TWI452949B - Laminated sheet, metal foil-clad laminated sheet, printed wiring sheet and circuit sheet and led backlight unit, led lighting installation, manufacturing method of laminated sheet - Google Patents

Description

Multilayer board, metal foil laminated board, printed wiring board and circuit board, LED backlight unit, LED lighting device, and manufacturing method of laminated board

The present invention relates to a laminated board for various electronic devices, a metal foil-clad laminate, a printed wiring board and a circuit board, an LED backlight unit, and a method of manufacturing the laminated board. In particular, it is suitable for a laminate which is suitable for mounting a heat generating element such as a light emitting diode (LED).

Conventionally, there has been provided a laminate in which a surface of a non-woven fabric layer comprising a non-woven fabric substrate containing a resin composition and a surface layer of a woven fabric substrate containing a resin composition are laminated (for example, a reference patent) Document 1). Such a laminate is processed into a printed wiring board for mounting an electric and electronic component by forming a conductor pattern on the surface thereof, and is formed into a circuit board by forming a circuit using the conductor pattern.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-272671

However, recently, electrical and electronic components mounted on laminated boards may use a large amount of heat generation or an increase in the mounting density of electrical and electronic parts that generate heat. In order to cope with such a situation, it is desirable to have a laminate having high heat dissipation properties. When a laminated board having high heat dissipation property is used, the heat generated by the electric and electronic parts can be easily dissipated by heat, and the service life of the electric and electronic parts can be lengthened.

The present invention has been made in view of the above problems, and it is an object of the invention to provide a laminated board which does not impair heat resistance and drilling processability and has high heat dissipation properties. And its manufacturing method. Further, another object of the present invention is to provide a metal foil-clad laminate, a printed wiring board, a circuit board, an LED backlight unit, and an LED illumination device having high heat dissipation properties.

The laminated board of the present invention is obtained by integrating a nonwoven fabric layer obtained from a nonwoven fabric substrate impregnated with a thermosetting resin composition and a woven fabric layer laminated on both surfaces of the nonwoven fabric layer. The thermosetting resin composition contains an inorganic filler in a proportion of 80 to 150 parts by volume with respect to 100 parts by volume of the thermosetting resin. The inorganic filler contains gibbsite-type aluminum hydroxide particles (A) and fine particle components (B). The gibbsite-type aluminum hydroxide particles (A) have an average particle diameter (D ₅₀ ) of 2 to 15 μm . The fine particle component (B) is composed of alumina particles having an average particle diameter of 1.5 μm or less. The particle size distribution of the fine particle component (B) is 5 μm or more and 5 mass% or less, a particle diameter of 1 μm or more and less than 5 μm is 40 mass% or less, and a particle diameter of less than 1 μm is 55 mass%. the above. The fine particle component (B) contains 30% by mass or more of the crushed alumina particles. The blending 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 present invention, it is preferable that the fine particle component (B) contains 30% by mass or more of the crushed alumina particles.

In the present invention, it is preferred that the thermosetting resin contains an epoxy resin.

In the present invention, it is preferred that the thermosetting resin contains a phenol compound as a curing agent component of the epoxy resin.

In the present invention, it is preferred that the thermosetting resin contains an epoxy vinyl ester resin, a radical polymerizable unsaturated monomer, and a polymerization initiator.

The metal foil-clad laminate of the present invention is characterized in that it is in the aforementioned product A metal foil is formed on at least one surface of the laminate.

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 laminated board.

The circuit board of the present invention is characterized in that an electric circuit is provided on at least one surface of the laminated board.

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

An LED lighting device according to the present invention is characterized in that an LED is mounted on at least one surface of the laminated board.

In the method for producing a laminated board according to the present invention, the nonwoven fabric substrate is continuously transferred, and the thermosetting resin composition is impregnated into the nonwoven substrate, and the nonwoven fabric substrate is continuously transferred while the woven fabric is laminated on both surfaces thereof. Then, the laminate is pressed and heated by a roll to cure the thermosetting resin composition to form a nonwoven fabric layer and a woven fabric layer. The thermosetting resin composition contains an inorganic filler in an amount of 80 to 150 parts by volume based on 100 parts by volume of the thermosetting resin. The inorganic filler contains gibbsite-type aluminum hydroxide particles (A) and fine particle components (B). The gibbsite-type aluminum hydroxide particles (A) have an average particle diameter (D ₅₀ ) of 2 to 15 μm . The fine particle component (B) is composed of alumina particles having an average particle diameter of 1.5 μm or less, and has a particle diameter distribution particle size of 5 μm or more and less than 5% by mass or less, and a particle diameter of 1 μm or more and less than 5 μ. m is 40% by mass or less, and the particle diameter is less than 1 μm, which is 55% by mass or more. The fine particle component (B) contains 30% by mass or more of the crushed alumina particles. The blending ratio (volume ratio) of the gibbsite-type aluminum hydroxide particles (A) and the fine particle component (B) is 1:0.2 to 0.5.

The laminated board of the present invention can improve heat dissipation without impairing heat resistance and drilling processability.

The metal foil-clad laminate, the printed wiring board, the circuit board, the LED backlight unit, and the LED lighting device of the present invention can improve heat dissipation.

The method for producing a laminated board of the present invention can continuously produce a laminated board, which is improved in productivity compared to a batch type.

Hereinafter, the form for carrying out the invention will be described.

As shown in Fig. 1, the laminated board A of the present invention is formed by a nonwoven fabric layer 1 containing a thermosetting resin composition and a woven fabric layer 2 containing a thermosetting resin composition, and is a so-called composite laminated board. The composite laminated board is sometimes inferior in heat dissipation properties to a conventional laminated board (formed solely by the nonwoven fabric layer 1 and not using a woven fabric). However, the composite laminate is inexpensive and excellent in dimensional stability and mechanical properties. The nonwoven fabric layer 1 can be formed by a cured product of a prepreg containing a thermosetting resin composition in a nonwoven fabric substrate. Further, the woven fabric layer 2 can be formed by a cured product of a prepreg containing a thermosetting resin composition in a woven fabric substrate.

As the nonwoven fabric substrate, for example, synthetic resin non-woven fabric or paper selected from synthetic resin fibers such as glass fiber nonwoven fabric, cellophane, or aromatic polyamide fiber, polyester fiber, or polyamide fiber (nylon) can be used. Any of them. The thickness of the nonwoven substrate is preferably set to 0.20 to 1.00 mm. When the thickness of the nonwoven fabric substrate is within this range, the thickness of the nonwoven fabric layer 1 is not too thin or too thick, and heat resistance, heat dissipation property, and drilling processability are good. A more preferable range of the thickness of the nonwoven substrate is 0.3 to 0.9 mm. As the binder of the nonwoven fabric substrate, an epoxy resin compound excellent in heat resistance is preferably used. The binder is a fiber used to form a nonwoven fabric substrate constituting the fiber The adhesive is then fixed and fixed. As the epoxy resin compound as a binding agent, epoxy oxirane or the like can be used. Further, it is preferred to prepare a ratio of 5 to 25 parts by mass based on 100 parts by mass of the binder of the fiber.

The thermosetting resin composition contains a thermosetting resin and an inorganic filler. As the thermosetting resin, for example, a thermosetting resin which is liquid at normal temperature can be used. Further, as the thermosetting resin, for example, a mixture of a resin component and a hardener component can be used. Further, as the resin component, a radical polymerization type thermosetting resin such as an epoxy resin, an unsaturated polyester resin or a vinyl ester resin can be used.

As a specific thermosetting resin, as a resin component, the epoxy resin is illustrated. In this case, it can be used from bisphenol A type, bisphenol F type, cresol novolak type, novolak type, biphenyl type, naphthalene type, anthracene type, dibenzopyran type, dicyclopentadiene type, At least one epoxy resin in the group of 蒽 type or the like. Further, as the curing agent component of the epoxy resin, dicyandiamide or a phenol compound can be used, but in order to improve the heat resistance of the laminated plate A, a phenol compound is preferably used. As the phenol compound, self-allyl phenol, novolac, alkyl novolac, novolac-containing novolac, bisphenol A novolac, phenol resin having a dicyclopentadiene structure, phenol aralkyl may be used. At least one of a group of a phenol, a terpene-modified phenol, a polyvinyl phenol, a phenol-based curing agent containing a naphthalene structure, and a phenol-based curing agent containing a fluorene structure. Moreover, the ratio of the curing agent component of the phenol compound is preferably from 30 to 120 parts by mass, more preferably from 60 to 110 parts by mass, per 100 parts by mass of the epoxy resin.

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

As an epoxy resin used to obtain epoxy vinyl ester resin, there is no special The limitation includes, for example, a bisphenol type epoxy resin, a novolac type epoxy resin, an alicyclic epoxy resin, a glycidyl ester, a glycidyl amine, a heterocyclic epoxy resin, and a brominated epoxy resin. Resin, etc. Examples of the bisphenol type epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy resin. Examples of the above-mentioned novolac type epoxy resin include a novolac type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A novolak type epoxy resin, and a dicyclopentadiene novolac type epoxy resin. Wait. As the above alicyclic epoxy resin, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, and the like. Examples of the glycidyl esters include diglycidyl phthalate, diglycidyl phthalate, and dimer acid glycidyl ester. Examples of the glycidylamines include tetraglycidyldiaminediphenylmethane, triglycidylphosphoniumaminophenol, and N,N-diglycidylaniline. Examples of the heterocyclic epoxy resin include 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate.

Further, as the brominated epoxy resin, a tetrabromobisphenol A type epoxy resin, a tetrabromobisphenol F type epoxy resin, a brominated cresol novolac type epoxy resin, a brominated novolac type ring may be mentioned. Oxygen resin, etc.

Among the epoxy resins for obtaining the above-mentioned epoxy vinyl ester resin, in particular, in view of excellent flame retardancy, a brominated epoxy resin is preferably used. Further, an epoxy resin obtained by reacting a part of the epoxy group of the epoxy resin with a carboxyl group-containing rubber polymer may also be used. The epoxy resin obtained by reacting the carboxyl group-containing rubber-like polymer improves the punching resistance, punching workability, and interlayer adhesion of the laminated sheet A of the obtained copper-clad laminate or the like. The consideration is very good.

The carboxyl group-containing rubber-like polymer may be one obtained by copolymerizing a carboxyl group-containing monomer with a conjugated diene monomer and, if necessary, another monomer, or a carboxyl group introduced into the conjugate. A method in which a diene monomer is copolymerized with another monomer or the like. The carboxyl group may be located at one end of the molecule or at the side chain, and the number thereof is preferably from 1 to 5, more preferably from 1.5 to 3, in one molecule.

The conjugated diene monomer is butadiene, isoprene, chloroprene or the like. Further, other monomers used as needed include acrylonitrile, styrene, methyl styrene, halogenated styrene, and the like. Among these, in consideration of the compatibility of the obtained reactant with the radically polymerizable unsaturated monomer, it is preferred to copolymerize acrylonitrile in an amount of 10 to 40% by weight in the rubbery polymer. More preferably, it is copolymerized by 15 to 30% by weight.

Further, in the production of the epoxy vinyl ester resin, the respective components of the epoxy resin, the carboxyl group-containing rubbery polymer, and the ethylenically unsaturated monobasic acid may be simultaneously reacted. Further, in the production of the epoxy vinyl ester resin, the epoxy resin may be reacted with the ethylenically unsaturated monobasic acid after reacting with the carboxyl group-containing rubbery polymer. In this case, the reaction ratio of the epoxy resin used for obtaining the epoxy vinyl ester resin to the carboxyl group-containing rubbery polymer and the ethylenically unsaturated monobasic acid is not particularly limited. However, the above reaction ratio is preferably 1 equivalent to the epoxy group of the epoxy resin, and the total carboxyl group of the carboxyl group-containing rubber polymer and the ethylenically unsaturated monobasic acid is in the range of 0.8 to 1.1 equivalents. Further, in particular, in consideration of a resin excellent in storage stability, the reaction ratio is preferably set to a range of from 0.9 to 1.0 equivalent.

Further, in the production of the ethylene oxide resin, as the ethylenically unsaturated monobasic acid used for the reaction with the epoxy resin, for example, (meth) propylene is exemplified. Acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethyl maleate, monobutyl maleate, hexadienoic acid, and the like. Among these, (meth)acrylic acid is preferred.

The radically polymerizable unsaturated monomer is one having at least one radical polymerizable unsaturated group in one molecule. Examples of such a radically polymerizable unsaturated monomer include diallyl phthalate, styrene, methyl styrene, halogenated styrene, (meth)acrylic acid, and methyl methacrylate. Ethyl methacrylate, butyl acrylate, divinyl benzene, ethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tris(meth)acrylate or pentaerythritol tetra(meth)acrylate may be used alone or in combination of two or more.

In addition, the amount of the radically polymerizable unsaturated monomer is preferably set to 25 parts by mass or more based on 100 parts by mass of the total of the ethylene oxide resin and the radically polymerizable unsaturated monomer. A ratio of 45 parts by mass or less. The reason for this is that the thermosetting resin composition obtained is excellent in the impregnation property of the nonwoven fabric substrate and the woven fabric substrate, and the thermosetting resin composition is used in an amount of 45 parts by mass or less. The obtained laminated board A is excellent in dimensional stability and excellent in high heat resistance. The preferred range of the amount of the radically polymerizable unsaturated monomer is 25 to 40 parts by mass based on 100 parts by mass of the total of the ethylene oxide resin and the radically polymerizable unsaturated monomer.

Examples of the polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, and cyclohexanone peroxide; benzoyl peroxide, isobutyl peroxide, and the like. Dihydric oxyhydroxides; hydrogen peroxides such as cumene hydroperoxide or tributyl hydride; diperoxy peroxides such as dicumyl peroxide and di-tert-butyl peroxide Peroxidation 1,1- Peroxy acetals of di-t-butyl-3,3,5-trimethylcyclohexanone, 2,2-di-(t-butylperoxy)-butane, etc.; Alkyl peroxyesters such as benzoic acid esters, tributyl-2-ethylcyclohexanoate peroxide, bis(4-tert-butylcyclohexyl)dicarbonate peroxide, An organic peroxide such as peroxycarbonate such as tributyl isobutyl carbonate is oxidized. These may be used alone or in combination of two or more. By using such an organic peroxide, the thermosetting resin composition becomes heat-curable.

The amount of the polymerization initiator to be added to the thermosetting resin is not particularly limited, and is preferably set to 0.5 to 5.0 with respect to 100 parts by mass of the total of the ethylene oxide resin and the radically polymerizable unsaturated monomer. The range of ratios around the mass. In particular, the varnish life and hardenability of the thermosetting resin composition are more preferably set to a ratio of 0.9 to 2.0 parts by mass.

As the inorganic filler, those containing the gibbsite-type aluminum hydroxide particles (A) and the fine particle component (B) can be used. In the present embodiment, the inorganic filler may contain only the gibbsite-type hydrogen. Alumina particles (A) and the fine particle component (B). The average particle diameter (D ₅₀ ) of the gibbsite-type aluminum hydroxide particles (A) is 2 to 15 μm. Further, the fine particle component (B) is a fine particle component composed of alumina particles having an average particle diameter (D ₅₀ ) of 1.5 μm or less. In addition, the particle size distribution system using the fine particle component (B) is a particle diameter of 5 μm or more and 5% by mass or less, a particle diameter of 1 μm or more and less than 5 μm of 40% by mass or less, and a particle diameter of less than 1 μm of 55% by mass or more. In the present specification, the average particle diameter of the inorganic filler refers to a cumulative curve obtained by measuring the total volume of the powder agglomerates by a laser diffraction type particle size distribution measuring apparatus, and the cumulative curve is obtained. It is the particle size at 50%. Further, the particle size distribution of the fine particle component can also be measured by a laser diffraction type particle size distribution measuring apparatus.

The gibbsite-type aluminum hydroxide particles (A) are aluminum compounds represented by Al(OH) ₃ or Al ₂ O ₃ ‧3H ₂ O, and have imparted thermal conductivity, flame retardancy, and drilling processability to the laminated sheet A. A good balance of ingredients. Further, the gibbsite-type aluminum hydroxide particles (A) have an average particle diameter (D ₅₀ ) of 2 to 15 μm, preferably 3 to 12 μm. When the average particle diameter (D ₅₀ ) of the gibbsite-type aluminum hydroxide particles (A) is 15 μm or less, the drilling processability is not easily lowered, and when it is 2 μm or more, the thermal conductivity is not easily lowered and the productivity is not easily lowered. Further, as the gibbsite-type aluminum hydroxide particles (A), the first gibbsite-type aluminum hydroxide having an average particle diameter (D ₅₀ ) of 2 to 10 μm and an average particle diameter (D ₅₀ ) can be used. A formulation of 10 to 15 μm of gibbsite-type aluminum hydroxide. In this case, heat dissipation can be further improved by the tighter filling of the filler, which is preferable.

The fine particle component (B) is a component which imparts high thermal conductivity to the obtained laminated board. The alumina particles constituting the fine particle component (B) have an average particle diameter (D ₅₀ ) of 1.5 μm or less, and preferably have an average particle diameter (D ₅₀ ) of 0.4 to 0.8 μm. When the average particle diameter of the fine particle component (B) is 1.5 μm or less, the laminated plate A can be easily filled with a sufficient amount of mixing, and the drilling processability is not easily lowered. Further, when the average particle diameter of the fine particle component (B) is 0.4 μm or more, the laminated plate A can obtain a sufficient thermal conductivity. Further, although the alumina particles are hard and have a Mohs hardness of 12, the average particle diameter (D ₅₀ ) is 1.5 μm or less, so that the drilling processability can be prevented.

Further, the particle size distribution of the fine particle component (B) is 5 μm or more in the particle diameter of 5 μm or more, 40 μ mass % or less in the particle diameter of 1 μm or more and less than 5 μm, and 55 mass % or more in the particle diameter of less than 1 μm. By using alumina particles having such a particle size distribution, the drilling processability can be improved. The particle size distribution of the fine particle component (B) is preferably in the range of 0 to 5% by mass of the alumina particles having a particle diameter of 5 μm or more, and 0 to 5 μm of the alumina particles having a particle diameter of 1 μm or more and less than 5 μm. 30% by mass, and the balance is alumina particles having a particle diameter of less than 1 μm.

Further, the fine particle component (B) contains 30% by mass or more of the crushed (non-spherical) alumina particles. In the method for producing alumina, the non-spherical alumina obtained by the method of pulverizing the bulk alumina is a different from the spherical alumina. The crushed alumina particles are obtained from an SEM image of an arbitrarily sampled alumina particle sample, and the aspect ratio of any ten alumina particles is calculated, and the alumina particles having an average aspect ratio ≧1.3 are defined as broken. . Further, the alumina particles having an average aspect ratio of <1.3 can be defined as alumina particles other than the fractured shape (for example, spherical). When the amount of the crushed alumina particles is 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 drilling processability can be improved. Further, the crushed alumina particles may be 100% by mass based on the total amount of the fine particle component (B).

The compounding ratio (volume ratio) of the gibbsite-type aluminum hydroxide particles (A) and the fine particle component (B) is 1:0.2 to 0.5. When the amount of the fine particle component (B) is 0.2 to 0.5 with respect to the compounding amount 1 of the gibbsite-type aluminum hydroxide particle (A), the drilling processability, thermal conductivity, and heat resistance of the laminated plate A obtained are obtained. Sex will not be easy to reduce.

In the above-described inorganic filler, the third component may be contained in addition to the gibbsite-type aluminum hydroxide particles (A) and the fine particle component (B) as needed. For example, the boehmite particles described in Japanese Laid-Open Patent Publication No. 2010-774 are used to improve the heat resistance and flame retardancy of the substrate and to reduce the wear of the drill when the filler is highly filled. The effect, on the other hand, the boehmite particles are not only costly, but also cause the varnish to become highly shaken, resulting in a problem that the production speed cannot be improved. On the other hand, in the present embodiment, the average particle diameter of the alumina of the fine particle component (B) and the shape of the alumina (the main component of the crushed form) are defined, and the third layer of the boehmite particles or the like is not added. Further, the composition can also have an effect of improving the heat resistance and flame retardancy of the substrate and reducing the wear of the drill. The third component can be used insofar as it does not impair the heat resistance, the drilling processability, and the heat dissipation property, and for example, ruthenium oxide or the like can be used. Cerium oxide is preferably used in order to reduce the linear expansion coefficient of the substrate. The average particle diameter (D ₅₀ ) as the third component is preferably set to 1 to 30 μm, more preferably 5 to 15 μm.

In the present invention, the shaking property (TI value) is η6 and η30 at a viscosity of 6 rpm and 30 rpm, respectively, and when TI value = η6 / η30, the TI value ≦ 2 is important in reducing the molding failure rate. Although the diaspore particles are excellent in heat resistance and flame retardancy, the TI value of >2 cannot be avoided in a highly filled system, so that a certain degree of appearance defects are inevitably caused under the conventional molding conditions.

The proportion of the inorganic filler to be contained in an amount of from 100 parts by volume to the thermosetting resin is preferably from 80 to 150 parts by volume, preferably from 90 to 150 parts by volume, more preferably from 100 to 150 parts by volume. When the blending ratio of the inorganic filler is 80 parts by volume or more, the thermal conductivity of the obtained laminated board A is not easily lowered, and when it is 150 parts by volume or less, the drilling processability is not easily lowered, and the manufacturability of the laminated board A (resin impregnation) Sex, formability) is also not easy to reduce. In addition, when the blending ratio of the gibbsite-type aluminum hydroxide particles (A) is 100 parts by volume or less, a large amount of crystal water is unlikely to be generated, and heat resistance tends to be less likely to be lowered. Moreover, when the third component is blended, it can be used in a range that does not impair heat resistance, drilling processability, and heat dissipation. For example, the blending amount of the third component can be set to be relative to the inorganic filler. The total amount is 0 to 15% by volume.

The thermosetting resin composition may be formulated into an inorganic filler containing the gibbsite-type aluminum hydroxide particles (A) and the fine particle component (B) in the above-mentioned thermosetting resin such as a liquid (optional if necessary) Three components), use A disperser, a ball mill, a roll, or the like is prepared by a known modulation method for dispersing particles of each inorganic filler. Further, in the thermosetting resin composition, various additives such as a curing catalyst of a thermosetting resin may be blended as needed. In addition, it is possible to adjust the viscosity of the thermosetting resin composition and the impregnation property to the nonwoven substrate, and if necessary, a processing aid such as a solvent such as an organic solvent, a viscosity reducing agent, or a coupling agent may be added.

The prepreg for forming the nonwoven fabric layer 1 can be obtained by impregnating the nonwoven fabric substrate with a thermosetting resin composition, and then the thermosetting resin composition impregnated with the nonwoven fabric substrate is semi-hardened by heat drying or the like. Obtained in the state (B-stage state). The prepreg for forming the nonwoven fabric layer 1 may have a content of the thermosetting resin composition of 40 to 95% by mass, preferably 60 to 95% by mass, based on the total amount of the prepreg, but is not limited thereto. herein.

As the woven fabric substrate for forming the woven fabric layer 2, for example, a synthetic resin selected from synthetic resin fibers using glass cloth or aromatic amide fiber, polyester fiber, polyamide fiber (nylon) or the like can be used. Any of the cloths. The thickness of the woven base material can be set to 50 to 500 μm, but is not limited thereto.

The thermosetting resin composition for forming the woven fabric layer 2 may be the same as or different from the above-described thermosetting resin composition for forming the nonwoven fabric layer 1. In different cases, the type of the thermosetting resin to be used, the type of the inorganic filler, the content of the inorganic filler relative to the thermosetting resin, and the like can be changed. In particular, it is preferable to use an inorganic filler from the above-mentioned thermosetting resin composition for forming the nonwoven fabric layer 1, that is, a solvent or an additive which is prepared by the above-mentioned thermosetting resin and other optional ones. Thereby, the impregnation property of the thermosetting resin composition with the woven fabric substrate can be improved. In the case where the woven fabric layer 2 contains an inorganic filler, in order to improve the antitracking property of the laminate, aluminum hydroxide is preferably used as the inorganic filler. It is considered that the crystal water of aluminum hydroxide hinders thermal decomposition and carbonization of the surface of the laminated board A, so that the creep resistance of the laminated board A can be improved. Moreover, in order to improve the creep resistance of the laminated board A, it is preferable that the ratio of the aluminum hydroxide in the woven fabric layer 2 is 25 to 150 parts by volume, more preferably 30 to 100, with respect to 100 parts by volume of the thermosetting resin. Parts by volume. Further, it is preferred to use aluminum hydroxide having an average particle diameter (D ₅₀ ) of 2 to 15 μm, more preferably 4 to 15 μm.

The prepreg for forming the woven fabric layer 2 can be made into a semi-hardened state by impregnating the woven fabric substrate with a thermosetting resin composition, and then heating and drying the thermosetting resin composition impregnated with the woven fabric substrate. Obtained from the stage state). The prepreg for forming the woven fabric layer 2 may have a content of the thermosetting resin composition of 40 to 95% by mass, more preferably 60 to 95% by mass, based on the total amount of the prepreg, but is not limited thereto. herein.

Further, when forming the composite laminated board of the laminated board A of the present invention shown in Fig. 1, the prepreg for forming the nonwoven fabric layer 1 and the prepreg for forming the woven fabric layer 2 can be laminated. Thereafter, it is formed by heat and pressure. Thereby, the thermosetting resin in each prepreg is cured 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 can be laminated one by one by hardening the thermosetting resin. Chemical. Here, each of the nonwoven fabric layer 1 and the woven fabric layer 2 may be formed by laminating one or a plurality of prepregs. Further, the woven fabric layer 2 can be formed on both surfaces of the non-woven fabric layer 1. Further, by using the metal foil-clad laminate of the composite laminate, a metal foil 3 such as a copper foil or a nickel foil can be further provided on the surface of the woven fabric layer 2 to form a composite laminate or a double-sided insulating layer. Metal foil laminated board. In this case, the prepreg for forming the nonwoven fabric layer 1, the prepreg for forming the woven fabric layer 2, and the metal foil 3 are laminated, and then the nonwoven fabric layer is formed by heat and pressure molding. versus The woven fabric layer 2 and the metal foil 3 are laminated to be integrated. The conditions of the heat and pressure forming are the same as those described above.

Composite laminates can be produced continuously. Fig. 2 shows an example of a method of manufacturing a double-sided metal foil-clad composite laminate. The glass non-woven fabric of the nonwoven fabric substrate is not particularly limited as long as it is a glass fiber paper, an elongated material that can be continuously supplied, a void between the inside and the surface, and a thermosetting resin composition. The thickness of the glass non-woven fabric is usually 0.3 to 0.8 mm, but is not limited to this thickness. Further, the glass woven fabric of the woven fabric base material is not limited to a glass woven fabric made of glass fiber, a long product which can be continuously supplied, a void between the inside and the surface, and a thermoplastic resin composition. limited. The thickness of the glass woven fabric is usually 0.015 to 0.25 mm, but is not limited to this thickness.

Next, first, the above-mentioned thermosetting resin composition is impregnated into a glass nonwoven fabric which is a nonwoven fabric substrate. Then, both surfaces of the glass nonwoven fabric impregnated with the superheat-curable resin composition were continuously laminated with a thermosetting resin impregnated glass woven fabric, and the laminate was pressed and heated by a roll to produce a composite laminated board. Here, one piece or a plurality of glass non-woven fabrics impregnated with the thermosetting resin composition may be used in combination. Further, the thermosetting resin impregnated glass woven fabric is a glass woven fabric obtained by impregnating a thermosetting resin or a thermoplastic resin composition as described above. Further, the thermosetting resin-impregnated glass woven fabric may be used in one piece or in a plurality of sheets. Further, the metal foil 3 may be laminated on the surface of one or both sides thereof. The metal foil 3 is not particularly limited as long as it can be continuously supplied as an elongated metal foil, and examples thereof include copper foil and nickel foil. The thickness of the metal foil 3 is usually 0.012 to 0.07 mm, but is not limited to this thickness.

Next, as shown in Fig. 2, the above thermosetting resin composition 11 is impregnated. The two sheets of thermosetting resin impregnated with the glass nonwoven fabric 10 are impregnated with the glass nonwoven fabric 12, and the two sheets of the thermosetting resin-impregnated glass woven fabric 9 continuously supplied are laminated with the two metal foils 13 continuously supplied. In this case, a thermosetting resin impregnated glass nonwoven fabric 12 is used as a core, and a thermosetting resin impregnated glass woven fabric 9 is disposed on both sides (upper and lower sides), and the metal foil 13 is placed on both surface layers to be laminated. Then, the laminate obtained by laminating was laminated by a lamination roll. Then, the press-fitted pressure-sensitive adhesive 15 is pulled out and tensioned by the roller 18 to carry out the temperature at which the thermosetting resin composition 11 in the pressure-sensitive adhesive 15 is cured in the heat-hardening furnace 17 while being advanced. The pressure compound 15 is heated to harden it. Then, it is cut into a predetermined size by a cutter 19, and a composite laminated board A having a metal foil 3 on its surface layer is continuously obtained. Reference numeral 171 is a transfer roller disposed in the heat-hardening furnace 17.

In addition, the conditions for the press-bonding of the build-up roll 14 are not particularly limited, and can be appropriately adjusted depending on the type of the glass nonwoven fabric 10 to be used, the type of the glass woven fabric, and the viscosity of the thermosetting resin composition 11. Further, the conditions such as the temperature and time of heat curing are not particularly limited, and may be appropriately set depending on the component ratio of the thermosetting resin composition 11 to be used and the degree of curing to be cured. Heating (post-hardening) for promoting the hardening of the laminate A may be further performed after the cutting.

The number of the thermosetting resin impregnated glass nonwoven fabric 12 may be two, and the thermosetting resin impregnated glass nonwoven fabric 12 may be one sheet or three or more sheets. Further, the number of the metal foils 13 may be two or a single sheet. When the thermosetting resin impregnated glass nonwoven fabric 12 is a plurality of sheets, the thermosetting resin impregnated glass nonwoven fabric may be further laminated with a metal foil. Further, the non-woven base material and the woven base material are not limited to those using glass fibers, and those using other materials may be used. Furthermore, if thermosetting The resin composition contains a wetting dispersant in an amount of 0.05 to 5% by mass based on the inorganic filler, and the inorganic filler can be uniformly dispersed in the thermosetting resin impregnated glass woven fabric 9 and the thermosetting resin impregnated glass nonwoven fabric 12. Therefore, the composite laminated board is less likely to warp and the solder heat resistance can be improved.

The printed wiring board of the present invention using the above composite laminated board can be formed by providing a conductor pattern on the surface of the composite laminated board. In this case, the metal foil-clad laminate may be processed into a printed wiring board by a circuit processing or a through hole processing such as an additive method or a subtractive method. Further, the circuit board of the present invention using a composite laminate can be formed by providing an electrical and electronic circuit on the composite laminate. In this case, an electric and electronic circuit can be formed by a conductor pattern of a printed wiring board formed of the above-mentioned metal foil-clad laminate. Moreover, the LED mounting circuit board of the present invention using the composite laminated board can be formed by providing an LED mounting electric and electronic circuit on the composite laminated board. In this case, an electric and electronic circuit of the above circuit board can be used as an electric and electronic circuit for mounting an LED.

Next, since the laminated board (including the composite laminated board) A of the present invention is prepared by mixing the non-woven fabric layer 1 with a high degree of filling of the inorganic filler, a high thermal conductivity can be achieved, so that heat can be immediately diffused to the laminate A. The overall heat dissipation is high. Therefore, the metal foil-clad laminate, the printed wiring board, and the circuit board formed of the laminated board A of the present invention can exhibit the same operational effects. By mounting an electric and electronic component that generates heat, such as an LED, on a metal foil laminate or the like, the heat generated by the electric and electronic components is easily conducted and diffused to a metal foil-clad laminate, a printed wiring board, and a circuit having high thermal conductivity. Substrate. As a result, the heat dissipation property of the metal foil-clad laminate, the printed wiring board, and the circuit board is increased, and the electrical and electronic components can be deteriorated due to heat, and the electrical growth can be increased. The service life of electronic components. Further, in the LED mounting circuit board of the present invention, by mounting the LED, heat generated by the LED can be easily conducted and diffused. As a result, the heat dissipation property of the LED mounting circuit board is increased, and the thermal deterioration of the LED can be reduced, and the life of the LED can be increased.

Further, in the laminated board A of the present invention, the gibbsite-type aluminum hydroxide particles (A) are blended in the thermosetting resin composition constituting the nonwoven fabric layer 1, and the average particle diameter is small and has a predetermined amount in a predetermined amount. Particle size distribution of the fine particle component (B). Therefore, the wear of the drill blade at the time of drilling of the laminated board A can be suppressed, and as a result, the service life of the drill can be increased. Further, even if it is applied to a drilling process for forming a through hole, irregularities are less likely to be formed on the inner surface of the formed hole, and the inner surface of the hole can be smoothly formed. Therefore, when the hole is plated on the inner surface of the hole to form a through hole, the through hole can be provided with high conduction reliability. Moreover, by disposing the fine particle component (B) having excellent thermal conductivity, the thermal conductivity of the laminated plate A can be remarkably improved. Further, since the fine particle component (B) having a small particle diameter is blended, the drilling processability of the laminated plate is not remarkably lowered.

The laminated board A of the present invention can be preferably used for applications requiring high heat dissipation such as a printed wiring board mounted on an LED backlight unit of a liquid crystal display or a circuit board for an LED lighting device. In such an LED mounting application, a high heat dissipation substrate is necessary, and it is preferably a high heat dissipation substrate having a thermal conductivity of 0.9 W/m‧K or more, preferably 1.5 W/m‧K or more. Specifically, as one of the uses of the LED, an LED backlight unit 20 such as a direct type mounted on a liquid crystal display as shown in FIG. 3 can be cited. In the LED backlight unit 20 of FIG. 3, a plurality of LED modules in which a plurality of LEDs 22 (three in FIG. 3) are mounted are arranged on the circuit board 21 formed of the laminated board A or the laminated board A. 23 constitutes. By disposing such a circuit board 21 on the back surface of the liquid crystal panel, a backlight which is a liquid crystal display or the like can be used. Also, use this The laminated board A of the present invention can form an edge type LED backlight unit 20 mounted on a liquid crystal display as shown in Figs. 4(a) and 4(b). The LED backlight unit 20 in FIGS. 4(a) and 4(b) is an LED module 23 in which a plurality of LEDs 22 are mounted on the laminated board A or the elongated circuit board 21 formed by the laminated board A. Composition. The LED backlight unit 20 can be used as a backlight of a liquid crystal display or the like by disposing the LED modules 23 on the upper and lower sides (or left and right) of the light guide plate 24 or the like. The edge-type LED backlight unit 20 is provided with a high density in comparison with the LED backlight unit 20 of the direct type, and therefore it is preferable to use a laminate board A of the present invention with high heat dissipation. In a liquid crystal display of a type widely used in the past, as a backlight of a liquid crystal display, a backlight of a cold cathode tube (CCFL) type has been widely used. However, in recent years, compared with the backlight of the cold cathode tube method, the color gamut can be wider, the image quality can be improved, and the environmental burden is small without using mercury, and the advantages of thinning can be achieved. LED backlight units are actively being developed. LED modules typically consume more power than cold cathode tubes and therefore generate more heat. As the circuit board 21 which is required to have high heat dissipation properties, the problem of heat dissipation can be greatly improved by using the laminated board A of the present invention. Therefore, the luminous efficiency of the LED can be improved.

Further, the LED lighting device can be formed using the laminated board A of the present invention. In the LED lighting device, a plurality of LEDs can be mounted on the laminated board A or the circuit board 21 formed of the laminated board A, and a power supply unit for causing the LED to emit light can be formed.

[Examples]

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

(Example 1)

As a non-woven substrate, a glass non-woven fabric with a thickness of 0.6 mm is used. (VILENE), the binder is epoxy decane, and the amount of the binder is 5 to 25 parts by mass based on 100 parts by mass of the glass fiber.

As a woven base material, a glass cloth having a thickness of 0.18 mm (7628 manufactured by Nitto Spin Co., Ltd.) was used.

As the thermosetting resin, a phenol varnish resin containing a bisphenol A type epoxy resin as a resin component and a curing agent component is used. 850S (manufactured by Dainippon Ink and Chemicals, Inc.) was used for the bisphenol A type epoxy resin, and TD-2090-60M (manufactured by Dainippon Ink Chemicals Co., Ltd.) was used for the novolac resin. The blending ratio is 40 parts by mass based on 100 parts by mass of the bisphenol A type epoxy resin.

The gibbsite-type aluminum hydroxide particles (A) used as the inorganic filler are those having an average particle diameter (D ₅₀ ) of 12 μm manufactured by Sumitomo Chemical Co., Ltd. As the fine particle component (B) of the inorganic filler, alumina 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 the fine particle component (B) is 5 μm or more and 5 mass%, the particle diameter of 1 μm or more and less than 5 μm is 30% by mass, and the particle diameter of less than 1 μm is 65% by mass. Further, in the fine particle component (B), the crushed alumina particles (average aspect ratio: 1.6) are contained in an amount of 60% by mass based on the total amount, and the rest are spherical alumina particles (average aspect ratio of 1.1). proportion. In addition, the inorganic filler is blended in a volume ratio of 100 parts by volume of the gibbsite-type aluminum hydroxide particles (A) so that the fine particle component (B) is 20 parts by volume (volume ratio 1). :0.2).

In addition, the thermosetting resin composition for the nonwoven fabric layer was prepared by blending the inorganic filler in an amount of 80 parts by volume with respect to 100 parts by volume of the thermosetting resin. Further, a thermosetting resin varnish for a non-woven layer is impregnated with a coating amount of 60 g/m ² and a glass non-woven fabric having a thickness of 400 μm (a glass non-woven fabric made of VILENE, a binder is an epoxy decane, etc., and a ratio of a binding agent to a glass fiber) In the case of 100 parts by mass, it is 5 to 25 parts by mass), and a prepreg for a non-woven layer is obtained. On the other hand, a glass cloth (woven fabric) having a coating amount of 200 g/m ² and a thickness of 180 μm (7628, manufactured by Nitto Bose Co., Ltd.) contains aluminum hydroxide (manufactured by Sumitomo Chemical Co., Ltd.) in the thermosetting resin. The thermosetting resin varnish having D ₅₀ : 4.3 μm was impregnated with a glass cloth to be in a semi-hardened state, thereby preparing a prepreg for a woven fabric layer.

In addition, the preparation of the thermosetting resin varnish for the nonwoven fabric layer is prepared by blending a ratio of 6 parts by mass of methyl ethyl ketone as a solvent to 100 parts by mass of the thermosetting resin composition for the nonwoven fabric layer.

Further, in the preparation of the thermosetting resin varnish for the woven fabric layer, first, aluminum hydroxide is blended in a ratio of 10 parts by volume with respect to 100 parts by volume of the thermosetting resin for the nonwoven fabric, and a thermosetting resin for woven fabric layer is prepared. Things. Then, with respect to 100 parts by mass of the thermosetting resin composition for the woven fabric layer, methyl ethyl ketone as a solvent was prepared in a ratio of 6 parts by mass to prepare a thermosetting resin varnish for a woven fabric layer.

Next, two prepregs for the nonwoven fabric layer were laminated, and on each of the outer surfaces, one sheet of the prepreg for the woven fabric layer and the copper foil having a thickness of 0.018 mm were sequentially coated to obtain a laminate. This laminated body was sandwiched between two metal plates, and heat-molded at a temperature of 180 ° C and a pressure of 0.3 kPa (30 kgf / m ² ) to obtain a copper-clad composite laminated plate having a thickness of 1.0 mm.

(Example 2)

A copper-clad composite laminate was obtained in the same manner as in Example 1 except that the inorganic filler was blended in an amount of 90 parts by volume with respect to 100 parts by volume of the thermosetting resin to prepare a thermosetting resin composition for the nonwoven fabric layer.

(Example 3)

A copper-clad composite laminate was obtained in the same manner as in Example 1 except that the inorganic filler was blended in an amount of 120 parts by volume with respect to 100 parts by volume of the thermosetting resin to prepare a thermosetting resin composition for the nonwoven fabric layer.

(Example 4)

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

(Example 5)

A copper-clad composite laminate was obtained in the same manner as in Example 1 except that the inorganic filler was blended in a ratio of 150 parts by volume with respect to 100 parts by volume of the thermosetting resin to prepare a thermosetting resin composition for the nonwoven fabric layer.

(Comparative Example 1)

A copper-clad composite laminate was obtained in the same manner as in Example 1 except that the inorganic filler was blended in an amount of 70 parts by volume with respect to 100 parts by volume of the thermosetting resin to prepare a thermosetting resin composition for the nonwoven fabric layer.

(Comparative Example 2)

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

(Example 6)

A copper-clad composite laminate was obtained in the same manner as in Example 3 except that the gibbsite-type aluminum hydroxide particles (A) had an average particle diameter (D ₅₀ ) of 8.5 μm.

(Example 7)

A copper-clad composite laminate was obtained in the same manner as in Example 3 except that the gibbsite-type aluminum hydroxide particles (A) had an average particle diameter (D ₅₀ ) of 15 μm.

(Comparative Example 3)

A copper-clad composite laminate was obtained in the same manner as in Example 3 except that the gibbsite-type aluminum hydroxide particles (A) had an average particle diameter (D ₅₀ ) of 1.5 μm.

(Comparative Example 4)

A copper-clad composite laminate was obtained in the same manner as in Example 3 except that the gibbsite-type aluminum hydroxide particles (A) were used in an average particle diameter (D ₅₀ ) of 16 μm.

(Example 8)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 0.8 μm were used. The particle size distribution of the fine particle component (B) is 1% by mass or more of the particle diameter of 5 μm or more, 25% by mass or less and 25% by mass or less, and the particle diameter is less than 1 μm, which is 74% by mass. Except for this, a copper clad composite laminate was obtained in the same manner as in Example 1.

(Example 9)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 0.2 μm were used. The particle size distribution of the fine particle component (B) is 0% by mass or more, a particle diameter of 5 μm or more, a particle diameter of 1 μm or more and less than 5 μm, and a particle diameter of less than 1 μm of 88% by mass. Except for this, a copper clad composite laminate was obtained in the same manner as in Example 1.

(Comparative Example 5)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 1.6 μm were used. The particle size distribution of the fine particle component (B) is 4% by mass or more of the particle diameter of 5 μm or more, 36% by mass or less of the particle diameter of 1 μm or more, and 60% by mass of the particle diameter of less than 1 μm. Except for this, a copper clad composite laminate was obtained in the same manner as in Example 1.

(Comparative Example 6)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 μm were used. The particle size distribution of the fine particle component (B) is 6% by mass in a particle diameter of 5 μm or more, 24% by mass in a particle diameter of 1 μm or more and less than 5 μm, and 70% by mass in a particle diameter of less than 1 μm. Except for this, a copper clad composite laminate was obtained in the same manner as in Example 1.

(Comparative Example 7)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 μm were used. The particle size distribution of the fine particle component (B) is 3% by mass in a particle diameter of 5 μm or more, 43% by mass in a particle diameter of 1 μm or more and less than 5 μm, and 54% by mass in a particle diameter of less than 1 μm. Except for this, a copper clad composite laminate was obtained in the same manner as in Example 1.

(Comparative Example 8)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 μm were used. The particle size distribution of the fine particle component (B) is 23 mass% of a particle diameter of 5 μm or more, 29 mass% of a particle diameter of 1 μm or more and less than 5 μm, and a particle diameter of less than 1 μm of 48% by mass. Except for this, a copper clad composite laminate was obtained in the same manner as in Example 1.

(Embodiment 10)

As the inorganic filler, a particulate component (B) in a ratio of 35 parts by volume based on 100 parts by volume of the gibbsite-type aluminum hydroxide particles (A) was used in a volume ratio (volume ratio 1:0.35). Further, as the fine particle component (B), those having 40% by mass of crushed alumina particles are used. Except for this, a copper clad composite laminate was obtained in the same manner as in Example 3.

(Example 11)

As the inorganic filler, a microparticle component (B) in a volume ratio of 50 parts by volume to 100 parts by volume of the gibbsite-type aluminum hydroxide particles (A) was used in a volume ratio (volume ratio: 1:0.5). Except for this, a copper clad composite laminate was obtained in the same manner as in Example 10.

(Comparative Example 9)

As the inorganic filler, a microparticle component (B) in a volume ratio of 10 parts by volume to 100 parts by volume of the gibbsite-type aluminum hydroxide particles (A) was used in a volume ratio (volume ratio: 1:0.1). A copper-clad composite laminate was obtained in the same manner as in Example 11 except for the above.

(Comparative Example 10)

As the inorganic filler, a fine particle component (B) in a ratio of 60 parts by volume based on 100 parts by volume of the gibbsite-type aluminum hydroxide particles (A) was used in a volume ratio (volume ratio: 1:0.6). A copper-clad composite laminate was obtained in the same manner as in Example 11 except for the above.

(Comparative Example 11)

A copper-clad composite laminate was obtained in the same manner as in Example 3 except that the fine particle component (B) was used in an amount of 25% by mass of the crushed alumina particles.

(Embodiment 12)

The copper clad composite laminate is continuously formed by the manufacturing method shown in FIG. As the thermosetting resin composition, those containing an epoxy vinyl ester resin and a radical polymerizable unsaturated monomer and a polymerization initiator are used. That is, 400 parts by mass of tetrabromobisphenol A type epoxy resin ("trade name EPICLON 153" (manufactured by Dainippon Ink Chemicals Co., Ltd.)) having an epoxy equivalent of 400 g/eq was placed in a 4-neck flask. HYCARCTBN 1300X13 (manufactured by BFGooDrich Chemical Co., Ltd.) having a molecular weight of 3,500 and a bonded acrylonitrile of 27%, a carboxyl group of 1.9/mole of butadiene and acrylonitrile having a carboxyl group at both ends thereof, 92 parts by mass of methacrylic acid The fraction (number of epoxy groups: total number of carboxyl groups = 1:1), hydroquinone 0.29 parts by mass, and 0.58 parts by mass of triphenylphosphine were reacted at 110 °C. Then, after confirming that the acid value has become 10 mg-KOH/g or less, 309 parts by mass of styrene is further added. Then, 1.32 parts by mass of acetamidineacetone was added to obtain an epoxy vinyl ester resin composition.

Then, 80 parts by volume of the same inorganic filler as in Example 1 and a third butyl peroxybenzoate ("trade name PERBUTYL Z" [Japanese fats and oils (Japanese fats and oils) were added to 100 parts by volume of the epoxy resin resin composition. The ratio of 1.0 part by volume was uniformly mixed by a homogenizer to prepare a thermosetting resin composition for a nonwoven fabric layer. The thermosetting resin composition for the nonwoven fabric layer is impregnated with a nonwoven fabric substrate to be semi-cured, thereby producing a prepreg for the nonwoven fabric layer.

In addition, a ratio of 1.0 part by volume of the above-mentioned third butyl peroxybenzoate to 100 parts by volume of the above-mentioned epoxy vinyl ester resin composition is uniformly mixed by a homogenizer to prepare a thermosetting resin for a woven fabric layer. Composition. The woven fabric substrate similar to that of Example 1 was impregnated with the thermosetting resin composition for the woven fabric layer, and the prepreg for the woven fabric layer was produced in a semi-cured state. Then, a copper clad composite laminate was formed in the same manner as in Example 1 using the prepreg for the nonwoven fabric layer and the prepreg for the woven fabric layer.

(Example 13)

A copper-clad composite laminate was obtained in the same manner as in Example 12, except that a thermosetting resin composition for a nonwoven fabric layer was prepared in an amount of 90 parts by volume based on the inorganic filler in an amount of 90 parts by volume of the thermosetting resin.

(Example 14)

A copper-clad composite laminate was obtained in the same manner as in Example 12 except that a thermosetting resin composition for a nonwoven fabric layer was prepared in an amount of 120 parts by volume of the inorganic filler with respect to 100 parts by volume of the thermosetting resin.

(Example 15)

A copper-clad composite laminate was obtained in the same manner as in Example 12 except that a thermosetting resin composition for a nonwoven fabric layer was prepared in a ratio of 140 parts by volume of the inorganic filler to 100 parts by volume of the thermosetting resin.

(Embodiment 16)

A copper-clad composite laminate was obtained in the same manner as in Example 12 except that a thermosetting resin composition for a nonwoven fabric layer was prepared in an amount of 150 parts by volume based on the inorganic filler in an amount of 150 parts by volume of the thermosetting resin.

(Comparative Example 12)

A copper-clad composite laminate was obtained in the same manner as in Example 12, except that a thermosetting resin composition for a nonwoven fabric layer was prepared in an amount of 70 parts by volume based on the inorganic filler in an amount of 70 parts by volume of the thermosetting resin.

(Comparative Example 13)

A copper-clad composite laminate was obtained in the same manner as in Example 12 except that a thermosetting resin composition for a nonwoven fabric layer was prepared in an amount of 160 parts by volume based on the inorganic filler in an amount of 160 parts by volume of the thermosetting resin.

(Example 17)

A copper-clad composite laminate was obtained in the same manner as in Example 14 except that the gibbsite-type aluminum hydroxide particles (A) had an average particle diameter (D ₅₀ ) of 8.5 μm.

(Embodiment 18)

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

(Comparative Example 14)

A copper-clad composite laminate was obtained in the same manner as in Example 14 except that the gibbsite-type aluminum hydroxide particles (A) had an average particle diameter (D ₅₀ ) of 1.5 μm.

(Comparative Example 15)

A copper-clad composite laminate was obtained in the same manner as in Example 14 except that the gibbsite-type aluminum hydroxide particles (A) were used, and the average particle diameter (D ₅₀ ) was 16 μm.

(Embodiment 19)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 0.8 μm were used. The particle size distribution of the fine particle component (B) is 1% by mass or more of the particle diameter of 5 μm or more, 25% by mass or less and 25% by mass or less, and the particle diameter is less than 1 μm, which is 74% by mass. A copper-clad composite laminate was obtained in the same manner as in Example 12 except for the above.

(Embodiment 20)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 0.2 μm were used. The particle size distribution of the fine particle component (B) is 0% by mass or more, a particle diameter of 5 μm or more, a particle diameter of 1 μm or more and less than 5 μm, and a particle diameter of less than 1 μm of 88% by mass. A copper-clad composite laminate was obtained in the same manner as in Example 12 except for the above.

(Comparative Example 16)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 1.6 μm were used. The particle size distribution of the fine particle component (B) is 7 μ mass% in a particle diameter of 5 μm or more, 35 mass % in a particle diameter of 1 μm or more and less than 5 μm, and 58 mass % in a particle diameter of less than 1 μm. A copper-clad composite laminate was obtained in the same manner as in Example 12 except for the above.

(Comparative Example 17)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 μm were used. The particle size distribution of the fine particle component (B) is 5% by mass of 5 μm or more, 33% by mass or less, and 33% by mass or less, and 62% by mass or less. A copper-clad composite laminate was obtained in the same manner as in Example 12 except for the above.

(Comparative Example 18)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 μm were used. The particle size distribution of the fine particle component (B) is 5% by mass in a particle diameter of 5 μm or more, 42% by mass in a particle diameter of 1 μm or more and less than 5 μm, and 50% by mass in a particle diameter of less than 1 μm. A copper-clad composite laminate was obtained in the same manner as in Example 12 except for the above.

(Comparative Example 19)

As the fine particle component (B), alumina particles (alumina) having an average particle diameter (D ₅₀ ) of 1.5 μm were used. The particle size distribution of the fine particle component (B) is 17 mass% of a particle diameter of 5 μm or more, 40 mass% of particle diameter of 1 μm or more and less than 5 μm, and 43 mass% of particle diameter of less than 1 μm. A copper-clad composite laminate was obtained in the same manner as in Example 12 except for the above.

(Example 21)

As an inorganic filler, it is used in volume ratio relative to gibbsite type. The aluminum hydroxide particles (A) were formulated in a volume of 35 parts by volume of the fine particle component (B) (volume ratio 1: 0.35). Further, as the fine particle component (B), those having 40% by mass of crushed alumina particles are used. A copper-clad composite laminate was obtained in the same manner as in Example 14 except for the above.

(Example 22)

As the inorganic filler, a microparticle component (B) in a volume ratio of 50 parts by volume to 100 parts by volume of the gibbsite-type aluminum hydroxide particles (A) was used in a volume ratio (volume ratio: 1:0.5). A copper-clad composite laminate was obtained in the same manner as in Example 21 except for the above.

(Comparative Example 20)

As the inorganic filler, a microparticle component (B) in a volume ratio of 10 parts by volume to 100 parts by volume of the gibbsite-type aluminum hydroxide particles (A) was used in a volume ratio (volume ratio: 1:0.1). A copper-clad composite laminate was obtained in the same manner as in Example 21 except for the above.

(Comparative Example 21)

As the inorganic filler, a fine particle component (B) in a ratio of 60 parts by volume based on 100 parts by volume of the gibbsite-type aluminum hydroxide particles (A) was used in a volume ratio (volume ratio: 1:0.6). A copper-clad composite laminate was obtained in the same manner as in Example 21 except for the above.

(Comparative Example 22)

A copper-clad composite laminate was obtained in the same manner as in Example 21 except that the particulate component (B) was used in an amount of 25% by mass of the alumina particles containing the crushed particles.

(Comparative Example 23)

18 parts by volume of diaspore (C) was prepared, and the proportion of each component was as shown in FIG. Except for this, a copper-clad composite was obtained in the same manner as in Example 21. Laminated board.

<thermal conductivity>

The density of the obtained copper clad laminate was measured by a water replacement method, and the specific heat was measured by DSC (differential scanning calorimetry), and the thermal diffusivity was measured by a laser flash method.

Then, the thermal conductivity was obtained from the following formula.

Thermal conductivity (W/m‧K) = density (kg/m ³ ) × specific heat (kJ/kg‧K) × thermal diffusivity (m ² /S) × 1000

<Oven heat test>

Using the obtained copper-clad laminate, the test piece prepared in accordance with JIS C 6481 was measured in a copper foil and a laminate on a copper foil and a laminate in an oven equipped with an air circulation device set at 200 to 240 ° C for 1 hour. The temperature at which bulging and peeling occur. In addition, the evaluation of the heat resistance test of the oven is preferably at least 220 ° C or more for use as a substrate for mounting an LED, and if it is lower than 220 ° C, heat resistance is insufficient.

<Drilling processability>

The copper-clad laminate obtained by laminating three sheets was drilled with a drill bit (drill diameter 0.5 mm, skew angle 35°) at 6000 rpm, and the wear rate of the drill blade was determined to be relative to the drill. The drilling (machining) of the size (area) of the drill blade before hole machining results in an evaluation of the (area) ratio (percentage) of the worn drill blade. In addition, when the wear rate is 40% or less, it is judged as ○, the wear rate is more than 40%, and when it is less than 60%, it is judged as Δ, and the wear rate is 60% or more, and it is judged as ×. Further, the smaller the wear rate of the drill blade, the smaller the loss of the drill blade, which is said to be high in drilling processability. Further, the drill blade can be used as long as it remains at 10%. The wear rate of the drill blade after the 3,000 holes are generally used is 90% or less, and the drill does not need to be frequently replaced.

<Appearance evaluation>

Twenty or more pieces were formed, and the number of defects which were visually confirmed by unevenness and swelling of the surface was calculated, and when it was 5% or more, it was judged as Δ, and when it was 10% or more, it was judged as ×.

A‧‧‧ laminate

1‧‧‧non-woven layer

2‧‧‧Weaving layer

3‧‧‧metal foil

9‧‧‧ thermosetting resin impregnated glass woven fabric

10‧‧‧glass non-woven fabric

11‧‧‧ thermosetting resin composition

12‧‧‧ thermosetting resin impregnated glass non-woven fabric

13‧‧‧metal foil

14‧‧‧Laminating rolls

15‧‧‧Compound

17‧‧‧heating and hardening furnace

18‧‧‧ Roll

19‧‧‧Cutter

20‧‧‧LED backlight unit

21‧‧‧ circuit board

22‧‧‧LED

23‧‧‧LED module

24‧‧‧Light guide

171‧‧‧Transfer roller

Fig. 1 is a cross-sectional view showing an example of an embodiment of a laminated plate of the present invention.

Fig. 2 is a schematic view showing an example of an embodiment of a method for producing a laminated board of the present invention.

Fig. 3 is a schematic view showing an example of an embodiment of an LED backlight unit of the present invention.

Fig. 4 is a view showing another example of the embodiment of the LED backlight unit of the present invention, and Figs. 4(a) and 4(b) are schematic views.

A‧‧‧ laminate

1‧‧‧non-woven layer

2‧‧‧Weaving layer

3‧‧‧metal foil

Claims (10)

A laminated board obtained by integrating a non-woven fabric layer obtained by impregnating a nonwoven fabric substrate with a non-woven fabric substrate and a woven fabric layer laminated on both surfaces of the non-woven fabric layer, characterized in that: 100 parts by volume of the thermosetting resin, the thermosetting resin composition contains 80 to 150 parts by volume of an inorganic filler, and the inorganic filler contains gibbsite type aluminum hydroxide particles (A) and fine particle components. (B) The gibbsite-type aluminum hydroxide particles (A) have an average particle diameter (D ₅₀ ) of 2 to 15 μm, and the fine particle component (B) is oxidized by an average particle diameter of 1.5 μm or less. It is composed of aluminum particles, and has a particle size distribution of 5 μm or more and a particle diameter of 5 μm or less, a particle diameter of 1 μm or more and less than 5 μm of 40% by mass or less, and a particle diameter of less than 1 μm of 55% by mass or more, and the fine particle component (B) contains The crushed alumina particles are 30% by mass or more, and the blending ratio (volume ratio) of the gibbsite-type aluminum hydroxide particles (A) and the fine particle component (B) is 1:0.2 to 0.5. The laminate of claim 1, wherein the thermosetting resin contains an epoxy resin. The laminate according to the second aspect of the invention, wherein the thermosetting resin contains a phenol compound as a hardener component of the epoxy resin. The laminate according to the first aspect of the invention, wherein the thermosetting resin contains an epoxy vinyl ester resin and a radical polymerizable unsaturated monomer and a polymerization initiator. A metal foil-clad laminate, characterized in that it is provided with gold on at least one surface of a laminate according to any one of claims 1 to 4. It is a foil maker. A printed wiring board characterized in that a conductor pattern is provided on at least one surface of a laminated board according to any one of claims 1 to 4. A circuit board in which an electric circuit is provided on at least one surface of a laminated board according to any one of claims 1 to 4. An LED backlight unit characterized in that an LED is mounted on at least one surface of a laminate according to any one of claims 1 to 4. An LED lighting device characterized in that an LED is mounted on at least one surface of a laminated board according to any one of claims 1 to 4. A method for producing a laminated board, wherein a nonwoven fabric substrate is continuously transferred, and a thermosetting resin composition is impregnated into the nonwoven fabric substrate, and the nonwoven fabric substrate is continuously transferred while the woven fabric is laminated on both surfaces thereof, and then rolled. The laminate is heated to form a nonwoven fabric layer and a woven fabric layer, and the thermosetting resin composition contains 80 to 150 parts by volume with respect to 100 parts by volume of the thermosetting resin. In the inorganic filler of the ratio, the inorganic filler contains the gibbsite-type aluminum hydroxide particles (A) and the fine particle component (B), and the average particle of the gibbsite-type aluminum hydroxide particle (A) The particle diameter (D ₅₀ ) is 2 to 15 μm, and the fine particle component (B) is composed of alumina particles having an average particle diameter of 1.5 μm or less, and the particle diameter distribution is 5 μm or more and less than 5% by mass or less. 1 μm or more and less than 5 μm is 40% by mass or less, and the particle diameter is less than 1 μm is 55% by mass or more. The fine particle component (B) contains 30% by mass or more of the crushed alumina particles, and the gibbsite-type aluminum hydroxide. Child (A) and the particulate component (B) of the formulation ratio (volume ratio) of 1: 0.2 to 0.5.