KR20140032420A - Laminate sheet, application therefor, and method for producing same - Google Patents

Abstract

This invention provides the laminated board with high heat dissipation, without reducing heat resistance and a drill workability. The present invention is a laminated plate A in which a nonwoven fabric layer (1) obtained by impregnating a thermosetting resin composition on a nonwoven fabric substrate and a woven fabric layer (2) laminated on both surfaces of the nonwoven fabric layer are laminated and integrated to form a thermosetting resin composition. 80-150 volume parts of silver inorganic fillers are contained with respect to 100 volume parts of thermosetting resins, an inorganic filler contains gibbsite type | mold aluminum hydroxide particle (A) and a fine particle component (B), (A) is 2- have a mean particle size of _{15 ㎛ (D 50), (} B) is made of aluminum oxide particles having an average particle diameter (D50) of less than 1.5㎛, particle size distribution, a particle diameter of more than 5% by weight 5㎛ Hereinafter, 40 mass% or less of particle diameters 1 micrometer or more and less than 5 micrometers are 55 mass% or less, and particle | grains of (B) contain 30 mass% or more of crushed aluminum oxide particles, The compounding ratio (volume ratio) of (A) and (B) is related with the laminated board which is 1: 0.2-0.5.

Description

Laminate, its use and manufacturing method {LAMINATE SHEET, APPLICATION THEREFOR, AND METHOD FOR PRODUCING SAME}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a laminate for various electronic devices, a laminate with a metal foil, a printed wiring board, a circuit board, an LED backlight unit, and a method for producing the laminate. In particular, it is related with the laminated board used preferably for mounting heat generating components, such as a light emitting diode (LED).

 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, , Patent Document 1). 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.

Japanese Patent Application Publication No. 2006-272671

However, in recent years, a lot of heat generation is used as an electric and electronic component mounted in a laminated board, or the mounting density of the electric and electronic component which generate | occur | produces heat may be raised. In order to cope with such a case, the laminated board with high heat dissipation is desired. This is because when the laminated board with high heat dissipation is used, heat generated from the electrical and electronic components is easily radiated through the laminated board, thereby extending the life of the electrical and electronic components.

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 reducing heat resistance and a drill workability. Moreover, an object of this invention is to provide the laminated board with a metal foil, a printed wiring board, a circuit board, a LED backlight unit, and an LED illuminating device with high heat dissipation.

The laminated board which concerns on this invention is a laminated board in which the nonwoven fabric layer obtained by impregnating a thermosetting resin composition to the nonwoven fabric base material, and the woven fabric layer laminated | stacked on both surfaces of the said nonwoven fabric layer were laminated | stacked, and were integrated. The said thermosetting resin composition contains an inorganic filler in the ratio of 80-150 volume parts with respect to 100 volume parts of thermosetting resins. The inorganic filler contains a gibbsite type aluminum hydroxide particle (A) and a fine particle component (B). The gibbsite-type aluminum hydroxide particles (A), has an average particle size of 2~15 ㎛ (D _50). The particulate component (B) is constituted by aluminum oxide particles having an average particle diameter (D ₅₀₎ of less than 1.5㎛. The particle size distribution of the said fine particle component (B) is 5 mass% or less of 5 micrometers or more of particle diameters, 40 mass% or less of particle diameters 1 micrometer or more and less than 5 micrometers, and 55 mass% or less of particle diameters less than 1 micrometer. This fine particle component (B) contains 30 mass% or more of crushed aluminum oxide particles. The compounding ratio (volume ratio) of the said gibbsite type aluminum hydroxide particle (A) and the said microparticles | fine-particles component (B) is 1: 0.2-0.5.

In this invention, it is preferable that the said fine particle component (B) contains 30 mass% or more of crushed aluminum oxide particles.

In this invention, it is preferable that the said thermosetting resin contains the epoxy resin.

In this invention, it is preferable that the said thermosetting resin contains the phenol compound as a hardening | curing agent component of the said epoxy resin.

In this invention, it is preferable that the said thermosetting resin contains the epoxy vinyl ester resin, a radically polymerizable unsaturated monomer, and a polymerization initiator.

The laminated sheet with a metal foil which concerns on this invention is characterized by the metal foil provided in at least one surface among the said laminated sheets.

A printed wiring board according to the present invention is characterized in that a conductor pattern is provided on at least one surface of the laminate.

A circuit board according to the present invention is characterized in that a circuit is provided on at least one surface of the laminate.

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

The LED lighting apparatus according to the present invention is characterized in that the LED is mounted on at least one surface of the laminate.

The manufacturing method of the laminated board which concerns on this invention impregnates the said nonwoven fabric base material with the thermosetting resin composition continuously conveying a nonwoven fabric base material, laminates a woven fabric on both surfaces, conveying this nonwoven fabric base material continuously, and this lamination | stacking The thermosetting resin composition is cured by pressing water with a roll and heating to form a nonwoven fabric layer and a woven fabric layer. The said thermosetting resin composition contains an inorganic filler in the ratio of 80-150 volume parts with respect to 100 volume parts of thermosetting resins. The said inorganic filler contains gibbsite type | mold aluminum hydroxide particle | grains (A) and a microparticle component (B). The gibbsite-type aluminum hydroxide particles (A), has an average particle size of 2~15 ㎛ (D _50). The particulate component (B) is constituted by aluminum oxide particles having an average particle diameter (D ₅₀₎ of less than 1.5㎛. The particle size distribution of the said fine particle component (B) is 5 mass% or less of 5 micrometers or more of particle diameters, 40 mass% or less of particle diameters 1 micrometer or more and less than 5 micrometers, and 55 mass% or less of particle diameters less than 1 micrometer. This fine particle component (B) contains 30 mass% or more of crushed aluminum oxide particles. The mixing ratio (volume ratio) of the gibbsite type aluminum hydroxide particles (A) and the fine particle component (B) is 1: 0.2 to 0.5.

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

In the laminated plate with a metal foil, a printed wiring board, a circuit board, an LED backlight unit, and an LED lighting apparatus of this 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.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of embodiment of the laminated board of this invention.
It is a schematic diagram which shows an example of embodiment of the manufacturing method of the laminated board of this invention.
3 is a schematic view showing an example of an embodiment of the LED backlight unit of the present invention.
4 shows another example of an embodiment of the LED backlight unit of the present invention, wherein (a) and (b) are schematic diagrams.

EMBODIMENT OF THE INVENTION Below, the form for implementing this invention is demonstrated.

As shown in FIG. 1, the laminated board A of this invention 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. to be. In terms of heat dissipation, a composite laminate may be inferior to a conventional laminate (in which an insulating layer is formed only by the nonwoven fabric layer 1 and no woven fabric is used). However, composite laminates are inexpensive and excellent in dimensional stability and mechanical properties. The nonwoven fabric layer 1 can be formed by the hardened | cured material of the prepreg etc. which contain a thermosetting resin composition in a nonwoven fabric base material. In addition, the woven fabric layer 2 can be formed by hardened | cured material of the prepreg etc. which contain a thermosetting resin composition in a woven fabric base material.

Examples of the nonwoven fabric substrate include any one selected from glass nonwoven fabric and glass paper, or synthetic resin nonwoven fabric and paper using synthetic resin fibers such as aramid fiber, polyester fiber, and polyamide fiber (nylon). You can use one. It is preferable that the thickness of a nonwoven fabric base material shall be 0.20-1.0 mm. If the thickness of the nonwoven fabric base material is in the above-mentioned range, the thickness of the nonwoven fabric layer 1 will not become too thin and will not become too thick, and heat resistance, heat dissipation, drill workability, etc. can be made favorable. The more preferable range of the thickness of a nonwoven fabric base material is 0.3-0.9 mm. As a binder of a nonwoven fabric base, it is preferable to use the epoxy compound which is excellent in thermal strength. 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 a binder in the ratio of 5-25 mass parts 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, unsaturated polyester resin, and a vinyl ester resin, can be used.

As specific thermosetting resin, what used the epoxy resin as a resin component can be illustrated. In this case, it is selected from the group of bisphenol A type, bisphenol F type, cresol novolak type, phenol novolak type, biphenyl type, naphthalene type, fluorene type, xanthene type, dicyclopentadiene type, anthracene type and the like. At least 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 heat resistance improvement of the laminated board A. As this phenolic compound, allylphenol, a phenol novolak, an alkylphenol novolak, a triazine structure containing phenol novolak, bisphenol A novolak, a dicyclopentadiene structure containing phenol resin, a xylox phenol, a terpene modified phenol At least one selected from the group consisting of polyvinyl phenols, naphthalene structure-containing phenol curing agents, and fluorene structure-containing phenol curing agents. Moreover, the hardening | curing agent component of a phenol compound can be mix | blended in the ratio of 30-120 mass parts, More preferably, 60-110 mass parts with respect to 100 mass parts of epoxy resins.

As another example of specific thermosetting resin, an 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.

Although the structure is not specifically limited as an epoxy resin used for obtaining an epoxy vinyl ester resin, For example, a bisphenol-type epoxy resin, a novolak-type epoxy resin, an alicyclic epoxy resin, glycidyl esters, glycidyl Esters, glycidylamines, 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, a triglycidyl isocyanurate, etc. are mentioned.

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

Among the epoxy resins for obtaining the above-mentioned epoxy vinyl ester resins, brominated epoxy resins are preferably used from the viewpoint of particularly excellent flame retardancy. 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 a carboxyl group-containing rubbery polymer react is especially preferable at the point which improves the impact resistance, punching workability, and interlayer adhesiveness of laminated board A, such as a laminated board with copper obtained.

Examples of the carboxyl group-containing rubbery polymer include those in which a carboxyl group-containing monomer and a conjugated diene monomer are copolymerized with other monomers as necessary, or a copolymerized diene monomer with another monomer. . A carboxyl group may be located in the terminal of a molecule | numerator and a side chain, 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. Moreover, as another monomer used as needed, acrylonitrile, styrene, methyl styrene, halogenated styrene, etc. are mentioned. Among these, from the viewpoint of compatibility with the radically polymerizable unsaturated monomer of the reactant obtained, it is preferable to copolymerize acrylonitrile to the rubbery polymer in an amount of 10 to 40% by weight, and to copolymerize 15 to 30% by weight. More preferred.

And in manufacturing epoxy vinyl ester resin, each component of an epoxy resin, a carboxyl group-containing rubber-like polymer, and ethylenic unsaturated monobasic acid can also be made to react simultaneously. Moreover, in manufacturing an epoxy vinyl ester resin, after making an epoxy resin and a carboxyl group-containing rubbery polymer react, an ethylenic unsaturated monobasic acid can also be made to react. At this time, the reaction ratio of the epoxy resin, the carboxyl group-containing rubbery polymer, and the ethylenically unsaturated monobasic acid used to obtain the epoxy vinyl ester resin is not particularly limited. However, it is preferable that the said reaction ratio exists in the range which the total carboxyl group of a carboxyl group-containing rubber-like polymer and ethylenically unsaturated monobasic acid per 0.8 equivalent of epoxy group of an epoxy resin becomes. Moreover, since the resin which is especially excellent in storage stability can be obtained, it is preferable to make the said reaction ratio into the range used as 0.9-1.0 equivalent.

In addition, in manufacture of an 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, mono, for example. Butyl maleate, sorbic acid and the like. Among these, (meth) acrylic acid is preferable.

The said radically polymerizable unsaturated monomer has at least 1 radically polymerizable unsaturated group in 1 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. 1 type, or 2 or more types are used.

And it is preferable to make the compounding quantity of a radically polymerizable unsaturated monomer into 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. If it is 25 mass parts or more, the impregnation with the nonwoven fabric base material and a woven fabric base material of the thermosetting resin composition obtained will become favorable, and if it is 45 mass parts or less, the laminated board A obtained using this thermosetting resin composition will have dimensional stability. This is because it is excellent and also high heat resistance is excellent. The range with the more preferable compounding quantity of a radically polymerizable unsaturated monomer is 25-40 mass parts with respect to 100 mass parts of total amounts of an epoxy vinyl ester resin and a radically polymerizable unsaturated monomer.

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, tert-butylperbenzoate and tert-butylperoxy-2-ethylhexanoate Organic peroxides, such as alkyl perester, bis (4-tert- butylcyclohexyl) peroxy dicarbonate, and tert- butyl peroxy isobutyl carbonate, are mentioned, for example, 1 type or 2 types of these are mentioned. The above is 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 a polymerization initiator to the thermosetting resin, It is preferable to set in the range of the ratio of 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. Do. In particular, it is more preferable to set it as the range of the ratio of 0.9-2.0 mass parts from the varnish life and curability point of a thermosetting resin composition.

As the inorganic filler, those containing gibbsite-type aluminum hydroxide particles (A) and fine particle components (B) are used. In this embodiment, only the gibbsite type aluminum hydroxide particles (A) and the fine particle component (B) can be contained as the inorganic filler. The gibbsite type aluminum hydroxide particles (A) have an average particle diameter (D ₅₀ ) of 2 to 15 µm. Further, the fine particle component (B) is a fine particle component consisting of aluminum oxide particles having an average particle diameter (D ₅₀₎ of less than 1.5㎛. In addition, the particle size distribution of this microparticles | fine-particles component (B) uses 5 mass% or less of particle diameters 5 micrometers or less, 40 mass% or less of particle diameters 1 micrometer or more and less than 5 micrometers, and 55 mass% or less of particle diameters less than 1 micrometer are used. do. In addition, in this specification, the average particle diameter of an inorganic filler makes a cumulative curve by making 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 It means the particle diameter of 50% of the point. Moreover, the particle size distribution of a microparticle component is obtained by measuring by the laser diffraction type particle size distribution measuring apparatus.

Gibbsite-type aluminum hydroxide particles (A) are aluminum compounds represented by Al (OH) ₃ or Al ₂ O ₃ · 3H 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, the average particle diameter (D ₅₀₎ of the gibbsite-type aluminum hydroxide particles (A) is a ㎛ 2~15, preferably 3~12㎛. When the average particle diameter (D ₅₀ ) of the gibbsite-type aluminum hydroxide particles (A) is 15 μm or less, the drill workability does not easily decrease. When the average particle diameter (D ₅₀ ) is 2 μm or more, the thermal conductivity does not easily decrease, and the productivity also decreases. Becomes difficult. In addition, the gibbsite-type aluminum as the particles (A) hydroxide, an average particle diameter (D ₅₀₎ is 2~10 ㎛ the first gibbsite-type aluminum hydroxide with an average particle diameter (D ₅₀₎ is 10~15 ㎛ second Gibb Combinations with cite type aluminum hydroxide can be used. In this case, it is preferable that the heat dissipation property is further improved by filling the filler more densely.

The fine particle component (B) is a component that gives high thermal conductivity to the laminate obtained. The aluminum oxide particles constituting the fine particle component (B) have an average particle diameter (D ₅₀ ) of 1.5 μm or less, and preferably an average particle diameter (D ₅₀ ) of 0.4 to 0.8 μm. When the average particle diameter of a microparticle component (B) is 1.5 micrometers or less, it is easy to fill with the compounding quantity sufficient for the laminated board A, and also drill property does not fall easily. Moreover, when the average particle diameter of a microparticle component (B) is 0.4 micrometer or more, the thermal conductivity of the laminated board A can fully be obtained. 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㎛, it is possible to avoid lowering the drill workability.

In addition, the particle size distribution of the fine particle component (B) is 5 mass% or less of 5 micrometers of particle diameters, 40 mass% or less of particle diameters 1 micrometer or more and less than 5 micrometers, and 55 mass% or more of particle diameters less than 1 micrometer. By using the aluminum oxide particle which has such a particle size distribution, drill workability can be made favorable. The particle size distribution of the fine particle component (B) is more preferably in the range of 0 to 5% by mass of aluminum oxide particles having a particle diameter of 5 µm or more, 0 to 30% by mass of aluminum oxide particles having a particle diameter of 1 µm or more and less than 5 µm. It is an aluminum oxide particle with a particle diameter of less than 1 micrometer.

In addition, the fine particle component (B) contains 30 mass% or more of crushed (not spherical) aluminum oxide particles. A crushed aluminum oxide particle is a non-spherical alumina obtained by the manufacturing method which grinds agglomerated alumina in the manufacturing method of alumina, and is different from spherical alumina. The crushed aluminum oxide particle calculates the aspect ratio of arbitrary 10 aluminum oxide particles from the SEM image of the sample of the aluminum oxide particle sample which was taken arbitrarily, and this aluminum oxide particle whose average aspect ratio is ≧ 1.3 is called crushed phase. . The aluminum oxide particles having an average aspect ratio of <1.3 can be defined as aluminum oxide particles other than a crushed phase (for example, spherical). When the crushed aluminum oxide particles are contained in an amount of 30% by mass or more based on the total amount of the fine particle component (B), the wear of the drill blade is reduced, and the drill workability is improved. The crushed aluminum oxide particles may be 100% by mass with respect to the total amount of the fine particle component (B).

The compounding ratio (volume ratio) of the said gibbsite type aluminum hydroxide particle (A) and the said microparticles | fine-particles component (B) is 1: 0.2-0.5. When the compounding quantity of the microparticles | fine-particles component (B) is 0.2-0.5 with respect to the compounding quantity 1 of a gibbsite type | mold aluminum hydroxide particle | grains (A), the drill workability, thermal conductivity, heat resistance, etc. of the laminated board A obtained do not fall easily.

In this embodiment, in addition to the said gibbsite type aluminum hydroxide particle (A) and the said microparticle component (B), the said inorganic filler can also contain a 3rd component as needed. As the third component, for example, the boehmite particles described in Japanese Patent Application Laid-open No. 2010-774 have the advantages of improving the heat resistance and flame resistance of the substrate when the filler is high-filled, and reducing the drill wear resistance. Although effective, on the other hand, not only boehmite particles are expensive, but the fluidity of the varnish becomes thixotropy, and there is a problem that the production speed cannot be increased. On the other hand, in this embodiment, by defining the average particle diameter of aluminum oxide and the shape of aluminum oxide of a microparticle component (B) (mainly using a crushed phase), it is not necessary to provide 3rd components, such as boehmite particle | grains. The effect of improving the heat resistance and flame retardance of the substrate and reducing the drill wear resistance can be obtained. The 3rd component can be used within the range which does not reduce heat resistance, drillability, and heat dissipation, For example, a silica etc. can be used. It is preferable to use silica when reducing the linear expansion rate of a board | substrate. The make it preferable, and more preferable that as in 1~30 ㎛ average particle diameter (D ₅₀₎ of the third component is 5~15 ㎛.

In the present invention, when the viscosity at thixotropy (TI value) 6 rpm and 30 rpm is defined as η 6 and η 30, respectively, and TI value is defined as η 6 / η 30, the TI value ≤ 2 is used to reduce the molding failure rate. It is important. Although the boehmite particles are excellent in heat resistance and flame retardancy, they do not avoid TI values> 2 in high-charge systems and cannot avoid appearance defects that are conventional molding conditions.

The blending ratio of the inorganic filler with respect to 100 volume parts of thermosetting resins is 80-150 volume parts, Preferably it is 90-150 volume parts, More preferably, it is 100-150 volume parts. When the mixing ratio of the inorganic filler is 80 volume parts or more, the thermal conductivity of the laminated plate A obtained is not easily lowered, and when it is 150 volume parts or less, the drill workability does not easily decrease, and the manufacturability (resin impregnability, Moldability) also does not fall easily. Moreover, especially when the mixing | blending ratio of a gibbsite type aluminum hydroxide particle (A) is 100 volume parts or less, it exists in the tendency for a lot of crystal water to be hard to generate | occur | produce and heat resistance does not fall easily. In addition, when mix | blending the said 3rd component, it can use within the range which does not reduce heat resistance, a drillability, and heat dissipation, For example, as a compounding quantity of a 3rd component, 0-15 volume% with respect to the inorganic filler whole quantity. You can do

The thermosetting resin composition mix | blends the above-mentioned inorganic filler (containing a 3rd component if necessary) containing the above-mentioned gibbsite type aluminum hydroxide particle (A) and microparticle component (B) with said thermosetting resin, such as a liquid phase, 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 roll, etc. And various additives, such as a curing catalyst of a thermosetting resin, can also be mix | blended with a thermosetting resin composition. Moreover, in consideration of viscosity adjustment of a thermosetting resin composition, impregnation with a nonwoven fabric base material, etc., you may mix | blend processing aids, such as solvents, such as an organic solvent, a viscosity reducing agent, and a coupling agent, as needed.

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 a semi-hardened state (B stage state) by heat drying etc. You can get it. In the prepreg for forming the nonwoven fabric layer 1, the content of the thermosetting resin composition can be 40 to 95% by mass, more preferably 60 to 95% by mass, based on the total amount of the prepreg. no.

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

The thermosetting resin composition for forming the woven fabric layer 2 may be the same as or different from the said thermosetting resin composition for forming the nonwoven fabric layer 1. When making it different, the kind of thermosetting resin and inorganic filler to be used, content of the 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 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. Accordingly, it is believed that the crystal water of aluminum hydroxide inhibits thermal decomposition and carbonization of the surface of the laminated plate A, and the tracking resistance of the laminated plate A is improved. In addition, in order to improve the tracking resistance of laminated board A, it is preferable that aluminum hydroxide is the ratio of 25-150 volume parts with respect to 100 volume parts of thermosetting resins in the woven fabric layer 2, More preferably, it is 30-100 volume parts. In addition, the average particle diameter (D ₅₀₎ is preferably used for 2~15 ㎛ of aluminum hydroxide, and more preferably 4~15 ㎛.

The prepreg for forming the woven fabric layer 2 can be obtained 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. have. 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 whole prepreg whole quantity, More preferably, it is 60-95 mass%, It is limited to this no.

And when forming the composite laminated board as the laminated board A of this invention shown in FIG. 1, after prepreg for forming the nonwoven fabric layer 1, and the prepreg for forming the woven fabric layer 2 are superposed, it heat-presses this. It can be molded. Thereby, the thermosetting resin in each prepreg is hardened to form the nonwoven fabric layer 1 and the woven fabric layer 2, and the nonwoven fabric layer 1 and the woven fabric layer 2 are bonded together by lamination of these thermosetting resins, and integrated. do. 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 laminated sheet with a metal foil using this composite laminated sheet is further provided with the metal foil 3, such as copper foil and nickel foil, on the surface of the woven fabric layer 2 as a laminated board with one side or double-sided metal foil in which a composite laminated sheet became an insulating layer. Can be formed. 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 The woven fabric layer 2 and the metal foil 3 are laminated and integrated. The conditions of hot press molding are as above-mentioned.

Composite laminates can be produced continuously. An example of the manufacturing method of the composite laminated board with a double-sided metal foil 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 an air gap in an inside and a surface and can impregnate a thermosetting resin composition, it will not specifically limit. Although the thickness of a glass nonwoven fabric is 0.3-0.8 mm in general, it is not limited to this thickness. In addition, the glass woven fabric which is a woven fabric base material is a glass cloth made of glass fiber, and is a long material 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 for the thickness of a glass woven fabric, 0.015-0.25 mm is common, but it is not limited to 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 roll and heated to produce a composite laminate. Here, the glass nonwoven fabric in which the thermosetting resin composition was impregnated can also be used by 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. In addition, one or more sheets of thermosetting resin-impregnated glass woven fabrics may also be used. Moreover, the metal foil 3 can also be laminated | stacked on the surface layer of one side or both surfaces. As metal foil 3, if it is a long metal foil which can be supplied continuously, it will not specifically limit, Copper foil, nickel foil, etc. are mentioned. The thickness of the metal foil 3 is generally 0.012 to 0.07 mm, but is not limited to this thickness.

Next, as shown in FIG. 2, two thermosetting resin-impregnated glass nonwoven fabrics 12 impregnated into the glass nonwoven fabric 10 to which the thermosetting resin composition 11 is continuously supplied, and two thermosetting resin-impregnated glass supplied continuously. The woven fabric 9 and two metal foils 13 continuously supplied are laminated. In this case, using the thermosetting resin impregnated glass nonwoven fabric 12 as a core, the thermosetting resin impregnated glass woven fabric 9 is arrange | positioned at both (upper and lower sides), and it laminates so that the metal foil 13 may be arrange | positioned at both surface layers. Thereafter, the laminated laminate is crimped with a laminate roll 14. Subsequently, the crimped material 15 is pressed at the draw roll 18 while being pushed forward, while the thermally curable resin composition 11 in the crimped material 15 is cured in the heat curing furnace 17. ) Is cured by heating. Thereafter, the cutter 19 is cut into a predetermined size to obtain a composite laminate A in which the metal foil 3 is continuously laminated on the surface. Reference numeral 171 denotes a conveying roll disposed in the heat curing furnace 17.

In addition, the conditions to crimp with the laminate roll 14 are not specifically limited, It can adjust suitably according to the kind of glass nonwoven fabric 10 used, the kind of glass woven fabric, 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 be suitably set according to the component mix of the thermosetting resin composition 11 to be used, and the degree of hardening to harden it. After cutting, in order to further advance the curing of the laminated sheet A, it may be heated (aftercure).

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 multiple sheets of thermosetting resin impregnated glass nonwoven fabric 12, 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. do. Therefore, the composite laminate does not easily bend, and the soldering heat resistance becomes high.

The printed wiring board of the present invention using the composite laminate as described above can be formed by forming a conductor pattern on the surface of the composite laminate. In this case, it can be processed into a printed wiring board by performing a circuit processing process, such as an additive method or a subtractive method, or through-hole processing to the said laminated sheet with a metal foil. 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 in the said laminated sheet with metal foil. Moreover, the LED mounting circuit board of this invention using a composite laminated board can be formed by forming an LED electronics electronic circuit in the said composite laminated board. In this case, the electric / electronic circuit of the circuit board can be formed as an LED-mounted electric / electronic circuit.

In addition, since the laminate A (including the composite laminate) A of the present invention has a high filler compounded with the inorganic filler in the nonwoven fabric layer 1, the thermal conductivity can be increased and heat can be quickly diffused throughout the laminate A, so that the heat dissipation property is excellent. Is higher. Therefore, the same effect can be acquired also in the laminated board with metal foil, the printed wiring board, and the circuit board which are formed from the laminated board A of this invention. By mounting the electric-electronic parts which generate heat | fever, such as LED, etc. in these laminated sheets with metal foil, the heat which generate | occur | produces from an electrical and electronic component can be conducted to the metal foil with high thermal conductivity, a printed wiring board, and a circuit board, and can be spread easily. As a result, the heat dissipation from a metal foil laminated board, a printed wiring board, and a circuit board becomes high, the deterioration by the heat of an electrical and electronic component can be reduced, and long life of an electrical and electronic component can be aimed at. In addition, the LED mounting circuit board of the present invention can be easily diffused by conducting heat generated from the LED by mounting the LED. As a result, the heat dissipation from an LED mounting circuit board becomes high, the deterioration by heat of LED can be reduced, and long life of LED can be aimed at.

In addition, in the laminated board A of this invention, a gibbsite type aluminum hydroxide particle (A) is mix | blended with the thermosetting resin composition which comprises the nonwoven fabric layer 1, and the microparticles | fine-particles which have a small average particle diameter and have a predetermined particle size distribution are also included. A predetermined amount is mix | blended with component (B). For this reason, the abrasion of the drill blade at the time of the drill processing of the laminated board A can be suppressed, and as a result, a drill can be extended for a long life. Moreover, even if a drill process is applied for through-hole formation, unevenness | corrugation is hard to form in the inner surface of the hole formed, and the inner surface of this hole can also be formed smoothly. For this reason, when through-hole plating is formed on the inner surface of the hole, a high conduction reliability can also be imparted to the through-hole. Moreover, by mix | blending the fine particle component (B) excellent in thermal conductivity, the thermal conductivity of the laminated board A can be improved significantly. And since the fine particle component (B) of a small particle diameter is mix | blended, it does not significantly reduce the drillability of a laminated board.

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 higher, preferably 1.5 W / m · K or higher. 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 includes a plurality of LED modules 23 in which a plurality of LEDs 22 are mounted on the laminate A or the circuit board 21 formed from the laminate A. FIG. It is arranged in an arrangement. By providing such a circuit board 21 on the back of the liquid crystal panel, it is used as a backlight of a liquid crystal display or 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 from the laminate A or the laminate A. FIG. It consists of the LED module 23. Such LED backlight unit 20 is used as a backlight such as a liquid crystal display by providing each LED module 23 above and below (or left and right) such as the light guide plate 24. 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 a high heat dissipation material such as the laminate A of the present invention. BACKGROUND ART A cold cathode tube (CCFL) type backlight has been widely used as a backlight of a liquid crystal display in a liquid crystal display of a type that has been widely used in the past. However, in recent years, since the color gamut can be improved and the image quality can be improved compared to the cold cathode tube type backlight, and since mercury is not used, the environmental load is small and the thickness can be reduced. Such LED backlight units are being actively developed. Since an LED module generally has larger power consumption than a cold cathode tube, it has a large amount of heat generation. By using the laminate A of the present invention as the circuit board 21 requiring such high heat dissipation, the heat dissipation problem 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 21 formed from 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.

(Example 1)

As a nonwoven fabric base material, the glass nonwoven fabric (Billin Co., Ltd. make, a binder is epoxy silane, etc.) of thickness 0.6mm was used, and the compounding quantity of a binder was 5-25 mass parts with respect to 100 mass parts of glass fibers.

As a woven fabric base material, the glass cloth (Nittobo Co., Ltd. product, 7628) of thickness 0.18mm was used.

As thermosetting resin, the thing containing bisphenol-A epoxy resin which is a resin component, and the phenol novolak resin which is a hardening | curing agent component was used. Bisphenol A type epoxy resin used 850S (made by the Japan ink chemical company), and TD-2090-60M (made by the Japan ink chemical company) was used for the phenol novolak resin, respectively. These compounding ratios are 40 mass parts of phenol novolak resin with respect to 100 mass parts of bisphenol-A epoxy resins.

As the gibbsite-type aluminum hydroxide particles (A) of the inorganic filler, those having an average particle diameter (D ₅₀ ) manufactured by Sumitomo Chemical Co., Ltd. were 12 µm. As the fine particle component (B) of the inorganic filler, aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 µm manufactured by Sumitomo Chemical Co., Ltd. were used. The particle size distribution of this fine particle component (B) was 5 mass% of 5 micrometers or more of particle diameters, 30 mass% of 1 micrometer or more and less than 5 micrometers of particle diameters, and 65 mass% of less than 1 micrometer of particle diameters. Moreover, 60 mass% of crushed aluminum oxide particles (average aspect ratio 1.6) are contained in this microparticle component (B), and remainder is mix | blended with spherical aluminum oxide particles (average aspect ratio 1.1). . And the inorganic filler mix | blended the microparticles | fine-particles component (B) in the ratio of 20 volume parts with respect to 100 volume parts of a gibbsite type aluminum hydroxide particle (A) by volume ratio (volume ratio 1: 0.2).

And the inorganic filler was mix | blended in the ratio of 80 volume parts with respect to 100 volume parts of thermosetting resins, and the thermosetting resin composition for nonwoven fabric layers was prepared. In addition, the glass nonwoven fabric (The glass nonwoven fabric made from valine, the binder is epoxy silane, etc.) of 60 g / m <^2> and 400 micrometers in thickness which used the thermosetting resin varnish for nonwoven fabric layers, and the compounding ratio of a binder is glass fiber 5-25 mass parts) with respect to 100 mass parts, and obtained the prepreg for nonwoven fabric layers. On the other hand, per square meter usage 200 g / m ^2, thickness 180㎛ glass cloth (woven fabric) (units tobo Co., Ltd., 7628), aluminum hydroxide in the thermosetting resin (manufactured by Sumitomo Chemical Co., Ltd., D ₅₀ of: The prepreg for woven fabric layers was produced by impregnating the glass cloth with a thermosetting resin varnish containing 4.3 micrometers) and making it semi-hardened.

And the thermosetting resin varnish for nonwoven fabric layers was prepared by mix | blending methyl ethyl ketone in the ratio of 6 mass parts as a solvent with respect to 100 mass parts of thermosetting resin compositions for nonwoven fabric layers.

In addition, the thermosetting resin varnish for a woven fabric layer was first mix | blended aluminum hydroxide in the ratio of 10 volume parts with respect to 100 volume parts of said thermosetting resins for nonwoven fabrics, and the thermosetting resin composition for woven fabric layers was prepared. Next, methyl ethyl ketone was blended in the ratio of 6 mass parts as a solvent with respect to 100 mass parts of this thermosetting resin compositions for woven fabric layers, and the thermosetting resin varnish for woven fabric layers was prepared.

Next, two prepregs for nonwoven fabric layers were superimposed, one prepreg for woven fabric layers, and copper foil with a thickness of 0.018 mm were sequentially mounted on both outer surfaces thereof to obtain a laminate. This laminated body was sandwiched between two metal plates, and the composite laminated board with a copper foil of 1.0 mm was obtained by heat-molding on condition of the temperature of 180 degreeC, and the pressure of 0.3 kPa (30 kgf / m <^2> ).

(Example 2)

A composite laminate plate with copper foil was obtained in the same manner as in Example 1 except that the inorganic filler was blended in a ratio of 90 volume parts to 100 volume parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Example 3)

A composite laminate with copper foil was obtained in the same manner as in Example 1 except that the inorganic filler was blended in a proportion of 120 vol. Parts to 100 vol. Parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Example 4)

A composite laminate with copper foil was obtained in the same manner as in Example 1, except that the inorganic filler was blended in a ratio of 140 volume parts to 100 volume parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Example 5)

A composite laminate with copper foil was obtained in the same manner as in Example 1 except that the inorganic filler was blended in a proportion of 150 vol parts to 100 vol parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Comparative Example 1)

A composite laminate with copper foil was obtained in the same manner as in Example 1 except that the inorganic filler was blended in a ratio of 70 vol parts to 100 vol parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Comparative Example 2)

A composite laminate with copper foil was obtained in the same manner as in Example 1 except that the inorganic filler was blended at a ratio of 160 vol parts to 100 vol parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Example 6)

A composite laminate plate with copper foil was obtained in the same manner as in Example 3 except that the average particle diameter (D ₅₀ ) was used as the gibbsite type aluminum hydroxide particles (A).

(Example 7)

A composite laminate plate with copper foil was obtained in the same manner as in Example 3 except that the average particle diameter (D ₅₀ ) was 15 μm as the gibbsite type aluminum hydroxide particles (A).

(Comparative Example 3)

A composite laminate plate with copper foil was obtained in the same manner as in Example 3 except that the average particle diameter (D ₅₀ ) was used as the gibbsite type aluminum hydroxide particles (A).

(Comparative Example 4)

A composite laminate plate with copper foil was obtained in the same manner as in Example 3 except that the average particle diameter (D ₅₀ ) was used as the gibbsite type aluminum hydroxide particles (A).

(Example 8)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 0.8 μm were used. As for the particle size distribution of this microparticles | fine-particles component (B), 1 mass% of particle diameters 5 micrometers or more, 25 mass% of particle diameters 1 micrometer or more and less than 5 micrometers were 74 mass%. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 1.

(Example 9)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 0.2 μm were used. The particle size distribution of this fine particle component (B) was 0 mass% of 5 micrometers or more of particle diameters, 12 mass% of 1 micrometer or more and less than 5 micrometers of particle diameters, and 88 mass% of less than 1 micrometer of particle diameters. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 1.

(Comparative Example 5)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 1.6 µm were used. As for the particle size distribution of this microparticles | fine-particles component (B), 4 mass% of particle diameters 5 micrometers or more, 36 mass% of particle diameters 1 micrometer or more and less than 5 micrometers were 60 mass%. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 1.

(Comparative Example 6)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 µm were used. The particle size distribution of this fine particle component (B) was 6 mass% of particle diameter 5 micrometers or more, 24 mass% of particle diameters 1 micrometer or more and less than 5 micrometers, and 70 mass% of less than 1 micrometer of particle diameters. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 1.

(Comparative Example 7)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 µm were used. The particle size distribution of this fine particle component (B) was 3 mass% of 5 micrometers or more of particle diameters, 43 mass% of 1 micrometer or more and less than 5 micrometers of particle diameters, and 54 mass% of less than 1 micrometer of particle diameters. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 1.

(Comparative Example 8)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 µm were used. As for the particle size distribution of this microparticles | fine-particles component (B), 23 mass% of particle diameters 5 micrometers or more, 29 mass% of particle diameters 1 micrometer or more and less than 5 micrometers were 48 mass%. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 1.

(Example 10)

As an inorganic filler, what mix | blended the microparticles | fine-particles component (B) with respect to 100 volume parts of gibbsite-type aluminum hydroxide particles (A) in 35 volume parts by volume ratio (volume ratio 1: 0.35) was used. As the fine particle component (B), one containing 40% by mass of crushed aluminum oxide particles was used. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 3.

(Example 11)

As an inorganic filler, what mix | blended the microparticles | fine-particles component (B) with respect to 100 volume parts of gibbsite type aluminum hydroxide particles (A) by 50 volume parts by volume ratio (volume ratio 1: 0.5) was used. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 11.

(Comparative Example 9)

As an inorganic filler, what mix | blended the microparticles | fine-particles component (B) with respect to 100 volume parts of gibbsite type | mold aluminum hydroxide particles (A) by volume ratio (volume ratio 1: 0.1) was used for volume ratio. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 11.

(Comparative Example 10)

As an inorganic filler, what mix | blended the microparticles | fine-particles component (B) with the volume ratio of 60 volume parts with respect to 100 volume parts of gibbsite-type aluminum hydroxide particles (A) was used by volume ratio (volume ratio 1: 0.6). Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 11.

(Comparative Example 11)

A composite laminate plate with copper foil was obtained in the same manner as in Example 3, except that 25 mass% of crushed aluminum oxide particles were used as the fine particle component (B).

(Example 12)

The composite laminated board with copper foil was formed continuously by the manufacturing method shown in FIG. 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 molecular weight is 3500, a bond with an epoxy equivalent of 400 grams / equivalent tetrabromobisphenol A type epoxy resin ("brand name EPICLON153" (made by Nippon Ink Chemical Co., Ltd.)) to a four neck flask. HYCARCTBN1300X13 [B. wherein acrylonitrile has a carboxyl group at both ends of the molecule of a copolymer of acrylonitrile with 27% of carboxyl groups and 1.9 of carboxyl groups / molecule. F. Goodrich Chemical Co., Ltd.] 92 parts by mass, methacrylic acid 82 parts by mass (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 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, 80 parts by volume of the same inorganic filler as in Example 1, and tert-butyl peroxybenzoate ("brand name perbutyl Z" [manufactured by Nippon Oil Industries, Ltd.)) were added to 100 parts by volume of this epoxy vinyl ester resin composition. The thermosetting resin composition for nonwoven fabric layers was produced by adding in a volume ratio of 1.0 volume part and mixing uniformly with a homo mixer. The prepreg for nonwoven fabric layers was produced by impregnating this thermosetting resin composition for nonwoven fabric layers in a nonwoven fabric base material, and making it semi-hardened.

Further, tert-butylperoxybenzoate was added to a volume of 100 parts of the epoxy vinyl ester resin composition in a proportion of 1.0 parts by volume, and uniformly mixed with a homo mixer to prepare a thermosetting resin composition for a woven fabric layer. The prepreg for woven fabric layers was produced by impregnating this thermosetting resin composition for woven fabric layers in the same woven fabric base material as Example 1, and making it semi-hardened. Then, the composite laminated board with copper foil was formed in the same method as Example 1 using the prepreg for nonwoven fabric layers and the prepreg for woven fabric layers.

(Example 13)

A composite laminate plate with copper foil was obtained in the same manner as in Example 12, except that the inorganic filler was blended in a ratio of 90 vol parts to 100 vol parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Example 14)

A composite laminate plate with copper foil was obtained in the same manner as in Example 12, except that the inorganic filler was blended in a ratio of 120 volume parts to 100 volume parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Example 15)

A composite laminate with copper foil was obtained in the same manner as in Example 12, except that the inorganic filler was blended in a ratio of 140 volume parts to 100 volume parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Example 16)

A composite laminate plate with copper foil was obtained in the same manner as in Example 12, except that the inorganic filler was blended in a proportion of 150 volume parts to 100 volume parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Comparative Example 12)

A composite laminate with copper foil was obtained in the same manner as in Example 12, except that an inorganic filler was blended in a proportion of 70 vol parts to 100 vol parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Comparative Example 13)

A composite laminate plate with copper foil was obtained in the same manner as in Example 12 except that the inorganic filler was blended in a proportion of 160 vol parts to 100 vol parts of the thermosetting resin to prepare a thermosetting resin composition for a nonwoven fabric layer.

(Example 17)

A composite laminate plate with copper foil was obtained in the same manner as in Example 14, except that the average particle diameter (D ₅₀ ) of the gibbsite type aluminum hydroxide particles (A) was 8.5 μm.

(Example 18)

A copper clad composite laminate was obtained in the same manner as in Example 14, except that the average particle diameter (D ₅₀ ) was 15 μm as the gibbsite type aluminum hydroxide particles (A).

(Comparative Example 14)

A composite laminate plate with copper foil was obtained in the same manner as in Example 14 except that the average particle diameter (D ₅₀ ) was used as the gibbsite type aluminum hydroxide particles (A).

(Comparative Example 15)

A composite laminate plate with copper foil was obtained in the same manner as in Example 14, except that the average particle diameter (D ₅₀ ) was used as the gibbsite type aluminum hydroxide particles (A).

(Example 19)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 0.8 μm were used. As for the particle size distribution of this microparticles | fine-particles component (B), 1 mass% of particle diameters 5 micrometers or more, 25 mass% of particle diameters 1 micrometer or more and less than 5 micrometers were 74 mass%. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 12.

(Example 20)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 0.2 μm were used. The particle size distribution of this fine particle component (B) was 0 mass% of 5 micrometers or more of particle diameters, 12 mass% of 1 micrometer or more and less than 5 micrometers of particle diameters, and 88 mass% of less than 1 micrometer of particle diameters. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 12.

(Comparative Example 16)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 1.6 µm were used. As for the particle size distribution of this microparticles | fine-particles component (B), 7 mass% of particle diameters 5 micrometers or more, 35 mass% of particle diameters 1 micrometer or more and less than 5 micrometers were 58 mass%. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 12.

(Comparative Example 17)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 µm were used. The particle size distribution of this fine particle component (B) was 5 mass% of 5 micrometers or more of particle diameters, 33 mass% of 1 micrometer or more and less than 5 micrometers of particle diameters, and 62 mass% of less than 1 micrometer of particle diameters. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 12.

(Comparative Example 18)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 µm were used. As for the particle size distribution of this microparticles | fine-particles component (B), 8 mass% of particle diameters 5 micrometers or more, 42 mass% of particle diameters 1 micrometer or more and less than 5 micrometers were 50 mass%. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 12.

(Comparative Example 19)

As the fine particle component (B), aluminum oxide particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 µm were used. The particle size distribution of this fine particle component (B) was 17 mass% of particle diameter 5 micrometers or more, 40 mass% of particle diameters 1 micrometer or more and less than 5 micrometers, and 43 mass% of particle diameters less than 1 micrometer. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 12.

(Example 21)

As an inorganic filler, what mix | blended the microparticles | fine-particles component (B) in the ratio of 35 volume parts with respect to 100 volume parts of gibbsite-type aluminum hydroxide particles (A) by volume ratio (volume ratio 1: 0.35) was used. As the fine particle component (B), one containing 40% by mass of crushed aluminum oxide particles was used. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 14.

(Example 22)

As an inorganic filler, what mix | blended the microparticles | fine-particles component (B) with respect to 100 volume parts of gibbsite type aluminum hydroxide particles (A) by 50 volume parts by volume ratio (volume ratio 1: 0.5) was used. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 21.

(Comparative Example 20)

As an inorganic filler, what mix | blended the microparticles | fine-particles component (B) with respect to 100 volume parts of gibbsite type | mold aluminum hydroxide particles (A) by volume ratio (volume ratio 1: 0.1) was used for volume ratio. Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 21.

(Comparative Example 21)

As an inorganic filler, what mix | blended the microparticles | fine-particles component (B) with the volume ratio of 60 volume parts with respect to 100 volume parts of gibbsite-type aluminum hydroxide particles (A) was used by volume ratio (volume ratio 1: 0.6). Except the point mentioned above, the composite laminated board with copper foil was obtained using the method similar to Example 21.

(Comparative Example 22)

A composite laminate plate with copper foil was obtained in the same manner as in Example 21, except that 25 mass% of crushed aluminum oxide particles were used as the fine particle component (B).

(Comparative Example 23)

18 volume parts of boehmite (C) were mix | blended, and the compounding ratio of each component was carried out as shown in Table 8. Others obtained the composite laminated board with copper foil using the method similar to Example 21.

<Thermal conductivity>

The density of the obtained copper foil laminated board was measured by the underwater substitution method, and 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.

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

<Oven heat resistance test>

When the test piece produced according to JISC 6481 was processed for 1 hour in a thermostat equipped with the air circulation apparatus set to 200-240 degreeC using the obtained copper clad laminated board, the temperature which swelled and peeled to copper foil and a laminated board was measured. It was. And for evaluation of oven heat test, in order 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 laminated sheets with copper foil were piled up, and the wear rate of the drill blade after forming 6000 holes at 60000 rotation / min by drill (drill diameter 0.5mm, displacement angle 35 degrees) is the size of the drill blade before drill processing ( It calculated | required and evaluated by the ratio (percentage) of the drill area (area) worn by the drill process with respect to the area). (Circle) and the wear rate are less than 50%, (triangle | delta) and the thing with a wear rate 60% or more were made into (circle) what the wear rate is 40% or less. And the smaller the wear rate of the drill blade is, the smaller the loss of the drill blade is, and the higher the workability of the drill. 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.

<Appearance Evaluation>

20 or more pieces were molded, and defects that could be confirmed by visual observation such as irregularities and bubbles on the surface were counted. When 5% or more defects occurred, Δ and 10% or more defects occurred.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

TABLE 6

[Table 7]

[Table 8]

A: laminated sheet 1: nonwoven fabric layer
2: woven fabric layer 3: metal foil
20: LED backlight unit 21: circuit board

Claims (10)

A nonwoven fabric layer obtained by impregnating a non-woven fabric base material with a thermosetting resin composition,
As a laminated board integrally laminated with a woven fabric layer laminated on both surfaces of the nonwoven fabric layer,
The said thermosetting resin composition contains an inorganic filler in the ratio of 80-150 volume parts with respect to 100 volume parts of thermosetting resins,
The inorganic filler contains a gibbsite type aluminum hydroxide particle (A) and a fine particle component (B),
The gibbsite-type aluminum hydroxide particles (A) is, with a mean particle size of 2~15 ㎛ (D _50),
The particulate component (B) is made of a aluminum oxide particles having an average particle diameter (D ₅₀₎ of less than 1.5㎛, the particle size distribution, particle diameter 5㎛ than 5 mass%, particle size of more than 5 1㎛ Less than 40 micrometers and less than 1 micrometer of particle diameters are 55 mass% or more, and the said fine particle component (B) contains 30 mass% or more of crushed aluminum oxide particles, The said gibbsite type The laminated board whose compounding ratio (volume ratio) of an aluminum hydroxide particle (A) and the said microparticles | fine-particles component (B) is 1: 0.2-0.5. The method of claim 1,
The laminated board in which the said thermosetting resin contains an epoxy resin. 3. The method of claim 2,
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 laminated sheet with a metal foil by which metal foil is provided in at least one surface among the laminated sheets in any one of Claims 1-4. The printed wiring board in which a conductor pattern is provided in at least one surface among the laminated boards in any one of Claims 1-4. The circuit board in which a circuit is provided in at least one surface of the laminated board in any one of Claims 1-4. An LED backlight unit in which an LED is mounted on at least one surface of the laminate according to any one of claims 1 to 4. The LED illuminating device in which LED is mounted in at least one surface among the laminated boards in any one of Claims 1-4. The thermosetting resin composition is cured by impregnating the thermosetting resin composition into the nonwoven substrate while continuously conveying the nonwoven fabric, laminating the woven fabric on both surfaces thereof while continuously conveying the nonwoven substrate, and pressing and heating the laminate with a roll. As a manufacturing method of the laminated board which makes a nonwoven fabric layer and a woven fabric layer,
The said thermosetting resin composition contains an inorganic filler in the ratio of 80-150 volume parts with respect to 100 volume parts of thermosetting resins,
The said inorganic filler contains gibbsite type | mold aluminum hydroxide particle | grains (A) and a microparticle component (B),
The gibbsite-type aluminum hydroxide particles (A) is, with a mean particle size of 2~15 ㎛ (D _50),
The particulate component (B) is made of a aluminum oxide particles having an average particle diameter (D ₅₀₎ of less than 1.5㎛, the particle size distribution, particle diameter 5㎛ than 5 mass%, particle size of more than 5 1㎛ Less than 40 micrometers is less than 40 mass%, less than 1 micrometer of particle diameters is 55 mass% or more, The said fine particle component (B) contains 30 mass% or more of crushed aluminum oxide particles,
The manufacturing method of the laminated board whose compounding ratio (volume ratio) of the said gibbsite type aluminum hydroxide particle (A) and the said microparticles | fine-particles component (B) is 1: 0.2-0.5.

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