WO2023020226A1 - 一种树脂组合物及其应用 - Google Patents

一种树脂组合物及其应用 Download PDF

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Publication number
WO2023020226A1
WO2023020226A1 PCT/CN2022/108291 CN2022108291W WO2023020226A1 WO 2023020226 A1 WO2023020226 A1 WO 2023020226A1 CN 2022108291 W CN2022108291 W CN 2022108291W WO 2023020226 A1 WO2023020226 A1 WO 2023020226A1
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WIPO (PCT)
Prior art keywords
resin
silicon dioxide
resin composition
copper foil
adhesive film
Prior art date
Application number
PCT/CN2022/108291
Other languages
English (en)
French (fr)
Inventor
佘乃东
刘潜发
黄增彪
许永静
柴颂刚
张艳华
Original Assignee
广东生益科技股份有限公司
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Publication date
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 KR1020237045384A priority Critical patent/KR20240015684A/ko
Priority to JP2024500494A priority patent/JP2024526664A/ja
Priority to US18/575,212 priority patent/US20240287282A1/en
Publication of WO2023020226A1 publication Critical patent/WO2023020226A1/zh

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    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
    • 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
    • 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
    • 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
    • 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
    • C08J5/241—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09J157/02—Copolymers of mineral oil hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09J171/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • 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
    • 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
    • B32B2250/40—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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
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    • C09J2400/166—Metal in the pretreated surface to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • 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
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    • 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

Definitions

  • the invention belongs to the technical field of laminated boards, and relates to a resin composition and its application.
  • the printed circuit substrate which is the main support of electronic components, is also continuously improving its technical level to provide high-density wiring, thin shape, and micro-aperture. , High heat dissipation.
  • the substrate material determines the performance of the printed circuit substrate to a large extent, so it is urgent to develop a new generation of substrate materials.
  • Adhesive film or resin-coated copper foil without reinforcing material is developed and applied as a new generation of substrate materials because it can achieve thinner shape, high-density wiring, and fine pore size. Since there is no reinforcing material, inorganic fillers are generally added to improve the thermal expansion coefficient, chemical resistance, mechanical strength and processing performance of the film. Silica powder is an ideal inorganic filler. However, due to the wide particle size distribution and high hardness of general silica powder, there are problems such as insignificant increase in tensile strength, poor fluidity, and difficult processing after adding a large amount.
  • CN112526823A discloses a photosensitive resin composition, which contains (A) photosensitive resin, (B) silicon dioxide, (C) photopolymerization initiator, (D) reactive diluent and (E) epoxy compound, Wherein, the cumulative volume percentage of the (B) silicon dioxide is 50 volume %, and the particle diameter D50 is not less than 0.50 ⁇ m and not more than 2.00 ⁇ m.
  • D1.0 is not less than 0.20 ⁇ m and not more than 0.54 ⁇ m
  • D99 is not less than 5.00 ⁇ m and not more than 8.40 ⁇ m.
  • the invention converts D99/D50 to greater than 2.5, and does not limit D100 at the same time, and the filler particles are relatively large.
  • thermosetting resin composition which comprises 20-70wt% of thermosetting resin, 1-30wt% of curing agent, 0-10wt% of accelerator, 1-50wt% of the average particle size of 1-10 microns
  • a chemically synthesized micron-scale aggregate of silicon dioxide which can be made into a prepreg by impregnation or a coated product by coating.
  • the resin composition can make the adhesive film and the resin-coated copper foil have high relative tensile strength and peel strength, good drilling processability, controllable fluidity, good glue filling ability and higher electric strength.
  • the object of the present invention is to provide a resin composition and its application.
  • the resin composition of the present invention can make the prepared adhesive film and resin-coated copper foil have high relative tensile strength and peel strength, good drilling processability, controllable fluidity, good glue filling ability, and high electrical strength. It is higher and can realize finer circuit processing capability. It is a printed circuit board material that can be applied to multi-layer laminated boards, especially printed circuit board materials for multi-layer laminated boards with thin lines.
  • the present invention provides a kind of resin composition, and described resin composition comprises the following components by weight percentage: 15-39% of cross-linkable curable resin and 61-85% of filler;
  • the silicon dioxide prepared by solution method, the average particle size D50 of the silicon dioxide is 0.1-3 ⁇ m, the ratio of D100:D10 is ⁇ 2.5, and the purity of the silicon dioxide is greater than 99.9%.
  • the silicon dioxide obtained by using the organosilicon hydrolysis method in the resin composition is used as a filler, the average particle diameter D50 is 0.1-3 ⁇ m, the ratio of D100:D10 is ⁇ 2.5, and the content is greater than 99.9%, so that the composition It can have higher tensile strength and peel strength, better drilling processability, and higher electrical strength.
  • the content of the cross-linkable curable resin is 15-39%, which refers to 15-39% of the entire resin composition, for example, it can be 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 34%, 36%, 38% or 39%, as well as specific point values between the above-mentioned point values, due to space limitations and for the sake of brevity, the present invention does not An exhaustive enumeration of the specific point values included in the range is then made.
  • the content of the filler is 61-85%, which refers to 61-85% of the entire resin composition, such as 61%, 63%, 65%, 68%, 70% %, 72%, 74%, 76%, 78%, 80%, 82% or 85%, and the specific point values between the above-mentioned point values, due to space limitations and for the sake of simplicity, the present invention will not exhaustively list all Specific point values covered by the stated ranges.
  • the filler content is less than 61%, the tensile strength will not be significantly improved, and if the filler content is greater than 85%, the material will be brittle and the peel strength will decrease.
  • the average particle diameter D50 of the silica is 0.1-3 ⁇ m (such as 0.3 ⁇ m, 0.5 ⁇ m, 0.8 ⁇ m, 1 ⁇ m, 1.3 ⁇ m, 1.5 ⁇ m, 1.8 ⁇ m, 2 ⁇ m, 2.3 ⁇ m, 2.5 ⁇ m, 2.8 ⁇ m or 3 ⁇ m), the ratio of D100:D10 is less than 2.5 (such as 2.4, 2.3, 2.2, 2.0, 1.8, 1.7, 1.5, 1.3, 1.0, etc.), the purity of the silicon dioxide is greater than 99.9% (such as 99.91 %, 99.93%, 99.95%, 99.97%, 99.99%, etc.).
  • the silicon dioxide of the present invention has sharper particle size and higher purity, which can make the prepared adhesive film and resin-coated copper foil have higher tensile strength and peel strength, better drilling processability, and fluidity Controllable, good glue filling ability, higher electrical strength, and can achieve finer line processing capabilities.
  • the particle diameters (such as D50, D10, D100, etc.) involved in the present invention are all tested by laser diffraction method, and the testing instrument Malvern laser particle size analyzer, model MS3000; Determination.
  • the crosslinkable curable resin is a thermosetting resin or a photocurable resin.
  • the crosslinkable curable resin is selected from epoxy resin, phenolic resin, cyanate ester, active ester, polyphenylene ether resin, maleimide resin, silicone resin, polybenzoxazole resin, poly Any one or a combination of at least two of imide resin, hydrocarbon resin or acrylate resin, preferably a combination of epoxy resin and phenolic resin.
  • the combination of epoxy resin and phenolic resin is preferred for better tensile strength and peel strength.
  • the epoxy resin includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, phosphorus epoxy resin, MDI modified epoxy resin, novolac epoxy resin, biphenyl type epoxy resin, One or a combination of at least two of dicyclopentadiene-type epoxy resins, naphthalene-containing epoxy resins or alicyclic epoxy resins.
  • the phenolic resin includes one or a combination of at least two of bisphenol A phenolic resins, phenolic phenolic resins, biphenyl phenolic resins, dicyclopentadiene phenolic resins or naphthyl phenolic resins.
  • the silicon dioxide is obtained by firing the primary product obtained through the hydrolysis reaction of organosilicon.
  • the firing temperature is 800-1300°C, such as 850°C, 900°C, 905°C, 910°C, 920°C, 930°C, 950°C, 980°C, 990°C, 1000°C, 1050°C, 1100°C °C, 1200 °C, 1250 °C.
  • the silicone is an alkoxysilane.
  • the alkoxysilane includes tetraethoxysilane, tetramethoxysilane, tetraphenoxysilane, tetra-n-butoxysilane, tetraisobutyloxysilane, methyltriethoxysilane , Dimethyldiethoxysilane; more preferably tetraethoxysilane.
  • the average particle diameter D50 of the silica is 0.3-1 ⁇ m.
  • the present invention provides a resin glue, which is obtained by dissolving or dispersing the above resin composition in a solvent.
  • the solvent in the present invention is not particularly limited, but specific examples include alcohols such as methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, butanol, etc.
  • Carbitol and other ethers acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, toluene, xylene, mesitylene and other aromatic hydrocarbons, ethoxy Ethyl acetate, ethyl acetate and other esters, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other nitrogen-containing solvents.
  • the above-mentioned solvents can be used alone or in combination of two or more, preferably aromatic hydrocarbon solvents such as toluene, xylene, mesitylene and acetone, butanone, methyl ethyl ketone, methyl iso Butyl ketone, cyclohexanone and other ketone solvents are used in combination.
  • aromatic hydrocarbon solvents such as toluene, xylene, mesitylene and acetone, butanone, methyl ethyl ketone, methyl iso Butyl ketone, cyclohexanone and other ketone solvents are used in combination.
  • the usage amount of the solvent can be selected by those skilled in the art according to their own experience, so that the obtained resin glue reaches a viscosity suitable for use.
  • the present invention provides an adhesive film, which is prepared by drying and/or baking the resin composition described in any one of the above-mentioned items after being coated on a release material.
  • the adhesive film may also include a protective film covering the other side of the resin composition.
  • the film thickness is 5-300 ⁇ m, such as 8 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 30 ⁇ m, 50 ⁇ m, 80 ⁇ m, 100 ⁇ m, 120 ⁇ m, 150 ⁇ m, 180 ⁇ m, 200 ⁇ m, 250 ⁇ m, 280 ⁇ m, 300 ⁇ m, preferably 10-200 ⁇ m; More preferably, it is 10-100 ⁇ m.
  • the present invention provides a resin-coated copper foil, which includes a copper foil and the above-mentioned resin composition adhered to the copper foil after coating and drying.
  • the resin-coated copper foil further includes a protective film coated on the resin composition.
  • the resin layer of the resin-coated copper foil (referring to the resin layer formed by the resin composition on the copper foil) has a thickness of 5-300 ⁇ m, such as 8 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 30 ⁇ m, 50 ⁇ m, 80 ⁇ m, 100 ⁇ m, 120 ⁇ m, 150 ⁇ m, 180 ⁇ m, 200 ⁇ m, 250 ⁇ m, 280 ⁇ m, 300 ⁇ m, preferably 10-200 ⁇ m; more preferably 10-100 ⁇ m.
  • the copper foil thickness of the resin-coated copper foil is 1-105 ⁇ m, such as 3 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 50 ⁇ m, 80 ⁇ m, 100 ⁇ m, 104 ⁇ m, etc., preferably 3-35 ⁇ m; more preferably 3 -12 ⁇ m.
  • the present invention provides a semi-cured adhesive sheet, which is formed by impregnating the above-mentioned resin composition with glass cloth and then drying.
  • the glass cloth can be 7628, 2116, 1131, 1080, 106, 1027, 1037, 1078 glass cloth.
  • the present invention provides a copper-clad laminate, which uses one or at least two of the above-mentioned adhesive film, the above-mentioned resin-coated copper foil, and the above-mentioned prepreg adhesive sheet .
  • the present invention provides a multi-layer board, the multi-layer board uses one of the above-mentioned adhesive film, the above-mentioned resin-coated copper foil, the above-mentioned prepreg adhesive sheet, and the above-mentioned copper-clad laminate Or at least two.
  • the present invention has the following beneficial effects:
  • the particle size uniformity of the silicon dioxide of the present invention is good, and the particle size distribution is sharper.
  • the prepared film can obtain better stretching than the film produced by ordinary silicon dioxide. modulus and peel strength.
  • the average particle size of the silica is small, and the uniformity is good, which can avoid the impact of large particles on the withstand voltage of the thin insulating layer and the reliability of the thin circuit, and is more suitable for thin circuit laminates.
  • the purity of the silica is high Electrical properties (Df) will be better.
  • the adhesive film prepared by the resin composition of the present invention has a tensile strength of 50-100Mpa, a peel strength of 7.0-9.0N/cm, an electrical strength of 83-90kV/mm, a DK of 2.95-3.32, and a DF of As low as 0.004-0.014, and has good drilling processability and good glue filling ability, and the comprehensive performance is good.
  • Epoxy resin NC-3000H (Nippon Kayaku);
  • Phenolic resin SN-485 (Nippon Steel);
  • Hydrocarbon resin B3000 (Nippon Soda);
  • Polyphenylene ether MX9000 (Saudi Shabik);
  • silicon dioxide 3 (D50 is 0.5 ⁇ m, D100:D10 is 2.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • the above solution was coated on the release film, and after drying, it was put into an oven at 100°C and baked for 5 minutes to obtain an adhesive film of a semi-cured resin layer. Press and cure the semi-cured adhesive film (thickness 40 ⁇ m) and the browned PCB board, tear off the release film and then perform surface treatment, copper electroplating, to form a laminated printed circuit board with lines.
  • Example 1 Except changing the ratio of silicon dioxide synthesized by the chemical method used in Example 1, the same method as in Example 1 was used to manufacture the adhesive film.
  • silicon dioxide 3 (D50 is 0.5 ⁇ m, D100:D10 is 2.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • Example 1 Except changing the ratio of the chemically synthesized silicon dioxide used in Example 1, the same method as in Example 1 was used to manufacture the adhesive film.
  • silicon dioxide 3 (D50 is 0.5 ⁇ m, D100:D10 is 2.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • Example 2 Using the resin composition of Example 1, a resin-coated copper foil was produced.
  • silicon dioxide 3 (D50 is 0.5 ⁇ m, D100:D10 is 2.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • the above solution was coated on the copper foil, and after drying, it was baked in an oven at 100° C. for 5 minutes to obtain a resin-coated copper foil with a resin layer in a semi-cured state.
  • the resin-coated copper foil (thickness 40 ⁇ m) and the browned PCB board are pressed and cured, and then etched and electroplated to obtain a circuit laminated printed circuit board.
  • Example 1 The same method as in Example 1 was used to manufacture the adhesive film except that the chemically synthesized silica used in Example 1 was changed.
  • silicon dioxide 1 (D50 is 3.0 ⁇ m, D100:D10 is 2.5, and the purity is 99.98%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • Example 1 The same method as in Example 1 was used to manufacture the adhesive film except that the chemically synthesized silica used in Example 1 was changed.
  • silicon dioxide 2 (D50 is 0.1 ⁇ m, D100:D10 is 2.5, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • An adhesive film was produced in the same manner as in Example 1 except that the type of resin used in Example 1 was changed.
  • silicon dioxide 3 (D50 is 0.5 ⁇ m, D100:D10 is 2.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • An adhesive film was produced in the same manner as in Example 1 except that the type of resin used in Example 1 was changed.
  • silicon dioxide 3 (D50 is 0.5 ⁇ m, D100:D10 is 2.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • An adhesive sheet was produced using the resin composition of Example 7.
  • silicon dioxide 3 (D50 is 0.5 ⁇ m, D100:D10 is 2.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • Example 1 The same method as in Example 1 was used to manufacture the adhesive film except that the chemically synthesized silica used in Example 1 was changed.
  • the above solution is coated on the release film, and after drying, it is placed in an oven at 100°C and baked for 3-5 minutes to obtain a semi-cured resin layer film. Press and cure the semi-cured adhesive film (thickness 40 ⁇ m) and the browned PCB board, tear off the release film and then perform surface treatment, copper electroplating, to form a laminated printed circuit board with lines.
  • Example 1 Except changing the silica synthesized by the chemical method used in Example 1, the same method as Example 1 was used to manufacture the adhesive film.
  • silicon dioxide 5 (D50 is 2.0 ⁇ m, D100:D10 is 5.0, and the purity is 99.00%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • the above solution is coated on the release film, and after drying, it is placed in an oven at 100°C and baked for 3-5 minutes to obtain a semi-cured resin layer film. Press and cure the semi-cured adhesive film (thickness 40 ⁇ m) and the browned PCB board, tear off the release film and then perform surface treatment, copper electroplating, to form a laminated printed circuit board with lines.
  • Example 1 Change the chemically synthesized silicon dioxide in Example 1 into silicon micropowder, and use the same method as in Example 1 to make a film.
  • the above solution is coated on the release film, and after drying, it is placed in an oven at 100°C and baked for 3-5 minutes to obtain a semi-cured resin layer film. Press and cure the semi-cured adhesive film (thickness 40 ⁇ m) and the browned PCB board, tear off the release film and then perform surface treatment, copper electroplating, to form a laminated printed circuit board with lines.
  • Example 1 Except changing the ratio of the chemically synthesized silicon dioxide used in Example 1, the same method as in Example 1 was used to manufacture the adhesive film.
  • silicon dioxide 3 (D50 is 0.5 ⁇ m, D100:D10 is 2.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • Example 1 Except changing the ratio of the chemically synthesized silicon dioxide used in Example 1, the same method as in Example 1 was used to manufacture the adhesive film.
  • Example 7 Except for changing the silicon dioxide synthesized by chemical method used in Example 7, the same method as in Example 7 was used to manufacture the adhesive film.
  • silicon dioxide 4 (D50 is 3.5 ⁇ m, D100:D10 is 5.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • the above solution is coated on the release film, and after drying, it is placed in an oven at 100°C and baked for 3-5 minutes to obtain a semi-cured resin layer film. Press and cure the semi-cured adhesive film (thickness 40 ⁇ m) and the browned PCB board, tear off the release film and then perform surface treatment, copper electroplating, to form a laminated printed circuit board with lines.
  • Example 7 Except for changing the silicon dioxide synthesized by chemical method used in Example 7, the same method as in Example 7 was used to manufacture the adhesive film.
  • silicon dioxide 5 (D50 is 2.0 ⁇ m, D100:D10 is 5.0, and the purity is 99.00%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • the above solution is coated on the release film, and after drying, it is placed in an oven at 100°C and baked for 3-5 minutes to obtain a semi-cured resin layer film. Press and cure the semi-cured film (thickness 40 ⁇ m) and the browned PCB board, tear off the release film and perform surface treatment, copper electroplating to form a laminated printed circuit board with circuits.
  • Example 7 Change the chemically synthesized silicon dioxide in Example 7 into silicon micropowder, and use the same method as Example 7 to make a film.
  • the above solution is coated on the release film, and after drying, it is placed in an oven at 100°C and baked for 3-5 minutes to obtain a semi-cured resin layer film. Press and cure the semi-cured film (thickness 40 ⁇ m) and the browned PCB board, tear off the release film and perform surface treatment, copper electroplating to form a laminated printed circuit board with lines.
  • Example 7 Except changing the ratio of the chemically synthesized silicon dioxide used in Example 7, the same method as in Example 7 was used to manufacture the adhesive film.
  • silicon dioxide 3 (D50 is 0.5 ⁇ m, D100:D10 is 2.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • Example 8 Except that the silicon dioxide synthesized by chemical method used in Example 8 was changed, the adhesive film was produced in the same manner as in Example 8.
  • silicon dioxide 4 (D50 is 3.5 ⁇ m, D100:D10 is 5.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • the above solution is coated on the release film, and after drying, it is placed in an oven at 100°C and baked for 3-5 minutes to obtain a semi-cured resin layer film. Press and cure the semi-cured adhesive film (thickness 40 ⁇ m) and the browned PCB board, tear off the release film and then perform surface treatment, copper electroplating, to form a laminated printed circuit board with lines.
  • Example 8 Except that the silicon dioxide synthesized by chemical method used in Example 8 was changed, the adhesive film was produced in the same manner as in Example 8.
  • silicon dioxide 5 (D50 is 2.0 ⁇ m, D100:D10 is 5.0, and the purity is 99.00%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • the above solution is coated on the release film, and after drying, it is placed in an oven at 100°C and baked for 3-5 minutes to obtain a semi-cured resin layer film. Press and cure the semi-cured adhesive film (thickness 40 ⁇ m) and the browned PCB board, tear off the release film and then perform surface treatment, copper electroplating, to form a laminated printed circuit board with lines.
  • the above solution is coated on the release film, and after drying, it is placed in an oven at 100°C and baked for 3-5 minutes to obtain a semi-cured resin layer film. Press and cure the semi-cured film (thickness 40 ⁇ m) and the browned PCB board, tear off the release film and perform surface treatment, copper electroplating to form a laminated printed circuit board with circuits.
  • Example 8 Except changing the ratio of the chemically synthesized silicon dioxide used in Example 8, the same method as in Example 8 was used to manufacture the adhesive film.
  • silicon dioxide 3 (D50 is 0.5 ⁇ m, D100:D10 is 2.0, and the purity is 99.90%) obtained by organosilicon hydrolysis, and continue to stir for more than 4 hours, and mix well to form a solid content of 70%. solution.
  • the build-up printed circuit board or copper-clad laminate of above-mentioned embodiment and comparative example is carried out performance test, and test item and method are as follows:
  • DK/DF Tested by SPDR (Splite Post Dielectric Resonator) method, the test condition is A state, and the frequency is 10GHz;
  • Comparative Example 1 and Comparative Example 2 used silicon dioxide obtained by the organosilicon hydrolysis method whose particle size was not within the scope of the invention, and the tensile strength, peel strength and electrical strength of the obtained adhesive film were all on the low side At the same time, the drilling processability and glue filling ability become worse; in comparative example 3, microsilica powder is used, and the tensile strength and electric strength of the prepared film decrease significantly.
  • Comparative Example 4 reduced the proportion of silicon dioxide to 55%, and the tensile strength of the obtained adhesive film decreased significantly; Comparative Example 5 increased the proportion of silicon dioxide to 90%, and the tensile strength of the obtained adhesive film decreased The tensile strength and electrical strength are low, the peel strength drops significantly, and the glue filling ability becomes poor.
  • Comparative Example 6 and Comparative Example 7 used the silicon dioxide obtained by the organosilicon hydrolysis method whose particle size was not within the scope of the invention, and the tensile strength, peel strength and electrical strength of the obtained adhesive film were all on the low side
  • the drilling processability and glue filling ability become worse; in comparative example 8, microsilica powder is used, and the tensile strength and electric strength of the prepared film decrease significantly.
  • the DK/DF is also too large, and the line processing ability also becomes Poor; in Comparative Example 9, the proportion of silicon dioxide was reduced to 55%, and the tensile strength of the prepared film decreased significantly.
  • Comparative Example 10 and Comparative Example 11 used the silicon dioxide obtained by the organosilicon hydrolysis method whose particle size was not within the scope of the invention, and the tensile strength, peel strength and electrical strength of the obtained adhesive film were all on the low side At the same time, the drilling processability and glue filling ability become worse; in comparative example 12, microsilica powder is used, and the tensile strength and electric strength of the prepared film decrease significantly. At the same time, the DK/DF is also too large, and the line processing ability also becomes Poor; in Comparative Example 13, the proportion of silicon dioxide was reduced to 55%, and the tensile strength of the prepared film decreased significantly.
  • the present invention illustrates the resin composition of the present invention and its application through the above examples, but the present invention is not limited to the above examples, that is, it does not mean that the present invention can only be implemented depending on the above examples.
  • Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

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Abstract

本发明提供一种树脂组合物及其应用，所述树脂组合物包括如下重量百分比的组分：可交联固化树脂15-39％和填料61-85％；所述的填料为通过有机硅水解法制备得到的二氧化硅，所述二氧化硅的平均粒径D50为0.1-3μm，D100:D10的比小于等于2.5，所述二氧化硅的纯度大于99.9％。本发明的树脂组合物，能够使得制备得到的胶膜和涂树脂铜箔具有较高的拉伸强度和剥离强度，较好的钻孔加工性，流动性可控，填胶能力好，电气强度更高，可实现更细的线路加工能力，是可应用于多层积层板的印制电路板材料，特别是细线路的多层积层板的印制电路板材料。

Description

一种树脂组合物及其应用 技术领域
本发明属于层压板技术领域，涉及一种树脂组合物及其应用。
背景技术
随着电子信息产品大量生产，并且朝向轻薄短小、多功能的设计趋势，作为电子零组件主要支撑的印制电路基板，也随着不断提高技术层面，以提供高密度布线、薄形、微细孔径、高散热性。而基板材料在很大程度上决定了印制电路基板的性能，因此急需开发新一代的基体材料。
无增强材料的胶膜或涂树脂铜箔由于可实现更薄形化、高密度布线、微细孔径，被作为新一代的基体材料开发应用。由于无增强材料，一般会添加无机填料，以改善胶膜的热膨胀系数，耐化学性、机械强度及加工性能等。硅微粉是较理想的无机填料，但是由于一般硅微粉粒径分布宽，并且硬度大，添加量大后存在拉伸强度提升不明显，流动性差，加工困难等问题。
CN112526823A公开了一种感光性树脂组合物，其含有(A)感光性树脂、(B)二氧化硅、(C)光聚合引发剂、(D)反应性稀释剂以及(E)环氧化合物，其中，所述(B)二氧化硅的累计体积百分比为50体积％，粒径D50为0.50μm以上2.00μm以下。D1.0为0.20μm以上且0.54μm以下，D99为5.00μm以上且8.40μm以下。该发明换算D99/D50大于2.5，同时没有限定D100，填料颗粒较大。
CN103467927A公开了一种热固性树脂组合物，该组成物包括20-70wt％的热固性树脂，1-30wt％固化剂，0-10wt％促进剂，1-50wt％的平均粒径为1-10微米的化学法合成的二氧化硅微米级团聚体，其可通过含浸方式制成预浸料或通过涂布方式制成涂成物。
如上现有技术中都没有限定D100，存在大粒径二氧化硅存在的缺陷，无法获得高的拉伸强度和剥离强度，无法满足细线路的应用，因此，在本发明中，期望开发一种能够使得胶膜和涂树脂铜箔具有高的较拉伸强度和剥离强度、较好的钻孔加工性、流动性可控、填胶能力好以及电气强度更高的树脂组合物。
发明内容
针对现有技术的不足，本发明的目的在于提供一种树脂组合物及其应用。 本发明的树脂组合物，能够使得制备得到的胶膜和涂树脂铜箔具有高的较拉伸强度和剥离强度，较好的钻孔加工性，流动性可控，填胶能力好，电气强度更高，可实现更细的线路加工能力，是可应用于多层积层板的印制电路板材料，特别是细线路的多层积层板的印制电路板材料。
为达此目的，本发明采用以下技术方案：
一方面，本发明提供一种树脂组合物，所述树脂组合物包括如下重量百分比的组分：可交联固化树脂15-39％和填料61-85％；所述的填料为通过有机硅水解法制备得到的二氧化硅，所述二氧化硅的平均粒径D50为0.1-3μm，D100:D10的比≤2.5，所述二氧化硅的纯度大于99.9％。
在本发明中，通过在树脂组合物中使用有机硅水解法得到的二氧化硅作为填料，其平均粒径D50为0.1-3μm，D100:D10的比≤2.5，含量大于99.9％，使得组合物可以具有较高的拉伸强度和剥离强度，较好的钻孔加工性，电气强度更高。
在本发明的所述树脂组合物中，所述可交联固化树脂的含量15-39％，是指占整个树脂组合物的15-39％，例如可以为15％、18％、20％、22％、25％、28％、30％、32％、34％、36％、38％或39％，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
在本发明的所述树脂组合物中，所述填料的含量61-85％，是指占整个树脂组合物的61-85％，例如可以为61％、63％、65％、68％、70％、72％、74％、76％、78％、80％、82％或85％，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
在本发明中，如果填料的含量小于61％，则拉伸强度提升不明显，如果填料的含量大于85％，则材料脆性大，同时剥离强度下降。
在本发明中，所述二氧化硅，其平均粒径D50为0.1-3μm(例如0.3μm、0.5μm、0.8μm、1μm、1.3μm、1.5μm、1.8μm、2μm、2.3μm、2.5μm、2.8μm或3μm)，D100:D10的比小于2.5(例如可以为2.4、2.3、2.2、2.0、1.8、1.7、1.5、1.3、1.0等)，所述二氧化硅的纯度大于99.9％(例如99.91％、99.93％、99.95％、99.97％、99.99％等)。本发明的二氧化硅的粒径更尖锐、纯度更高，可以使得所制备得到的胶膜和涂树脂铜箔具有较高的拉伸强度和剥离强度，较好的钻孔加工性，流动性可控，填胶能力好，电气强度更高，可实现更细的线路加工能力。
本发明涉及的粒径(例如D50、D10、D100等)均采用激光衍射法测试，测试仪器马尔文激光粒度仪，型号MS3000；本发明涉及的二氧化硅纯度采用电感耦合原子发射光谱仪ICP-AES测定。
优选地，所述可交联固化树脂为热固化树脂或光固化树脂。
优选地，所述可交联固化树脂选自环氧树脂、酚醛树脂、氰酸酯、活性酯、聚苯醚树脂、马来酰亚胺树脂、有机硅树脂、聚苯并恶唑树脂、聚酰亚胺树脂、碳氢树脂或丙烯酸酯树脂中的任意一种或至少两种的组合，优选环氧树脂和酚醛树脂的组合。优选环氧树脂和酚醛树脂的组合，可获得更优的拉伸强度和剥离强度。
优选地，所述环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、含磷环氧树脂、MDI改性环氧树脂、酚醛环氧树脂、联苯型环氧树脂、双环戊二烯型环氧树脂、含萘环氧树脂或脂环族环氧树脂中的一种或至少两种的组合。
优选地，所述酚醛树脂包括双酚A型酚醛树脂、苯酚型酚醛树脂、联苯型酚醛树脂、双环戊二烯型酚醛树脂或含萘酚醛树脂中的一种或至少两种的组合。
优选地，所述二氧化硅为通过有机硅的水解反应得到初产物，将初产物进行烧制得到。优选地，所述烧制的温度为800～1300℃，例如850℃、900℃、905℃、910℃、920℃、930℃、950℃、980℃、990℃、1000℃、1050℃、1100℃、1200℃、1250℃。
优选地，所述有机硅为烷氧基硅烷。
优选地，所述烷氧基硅烷包括四乙氧基硅烷、四甲氧基硅烷、四苯氧基硅烷、四正丁氧基硅烷、四异丁基氧基硅烷、甲基三乙氧基硅烷、二甲基二乙氧基硅烷；进一步优选四乙氧基硅烷。
优选地，所述二氧化硅的平均粒径D50为0.3-1μm。
另一方面，本发明提供一种树脂胶液，其是将如上所述的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，使得到的树脂胶液达到适于使用的粘度即可。
另一方面，本发明提供一种胶膜，所述胶膜为如上所述中任一项所述树脂组合物通过涂覆在离型材料后，经过干燥和/或烘烤制得。
优选地，所述胶膜还可以包括覆于树脂组合物另一侧的保护膜。
优选地，所述胶膜厚度为5-300μm，例如8μm、10μm、15μm、20μm、30μm、50μm、80μm、100μm、120μm、150μm、180μm、200μm、250μm、280μm、300μm，优选为10-200μm；进一步优选为10-100μm。
另一方面，本发明提供一种涂树脂铜箔，所述涂树脂铜箔包括铜箔以及通过涂布干燥后附着在铜箔上的如上所述树脂组合物。
优选地，所述涂树脂铜箔还包括覆于树脂组合物上的保护膜。
优选地，所述涂树脂铜箔的树脂层(是指铜箔上的所述树脂组合物形成的树脂层)厚度为5-300μm，例如8μm、10μm、15μm、20μm、30μm、50μm、80μm、100μm、120μm、150μm、180μm、200μm、250μm、280μm、300μm，优选为10-200μm；进一步优选为10-100um。
优选地，所述涂树脂铜箔的铜箔厚度为1-105μm，例如3μm、5μm、8μm、10μm、20μm、30μm、50μm、80μm、100μm、104μm等，优选为3-35μm；进一步优选为3-12μm。
另一方面，本发明提供一种半固化粘结片，所述半固化粘结片通过玻璃布浸渍上述树脂组合物后烘干而成。
在本发明中，所述玻璃布可选用7628、2116、1131、1080、106、1027、1037、1078玻璃布。
另一方面，本发明提供一种覆铜箔层压板，所述覆铜箔层压板使用上述的胶膜、上述的涂树脂铜箔、上述的半固化粘结片中的一种或至少两种。
另一方面，本发明提供一种多层板，所述多层板使用上述的胶膜、上述的涂树脂铜箔、上述的半固化粘结片、上述的覆铜箔层压板中的一种或至少两种。
相对于现有技术，本发明具有以下有益效果：
本发明的二氧化硅粒径均匀性好，粒径分布更尖锐，添加61-85％时可以使 得所制得的胶膜相对普通二氧化硅所制得的胶膜可获得更好的拉伸模量和剥离强度。所述二氧化硅平均粒径小，并且均匀性好，可避免大颗粒对薄绝缘层耐压及细线路的可靠性影响，更适合做细线路积层压板，所述二氧化硅纯度高，电性(Df)会更优。
本发明的树脂组合物制备得到的胶膜，其拉伸强度可达50-100Mpa，剥离强度达到7.0-9.0N/cm，电气强度高达83-90kV/mm，DK可低至2.95-3.32，DF低至0.004-0.014，并且具有较好的钻孔加工性和较好的填胶能力，综合性能良好。
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。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
在以下实施例以及比较例中使用的原料如下：
环氧树脂：NC-3000H(日本化药)；
酚醛树脂：SN-485(日本新日铁)；
活性酯：HP-8000-65T(日本DIC)；
氰酸酯：XU-371(HUNTSMAN)；
碳氢树脂：B3000(日本曹达)；
聚苯醚：MX9000(沙特沙比克)；
有机硅水解法得到的二氧化硅1：D50为3.0μm，D100:D10为2.5，纯度为99.98％，来自江苏辉迈；
有机硅水解法得到的二氧化硅2：D50为0.1μm，D100:D10为2.5，纯度为99.90％，来自江苏辉迈；
有机硅水解法得到的二氧化硅3：D50为0.5μm，D100:D10为2.0，纯度为99.90％，来自江苏辉迈；
有机硅水解法得到的二氧化硅4：D50为3.5μm，D100:D10为5.0，纯度为99.90％，来自江苏辉迈；
有机硅水解法得到的二氧化硅5：D50为2.0μm，D100:D10为5.0，纯度为 99.00％，来自江苏辉迈；
实施例1
先用适量的溶剂将28份环氧树脂(NC-3000H)和21份酚醛树脂(SN-485)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅3(D50为0.5μm，D100:D10为2.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤5分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
实施例2
除了改变实施例1所用的化学法合成的二氧化硅氧的比例外，用和实施例1相同方法制造胶膜。
先用适量的溶剂将28份环氧树脂(NC-3000H)和21份酚醛树脂(SN-485)溶解，并搅拌2小时以上。
再加入73％的有机硅水解法得到的二氧化硅3(D50为0.5μm，D100:D10为2.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
实施例3
除了改变实施例1所用的化学法合成的二氧化硅的比例外，用和实施例1相同方法制造胶膜。
先用适量的溶剂将28份环氧树脂(NC-3000H)和21份酚醛树脂(SN-485)溶解，并搅拌2小时以上。
再加入85％的有机硅水解法得到的二氧化硅3(D50为0.5μm，D100:D10 为2.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
实施例4
采用实施例1的树脂组合物制造涂树脂铜箔。
先用适量的溶剂将28份环氧树脂(NC-3000H)和21份酚醛树脂(SN-485)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅3(D50为0.5μm，D100:D10为2.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在铜箔上，晾干后，放进100℃烘箱中烘烤5分钟，得到半固化状态树脂层的涂树脂铜箔。将涂树脂铜箔(厚度40μm)和棕化后的PCB板进行压合和固化，然后蚀刻和电镀得到线路的积层印制电路板。
实施例5
除了改变实施例1所用的化学法合成的二氧化硅外，用和实施例1相同方法制造胶膜。
先用适量的溶剂将28份环氧树脂(NC-3000H)和21份酚醛树脂(SN-485)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅1(D50为3.0μm，D100:D10为2.5，纯度为99.98％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
实施例6
除了改变实施例1所用的化学法合成的二氧化硅外，用和实施例1相同方法制造胶膜。
先用适量的溶剂将28份环氧树脂(NC-3000H)和21份酚醛树脂(SN-485)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅2(D50为0.1μm，D100:D10为2.5，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
实施例7
除了改变实施例1所用的树脂类型外，用和实施例1相同方法制造胶膜。
先用适量的溶剂将20份环氧树脂(NC-3000H)、10份氰酸酯(XU-371)和10份活性酯(HP-8000-65T)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅3(D50为0.5μm，D100:D10为2.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
实施例8
除了改变实施例1所用的树脂类型外，用和实施例1相同方法制造胶膜。
先用适量的溶剂将20份碳氢树脂(XU-371)和20份聚苯醚树脂(MX9000)及5份助交联剂(DVB)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅3(D50为0.5μm，D100:D10为2.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量 为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
实施例9
采用实施例7的树脂组合物制造粘结片。
先用适量的溶剂将20份环氧树脂(NC-3000H)、10份氰酸酯(XU-371)和10份活性酯(HP-8000-65T)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅3(D50为0.5μm，D100:D10为2.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
使用上述溶液对玻璃布进行上胶，晾干后，放进100℃烘箱中烘烤5分钟，得到半固化状态粘结片。将多张粘结片叠在一起，并上下配上铜箔，压合和固化，得到覆铜箔层压板。
对比例1
除了改变实施例1所用的化学法合成的二氧化硅外，用和实施例1相同方法制造胶膜。
先用适量的溶剂将环氧树脂(NC-3000H)和21份酚醛树脂(SN-485)溶解，并搅拌2小时以上。
再将加入61％的有机硅水解法得到的二氧化硅4(D50为3.5μm，D100:D10为5.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3-5分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例2
除了改变实施例1所用的化学法合成的二氧化硅外，用和实施例1相同方 法制造胶膜。
先用适量的溶剂将环氧树脂(NC-3000H)和21份酚醛树脂(SN-485)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅5(D50为2.0μm，D100:D10为5.0，纯度为99.00％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3-5分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例3
将实施例1中的化学法合成的二氧化硅氧改为硅微粉，用和实施例1相同方法制造胶膜。
先用适量的溶剂将环氧树脂(NC-3000H)和21份酚醛树脂(SN-485)溶解，并搅拌2小时以上。
再加入61％的硅微粉(SC2500-SQ)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3-5分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例4
除了改变实施例1所用的化学法合成的二氧化硅的比例外，用和实施例1相同方法制造胶膜。
先用适量的溶剂将28份环氧树脂(NC-3000H)和21份酚醛树脂(SN-485)溶解，并搅拌2小时以上。
再加入55％的有机硅水解法得到的二氧化硅3(D50为0.5μm，D100:D10为2.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例5
除了改变实施例1所用的化学法合成的二氧化硅的比例外，用和实施例1相同方法制造胶膜。
先用适量的溶剂将28份环氧树脂(NC-3000H)和21份酚醛树脂(SN-485)溶解，并搅拌2小时以上。
再加入90％的有机硅水解法得到的二氧化硅3(D50为0.5μm，D100:D10为2.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例6
除了改变实施例7所用的化学法合成的二氧化硅外，用和实施例7相同方法制造胶膜。
先用适量的溶剂将20份环氧树脂(NC-3000H)、10份氰酸酯(XU-371)和10份活性酯(HP-8000-65T)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅4(D50为3.5μm，D100:D10为5.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3-5分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例7
除了改变实施例7所用的化学法合成的二氧化硅外，用和实施例7相同方法制造胶膜。
先用适量的溶剂将20份环氧树脂(NC-3000H)、10份氰酸酯(XU-371)和10份活性酯(HP-8000-65T)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅5(D50为2.0μm，D100:D10为5.0，纯度为99.00％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3-5分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例8
将实施例7中的化学法合成的二氧化硅氧改为硅微粉，用和实施例7相同方法制造胶膜。
先用适量的溶剂将20份环氧树脂(NC-3000H)、10份氰酸酯(XU-371)和10份活性酯(HP-8000-65T)溶解，并搅拌2小时以上。
再加入61％的硅微粉(SC2500-SQ)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3-5分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例9
除了改变实施例7所用的化学法合成的二氧化硅的比例外，用和实施例7相同方法制造胶膜。
先用适量的溶剂将20份环氧树脂(NC-3000H)、10份氰酸酯(XU-371)和10份活性酯(HP-8000-65T)溶解，并搅拌2小时以上。
再加入55％的有机硅水解法得到的二氧化硅3(D50为0.5μm，D100:D10为2.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量 为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例10
除了改变实施例8所用的化学法合成的二氧化硅外，用和实施例8相同方法制造胶膜。
先用适量的溶剂将20份碳氢树脂(XU-371)和20份聚苯醚树脂(MX9000)及5份助交联剂(DVB)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅4(D50为3.5μm，D100:D10为5.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3-5分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例11
除了改变实施例8所用的化学法合成的二氧化硅外，用和实施例8相同方法制造胶膜。
先用适量的溶剂将20份碳氢树脂(XU-371)和20份聚苯醚树脂(MX9000)及5份助交联剂(DVB)溶解，并搅拌2小时以上。
再加入61％的有机硅水解法得到的二氧化硅5(D50为2.0μm，D100:D10为5.0，纯度为99.00％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3-5分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例12
将实施例8中的化学法合成的二氧化硅氧改为硅微粉，用和实施例8相同方法制造胶膜。
先用适量的溶剂将20份碳氢树脂(XU-371)和20份聚苯醚树脂(MX9000)及5份助交联剂(DVB)溶解，并搅拌2小时以上。
再加入61％的硅微粉(SC2500-SQ)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3-5分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对比例13
除了改变实施例8所用的化学法合成的二氧化硅的比例外，用和实施例8相同方法制造胶膜。
先用适量的溶剂将20份碳氢树脂(XU-371)和20份聚苯醚树脂(MX9000)及5份助交联剂(DVB)溶解，并搅拌2小时以上。
再加入55％的有机硅水解法得到的二氧化硅3(D50为0.5μm，D100:D10为2.0，纯度为99.90％)，继续搅拌4小时以上，充分混合均匀，形成固体含量为70％的溶液。
将上述溶液涂布在离型膜上，晾干后，放进100℃烘箱中烘烤3分钟，得到半固化状态树脂层的胶膜。将半固化的胶膜(厚度40μm)和棕化后的PCB板进行压合和固化，撕掉离型膜再进行表面处理，化铜电镀，形成带线路的积层印制电路板。
对上述实施例和比较例的积层印制电路板或覆铜箔层压板进行性能测试，测试项目和方法如下：
(1)拉伸强度(30℃)：采用DMA方法，30℃恒温5min，预加力0.01N，3N/min升至17.5N/min；
(2)剥离强度：采用IPC-TM-650 2.4.9方法进行测试；
(3)钻孔加工性：激光钻孔后，切片观察孔型垂直度，垂直度90-95度为 优，96-100度为良，101-110度为中，大于110度为差；
(4)填胶效果：用胶膜压制线路板，然后进行切片，观察线路间的填胶情况：线路间树脂层无气泡为“优”；线路间树脂层有气泡，气泡直径小于1微米为“良”；线路间树脂层有气泡，气泡直径大于1微米为“差”；
(5)电气强度：采用IPC-TM-650 2.5.6.2A方法进行测试；
(6)可实现细线路能力：测量最小能制作的线宽/线距；
(7)DK/DF：采用SPDR(Splite Post Dielectric Resonator)法进行测试，测试条件为A态，频率为10GHz；
性能测试比较如下表1-表4:
表1
Figure PCTCN2022108291-appb-000001
Figure PCTCN2022108291-appb-000002
表2
Figure PCTCN2022108291-appb-000003
Figure PCTCN2022108291-appb-000004
表3
Figure PCTCN2022108291-appb-000005
表4
Figure PCTCN2022108291-appb-000006
Figure PCTCN2022108291-appb-000007
从表1-表4可见，实施例的拉伸强度(50-100Mpa)和剥离强度(7.0-9.0N/cm)高，具有较好的钻孔加工性，填胶能力好，电气强度更高(83-90kV/mm)和DK/DF更低，DK可低至2.95-3.32，DF低至0.004-0.014，可实现更细的线路加工能力，同时可获得更优的电性能。
和实施例1对比，对比例1和对比例2使用了粒径不在发明范围内的有机硅水解法得到的二氧化硅，制得的胶膜的拉伸强度、剥离强度和电气强度都偏低，同时钻孔加工性和填胶能力变差；对比例3使用了硅微粉，制得的胶膜的拉伸强度和电气强度下降明显，同时DK/DF也偏大，同时线路加工能力也变差；对比例4降低了二氧化硅比例到55％，制得的胶膜的拉伸强度降低明显；对比例5增加了二氧化硅比例到90％，制得的胶膜的拉伸强度拉伸强度、电气强度都偏低，剥离强度下降明显，同时填胶能力变差。
和实施例7对比，对比例6和对比例7使用了粒径不在发明范围内的有机硅水解法得到的二氧化硅，制得的胶膜的拉伸强度、剥离强度和电气强度都偏低，同时钻孔加工性和填胶能力变差；对比例8使用了硅微粉，制得的胶膜的拉伸强度和电气强度下降明显，同时DK/DF也偏大，同时线路加工能力也变差；对比例9降低了二氧化硅比例到55％，制得的胶膜的拉伸强度降低明显。
和实施例8对比，对比例10和对比例11使用了粒径不在发明范围内的有机硅水解法得到的二氧化硅，制得的胶膜的拉伸强度、剥离强度和电气强度都偏低，同时钻孔加工性和填胶能力变差；对比例12使用了硅微粉，制得的胶膜的拉伸强度和电气强度下降明显，同时DK/DF也偏大，同时线路加工能力也变差；对比例13降低了二氧化硅比例到55％，制得的胶膜的拉伸强度降低明显。
申请人声明，本发明通过上述实施例来说明本发明的树脂组合物及其应用，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。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 (10)

  1. 一种树脂组合物，其特征在于，所述树脂组合物包括如下重量百分比的组分：可交联固化树脂15-39％和填料61-85％；所述的填料为通过有机硅水解法制备得到的二氧化硅，所述二氧化硅的平均粒径D50为0.1-3μm，D100:D10的比≤2.5，所述二氧化硅的纯度大于99.9％。
  2. 根据权利要求1所述的树脂组合物，其特征在于，所述可交联固化树脂为热固化树脂或光固化树脂；
    优选地，所述可交联固化树脂选自环氧树脂、酚醛树脂、氰酸酯、活性酯、聚苯醚树脂、马来酰亚胺树脂、有机硅树脂、聚苯并恶唑树脂、聚酰亚胺树脂、碳氢树脂或丙烯酸酯树脂中的任意一种或至少两种的组合，优选环氧树脂和酚醛树脂的组合；
    优选地，所述环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、含磷环氧树脂、MDI改性环氧树脂、酚醛环氧树脂、联苯型环氧树脂、双环戊二烯型环氧树脂、含萘环氧树脂或脂环族环氧树脂中的一种或至少两种的组合。
    优选地，所述酚醛树脂包括双酚A型酚醛树脂、苯酚型酚醛树脂、联苯型酚醛树脂、双环戊二烯型酚醛树脂或含萘酚醛树脂中的一种或至少两种的组合。
  3. 根据权利要求1或2所述的树脂组合物，其特征在于，所述二氧化硅为通过有机硅的水解反应得到初产物，所述初产物经过烧制，得到所述二氧化硅；
    优选地，所述烧制的温度为800～1300℃。
  4. 根据权利要求3所述的树脂组合物，其特征在于，所述有机硅为烷氧基硅烷；
    优选地，所述烷氧基硅烷包括四乙氧基硅烷、四甲氧基硅烷、四苯氧基硅烷、四正丁氧基硅烷、四异丁基氧基硅烷、甲基三乙氧基硅烷、二甲基二乙氧基硅烷；进一步优选四乙氧基硅烷。
  5. 根据权利要求1-4中任一项所述的树脂组合物，其特征在于，所述二氧化硅的平均粒径D50为0.3-1μm。
  6. 一种胶膜，其特征在于，所述胶膜为如权利要求1-5中任一项所述树脂组合物通过涂覆在离型材料后，经过干燥和/或烘烤制得；
    优选地，所述胶膜厚度为5-300μm，优选为10-200μm；进一步优选为10-100μm。
  7. 一种涂树脂铜箔，其特征在于，所述涂树脂铜箔包括铜箔以及通过涂布 干燥后附着在铜箔上的如权利要求1-5中任一项所述树脂组合物；
    优选地，所述涂树脂铜箔的树脂层厚度为5-300μm，优选为10-200μm；进一步优选为10-100μm；
    优选地，所述涂树脂铜箔的铜箔厚度为1-105μm，优选为3-35μm；进一步优选为3-12μm。
  8. 一种半固化粘结片，其特征在于，所述半固化粘结片通过玻璃布浸渍如权利要求1-5中任一项所述的树脂组合物后烘干而成。
  9. 一种覆铜箔层压板，其特征在于，所述覆铜箔层压板使用如权利要求6所述的胶膜、如权利要求7所述的涂树脂铜箔、如权利要求8所述的半固化粘结片中的一种或至少两种。
  10. 一种多层板，其特征在于，所述多层板使用如权利要求6所述的胶膜、如权利要求7所述的涂树脂铜箔、如权利要求8所述的半固化粘结片、如权利要求9所述的覆铜板层压板中的一种或至少两种。
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