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
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 Download PDFInfo
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- TWI452949B TWI452949B TW101114156A TW101114156A TWI452949B TW I452949 B TWI452949 B TW I452949B TW 101114156 A TW101114156 A TW 101114156A TW 101114156 A TW101114156 A TW 101114156A TW I452949 B TWI452949 B TW I452949B
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- thermosetting resin
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- 229910052751 metal Inorganic materials 0.000 title claims description 32
- 239000002184 metal Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000009434 installation Methods 0.000 title 1
- 239000002245 particle Substances 0.000 claims description 217
- 229920001187 thermosetting polymer Polymers 0.000 claims description 125
- 239000004745 nonwoven fabric Substances 0.000 claims description 86
- 229920005989 resin Polymers 0.000 claims description 79
- 239000011347 resin Substances 0.000 claims description 79
- 239000010419 fine particle Substances 0.000 claims description 74
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 63
- 239000002759 woven fabric Substances 0.000 claims description 55
- 239000011256 inorganic filler Substances 0.000 claims description 51
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 51
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 50
- 239000003822 epoxy resin Substances 0.000 claims description 47
- 229920000647 polyepoxide Polymers 0.000 claims description 47
- 239000000758 substrate Substances 0.000 claims description 40
- 238000009826 distribution Methods 0.000 claims description 25
- 239000011888 foil Substances 0.000 claims description 19
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- -1 phenol compound Chemical class 0.000 claims description 15
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- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
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- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 2
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- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- WPZJSWWEEJJSIZ-UHFFFAOYSA-N tetrabromobisphenol-F Natural products C1=C(Br)C(O)=C(Br)C=C1CC1=CC(Br)=C(O)C(Br)=C1 WPZJSWWEEJJSIZ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- H05K1/036—Multilayers with layers of different types
-
- 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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- 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
- B32B5/02—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 structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- 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
- B32B5/02—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 structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
-
- 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
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/05—5 or more layers
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/64—Heat extraction or cooling elements
- H01L33/641—Heat extraction or cooling elements characterized by the materials
-
- 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
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Description
本發明係關於各種電子器材用的積層板,覆金屬箔積層板、印刷配線板及電路基板以及LED背光單元、上述積層板之製造方法。尤其是關於適合於用以搭載發光二極體(LED)等的發熱元件的積層板。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).
以往提供有一種積層板,其係由含有樹脂組成物的不織布基材的不織布層之表面,與含有樹脂組成物的織布基材的表材層積層一體化而成的積層板(例如參照專利文獻1)。此種積層板,係藉由在其表面形成導體圖案,加工成為用來搭載電氣電子元件的印刷配線板者;又,其係藉由用此導體圖案來形成電路並加工成電路基板者。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.
〔專利文獻1〕日本特開2006-272671號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-272671
然而,最近對於搭載於積層板的電氣電子零件,有時會使用發熱量大者,或提高發熱的電氣電子零件的搭載密度。為了因應此種情況,期望有散熱性高的積層板。若使用散熱性高的積層板,由電氣電子零件所產生的熱透過積層板可容易地散熱,而可謀求加長電氣電子零件的使用壽命。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.
本發明係有鑑於上述問題點而提出者,目的在於提供一種在不損及耐熱性與鑽孔加工性且散熱性高的積層板、 及其製造方法。又,本發明之目的亦在於提供一種散熱性高的覆金屬箔積層板、印刷配線板及電路基板、及LED背光單元、LED照明裝置。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.
本發明之積層板,係由含浸熱固性樹脂組成物的不織布基材所得的不織布層、與分別積層在前述不織布層之兩表面的織布層積層一體化而成者。其相對於熱固性樹脂100體積份而言,前述熱固性樹脂組成物中含有80~150體積份的比例的無機填充材。前述無機填充材係含有三水鋁石(gibbsite)型氫氧化鋁粒子(A)與微粒子成分(B)而成者。前述三水鋁石型氫氧化鋁粒子(A)之平均粒徑(D50 )為2~15μ m。前述微粒子成分(B)係由平均粒徑為1.5μ m以下的氧化鋁粒子所構成。前述微粒子成分(B)之粒徑分布係:粒徑5μ m以上為5質量%以下、粒徑1μ m以上小於5μ m為40質量%以下、粒徑小於1μ m為55質量%以上。此微粒子成分(B)中含有破碎狀的氧化鋁粒子30質量%以上。前述三水鋁石型氫氧化鋁粒子(A)與前述微粒子成分(B)之調配比(體積比)為1:0.2~0.5。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.
本發明中,較佳為前述微粒子成分(B)中含有破碎狀的氧化鋁粒子30質量%以上。In the present invention, it is preferable that the fine particle component (B) contains 30% by mass or more of the crushed alumina particles.
本發明中,較佳為前述熱固性樹脂中含有環氧樹脂。In the present invention, it is preferred that the thermosetting resin contains an epoxy resin.
本發明中,較佳為前述熱固性樹脂中含有苯酚化合物做為前述環氧樹脂的硬化劑成分。In the present invention, it is preferred that the thermosetting resin contains a phenol compound as a curing agent component of the epoxy resin.
本發明中,較佳為前述熱固性樹脂中含有環氧乙烯酯樹脂與自由基聚合性不飽和單體與聚合起始劑。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.
本發明之覆金屬箔積層板,其特徵在於其係在前述積 層板的至少一表面上設置有金屬箔而成者。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.
本發明之印刷配線板,其特徵在於其係在前述積層板的至少一表面上設置有導體圖案而成者。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.
本發明之電路基板,其特徵在於其係在前述積層板的至少一表面上設置有電路而成者。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.
本發明之LED背光單元,其特徵在於其係在前述積層板的至少一表面上安裝有LED而成者。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.
本發明之LED照明裝置,其特徵在於其係在前述積層板的至少一表面上安裝有LED而成者。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.
本發明之積層板之製造方法,其特徵在於其係一邊連續移送不織布基材一邊將熱固性樹脂組成物含浸於前述不織布基材,再一邊連續移送此不織布基材一邊將織布積層在其兩表面,再以軋輥壓合並加熱此積層物,藉此使前述熱固性樹脂組成物硬化而形成不織布層及織布層。相對於熱固性樹脂100體積份而言,前述熱固性樹脂組成物中含有80~150體積份比例的無機填充材。前述無機填充材係含有三水鋁石型氫氧化鋁粒子(A)與微粒子成分(B)而成。前述三水鋁石型氫氧化鋁粒子(A)之平均粒徑(D50 )為2~15μ m。前述微粒子成分(B)係由平均粒徑為1.5μ m以下的氧化鋁粒子所構成,其粒徑分布係粒徑5μ m以上為小於5質量%以下、粒徑1μ m以上小於5μ m為40質量%以下、粒徑小於1μ m為55質量%以上。此微粒子成分(B)中含有破碎狀的氧化鋁粒子30質量%以上。前述三水鋁石型氫氧化鋁粒子(A)與前述微粒子成分(B)之調配比(體積比)為1:0.2~0.5。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.
本發明之積層板,係可不損及耐熱性與鑽孔加工性而可提高散熱性者。The laminated board of the present invention can improve heat dissipation without impairing heat resistance and drilling processability.
本發明之覆金屬箔積層板、印刷配線板及電路基板以及LED背光單元、LED照明裝置,係可提高散熱性者。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.
本發明之積層板之製造方法可連續地製造積層板,係相較於批次式,可提高生產性者。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.
以下,說明用以實施本發明之形態。Hereinafter, the form for carrying out the invention will be described.
如圖1所示,本發明之積層板A係具備有含有熱固性樹脂組成物的不織布層1、與含有熱固性樹脂組成物的織布層2而形成,為所謂的複合積層板。複合積層板在散熱性方面有時較通常的積層板(單獨由不織布層1形成,未使用織布)差。然而,複合積層板廉價,且於尺寸安定性、力學物性方面皆優異。不織布層1可藉由在不織布基材中含有熱固性樹脂組成物的預浸物之硬化物等來形成。又,織布層2可藉由在織布基材中含有熱固性樹脂組成物的預浸物之硬化物等來形成。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.
做為不織布基材,可使用例如:選自用玻璃纖維不織布、玻璃紙、或芳香族聚醯胺纖維、聚酯纖維、聚醯胺纖維(尼龍)等合成樹脂纖維所成的合成樹脂不織布或紙之中的任一者。不織布基材的厚度較佳為定為0.20~1.00mm。不織布基材的厚度若在此範圍內,則不織布層1的厚度不會太薄也不會太厚,可使得耐熱性、散熱性與鑽孔加工性良好。不織布基材的厚度之更佳的範圍為0.3~0.9mm。做為不織布基材的結著劑,較佳為使用耐熱度優異的環氧樹脂化合物。此結著劑為用來將構成纖維的不織布基材的纖 維接著並固定的黏合劑。做為結著劑之環氧樹脂化合物可使用環氧矽氧烷等。又,較佳為相對於纖維100質量份結著劑調配5~25質量份的比例。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.
熱固性樹脂組成物係含有熱固性樹脂與無機填充材者。做為熱固性樹脂可使用例如於常溫為液狀的熱固性樹脂。又,做為熱固性樹脂可使用例如樹脂成分與硬化劑成分的混合物。又,做為樹脂成分,可使用環氧樹脂、不飽和聚酯樹脂、乙烯酯樹脂等之自由基聚合型熱固性樹脂等。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.
做為具體的熱固性樹脂,做為樹脂成分可例示使用環氧樹脂者。此情況下可使用自雙酚A型、雙酚F型、甲酚酚醛清漆型、酚醛清漆型、聯苯型、萘型、茀型、二苯并哌喃型、二環戊二烯型、蒽型等的群組中之至少一種環氧樹脂。又,做為環氧樹脂的硬化劑成分可使用雙氰胺或苯酚化合物,但為了提高積層板A的耐熱性較佳宜使用苯酚化合物。做為此苯酚化合物,可使用自烯丙基苯酚、酚醛清漆、烷基酚醛清漆、含三嗪構造之酚醛清漆、雙酚A酚醛清漆、含二環戊二烯構造之苯酚樹脂、苯酚芳烷基型苯酚、萜烯改質苯酚、聚乙烯基苯酚類、含萘構造之苯酚系硬化劑、含茀構造之苯酚系硬化劑等的群組中之至少一種。又,苯酚化合物的硬化劑成分的調配比例,較佳為相對於環氧樹脂100質量份為30~120質量份、更佳為60~110質量份的比例。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.
做為具體的熱固性樹脂之其他之一例,做為樹脂成分可使用環氧乙烯酯樹脂,此情況下,做為硬化劑成分可使用自由基聚合性不飽和單體與聚合起始劑。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.
做為用來得到環氧乙烯酯樹脂的環氧樹脂,並無特別 限定,可列舉例如:雙酚型環氧樹脂、酚醛清漆型環氧樹脂、脂環型環氧樹脂、縮水甘油基酯類、縮水甘油基胺類、雜環型環氧樹脂、溴化環氧樹脂等。做為上述雙酚型環氧樹脂,可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂等。做為上述酚醛清漆型環氧樹脂,可列舉:酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、二環戊二烯酚醛清漆型環氧樹脂等。做為上述脂環型環氧樹脂可列舉:3,4-環氧基-6-甲基環己基甲基-3,4-環氧基-6-甲基環己烷羧酸酯、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、1-環氧基乙基-3,4-環氧基環己烷等。做為上述縮水甘油基酯類,可列舉:苯二甲酸二縮水甘油基酯、四氫苯二甲酸二縮水甘油基酯、二聚物酸縮水甘油基酯等。做為上述縮水甘油基胺類可列舉:四縮水甘油基二胺基二苯基甲烷、三縮水甘油基對胺基苯酚、N,N-二縮水甘油基苯胺等。做為上述雜環型環氧樹脂,可列舉:1,3-二縮水甘油基-5,5-二甲基乙內醯脲、三縮水甘油基異三聚氰酸酯等。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.
又,做為溴化環氧樹脂,可列舉:四溴雙酚A型環氧樹脂、四溴雙酚F型環氧樹脂、溴化甲酚酚醛清漆型環氧樹脂、溴化酚醛清漆型環氧樹脂等。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.
用以得到上述環氧乙烯酯樹脂的環氧樹脂之中,尤其就阻燃性優異之考量,較佳為使用溴化環氧樹脂。再者,亦可使用對此等環氧樹脂的環氧基之一部分以含羧基橡膠狀聚合物進行反應而成的環氧樹脂。此種以含羧基橡膠狀聚合物進行反應而成的環氧樹脂,就提高所得到的覆銅積層板等之積層板A的耐衝撃性、衝孔加工性、層間密合性 的考量為特佳。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.
做為上述含羧基橡膠狀聚合物,可列舉:使含羧基之單體與共軛二烯系單體以及依需要而使用之其他單體進行共聚合所得者,或將羧基導入到由共軛二烯系單體與其他單體所共聚合而成者等。羧基可位於分子末端、側鏈之任一處,其個數較佳為在1分子中為1~5個,更佳為1.5~3個。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.
做為上述共軛二烯系單體有丁二烯、異戊二烯、氯丁二烯等。又,做為依需要而使用之其他單體有丙烯腈、苯乙烯、甲基苯乙烯、鹵化苯乙烯等。此等之中,就得到之反應物之與自由基聚合性不飽和單體的相容性之考量,較佳為在橡膠狀聚合物中使丙烯腈以10~40重量%進行共聚合而成者,更佳為以15~30重量%進行共聚合而成者。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.
又,於製造環氧乙烯酯樹脂時,亦可使環氧樹脂、含羧基橡膠狀聚合物及乙烯性不飽和一元酸之各成分同時進行反應。又,於製造環氧乙烯酯樹脂時,亦可於使環氧樹脂與含羧基橡膠狀聚合物反應之後,再與乙烯性不飽和一元酸反應。此時,有關用以得到環氧乙烯酯樹脂所用的環氧樹脂與含羧基橡膠狀聚合物及乙烯性不飽和一元酸之反應比例,並無特別限制。然而,上述反應比例較佳為對於環氧樹脂的環氧基1當量,含羧基橡膠狀聚合物與乙烯性不飽和一元酸的總羧基為0.8~1.1當量的範圍。又,尤其就得到貯藏安定性優異的樹脂之考量,上述反應比例較佳宜設定為0.9~1.0當量的範圍。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.
又,於環氧乙烯酯樹脂之製造中,做為與環氧樹脂反應所使用的乙烯性不飽和一元酸,可列舉例如:(甲基)丙烯 酸、丁烯酸、桂皮酸、丙烯酸二聚物、單甲基順丁烯二酸酯、單丁基順丁烯二酸酯、己二烯酸等。此等之中較佳為(甲基)丙烯酸。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.
上述自由基聚合性不飽和單體為在1分子中有至少1個自由基聚合性不飽和基者。做為此種自由基聚合性不飽和單體,可列舉例如:二烯丙基苯二甲酸酯、苯乙烯、甲基苯乙烯、鹵化苯乙烯、(甲基)丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丁酯、二乙烯基苯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯,此等可使用1種或使用2種以上。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.
又,關於自由基聚合性不飽和單體的調配量,相對於環氧乙烯酯樹脂與自由基聚合性不飽和單體的合計量100質量份而言,較佳為設定為25質量份以上、45質量份以下的比例。理由在於:若設定為25質量份以上,得到的熱固性樹脂組成物之對於不織布基材與織布基材的含浸性可成為良好,又,設定為45質量份以下,則使用此熱固性樹脂組成物所得的積層板A之尺寸安定性優異,且於高耐熱性也優異。自由基聚合性不飽和單體調配量的較佳範圍,相對於環氧乙烯酯樹脂與自由基聚合性不飽和單體的合計量100質量份而言為25~40質量份。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.
做為上述聚合起始劑,可列舉:過氧化甲乙酮、過氧化甲基異丁酮、過氧化環己酮等之過氧化酮類;過氧化苯甲醯基、過氧化異丁基等之過氧化二醯基類;過氧化氫異丙苯、過氧化氫第三丁基等之過氧化氫類;過氧化二異丙苯、過氧化二-第三丁基等之過氧化二烷基類;過氧化1,1- 二-第三丁基-3,3,5-三甲基環己酮、2,2-二-(過氧化第三丁基)-丁烷等之過氧化縮醛類;過氧化第三丁基-苯甲酸酯、過氧化第三丁基-2-乙基環己酸酯等之烷基過氧酸酯類、過氧化雙(4-第三丁基環己基)二碳酸酯、過氧化第三丁基異丁基碳酸酯等之過氧化碳酸酯類等之有機過氧化物。此等可使用1種或使用2種以上。藉由使用此種有機過氧化物,熱固性樹脂組成物成為可加熱硬化者。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.
有關聚合起始劑於熱固性樹脂中的調配量並無特別限制,相對於環氧乙烯酯樹脂與自由基聚合性不飽和單體的合計量100質量份而言,較佳為設定於0.5~5.0質量份左右的比例之範圍。尤其,就熱固性樹脂組成物的清漆使用壽命與硬化性的考量,更佳為設定於0.9~2.0質量份的比例之範圍。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.
做為無機填充材,可使用含有三水鋁石型氫氧化鋁粒子(A)與微粒子成分(B)者。於本實施形態中,做為無機填充材可只含有三水鋁石型氫.氧化鋁粒子(A)與微粒子成分(B)。三水鋁石型氫氧化鋁粒子(A)之平均粒徑(D50 )為2~15μm。又,微粒子成分(B)係由平均粒徑(D50 )為1.5μm以下的氧化鋁粒子所構成之微粒子成分。又,係使用此微粒子成分(B)的粒度分布係:粒徑5μm以上為5質量%以下,粒徑1μm以上小於5μm為40質量%以下,粒徑小於1μm為55質量%以上者。又,本說明書中,無機填充材的平均粒徑,係指用雷射繞射式粒度分布測定裝置測定所得的以粉體團塊的總體積做為100%而求出累積曲線,該累積曲線為50%處的粒徑。又,微粒子成分的粒度分布也可用雷射繞射式粒度分布測定裝置測定而得到。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.
三水鋁石型氫氧化鋁粒子(A)為以Al(OH)3 或Al2 O3 ‧3H2 O代表的鋁化合物,為賦予積層板A導熱性、阻燃性、鑽孔加工性有良好的均衡性的成分。又,三水鋁石型氫氧化鋁粒子(A)的平均粒徑(D50 )為2~15μm,較佳為3~12μm。當三水鋁石型氫氧化鋁粒子(A)的平均粒徑(D50 )為15μm以下時,鑽孔加工性不易降低,為2μm以上時,導熱性不易降低且生產性也不易降低。又,做為三水鋁石型氫氧化鋁粒子(A),可使用平均粒徑(D50 )為2~10μm的第1三水鋁石型氫氧化鋁與平均粒徑(D50 )為10~15μm的第2三水鋁石型氫氧化鋁之調配物。此情況下,藉由填充材之更緊密的填充,散熱性可更加提高,故較佳。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.
微粒子成分(B)為對得到的積層板賦予高導熱性的成分。構成微粒子成分(B)的氧化鋁粒子的平均粒徑(D50 )為1.5μm以下,較佳為平均粒徑(D50 )為0.4~0.8μm。當微粒子成分(B)的平均粒徑為1.5μm以下時,可容易地對積層板A填充入充分的調配量,又,鑽孔加工性也不易降低。又,當微粒子成分(B)的平均粒徑為0.4μm以上時,積層板A可得到充分的導熱率。又,雖然氧化鋁粒子堅硬,其莫氏硬度為12,但由於平均粒徑(D50 )為1.5μm以下,故可以不損及鑽孔加工性。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.
又,微粒子成分(B)的粒度分布為:粒徑5μm以上為5質量%以下、粒徑1μm以上小於5μm為40質量%以下、粒徑小於1μm為55質量%以上。藉由使用具有此種粒度分布的氧化鋁粒子,可使鑽孔加工性良好。微粒子成分(B)的粒度分布的較佳範圍可設定為粒徑5μm以上的氧化鋁粒子為0~5質量%、粒徑1μm以上小於5μm的氧化鋁粒子為0~ 30質量%、其餘為粒徑小於1μm的氧化鋁粒子。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.
又,微粒子成分(B)中含有破碎(非球狀)的氧化鋁粒子30質量%以上。所謂破碎狀的氧化鋁粒子,係指於氧化鋁的製法中,藉由將塊狀的氧化鋁粉碎的製法等所得之非球狀的氧化鋁,為不同於球狀的氧化鋁者。破碎狀的氧化鋁粒子,係由任意採樣的氧化鋁粒子試樣的SEM圖像,算出任意10個氧化鋁粒子的長寬比,以此平均長寬比≧1.3之氧化鋁粒子定義為破碎狀。又,上述平均長寬比<1.3的氧化鋁粒子則可定義為破碎狀以外(例如球狀)的氧化鋁粒子。破碎狀的氧化鋁粒子,相對於微粒子成分(B)的總量而言,若含有30質量%以上,則鑽頭刀刃的磨損會減少,而可提高鑽孔加工性。又,破碎狀的氧化鋁粒子,相對於微粒子成分(B)的全量而言,亦可為100質量%。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).
前述三水鋁石型氫氧化鋁粒子(A)與前述微粒子成分(B)的調配比(體積比)為1:0.2~0.5。當微粒子成分(B)的調配量相對於三水鋁石型氫氧化鋁粒子(A)的調配量1而言為0.2~0.5時,得到之積層板A的鑽孔加工性、導熱性、耐熱性會不容易降低。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.
於本實施形態中,前述無機填充材中,於前述三水鋁石型氫氧化鋁粒子(A)與前述微粒子成分(B)之外,視需要亦可含有第三成分。做為此第三成分,例如,記載於日本特開2010-774號公報中的水鋁石(boehmite)粒子,於高度填充填料時有提高基板的耐熱性與阻燃性、降低鑽頭磨損性方面的效果,但另一方面,水鋁石粒子不僅成本高,且會使清漆的流動性成為高搖變性,致有生產速度無法提升的問題。相對於此,本實施形態中,藉由規定微粒子成分(B)的 氧化鋁之平均粒徑與氧化鋁的形狀(以破碎狀者做為主體),即使不加入水鋁石粒子等的第三成分,也可得到提高基板的耐熱性與阻燃性,減低鑽頭磨損性的效果。在不損及耐熱性與鑽孔加工性及散熱性的範圍內可使用第三成分,可使用例如氧化矽等。氧化矽較佳為在用以減低基板的線膨脹係數時使用。做為第三成分的平均粒徑(D50 )較佳宜設定為1~30μm,更佳為5~15μm。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.
本發明中,搖變性(TI值)於以6rpm與30rpm的黏度分別做為η6、η30,定義為TI值=η6/η30時,TI值≦2,在減低成形不良率上是重要的。水鋁石粒子雖為有優異的耐熱性、阻燃性的材料,但於高度填充系統中無法避免TI值>2,故於以往的成形條件下仍難免發生一定程度的外觀不良。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.
相對於熱固性樹脂100體積份之無機填充材的調配比例宜為80~150體積份,較佳為90~150體積份,更佳為100~150體積份。當無機填充材的調配比例為80體積份以上時,得到之積層板A的導熱率不易變低,為150體積份以下時,鑽孔加工性不易降低,並且積層板A的製造性(樹脂含浸性、成形性)也不易降低。又,尤其於三水鋁石型氫氧化鋁粒子(A)的調配比例為100體積份以下時,會有不易產生多量的結晶水、耐熱性不易降低的傾向。又,當調配上述第三成分時,可在不損及耐熱性與鑽孔加工性及散熱性的範圍內使用,例如,做為第三成分的調配量,可設定為相對於無機填充材的總量而言為0~15體積%。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.
熱固性樹脂組成物之調製,可於液狀等之前述熱固性樹脂中,調配入含有上述三水鋁石型氫氧化鋁粒子(A)與微粒子成分(B)的無機填充材(視需要可含有第三成分),使用 分散機、球磨機、輥等,藉由用以使各無機填充材的粒子分散之公知調製方法來調製。又,於熱固性樹脂組成物中,可視需要調配入熱固性樹脂的硬化觸媒等之各種添加劑。又,考慮及熱固性樹脂組成物的黏度調整與對不織布基材的含浸性等,視需要也可調配有機溶劑等之溶劑、減黏劑、偶合劑等之加工助劑。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.
用以形成不織布層1的預浸物之製得,可藉由以熱固性樹脂組成物含浸前述不織布基材,然後,將含浸不織布基材的熱固性樹脂組成物藉由加熱乾燥等使其成為半硬化狀態(B階段狀態)而得到。用以形成不織布層1的預浸物中,相對於預浸物總量而言,熱固性樹脂組成物的含有量可設定為40~95質量%,較佳為60~95質量%,但並非限定於此。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.
做為用以形成織布層2的織布基材,可使用例如:選自使用玻璃布或芳族醯胺纖維、聚酯纖維、聚醯胺纖維(尼龍)等之合成樹脂纖維的合成樹脂布中之任一者。織布基材的厚度可設定為50~500μm,但並非限定於此。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.
做為用以形成織布層2的熱固性樹脂組成物,可為與用以形成不織布層1的上述熱固性樹脂組成物相同,也可不同。於不同的情況,可改變使用之熱固性樹脂、無機填充材的種類、相對於熱固性樹脂之無機填充材的含有量等。尤其,較佳為:可使用自用以形成不織布層1的上述熱固性樹脂組成物中排除無機填充材者,亦即,使用由上述熱固性樹脂與其他視需要而調配的溶劑或添加劑所構成者。藉此,可提高熱固性樹脂組成物對織布基材的含浸性。於織布層2中含有無機填充材的情況,為了提高積層板的 防爬電性(antitracking),做為無機填充材較佳可用氫氧化鋁。一般認為因氫氧化鋁的結晶水會阻礙積層板A表面的熱分解、碳化,故可提高積層板A的防爬電性。又,為了提高積層板A的防爬電性,較佳為相對於熱固性樹脂100體積份而言,織布層2中的氫氧化鋁為25~150體積份的比例,更佳為30~100體積份。又,較佳為使用平均粒徑(D50 )為2~15μm的氫氧化鋁,更佳為4~15μm者。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.
用以形成織布層2的預浸物,可藉由以熱固性樹脂組成物含浸前述織布基材,然後,將含浸織布基材的熱固性樹脂組成物加熱乾燥等而成為半硬化狀態(B階段狀態)而得到。用以形成織布層2的預浸物,相對於預浸物總量而言,熱固性樹脂組成物的含有量可設定為40~95質量%,更佳為60~95質量%,但並非限定於此。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.
又,於形成做為圖1中記載的本發明之積層板A之複合積層板時,可將用以形成不織布層1的預浸物、與用以形成織布層2的預浸物疊合後,將其加熱加壓成形。藉此,於使各預浸物中的熱固性樹脂硬化而形成不織布層1及織布層2的同時,可藉由此等熱固性樹脂的硬化而使不織布層1與織布層2接著而積層一體化。此處,可將不織布層1及織布層2分別各一片或複數片的預浸物疊合來形成。又,可在不織布層1的兩表面形成織布層2。又,使用此複合積層板的覆金屬箔積層板,可藉由在織布層2的表面進一步設置銅箔或鎳箔等的金屬箔3,而形成單面為絕緣層的複合積層板或兩面覆金屬箔積層板。此情況下,係將用以形成不織布層1的預浸物、與用以形成織布層2的預浸物、與金屬箔3疊合後,藉由加熱加壓成形,而將不織布層1與 織布層2與金屬箔3積層予以一體化。加熱加壓成形的條件係與上述者相同。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.
複合積層板可連續生產。圖2表示兩面覆金屬箔複合積層板的製造方法之一例。不織布基材之玻璃不織布,只要是玻璃纖維製的紙、為可連續供給的長形物、在內部與表面有空隙、可含浸熱固性樹脂組成物者皆可,並無特別限定。做為玻璃不織布的厚度,通常為0.3~0.8mm,但不限定於此厚度。又,織布基材之玻璃織布,只要是玻璃纖維製的玻璃製織布、可連續供給的長形物、在內部與表面有空隙、可含浸熱固性樹脂組成物者皆可,並無特別限定。做為玻璃織布的厚度,通常為0.015~0.25mm,但非限定於此厚度。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.
其次,首先以上述熱固性樹脂組成物含浸做為不織布基材之玻璃不織布。然後,將含浸過熱固性樹脂組成物的玻璃不織布的兩表面以熱固性樹脂含浸玻璃織布連續積層,以輥將此積層物壓合並加熱而製造複合型的積層板。此處,可將含浸熱固性樹脂組成物的玻璃不織布1片或複數片疊合而使用。又,熱固性樹脂含浸玻璃織布,係如上述說明的含浸熱固性樹脂或熱可塑性樹脂組成物而成的上述玻璃製織布。又,熱固性樹脂含浸玻璃織布亦可使用一片或疊合複數片而使用。再者,亦可在其一面或兩面的表層積層金屬箔3。做為金屬箔3,只要是可連續供給的長形的金屬製箔皆可,並無特別限定,可列舉:銅箔、鎳箔等。做為金屬箔3的厚度,通常為0.012~0.07mm,但並非限定於此厚度。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.
其次,如圖2般,將以上述熱固性樹脂組成物11含浸 連續供給的玻璃不織布10而得到的二片熱固性樹脂含浸玻璃不織布12、與連續供給的二片熱固性樹脂含浸玻璃織布9、與連續供給的二片金屬箔13進行積層。此情況下,係以熱固性樹脂含浸玻璃不織布12做為芯,在其兩側(上下)配置熱固性樹脂含浸玻璃織布9,再於其兩表層配置金屬箔13而進行積層。然後,將該積層所得的積層物以積層輥壓合。接著,將該經壓合的壓合物15拉引出並用輥18拉緊,使其一邊行進,一邊於加熱硬化爐17中在使該壓合物15中的熱固性樹脂組成物11硬化的溫度,對壓合物15加熱使其硬化。然後,用切刀19裁切成預定的大小,連續地得到在表面積層有金屬箔3的複合積層板A。符號171為配設在加熱硬化爐17內的移送輥。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.
又,做為以積層輥14壓合之條件並無特別限定,可依所用的玻璃不織布10與玻璃織布的種類與熱固性樹脂組成物11的黏度等而適宜調整。又,加熱硬化的溫度與時間等之條件,並無特別限定,可依使用的熱固性樹脂組成物11的成分比例與所要硬化的硬化程度而適宜設定。亦可在裁切後進一步進行用以促進此積層板A的硬化之加熱(後硬化)。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.
上述係熱固性樹脂含浸玻璃不織布12的片數為二片的情況,而熱固性樹脂含浸玻璃不織布12的片數可為一片,亦可為三片以上。又,上述係金屬箔13的片數為二片,亦可為一片,於熱固性樹脂含浸玻璃不織布12為複數片的情況,熱固性樹脂含浸玻璃不織布彼此之間亦可進一步積層金屬箔。又,不織布基材及織布基材並非限於使用玻璃纖維者,也可為使用其他材質的纖維者。再者,若熱固性 樹脂組成物含有濕潤分散劑,其調配量相對於無機填充材而言為0.05~5質量%,則無機填充材可在熱固性樹脂含浸玻璃織布9與熱固性樹脂含浸玻璃不織布12中均勻分散。因此,複合積層板不易發生翹曲,且可提高焊接耐熱性。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.
使用上述的複合積層板之本發明的印刷配線板,可藉由在上述複合積層板表面設置導體圖案而形成。此情況下,可對上述覆金屬箔積層板施行藉由加成(additive)法或減去(substractive)法等之電路加工處理或通孔(through hole)加工而加工成印刷配線板。又,使用複合積層板之本發明的電路基板,可藉由在上述複合積層板設置電氣電子電路而形成。此情況下,可用由上述覆金屬箔積層板所形成的印刷配線板之導體圖案來形成電氣電子電路。又,使用複合積層板之本發明的LED搭載用電路基板可藉由在上述複合積層板設置LED搭載用電氣電子電路而形成。此情況下,可用上述電路基板的電氣電子電路做為LED搭載用的電氣電子電路而形成。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.
其次,由於本發明的積層板(包含複合積層板)A係對不織布層1以無機填充材高度填充而調配所成,故可做成高的導熱率,為可使熱立即擴散到積層板A的全體之散熱性高者。因而,由本發明的積層板A所形成的覆金屬箔積層板、印刷配線板、電路基板亦可發揮相同的作用效果。藉由搭載LED等會發熱的電氣電子零件於此等覆金屬箔積層板等,由電氣電子零件所產生的熱會容易傳導而擴散到導熱性高的覆金屬箔積層板、印刷配線板、電路基板。其結果,覆金屬箔積層板、印刷配線板、電路基板的散熱性會變高而可降低電氣電子零件因熱而劣化,可謀求增長電氣 電子零件的使用壽命。又,本發明之LED搭載用電路基板,藉由搭載LED,可使由LED所產生的熱容易地傳導並擴散。其結果,LED搭載用電路基板的散熱性變高,可減低LED之熱劣化,而可謀求增長LED的使用壽命。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.
又,於本發明之積層板A中,係於構成不織布層1的熱固性樹脂組成物中調配三水鋁石型氫氧化鋁粒子(A),而且以預定量調配平均粒徑小且具有預定的粒度分布的微粒子成分(B)。因此,可抑制於積層板A的鑽孔加工時之鑽頭刀刃的磨損,其結果,可增長鑽頭的使用壽命。又,即使應用在用以形成通孔的鑽孔加工,於所形成的孔之內面不易形成凹凸,此孔的內面可平滑地形成。因此,在孔的內面施行孔電鍍而形成通孔時,可賦予此通孔高的導通可靠性。又,藉由調配導熱性優異的微粒子成分(B),可顯著地提高積層板A的導熱性。又,由於調配小粒徑的微粒子成分(B),故不會使積層板的鑽孔加工性顯著地降低。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.
本發明之積層板A可較佳地使用於搭載於液晶顯示器之LED背光單元的印刷配線基板、LED照明裝置用之電路基板等之要求高散熱性的用途。在此種LED搭載用途中,高散熱基板是必要的,宜為導熱率為0.9W/m‧K以上,較佳為1.5W/m‧K以上的高散熱基板。具體而言,做為LED的用途之一,可舉出如圖3所示之搭載於液晶顯示器的直下式等的LED背光單元20。圖3中之LED背光單元20,係在由上述積層板A或由上述積層板A所形成的電路基板21上排列著多數的安裝有複數(圖3中為3個)的LED22之LED模組23所構成。藉由將此種電路基板21配設於液晶面板的背面,可使用做為液晶顯示器等的背光。又,用本 發明的積層板A,可形成如圖4(a)(b)所示般之搭載於液晶顯示器的側照(edge)型LED背光單元20。圖4(a)(b)中之LED背光單元20,係在上述積層板A或由上述積層板A所形成的細長形的電路基板21上安裝有複數的LED22之一對的LED模組23所構成。此種LED背光單元20,藉由使各LED模組23配設於導光板24等的上下(或左右),可做為液晶顯示器等的背光使用。邊端型的LED背光單元20,與正下方方式的LED背光單元20相比較,係高密度地設置LED,故較佳為使用本發明的積層板A般的散熱性高者。在向來所廣泛普及的型式的液晶顯示器中,做為液晶顯示器的背光,冷陰極管(CCFL)方式的背光一向廣為使用。然而,近年來,基於與冷陰極管方式的背光相比較,色域可較廣,畫質可提高,且不使用水銀而環境負擔較小,進而可達成薄型化諸優點的考量,上述般的LED背光單元積極地被開發著。LED模組通常比冷陰極管消耗較多電力,因而發熱量多。做為如此之須要求高散熱性的電路基板21,藉由使用本發明的積層板A,可大幅改善散熱的問題。因而可提高LED的發光效率。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.
又,可使用本發明的積層板A形成LED照明裝置。LED照明裝置,可在上述積層板A或由上述積層板A所形成的電路基板21上安裝複數的LED,並具備有用以使此LED發光的供電部等而形成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.
以下,藉由實施例就本發明進行具體說明。Hereinafter, the present invention will be specifically described by way of examples.
做為不織布基材,係使用厚度0.6mm的玻璃不織布 (VILENE(股)製,結著劑為環氧矽烷等,結著劑的調配量,相對於玻璃纖維100質量份而言,為5~25質量份)。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.
做為織布基材,係用厚度0.18mm的玻璃布(日東紡(股)製之7628)。As a woven base material, a glass cloth having a thickness of 0.18 mm (7628 manufactured by Nitto Spin Co., Ltd.) was used.
做為熱固性樹脂,係用含有做為樹脂成分之雙酚A型環氧樹脂、做為硬化劑成分之酚醛清漆樹脂者。雙酚A型環氧樹脂係使用850S(大日本油墨化學工業公司製),酚醛清漆樹脂係使用TD-2090-60M(大日本油墨化學工業公司製)。此等之調配比例為相對於雙酚A型環氧樹脂100質量份而言酚醛清漆樹脂為40質量份。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.
做為無機填充材的三水鋁石型氫氧化鋁粒子(A),係使用住友化學股份有限公司製之平均粒徑(D50 )為12μm者。做為無機填充材的微粒子成分(B),係使用住友化學股份有限公司製之平均粒徑(D50 )為1.5μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係粒徑5μm以上為5質量%、粒徑1μm以上小於5μm為30質量%、粒徑小於1μm為65質量%。又,此微粒子成分(B)中破碎狀的氧化鋁粒子(平均長寬比1.6)相對於總量而言係含有60質量%,其餘為球狀的氧化鋁粒子(平均長寬比1.1)的比例。又,無機填充材,以體積比計,相對於三水鋁石型氫氧化鋁粒子(A)100體積份而言,係使微粒子成分(B)為20體積份的比例而調配(體積比1:0.2)。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).
又,相對於熱固性樹脂100體積份而言,使無機填充材為80體積份的比例調配而調製不織布層用之熱固性樹脂組成物。又,以不織布層用的熱固性樹脂清漆含浸塗布量60g/m2 ,厚度400μm的玻璃不織布(VILENE製之玻璃不織 布,結著劑為環氧矽烷等,結著劑之調配比例,相對於玻璃纖維100質量份而言,為5~25質量份),得到不織布層用的預浸物。另一方面,對塗布量200g/m2 、厚度180μm的玻璃布(織布)(日東紡(股)製之7628),以於上述熱固性樹脂中含有氫氧化鋁(住友化學(股)製、D50 :4.3μm)之熱固性樹脂清漆含浸玻璃布,做成為半硬化狀態,藉此製作成織布層用的預浸物。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.
又,不織布層用之熱固性樹脂清漆之調製,係相對於不織布層用的熱固性樹脂組成物100質量份而言調配做為溶劑之甲乙酮6質量份的比例而調製。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.
又,織布層用的熱固性樹脂清漆之調製,首先,相對於上述不織布用的熱固性樹脂100體積份而言以10體積份的比例調配氫氧化鋁,而調製成織布層用的熱固性樹脂組成物。接著,相對於此織布層用的熱固性樹脂組成物100質量份而言,以6質量份的比例調配做為溶劑之甲乙酮,調製成織布層用的熱固性樹脂清漆。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.
接著,疊合2片不織布層用的預浸物,分別在其兩外表面,依序覆以織布層用的預浸物1片與厚度0.018mm的銅箔而得到積層體。將此積層體包夾於2片金屬板間,藉由在溫度180℃、壓力0.3kPa(30kgf/m2 )的條件下進行加熱成形,得到厚度1.0mm的覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份而言以90體積份的比例調配無機填充材而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例1相同的做法得到覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份而言以120體積份的比例調配無機填充材而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例1相同的做法得到覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份而言以140體積份的比例調配無機填充材而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例1相同的做法得到覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份而言以150體積份的比例調配無機填充材而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例1相同的做法得到覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份而言以70體積份的比例調配無機填充材而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例1相同的做法得到覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份而言以160體積份的比例調配無機填充材而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例1相同的做法得到覆銅複合積層板。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.
除了做為三水鋁石型氫氧化鋁粒子(A)係使用平均粒徑(D50 )為8.5μm者之外,係以與實施例3相同的做法得到覆銅複合積層板。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.
除了做為三水鋁石型氫氧化鋁粒子(A)係使用平均粒徑(D50 )為15μm者之外,係以與實施例3相同的做法得到覆銅複合積層板。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.
除了做為三水鋁石型氫氧化鋁粒子(A)係使用平均粒徑(D50 )為1.5μm者之外,係以與實施例3相同的做法得到覆銅複合積層板。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.
除了做為三水鋁石型氫氧化鋁粒子(A)係使用平均粒徑(D50 )為16μm者之外,係以與實施例3相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為0.8μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為1質量%、粒徑1μm以上小於5μm為25質量%、粒徑小於1μm為74質量%。除此之外,係以與實施例1相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為0.2μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為0質量%、粒徑1μm以上小於5μm為12質量%、粒徑小於1μm為88質量%。除此之外,係以與實施例1相 同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為1.6μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為4質量%、粒徑1μm以上小於5μm為36質量%、粒徑小於1μm為60質量%。除此之外,係以與實施例1相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為1.5μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為6質量%、粒徑1μm以上小於5μm為24質量%、粒徑小於1μm為70質量%。除此之外,係以與實施例1相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為1.5μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為3質量%、粒徑1μm以上小於5μm為43質量%、粒徑小於1μm為54質量%。除此之外,係以與實施例1相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為1.5μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為23質量%、粒徑1μm以上小於5μm為29質量%、粒徑小於1μm為48質量%。除此之外,係以與實施例1相同的做法得到覆銅複合積層板。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.
做為無機填充材係使用以體積比計相對於三水鋁石型氫氧化鋁粒子(A)100體積份調配35體積份比例之微粒子成分(B)者(體積比1:0.35)。又,做為微粒子成分(B),係使用含有40質量%的破碎狀氧化鋁粒子者。除此之外,係以與實施例3相同的做法得到覆銅複合積層板。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.
做為無機填充材係使用以體積比計相對於三水鋁石型氫氧化鋁粒子(A)100體積份調配50體積份比例之微粒子成分(B)者(體積比1:0.5)。除此之外,係以與實施例10相同的做法得到覆銅複合積層板。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.
做為無機填充材係使用以體積比計相對於三水鋁石型氫氧化鋁粒子(A)100體積份調配10體積份比例之微粒子成分(B)者(體積比1:0.1)。除此之外,係以與實施例11相同的做法得到覆銅複合積層板。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.
做為無機填充材係使用以體積比計相對於三水鋁石型氫氧化鋁粒子(A)100體積份調配以60體積份比例之微粒子成分(B)者(體積比1:0.6)。除此之外,係以與實施例11相同的做法得到覆銅複合積層板。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.
除了做為微粒子成分(B)係使用含有25質量%的破碎狀氧化鋁粒子者之外,係以與實施例3相同的做法得到覆銅複合積層板。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.
藉由圖2所示之製造方法連續形成覆銅複合積層板。 做為熱固性樹脂組成物,係使用含有環氧乙烯酯樹脂與自由基聚合性不飽和單體與聚合起始劑者。亦即,於4口燒瓶中,加入環氧當量為400克/當量的四溴雙酚A型環氧樹脂(「商品名EPICLON 153」〔大日本油墨化學工業(股)製〕)400質量份、分子量為3500且鍵結丙烯腈為27%、羧基1.9個/分子的丁二烯與丙烯腈的分子兩末端有羧基的HYCARCTBN 1300X13〔B.F.GooDrich Chemical公司製〕92質量份、甲基丙烯酸82質量份(環氧基數:總羧基數=1:1)、氫醌0.29質量份、與三苯膦0.58質量份,於110℃下進行反應。然後,經確認酸價已成為10mg-KOH/g以下後,再添加苯乙烯309質量份。然後,添加乙醯丙酮1.32質量份,得到環氧乙烯酯樹脂組成物。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.
接著,對此環氧乙烯酯樹脂組成物100體積份,添加與實施例1相同的無機填充材80體積份、第三丁基過氧化苯甲酸酯(「商品名PERBUTYL Z」〔日本油脂(股)製〕)1.0體積份的比例,用均質機均勻混合,藉此製作不織布層用的熱固性樹脂組成物。用此不織布層用的熱固性樹脂組成物含浸不織布基材,做成為半硬化狀態,藉此製作成不織布層用的預浸物。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.
又,於上述環氧乙烯酯樹脂組成物100體積份中添加上述第三丁基過氧化苯甲酸酯1.0體積份的比例,用均質機均勻混合,藉此製作成織布層用的熱固性樹脂組成物。用此織布層用的熱固性樹脂組成物含浸與實施例1相同的織布基材,做成為半硬化狀態,藉此製作成織布層用的預浸物。然後,用不織布層用的預浸物與織布層用的預浸物,以與實施例1相同的做法形成覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份調配以無機填充材90體積份的比例而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份調配以無機填充材120體積份的比例而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份調配以無機填充材140體積份的比例而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份調配以無機填充材150體積份的比例而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份調配以無機填充材70體積份的比例而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
除了相對於熱固性樹脂100體積份調配以無機填充材160體積份的比例而調製成不織布層用的熱固性樹脂組成物之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
除了做為三水鋁石型氫氧化鋁粒子(A)係使用平均粒 徑(D50 )為8.5μm者之外,係以與實施例14相同的做法得到覆銅複合積層板。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.
除了做為三水鋁石型氫氧化鋁粒子(A)係使用平均粒徑(D50 )為15μm者之外,係以與實施例14相同的做法得到覆銅複合積層板。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.
除了做為三水鋁石型氫氧化鋁粒子(A)係使用平均粒徑(D50 )為1.5μm者之外,係以與實施例14相同的做法得到覆銅複合積層板。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.
除了做為三水鋁石型氫氧化鋁粒子(A)係使用平均粒徑(D50 )為16μm者之外,係以與實施例14相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為0.8μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為1質量%、粒徑1μm以上小於5μm為25質量%、粒徑小於1μm為74質量%。除此之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為0.2μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為0質量%、粒徑1μm以上小於5μm為12質量%、粒徑小於1μm為88質量%。除此之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為1.6μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為7質量%、粒徑1μm以上小於5μm為35質量%、粒徑小於1μm為58質量%。除此之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為1.5μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為5質量%、粒徑1μm以上小於5μm為33質量%、粒徑小於1μm為62質量%。除此之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為1.5μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為8質量%、粒徑1μm以上小於5μm為42質量%、粒徑小於1μm為50質量%。除此之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B)係使用平均粒徑(D50 )為1.5μm的氧化鋁粒子(氧化鋁)。此微粒子成分(B)的粒度分布係:粒徑5μm以上為17質量%、粒徑1μm以上小於5μm為40質量%、粒徑小於1μm為43質量%。除此之外,係以與實施例12相同的做法得到覆銅複合積層板。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.
做為無機填充材係使用以體積比計相對於三水鋁石型 氫氧化鋁粒子(A)100體積份調配35體積份比例之微粒子成分(B)者(體積比1:0.35)。又,做為微粒子成分(B)係使用含有40質量%的破碎狀氧化鋁粒子者。除此之外,係以與實施例14相同的做法得到覆銅複合積層板。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.
做為無機填充材係使用以體積比計相對於三水鋁石型氫氧化鋁粒子(A)100體積份調配50體積份比例之微粒子成分(B)者(體積比1:0.5)。除此之外,係以與實施例21相同的做法得到覆銅複合積層板。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.
做為無機填充材係使用以體積比計相對於三水鋁石型氫氧化鋁粒子(A)100體積份調配10體積份比例之微粒子成分(B)者(體積比1:0.1)。除此之外,係以與實施例21相同的做法得到覆銅複合積層板。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.
做為無機填充材,係使用以體積比計相對於三水鋁石型氫氧化鋁粒子(A)100體積份調配以60體積份比例之微粒子成分(B)者(體積比1:0.6)。除此之外,係以與實施例21相同的做法得到覆銅複合積層板。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.
做為微粒子成分(B),係使用含有破碎狀的氧化鋁粒子25質量%者之外,係以與實施例21相同的做法得到覆銅複合積層板。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.
調配水鋁石(C)18體積份,各成分的調配比例如圖8所示。除此之外,係以與實施例21相同的做法得到覆銅複合 積層板。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.
藉由水中替換法測定所得之覆銅積層板的密度,又,藉由DSC(示差掃描熱量測定)測定比熱,再者,藉由雷射閃光(laser flash)法測定熱擴散率。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.
然後,由下式求出導熱率。Then, the thermal conductivity was obtained from the following formula.
導熱率(W/m‧K)=密度(kg/m3 )×比熱(kJ/kg‧K)×熱擴散率(m2 /S)×1000Thermal conductivity (W/m‧K) = density (kg/m 3 ) × specific heat (kJ/kg‧K) × thermal diffusivity (m 2 /S) × 1000
用得到的覆銅積層板,對依據JIS C 6481製作的試驗片,在設定於200~240℃的附設有空氣循環裝置的恒溫槽中處理1小時之時,測定在銅箔及積層板上之發生鼓起及剝離的溫度。又,烤箱耐熱試驗的評價,於做為LED搭載用的基板之用途中,宜為至少220℃以上,若低於220℃則會有耐熱性不足之虞。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.
疊合3片所得的覆銅積層板,用鑽頭(鑽頭徑0.5mm、偏斜角35°)以6000轉/分鐘穿設6000個孔之後的鑽頭刀刃之磨損率,係求出以相對於鑽孔加工前鑽頭刀刃的大小(面積)的鑽孔加工導致磨損的鑽頭刀刃的(面積)比例(百分率)進行評價。又,磨損率為40%以下者判定為○、磨損率大於40%、小於60%者判定為△、磨損率為60%以上者判定為×。又,鑽頭刀刃的磨損率愈小鑽頭刀刃的損失愈小,謂之為鑽孔加工性高。又,鑽頭刀刃只要殘存有10%即可使用,上述般穿設3000個孔後的鑽頭刀刃之磨損率只要在90%以下,鑽頭即無須頻繁更換。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.
進行20片以上的成形,算出表面的凹凸、鼓起等以目視可確認的不良的數目,於發生5%以上的不良時判定為△,發生10%以上的不良時判定為×。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‧‧‧積層板A‧‧‧ laminate
1‧‧‧不織布層1‧‧‧non-woven layer
2‧‧‧織布層2‧‧‧Weaving layer
3‧‧‧金屬箔3‧‧‧metal foil
9‧‧‧熱固性樹脂含浸玻璃織布9‧‧‧ thermosetting resin impregnated glass woven fabric
10‧‧‧玻璃不織布10‧‧‧glass non-woven fabric
11‧‧‧熱固性樹脂組成物11‧‧‧ thermosetting resin composition
12‧‧‧熱固性樹脂含浸玻璃不織布12‧‧‧ thermosetting resin impregnated glass non-woven fabric
13‧‧‧金屬箔13‧‧‧metal foil
14‧‧‧積層輥14‧‧‧Laminating rolls
15‧‧‧壓合物15‧‧‧Compound
17‧‧‧加熱硬化爐17‧‧‧heating and hardening furnace
18‧‧‧輥18‧‧‧ Roll
19‧‧‧切刀19‧‧‧Cutter
20‧‧‧LED背光單元20‧‧‧LED backlight unit
21‧‧‧電路基板21‧‧‧ circuit board
22‧‧‧LED22‧‧‧LED
23‧‧‧LED模組23‧‧‧LED module
24‧‧‧導光板24‧‧‧Light guide
171‧‧‧移送輥171‧‧‧Transfer roller
圖1係表示本發明之積層板的實施形態之一例的剖面圖。Fig. 1 is a cross-sectional view showing an example of an embodiment of a laminated plate of the present invention.
圖2係表示本發明之積層板之製造方法的實施形態的一例之概略圖。Fig. 2 is a schematic view showing an example of an embodiment of a method for producing a laminated board of the present invention.
圖3係表示本發明之LED背光單元的實施形態的一例之概略圖。Fig. 3 is a schematic view showing an example of an embodiment of an LED backlight unit of the present invention.
圖4係表示本發明之LED背光單元的實施形態之另一例,圖4(a)、(b)為概略圖。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‧‧‧積層板A‧‧‧ laminate
1‧‧‧不織布層1‧‧‧non-woven layer
2‧‧‧織布層2‧‧‧Weaving layer
3‧‧‧金屬箔3‧‧‧metal foil
Claims (10)
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KR (1) | KR101715717B1 (en) |
CN (1) | CN103582564B (en) |
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JP6277543B2 (en) * | 2013-11-27 | 2018-02-14 | パナソニックIpマネジメント株式会社 | Composite laminate and method for manufacturing the same |
CN105916308A (en) * | 2016-06-30 | 2016-08-31 | 广德宝达精密电路有限公司 | Method for processing pressure-resisting printed board for protecting circuit |
CN106365507A (en) * | 2016-08-23 | 2017-02-01 | 廊坊市高瓷新材料科技有限公司 | Organic ceramic substrate composition, organic ceramic substrate, and copper-clad plate |
KR101924298B1 (en) | 2018-05-18 | 2018-11-30 | 양선일 | Non woven for LED illumination device, Circuit board for LED illumination device containing the same and LED illumination device using the same |
JP2020170828A (en) * | 2019-04-05 | 2020-10-15 | Tdk株式会社 | Substrate and laminated substrate |
CN115073864B (en) * | 2022-07-05 | 2023-11-10 | 陕西生益科技有限公司 | Magneto-dielectric non-woven fabric prepreg, copper-clad plate containing same and application |
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JPH10182985A (en) * | 1996-12-24 | 1998-07-07 | Matsushita Electric Works Ltd | Resin composition for laminated plate and laminated plate |
TW200907493A (en) * | 2007-05-18 | 2009-02-16 | Denki Kagaku Kogyo Kk | Metal base circuit substrate |
TW201008778A (en) * | 2008-05-19 | 2010-03-01 | Panasonic Elec Works Co Ltd | Laminate, metal-foil-clad laminate, circuit board, and circuit board for led mounting |
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JPH11179841A (en) * | 1997-12-24 | 1999-07-06 | Shin Kobe Electric Mach Co Ltd | Composite metal-foiled laminated body |
JP3415610B2 (en) * | 2001-09-27 | 2003-06-09 | 松下電工株式会社 | Resin composition for copper clad laminate and copper clad laminate |
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WO2009142192A1 (en) * | 2008-05-19 | 2009-11-26 | パナソニック電工株式会社 | Laminate, metal-foil-clad laminate, circuit board, and circuit board for led mounting |
JP2010212210A (en) * | 2009-03-12 | 2010-09-24 | Sekisui Chem Co Ltd | Insulating sheet, laminated plate, and multilayer laminated plate |
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JPH10182985A (en) * | 1996-12-24 | 1998-07-07 | Matsushita Electric Works Ltd | Resin composition for laminated plate and laminated plate |
TW200907493A (en) * | 2007-05-18 | 2009-02-16 | Denki Kagaku Kogyo Kk | Metal base circuit substrate |
TW201008778A (en) * | 2008-05-19 | 2010-03-01 | Panasonic Elec Works Co Ltd | Laminate, metal-foil-clad laminate, circuit board, and circuit board for led mounting |
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WO2012164997A1 (en) | 2012-12-06 |
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JP2013010344A (en) | 2013-01-17 |
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