WO2011065372A1 - 積層板、その用途及びその製造方法 - Google Patents
積層板、その用途及びその製造方法 Download PDFInfo
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- WO2011065372A1 WO2011065372A1 PCT/JP2010/070910 JP2010070910W WO2011065372A1 WO 2011065372 A1 WO2011065372 A1 WO 2011065372A1 JP 2010070910 W JP2010070910 W JP 2010070910W WO 2011065372 A1 WO2011065372 A1 WO 2011065372A1
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- thermosetting resin
- laminate
- nonwoven fabric
- component
- average particle
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
Definitions
- the present invention relates to a laminate for various electronic devices, a metal foil-clad laminate, a printed wiring board and a circuit board, an LED backlight unit, and a method for producing the laminate, and in particular, a light emitting diode (LED) and the like.
- the present invention relates to a laminated board suitably used for mounting a heat generating component.
- a laminated board in which a surface layer containing a resin composition in a woven fabric base material is laminated and integrated on the surface of the nonwoven fabric layer containing the resin composition in the nonwoven fabric base material (for example, (See Patent Application Publication No. 2006-272671).
- a laminate is formed into a printed wiring board for mounting electrical and electronic parts by forming a conductor pattern on its surface, and an electric circuit is formed using this conductor pattern. Is processed into a circuit board.
- the present invention has been made in view of the above points, and an object of the present invention is to provide a laminated board having high heat dissipation and a method for manufacturing the same without impairing heat resistance and drilling workability. 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 lighting device with high heat dissipation.
- thermosetting resin composition has an inorganic filler of 80 to 400 volumes with respect to 100 parts by volume of the thermosetting resin.
- the inorganic filler comprises (A) gibbsite-type aluminum hydroxide particles having an average particle size (D 50 ) of 2 to 15 ⁇ m, and (B) an average particle size (D) of 1.5 to 15 ⁇ m. boehmite particles having a 50), the group consisting of 1.5 the average particle size of ⁇ 15 [mu] m with a (D 50), the free starting temperature contains water of crystallization is 400 ° C.
- a woven fabric layer is formed on the surface of the nonwoven fabric layer.
- thermosetting resin contains an epoxy resin.
- thermosetting resin contains a phenol compound as a curing agent component of the epoxy resin.
- the thermosetting resin preferably contains an epoxy vinyl ester resin, a radical polymerizable unsaturated monomer, and a polymerization initiator.
- the binder of the nonwoven fabric base material of the nonwoven fabric layer is preferably an epoxy compound.
- the woven fabric layer contains aluminum hydroxide.
- the metal foil-clad laminate of the present invention is characterized in that a metal foil is provided on at least one surface of the laminate.
- the printed wiring board of 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 a circuit is provided on at least one surface of the laminate.
- the LED backlight unit of the present invention is characterized in that an LED is mounted on at least one surface of the laminate.
- the LED lighting device of the present invention is characterized in that an LED is mounted on at least one surface of the laminated plate.
- the method for producing a laminate according to the present invention comprises impregnating the non-woven fabric substrate with the thermosetting resin composition while continuously conveying the non-woven fabric substrate, and both surfaces of the non-woven fabric substrate while continuously conveying the non-woven fabric substrate.
- Type aluminum hydroxide particles, (B) boehmite particles having an average particle size (D 50 ) of 1.5 to 15 ⁇ m, and an average particle size (D 50 ) of 1.5 to 15 ⁇ m, and a release starting temperature of 400 Contains water of crystallization that is higher than or equal to °C or water of crystallization Contains at least one inorganic component selected from the group consisting of inorganic particles which do not contain, and particulate components of aluminum oxide particles having a (C) 1.5 [mu] m or less in average particle diameter (D 50), the gibbsite
- the compounding ratio (volume ratio) of the type aluminum hydroxide particles (A), the inorganic component (B), and the fine particle component (C) is 1: 0.1-3: 0.1-3. To do.
- heat dissipation can be enhanced without impairing heat resistance and drilling workability.
- the heat dissipation can be increased.
- the method for producing a laminate of the present invention can produce a laminate continuously, and can improve productivity as compared with a batch type.
- (A) is sectional drawing which shows an example of embodiment of the laminated board of this invention
- (b) is sectional drawing which shows an example of other embodiment. It is the schematic which shows an example of embodiment of the manufacturing method of the laminated board of this invention. It is the schematic which shows an example of embodiment of the LED backlight unit of this invention. The other example of embodiment of the LED backlight unit of this invention is shown, (a) (b) is schematic.
- the laminate A of the present invention is formed with a nonwoven fabric layer 1 containing a thermosetting resin composition.
- the nonwoven fabric layer 1 can be formed of a cured product of a prepreg containing a thermosetting resin composition on a nonwoven fabric substrate.
- the nonwoven fabric substrate for example, any one selected from glass nonwoven fabric and glass paper, or synthetic resin nonwoven fabric and paper using synthetic resin fibers such as aramid fiber, polyester fiber, and polyamide fiber (nylon) can be used.
- the thickness of the nonwoven fabric substrate can be 10 to 300 ⁇ m, but is not limited thereto.
- an epoxy compound having excellent thermal strength as the binder for the nonwoven fabric substrate.
- the binder is a binder for bonding and solidifying the fibers constituting the nonwoven fabric substrate.
- An epoxy silane or the like can be used as the binder epoxy compound.
- the binder is preferably blended in an amount of 5 to 25 parts by mass with respect to 100 parts by mass of the fibers constituting the nonwoven fabric substrate.
- the thermosetting resin composition contains a thermosetting resin and an inorganic filler.
- a thermosetting resin for example, a thermosetting resin that is liquid at room temperature can be used.
- a thermosetting resin the mixture of a resin component and a hardening
- a radical polymerization type thermosetting resin such as an epoxy resin, an unsaturated polyester resin, and a vinyl ester resin can be used.
- thermosetting resin examples include those using an epoxy resin as a resin component.
- an epoxy resin 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, etc.
- dicyandiamide and a phenol compound can be used as a hardening
- phenol compound examples include allylphenol, phenol novolak, alkylphenol novolak, triazine structure-containing phenol novolak, bisphenol A novolak, dicyclopentadiene structure-containing phenol resin, zyloc-type phenol, terpene-modified phenol, polyvinylphenol, and naphthalene structure-containing phenol.
- a curing agent a fluorene structure-containing phenolic curing agent, and the like can be used.
- the phenol compound curing agent component can be blended in an amount of 30 to 120 parts by mass with respect to 100 parts by mass of the epoxy resin.
- thermosetting resin an epoxy vinyl ester resin can be used as a resin component, and in this case, a radical polymerizable unsaturated monomer and a polymerization initiator can be used as a curing agent component. it can.
- the epoxy resin used for obtaining the epoxy vinyl ester resin is not particularly limited in structure.
- the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.
- Examples of the novolak type epoxy resin include phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin and the like.
- Examples of the alicyclic epoxy resins include 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Examples thereof include carboxylate and 1-epoxyethyl-3,4-epoxycyclohexane.
- Examples of the glycidyl esters include phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and dimer acid glycidyl ester.
- Examples of the glycidylamines include tetraglycidyldiaminodiphenylmethane, triglycidyl P-aminophenol, N, N-diglycidylaniline, and the like.
- Examples of the heterocyclic epoxy resin include 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate, and the like.
- brominated epoxy resins examples include tetrabromobisphenol A type epoxy resins, tetrabromobisphenol F type epoxy resins, brominated cresol novolak type epoxy resins, brominated phenol novolak type epoxy resins and the like.
- epoxy resins it is preferable to use a brominated epoxy resin because it is particularly excellent in flame retardancy. Furthermore, an epoxy resin obtained by reacting a part of the epoxy groups of these epoxy resins with a carboxyl group-containing rubber-like polymer can also be used. An epoxy resin obtained by reacting such a carboxyl group-containing rubber-like polymer is particularly preferable in terms of improving impact resistance, punching workability, and interlayer adhesion of a laminate such as a copper clad laminate.
- the above carboxyl group-containing rubbery polymer is a copolymer obtained by copolymerizing a carboxyl group-containing monomer and a conjugated diene monomer as required, or a conjugated diene monomer. And those obtained by copolymerizing the product with other monomers and introducing a carboxyl group.
- the carboxyl group may be located at either the terminal or the side chain of the molecule, and the amount thereof is preferably 1 to 5 and more preferably 1.5 to 3 in one molecule.
- conjugated diene monomer examples include butadiene, isoprene and chloroprene.
- Other monomers used as necessary include acrylonitrile, styrene, methyl styrene, halogenated styrene, etc., but the resulting reaction product is compatible with radically polymerizable unsaturated monomers. Therefore, acrylonitrile is preferably copolymerized with the rubber-like polymer in an amount of 10 to 40% by weight, more preferably 15 to 30% by weight.
- the epoxy resin, the carboxyl group-containing rubber-like polymer, and the ethylenically unsaturated monobasic acid may be reacted at the same time. You may make it react an ethylenically unsaturated monobasic acid after making a containing rubber-like polymer react. At this time, the reaction ratio between the epoxy resin used for obtaining the epoxy vinyl ester resin, the carboxyl group-containing rubbery polymer and the ethylenically unsaturated monobasic acid is not particularly limited, but the epoxy resin epoxy is not limited.
- the total carboxyl group of the carboxyl group-containing rubbery polymer and the ethylenically unsaturated monobasic acid is preferably in the range of 0.8 to 1.1 equivalents per equivalent of the group. From the viewpoint of obtaining, it is preferably in the range of 0.9 to 1.0 equivalent.
- examples of the ethylenically unsaturated monobasic acid used for the reaction with the epoxy resin include (meth) acrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethylmalate, Examples thereof include monobutyl malate and sorbic acid. Among them, methacrylic acid is preferable.
- the above radical polymerizable unsaturated monomer has at least one radical polymerizable unsaturated group in one molecule.
- radically polymerizable unsaturated monomers include diallyl phthalate, styrene, methyl styrene, halogenated styrene, (meth) acrylic acid, methyl methacrylate, ethyl methacrylate, butyl acrylate, divinyl benzene, ethylene glycol di ( (Meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and one or more of these are used. It is done.
- the compounding quantity of a radically polymerizable unsaturated monomer it is 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 radically polymerizable unsaturated monomer. A ratio is preferable. If the amount is 25 parts by mass or more, the resulting thermosetting resin composition has good impregnation properties with respect to the nonwoven fabric base material and the woven fabric base. If the amount is 45 parts by mass or less, the thermosetting resin composition is This is because the laminated plate obtained by using it has excellent dimensional stability and excellent heat resistance.
- polymerization initiator examples include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide and cyclohexanone peroxide, diacyl peroxides such as benzoyl peroxide and isobutyl peroxide, cumene hydroperoxide, and t-butyl.
- ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide and cyclohexanone peroxide
- diacyl peroxides such as benzoyl peroxide and isobutyl peroxide
- cumene hydroperoxide and t-butyl.
- Hydroperoxides such as hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexanone, Peroxyketals such as 2,2-di- (t-butylperoxy) -butane, alkyl peresters such as t-butylperbenzoate and t-butylperoxy-2-ethylhexanoate, bis (4 -T-butylcyclohex Le) peroxydicarbonate, etc. percarbonates such as t- butyl peroxy isobutyl carbonate, and organic peroxides, these one or more is used.
- the thermosetting resin composition is heat-cured.
- the blending amount of the polymerization initiator to the thermosetting resin is not particularly limited, but is 0.1% relative to 100 parts by mass of the total amount of the epoxy vinyl ester resin and the radical polymerizable unsaturated monomer. It is preferably set in the range of about 5 to 5.0 parts by mass. In particular, the range of 0.9 to 2.0 parts by mass is more preferable in terms of varnish life and curability of the thermosetting resin composition.
- the average particle size of the inorganic filler is determined by calculating the cumulative curve with the total volume of the powder population obtained by measurement with a laser diffraction particle size distribution measuring device as 100%. It means the particle diameter at the point of 50%.
- Gibbsite type aluminum hydroxide particles (A) are aluminum compounds represented by Al (OH) 3 or Al 2 O 3 .3H 2 O, and the laminated plate A has thermal conductivity, flame retardancy, and drillability. Is a component that imparts a good balance.
- the average particle diameter (D 50 ) of the gibbsite type aluminum hydroxide particles (A) is 2 to 15 ⁇ m, preferably 3 to 10 ⁇ m. When the average particle diameter (D 50 ) of the gibbsite type aluminum hydroxide particles (A) exceeds 15 ⁇ m, the drilling processability decreases, and when it is less than 2 ⁇ m, the thermal conductivity decreases and the productivity decreases. To do.
- the gibbsite-type aluminum hydroxide particles (A) include a first gibbsite-type aluminum hydroxide having an average particle diameter (D 50 ) of 2 to 10 ⁇ m and a second gibbsite-type aluminum hydroxide particle (D 50 ) of 10 to 15 ⁇ m. It is preferable to use a blend with Gibbsite type aluminum hydroxide from the viewpoint that heat dissipation is further improved by more densely filling the filler.
- the inorganic component (B) is at least one selected from the group consisting of boehmite particles and inorganic particles that contain crystallization water having a liberation start temperature of 400 ° C. or higher or no crystallization water.
- Boehmite particles are an aluminum compound represented by (AlOOH) or (Al 2 O 3 .H 2 O), and a component that imparts thermal conductivity and flame retardancy without reducing the heat resistance of the laminate A It is.
- the average particle diameter (D 50 ) of the boehmite particles is 1.5 to 15 ⁇ m, preferably 3 to 10 ⁇ m. When the average particle diameter (D 50 ) of the boehmite particles exceeds 15 ⁇ m, the drill workability decreases, and when it is less than 1.5 ⁇ m, the thermal conductivity decreases and the productivity decreases.
- Inorganic particles containing crystallization water having a liberation starting temperature of 400 ° C. or higher or having no crystallization water are components that impart thermal conductivity and flame retardancy without reducing the heat resistance of the circuit board.
- Specific examples of such inorganic particles include inorganic oxides such as titanium oxide (no crystallization water), magnesium oxide (no crystallization water), crystalline silica (no crystallization water); boron nitride (no crystallization water), nitriding Inorganic nitrides such as aluminum (no crystallization water), silicon nitride (no crystallization water); inorganic carbides such as silicon carbide (no crystallization water); and talc (freezing start temperature 950 ° C.), kaolin (freezing start temperature 500 to 1000) Natural minerals such as ° C.).
- the freezing temperature of crystal water can be measured using heat loss analysis (TGA) or suggested scanning calorimetry (DSC).
- the average particle diameter (D 50 ) of the inorganic particles is 1.5 to 15 ⁇ m, preferably 3 to 10 ⁇ m. When the average particle diameter (D 50 ) of the inorganic particles exceeds 15 ⁇ m, drill workability may be reduced.
- the upper limit of the liberation start temperature is not particularly set, but is, for example, 1000 ° C.
- the Mohs hardness needs to be smaller than the Mohs hardness 12 of aluminum oxide, preferably 7.5 or less, more preferably 6 0.0 or less, and most preferably 5.0 or less.
- the Mohs hardness of the inorganic component (B) is 5.5 to 6.0 for titanium oxide (anatase type), 7.0 to 7.5 for titanium oxide (rutile), 2.5 for magnesium oxide, crystals Silica is 7.0, boron nitride is 2.0, aluminum nitride is 7.0, silicon nitride is 9.5, talc is 1.0, calcined kaolin is 2.0, and clay is 2.0.
- the fine particle component (C) is a component that imparts high thermal conductivity to the resulting laminate.
- the aluminum oxide particles constituting the fine particle component (C) have an average particle diameter (D 50 ) of 1.5 ⁇ m or less, preferably 0.4 to 0.8 ⁇ m.
- D 50 average particle diameter
- the aluminum oxide particles have a Mohs hardness of 12, but the average particle diameter (D 50 ) is 1.5 ⁇ m or less, so that drillability can be prevented from being impaired.
- the mixing ratio (volume ratio) of the gibbsite type aluminum hydroxide particles (A), the inorganic component (B) and the fine particle component (C) is 1: 0.1-3: 0.1-3, preferably Is from 1: 0.1 to 2: 0.1 to 2, more preferably from 1: 0.1 to 1: 0.1 to 1.
- the blending amount of the inorganic component (B) exceeds 3 with respect to the blending amount 1 of the gibbsite-type aluminum hydroxide particles (A)
- the drilling workability and heat dissipation of the resulting laminate A are reduced. If it is less than 1, the heat resistance is lowered.
- the drill workability is deteriorated, and when it is less than 0.1, Further, the thermal conductivity is lowered, and it is difficult to add a high amount of the inorganic filler, which may deteriorate the moldability.
- the blending ratio of the inorganic filler to 100 parts by volume of the thermosetting resin is 80 to 400 parts by volume, preferably 90 to 400 parts by volume, and more preferably 100 to 400 parts by volume.
- the thermal conductivity of the resulting laminate A is low, and when it exceeds 400 parts by volume, the drillability is lowered and the laminate A Manufacturability (resin impregnation property, moldability) also decreases.
- the blending ratio of the gibbsite type aluminum hydroxide particles (A) is too large, specifically when it exceeds 100 parts by volume, the heat resistance tends to decrease due to the generation of a large amount of crystal water. There is.
- an inorganic component (B) when boehmite particles and inorganic particles containing a crystal water having a liberation start temperature of 400 ° C. or higher or having no crystal water are blended, blending of inorganic particles The ratio is preferably 50% by volume or less, more preferably 30% by volume or less, and particularly preferably 20% by volume or less in the total amount of the inorganic filler.
- the thermosetting resin composition is an inorganic filler containing the above-described gibbsite type aluminum hydroxide particles (A), the inorganic component (B), and the fine particle component (C) in the liquid thermosetting resin.
- various additives such as a curing catalyst of a thermosetting resin, can be mix
- blending processing aids such as solvents such as organic solvents, thickeners, coupling agents, etc. as necessary You can also.
- the prepreg for forming the nonwoven fabric layer 1 is obtained by impregnating the nonwoven fabric base material with a thermosetting resin composition, and then semi-curing the thermosetting resin composition impregnated with the nonwoven fabric base material by heat drying or the like. (B stage state) can be obtained.
- the content of the thermosetting resin composition can be 40 to 95% by mass with respect to the total amount of the prepreg, but is not limited thereto.
- the metal foil-clad laminate of the present invention is a single-sided or double-sided metal foil-clad laminate in which the laminate A is an insulating layer by providing a metal foil 3 such as copper foil or nickel foil on the surface of the nonwoven fabric layer 1.
- a metal foil 3 such as copper foil or nickel foil on the surface of the nonwoven fabric layer 1.
- the conditions for the heat and pressure molding in producing the laminate A and the metal foil-clad laminate can be appropriately set according to the type of the thermosetting resin, for example, a temperature of 80 to 250 ° C., a pressure of 0. 05 to 0.98 kPa (5 to 100 kgf / m 2 ), and 20 to 300 minutes.
- the printed wiring board of the present invention can be formed by providing a conductor pattern on the surface of the laminate A.
- the metal foil-clad laminate can be processed into a printed wiring board by performing circuit processing such as an additive method or a subtractive method or through-hole processing.
- the circuit board of the present invention can be formed by providing an electrical / electronic circuit on the laminate A.
- an electric / electronic circuit can be formed using a conductor pattern of a printed wiring board formed from the metal foil-clad laminate.
- the circuit board for LED mounting of this invention can be formed by providing the electrical-electronic circuit for LED mounting in the said laminated board A.
- the electrical / electronic circuit of the circuit board can be formed as an electrical / electronic circuit for LED mounting.
- FIG. 1B shows another embodiment of the laminate A of the present invention.
- the laminate A is a so-called composite laminate formed by including a nonwoven fabric layer 1 containing a thermosetting resin composition and a woven fabric layer 2 containing a thermosetting resin composition.
- the composite laminate is inferior to the above laminate (in which an insulating layer is formed only from the nonwoven fabric layer 1 and does not use a woven fabric) in terms of heat dissipation, but is inexpensive and excellent in terms of dimensional stability and mechanical properties. It is.
- the nonwoven fabric layer 1 can be formed of a cured prepreg containing a thermosetting resin composition on a nonwoven fabric substrate.
- the woven fabric layer 2 can be formed of a prepreg cured product containing a thermosetting resin composition on a woven fabric substrate.
- the nonwoven fabric layer 1 can be formed in the same manner as described above, but the blending ratio of the inorganic filler to 100 parts by volume of the thermosetting resin is preferably 150 to 400 parts by volume. .
- the blending ratio of the inorganic filler is less than 150 parts by volume, the thermal conductivity of the resulting laminate A may be lowered, and when it exceeds 400 parts by volume, the drilling processability is reduced or the laminate is laminated.
- the manufacturability (resin impregnation property, moldability) of the plate A may be reduced.
- 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 fiber, polyester fiber, polyamide fiber (nylon) is used. be able to.
- the thickness of the woven fabric substrate can be 50 to 500 ⁇ m, 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 thermosetting resin composition for forming the nonwoven fabric layer 1.
- the type of the thermosetting resin and inorganic filler used, the content of the inorganic filler relative to the thermosetting resin, and the like can be changed.
- from the above thermosetting resin composition for forming the nonwoven fabric layer 1 excluding the inorganic filler that is, from the thermosetting resin and other solvents and additives blended as necessary. Can be used. Thereby, the impregnation property of the thermosetting resin composition to a woven fabric base material can be improved.
- the woven fabric layer 2 contains an inorganic filler
- aluminum hydroxide as the inorganic filler in order to improve the tracking resistance of the laminate.
- the crystal water of aluminum hydroxide is considered to inhibit the thermal decomposition and carbonization of the surface of the laminate, and the tracking resistance of the laminate is considered to be improved.
- the aluminum hydroxide is preferably 25 to 150 parts by volume with respect to 100 parts by volume of the thermosetting resin in the woven fabric layer 2. It is preferable to use aluminum hydroxide having an average particle diameter (D 50 ) of 2 to 15 ⁇ m.
- the prepreg for forming the woven fabric layer 2 is obtained by impregnating the woven fabric base material with a thermosetting resin composition, and then heating and drying the thermosetting resin composition impregnated into the woven fabric base material. A semi-cured state (B stage state) can be obtained.
- the content of the thermosetting resin composition can be 40 to 95% by mass with respect to the total amount of the prepreg, but is not limited thereto.
- the prepreg for forming the nonwoven fabric layer 1 and the prepreg for forming the woven fabric layer 2 are piled up. Then, 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 is cured by curing these thermosetting resins. And the woven fabric layer 2 are laminated and integrated.
- the nonwoven fabric layer 1 and the woven fabric layer 2 can each be formed by overlapping one or a plurality of prepregs.
- the woven fabric layer 2 can be formed on both surfaces of the nonwoven fabric layer 1.
- the metal foil-clad laminate using this composite laminate is provided with a metal foil 3 such as a copper foil or a nickel foil on the surface of the woven fabric layer 2 so that the composite laminate becomes an insulating layer or It can be formed as a double-sided metal foil-clad laminate.
- a metal foil 3 such as a copper foil or a nickel foil on the surface of the woven fabric layer 2 so that the composite laminate becomes an insulating layer or It can be formed as a double-sided metal foil-clad laminate.
- the nonwoven fabric layer 1 and the woven fabric are formed by heating and pressing.
- the layer 2 and the metal foil 3 are laminated and integrated. The conditions for heat and pressure molding are the same as described above.
- FIG. 2 shows an example of a method for producing a double-sided metal foil-clad composite laminate.
- Glass nonwoven fabric which is a nonwoven fabric base material, is a paper made of glass fiber and is a long product that can be continuously supplied. It has voids inside and on the surface and can be impregnated with a thermosetting resin composition. There is no particular limitation as long as it is.
- the thickness of the glass nonwoven fabric is generally 0.03 to 0.4 mm, but is not limited to this thickness.
- the glass woven fabric which is a woven fabric base material, is a glass woven fabric made of glass fiber, which is a long product that can be continuously supplied, has voids inside and on the surface, There is no particular limitation as long as it can be impregnated with the curable resin composition.
- the thickness of the glass woven fabric is generally 0.015 to 0.25 mm, but is not limited to this thickness.
- thermosetting resin-impregnated glass woven fabric is continuously laminated on both surfaces of the glass nonwoven fabric impregnated with the thermosetting resin composition, and this laminate is pressure-bonded with a roll and heated to be a composite type laminate. Manufacturing.
- one or more glass nonwoven fabrics impregnated with the thermosetting resin composition may be used in an overlapping manner.
- the thermosetting resin-impregnated glass woven fabric is the glass woven fabric described above that is impregnated with the thermosetting resin or thermoplastic resin composition described above.
- the thickness of the glass woven fabric is generally 0.015 to 0.25 mm, but is not limited to this thickness.
- thermosetting resin-impregnated glass woven fabrics may be used. Furthermore, you may laminate
- the metal foil is not particularly limited as long as it is a long metal foil that can be continuously supplied, and examples thereof include copper foil and nickel foil.
- the thickness of the metal foil is generally 0.012 to 0.07 mm, but is not limited to this thickness.
- thermosetting resin-impregnated glass nonwoven fabrics 12 impregnated in the glass nonwoven fabric 10 continuously supplied with the thermosetting resin composition 11 described above and two continuously supplied A sheet of thermosetting resin-impregnated glass woven fabric 9 and two metal foils 13 that are continuously supplied are cored with a thermosetting resin-impregnated glass nonwoven fabric 12, and the thermosetting resin on both sides (up and down).
- the impregnated glass woven fabric 9 is disposed and further laminated so that the metal foil 13 is disposed on both surface layers thereof.
- the laminated laminate is pressure-bonded by the laminate roll 14, and then the pressure-bonded pressure-bonded article 15 is pulled and advanced by the pulling roll 18, and the thermosetting resin composition in the pressure-bonded article 15 is heated in the heat curing furnace 17.
- the pressure-bonded material 15 is heated and cured to a temperature at which 11 is cured, it is cut into a predetermined size by a cutter 19 to obtain a composite laminate A in which metal foil is continuously laminated on the surface.
- Reference numeral 171 denotes a transport roll disposed in the heat curing furnace 17.
- bonding by the laminate roll 14 According to the kind of used glass nonwoven fabric 10 or glass woven fabric, the viscosity of the thermosetting resin composition 11, etc., it can adjust suitably.
- the conditions such as the temperature and time for heat curing are not particularly limited, and can be appropriately set according to the composition of the thermosetting resin composition 11 to be used and the degree of curing desired to be cured. After cutting, the laminate A may be heated (aftercured) to further cure the laminate A.
- the number of the thermosetting resin-impregnated glass nonwoven fabric 12 is two, but the number of the thermosetting resin-impregnated glass nonwoven fabric 12 may be one or three or more.
- the number of the metal foils 13 is two, but may be one, or in the case where there are a plurality of the thermosetting resin-impregnated glass nonwoven fabrics 12, the thermosetting resin-impregnated glass nonwoven fabrics may be A metal foil may be further laminated between the two.
- the nonwoven fabric base material and the woven fabric base material are not limited to those using glass fibers, and may be those using fibers of other materials.
- the thermosetting resin composition contains a wetting and dispersing agent and the blending amount thereof is 0.05 to 5% by mass with respect to the inorganic filler
- the inorganic filler is the thermosetting resin-impregnated glass woven fabric 9 or heat Since it comes to disperse
- the printed wiring board of the present invention using the composite laminate as described above can be formed by providing a conductor pattern on the surface of the composite laminate. In this case, it can be processed into a printed wiring board by subjecting the metal foil-clad laminate to circuit processing such as an additive method or a subtractive method or through-hole processing.
- the circuit board of the present invention using the composite laminate can be formed by providing an electrical and electronic circuit on the composite laminate. In this case, an electric / electronic circuit can be formed using a conductor pattern of a printed wiring board formed from the metal foil-clad laminate.
- the LED mounting circuit board of the present invention using the composite laminate can be formed by providing the composite laminate A with an electrical / electronic circuit for LED mounting. In this case, the electrical / electronic circuit of the circuit board can be formed as an electrical / electronic circuit for LED mounting.
- the laminated board A (including the composite laminated board) A of the present invention is blended with the nonwoven fabric layer 1 in a highly filled inorganic filler, the thermal conductivity can be increased, and the entire laminated board A is heated. Is easy to diffuse immediately and the heat dissipation becomes high. Therefore, the metal foil-clad laminate, the printed wiring board, and the circuit board formed from the laminate A of the present invention have the same effects, and by mounting electric and electronic parts that generate heat, such as LEDs, on them. , Heat generated from electrical and electronic components is easily conducted and diffused to metal foil-clad laminates, printed wiring boards, and circuit boards with high thermal conductivity.
- the LED mounting circuit board of the present invention is easy to conduct and diffuse the heat generated from the LED by mounting the LED, and as a result, the heat dissipation from the LED mounting circuit board becomes high. Thus, the thermal deterioration of the LED can be reduced, and the life of the LED can be extended.
- mold aluminum hydroxide particle (A) is mix
- the heat conductivity of a laminated board can be improved significantly by mix
- blend the microparticle component (C) of a small particle diameter the drill workability of a laminated board does not fall remarkably.
- heat conductivity can be provided by mix
- the laminate A of the present invention is preferably used for applications requiring high heat dissipation such as a printed wiring board of an LED backlight unit mounted on a liquid crystal display or a circuit board for an LED lighting device. .
- a high heat dissipation substrate is required, and 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 is desirable.
- an LED backlight unit 20 such as a direct type mounted on a liquid crystal display as shown in FIG.
- the LED backlight unit 20 in FIG. 3 is configured by arranging a large number of LED modules 23 each having a plurality of (three in FIG.
- LEDs 22 mounted on the laminated board A or a circuit board 21 formed from the laminated board A It is used as a backlight for a liquid crystal display or the like by being disposed on the back surface of the liquid crystal panel.
- an edge-type LED backlight unit 20 mounted on a liquid crystal display can be formed by using the laminate A of the present invention.
- the LED backlight unit 20 in FIGS. 4A and 4B includes a pair of LED modules 23 in which a plurality of LEDs 22 are mounted on the laminated board A or a strip-shaped circuit board 21 formed from the laminated board A.
- the LED modules 23 are arranged on the top and bottom (or left and right) of the light guide plate 24 and the like to be used as backlights for liquid crystal displays and the like.
- the edge type LED backlight unit 20 is provided with a higher density of LEDs than the direct type LED backlight unit 20, and therefore, it is preferable to use a highly heat-radiating one such as the laminate A of the present invention. .
- a cold cathode tube (CCFL) type backlight has been widely used as a backlight of the liquid crystal display, but in recent years, compared with a cold cathode tube type backlight.
- the color gamut can be widened, the image quality can be improved, the environmental load is small because mercury is not used, and the LED backlight unit as described above can be reduced in thickness. Is being actively developed.
- An LED module generally consumes more power than a cold cathode tube, and therefore generates a large amount of heat.
- the laminated board A of the present invention as the circuit board 21 that requires such high heat dissipation, the problem of heat dissipation is greatly improved. Therefore, the luminous efficiency of the LED can be improved.
- an LED lighting device can be formed using the laminate A of the present invention.
- the LED lighting device can be formed by mounting a plurality of LEDs on the laminated board A or a circuit board formed from the laminated board A, and including a power feeding unit that causes the LEDs to emit light.
- Examples 1 to 14, Comparative Examples 1 to 3 Compound shown in Table 1 with respect to 100 parts by volume of thermosetting resin in thermosetting resin varnish containing bisphenol A type epoxy resin as resin component and dicyandiamide (Dicy) type curing agent as curing agent component An inorganic filler was blended in an amount (unit: volume) and dispersed uniformly.
- component (A) gibbsite type aluminum hydroxide particles (manufactured by Sumitomo Chemical Co., Ltd., D 50 : 5.4 ⁇ m) and gibbsite type aluminum hydroxide particles (manufactured by Sumitomo Chemical Co., Ltd., D 50 : 12.6 ⁇ m) was used.
- the component (B) boehmite particles (D 50 : 3.0 ⁇ m) were used.
- the component (C) aluminum oxide particles (manufactured by Sumitomo Chemical Co., Ltd., D 50 : 0.5 ⁇ m, alumina) were used.
- the compounding amount of the inorganic filler with respect to 100 parts by volume of the thermosetting resin is a solid content excluding the solvent of the thermosetting resin varnish (bisphenol A type epoxy resin (resin component) and dicyandiamide type curing agent (curing agent component). The total amount of the inorganic filler is 100 parts by volume.
- thermosetting resin varnish blended with the above inorganic filler is a glass nonwoven fabric having a basis weight of 60 g / m 2 and a thickness of 400 ⁇ m (a glass nonwoven fabric manufactured by Vilene Co., Ltd., a binder is epoxysilane, etc.
- the compounding amount of the agent was impregnated into 5 to 25 parts by mass of 100 parts by mass of glass fiber) to obtain a prepreg for the nonwoven fabric layer.
- the obtained copper foil-clad laminate was evaluated for thermal conductivity, oven heat resistance test, drill workability, and flame retardancy according to the following evaluation methods. The results are shown in Table 1 below.
- the density of the obtained copper foil-clad laminate was measured by an underwater substitution method, the specific heat was measured by DSC (differential scanning calorimetry), and the thermal diffusivity was further measured by a laser flash method.
- Thermal conductivity (W / m ⁇ K) density (kg / m 3 ) ⁇ specific heat (kJ / kg ⁇ K) ⁇ thermal diffusivity (m 2 / S) ⁇ 1000 ⁇ Oven heat resistance test>
- the evaluation of the oven heat resistance test is preferably at least 220 ° C. or more when used as a substrate for mounting an LED, and if it is less than 220 ° C., the heat resistance may be insufficient.
- the wear rate of the drill blade the smaller the loss of the drill blade and the higher the drill workability. Also, if 10% of the drill blade remains, it can be used. If the wear rate of the drill blade after drilling 3000 holes as described above is 90% or less, the drill is frequently replaced. There is no need to do.
- the obtained copper foil-clad laminate was cut out to a predetermined size and subjected to a combustion test in accordance with the UL-94 combustion test method for determination.
- the UL94-V0 was marked with ⁇
- the UL94-V1 was marked with X.
- Examples 15 to 20, Comparative Examples 4 to 6 In Examples 1 to 14 and Comparative Examples 1 to 3, talc (manufactured by Nippon Talc Co., Ltd., D 50 : 5 ⁇ m) was used as the component (B) instead of boehmite particles. Except this, the procedure was the same as in Examples 1 to 14 and Comparative Examples 1 to 3. The obtained copper foil-clad laminate was evaluated in the same manner as described above. The results are shown in Table 2 below.
- Example 21 to 26, Comparative Examples 7 to 9 In Examples 1-14 and Comparative Examples 1-3, as the component (B), instead of the boehmite particles, silica (Denki Kagaku Kogyo Co., Ltd., D 50: 5 [mu] m) was used. Except this, the procedure was the same as in Examples 1 to 14 and Comparative Examples 1 to 3. The obtained copper foil-clad laminate was evaluated in the same manner as described above. The results are shown in Table 3 below.
- Example 9 (Examples 27 to 32, Comparative Example 10)
- a plurality of types of aluminum oxide particles having different average particle diameters were used as the component (C). Except this, it was the same as Example 9.
- the obtained copper foil-clad laminate was evaluated in the same manner as described above. The results are shown in Table 4 below.
- thermosetting resin varnish in an amount shown in Table 5 with respect to 100 parts by volume of the thermosetting resin and uniformly dispersed. I let you.
- a glass non-woven fabric was impregnated with the thermosetting resin varnish containing the inorganic filler in the same manner as above to obtain a prepreg for the non-woven fabric layer.
- thermosetting resin varnish without blending the filler into a glass cloth (woven fabric) having a basis weight of 200 g / m 2 and a thickness of 180 ⁇ m (7628 manufactured by Nittobo Co., Ltd.)
- a prepreg for the woven fabric layer was obtained.
- two prepregs for the nonwoven fabric layer were stacked, and one prepreg for the woven fabric layer and a copper foil having a thickness of 0.018 mm were sequentially placed on both outer surfaces to obtain a laminate.
- the laminate was sandwiched between two metal plates and heat-molded under conditions of a temperature of 180 ° C.
- Example 47 to 52 Comparative Examples 14 to 16
- talc (D 50 : 5 ⁇ m) similar to the above was used instead of boehmite particles. Except this, the procedure was the same as in Examples 33 to 46 and Comparative Examples 11 to 13.
- the obtained copper foil-clad composite laminate was evaluated in the same manner as described above. The results are shown in Table 6 below.
- Example 53 to 58 Comparative Examples 17 to 19
- silica (D 50 : 5 ⁇ m) similar to the above was used as the component (B) instead of boehmite particles. Except this, the procedure was the same as in Examples 33 to 46 and Comparative Examples 11 to 13.
- the obtained copper foil-clad composite laminate was evaluated in the same manner as described above. The results are shown in Table 7 below.
- Example 41 a plurality of types of aluminum oxide particles having different average particle diameters were used as the component (C). Except this, the procedure was the same as in Example 41. The obtained copper foil-clad composite laminate was evaluated in the same manner as described above. The results are shown in Table 8 below.
- Example 41 (Examples 65 to 68, Comparative Examples 21 and 22)
- a thermosetting resin varnish containing aluminum hydroxide manufactured by Sumitomo Chemical Co., Ltd., D 50 : 4.3 ⁇ m
- a prepreg for a woven fabric layer containing aluminum hydroxide was used by impregnation. Except this, the procedure was the same as in Example 41.
- the obtained copper foil-clad composite laminate was evaluated in the same manner as described above, tracking resistance, and surface protrusions. The results are shown in Table 9 below.
- Comparative Examples 23 to 30 In Comparative Examples 23 to 26, copper foil-clad laminates were obtained in the same manner as in Example 1 except that the blending ratio of the components (A), (B), and (C) was as shown in Table 10. In Comparative Examples 27 to 30, copper foil-clad composite laminates were obtained in the same manner as in Example 33 except that the blending ratio of the components (A), (B), and (C) was as shown in Table 10. The obtained copper foil-clad laminate and copper foil-clad composite laminate were evaluated in the same manner as described above. The results are shown in Table 10 below. The blending ratio of the component (A), the component (B), and the component (C) in each example and comparative example is as follows.
- Comparative Examples 26 and 30 since the blending amount of the fine particle component (C) is small, only an inorganic filler having a large average particle diameter is obtained. As a result, high filling becomes difficult and moldability tends to be lowered. Therefore, the moldability of Comparative Examples 26 and 30 is worse than those of other Examples and Comparative Examples.
- Examples 69 to 78, Comparative Examples 31 to 33 A copper foil-clad laminate was formed in the same manner as in Example 1 except that a phenol compound (phenol novolac resin) was used as the curing agent component and the blending ratio of the inorganic filler was as shown in Table 11.
- the obtained copper foil-clad laminate was evaluated in the same manner as described above. The results are shown in Table 11 below.
- talc and silica are the same as those described above, kaolin is manufactured by Keiwa Furnace Co., Ltd. and D 50 is 5 ⁇ m, and titanium oxide (anatase type) is manufactured by Wako Pure Chemical Industries, Ltd. 50 having a thickness of 5 ⁇ m was used.
- Example 79 to 88 Comparative Examples 34 to 36
- a copper foil-clad composite laminate was formed in the same manner as in Example 33 except that a phenol compound (phenol novolac resin) was used as the curing agent component and the blending ratio of the inorganic filler was as shown in Table 12.
- the obtained copper foil-clad composite laminate was evaluated in the same manner as described above. The results are shown in Table 12 below.
- thermosetting resin composition one containing an epoxy vinyl ester resin, a radical polymerizable unsaturated monomer, and a polymerization initiator was used. That is, in a four-necked flask, 400 parts by mass of an epoxy equivalent of 400 g / equivalent tetrabromobisfer A type epoxy resin (“trade name EPICLON 153” [manufactured by Dainippon Ink & Chemicals, Inc.]) and a molecular weight HYCAR CTBN 1300X13 [B.
- thermosetting resin composition 100 parts by volume of the epoxy vinyl ester resin composition was mixed with an inorganic filler having a blending ratio shown in Table 13 and t-butyl peroxybenzoate (“trade name perbutyl Z” [manufactured by NOF Corporation)] 1 0.0 volume part was added, and the thermosetting resin composition was produced by mixing uniformly with a homomixer.
- Other configurations were the same as in Example 33 to form a copper foil-clad composite laminate.
- the obtained copper foil-clad composite laminate was evaluated in the same manner as described above. The results are shown in Table 13 below.
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Planar Illumination Modules (AREA)
- Led Device Packages (AREA)
- Epoxy Resins (AREA)
- Fastening Of Light Sources Or Lamp Holders (AREA)
Abstract
Description
樹脂成分であるビスフェノールA型エポキシ樹脂と、硬化剤成分であるジシアンジアミド(Dicy)系硬化剤とを含有する熱硬化性樹脂ワニスに、熱硬化性樹脂100体積部に対して、表1に示す配合量(単位は体積部)で無機充填材を配合して均一に分散させた。(A)成分としては、ギブサイト型水酸化アルミニウム粒子(住友化学(株)製、D50:5.4μm)とギブサイト型水酸化アルミニウム粒子(住友化学(株)製、D50:12.6μm)を用いた。(B)成分としては、ベーマイト粒子(D50:3.0μm)を用いた。(C)成分としては、酸化アルミニウム粒子(住友化学(株)製、D50:0.5μm、アルミナ)を用いた。尚、熱硬化性樹脂100体積部に対する無機充填材の配合量は、熱硬化性樹脂ワニスの溶媒を除いた固形分(ビスフェノールA型エポキシ樹脂(樹脂成分)とジシアンジアミド系硬化剤(硬化剤成分)の合計量)100体積部に対する無機充填材の配合量である。
得られた銅箔張積層板の密度を水中置換法により測定し、また、比熱をDSC(示差走査熱量測定)により測定し、さらに、レーザーフラッシュ法により熱拡散率を測定した。
熱伝導率(W/m・K)=密度(kg/m3)×比熱(kJ/kg・K)×熱拡散率(m2/S)×1000
〈オーブン耐熱試験〉
得られた銅箔張積層板を用いて、JIS C 6481に準じて作製した試験片を200~240℃に設定した空気循環装置付き恒温槽中で一時間処理したときに、銅箔および積層板にふくれ及びはがれが生じた温度を測定した。尚、オーブン耐熱試験の評価は、LED搭載用の基板としての使用では少なくとも220℃以上が好ましく、220℃未満では耐熱性が不足する恐れがある。
得られた銅箔張積層板を3枚重ね、ドリル(ドリル径0.5mm、振れ角35°)にて60000回転/minで孔を3000個穿設した後のドリルの刃の摩耗率を、ドリル加工前のドリル刃の大きさ(面積)に対するドリル加工により摩耗したドリル刃の(面積)の割合(百分率)により求めて評価した。そして、摩耗率が90%以下のものを○、摩耗率が99%より小さく、90%より大きいものを△、摩耗率が99%以上のものを×とした。尚、ドリルの刃の摩耗率が小さいものほど、ドリルの刃の損失が小さく、ドリル加工性が高いといえる。また、ドリルの刃は10%残っていれば使用可能であり、上記のようにして孔を3000個穿設した後のドリルの刃の摩耗率が90%以下であれば、ドリルを頻繁に交換する必要がない。
得られた銅箔張積層板を所定の大きさに切り出し、UL-94の燃焼試験法に準じて燃焼試験を行い、判定した。そして、UL94-V0のものを○、UL94-V1のものを×とした。
実施例1~14及び比較例1~3において、(B)成分として、ベーマイト粒子の代わりに、タルク(日本タルク(株)製、D50:5μm)を用いた。これ以外は、実施例1~14及び比較例1~3と同様にした。得られた銅箔張積層板について上記と同様の評価をした。その結果を下記表2に示す。
実施例1~14及び比較例1~3において、(B)成分として、ベーマイト粒子の代わりに、シリカ(電気化学工業(株)製、D50:5μm)を用いた。これ以外は、実施例1~14及び比較例1~3と同様にした。得られた銅箔張積層板について上記と同様の評価をした。その結果を下記表3に示す。
実施例9において、(C)成分として、平均粒子径の異なる複数種の酸化アルミニウム粒子を用いた。これ以外は、実施例9と同様にした。得られた銅箔張積層板について上記と同様の評価をした。その結果を下記表4に示す。
実施例1~14及び比較例1~3と同様にして、熱硬化性樹脂ワニスに熱硬化性樹脂100体積部に対して、表5に示す配合量で無機充填材を配合して均一に分散させた。この無機充填材が配合された熱硬化性樹脂ワニスを上記と同様にガラス不織布に含浸させ不織布層用のプリプレグを得た。一方、目付け200g/m2、厚み180μmのガラスクロス(織布)(日東紡(株)製の7628)に、上記の熱硬化性樹脂ワニスを、充填材を配合せずに含浸させることにより、織布層用のプリプレグを得た。そして、不織布層用のプリプレグを2枚重ね、その両外表面それぞれに、織布層用のプリプレグ1枚と厚み0.018mmの銅箔を順に載せて積層体を得た。この積層体を2枚の金属プレート間に挟み、温度180℃、圧力0.3kPa(30kgf/m2)の条件で加熱成型することにより、厚み1.0mmの銅箔張コンポジット積層板を得た。得られた銅箔張コンポジット積層板について上記と同様の評価をした。その結果を下記表5に示す。
実施例33~46及び比較例11~13において、(B)成分として、ベーマイト粒子の代わりに、上記と同様のタルク(D50:5μm)を用いた。これ以外は、実施例33~46及び比較例11~13と同様にした。得られた銅箔張コンポジット積層板について上記と同様の評価をした。その結果を下記表6に示す。
実施例33~46及び比較例11~13において、(B)成分として、ベーマイト粒子の代わりに、上記と同様のシリカ(D50:5μm)を用いた。これ以外は、実施例33~46及び比較例11~13と同様にした。得られた銅箔張コンポジット積層板について上記と同様の評価をした。その結果を下記表7に示す。
実施例41において、(C)成分として、平均粒子径の異なる複数種の酸化アルミニウム粒子を用いた。これ以外は、実施例41と同様にした。得られた銅箔張コンポジット積層板について上記と同様の評価をした。その結果を下記表8に示す。
実施例41において、充填材を含有しない織布層用のプリプレグの代わりに、水酸化アルミニウム(住友化学(株)製、D50:4.3μm)を含有する熱硬化性樹脂ワニスをガラスクロスに含浸させることにより、水酸化アルミニウムを含有する織布層用のプリプレグを用いた。これ以外は、実施例41と同様にした。得られた銅箔張コンポジット積層板について上記と同様の評価及び耐トラッキング性の評価並びに表面突起の評価をした。その結果を下記表9に示す。
耐トラッキング性の試験は、規格IEC60112第4版(JIS C2134)に準拠して行った。そして、CTIによる評価で最大電圧を求めた。
得られた銅箔張コンポジット積層板の表面を観察した。そして、成形上及び実用上で問題がない程度の表面突起が存在するものに○を、成形上又は実用上にやや問題が生じるものに×を付した。
比較例23~26は、(A)成分と(B)成分と(C)成分の配合比を表10のようにした以外は実施例1と同様に銅箔張積層板を得た。比較例27~30は、(A)成分と(B)成分と(C)成分の配合比を表10のようにした以外は実施例33と同様に銅箔張コンポジット積層板を得た。得られた銅箔張積層板及び銅箔張コンポジット積層板について上記と同様の評価をした。その結果を下記表10に示す。各実施例及び比較例の(A)成分と(B)成分と(C)成分の配合比は以下の通りである。
比較例24及び28:(A)成分:(B)成分:(C)成分=1:0:0.44
比較例25及び29:(A)成分:(B)成分:(C)成分=1:3:4.3
比較例26及び30:(A)成分:(B)成分:(C)成分=1:0.56:0
硬化剤成分としてフェノール化合物(フェノールノボラック樹脂)を用いると共に無機充填材の配合比を表11のようにした以外は、実施例1と同様にして銅箔張積層板を形成した。得られた銅箔張積層板について上記と同様の評価をした。その結果を下記表11に示す。尚、タルクとシリカは上記と同様のものを用い、カオリンは啓和炉材(株)製でD50が5μmのものを、酸化チタン(アナターゼ型)は和光純薬工業(株)製でD50が5μmのものをそれぞれ用いた。
硬化剤成分としてフェノール化合物(フェノールノボラック樹脂)を用いると共に無機充填材の配合比を表12のようにした以外は、実施例33と同様にして銅箔張コンポジット積層板を形成した。得られた銅箔張コンポジット積層板について上記と同様の評価をした。その結果を下記表12に示す。
図2に示す製造方法により銅箔張コンポジット積層板を連続的に形成した。熱硬化性樹脂組成物としては、エポキシビニルエステル樹脂とラジカル重合性不飽和単量体と重合開始剤とを含有するものを用いた。すなわち、4つ口フラスコに、エポキシ当量が400グラム/当量のテトラブロモビスフェールA型エポキシ樹脂(「商品名 EPICLON 153」〔大日本インキ化学工業(株)製〕)400質量部と、分子量が3500、結合アクリロニトリルが27%、カルボキシル基1.9個/分子のブタジエンとアクリロニトリルの共重合体の分子両末端にカルボキシル基を有するHYCAR CTBN 1300X13〔B.F.Goodrich Chemical社製〕92質量部と、メタクリル酸82質量部(エポキシ基の数:総カルボキシル基の数=1:1)と、ハイドロキノン0.29質量部と、トリフェニルホスフィン0.58質量部とを仕込み、110℃で反応させた。そして、酸価が10mg-KOH/g以下になったことを確認してスチレン309質量部を添加した。その後、アセチルアセトン1.32質量部を添加して、エポキシビニルエステル樹脂組成物を得た。次いで、このエポキシビニルエステル樹脂組成物100体積部に、表13に示す配合比の無機充填材と、t-ブチルパーオキシベンゾエート(「商品名パーブチルZ」〔日本油脂社(株)製〕)1.0体積部とを添加し、ホモミキサーで均一混合することにより、熱硬化性樹脂組成物を作製した。その他の構成は実施例33と同様にして銅箔張コンポジット積層板を形成した。得られた銅箔張コンポジット積層板について上記と同様の評価をした。その結果を下記表13に示す。
Claims (13)
- 熱硬化性樹脂組成物を含有する不織布層を備えた積層板であって、
前記熱硬化性樹脂組成物には無機充填材が熱硬化性樹脂100体積部に対して80~400体積部含有されており、
前記無機充填材は、
(A)2~15μmの平均粒子径(D50)を有するギブサイト型水酸化アルミニウム粒子と、
(B)1.5~15μmの平均粒子径(D50)を有するベーマイト粒子と、1.5~15μmの平均粒子径(D50)を有する、遊離開始温度が400℃以上である結晶水を含有する又は結晶水を含有しない無機粒子とからなる群から選ばれる少なくとも1種類の無機成分と、
(C)1.5μm以下の平均粒子径(D50)を有する酸化アルミニウム粒子からなる微粒子成分とを含有し、
前記ギブサイト型水酸化アルミニウム粒子(A)と前記無機成分(B)と前記微粒子成分(C)との配合比(体積比)が1:0.1~3:0.1~3であることを特徴とする積層板。 - 前記不織布層の表面に織布層が形成されて成ることを特徴とする請求項1に記載の積層板。
- 前記熱硬化性樹脂にはエポキシ樹脂が含有されていることを特徴とする請求項1又は2に記載の積層板。
- 前記熱硬化性樹脂には前記エポキシ樹脂の硬化剤成分としてフェノール化合物が含有されていることを特徴とする請求項3に記載の積層板。
- 前記熱硬化性樹脂には、エポキシビニルエステル樹脂とラジカル重合性不飽和単量体と重合開始剤とが含有されていることを特徴とする請求項1又は2に記載の積層板。
- 前記不織布層の不織布基材の結着剤がエポキシ化合物であることを特徴とする請求項1乃至5のいずれか1項に記載の積層板。
- 前記織布層には水酸化アルミニウムが含有されていることを特徴とする請求項2乃至6のいずれか1項に記載の積層板。
- 請求項1乃至7のいずれか1項に記載の積層板の少なくとも一表面に金属箔を設けて成ることを特徴とする金属箔張り積層板。
- 請求項1乃至7のいずれか1項に記載の積層板の少なくとも一表面に導体パターンを設けて成ることを特徴とするプリント配線板。
- 請求項1乃至7のいずれか1項に記載の積層板の少なくとも一表面に回路を設けて成ることを特徴とする回路基板。
- 請求項1乃至7のいずれか1項に記載の積層板の少なくとも一表面にLEDを実装して成ることを特徴とするLEDバックライトユニット。
- 請求項1乃至7のいずれか1項に記載の積層板の少なくとも一表面にLEDを実装して成ることを特徴とするLED照明装置。
- 不織布基材を連続的に搬送しながら熱硬化性樹脂組成物を前記不織布基材に含浸し、この不織布基材を連続的に搬送しながらその両表面に織布を積層し、この積層物をロールで圧着し加熱することにより前記熱硬化性樹脂組成物を硬化させて不織布層及び織布層を形成する積層板の製造方法であって、
前記熱硬化性樹脂組成物には、熱硬化性樹脂100体積部に対して80~400体積部含有されており、
前記無機充填材は、
(A)2~15μmの平均粒子径(D50)を有するギブサイト型水酸化アルミニウム粒子と、
(B)1.5~15μmの平均粒子径(D50)を有するベーマイト粒子と、1.5~15μmの平均粒子径(D50)を有する、遊離開始温度が400℃以上である結晶水を含有する又は結晶水を含有しない無機粒子とからなる群から選ばれる少なくとも1種類の無機成分と、
(C)1.5μm以下の平均粒子径(D50)を有する酸化アルミニウム粒子からなる微粒子成分とを含有し、
前記ギブサイト型水酸化アルミニウム粒子(A)と前記無機成分(B)と前記微粒子成分(C)との配合比(体積比)が1:0.1~3:0.1~3であることを特徴とする積層板の製造方法。
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CN103131133A (zh) * | 2011-12-02 | 2013-06-05 | 达航工业股份有限公司 | 用于印刷电路板的充填用热固化型组成物 |
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