and the woven fabric layer 2 can be formed overlapping one or several prepregs, respectively. In addition, the woven fabric layer 2 can be formed on both surfaces of the nonwoven fabric layer 1. In addition, the metal foil clad laminate using the composite laminate is further formed on the surface of the woven fabric layer 2 as a metal foil 3 such as copper foil or nickel foil, thereby forming a single-sided or double-sided metal foil clad laminate in which the composite laminate becomes an insulating layer. can do. In this case, after superposing the prepreg for forming the nonwoven fabric layer 1, the prepreg for forming the woven fabric layer 2, and the metal foil 3, and heat-molding, the nonwoven fabric layer 1 and a woven fabric The layer 2 and the metal foil 3 are laminated and integrated. The conditions of hot press molding are the same as those mentioned above.

Composite laminates can be produced continuously. An example of the manufacturing method of a double-sided metal foil clad composite laminated board is shown in FIG. The glass nonwoven fabric which is a nonwoven fabric base material is a glass fiber paper, and is a long object which can be supplied continuously, and if it has a space | gap in an inside and a surface and can impregnate a thermosetting resin composition, it will not specifically limit. As thickness of a glass nonwoven fabric, 0.03-0.4 mm is common, but it is not limited to what became this thickness. In addition, the glass woven fabric which is a woven fabric base material is a woven fabric made of glass fiber, and is a long object which can be supplied continuously, It will not specifically limit, if it has a space | gap in an inside and a surface and can impregnate a thermosetting resin composition. As thickness of a glass cloth, 0.015-0.25 mm is common, but it is not limited to what became this thickness.

And first, the thermosetting resin composition is impregnated into the glass nonwoven fabric which is a nonwoven fabric base material. Next, a thermosetting resin impregnated glass woven fabric is continuously laminated on both surfaces of the glass nonwoven fabric impregnated with the thermosetting resin composition, and the laminate is pressed with a roller and heated to produce a composite laminate. Here, you may use the glass nonwoven fabric in which the thermosetting resin composition was impregnated, overlapping one or several sheets. In addition, a thermosetting resin impregnated glass woven fabric is the said glass woven fabric formed by impregnating the above-mentioned thermosetting resin and a thermoplastic resin composition. As thickness of a glass woven fabric, 0.015-0.25 mm is common, but it is not limited to what became this thickness. Moreover, you may overlap and use one or more sheets of thermosetting resin impregnated glass woven fabric. In addition, you may laminate | stack metal foil on the surface layer of the single side | surface or both surfaces. It will not specifically limit, if it is a long metal foil which can be supplied continuously as a metal foil, Copper foil, nickel foil, etc. are mentioned as an example. As thickness of a metal foil, 0.012-0.07 mm is common, It is not limited to what became this thickness.

As shown in Fig. 2, two thermosetting resin-impregnated glass nonwoven fabrics 12 impregnated with the glass nonwoven fabric 10 continuously supplied with the thermosetting resin composition 11, and two thermosetting resin-impregnated glass woven fabrics continuously supplied. The thermosetting resin impregnated glass woven fabric 9 is arrange | positioned on both (upper and lower sides) using the thermosetting resin impregnated glass nonwoven fabric 12 as a core, and the metal foil 13 supplied continuously (9) and two sheets. The metal foil 13 is laminated so as to be disposed on both surface layers. Thereafter, the laminated laminate is compressed with a laminate roller 14, and then the compressed article 15 is pressed in the heat roller 17 while being pulled out by the extraction roller 18 to carry out the compressed article. After the hardened | cured material 15 was hardened by heating the hardened | cured material 15 at the temperature which the thermosetting resin composition 11 in (15) hardens, it cut | disconnects to the predetermined magnitude | size by the cutter 19, and the composite laminated board A by which metal foil was continuously laminated | stacked on the surface was carried out. Get Reference numeral 171 denotes a conveying roller disposed in the heat curing furnace 17.

And it does not specifically limit as conditions crimped | bonded by the lamination roller 14, It can adjust suitably according to the kind of glass nonwoven fabric 10 and glass woven fabric used, the viscosity of the thermosetting resin composition 11, etc. In addition, conditions, such as temperature and time of heat hardening, are not specifically limited, It can set suitably according to the component mix of the thermosetting resin composition 11 to be used, and the hardening degree to harden. You may heat (aftercure) after cutting | disconnection to further advance hardening of this laminated board A. FIG.

Although the thermosetting resin impregnated glass nonwoven fabric 12 was two sheets in the above, the thermosetting resin impregnated glass nonwoven fabric 12 may be one piece, or may be three or more pieces. In addition, although two pieces of metal foils 13 were mentioned above, one piece may be sufficient, and when there are two or more sheets of thermosetting resin impregnated glass nonwoven fabrics, you may further laminate | stack metal foil between thermosetting resin impregnated glass nonwoven fabrics. In addition, a nonwoven fabric base material and a woven fabric base material are not limited to using glass fiber, The fiber of another material may be used. In addition, if the thermosetting resin composition contains a wet dispersing agent and the compounding quantity is 0.05-5 mass% with respect to an inorganic filler, an inorganic filler will disperse | distribute uniformly in the thermosetting resin impregnated glass woven fabric 9 or the thermosetting resin impregnated glass nonwoven fabric 12. Therefore, it is not easily bent and solder heat resistance becomes high.

The printed wiring board of the present invention using the composite laminate can be formed by forming a conductor pattern on the surface of the composite laminate. In this case, the metal foil clad laminate can be processed into a printed wiring board by performing a circuit processing treatment such as an additive method or a subtractive method or through-hole processing. In addition, the circuit board of the present invention using the composite laminate can be formed by forming an electric and electronic circuit on the composite laminate. In this case, an electric and electronic circuit can be formed using the conductor pattern of the printed wiring board formed by the said metal foil clad laminated board. In addition, the LED mounting circuit board of this invention using a composite laminated board can be formed by forming the LED mounting electrical and electronic circuit in the said composite laminated board A. FIG. In this case, the electric and electronic circuit of the said circuit board can be formed as an electric and electronic circuit for LED mounting.

In addition, since the laminate A (including the composite laminate) A of the present invention blends the inorganic filler with the nonwoven fabric layer 1 with a high degree of filling, the thermal conductivity can be increased, and it is easy to diffuse heat immediately throughout the laminate A so that the heat dissipation property is excellent. It is getting higher. Therefore, the same effect can be acquired also in the metal foil clad laminated board formed by the laminated board A of this invention, a printed wiring board, and a circuit board. It is easy to spread and spread heat to metal foil clad laminates, printed wiring boards, and circuit boards with high thermal conductivity. As a result, heat dissipation from metal foil clad laminates, printed wiring boards, and circuit boards is increased, thereby reducing deterioration due to heat of electrical and electronic components. This makes it possible to extend the lifespan of the electrical and electronic components. In addition, the LED mounting circuit board of the present invention is easy to conduct heat spreading from the LED by mounting the LED, and as a result, the heat dissipation from the LED mounting circuit board is increased, thereby reducing the deterioration due to the heat of the LED. It is possible to extend the life of the LED.

In addition, in the laminated board A of this invention, a gibbsite-type aluminum hydroxide particle (A) is mix | blended with the resin composition which comprises the nonwoven fabric layer 1, and the predetermined amount of the microparticle component (C) with a small average particle diameter is carried out. Since it mix | blends, the wear of the drill blade at the time of the drill processing of the laminated board A can be suppressed. As a result, the drill can be extended in life. In addition, even when a drill process is applied for forming a through hole, irregularities are hardly formed on the inner surface of the hole to be formed, and the inner surface of the hole can be smoothly formed. For this reason, when through-hole plating is formed in the inner surface of a hole, high through-reliability can also be provided to this through-hole. Moreover, by mix | blending the fine particle component (C) excellent in thermal conductivity, the thermal conductivity of a laminated board can be improved significantly. And since the microparticles | fine-particles component (C) of a small particle diameter is mix | blended, the drillability of a laminated board does not fall remarkably. Moreover, by mix | blending the said inorganic component (B), thermal conductivity can be provided, without notably reducing heat resistance and a drill workability.

The laminated board A of this invention is used suitably for the application which requires high heat dissipation, such as the printed wiring board of the LED backlight unit mounted in a liquid crystal display, the circuit board for LED lighting devices, etc. In such LED mounting applications, a high heat dissipation substrate is required, and the thermal conductivity is preferably 0.9 W / m · K or more, and more preferably 1.5 W / m · K or more. Specifically, as one of uses of LED, the LED backlight unit 20, such as a direct type | mold which is mounted in a liquid crystal display as shown in FIG. 3, is mentioned. The LED backlight unit 20 in FIG. 3 is an LED module 23 in which a plurality of LEDs 22 (in FIG. 3) are mounted on a circuit board 21 formed by the laminate A or the laminate A. FIG. Are arranged so as to be arranged on the back surface of the liquid crystal panel, and are used as backlights of liquid crystal displays and the like. In addition, using the laminated plate A of this invention, as shown to FIG.4 (a) and (b), the edge type LED backlight unit 20 mounted in a liquid crystal display can also be formed. The LED backlight unit 20 in FIGS. 4A and 4B is a pair in which a plurality of LEDs 22 are mounted on a rectangular circuit board 21 formed by the laminate A or the laminate A. FIG. It is comprised by the LED module 23, and each LED module 23 is installed in the upper and lower sides (or right and left), such as the light guide plate 24, and is used as backlights, such as a liquid crystal display. In the edge type LED backlight unit 20, since the LED is installed at a higher density than the direct type LED backlight unit 20, it is preferable to use one having high heat dissipation as in the laminate A of the present invention. In the liquid crystal display of the type that has been widely used in the past, a cold cathode tube (CCFL) backlight has been widely used as a backlight of the liquid crystal display, but in recent years, since the color gamut can be widened compared to the backlight of the cold cathode tube system. Since the image quality can be improved and the mercury is not used and the environmental load is small and the thickness can be reduced, further, the LED backlight unit as described above has been actively developed. In general, the LED module has a larger power consumption than the cold cathode tube, and thus generates a large amount of heat. By using the laminate A of the present invention as the circuit board 21 requiring such high heat dissipation, the problem of heat dissipation is greatly improved. Therefore, the luminous efficiency of LED can be improved.

Moreover, the LED illuminating device can also be formed using the laminated sheet A of this invention. The LED illuminating device can be formed by mounting a plurality of LEDs on the laminated board A or the circuit board formed by the laminated board A, and including a power supply unit for emitting the LEDs.

[Example]

Hereinafter, the present invention will be specifically described by way of examples.

(Examples 1-14, Comparative Examples 1-3)

The thermosetting resin varnish containing the bisphenol A type epoxy resin which is a resin component, and the dicyandiamide type | system | group hardening | curing agent which is a hardening | curing agent is an inorganic filler by the compounding quantity (unit is a volume part) shown in Table 1 with respect to 100 volume parts of thermosetting resins. Was mixed and uniformly dispersed. As the component (A), Gibbsite-type aluminum hydroxide particles (manufactured by Sumitomo Chemical Co., Ltd., D ₅₀ : 5.4 μm) and Gibbsite-type aluminum hydroxide particles (manufactured by Sumitomo Chemical Co., Ltd., D ₅₀ : 12.6 μm) were used. . As the component (B), boehmite particles (D ₅₀ : 3.0 μm) were used. As the component (C), aluminum oxide particles (manufactured by Sumitomo Chemical Co., Ltd., D ₅₀ : 0.5 μm, alumina) were used. And the compounding quantity of the inorganic filler with respect to 100 volume parts of thermosetting resins is 100 volume parts of solid content [the total amount of bisphenol-A epoxy resin (resin component) and the dicyandiamide type hardening | curing agent (hardening | curing agent component) except the solvent of a thermosetting resin varnish. It is a compounding quantity of the inorganic filler about.

The thermosetting resin varnish to which the said inorganic filler was mix | blended is a glass nonwoven fabric (glass nonwoven fabric manufactured by Byron Co., Ltd., and a binder is epoxy silane etc.) of 60 g / m <^2> and 400 micrometers in thickness total used per unit area, The compounding quantity of a binder It was impregnated with 5-25 mass parts with respect to 100 mass parts of silver glass fibers, and the prepreg for nonwoven fabric layers was obtained.

And the two prepregs for nonwoven fabric layers were superposed | superposed, and the copper foil of thickness 0.018mm was mounted on each of both outer surfaces, and the laminated body was obtained. This laminated body was sandwiched between two metal plates and heat-molded on the conditions of the temperature of 180 degreeC, and the pressure of 0.3 kPa (30 kgf / m <^2> ), and the copper clad clad laminated board of thickness 1.0mm was obtained.

The obtained copper foil clad laminate was evaluated for thermal conductivity, oven heat resistance test, drillability, and flame retardancy according to the following evaluation method. The results are shown in Table 1 below.

<Thermal conductivity>

The density of the obtained copper foil clad laminated board was measured by the submerged method, and the specific heat was measured by DSC (differential scanning calorimetry), and the thermal diffusivity was measured by the laser flash method.

And thermal conductivity was computed by the following formula | equation.

Thermal Conductivity (W / m? K) = Density (kg / m ³ ) × Specific Heat (kJ / kg? K) × Thermal Diffusion (m ² / S) × 1000

<Oven heat test>

When the test piece manufactured according to JIS C6481 was processed for 1 hour in the thermostat with an air circulation apparatus set to 200-240 degreeC using the obtained copper clad clad laminated board, the temperature which swelled and peeled to copper foil and a laminated board was measured. And in order for evaluation of oven heat test to use as a board | substrate for LED mounting, at least 220 degreeC or more is preferable, and below 220 degreeC, there exists a possibility that heat resistance may run short.

<Drill Machinability>

Three pieces of the obtained copper clad clad laminates were superimposed, and the wear rate of the drill blade after drilling 3000 holes at 60000 revolutions / min was drilled by a drill (drill diameter 0.5 mm, vibration angle 35 °). The ratio (percentage) of the drill blade (area) worn by the drilling process with respect to the size (area) of the blade was evaluated. In addition, "(circle)" which has a wear rate of 90% or less, "(DELTA)" which has a wear rate smaller than 99%, larger than 90% was shown by "x". The smaller the wear rate of the drill blade is, the smaller the loss of the drill blade is and the higher the drill workability is. In addition, the drill blade can be used if 10% remains. If the wear rate of the drill blade after forming 3000 holes as described above is 90% or less, it is not necessary to frequently change the drill.

<Flammability>

The obtained copper clad clad laminate was cut out to a predetermined size, subjected to a combustion test in accordance with the combustion test method of UL-94, and determined. In addition, the thing by UL94-V0 was represented by "(circle)" and the thing by UL94-V1 by "x".

[Table 1]

(Examples 15-20, Comparative Examples 4-6)

In Examples 1 to 14 and Comparative Examples 1 to 3, as a component (B) instead of the boehmite particles, talc (talc Japan (Co., Ltd.), D _50: 5㎛) was used. Others were the same as Examples 1-14 and Comparative Examples 1-3. Evaluation similar to the above was performed about the obtained copper clad clad laminated board. The results are shown in Table 2 below.

[Table 2]

(Examples 21-26, Comparative Examples 7-9)

In Examples 1 to 14 and Comparative Examples 1 to 3, as a component (B) instead of the boehmite particles, silica (Industrial Electric Chemical Co., Ltd. Preparation, D _50: 5㎛) was used. Others were the same as Examples 1-14 and Comparative Examples 1-3. Evaluation similar to the above was performed about the obtained copper clad clad laminated board. The results are shown in Table 3 below.

[Table 3]

(Examples 27-32, Comparative Example 10)

In Example 9, as the component (C), plural kinds of aluminum oxide particles having different average particle diameters were used. Others were the same as Example 9. Evaluation similar to the above was performed about the obtained copper clad clad laminated board. The results are shown in Table 4 below.

[Table 4]

(Examples 33-46, Comparative Examples 11-13)

In the same manner as in Examples 1 to 14 and Comparative Examples 1 to 3, the inorganic filler was blended and uniformly dispersed in the blending amount shown in Table 5 with respect to 100 parts by volume of the thermosetting resin varnish. The thermosetting resin varnish in which this inorganic filler was mix | blended was impregnated into the glass nonwoven fabric similarly to the above, and the prepreg for nonwoven fabric layers was obtained. On the other hand, prepreg for woven fabric layers is made by impregnating the said thermosetting resin varnish without using a filler in glass cloth (woven fabric) (Nittobo Co., Ltd. product 7628) of 200 g / m <^{2> of} used gross weight per unit area, and the filler. Got. And the two prepregs for nonwoven fabric layers were superposed | superposed, One prepreg for woven fabric layers, and copper foil of thickness 0.018mm were mounted one by one on both outer surfaces, and the laminated body was obtained. This laminated body was sandwiched between two metal plates, and was heat-molded on the conditions of the temperature of 180 degreeC, and the pressure of 0.3 kPa (30 kgf / m <^2> ), and the copper clad composite laminated board of thickness 1.0mm was obtained. Evaluation similar to the above was performed about the obtained copper clad composite laminate. The results are shown in Table 5 below.

[Table 5]

(Examples 47-52, Comparative Examples 14-16)

Example In the Comparative Examples 33-46 and 11-13, as the component (B), instead of the boehmite particles, the same talc as was used for (D ₅₀ 5㎛). Others were the same as Examples 33-46 and Comparative Examples 11-13. Evaluation similar to the above was performed about the obtained copper clad composite laminate. The results are shown in Table 6 below.

TABLE 6

(Examples 53-58, Comparative Examples 17-19)

In Examples 33 to 46 and Comparative Examples 11 to 13, the same silica (D ₅₀ : 5 μm) as above was used instead of the boehmite particles as the component (B). Others were the same as Examples 33-46 and Comparative Examples 11-13. Evaluation similar to the above was performed about the obtained copper clad composite laminate. The results are shown in Table 7 below.

[Table 7]

(Examples 59-64, Comparative Example 20)

In Example 41, as the component (C), plural kinds of aluminum oxide particles having different average particle diameters were used. Others were the same as Example 41. Evaluation similar to the above was performed about the obtained copper clad composite laminate. The results are shown in Table 8 below.

[Table 8]

(Examples 65-68, Comparative Examples 21 and 22)

In Example 41, the glass cloth was impregnated with a thermosetting resin varnish containing aluminum hydroxide (manufactured by Sumitomo Chemical Co., Ltd., D ₅₀ : 4.3 µm) in place of the prepreg for woven fabric layer containing no filler, thereby containing aluminum hydroxide. The prepreg for the woven fabric layer was used. Others were the same as Example 41. The copper foil clad composite laminate thus obtained was evaluated in the same manner as described above, tracking resistance and evaluation of surface protrusions. The results are shown in Table 9 below.

<Tracking resistance>

Testing of tracking resistance was performed based on the standard IEC60112 4th edition (JIS C2134). And the maximum voltage was calculated | required by evaluation by CTI.

<Surface turning>

The surface of the obtained copper clad composite laminate was observed. In addition, "(circle)" was attached | subjected to the presence of the surface protrusion of the grade on the shaping | molding phase and practically no problem, and "x" was given to the thing which generate | occur | produces a problem in shape | molding or practical practically.

TABLE 9

(Comparative Example 23-30)

Comparative Examples 23-26 obtained the copper foil clad laminated board similarly to Example 1 except having made the compounding ratio of (A) component, (B) component, and (C) component as Table 10. In Comparative Examples 27-30, the copper clad composite laminate was obtained in the same manner as in Example 33 except that the mixing ratios of the components (A), (B) and (C) were as in Table 10. Evaluation similar to the above was performed about the obtained copper clad clad laminated board and copper foil clad composite laminated board. The results are shown in Table 10 below. The compounding ratio of (A) component, (B) component, and (C) component of each Example and a comparative example is as follows.

Comparative Examples 23 and 27: (A) component: (B) component: (C) component = 1: 4.3: 2.3

Comparative Examples 24 and 28: (A) component: (B) component: (C) component = 1: 0: 0.44

Comparative Examples 25 and 29: (A) component: (B) component: (C) component = 1: 3: 4.3

Comparative Examples 26 and 30: (A) component: (B) component: (C) component = 1: 0.56: 0

[Table 10]

In Comparative Examples 26 and 30, since the blending amount of the fine particle component (C) is small, only the inorganic filler having a large average particle diameter is used. As a result, high filling becomes difficult and the moldability tends to be lowered. Therefore, Comparative Examples 26 and 30 are inferior in moldability to other Examples or Comparative Examples.

(Examples 69-78, Comparative Examples 31-33)

A copper clad clad laminated board was formed in the same manner as in Example 1 except that a phenol compound (phenol novolak resin) was used as the curing agent component, and the mixing ratio of the inorganic filler was as shown in Table 11. Evaluation similar to the above was performed about the obtained copper clad clad laminated board. The results are shown in Table 11 below. As the talc and the silica, the same ones as described above were used, and kaolin was manufactured by System Co., Ltd., and D ₅₀ was 5 μm. Titanium oxide (anatase type) was manufactured by Wako Pure Chemical Industries, Ltd. In the manufactured ones, each having a D ₅₀ of 5 µm was used.

TABLE 11

(Examples 79-88, Comparative Examples 34-36)

A copper foil clad composite laminate was formed in the same manner as in Example 33 except that a phenol compound (phenol novolac resin) was used as the curing agent component and the mixing ratio of the inorganic filler was as shown in Table 12. Evaluation similar to the above was performed about the obtained copper clad composite laminate. The results are shown in Table 12 below.

[Table 12]

(Examples 89-98, Comparative Examples 37-39)

The copper foil clad composite laminate was continuously formed by the manufacturing method shown in FIG. 2. As a thermosetting resin composition, what contains an epoxy vinyl ester resin, a radically polymerizable unsaturated monomer, and a polymerization initiator was used. That is, 400 mass parts of tetrabromobisphenol-A epoxy resin ("brand name EPICLON 153" (made by Nippon Ink Chemical Co., Ltd.)) whose epoxy equivalent is 400 grams / equivalent to a four neck flask, 3500, HYCAR CTBN 1300X13 having a carboxyl group at both ends of a molecule of a copolymer of butadiene and acrylonitrile having 27% of bound acrylonitrile and 1.9 carboxyl groups / molecule. F. Goodrich Chemical Co., Ltd.] 92 parts by mass, 82 parts by mass of methacrylic acid (number of epoxy groups: number of total carboxyl groups = 1: 1), 0.29 parts by mass of hydroquinone, and 0.58 parts by mass of triphenylphosphine were added thereto. And reacted at 110 ° C. And it confirmed that the acid value became 10 mg-KOH / g or less, and added 309 mass parts of styrene. Thereafter, 1.32 parts by mass of acetylacetone was added to obtain an epoxy vinyl ester resin composition. Subsequently, 1.0 volume part of inorganic filler of the compounding ratio and tert-butyl peroxy benzoate ("brand name perbutyl Z" [manufactured by Nippon Oil Industries, Ltd.)) were added to 100 volume of this epoxy vinyl ester resin composition. And the thermosetting resin composition was manufactured by mixing uniformly with a homomixer. The other structure was the same as Example 33, and the copper clad composite laminated board was formed. Evaluation similar to the above was performed about the obtained copper clad composite laminate. The results are shown in Table 13 below.

[Table 13]

Claims (17)

As a laminated board provided with the nonwoven fabric layer containing a thermosetting resin composition,
In the said thermosetting resin composition, an inorganic filler contains more than 150 volume parts with respect to 100 volume parts of thermosetting resins, and contains 400 volume parts or less,
The inorganic filler,
(A) a gibbsite type aluminum hydroxide particle having an average particle diameter (D ₅₀ ) of 2 to 15 μm,
(B) an average particle size of 1.5 to 15 ㎛ (D ₅₀₎ for having water of crystallization less than boehmite (boehmite) particles and 1.5 to an average particle size of 15 ㎛ (D ₅₀₎ for having, a glass starting temperature 400 ℃ ( At least one inorganic component selected from the group consisting of inorganic particles containing water or not containing crystal water;
(C) a particulate component consisting of aluminum oxide particles having an average particle diameter (D ₅₀ ) of 1.5 μm or less
Containing,
The laminated board whose compounding ratio (volume ratio) of the said gibbsite type aluminum hydroxide particle (A), the said inorganic component (B), and the said microparticles | fine-particles component (C) is 1: 0.1-3: 0.1-3. The method of claim 1,
The laminated board which a woven fabric layer is formed in the surface of the said nonwoven fabric layer. The method of claim 1,
The laminated board in which the said thermosetting resin contains an epoxy resin. The method of claim 2,
The laminated board in which the said thermosetting resin contains an epoxy resin. The method of claim 3,
The said thermosetting resin is a laminated board in which a phenol compound is contained as a hardening | curing agent component of the said epoxy resin. The method of claim 4, wherein
The said thermosetting resin is a laminated board in which a phenol compound is contained as a hardening | curing agent component of the said epoxy resin. The method of claim 1,
The laminated board in which the said thermosetting resin contains an epoxy vinyl ester resin, a radically polymerizable unsaturated monomer, and a polymerization initiator. The method of claim 2,
The laminated board in which the said thermosetting resin contains an epoxy vinyl ester resin, a radically polymerizable unsaturated monomer, and a polymerization initiator. The method of claim 1,
The laminated board whose binder of the nonwoven fabric base material of the said nonwoven fabric layer is an epoxy compound. The method of claim 2,
The laminated board whose binder of the nonwoven fabric base material of the said nonwoven fabric layer is an epoxy compound. The method of claim 2,
The laminated board in which the said woven fabric layer contains aluminum hydroxide. The metal foil clad laminated board formed by providing metal foil in at least one surface among the laminated boards in any one of Claims 1-11. The printed wiring board formed by providing a conductor pattern in at least one surface among the laminated boards in any one of Claims 1-11. The circuit board which provides a circuit in at least one surface among the laminated boards in any one of Claims 1-11. The LED backlight unit which mounts LED on at least one surface of the laminated board of any one of Claims 1-11. The LED lighting apparatus which mounts LED on at least one surface of the laminated board of any one of Claims 1-11. The thermosetting resin composition is impregnated with the thermosetting resin composition to the nonwoven fabric substrate while continuously conveying the nonwoven fabric substrate, the woven fabric is laminated on both surfaces thereof while the substrate is continuously conveyed, and the laminate is compressed with a roller to be heated. As a manufacturing method of the laminated board which hardens a resin composition and forms a nonwoven fabric layer and a woven fabric layer,
In the said thermosetting resin composition, an inorganic filler is contained more than 150 volume parts with respect to 100 volume parts of thermosetting resins, and contains 400 volume parts or less,
The inorganic filler,
(A) Gibbsite-type aluminum hydroxide particles having an average particle diameter (D ₅₀ ) of 2 to 15 ㎛,
(B) 1.5 ~ 15 ㎛ a mean particle diameter (D ₅₀₎ for having boehmite particles, 1.5 ~ 15 ㎛ a mean particle diameter (D ₅₀₎ for having, containing water of crystallization than the glass starting temperature is 400 ℃ or At least one inorganic component selected from the group consisting of inorganic particles containing no crystalline water,
(C) a particulate component consisting of aluminum oxide particles having an average particle diameter (D ₅₀ ) of 1.5 μm or less
Containing,
The manufacturing method of the laminated board whose compounding ratio (volume ratio) of the said gibbsite type aluminum hydroxide particle (A), the said inorganic component (B), and the said microparticles | fine-particles component (C) is 1: 0.1-3: 0.1-3.

Images