WO2016101535A1 - 一种有机硅树脂组合物及使用它的预浸料、层压板、覆铜板以及铝基板 - Google Patents

一种有机硅树脂组合物及使用它的预浸料、层压板、覆铜板以及铝基板 Download PDF

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WO2016101535A1
WO2016101535A1 PCT/CN2015/080474 CN2015080474W WO2016101535A1 WO 2016101535 A1 WO2016101535 A1 WO 2016101535A1 CN 2015080474 W CN2015080474 W CN 2015080474W WO 2016101535 A1 WO2016101535 A1 WO 2016101535A1
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silicone resin
resin composition
parts
composition according
laminate
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PCT/CN2015/080474
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English (en)
French (fr)
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叶素文
唐国坊
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广东生益科技股份有限公司
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Priority to KR1020177020792A priority Critical patent/KR101887841B1/ko
Priority to JP2017533822A priority patent/JP6514335B2/ja
Priority to US15/539,467 priority patent/US10308808B2/en
Priority to EP15871611.8A priority patent/EP3239244B1/en
Publication of WO2016101535A1 publication Critical patent/WO2016101535A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • 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
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs
    • 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
    • B32B2307/304—Insulating
    • 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
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0162—Silicon containing polymer, e.g. silicone
    • 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
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0358—Resin coated copper [RCC]
    • H—ELECTRICITY
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    • 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
    • H05K2201/06—Thermal details
    • H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important

Definitions

  • the present invention relates to a silicone resin composition, and more particularly to a silicone resin composition having high heat resistance, halogen-free and phosphorus-free, and low coefficient of thermal expansion, and a prepreg, a laminate, a copper clad laminate, and an aluminum substrate using the same.
  • PCBs are increasingly developing in the direction of high density, high reliability, multi-layer, low cost and automated continuous production, which puts higher heat resistance and reliability for PCB substrates.
  • FR-4 which has been mainly made of epoxy resin, has been disadvantageous in high temperature resistance and has been incapable of applying high temperature and high reliability circuits.
  • Silicone is a thermosetting resin and one of its most outstanding properties is its excellent thermal oxidative stability. This is mainly because the silicone resin is based on Si-O-Si, so the decomposition temperature is high, it can be used for a long time at 200-250 ° C without decomposition or discoloration, and the heat-resistant filler can withstand higher temperatures.
  • silicone resin has excellent electrical insulation properties. Since silicone resin does not contain polar groups, its dielectric constant and dielectric loss tangent have little variation over a wide temperature range and frequency range, and silicone is superior. Electrical insulation. Since silicone has less carbonizable components, its arc resistance and corona resistance are also outstanding. Silicone has outstanding weather resistance and is unmatched by any organic resin. Silicone is resistant to yellowing even under intense UV light.
  • a silicone resin composition comprising, by weight:
  • the content of the catalyst is, for example, 0.0005 part, 0.001 part, 0.005 part, 0.01 part, 0.05 part, 0.1 part, 0.5 part, 0.9 part, 1.3 part, 1.7 part, and 1.9 part.
  • the auxiliary agent is, for example, 0.001 parts, 0.005 parts, 0.01 parts, 0.05 parts, 0.1 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts or 9.5 parts.
  • the condensation type silicone resin is mainly any one of a methyl silicone resin, a methylphenyl silicone resin, or a phenyl silicone resin, or a mixture of at least two.
  • the condensation type silicone resin is any one of dehydration condensation, dealcohol condensation condensation or dehydrogenation condensation.
  • the meaning is one, and its reaction structure is as follows:
  • the catalyst is zinc naphthenate, tin naphthenate, cobalt naphthenate, iron naphthenate, bismuth naphthenate, zinc carboxylate, tin carboxylate, cobalt carboxylate, iron carboxylate, Any one or a combination of at least two of cerium carboxylate, perfluorosulfonic acid, phosphazene chloride, amines, quaternary ammonium base, zinc octoate, zinc isooctanoate, titanate or anthraquinone.
  • the auxiliary agent includes any one of a silane coupling agent, a titanate coupling agent, or a dispersing agent, or a mixture of at least two.
  • the silicone resin composition further includes a filler.
  • the filler includes silica, alumina, aluminum hydroxide, boron nitride, aluminum nitride, barium sulfate, mica powder, zinc borate, titanium dioxide, mica powder, silicon nitride or silicon carbide. Arbitrarily One or a mixture of at least two.
  • the content of the filler is 0 to 60 parts by weight, for example, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight.
  • An exemplary silicone resin composition comprising, by weight:
  • the silicone resin composition comprises, by weight:
  • the silicone resin composition may further contain various additives, and specific examples thereof include flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, or lubricants. Wait. These various additives may be used singly or in combination of two or more kinds.
  • Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing a silicone resin composition as described above in a solvent.
  • the solvent in the present invention is not particularly limited, and specific examples thereof include methanol and ethanol.
  • Alcohols such as butanol, ethyl cellosolve, butyl cellosolve, ethers such as ethylene glycol-methyl ether, carbitol, butyl carbitol, acetone, methyl ethyl ketone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and mesitylene; esters such as ethoxyethyl acetate and ethyl acetate; N,N-dimethylformamide a nitrogen-containing solvent such as N,N-dimethylacetamide or N-methyl-2-pyrrolidone.
  • solvents may be used alone or in combination of two or more.
  • aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, methyl ethyl ketone, methyl ethyl ketone, and methyl group.
  • a ketone flux such as butyl ketone or cyclohexanone is used in combination.
  • a third object of the present invention is to provide a prepreg comprising a reinforcing material and a silicone resin composition as described above adhered to the reinforcing material by impregnation and drying.
  • An exemplary prepreg is prepared by:
  • a fourth object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • a fifth object of the present invention is to provide a copper clad laminate comprising at least one laminated prepreg as described above and laminated on one side of the laminated prepreg Or copper foil on both sides.
  • a sixth object of the present invention is to provide an aluminum-based copper clad laminate comprising a copper foil layer and an aluminum base layer, and an insulating layer is provided between the copper foil layer and the aluminum base layer, the insulating layer being composed of the silicone resin composition as described above, and Add a thermally conductive filler.
  • the thermally conductive filler is any one of tri-alumina, silica, silicon carbide, boron nitride, aluminum nitride or magnesium oxide or a mixture of at least two.
  • the present invention has the following beneficial effects:
  • the silicone resin composition obtained by compounding a silicone resin, a catalyst and an auxiliary agent has high heat resistance (T300>60 min), halogen-free and phosphorus-free, and low coefficient of thermal expansion (the coefficient of thermal expansion (CTE) is less than 1.0%) and high peel strength characteristics;
  • the silicone resin composition of the invention has the advantages of no halogen, no phosphorus, low smoke, low toxicity, self-extinguishing and environmental protection, and provides new ideas and new methods for the flame retardant field of the laminate and the copper clad laminate;
  • a flat and smooth E-glass cloth with a thickness of 0.1 mm was selected, and the above glue was uniformly applied, and baked in an oven at 170 ° C for 5 minutes to obtain a prepreg.
  • Eight of the above prepregs were superposed, and 35 ⁇ m of copper foil was attached thereto, and placed in a vacuum hot press at 3 MPa pressure and 220 ° C for 3 hours to obtain a laminate.
  • a prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as in Example 1 except that the resin glue was used.
  • a prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as in Example 1 except that the resin glue was used.
  • a prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as in Example 1 except that the resin glue was used.
  • methyl phenyl vinyl silicone resin (1.0% vinyl content) was weighed, dissolved in 70 parts of solvent, dissolved uniformly, and then added to 3.1 parts of methylphenyl hydrogen hydride oil (hydrogen content: 1.2%). After stirring at a high speed, 0.001 part of hexynyl alcohol was weighed, and after stirring for 30 minutes, 0.01 part of platinum-methylphenyl vinyl complex was added. After stirring for 30 min, 1.5 parts of silane coupling agent ⁇ -methacryloxypropyltrimethoxysilane coupling agent (provided by Hubei Wuda Silicone New Material Co., Ltd.), 23 parts of silicon micropowder, and stirring at room temperature for 1 h were added. , emulsified for 20min, obtained silicone resin glue.
  • silane coupling agent ⁇ -methacryloxypropyltrimethoxysilane coupling agent provided by Hubei Wuda Silicone New Material Co., Ltd.
  • a prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as in Example 1 except that the resin glue was used.
  • a prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as in Example 1 except that the resin glue was used.
  • a prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as in Example 1 except that the resin glue was used.
  • a prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as in Example 1 except that the resin glue was used.
  • Test method Using IPC-TM-6502.4.24, the test data is shown in the table below.
  • Test method Using IPC-TM-6502.4.24.1, the test data is shown in the table below.
  • Test method Refer to the US UL94 standard, the test data is shown in the table below.
  • Test method Test using IPC-TM-6502.4.8 method, the test data can be found in the table below.
  • Examples 1 to 4 have both a very low coefficient of thermal expansion, a high thermal delamination time, a halogen-free and phosphorus-free flame retardant and a good peel strength, and satisfy the copper-clad laminate. demand.
  • Comparative Example 1 Compared with Example 2, since the silicone resin is methylphenyl vinyl silicone resin, the addition curing method is used, the expansion coefficient is large after curing, the peel strength is low, and the flame retarding effect is not prominent; Ratio 2 Compared with Example 2, the filler content was out of range, resulting in a decrease in peel strength with copper foil and a decrease in heat delamination time; Comparative Example 3 was used in comparison with Example 3, and the amount of the auxiliary agent was not in the protection range.
  • the agents are small molecules, and the excessive addition amount causes the laminate to release a large amount of small molecules at a high temperature, so that the coefficient of thermal expansion increases and the delamination time is shortened; compared with the example 4, the R/Si value exceeds In the range, the larger the R/Si, the lower the crosslink density of the resin, and the more prone to the thermoplastic resin, the higher the coefficient of thermal expansion, the lower the stability at high temperatures, and the lower the thermal delamination time.

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Abstract

本发明涉及一种有机硅树脂组合物及使用它的预浸料、层压板及铝基板。所述有机硅树脂组合物按重量份数包括：缩合型硅树脂100份；催化剂0.0001～2份；助剂0.001～10份。所述有机硅树脂组合物具有高耐热性、无卤无磷阻燃、与铜箔有较好的剥离强度以及低膨胀系数等优点，可用于制备高性能印制电路用预浸料、层压板及铝基板。

Description

一种有机硅树脂组合物及使用它的预浸料、层压板、覆铜板以及铝基板 技术领域
本发明涉及一种有机硅树脂组合物，具体涉及一种高耐热、无卤无磷和低热膨胀系数的有机硅树脂组合物及使用它的预浸料、层压板、覆铜板以及铝基板。
背景技术
随着电子信息技术的飞速发展，PCB越来越向高密度、高可靠、多层化、低成本和自动化连续生产的方向发展，对PCB用基板的耐热性及可靠性提出了更高的要求。而一直以来以环氧树脂为主体的FR-4由于耐高温性差的缺点，在要求耐高温以及高可靠性电路的应用已经力不从心。
硅树脂是一种热固性树脂，其最突出的性能之一是优异的热氧化稳定性。这主要是由于硅树脂是以Si-O-Si为骨架，因此分解温度高，可在200-250℃下长期使用而不分解或变色，并且配合耐热填料能耐更高温度。
同时硅树脂具有优异的电绝缘性能，由于硅树脂不含极性基团，故其介电常数及介电损耗角正切值在宽广的温度范围及频率范围内变化很小，同时硅树脂具有优越的电气绝缘性。由于硅树脂的可碳化成分较少，故其耐电弧及耐电晕性能也十分突出。硅树脂具有突出的耐候性，是任何一种有机树脂所望尘莫及的。即使在紫外线强烈照射下，硅树脂也耐泛黄。
目前，为了赋予层压板阻燃性，使用并用溴系阻燃剂的配方。可是，由于近来对环境问题的呼声的提高，渴求不使用卤系化合物的树脂组合物，进一步进行着代替卤系阻燃剂的磷化合物研究。磷化合物在燃烧时也可能产生膦等有毒化合物，因此期望开发出即使不使用卤系化合物和磷化合物也具有阻燃性、 且具有低的热膨胀系数的层压板。而硅树脂在不加入卤素及含磷阻燃剂时其本身也具有非常好的阻燃性能。
鉴于硅树脂高耐热、无卤无磷阻燃、兼备优越的电绝缘性能、突出的耐候性能、同时固化完全的硅树脂还具有非常低的热膨胀系数(＜2.0％)，配合功能性填料其性能会更加优越。因此，用硅树脂体系制成层压板正好满足市场需求一种高耐热的无卤无磷(高的玻璃化转变温度＞200℃，低的Z轴方向的膨胀系数＜2.0％)的高性能印制电路用覆铜箔层压板。
发明内容
鉴于此，本发明的目的之一在于提供一种有机硅树脂组合物，其具有高耐热性、无卤阻燃以及低膨胀系数等优点。
为了达到上述目的，本发明采用了如下技术方案：
一种有机硅树脂组合物，所述有机硅树脂组合物按重量份数包括：
缩合型硅树脂     100份；
催化剂           0.0001～2份；
助剂             0.001～10份。
所述催化剂的含量例如为0.0005份、0.001份、0.005份、0.01份、0.05份、0.1份、0.5份、0.9份、1.3份、1.7份、1.9份。
所述助剂的含量例如为0.001份、0.005份、0.01份、0.05份、0.1份、0.5份、1份、1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份、5.5份、6份、6.5份、7份、7.5份、8份、8.5份、9份或9.5份。
在本发明中，所述缩合型硅树脂主要为甲基硅树脂、甲基苯基硅树脂或苯基硅树脂中的任意一种或者至少两种的混合物。
在本发明中，所述缩合型硅树脂为脱水缩合、脱醇缩合或脱氢缩合中的任 意一种，其反应结构如下所示：
Figure PCTCN2015080474-appb-000001
在本发明中，所述缩合型硅树脂为R/Si＝1.0～1.7(例如1.1、1.2、1.3、1.4、1.5、1.6或1.7)(摩尔比)和Ph/(Me+Ph)＝0～1.0(例如0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9或1.0)(摩尔比)的甲基硅树脂、甲基苯基硅树脂或苯基硅树脂中的任意一种或者至少两种的混合物，其中Ph代表苯基基团，Me代表甲基基团，R代表有机官能团-CH3、-Ph、-OCH3、-OCH2CH3、-H或-OH。在缩合型硅树脂中，R/Si(摩尔比)过小，Ph/Si(摩尔比)过低，硅树脂固化后柔软性差，漆膜变硬，而R/Si(摩尔比)过大，Ph/Si(摩尔比)过高层压板硬度低，固化慢，热固性低，故所述缩合型硅树脂优选为R/Si＝1.2～1.7(摩尔比)且Ph/(Me+Ph)＝0.2-0.6(摩尔比)的甲基苯基硅树脂。
在本发明中，所述催化剂为环烷酸锌、环烷酸锡、环烷酸钴、环烷酸铁、环烷酸铈、羧酸锌、羧酸锡、羧酸钴、羧酸铁、羧酸铈、全氟磺酸、氯化磷腈、胺类、季铵碱、辛酸锌、异辛酸锌、钛酸酯或胍类化合物等中的任意一种或者至少两种的组合。
在本发明中，所述助剂包括硅烷偶联剂、钛酸酯偶联剂或分散剂中的任意一种或者至少两种的混合物。
在本发明中，所述有机硅树脂组合物还包括填料。
在本发明中，所述填料包括二氧化硅、氧化铝、氢氧化铝、氮化硼、氮化铝、硫酸钡、云母粉、硼酸锌、二氧化钛、云母粉、氮化硅或碳化硅中的任意 一种或者至少两种的混合物。
在本发明中，所述填料的含量为0～60重量份，例如5重量份、10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份。
示例性的一种有机硅树脂组合物，所述有机硅树脂组合物按重量份数包括：
Figure PCTCN2015080474-appb-000002
优选地，所述有机硅树脂组合物按重量份数包括：
Figure PCTCN2015080474-appb-000003
本发明所述的“包括”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述有机硅树脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由……组成”。
例如，所述有机硅树脂组合物还可以含有各种添加剂，作为具体例，可以举出阻燃剂、抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
本发明的目的之二在于提供一种树脂胶液，其是将如上所述的有机硅树脂组合物溶解或分散在溶剂中得到。
作为本发明中的溶剂，没有特别限定，作为具体例，可以举出甲醇、乙醇、 丁醇等醇类，乙基溶纤剂、丁基溶纤剂、乙二醇-甲醚、卡必醇、丁基卡必醇等醚类，丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类，甲苯、二甲苯、均三甲苯等芳香族烃类，乙氧基乙基乙酸酯、醋酸乙酯等酯类，N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基-2-吡咯烷酮等含氮类溶剂。上述溶剂可以单独使用一种，也可以两种或者两种以上混合使用，优选甲苯、二甲苯、均三甲苯等芳香族烃类溶剂与丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类熔剂混合使用。
本发明的目的之三在于提供一种预浸料，其包括增强材料及通过含浸干燥后附着在增强材料上的如上所述的有机硅树脂组合物。
示例性的预浸料的制备方法为：
以如上所述的有机硅树脂组合物重量100份计算，加入甲苯或者二甲苯等有机溶剂制成固含量为50～70％(重量比)的树脂胶液，由增强材料如玻纤布浸渍该树脂胶液，然后在120～190℃下烘烤2～15分钟制备而得。
本发明的目的之四在于提供一种层压板，所述层压板含有至少一张如上所述的预浸料。
本发明的目的之五在于提供一种覆铜箔层压板，所述覆铜箔层压板包括至少一张叠合的如上所述的预浸料及压覆在叠合后的预浸料的一侧或两侧的铜箔。
本发明目的之六在于提供一种铝基覆铜板，包括铜箔层和铝基层，铜箔层和铝基层间设有绝缘层，所述绝缘层由如上所述的有机硅树脂组合物，并添加导热填料制成。
所述导热填料为三氧化铝、二氧化硅、碳化硅、氮化硼、氮化铝或氧化镁中的任意一种或者至少两种的混合物。
与已有技术相比，本发明具有如下有益效果：
(1)本发明通过将硅树脂、催化剂以及助剂复配，得到的有机硅树脂组合物具有高耐热(T300＞60min)、无卤无磷、低热膨胀系数(其热膨胀系数(CTE)小于1.0％)及较高的剥离强度的特点；
(2)本发明的有机硅树脂组合物具有无卤无磷、低烟、低毒、自熄和环保等优点，为层压板及覆铜板在阻燃领域提供了新思路和新方法；
(3)本发明的制备过程所有的工艺及设备为普通FR-4通用型，完全可以利用现有的生产设备来实施本发明，非常有利于产品的产业化。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
实施例1
称取R/Si＝1.1(摩尔比)，Ph/(Ph+Me)＝0(摩尔比)的甲基硅树脂100.0份，溶于60.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入异辛酸锌0.0001份，硅烷偶联剂γ-(2，3-环氧丙氧基)丙基三甲氧基硅烷(美国，道康宁公司提供)0.001份，搅拌混合均匀得到胶液。选取平整光洁、厚度为0.1mm的E-玻纤布，均匀涂覆上述胶液，在烘箱中用170℃烘烤5min得半固化片。将8张上述半固化片叠加，上下附上35μm的铜箔，置于真空热压机中在3MPa压力和220℃温度下压制3h得到层压板。
实施例2
称取R/Si＝1.4(摩尔比)，Ph/(Ph+Me)＝0.5(摩尔比)的甲基苯基硅树脂100.0份溶于70.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入硅微粉23.0份，乙酰丙酮钴0.1份，硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷偶联剂1.5份(湖北武大有机硅新材料股份有限公司提供)，搅拌均匀得胶 液。
除了使用该树脂胶液外，与实施例1同样进行，获得预浸料和厚度为1.0mm的双面覆铜层压板。
实施例3
称取R/Si＝1.7(摩尔比)，Ph/(Ph+Me)＝1.0(摩尔比)的苯基硅树脂100.0份溶于100.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入氧化铝50份，钛酸酯1.5份，硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷8.7份(湖北武大有机硅新材料股份有限公司提供)，搅拌均匀得胶液。
除了使用该树脂胶液外，与实施例1同样进行，获得预浸料和厚度为1.0mm的双面覆铜层压板。
实施例4
称取R/Si＝1.1(摩尔比)，Ph/(Ph+Me)＝0(摩尔比)的甲基硅树脂60.0份和R/Si＝1.7(摩尔比)，Ph/(Ph+Me)＝0.9(摩尔比)的甲基苯基硅树脂40.0份，溶于85.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入氧化铝25.0份，硅微粉10.0份，乙酰丙酮钴0.08份，硅烷偶联剂Y-甲基丙烯酰氧基丙基三甲氧基硅烷偶联剂1.5份(湖北武大有机硅新材料股份有限公司提供)，搅拌均匀得胶液。
除了使用该树脂胶液外，与实施例1同样进行，获得预浸料和厚度为1.0mm的双面覆铜层压板。
对比例1
称取甲基苯基乙烯基硅树脂100份(乙烯基含量为1.0％)，溶入70份溶剂中，溶解均匀后加入3.1份甲基苯基含氢硅油(含氢量为1.2％)，高速搅拌均匀后称取0.001份己炔醇，搅拌30min后加入0.01份铂-甲基苯基乙烯基络合物， 继续搅拌30min后加入硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷偶联剂1.5份(湖北武大有机硅新材料股份有限公司提供)，23份硅微粉，室温下搅拌1h，乳化20min，得硅树脂胶液。
除了使用该树脂胶液外，与实施例1同样进行，获得预浸料和厚度为1.0mm的双面覆铜层压板。
对比例2
称取R/Si＝1.4(摩尔比)，Ph/(Ph+Me)＝0.5(摩尔比)的甲基苯基硅树脂100.0份溶于70.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入硅微粉70.0份，乙酰丙酮钴0.1份，硅烷偶联剂Y-甲基丙烯酰氧基丙基三甲氧基硅烷偶联剂1.5份(湖北武大有机硅新材料股份有限公司提供)，搅拌均匀得胶液。
除了使用该树脂胶液外，与实施例1同样进行，获得预浸料和厚度为1.0mm的双面覆铜层压板。
对比例3
称取R/Si＝1.7(摩尔比)，Ph/(Ph+Me)＝1.0(摩尔比)的苯基硅树脂100.0份溶于100.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入氧化铝50份，钛酸酯1.5份，硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷12.0份(湖北武大有机硅新材料股份有限公司提供)，搅拌均匀得胶液。
除了使用该树脂胶液外，与实施例1同样进行，获得预浸料和厚度为1.0mm的双面覆铜层压板。
对比例4
称取R/Si＝1.9(摩尔比)，Ph/(Ph+Me)＝1.0(摩尔比)的苯基硅树脂100.0份溶于100.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入氧化 铝50份，钛酸酯1.5份，硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷8.7份(湖北武大有机硅新材料股份有限公司提供)，搅拌均匀得胶液。
除了使用该树脂胶液外，与实施例1同样进行，获得预浸料和厚度为1.0mm的双面覆铜层压板。
效果确认：
(1)Z-膨胀系数(CTE)的测试(热机械分析方法)
测试方法：使用IPC-TM-6502.4.24，测试数据见下表。
(2)热分层时间(T300)(热机械分析方法)
测试方法：使用IPC-TM-6502.4.24.1，测试数据见下表。
(3)燃烧等级
测试方法：参照美国UL94标准，测试数据见下表。
(4)剥离强度测试
测试方法：使用IPC-TM-6502.4.8方法进行测试，测试数据请见下表。
Figure PCTCN2015080474-appb-000004
Figure PCTCN2015080474-appb-000005
物性分析：
从上表的数据可以看出，实施例1～4同时具有非常低的热膨胀系数，高的热分层时间，无卤无磷阻燃及具有较好的剥离强度，满足覆铜箔层压板的需求。而对比例1与实施例2相比，由于硅树脂为甲基苯基乙烯基硅树脂，使用加成型固化方法，固化后膨胀系数大，剥离强度低，且阻燃效果也不突出；而对比例2与实施例2相比，填料含量超出范围，导致与铜箔的剥离强度降低，热分层时间减少；对比例3与实施例3相比，助剂的使用量不在保护范围，由于助剂多为小分子，加入量过多使得层压板在高温下小分子放出来较多，使得热膨胀系数增大，同时分层时间缩短；对比例4与实施例3相比，R/Si值超出范围，R/Si越大，树脂交联密度越低，越倾向于热塑性树脂，使得热膨胀系数上升，高温下稳定性下降，热分层时间降低。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (13)

  1. 一种有机硅树脂组合物，其特征在于，所述有机硅树脂组合物按重量份数包括：
    缩合型硅树脂   100份；
    催化剂         0.0001～2份；
    助剂           0.001～10份。
  2. 如权利要求1所述的有机硅树脂组合物，其特征在于，所述缩合型硅树脂为甲基硅树脂、甲基苯基硅树脂或苯基硅树脂中的任意一种或者至少两种的混合物。
  3. 如权利要求1或2所述的有机硅树脂组合物，其特征在于，所述缩合型硅树脂为R/Si＝1.0～1.7(摩尔比)和Ph/(Me+Ph)＝0～1.0(摩尔比)的甲基硅树脂、甲基苯基硅树脂或苯基硅树脂中的任意一种或者至少两种的混合物，其中Ph代表苯基基团，Me代表甲基基团，R代表有机官能团-CH3、-Ph、-OCH3、-OCH2CH3、-H或-OH。
  4. 如权利要求1-3之一所述的有机硅树脂组合物，其特征在于，所述缩合型硅树脂为R/Si＝1.2～1.7(摩尔比)且Ph/(Me+Ph)＝0.2-0.6(摩尔比)的甲基苯基硅树脂。
  5. 如权利要求1-4之一所述的有机硅树脂组合物，其特征在于，所述催化剂为环烷酸锌、环烷酸锡、环烷酸钴、环烷酸铁、环烷酸铈、羧酸锌、羧酸锡、羧酸钴、羧酸铁、羧酸铈、全氟磺酸、氯化磷腈、胺类、季铵碱、辛酸锌、异辛酸锌、钛酸酯或胍类化合物等中的任意一种或者至少两种的组合；
    优选地，所述助剂包括硅烷偶联剂、钛酸酯偶联剂或分散剂中的任意一种或者至少两种的混合物。
  6. 如权利要求1-5之一所述的有机硅树脂组合物，其特征在于，所述有机 硅树脂组合物还包括填料；
    优选地，所述填料包括二氧化硅、氧化铝、氢氧化铝、氮化硼、氮化铝、硫酸钡、云母粉、硼酸锌、二氧化钛、滑石粉、氮化硅或碳化硅中的任意一种或者至少两种的混合物；
    优选地，所述填料的含量为0～60重量份。
  7. 如权利要求1-6之一所述的有机硅树脂组合物，其特征在于，所述有机硅树脂组合物按重量份数包括：
    Figure PCTCN2015080474-appb-100001
    优选地，所述有机硅树脂组合物按重量份数包括：
    Figure PCTCN2015080474-appb-100002
  8. 一种树脂胶液，其特征在于，其是将如权利要求1-7之一所述的有机硅树脂组合物溶解或分散在溶剂中得到。
  9. 一种预浸料，其特征在于，其包括增强材料及通过含浸干燥后附着在增强材料上的如权利要求1-7之一所述的有机硅树脂组合物。
  10. 一种层压板，其特征在于，所述层压板含有至少一张如权利要求9所述的预浸料。
  11. 一种覆铜箔层压板，其特征在于，所述覆铜箔层压板包括至少一张叠 合的如权利要求9所述的预浸料及压覆在叠合后的预浸料的一侧或两侧的铜箔。
  12. 一种铝基覆铜板，包括铜箔层和铝基层，铜箔层和铝基层间涂有绝缘层，其特征在于，所述绝缘层是由如权利要求1-7之一所述硅树脂组合物，并添加导热填料制成。
  13. 如权利要求12所述的铝基覆铜板的制造方法，包括如下步骤：
    (1)按组分比例配制硅树脂组合物，并添加导热填料，搅拌均匀，制成导热胶液；
    (2)将配制好的导热胶液涂覆于铜箔上，在烘箱中用170℃烘烤5min得半固化涂覆铜箔；
    (3)将铝板与(2)所述的涂覆铜箔叠合在一起，置于真空状态下分步升温升压制得铝基覆铜板。
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TW201623450A (zh) 2016-07-01

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