WO2016101534A1 - 一种陶瓷化硅树脂组合物及使用它的预浸料与层压板 - Google Patents

一种陶瓷化硅树脂组合物及使用它的预浸料与层压板 Download PDF

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Publication number
WO2016101534A1
WO2016101534A1 PCT/CN2015/080473 CN2015080473W WO2016101534A1 WO 2016101534 A1 WO2016101534 A1 WO 2016101534A1 CN 2015080473 W CN2015080473 W CN 2015080473W WO 2016101534 A1 WO2016101534 A1 WO 2016101534A1
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Prior art keywords
silicone resin
parts
resin composition
laminate
ceramifying
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PCT/CN2015/080473
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English (en)
French (fr)
Inventor
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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Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to KR1020177020791A priority Critical patent/KR101915920B1/ko
Priority to US15/539,436 priority patent/US10030143B2/en
Priority to JP2017534272A priority patent/JP6617983B2/ja
Priority to EP15871610.0A priority patent/EP3239243B1/en
Publication of WO2016101534A1 publication Critical patent/WO2016101534A1/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K3/346—Clay
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K3/40—Glass
    • 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
    • C09D183/16—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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Definitions

  • the invention relates to a ceramicized silicone resin composition and a prepreg, a laminate and a printed circuit board using the same, which have the advantages of no halogen, low smoke, low toxicity, self-extinguishing and environmental protection, and high heat resistance and fire resistance.
  • the field of aerospace technology and other fields are very promising, providing new ideas and new methods for the field of flame retardant and refractory for laminates and copper clad laminates.
  • the ceramicized silicone laminate exhibits excellent performance of ordinary silicone resin at normal temperature, but can be converted into a complex ceramic structure at a high temperature and has ceramic characteristics, and becomes a hard self-supporting ceramic product with a certain strength and It can withstand a certain impact force, and can maintain the integrity of the laminate under the ablation of open flame above 1000 °C, thereby isolating the internal material from reacting with the external high temperature, which can play a better fireproof and flame retardant role in the fire process. The power and communication can still be guaranteed.
  • silica When the silicone resin is burned at a high temperature, silica is formed and is in the form of a powder. After adding silicate-based refractory fillers (mica, wollastonite, kaolin, etc.), silica and refractory fillers are produced by decomposition of silicone resin. The reaction takes place to form a "eutectic mixture" at the edges of the filler, thereby bridging between the silica particles and the filler particles, solidifying them at the ignition temperature, and forming agglomerated ceramization products upon cooling.
  • the ceramic body is self-supporting and can withstand certain mechanical shocks and vibrations. It can be used as a thermal protection material, a heat-resistant wave-transparent and absorbing integrated material or other functional laminates with high temperature requirements.
  • the ceramized silicone laminate has excellent electrical properties, good thermal shock resistance, halogen-free, low-smoke, low toxicity, self-extinguishing, environmental protection, etc. It provides new ideas and new methods in the field of flame retardancy and fire resistance, and accelerates. The research progress of passive fireproof technology of laminates has a broad prospect in the field of fire prevention and fire resistance.
  • a ceramic-free silicone resin composition, prepreg and laminate which are halogen-free, phosphorus-free, flame-retardant self-extinguishing and highly heat-resistant.
  • the laminate can form a hard self-supporting ceramized product after continuous combustion, has a certain strength and can withstand a certain impact force, and can ensure the smooth flow of electricity and communication during the fire.
  • a ceramifying silicone resin composition comprising, by weight:
  • the content of the condensation type silicone resin is, for example, 53 parts, 57 parts, 61 parts, 65 parts, 69 parts, 73 parts, 77 parts, 81 parts, 85 parts, 89 parts, 93 parts, 97 parts or 99 parts.
  • the content of the catalyst is, for example, 0.0001 part, 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, 2.0 part.
  • the content of the ceramic filler is, for example, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40, 45, 50, 55, 60, 65, 70, 75 or 80 parts.
  • the flux is contained in an amount of 0.01 to 50 parts by weight, for example, 0.03 parts, 0.1 parts, 0.5 parts, 1 part by weight, 5 parts by weight, 9 parts by weight, 13 parts by weight, 17 parts by weight, 21 parts by weight, and 25 parts by weight. 29 parts by weight, 33 parts by weight, 37 parts by weight, 41 parts by weight, 45 parts by weight or 49 parts by weight.
  • the fluxing agent refers to a substance capable of lowering the softening, melting or liquefying temperature of other substances.
  • the ceramic filler used in the ceramized silicone resin has a high melting point, and the ceramization temperature after combustion is also high. In order to be "low-temperature firing", it is possible to start ceramization at a lower temperature, obtain a ceramic body of a certain strength, and better exert the fireproof function of the ceramized silicone resin, and add a flux to the formulation.
  • the fluxing agent is any one of a glass additive, a boron-containing compound or zinc oxide or a mixture of at least two, preferably any one of glass powder, zinc oxide, iron oxide or zinc borate or at least a mixture of two.
  • the glass additive is one or more conforming to the resin composition in order to improve various properties in the ceramic forming process of the ceramic resin composition, to make it easier to melt, form, and minimize defects.
  • Raw materials including glass powder.
  • the ceramic filler is a layered silicate mineral filler, has a crystal structure, has a high melting point (high refractoriness) and a high degree of sintering, and has excellent electrical insulation properties, including mica and silica fume. Any one or a combination of at least two of stone or kaolin.
  • the invention combines a condensed silicone resin with a ceramic filler, and when burned at a high temperature, the silica generated by the decomposition of the silicone resin reacts with the ceramic filler to form a "eutectic mixture" at the edge of the filler, thereby
  • the silica particles and the filler particles act as a bridge to solidify at the ignition temperature, and form a cohesive self-supporting ceramization product upon cooling, which has a certain strength and can withstand a certain impact force, and can still be subjected to a fire process. Ensure the smooth flow of electricity and communication.
  • 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, and the reaction structure is as follows:
  • a group, R represents an organofunctional group -CH 3 , -Ph, -OCH 3 , -OCH 2 CH 3 or -OH.
  • the R/Si (molar ratio) is too small, the Ph/Si (molar ratio) is too low, the silicone resin is poorly cured, the paint film is hard, and the R/Si (molar ratio) is too large.
  • the catalyst is zinc naphthenate, tin naphthenate, cobalt naphthenate, iron naphthenate, bismuth naphthenate, zinc carboxylate, tin carboxylate, cobalt carboxylate, iron carboxylate, carboxylate Any one or a combination of at least two of acid strontium, perfluorosulfonic acid, phosphazene chloride, amines, quaternary ammonium base, zinc octoate, zinc isooctanoate, titanate or anthraquinone.
  • the ceramifying silicone resin composition further includes a non-ceramic filler or/and an auxiliary.
  • the auxiliary agent includes any one of a silane coupling agent, a titanate coupling agent, or a dispersing agent, or a combination of at least two.
  • the auxiliary agent is contained in an amount of 0.01 to 10 parts by weight, for example, 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, and 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 non-ceramic filler generally refers to a filler other than the porcelain-forming filler of the present invention.
  • the non-cemented filler comprises any one or a mixture of at least two of silicon dioxide, aluminum oxide, aluminum hydroxide, boron nitride, aluminum nitride, silicon nitride or silicon carbide.
  • the content of the non-ceramic filler is 5 to 80 parts by weight, for example, 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, 65 parts by weight, 70 parts by weight or 75 parts by weight.
  • An exemplary ceramifying silicone resin composition comprising, by weight:
  • the average particle diameter of the ceramic filler, the fluxing agent and the non-ceramic filler is not particularly limited, but is preferably 10 ⁇ m or less, preferably 5 ⁇ m or less, and each of the fillers may be used alone or in combination of two or more. Further, for example, a composition having a particle size distribution and a different average particle diameter may be used in combination as appropriate.
  • the ceramifying silicone resin composition may further contain various additives, and specific examples thereof include a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, or a lubricant. Agents, etc. 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 ceramifying silicone resin composition as described above in a solvent.
  • the solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl.
  • Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone. These 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.
  • the amount of the solvent used can be selected by a person skilled in the art according to his own experience, so that the solid content of the obtained resin glue can reach 50 to 70%.
  • a third object of the present invention is to provide a prepreg comprising a reinforcing material and a ceramifying silicone resin composition as described above adhered to the reinforcing material by impregnation and drying.
  • An exemplary prepreg is prepared by:
  • an organic solvent such as toluene or xylene is added to prepare a resin glue having a solid content of 50 to 70% by weight, and is impregnated with a reinforcing material such as a fiberglass cloth.
  • the resin glue is then prepared by baking at 120 to 190 ° C for 2 to 15 minutes.
  • a fourth object of the present invention is to provide a laminate comprising at least one of the above Prepreg as described.
  • 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.
  • the present invention has the following beneficial effects:
  • the ceramicized silicone resin laminate obtained by the invention can form a hard structure during continuous combustion, has a certain strength and can withstand a certain impact force, and can maintain the integrity of the laminate under continuous open flame ablation;
  • the ceramicized silicone resin laminate obtained by the present invention has extremely excellent heat resistance, and its decomposition temperature of 1% is as high as 548.7 ° C or higher, and can be applied not only to high-temperature electrical insulating materials of high-power motors, but also to application.
  • the high temperature resistant structural materials of aerospace vehicles have a very broad application prospect;
  • the ceramicized silicone resin composition of the invention has the advantages of no halogen, low smoke, low toxicity, self-extinguishing and environmental protection, and provides new ideas and new methods for the field of flame retardancy and fire resistance 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.
  • the ceramicized silicone glass cloth laminate has a flame retardant effect of UL V-0 grade, and its 1% thermal weight loss temperature is as high as 548.7 ° C, and has extremely excellent heat resistance; the double-sided copper clad plate is cut into a size of 200 mm x 200 mm and The etching treatment was carried out to obtain a silicone resin laminate, and the laminate was ablated under an open flame (800-1100 ° C) for 0.5 h, and the effect of forming the porcelain was obvious, and the laminate was hard and had no obvious pores.
  • 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.
  • the ceramicized silicone glass cloth laminate has a flame retarding effect of UL V-0 grade, and its 1% weight loss temperature is as high as 611.8 ° C, and has extremely excellent heat resistance.
  • the double-sided copper clad plate was cut into a size of 200 mm x 200 mm and etched to obtain a silicone resin laminate.
  • the laminate was ablated under an open flame (800-1100 ° C) for 0.5 h, and the effect of the porcelain was obvious.
  • the texture of the laminate was hard and no obvious. Hole.
  • 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.
  • the ceramicized silicone glass cloth laminate has a flame retardant effect of UL V-0, and its 1% weight loss temperature is as high as 581.9 ° C, and has extremely excellent heat resistance.
  • the double-sided copper clad plate was cut into a size of 200 mm x 200 mm and etched to obtain a silicone resin laminate.
  • the laminate was ablated under an open flame (800-1100 ° C) for 0.5 h, and the effect of the porcelain was obvious.
  • the texture of the laminate was hard and no obvious. Hole.
  • 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.
  • the ceramicized silicone glass cloth laminate has a flame retardant effect of UL V-0 grade and a 1% weight loss temperature of up to 567.3 ° C, and has extremely excellent heat resistance.
  • the double-sided copper clad plate was cut into a size of 200 mm x 200 mm and etched to obtain a silicone resin laminate.
  • the laminate was ablated under an open flame (800-1100 ° C) for 0.5 h, and the effect of the porcelain was obvious.
  • the texture of the laminate was hard and no obvious. Hole. Comparative example 1
  • 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.
  • the ceramicized silicone glass cloth laminate has a flame retardant effect of UL V-1 grade, and its 1% weight loss temperature is 296 ° C, and the heat resistance is inferior to that of the condensation type silicone resin.
  • the double-sided copper clad plate was cut into a size of 200 mm x 200 mm and etched to obtain a silicone resin laminate.
  • the laminate was ablated under an open flame (800-1100 ° C) for 0.5 h, and was burnt, and the effect of forming porcelain was not obvious.
  • 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.
  • the ceramifying silicone glass cloth laminate has a flame retarding effect of UL V-0, and its 1% weight loss temperature is 581.4 ° C, and is excellent in heat resistance.
  • the double-sided copper clad plate is cut into a size of 200 mm x 200 mm and etched to obtain a silicone resin laminate, and the laminate is ablated for 0.5 h after an open flame (800-1100 ° C). It is in powder form and cannot be made into porcelain.
  • 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.
  • the ceramicized silicone glass cloth laminate has a flame retardant effect of UL V-0, and its 1% weight loss temperature is 564.7 ° C, and the heat resistance is high.
  • the double-sided copper clad plate is cut into a size of 200 mm x 200 mm and etched to obtain a silicone resin laminate.
  • the laminate can be formed into a porcelain after ablation for 0.5 h under an open flame (800-1100 ° C), but a large amount of the laminate is formed after ablation. Large holes, the effect of porcelain is not good.
  • 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.
  • the ceramicized silicone glass cloth laminate has a flame retarding effect of UL V-0, and its 1% weight loss temperature is 547.4 ° C, and is excellent in heat resistance.
  • the double-sided copper clad plate was cut into a size of 200 mm x 200 mm and etched to obtain a silicone resin laminate. The laminate was ablated for 0.5 h under an open flame (800-1100 ° C) and was powdered, and could not be porcelain.

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Abstract

本发明涉及一种陶瓷化硅树脂组合物及使用它的预浸料与层压板。该陶瓷化硅树脂组合物包括：缩合型硅树脂50～100份；催化剂0.0001～2份；成瓷填料：5～80份；助熔剂0.01～50份。用所述陶瓷化硅树脂组合物制成的预浸料和层压板，使用时能在持续高温下转变为复杂的陶瓷化结构而具有陶瓷特性，能起到优越的防火与阻燃作用，并且层压板制作与普通FR-4层压板相似，工艺操作简便。该陶瓷化硅树脂组合物、预浸料及层压板具有无卤、低烟、低毒、阻燃和防火等优点，在阻燃和耐火方面提供了新思路和新方法，加快了层压板被动防火技术的研究进展，在防火和耐火领域前景十分广阔。

Description

一种陶瓷化硅树脂组合物及使用它的预浸料与层压板 技术领域
本发明涉及一种陶瓷化硅树脂组合物及使用它的预浸料、层压板与印制电路板，具有无卤、低烟、低毒、自熄和环保等优点，在高耐热、耐火及航空航天技术等领域前景十分广阔，为层压板及覆铜板在阻燃和耐火领域提供了新思路和新方法。
背景技术
目前为了赋予层压板阻燃性，使用并用溴系阻燃剂的配方。但由于近年来对环境问题越来越重视，渴求不使用卤素化合物的树脂组合物，从而进一步进行着代替卤素阻燃剂的磷化合物研究，而磷化合物在燃烧时也可能产生膦等有毒化合物，因此开发不含卤素不含磷化合物，且具有非常好的阻燃性的层压板迫在眉睫。
普通FR-4层压板及覆铜板虽然在火中燃烧具有难燃性和自熄性，但持续高温燃烧后，烧余物没有机械强度，变成灰烬，也不能保持制品的完整性，甚至会造成更危险的二次灾害，造成短路，无法应用于高耐火、高耐热领域。
而陶瓷化硅树脂层压板在常温下显示普通硅树脂的优良性能，然而在高温时却能转变为复杂的陶瓷化结构而具有陶瓷特性，成为坚硬的自支撑陶瓷化产物，具有一定的强度且能承受一定的冲击力，在1000℃以上明火的烧蚀下也能保持层压板的完整性，从而隔绝内部材料与外界高温发生反应，能起到较好的防火与阻燃作用，在火灾过程中仍然可以保证电力与通讯的畅通。
硅树脂在高温下燃烧时，生成二氧化硅，呈粉末状。而添加硅酸盐类耐火填料(云母、硅灰石、高岭土等)后，硅树脂分解产生的二氧化硅与耐火填料 发生反应，在填料的边缘处形成“低共熔混合物”，从而在二氧化硅粒子和填料粒子之间起桥接作用，在着火温度下使之固化，冷却时形成凝聚的陶瓷化产物。这种陶瓷体具有自支撑性，能够承受一定的机械冲击和振动，可为作热防护材料、耐热透波和吸波一体化材料或其他有高温要求的功能性层压板。
陶瓷化硅树脂层压板具有优良的电性能、抗热冲击性好、无卤、低烟、低毒、自熄、环保等优点，在阻燃和耐火领域提供了新思路和新方法，加快了层压板被动防火技术的研究进展，在防火、耐火领域前景十分广阔。
发明内容
鉴于此，本发明的目的在于提供一种无卤、无磷、阻燃自熄和高耐热的陶瓷化硅树脂组合物、预浸料及层压板。该层压板在持续燃烧后能形成坚硬的自支撑陶瓷化产物，具有一定的强度且能承受一定的冲击力，在火灾过程中仍然可以保证电力与通讯的畅通。
为了达到上述目的，本发明采用了如下技术方案：
一种陶瓷化硅树脂组合物，所述陶瓷化硅树脂组合物按重量份数包括：
Figure PCTCN2015080473-appb-000001
所述缩合型硅树脂的含量例如为53份、57份、61份、65份、69份、73份、77份、81份、85份、89份、93份、97份或99份。
所述催化剂的含量例如为0.0001份、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、2.0份。
所述成瓷填料的含量例如为10份、15份、20份、25份、30份、35份、 40份、45份、50份、55份、60份、65份、70份、75份或80份。
所述助熔剂的含量为0.01～50重量份，例如0.03份、0.1份、0.5份、1重量份、5重量份、9重量份、13重量份、17重量份、21重量份、25重量份、29重量份、33重量份、37重量份、41重量份、45重量份或49重量份。
在本发明中，所述助熔剂(flux，fluxing agent)是指能降低其他物质的软化、熔化或液化温度的物质。陶瓷化硅树脂所用成瓷填料的熔点都很高，燃烧后陶瓷化温度相应也很高。为了能“低温烧成”，即能在较低温度下开始陶瓷化，获得一定的强度的陶瓷体，更好地发挥陶瓷化硅树脂的防火功能，在配方中加入助熔剂。
在本发明中，所述助熔剂为玻璃添加剂、含硼化合物或氧化锌中的任意一种或者至少两种的混合物，优选玻璃粉、氧化锌、氧化铁或硼酸锌中的任意一种或者至少两种的混合物。
在本发明中，所述玻璃添加剂是为了改善陶瓷化树脂组合物成瓷过程中的各项性能，使更易熔化、成型且尽量减少缺陷产生而在树脂组合物中添加的一种或多种符合的原料，包括玻璃粉等。
在本发明中，所述成瓷填料是层状硅酸盐类矿物填料，呈晶体结构，具有高熔点(高耐火度)和高烧结度，且具有优良的电绝缘性能，包括云母、硅灰石或高岭土等中的任意一种或者至少两种的组合。
本发明通过将缩合型硅树脂与成瓷填料配合，在高温燃烧时，硅树脂分解产生的二氧化硅与成瓷填料发生反应，在填料的边缘处形成“低共熔混合物”，从而在二氧化硅粒子和填料粒子之间起桥接作用，在着火温度下使之固化，冷却时形成凝聚的自支撑陶瓷化产物，其具有一定的强度且能承受一定的冲击力，在火灾过程中仍然可以保证电力与通讯的畅通。
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 PCTCN2015080473-appb-000002
在本发明中，所述缩合型硅树脂为R/Si＝1.0～1.7(摩尔比)(例如1.1、1.2、1.3、1.4、1.5、1.6或1.7)和Ph/(Me+Ph)＝0～1.0(摩尔比)(例如0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9或1.0)的甲基或甲基苯基硅树脂，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。
根据本发明，所述催化剂是环烷酸锌、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，所述陶瓷化硅树脂组合物还包括非成瓷填料或/和助剂。
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组合。
所述助剂的含量为0.01～10重量份，例如为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，所述非成瓷填料泛指除本发明中成瓷填料以外的填料。
在本发明中，所述非成瓷填料包括二氧化硅、氧化铝、氢氧化铝、氮化硼、氮化铝、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，所述非成瓷填料的含量为5～80重量份，例如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、65重量份、70重量份或75重量份。
示例性的一种陶瓷化硅树脂组合物，所述陶瓷化硅树脂组合物按重量份数包括：
Figure PCTCN2015080473-appb-000003
根据本发明，所述成瓷填料、助熔剂及非成瓷填料平均粒径没有特别限定，但独立地优选为10μm以下，优选为5μm以下，并且每种填料可以单独使用一种或者两种以上，也可适当组合使用例如粒径分布、平均粒径不同的组合物。
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陶瓷化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，所述陶瓷化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，其是将如上所述的陶瓷化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。所述溶剂的使用量本领域技术人员可以根据自己的经验来选择，使得到的树脂胶液的固含量达到50～70％即可。
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陶瓷化硅树脂组合物。
示例性的预浸料的制备方法为：
以如上所述的陶瓷化硅树脂组合物重量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。
与已有技术相比，本发明具有如下有益效果：
(1)本发明得到的陶瓷化硅树脂层压板在持续燃烧时可以形成坚硬结构，具有一定的强度且能承受一定的冲击力，在持续明火烧蚀下也能保持层压板的完整性；
(2)本发明得到的陶瓷化硅树脂层压板具有极其优越的耐热性，其1％的分解温度高达548.7℃以上，不仅可应用与高功率电机的耐高温电气绝缘材料，还可应用与航空航天飞行器的耐高温结构材料，具有非常广泛的应用前景；
(3)本发明的陶瓷化硅树脂组合物具有无卤、低烟、低毒、自熄和环保等优点，为层压板及覆铜板在阻燃和耐火领域提供了新思路和新方法；
(4)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120.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入云母粉20.0份，高岭土35.0份，硅灰石35.0份，氧化锌15.0份，玻璃粉25.3份，异辛酸锌0.0001份，氧化铝10.0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)8.9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。
该陶瓷化硅树脂玻璃布层压板的阻燃效果为UL V-0级，并且其1％的热失重温度高达548.7℃，具有极其优异的耐热性；将双面覆铜板切割200mmx200mm的尺寸并进行蚀刻处理，得有机硅树脂层压板，将层压板在明火(800-1100℃)下烧蚀0.5h后成瓷效果明显，层压板质地坚硬，无明显孔洞。
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80.0份溶于65.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入高岭土40.4份，硼酸锌25.7份，硅微粉23.0份，乙酰丙酮钴0.08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。
该陶瓷化硅树脂玻璃布层压板的阻燃效果为UL V-0级，并且其1％热失重温度高达611.8℃，具有极其优异的耐热性。将双面覆铜板切割200mmx200mm的尺寸并进行蚀刻处理，得有机硅树脂层压板，将层压板在明火(800-1100℃)下烧蚀0.5h后成瓷效果明显，层压板质地坚硬，无明显孔洞。
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50.0份溶于80.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入硅灰石 7.0份，玻璃粉0.05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0.7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。
该陶瓷化硅树脂玻璃布层压板的阻燃效果为UL V-0级，其1％热失重温度高达581.9℃，具有极其优异的耐热性。将双面覆铜板切割200mmx200mm的尺寸并进行蚀刻处理，得有机硅树脂层压板，将层压板在明火(800-1100℃)下烧蚀0.5h后成瓷效果明显，层压板质地坚硬，无明显孔洞。
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40.0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份，溶于65.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入高岭土40.4份，硼酸锌25.7份，硅灰石15.0份，硅微粉23.0份，乙酰丙酮钴0.08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。
该陶瓷化硅树脂玻璃布层压板的阻燃效果为UL V-0级，并且其1％热失重温度高达567.3℃，具有极其优异的耐热性。将双面覆铜板切割200mmx200mm的尺寸并进行蚀刻处理，得有机硅树脂层压板，将层压板在明火(800-1100℃)下烧蚀0.5h后成瓷效果明显，层压板质地坚硬，无明显孔洞。比较例1
称取甲基乙烯基硅树脂100.0份(乙烯基质量分数5.0％)，己炔醇0.003 份，溶于120.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入含氢硅油(含氢质量分散1.2％)13.2份，铂-甲基乙烯基络合物0.001份，云母粉20.0份，高岭土35.0份，硅灰石35.0份，氧化锌15.0份，玻璃粉25.3份，氧化铝10.0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)8.9份，搅拌混合均匀得到胶液。
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。
该陶瓷化硅树脂玻璃布层压板的阻燃效果为UL V-1级，其1％热失重温度为296℃，耐热性较缩合型硅树脂较差。将双面覆铜板切割200mmx200mm的尺寸并进行蚀刻处理，得有机硅树脂层压板，将层压板在明火(800-1100℃)下烧蚀0.5h后呈烧焦状，成瓷效果不明显。
比较例2
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120.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入云母粉50.0份，高岭土35.0份，硅灰石35.0份，氧化锌15.0份，玻璃粉25.3份，硅灰石8.0，异辛酸锌0.0001份，氧化铝10.0份，硅烷偶联剂γ-(2，3-环氧丙氧基)丙基三甲氧基硅烷Z-6040(美国，道康宁公司提供)8.9份，搅拌混合均匀得到胶液。
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。
该陶瓷化硅树脂玻璃布层压板的阻燃效果为UL V-0级，其1％热失重温度为581.4℃，耐热性优异。将双面覆铜板切割200mmx200mm的尺寸并进行蚀刻处理，得有机硅树脂层压板，将层压板在明火(800-1100℃)下烧蚀0.5h后 呈粉末状，无法成瓷。
比较例3
称取R/Si＝1.7(摩尔比)，Ph/(Ph+Me)＝1.0(摩尔比)的苯基硅树脂50.0份溶于80.0份甲苯溶剂中，搅拌使其完全溶解。待硅树脂溶解完全后，加入硅灰石7.0份，玻璃粉0.005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0.7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。该陶瓷化硅树脂玻璃布层压板的阻燃效果为UL V-0级，其1％热失重温度为564.7℃，耐热性较高。将双面覆铜板切割200mmx200mm的尺寸并进行蚀刻处理，得有机硅树脂层压板，将层压板在明火(800-1100℃)下烧蚀0.5h后可以成瓷，但烧蚀后层压板出现大量大孔洞，成瓷效果欠佳。
比较例4
称取R/Si＝1.7(摩尔比)，Ph/(Ph+Me)＝1.0(摩尔比)的苯基硅树脂50.0份溶于80.0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0.7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。该陶瓷化硅树脂玻璃布层压板的阻燃效果为UL V-0级，其1％热失重温度为547.4℃，耐热性优异。将双面覆铜板切割200mmx200mm的尺寸并进行蚀刻处理，得有机硅树脂层压板，将层压板在明火(800-1100℃)下烧蚀0.5h后呈粉末状，无法成瓷。
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 (15)

  1. 一种陶瓷化硅树脂组合物，其特征在于，所述陶瓷化硅树脂组合物按重量份数包括：
    Figure PCTCN2015080473-appb-100001
  2. 如权利要求1所述的陶瓷化硅树脂组合物，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，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＝1.2～1.7(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或2所述的有机硅树脂组合物，其特征在于，所述催化剂是环烷酸锌、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中的任意一种或者至少两种的组合。
  6. 如权利要求1或2所述的有机硅树脂组合物，其特征在于，所述成瓷填料为云母粉、硅灰石或高岭土中的任意一种或者至少两种的组合；
    所述助熔剂为玻璃添加剂、含硼化合物或氧化锌中的任意一种或者至少两 种的混合物，优选玻璃粉、氧化锌、氧化铁或硼酸锌中的任意一种或者至少两种的混合物。
  7. 如权利要求1-3之一所述的陶瓷化硅树脂组合物，其特征在于，所述陶瓷化硅树脂组合物还包括非成瓷填料或/和助剂。
  8. 如权利要求7所述的陶瓷化硅树脂组合物，其特征在于，所述非成瓷填料包括二氧化硅、氧化铝、氢氧化铝、氮化硼、氮化铝、氮化硅或碳化硅中的任意一种或者至少两种的混合物，所述非成瓷填料的含量为5～80重量份；
  9. 如权利要求7所述的陶瓷化硅树脂组合物，其特征在于，所述助剂包括硅烷偶联剂、钛酸酯偶联剂以及分散剂中的一种或至少两种的混合物，所述助剂的含量为0.01～10重量份。
  10. 如权利要求1-4之一所述的陶瓷化硅树脂组合物，其特征在于，所述陶瓷化硅树脂组合物按重量份数包括：
    Figure PCTCN2015080473-appb-100002
    所述成瓷填料、助熔剂及非成瓷填料的平均粒径均独立地选自10μm以下，优选为5μm以下。
  11. 一种树脂胶液，其特征在于，其是将如权利要求1-10之一所述的陶瓷化硅树脂组合物溶解或分散在溶剂中得到。
  12. 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 如权利要求1-10之一所述的陶瓷化硅树脂组合物。
  13. 一种层压板，所述层压板含有至少一张如权利要求12所述的预浸料。
  14. 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权利要求12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。
  15. 一种印制电路板，含有至少一张如权利要求13所述的层压板。
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CN112280222A (zh) * 2020-11-25 2021-01-29 浙江工业大学温州科学技术研究院 一种可陶瓷化的pvc耐火板材及其制备方法
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