WO2018192106A1 - Thermosetting vinyl organosilicon resin composition and application thereof in high-frequency circuit board - Google Patents

Thermosetting vinyl organosilicon resin composition and application thereof in high-frequency circuit board Download PDF

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Publication number
WO2018192106A1
WO2018192106A1 PCT/CN2017/092371 CN2017092371W WO2018192106A1 WO 2018192106 A1 WO2018192106 A1 WO 2018192106A1 CN 2017092371 W CN2017092371 W CN 2017092371W WO 2018192106 A1 WO2018192106 A1 WO 2018192106A1
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weight
parts
resin
vinyl
substituted
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PCT/CN2017/092371
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French (fr)
Chinese (zh)
Inventor
陈广兵
曾宪平
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广东生益科技股份有限公司
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Publication of WO2018192106A1 publication Critical patent/WO2018192106A1/en

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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
    • 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
    • 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • H05K1/0373—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
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the present invention relates to a composition of a vinyl silicone resin, and in particular to a thermosetting vinyl silicone resin composition and its use in a high frequency circuit substrate.
  • dielectric constant on performance high-frequency circuits, signal transmission rate and the relationship between the insulating material is a dielectric constant D k: the lower the dielectric constant D k dielectric material, the faster the transmission rate of the signal. Therefore, in order to increase the speed of the signal transmission rate, it is necessary to develop a substrate having a low dielectric constant. As the signal frequency increases, the loss of signal in the substrate can no longer be ignored.
  • the relationship between the signal loss and the frequency, the dielectric constant D k , and the dielectric loss D f is such that the smaller the substrate dielectric constant D k is, the smaller the dielectric loss D f is, and the smaller the signal loss is. Therefore, the development of a high-frequency circuit substrate having a low dielectric constant D k and a low dielectric loss D f has become a research and development direction common to CCL manufacturers.
  • the olefin resin used in the high-frequency electronic circuit substrate is mainly a polybutadiene resin, a styrene-butadiene copolymer or the like.
  • the resin system although the prepared substrate has low dielectric constant and dielectric loss, such a resin has a low thermal decomposition temperature in a hot oxygen environment, is easily aging by thermal oxygen, and has a dielectric constant and a dielectric loss of the substrate along with heat. The problem of an increase in the degree of oxygen aging.
  • the vinyl silicone resin does not contain a polar group, imparting excellent low dielectric constant, low dielectric loss, and low water absorption performance.
  • Vinyl silicone resin main chain with Si-O-Si as the main chain, thermal decomposition temperature The high degree imparts excellent thermal and oxidative aging resistance to the resin, thereby ensuring long-term dielectric constant and dielectric loss stability of the substrate prepared using the resin.
  • CN105086417A discloses a resin composition
  • a resin composition comprising a vinyl-modified polyphenylene ether resin as a host resin and a vinyl MQ resin as a crosslinking agent.
  • the vinyl MQ resin is 10-100 parts by weight based on 100 parts by weight of the vinyl modified polyphenylene ether resin, and the prepared substrate has low dielectric constant, low dielectric loss, high glass transition temperature, and high heat resistance.
  • Comprehensive properties such as sex and low water absorption.
  • CN102993683A discloses a resin composition
  • a resin composition comprising a vinyl-modified polyphenylene ether resin as a host resin, a linear vinyl resin or a cyclic vinyl resin as a crosslinking agent.
  • the substrate has a low dielectric constant, a low dielectric loss, and a high glass transition, based on 100 parts by weight of the vinyl-modified polyphenylene ether resin, and a linear vinyl resin or a cyclic vinyl resin of 10 to 90 parts by weight.
  • Comprehensive properties such as temperature, high heat resistance and low water absorption.
  • the dielectric constant and dielectric loss performance of the vinyl modified polyphenylene ether resin are inferior to those of the vinyl silicone resin.
  • the above two patents all use vinyl modified polyphenylene ether resin as the main resin, vinyl silicone resin as the crosslinking agent, and the substrate dielectric loss is still not low enough to meet the market's high frequency substrate dielectric loss. The lower the demand.
  • the prepared substrate has a lower dielectric constant and dielectric loss, but the adhesion between the substrate layers is poor, and the adhesion between the copper-clad laminate and the substrate layer cannot be satisfied. Claim.
  • thermosetting vinyl silicone resin composition The substrate prepared by using the resin composition has a low dielectric constant, a low dielectric loss, a low water absorption rate, and an interlayer adhesion force can satisfy the requirement of adhesion between layers of a copper clad laminate.
  • thermosetting vinyl silicone resin composition comprising:
  • the vinyl silicone resin is any one or a mixture of at least two of a linear vinyl silicone resin, a cyclic vinyl silicone resin, a three-dimensional random network structure MQ vinyl silicone resin;
  • the weight of the vinyl-modified polyphenylene ether resin is from 10 to 30 parts by weight based on 100 parts by weight of the vinyl silicone resin.
  • the invention applies the vinyl silicone resin as the main resin in the field of copper clad laminates, and since the structure does not contain polar groups, the prepared substrate has low dielectric constant, low dielectric loss and low water absorption performance. Since the main chain of the vinyl silicone resin is Si-O-Si as the main chain, the high thermal decomposition temperature gives the resin excellent thermal and aging resistance, thereby ensuring the long-term preparation of the substrate prepared by using the resin. Medium constant and dielectric loss stability.
  • a vinyl silicone resin is used as a host resin, and a vinyl modified polyphenylene ether resin is used as a substrate interlaminar adhesion modifier, and a substrate layer prepared between the substrates is prepared with respect to a pure vinyl silicone resin system.
  • the adhesive force is greatly improved, which can meet the requirements of the adhesion between the copper-clad laminates on the substrate; at the same time, the inventors have unexpectedly found that the prepared substrate has a pure vinyl silicone system in terms of dielectric constant and dielectric loss performance.
  • the present invention uses a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier without impairing the dielectric constant and dielectric loss performance of the substrate, and the technical effect is beyond the reasonableness of those skilled in the art. expected.
  • the present invention can realize halogen-free and phosphorus-free by using a vinyl silicone resin as a host resin and a vinyl-modified polyphenylene ether resin as a substrate interlayer adhesion modifier without using a flame retardant. V-0 grade flame retardant.
  • the weight of the vinyl-modified polyphenylene ether resin is 10 to 30 parts by weight, for example, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, based on 100 parts by weight of the vinyl silicone resin. 22, 25, 28 or 30 parts, etc.
  • the structure of the linear vinyl silicone resin is:
  • a typical, but non-limiting example of such a linear vinyl silicone resin is the trade name DMS-V05 from Gelestd, wherein R 1 , R 2 , and R 3 are each a methyl group, a vinyl group, and a methyl group.
  • DMS-V05 resin the molecular weight contained therein is a distribution, and the molecular weight is large or small. In a strict sense, the m values corresponding to different molecular weights are different, and are a range rather than a value.
  • the molecular weight of the polymer is generally determined by gel chromatography GPC, and the obtained molecular weight Mn, or weight average molecular weight Mw, or viscosity average molecular weight Mp is a relative value.
  • the m value corresponding to the molecular weight of the resin cannot be given.
  • the structure of the cyclic vinyl silicone resin is:
  • R 4 is selected from substituted or unsubstituted C1 to C12 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C10 or C12, etc.) linear alkyl group or substituted or unsubstituted C1 to C12 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C10 or C12, etc.) branched alkyl; 2 ⁇ n ⁇ 10, n is a natural number (for example, n is 2, 3, 4, 5, 6 , 7, 8, 9, or 10, etc.).
  • the structure of the three-dimensional random network structure MQ vinyl silicone resin is:
  • 3 ⁇ x ⁇ 100 for example, x is 3, 5, 10, 20, 25, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc.
  • 6 ⁇ y ⁇ 100 for example, x is 6, 10, 20, 25, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc.
  • 9 ⁇ x + y ⁇ 200 for example, 9 ⁇ x + y ⁇ 14, 15 ⁇ x + y ⁇ 30, 40 ⁇ x+y ⁇ 52, 55 ⁇ x+y ⁇ 68, 70 ⁇ x+y ⁇ 82, 89 ⁇ x+y ⁇ 105, 121 ⁇ x+y ⁇ 153, 157 ⁇ x+y ⁇ 175 , 182 ⁇ x+y ⁇ 193, 195 ⁇ x+y ⁇ 200, etc.
  • 0.1 ⁇ x/y ⁇ 4 for example, x/y is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9) , 1.0, 1.2, 1.5, 1.8, 2.0, 2.3, 2.5
  • MQ vinyl silicone resin is the trade name of DY-VMQ102 of Shandong Dayi Chemical Co., Ltd., and R 5 , R 6 and R 7 are respectively methyl group and A.
  • Base vinyl.
  • the three-dimensional network structure has a plurality of nodes, and a structure in which a plurality of holes are formed, for example, the following structure (this structure is only exemplified, not exhaustive):
  • the vinyl modified polyphenylene ether resin has the following structure:
  • 1 ⁇ e ⁇ 100 (for example, e is 1, 3, 5, 7, 9, 15, 22, 32, 38, 48, 50, 61, 72, 81, 90, 92 or 100, etc.)
  • 1 ⁇ f ⁇ 100 (for example, f is 1, 3, 5, 7, 9, 15, 22, 32, 38, 48, 50, 61, 72, 81, 90, 92 or 100, etc.)
  • 2 ⁇ e + f ⁇ 100 (for example, 2 ⁇ e+f ⁇ 10, 10 ⁇ e+f ⁇ 20, 15 ⁇ e+f ⁇ 30, 25 ⁇ e+f ⁇ 40, 30 ⁇ e+f ⁇ 55, 60 ⁇ e+f ⁇ 85,65 ⁇ e + f ⁇ 75, 80 ⁇ e + f ⁇ 98 or 85 ⁇ e + f ⁇ 100, etc.; and M is selected from:
  • N is selected from any one of -O-, -CO-, -SO-, -SC-, -SO 2 -, -C(CH 3 ) 2 - or a combination of at least two;
  • R 8 , R 10 , R 12 , R 14 , R 17 , R 19 , R 21 and R 23 are each independently selected from substituted or unsubstituted C1 to C8 (eg, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) a linear alkyl group, a substituted or unsubstituted C1 to C8 (for example, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl group, substituted or unsubstituted phenyl group Any one or a combination of at least two;
  • R 9 , R 11 , R 13 , R 15 , R 18 , R 20 , R 22 and R 24 are each independently selected from a hydrogen atom, a substituted or unsubstituted C1 to C8 (for example, C1, C2, C3, C4, C5). , C6, C7 or C8, etc.) linear alkyl, substituted or unsubstituted C1-C8 (eg C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl, substituted or unsubstituted Any one of phenyl groups or a combination of at least two;
  • R 16 is selected from:
  • B is any one of an arylene group, a carbonyl group or an alkylene group having 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10); 25 , R 26 and R 27 are each independently selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10).
  • 25 , R 26 and R 27 are each independently selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10).
  • the vinyl modified polyphenylene ether resin has a number average molecular weight of 500 to 10000 g/mol, for example, 500 g/mol, 800 g/mol, 1000 g/mol, 1100 g/mol, 1500 g/mol, 4000 g/mol, 5600 g. /mol, 8000 g/mol or 10000 g/mol, etc., preferably 800 to 8000 g/mol, further preferably 1000 to 4000 g/mol.
  • the free radical initiator is a peroxide free radical initiator.
  • the radical initiator is selected from the group consisting of dicumyl peroxide, dibenzoyl peroxide, t-butyl peroxybenzoate or 4,4-di(tert-butylperoxy)pentanoic acid n-butylate Any one or a mixture of at least two of the esters, wherein a typical but non-limiting mixture is: a mixture of n-butyl 4,4-di(tert-butylperoxy)pentanoate and tert-butyl peroxybenzoate a mixture of dibenzoyl peroxide and dicumyl peroxide, a mixture of n-butyl 4,4-di(tert-butylperoxy)pentanoate and dibenzoyl peroxide, tert-butyl peroxybenzoate a mixture of an ester and dicumyl peroxide, a mixture of 4,4-di(tert-butylperoxy)pentanoic
  • the radical initiators may be used singly or in combination, and a mixed effect may be used to achieve a better synergistic effect.
  • the weight of the radical initiator is 1 to 3 parts, for example, 1 part, 1.2 parts, 1.5 parts, based on 100 parts by weight of the weight of the vinyl silicone resin and the vinyl modified polyphenylene ether resin. 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts or 3 parts, and the like.
  • the resin composition of the present invention may further comprise a powder filler.
  • the powder filler is selected from the group consisting of crystalline silica, amorphous silica, spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, Any one or a mixture of at least two of barium titanate or barium titanate, typically but not limiting
  • the mixture is: a mixture of crystalline silica and amorphous silica, a mixture of spherical silica and titanium dioxide, a mixture of silicon carbide and glass fibers, a mixture of aluminum oxide and aluminum nitride, boron nitride and titanic acid.
  • the powder filler functions to improve dimensional stability, lower thermal expansion coefficient, lower system cost, and the like.
  • the shape and particle diameter of the powder filler are not particularly limited in the invention, and the particle diameter generally used is 0.2 to 10 ⁇ m, for example, 0.2 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 5 ⁇ m, 8 ⁇ m, 9 ⁇ m or 10 ⁇ m, etc., for example.
  • a spherical silica having a particle diameter of 0.2 to 10 ⁇ m can be selected.
  • the weight of the powder filler is 100 to 300 parts, for example, 100 parts, 110 parts, 120 parts, 130 parts by weight of 100 parts by weight of the vinyl silicone resin and the vinyl modified polyphenylene ether resin. , 140 parts, 150 parts, 160 parts, 180 parts, 180 parts, 190 parts, 200 parts, 210, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280, 290 or 300 parts, and the like.
  • thermosetting vinyl silicone resin composition of the present invention may be added with a thermosetting resin, and specific examples thereof include an epoxy resin, a cyanate resin, a phenol resin, a polyurethane resin, a melamine resin, and the like. A curing agent or a curing accelerator of these thermosetting resins is added.
  • the resin composition may further contain various additives, and specific examples thereof include a silane coupling agent, a titanate coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, and a pigment. , colorants, lubricants, etc. These additives may be used singly or in combination of two or more.
  • the resin compositions of the present invention As a preparation method of one of the resin compositions of the present invention, it can be blended, stirred, and known by a known method.
  • the vinyl silicone resin, the vinyl modified polyphenylene ether resin, the radical initiator, the powder filler, and various thermosetting resins and various additives are mixed and prepared.
  • Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing the 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 to be used can be selected by a person skilled in the art according to his own experience, so that the obtained resin glue can reach a viscosity suitable for use.
  • An emulsifier may be added during the process of dissolving or dispersing the resin composition as described above in a solvent. By dispersing by an emulsifier, the powder filler or the like can be uniformly dispersed in the glue.
  • a third object of the present invention is to provide a prepreg obtained by dipping a glass fiber cloth in a resin glue as described above and drying it.
  • the glass fiber cloth is a reinforcing material, and functions to increase strength, improve dimensional stability, and reduce shrinkage of curing of the thermosetting resin in the composite material.
  • Different types of fiberglass cloth can be used depending on the thickness of the sheet and the like.
  • Exemplary glass fiber cloths are: 7628 fiberglass cloth, 2116 fiberglass cloth.
  • the weight of the glass fiber cloth is 40 to 150 parts, for example, 40 parts, 50 parts, 60 parts, 70, based on 100 parts by weight of the sum of the weight of the vinyl silicone resin, the vinyl modified polyphenylene ether resin, and the powder filler. Share, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts or 150 parts, and the like.
  • the drying temperature is 80-220 ° C, such as 80 ° C, 90 ° C, 110 ° C, 150 ° C, 170 ° C, 190 ° C, 200 ° C or 220 ° C, etc.; the drying time is 1 ⁇ 30min, such as 1min, 5min, 8min, 13min, 17min, 21min, 24min, 28min or 30min.
  • a fourth object of the present invention is to provide a high-frequency circuit substrate which is made of the prepreg as described above, and in particular, the high-frequency circuit substrate is produced by the following method:
  • At least one prepreg as described above is overlapped, and a copper foil is placed on the upper and lower sides of the overlapping prepreg, and is obtained by lamination molding.
  • the overlap preferably employs an automated stacking operation to make the process operation easier.
  • the laminate molding is preferably vacuum lamination molding, and the vacuum lamination molding can be carried out by a vacuum laminator.
  • the lamination time is 70-120 min, such as 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min or 120 min, etc.;
  • the lamination temperature is 180-220 ° C, for example 180 ° C 185 ° C, 190 ° C, 195 ° C, 200 ° C, 205 ° C, 210 ° C, 215 ° C or 220 ° C;
  • the pressure of the lamination is 40 ⁇ 60kg / cm 2 , for example 40kg / cm 2 , 45kg / cm 2 , 50kg / cm 2, 55kg / cm 2, 58kg / cm 2 or 60kg / cm 2 and the like.
  • a typical but non-limiting method for preparing a high frequency circuit substrate of the present invention is as follows:
  • the components are weighed: the weight of the vinyl-modified polyphenylene ether resin is 10 to 30 parts by weight based on 100 parts by weight of the vinyl silicone resin; The sum of the parts by weight of the silicone resin and the vinyl modified polyphenylene ether resin is 100 parts by weight, and the weight of the radical initiator is 1 to 3 parts; and the vinyl silicone resin and the vinyl modified polyphenylene ether resin are used.
  • the weight of the powder filler is 100 to 300 parts by weight;
  • a fifth object of the present invention is to provide an application of the above-described resin composition for preparing a resin glue, a prepreg, and a high-frequency circuit substrate.
  • the high-frequency circuit substrate having low dielectric constant, low dielectric loss, and low water absorption can be prepared by using the resin composition of the present invention, and the interlayer adhesion between the substrates can satisfy the adhesion between the copper-clad layers. The requirements of the joint force.
  • High frequency as used in the present invention means that the frequency is greater than 100 MHz.
  • the present invention has the following beneficial effects:
  • the present invention applies a vinyl silicone resin to the field of copper clad laminates, and its chemical structure does not contain a polar group, thereby ensuring that the prepared substrate has a low dielectric constant and a low dielectric loss performance;
  • the present invention adopts a vinyl silicone resin as a host resin, a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier, and a substrate layer prepared in comparison with a pure vinyl silicone system.
  • the inter-adhesive strength is greatly improved, which can meet the requirements of the adhesion between the copper-clad laminates on the substrate layer, and the prepared substrate dielectric constant and dielectric loss performance are consistent with the pure vinyl silicone system, vinyl-modified polyphenylene Ether as an interlayer adhesion modifier without impairing the dielectric constant and dielectric loss properties of the substrate;
  • the present invention uses a vinyl silicone resin as a host resin, and a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier, which can realize halogen-free and phosphorus-free V without using a flame retardant. -0 grade flame retardant;
  • the invention adopts a vinyl silicone resin as a main resin and a vinyl modified polyphenylene ether as a substrate interlayer adhesion modifier, and the prepared substrate has a low dielectric constant and a low dielectric loss, and a good base.
  • the adhesion between the layers can meet the needs of the copper clad laminate, and at the same time, it can realize the halogen-free and phosphorus-free V-0 flame retardant, which is very suitable for the circuit board for preparing high-frequency electronic equipment.
  • Table 1 below shows the materials used in the respective examples and comparative examples.
  • a linear vinyl silicone resin DMS-V05 80.0 parts by weight of a linear vinyl silicone resin DMS-V05, 20.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silicon fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • cyclic vinyl silicone resin WD-V4 100 parts by weight of the cyclic vinyl silicone resin WD-V4, 3.0 parts by weight of a radical initiator DCP, and 233.0 parts by weight of the silica fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • a linear vinyl silicone resin DMS-V05 20.0 parts by weight of a linear vinyl silicone resin DMS-V05, 80.0 parts by weight of a vinyl-modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the modified polyphenylene ether as an interlayer adhesion modifier does not impair the dielectric constant and dielectric loss properties of the substrate. Comparing Examples 1 to 3 with Comparative Examples 4 to 6, respectively, the substrates prepared in Examples 1 to 3 were able to achieve halogen-free and phosphorus-free V-0 flame retardant without using a flame retardant. Comparative Examples 4 to 6 failed to achieve V-0 flame retardancy; in addition, the substrates prepared in Examples 1 to 3 had lower dielectric constants and dielectric loss than Comparative Examples 4 to 6, indicating that the present invention was adopted.
  • a linear vinyl silicone resin DMS-V05 90.0 parts by weight of a linear vinyl silicone resin DMS-V05, 10.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • a linear vinyl silicone resin DMS-V05 10.0 parts by weight of a linear vinyl silicone resin DMS-V05, 90.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • a cyclic vinyl silicone resin WD-V4 90.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, and 233.0 parts by weight of a silica fine powder 525 were dissolved in In a toluene solvent, and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • a linear vinyl silicone resin DMS-V05 85.0 parts by weight of a linear vinyl silicone resin DMS-V05, 15.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • a linear vinyl silicone resin DMS-V05 15.0 parts by weight of a linear vinyl silicone resin DMS-V05, 85.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the substrates prepared in Examples 7 to 9 were able to realize halogen-free and phosphorus-free V without using a flame retardant.
  • -0 grade flame retardant while Comparative Examples 10-12 did not achieve V-0 flame retardant; in addition, the substrates prepared in Examples 7-9 had lower dielectric constants and media than Comparative Examples 10-12.
  • Loss indicating that the present invention uses a vinyl silicone resin as a host resin, a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier, and a vinyl-modified polyphenylene ether resin as a host resin, ethylene.
  • the base silicone resin is used as a crosslinking agent, and the prepared substrate has better dielectric constant and dielectric loss performance, and can realize halogen-free and phosphorus-free V-0 flame retardant.
  • the silicon micropowder 525 is dissolved in a toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, and drying in an oven to remove the toluene solvent.
  • a cyclic vinyl silicone resin WD-V4 30.0 parts by weight of a vinyl modified polyphenylene ether resin OPE-2ST, 1.0 part by weight of a radical initiator DCP, and 155.0 parts by weight of a silica fine powder 525, Dissolved in toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the silicon micropowder 525 is dissolved in a toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass cloth, controlling the single weight by the clamp shaft, and drying in an oven to remove the toluene solvent.
  • a cyclic vinyl silicone resin WD-V4 85.0 parts by weight of a cyclic vinyl silicone resin WD-V4, 15.0 parts by weight of a vinyl-modified polyphenylene ether resin OPE-2ST, 1.0 part by weight of a radical initiator DCP, and 155.0 parts by weight of a silica fine powder 525, Dissolved in toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • a cyclic vinyl silicone resin WD-V4 80.0 parts by weight of a cyclic vinyl silicone resin WD-V4, 20.0 parts by weight of a vinyl-modified polyphenylene ether resin OPE-2ST, 1.0 part by weight of a radical initiator DCP, and 155.0 parts by weight of a silicon micropowder SC- 2300SVJ, dissolved in toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the present invention adopts a vinyl silicone resin as a host resin and a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier, and the prepared substrate has a good substrate layer. Inter-adhesive force, can meet the requirements of adhesion between layers of CCL, and has low dielectric constant and low dielectric loss, and can achieve halogen-free and phosphorus-free V-0 flame retardant, which is very suitable for the circuit of high-frequency electronic equipment. Substrate.

Abstract

A thermosetting vinyl organosilicon resin composition, comprising: a vinyl organosilicon resin composed of one or at least two of linear vinyl organosilicon resin, ring vinyl organosilicon resin, and MQ vinyl organosilicon resin having a three-dimensional random network structure; a vinyl modified polyphenylene oxide resin, and a radical initiator. A high-frequency circuit board manufactured by the resin composition has a low dielectric constant, low dielectric loss, and low water absorption; the interlayer adhesive force can satisfy requirements for interlayer adhesive force of copper clad laminates; and non-halogen and non-phosphorus V-0 flame retardant can also be achieved.

Description

[根据细则37.2由ISA制定的发明名称]　热固性乙烯基有机硅树脂组合物及其在高频电路板中的应用[Invention name established by ISA according to Rule 37.2] Thermosetting vinyl silicone resin composition and its application in high frequency circuit boards 技术领域Technical field
本发明涉及一种乙烯基有机硅树脂的组合物，具体地，本发明涉及一种热固性乙烯基有机硅树脂组合物及其在高频电路基板中的应用。The present invention relates to a composition of a vinyl silicone resin, and in particular to a thermosetting vinyl silicone resin composition and its use in a high frequency circuit substrate.
背景技术Background technique
近年来，随着无线通讯技术、电子产品的迅速发展，电子电路步入信息处理高速化、信号传输高频化阶段，然而当频率大于300MHz，甚至达到GHz以上时，基板的电性能将严重影响电子电路的特征，因而对基板性能提出更高的要求。In recent years, with the rapid development of wireless communication technology and electronic products, electronic circuits have entered the stage of high-speed information processing and high-frequency signal transmission. However, when the frequency is greater than 300MHz or even above GHz, the electrical performance of the substrate will be seriously affected. The characteristics of electronic circuits thus place higher demands on substrate performance.
就介质常数性能而言，在高频电路中，信号的传输速率与绝缘材料介质常数Dk的关系为：绝缘材料介质常数Dk越低，信号传输速率越快。因此要实现信号传输速率的高速化，必须开发低介质常数的基板。随着信号频率的高速化，基板中信号的损耗不能再忽略不计。信号损耗与频率、介质常数Dk、介质损耗Df的关系为：基板介质常数Dk越小、介质损耗Df越小，信号损失就越小。因此开发具有低的介质常数Dk及低的介质损耗Df的高频电路基板，成为CCL厂家共同关注的研发方向。For dielectric constant on performance, high-frequency circuits, signal transmission rate and the relationship between the insulating material is a dielectric constant D k: the lower the dielectric constant D k dielectric material, the faster the transmission rate of the signal. Therefore, in order to increase the speed of the signal transmission rate, it is necessary to develop a substrate having a low dielectric constant. As the signal frequency increases, the loss of signal in the substrate can no longer be ignored. The relationship between the signal loss and the frequency, the dielectric constant D k , and the dielectric loss D f is such that the smaller the substrate dielectric constant D k is, the smaller the dielectric loss D f is, and the smaller the signal loss is. Therefore, the development of a high-frequency circuit substrate having a low dielectric constant D k and a low dielectric loss D f has become a research and development direction common to CCL manufacturers.
目前，高频电子电路基材采用的烯烃树脂主要为聚丁二烯树脂、丁苯共聚物等。采用该树脂体系，所制备的基材虽然介质常数和介质损耗低，但这类树脂在热氧环境中热分解温度低，易被热氧老化，存在基材的介质常数和介质损耗随着热氧老化程度的加深而升高的问题。At present, the olefin resin used in the high-frequency electronic circuit substrate is mainly a polybutadiene resin, a styrene-butadiene copolymer or the like. With the resin system, although the prepared substrate has low dielectric constant and dielectric loss, such a resin has a low thermal decomposition temperature in a hot oxygen environment, is easily aging by thermal oxygen, and has a dielectric constant and a dielectric loss of the substrate along with heat. The problem of an increase in the degree of oxygen aging.
乙烯基有机硅树脂不含极性基团，赋予了该种树脂优异的低介质常数、低介质损耗、低吸水率性能。乙烯基有机硅树脂主链以Si-O-Si为主链，热分解温 度高，赋予了该种树脂优异的抗热氧老化性能，从而保证了采用该种树脂制备的基材具有长期的介质常数和介质损耗稳定性。The vinyl silicone resin does not contain a polar group, imparting excellent low dielectric constant, low dielectric loss, and low water absorption performance. Vinyl silicone resin main chain with Si-O-Si as the main chain, thermal decomposition temperature The high degree imparts excellent thermal and oxidative aging resistance to the resin, thereby ensuring long-term dielectric constant and dielectric loss stability of the substrate prepared using the resin.
CN105086417A公开了一种树脂组合物，以乙烯基改性聚苯醚树脂为主体树脂，乙烯基MQ树脂为交联剂。以乙烯基改性聚苯醚树脂的重量为100份计，乙烯基MQ树脂为10-100重量份，所制备的基材具有低介质常数、低介质损耗、高玻璃化转变温度、高耐热性、低吸水率等综合性能。CN105086417A discloses a resin composition comprising a vinyl-modified polyphenylene ether resin as a host resin and a vinyl MQ resin as a crosslinking agent. The vinyl MQ resin is 10-100 parts by weight based on 100 parts by weight of the vinyl modified polyphenylene ether resin, and the prepared substrate has low dielectric constant, low dielectric loss, high glass transition temperature, and high heat resistance. Comprehensive properties such as sex and low water absorption.
CN102993683A公开了一种树脂组合物，以乙烯基改性聚苯醚树脂为主体树脂，线性乙烯基树脂或环形乙烯基树脂为交联剂。以乙烯基改性聚苯醚树脂的重量为100份计，线性乙烯基树脂或环形乙烯基树脂为10-90重量份，所制备的基材具有低介质常数、低介质损耗、高玻璃化转变温度、高耐热性、低吸水率等综合性能。CN102993683A discloses a resin composition comprising a vinyl-modified polyphenylene ether resin as a host resin, a linear vinyl resin or a cyclic vinyl resin as a crosslinking agent. The substrate has a low dielectric constant, a low dielectric loss, and a high glass transition, based on 100 parts by weight of the vinyl-modified polyphenylene ether resin, and a linear vinyl resin or a cyclic vinyl resin of 10 to 90 parts by weight. Comprehensive properties such as temperature, high heat resistance and low water absorption.
乙烯基改性聚苯醚树脂的介质常数和介质损耗性能比乙烯基有机硅树脂差。以上两篇专利都是以乙烯基改性聚苯醚树脂为主体树脂，乙烯基有机硅树脂为交联剂，所制备的基材介质损耗仍不够低，不能满足市场对高频基材介质损耗越来越低的需求。The dielectric constant and dielectric loss performance of the vinyl modified polyphenylene ether resin are inferior to those of the vinyl silicone resin. The above two patents all use vinyl modified polyphenylene ether resin as the main resin, vinyl silicone resin as the crosslinking agent, and the substrate dielectric loss is still not low enough to meet the market's high frequency substrate dielectric loss. The lower the demand.
如以乙烯基有机硅树脂作为全体树脂，所制备的基材虽然具有更低的介质常数和介质损耗，但基材层间粘合力差，不能满足覆铜板对基材层间粘合力的要求。If a vinyl silicone resin is used as the entire resin, the prepared substrate has a lower dielectric constant and dielectric loss, but the adhesion between the substrate layers is poor, and the adhesion between the copper-clad laminate and the substrate layer cannot be satisfied. Claim.
发明内容Summary of the invention
针对现有技术存在的问题，本发明的目的之一在于提供一种热固性乙烯基有机硅树脂组合物。应用该树脂组合物制备的基材具有低介质常数、低介质损耗、低吸水率，且层间粘合力能够满足覆铜板层间粘合力的要求。In view of the problems of the prior art, it is an object of the present invention to provide a thermosetting vinyl silicone resin composition. The substrate prepared by using the resin composition has a low dielectric constant, a low dielectric loss, a low water absorption rate, and an interlayer adhesion force can satisfy the requirement of adhesion between layers of a copper clad laminate.
为达此目的，本发明采用如下技术方案： To achieve this, the present invention adopts the following technical solutions:
本发明提供了一种热固性乙烯基有机硅树脂组合物，其包括：The present invention provides a thermosetting vinyl silicone resin composition comprising:
(1)乙烯基有机硅树脂；(1) a vinyl silicone resin;
该乙烯基有机硅树脂为线性乙烯基有机硅树脂、环形乙烯基有机硅树脂、三维无规网状结构MQ乙烯基有机硅树脂中的任意一种或至少两种的混合物；The vinyl silicone resin is any one or a mixture of at least two of a linear vinyl silicone resin, a cyclic vinyl silicone resin, a three-dimensional random network structure MQ vinyl silicone resin;
(2)乙烯基改性聚苯醚树脂；(2) a vinyl modified polyphenylene ether resin;
(3)自由基引发剂；(3) a free radical initiator;
以乙烯基有机硅树脂的重量为100份计，乙烯基改性聚苯醚树脂的重量为10～30份。The weight of the vinyl-modified polyphenylene ether resin is from 10 to 30 parts by weight based on 100 parts by weight of the vinyl silicone resin.
本发明通过将乙烯基有机硅树脂作为主体树脂应用于覆铜板领域，由于其结构中不含有极性基团，从而保证了所制备的基材具有低介质常数、低介质损耗和低吸水率性能；由于乙烯基有机硅树脂主链以Si-O-Si为主链，热分解温度高，赋予了该种树脂优异的抗热氧老化性能，从而保证了采用该种树脂制备的基材具有长期的介质常数和介质损耗稳定性。The invention applies the vinyl silicone resin as the main resin in the field of copper clad laminates, and since the structure does not contain polar groups, the prepared substrate has low dielectric constant, low dielectric loss and low water absorption performance. Since the main chain of the vinyl silicone resin is Si-O-Si as the main chain, the high thermal decomposition temperature gives the resin excellent thermal and aging resistance, thereby ensuring the long-term preparation of the substrate prepared by using the resin. Medium constant and dielectric loss stability.
本发明中采用乙烯基有机硅树脂作为主体树脂，乙烯基改性聚苯醚树脂作为基板层间粘合力改性剂，相对于纯乙烯基有机硅树脂体系，其所制备的基材层间粘合力大幅度提高，可满足覆铜板对基材层间粘合力的要求；同时，发明人意外发现，其所制备的基材在介质常数和介质损耗性能方面与纯乙烯基有机硅体系一致，也就是说，本发明采用乙烯基改性聚苯醚作为基板层间粘合力改性剂，没有损害基材的介质常数和介质损耗性能，该技术效果超出了本领域技术人员的合理预期。In the present invention, a vinyl silicone resin is used as a host resin, and a vinyl modified polyphenylene ether resin is used as a substrate interlaminar adhesion modifier, and a substrate layer prepared between the substrates is prepared with respect to a pure vinyl silicone resin system. The adhesive force is greatly improved, which can meet the requirements of the adhesion between the copper-clad laminates on the substrate; at the same time, the inventors have unexpectedly found that the prepared substrate has a pure vinyl silicone system in terms of dielectric constant and dielectric loss performance. Consistently, that is, the present invention uses a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier without impairing the dielectric constant and dielectric loss performance of the substrate, and the technical effect is beyond the reasonableness of those skilled in the art. expected.
另外，本发明通过采用乙烯基有机硅树脂作为主体树脂，乙烯基改性聚苯醚树脂作为基板层间粘合力改性剂，在没有使用阻燃剂的条件下，能够实现无卤无磷V-0级阻燃。 In addition, the present invention can realize halogen-free and phosphorus-free by using a vinyl silicone resin as a host resin and a vinyl-modified polyphenylene ether resin as a substrate interlayer adhesion modifier without using a flame retardant. V-0 grade flame retardant.
本发明中，以乙烯基有机硅树脂的重量为100重量份计，乙烯基改性聚苯醚树脂的重量为10～30份，例如10份、12份、15份、18份、20份、22份、25份、28份或30份等。In the present invention, the weight of the vinyl-modified polyphenylene ether resin is 10 to 30 parts by weight, for example, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, based on 100 parts by weight of the vinyl silicone resin. 22, 25, 28 or 30 parts, etc.
优选地，所述线性乙烯基有机硅树脂的结构为：Preferably, the structure of the linear vinyl silicone resin is:
Figure PCTCN2017092371-appb-000001
Figure PCTCN2017092371-appb-000001
其中，R1、R2、R3三者至少有一个为取代或未取代的C2～C10(例如C2、C3、C4、C5、C6、C7、C8、C9或C10等)含C＝C的基团；其余两者均独立地选自取代或未取代的C1～C8(例如C1、C2、C3、C4、C5、C6、C7或C8等)直链烷基、取代或未取代的C1～C8(例如C1、C2、C3、C4、C5、C6、C7或C8等)支链烷基、取代或未取代的苯基、取代或未取代的C2～C10(例如C2、C3、C4、C5、C6、C7、C8、C9或C10等)含C＝C的基团中的任意一种，且5≤m≤100(例如m为5、7、9、15、22、32、38、48、50、61、72、81、90、92或100等)。Wherein at least one of R 1 , R 2 and R 3 is a substituted or unsubstituted C 2 -C 10 (eg C2, C3, C4, C5, C6, C7, C8, C9 or C10, etc.) containing C=C a group; the other two are independently selected from a substituted or unsubstituted C1-C8 (eg, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) linear alkyl group, substituted or unsubstituted C1~ C8 (eg C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C2 to C10 (eg C2, C3, C4, C5) , C6, C7, C8, C9 or C10, etc.) any one of C=C-containing groups, and 5 ≤ m ≤ 100 (for example, m is 5, 7, 9, 15, 22, 32, 38, 48 , 50, 61, 72, 81, 90, 92 or 100, etc.).
所述线性乙烯基有机硅树脂的一个典型但非限制性实例是Gelestd的商品名为DMS-V05，其R1、R2、R3分别为甲基、乙烯基、甲基。对于DMS-V05树脂，其所含的分子量是一个分布，分子量有大有小，严格意义来说，不同分子量对应的m值不同，是一个范围，而不是一个值。在实验室，检测高分子的分子量一般采用的是凝胶色谱GPC，所得到数据分子量Mn，或重均分子量Mw，或粘均分子量Mp是一个相对值。因此对于DMS-V05树脂，不能给出该树脂分子量对应的m值。采用GPC仪器进行检测，以甲苯作为流动相，该树脂所得的分子量大小为Mn＝800。同理适用于三维无规网状结构MQ乙烯基有机硅树脂。 A typical, but non-limiting example of such a linear vinyl silicone resin is the trade name DMS-V05 from Gelestd, wherein R 1 , R 2 , and R 3 are each a methyl group, a vinyl group, and a methyl group. For the DMS-V05 resin, the molecular weight contained therein is a distribution, and the molecular weight is large or small. In a strict sense, the m values corresponding to different molecular weights are different, and are a range rather than a value. In the laboratory, the molecular weight of the polymer is generally determined by gel chromatography GPC, and the obtained molecular weight Mn, or weight average molecular weight Mw, or viscosity average molecular weight Mp is a relative value. Therefore, for the DMS-V05 resin, the m value corresponding to the molecular weight of the resin cannot be given. The detection was carried out by a GPC apparatus using toluene as a mobile phase, and the molecular weight of the resin was Mn = 800. The same applies to the three-dimensional random network structure MQ vinyl silicone resin.
优选地，所述环形乙烯基有机硅树脂的结构为：Preferably, the structure of the cyclic vinyl silicone resin is:
Figure PCTCN2017092371-appb-000002
Figure PCTCN2017092371-appb-000002
其中，R4选自取代或未取代的C1～C12(例如C1、C2、C3、C4、C5、C6、C7、C8、C10或C12等)直链烷基或取代或未取代的C1～C12(例如C1、C2、C3、C4、C5、C6、C7、C8、C10或C12等)支链烷基；2≤n≤10，n为自然数(例如n为2、3、4、5、6、7、8、9或10等)。Wherein R 4 is selected from substituted or unsubstituted C1 to C12 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C10 or C12, etc.) linear alkyl group or substituted or unsubstituted C1 to C12 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C10 or C12, etc.) branched alkyl; 2 ≤ n ≤ 10, n is a natural number (for example, n is 2, 3, 4, 5, 6 , 7, 8, 9, or 10, etc.).
所述环形乙烯基有机硅树脂的一个典型但非限制性实例是武大有机硅的商品名为WD-V4，其R4为甲基，n＝2。A typical, but non-limiting example of the cyclic vinyl silicone resin is the trade name WD-V4 of Wuda Silicon, where R 4 is methyl and n=2.
优选地，所述三维无规网状结构MQ乙烯基有机硅树脂的结构为：Preferably, the structure of the three-dimensional random network structure MQ vinyl silicone resin is:
(R5R6R7SiO1/2)x(5iO4/2)y (R 5 R 6 R 7 SiO 1/2 ) x (5iO 4/2 ) y
其中，3≤x≤100(例如x为3、5、10、20、25、31、40、52、61、70、80、92、95或100等)，6≤y≤100(例如x为6、10、20、25、31、40、52、61、70、80、92、95或100等)，9≤x+y≤200(例如9≤x+y≤14、15≤x+y≤30、40≤x+y≤52、55≤x+y≤68、70≤x+y≤82、89≤x+y≤105、121≤x+y≤153、157≤x+y≤175、182≤x+y≤193、195≤x+y≤200等)，且0.1≤x/y≤4(例如x/y为0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.2、1.5、1.8、2.0、2.3、2.5、2.8、3.0、3.3、3.5、3.8或4.0等)；Wherein 3≤x≤100 (for example, x is 3, 5, 10, 20, 25, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc.), 6≤y≤100 (for example, x is 6, 10, 20, 25, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc., 9 ≤ x + y ≤ 200 (for example, 9 ≤ x + y ≤ 14, 15 ≤ x + y ≤30, 40≤x+y≤52, 55≤x+y≤68, 70≤x+y≤82, 89≤x+y≤105, 121≤x+y≤153, 157≤x+y≤175 , 182≤x+y≤193, 195≤x+y≤200, etc., and 0.1≤x/y≤4 (for example, x/y is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9) , 1.0, 1.2, 1.5, 1.8, 2.0, 2.3, 2.5, 2.8, 3.0, 3.3, 3.5, 3.8 or 4.0, etc.);
R5、R6、R7三者至少有一个为含不饱和双键的基团，其余两者均独立地选自取代或未取代的C1～C8(例如C1、C2、C3、C4、C5、C6、C7或C8等)直链烷基、取代或未取代的C1～C8(例如C1、C2、C3、C4、C5、C6、C7或C8等)支链烷基、取代或未取代的苯基、取代或未取代的含C＝C的基团中的任意一种。 At least one of R 5 , R 6 and R 7 is a group containing an unsaturated double bond, and the other two are independently selected from substituted or unsubstituted C1 to C8 (for example, C1, C2, C3, C4, C5). , C6, C7 or C8, etc.) linear alkyl, substituted or unsubstituted C1-C8 (eg C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl, substituted or unsubstituted Any of a phenyl, substituted or unsubstituted C=C containing group.
所述三维无规网状结构MQ乙烯基有机硅树脂的一个典型但非限制性实例是山东大易化工的商品名为DY-VMQ102，其R5、R6、R7分别为甲基、甲基、乙烯基。采用GPC仪器进行检测，以甲苯作为流动相，该树脂所得的分子量大小为Mn＝2632。A typical but non-limiting example of the three-dimensional random network structure MQ vinyl silicone resin is the trade name of DY-VMQ102 of Shandong Dayi Chemical Co., Ltd., and R 5 , R 6 and R 7 are respectively methyl group and A. Base, vinyl. The detection was carried out by a GPC apparatus using toluene as a mobile phase, and the molecular weight of the resin was Mn = 2632.
所述三维网状结构具有多个节点，形成多个孔洞的结构，例如如下结构(该结构只作为例举，而不作为穷尽)：The three-dimensional network structure has a plurality of nodes, and a structure in which a plurality of holes are formed, for example, the following structure (this structure is only exemplified, not exhaustive):
Figure PCTCN2017092371-appb-000003
Figure PCTCN2017092371-appb-000003
优选地，所述乙烯基改性聚苯醚树脂具有如下结构：Preferably, the vinyl modified polyphenylene ether resin has the following structure:
Figure PCTCN2017092371-appb-000004
Figure PCTCN2017092371-appb-000004
其中，1≤e≤100(例如e为1、3、5、7、9、15、22、32、38、48、50、61、72、81、90、92或100等)，1≤f≤100(例如f为1、3、5、7、9、15、22、32、38、48、50、61、72、81、90、92或100等)，2≤e+f≤100(例如2≤e+f≤10、10≤e+f≤20、15≤e+f≤30、25≤e+f≤40、30≤e+f≤55，60≤e+f≤85、65≤e+f≤75、80≤e+f≤98或85≤e+f≤100等)；并且M选自： Where 1 ≤ e ≤ 100 (for example, e is 1, 3, 5, 7, 9, 15, 22, 32, 38, 48, 50, 61, 72, 81, 90, 92 or 100, etc.), 1 ≤ f ≤100 (for example, f is 1, 3, 5, 7, 9, 15, 22, 32, 38, 48, 50, 61, 72, 81, 90, 92 or 100, etc.), 2 ≤ e + f ≤ 100 ( For example, 2≤e+f≤10, 10≤e+f≤20, 15≤e+f≤30, 25≤e+f≤40, 30≤e+f≤55, 60≤e+f≤85,65 ≤ e + f ≤ 75, 80 ≤ e + f ≤ 98 or 85 ≤ e + f ≤ 100, etc.; and M is selected from:
Figure PCTCN2017092371-appb-000005
Figure PCTCN2017092371-appb-000005
其中，N选自-O-、-CO-、-SO-、-SC-、-SO2-、-C(CH3)2-中的任意一种或至少两种的组合；Wherein N is selected from any one of -O-, -CO-, -SO-, -SC-, -SO 2 -, -C(CH 3 ) 2 - or a combination of at least two;
R8、R10、R12、R14、R17、R19、R21和R23均独立地选自取代或未取代的C1～C8(例如C1、C2、C3、C4、C5、C6、C7或C8等)直链烷基、取代或未取代的C1～C8(例如C1、C2、C3、C4、C5、C6、C7或C8等)支链烷基、取代或未取代的苯基中的任意一种或至少两种的组合；R 8 , R 10 , R 12 , R 14 , R 17 , R 19 , R 21 and R 23 are each independently selected from substituted or unsubstituted C1 to C8 (eg, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) a linear alkyl group, a substituted or unsubstituted C1 to C8 (for example, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl group, substituted or unsubstituted phenyl group Any one or a combination of at least two;
R9、R11、R13、R15、R18、R20、R22和R24均独立地选自氢原子、取代或未取代的C1～C8(例如C1、C2、C3、C4、C5、C6、C7或C8等)直链烷基、取代或未取代的C1～C8(例如C1、C2、C3、C4、C5、C6、C7或C8等)支链烷基、取代或未取代的苯基中的任意一种或至少两种的组合；R 9 , R 11 , R 13 , R 15 , R 18 , R 20 , R 22 and R 24 are each independently selected from a hydrogen atom, a substituted or unsubstituted C1 to C8 (for example, C1, C2, C3, C4, C5). , C6, C7 or C8, etc.) linear alkyl, substituted or unsubstituted C1-C8 (eg C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl, substituted or unsubstituted Any one of phenyl groups or a combination of at least two;
R16选自：R 16 is selected from:
Figure PCTCN2017092371-appb-000006
Figure PCTCN2017092371-appb-000006
其中，B为亚芳香基、羰基或碳原子数为1～10(例如1、2、3、4、5、6、 7、8、9或10)的亚烷基中的任意一种；R25、R26和R27均独自地选自氢原子或碳原子数为1～10(例如1、2、3、4、5、6、7、8、9或10)的烷基中的任意一种。Wherein B is any one of an arylene group, a carbonyl group or an alkylene group having 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10); 25 , R 26 and R 27 are each independently selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10). One.
优选地，所述乙烯基改性聚苯醚树脂的数均分子量为500～10000g/mol，例如500g/mol、800g/mol、1000g/mol、1100g/mol、1500g/mol、4000g/mol、5600g/mol、8000g/mol或10000g/mol等，优选800～8000g/mol，进一步优选1000～4000g/mol。Preferably, the vinyl modified polyphenylene ether resin has a number average molecular weight of 500 to 10000 g/mol, for example, 500 g/mol, 800 g/mol, 1000 g/mol, 1100 g/mol, 1500 g/mol, 4000 g/mol, 5600 g. /mol, 8000 g/mol or 10000 g/mol, etc., preferably 800 to 8000 g/mol, further preferably 1000 to 4000 g/mol.
优选地，所述自由基引发剂为过氧化物自由基引发剂。Preferably, the free radical initiator is a peroxide free radical initiator.
进一步优选地，所述自由基引发剂选自过氧化二异丙苯、过氧化二苯甲酰、过氧化苯甲酸叔丁酯或4，4-二(叔丁基过氧化)戊酸正丁酯中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：4，4-二(叔丁基过氧化)戊酸正丁酯和过氧化苯甲酸叔丁酯的混合物，过氧化二苯甲酰和过氧化二异丙苯的混合物，4，4-二(叔丁基过氧化)戊酸正丁酯和过氧化二苯甲酰的混合物，过氧化苯甲酸叔丁酯和过氧化二异丙苯的混合物，4，4-二(叔丁基过氧化)戊酸正丁酯、过氧化苯甲酸叔丁酯和过氧化二苯甲酰的混合物。Further preferably, the radical initiator is selected from the group consisting of dicumyl peroxide, dibenzoyl peroxide, t-butyl peroxybenzoate or 4,4-di(tert-butylperoxy)pentanoic acid n-butylate Any one or a mixture of at least two of the esters, wherein a typical but non-limiting mixture is: a mixture of n-butyl 4,4-di(tert-butylperoxy)pentanoate and tert-butyl peroxybenzoate a mixture of dibenzoyl peroxide and dicumyl peroxide, a mixture of n-butyl 4,4-di(tert-butylperoxy)pentanoate and dibenzoyl peroxide, tert-butyl peroxybenzoate a mixture of an ester and dicumyl peroxide, a mixture of 4,4-di(tert-butylperoxy)pentanoic acid n-butyl ester, tert-butyl peroxybenzoate and dibenzoyl peroxide.
在本发明所述树脂组合物中，自由基引发剂可以单独使用，也可以混合使用，混合使用可以达到更好的协同效果。In the resin composition of the present invention, the radical initiators may be used singly or in combination, and a mixed effect may be used to achieve a better synergistic effect.
优选地，以乙烯基有机硅树脂和乙烯基改性聚苯醚树脂的重量份之和为100份计，自由基引发剂的重量为1～3份，例如1份、1.2份、1.5份、1.8份、2份、2.2份、2.5份、2.8份或3份等。Preferably, the weight of the radical initiator is 1 to 3 parts, for example, 1 part, 1.2 parts, 1.5 parts, based on 100 parts by weight of the weight of the vinyl silicone resin and the vinyl modified polyphenylene ether resin. 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts or 3 parts, and the like.
优选地，本发明所述树脂组合物还可以包括粉末填料。Preferably, the resin composition of the present invention may further comprise a powder filler.
优选地，所述粉末填料选自结晶型二氧化硅、无定形二氧化硅、球形二氧化硅、熔融二氧化硅、二氧化钛、碳化硅、玻璃纤维、氧化铝、氮化铝、氮化硼、钛酸钡或钛酸锶中的任意一种或至少两种的混合物，其中典型但非限制性 的混合物为：结晶型二氧化硅和无定形二氧化硅的混合物，球形二氧化硅和二氧化钛的混合物，碳化硅和玻璃纤维的混合物，氧化铝和氮化铝的混合物，氮化硼和钛酸钡的混合物，钛酸锶和碳化硅的混合物，球形二氧化硅、结晶型二氧化硅和无定形二氧化硅的混合物。Preferably, the powder filler is selected from the group consisting of crystalline silica, amorphous silica, spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, Any one or a mixture of at least two of barium titanate or barium titanate, typically but not limiting The mixture is: a mixture of crystalline silica and amorphous silica, a mixture of spherical silica and titanium dioxide, a mixture of silicon carbide and glass fibers, a mixture of aluminum oxide and aluminum nitride, boron nitride and titanic acid. A mixture of cerium, a mixture of barium titanate and silicon carbide, a mixture of spherical silica, crystalline silica and amorphous silica.
在本发明所述树脂组合物中，粉末填料起着提高尺寸稳定性、降低热膨胀系数、降低体系成本等作用。对于所述粉末填料的形状和粒径，本发明不作特殊限定，通常使用的粒径为0.2～10μm，例如0.2μm、0.5μm、1μm、2μm、3μm、5μm、8μm、9μm或10μm等，例如，可选择粒径为0.2～10μm的球形二氧化硅。In the resin composition of the present invention, the powder filler functions to improve dimensional stability, lower thermal expansion coefficient, lower system cost, and the like. The shape and particle diameter of the powder filler are not particularly limited in the invention, and the particle diameter generally used is 0.2 to 10 μm, for example, 0.2 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 5 μm, 8 μm, 9 μm or 10 μm, etc., for example. A spherical silica having a particle diameter of 0.2 to 10 μm can be selected.
优选地，以乙烯基有机硅树脂和乙烯基改性聚苯醚树脂的重量份之和为100份计，粉末填料的重量为100～300份，例如100份、110份、120份、130份、140份、150份、160份、180份、180份、190份、200份、210、220份、230份、240份、250份、260份、270份、280、290或300份等。Preferably, the weight of the powder filler is 100 to 300 parts, for example, 100 parts, 110 parts, 120 parts, 130 parts by weight of 100 parts by weight of the vinyl silicone resin and the vinyl modified polyphenylene ether resin. , 140 parts, 150 parts, 160 parts, 180 parts, 180 parts, 190 parts, 200 parts, 210, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280, 290 or 300 parts, and the like.
本发明所述的“包括”，意指其除所述组分外，还可以包括其他组分，这些其他组分赋予所述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”。The term "comprising" as used in the present invention means that it may include, in addition to the components, other components which impart different characteristics to the resin composition. In addition, the "include" of the present invention may also be replaced by a closed "for" or "consisting of".
例如，本发明所述热固性乙烯基有机硅树脂组合物可以添加配合的热固性树脂，作为具体例，可以举出环氧树脂、氰酸酯树脂、酚醛树脂、聚氨酯树脂、蜜胺树脂等，也可以添加这些热固性树脂的固化剂或者固化促进剂。For example, the thermosetting vinyl silicone resin composition of the present invention may be added with a thermosetting resin, and specific examples thereof include an epoxy resin, a cyanate resin, a phenol resin, a polyurethane resin, a melamine resin, and the like. A curing agent or a curing accelerator of these thermosetting resins is added.
另外，所述树脂组合物还可以含有各种添加剂，作为具体例，可以举出硅烷偶联剂、钛酸酯偶联剂、抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂、润滑剂等。这些添加剂可以单独使用，也可以两种或者两种以上混合使用。Further, the resin composition may further contain various additives, and specific examples thereof include a silane coupling agent, a titanate coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, and a pigment. , colorants, lubricants, etc. These additives may be used singly or in combination of two or more.
作为本发明树脂组合物之一的制备方法，可以通过公知的方法配合、搅拌、 混合所述的乙烯基有机硅树脂、乙烯基改性聚苯醚树脂、自由基引发剂、粉末填料，以及各种热固性树脂、各种添加剂，来制备。As a preparation method of one of the resin compositions of the present invention, it can be blended, stirred, and known by a known method. The vinyl silicone resin, the vinyl modified polyphenylene ether resin, the radical initiator, the powder filler, and various thermosetting resins and various additives are mixed and prepared.
本发明的目的之二在于提供一种树脂胶液，其是将如上所述的树脂组合物溶解或分散在溶剂中得到。Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing the resin composition as described above in a solvent.
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。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. Preferred are 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 to be used can be selected by a person skilled in the art according to his own experience, so that the obtained resin glue can reach a viscosity suitable for use.
在如上所述的树脂组合物溶解或分散在溶剂的过程中，可以添加乳化剂。通过乳化剂进行分散，可以使粉末填料等在胶液中分散均匀。An emulsifier may be added during the process of dissolving or dispersing the resin composition as described above in a solvent. By dispersing by an emulsifier, the powder filler or the like can be uniformly dispersed in the glue.
本发明的目的之三在于提供一种预浸料，其是将玻璃纤维布浸润在如上所述的树脂胶液后，干燥得到。A third object of the present invention is to provide a prepreg obtained by dipping a glass fiber cloth in a resin glue as described above and drying it.
在本发明中，玻璃纤维布为增强材料，在复合材料中起着提高强度、提高尺寸稳定性、降低热固性树脂固化的收缩等作用。根据板材厚度等要求不同，可选用不同类型的玻璃纤维布。示例性的玻璃纤维布如：7628玻纤布、2116玻纤布。In the present invention, the glass fiber cloth is a reinforcing material, and functions to increase strength, improve dimensional stability, and reduce shrinkage of curing of the thermosetting resin in the composite material. Different types of fiberglass cloth can be used depending on the thickness of the sheet and the like. Exemplary glass fiber cloths are: 7628 fiberglass cloth, 2116 fiberglass cloth.
以乙烯基有机硅树脂、乙烯基改性聚苯醚树脂和粉末填料的重量之和为100重量份计，玻璃纤维布的重量为40～150份，例如40份、50份、60份、70份、 80份、90份、100份、110份、120份、130份、140份或150份等。The weight of the glass fiber cloth is 40 to 150 parts, for example, 40 parts, 50 parts, 60 parts, 70, based on 100 parts by weight of the sum of the weight of the vinyl silicone resin, the vinyl modified polyphenylene ether resin, and the powder filler. Share, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts or 150 parts, and the like.
所述干燥温度为80～220℃，例如80℃、90℃、110℃、150℃、170℃、190℃、200℃或220℃等；所述干燥时间为1～30min，例如1min、5min、8min、13min、17min、21min、24min、28min或30min等。The drying temperature is 80-220 ° C, such as 80 ° C, 90 ° C, 110 ° C, 150 ° C, 170 ° C, 190 ° C, 200 ° C or 220 ° C, etc.; the drying time is 1 ~ 30min, such as 1min, 5min, 8min, 13min, 17min, 21min, 24min, 28min or 30min.
本发明的目的之四在于提供一种高频电路基板，其由如上所述的预浸料制成，具体地，所述高频电路基板是通过以下方法制得的：A fourth object of the present invention is to provide a high-frequency circuit substrate which is made of the prepreg as described above, and in particular, the high-frequency circuit substrate is produced by the following method:
重叠至少一张如上所述的预浸料，在重叠预浸料的上下两侧放置铜箔，进行层压成型制备得到。At least one prepreg as described above is overlapped, and a copper foil is placed on the upper and lower sides of the overlapping prepreg, and is obtained by lamination molding.
所述重叠优选采用自动堆叠操作，从而使工艺操作更加简便。The overlap preferably employs an automated stacking operation to make the process operation easier.
所述层压成型优选真空层压成型，真空层压成型可以通过真空层压机实现。所述层压的时间为70～120min，例如70min、75min、80min、85min、90min、95min、100min、105min、110min、115min或120min等；所述层压的温度为180～220℃，例如180℃、185℃、190℃、195℃、200℃、205℃、210℃、215℃或220℃；所述层压的压力为40～60kg/cm2，例如40kg/cm2、45kg/cm2、50kg/cm2、55kg/cm2、58kg/cm2或60kg/cm2等。The laminate molding is preferably vacuum lamination molding, and the vacuum lamination molding can be carried out by a vacuum laminator. The lamination time is 70-120 min, such as 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min or 120 min, etc.; the lamination temperature is 180-220 ° C, for example 180 ° C 185 ° C, 190 ° C, 195 ° C, 200 ° C, 205 ° C, 210 ° C, 215 ° C or 220 ° C; the pressure of the lamination is 40 ~ 60kg / cm 2 , for example 40kg / cm 2 , 45kg / cm 2 , 50kg / cm 2, 55kg / cm 2, 58kg / cm 2 or 60kg / cm 2 and the like.
本发明典型但非限制性的高频电路基板的制备方法如下：A typical but non-limiting method for preparing a high frequency circuit substrate of the present invention is as follows:
(1)按上述所述树脂组合物配方，称取各组分：以乙烯基有机硅树脂的重量为100份计，乙烯基改性聚苯醚树脂的重量为10～30份；以乙烯基有机硅树脂和乙烯基改性聚苯醚树脂的重量份之和为100份计，自由基引发剂的重量为1～3份；以乙烯基有机硅树脂和乙烯基改性聚苯醚树脂的重量份之和为100份计，所述粉末填料的重量为100～300份；(1) According to the resin composition formulation described above, the components are weighed: the weight of the vinyl-modified polyphenylene ether resin is 10 to 30 parts by weight based on 100 parts by weight of the vinyl silicone resin; The sum of the parts by weight of the silicone resin and the vinyl modified polyphenylene ether resin is 100 parts by weight, and the weight of the radical initiator is 1 to 3 parts; and the vinyl silicone resin and the vinyl modified polyphenylene ether resin are used. The weight of the powder filler is 100 to 300 parts by weight;
(2)将乙烯基有机硅树脂、乙烯基改性聚苯醚树脂、自由基引发剂和粉料填料混合，并加入适量溶剂，搅拌分散均匀，使粉料填料与阻燃剂均匀分散在 树脂胶液中；用制备的胶液浸润玻璃纤维布，烘干，除去溶剂，得到预浸料；(2) mixing vinyl silicone resin, vinyl modified polyphenylene ether resin, free radical initiator and powder filler, adding appropriate amount of solvent, stirring and dispersing evenly, so that the powder filler and flame retardant are evenly dispersed in In the resin glue; infiltrating the glass fiber cloth with the prepared glue, drying, removing the solvent to obtain a prepreg;
(3)重叠至少一张的预浸料，在预浸料的两侧放置铜箔，在真空层压机中层压固化，从而得到高频电路基板。(3) Overlaying at least one prepreg, placing copper foil on both sides of the prepreg, and laminating and solidifying in a vacuum laminator to obtain a high-frequency circuit substrate.
本发明的目的之五在于提供一种如上所述的树脂组合物在制备树脂胶液、预浸料和高频电路基板中的应用。A fifth object of the present invention is to provide an application of the above-described resin composition for preparing a resin glue, a prepreg, and a high-frequency circuit substrate.
采用本发明所述的树脂组合物可以制备得到具有低的介质常数、低的介质损耗，低的吸水率的高频电路基板，并且基材间的层间粘合力能够满足覆铜板层间粘合力的要求。The high-frequency circuit substrate having low dielectric constant, low dielectric loss, and low water absorption can be prepared by using the resin composition of the present invention, and the interlayer adhesion between the substrates can satisfy the adhesion between the copper-clad layers. The requirements of the joint force.
本发明中所述“高频”意指频率大于100MHz。"High frequency" as used in the present invention means that the frequency is greater than 100 MHz.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明通过将乙烯基有机硅树脂应用于覆铜板领域，其化学结构中由于不含极性基团，从而保证了所制备的基材具有低的介质常数和低的介质损耗性能；(1) The present invention applies a vinyl silicone resin to the field of copper clad laminates, and its chemical structure does not contain a polar group, thereby ensuring that the prepared substrate has a low dielectric constant and a low dielectric loss performance;
(2)本发明通过采用乙烯基有机硅树脂作为主体树脂，乙烯基改性聚苯醚作为基板层间粘合力改性剂，相对于纯乙烯基有机硅体系，其所制备的基材层间粘合力大幅度提高，可满足覆铜板对基材层间粘合力的要求，且所制备的基材介质常数和介质损耗性能与纯乙烯基有机硅体系一致，乙烯基改性聚苯醚作为层间粘合力改性剂，没有损害基材的介质常数和介质损耗性能；(2) The present invention adopts a vinyl silicone resin as a host resin, a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier, and a substrate layer prepared in comparison with a pure vinyl silicone system. The inter-adhesive strength is greatly improved, which can meet the requirements of the adhesion between the copper-clad laminates on the substrate layer, and the prepared substrate dielectric constant and dielectric loss performance are consistent with the pure vinyl silicone system, vinyl-modified polyphenylene Ether as an interlayer adhesion modifier without impairing the dielectric constant and dielectric loss properties of the substrate;
(3)本发明采用乙烯基有机硅树脂作为主体树脂，乙烯基改性聚苯醚作为基板层间粘合力改性剂，在没有使用阻燃剂的条件下，能够实现无卤无磷V-0级阻燃；(3) The present invention uses a vinyl silicone resin as a host resin, and a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier, which can realize halogen-free and phosphorus-free V without using a flame retardant. -0 grade flame retardant;
本发明通过采用乙烯基有机硅树脂作为主体树脂，乙烯基改性聚苯醚作为基板层间粘合力改性剂，所制备的基板具有低介质常数和低介质损耗，好的基 材层间粘合力，能满足覆铜板的使用需求，同时能够实现无卤无磷V-0级阻燃，非常适合制备高频电子设备的电路基板。The invention adopts a vinyl silicone resin as a main resin and a vinyl modified polyphenylene ether as a substrate interlayer adhesion modifier, and the prepared substrate has a low dielectric constant and a low dielectric loss, and a good base. The adhesion between the layers can meet the needs of the copper clad laminate, and at the same time, it can realize the halogen-free and phosphorus-free V-0 flame retardant, which is very suitable for the circuit board for preparing high-frequency electronic equipment.
具体实施方式detailed description
为便于理解本发明，本发明列举实施例如下。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，下述实施例和对比例中的4张2116也可以替换成1张2116、6张2116、2张1080等。To facilitate an understanding of the invention, the invention is set forth below. It should be understood by those skilled in the art that the present invention is only to be understood as an understanding of the present invention and should not be construed as a limitation of the present invention. The four sheets 2116 in the following examples and comparative examples may also be replaced by one sheet of 2116, six sheets. 2116, 2 1080, etc.
以下表1所示为各实施例及比较例所用原料。Table 1 below shows the materials used in the respective examples and comparative examples.
表1Table 1
Figure PCTCN2017092371-appb-000007
Figure PCTCN2017092371-appb-000007
实施例1Example 1
将80.0重量份的三维无规网状结构MQ乙烯基有机硅树脂DY-VMQ102， 20.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表2所示。80.0 parts by weight of a three-dimensional random network structure MQ vinyl silicone resin DY-VMQ102, 20.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of silicon The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.
实施例2Example 2
将80.0重量份的线性乙烯基有机硅树脂DMS-V05，20.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表2所示。80.0 parts by weight of a linear vinyl silicone resin DMS-V05, 20.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silicon fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.
实施例3Example 3
将80.0重量份的环形乙烯基有机硅树脂WD-V4，20.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表2所示。80.0 parts by weight of the cyclic vinyl silicone resin WD-V4, 20.0 parts by weight of the vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of the radical initiator DCP, 233.0 parts by weight of the silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.
比较例1 Comparative example 1
将100重量份的三维无规网状结构MQ乙烯基有机硅树脂DY-VMQ102，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表2所示。100 parts by weight of a three-dimensional random network structure MQ vinyl silicone resin DY-VMQ102, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silicon fine powder 525, dissolved in a toluene solvent, and adjusted to a suitable viscosity . The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.
比较例2Comparative example 2
将100重量份的线性乙烯基有机硅树脂DMS-V05，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表2所示。100 parts by weight of linear vinyl silicone resin DMS-V05, 3.0 parts by weight of a radical initiator DCP, and 233.0 parts by weight of silica fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.
比较例3Comparative example 3
将100重量份的环形乙烯基有机硅树脂WD-V4，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表2所示。100 parts by weight of the cyclic vinyl silicone resin WD-V4, 3.0 parts by weight of a radical initiator DCP, and 233.0 parts by weight of the silica fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.
比较例4Comparative example 4
将20.0重量份的三维无规网状结构MQ乙烯基有机硅树脂DY-VMQ102，80.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP， 233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表2所示。20.0 parts by weight of a three-dimensional random network structure MQ vinyl silicone resin DY-VMQ102, 80.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of silicon The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.
比较例5Comparative Example 5
将20.0重量份的线性乙烯基有机硅树脂DMS-V05，80.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表2所示。20.0 parts by weight of a linear vinyl silicone resin DMS-V05, 80.0 parts by weight of a vinyl-modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.
比较例6Comparative Example 6
将20.0重量份的环形乙烯基有机硅树脂WD-V4，80.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表2所示。20.0 parts by weight of the cyclic vinyl silicone resin WD-V4, 80.0 parts by weight of the vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of the radical initiator DCP, 233.0 parts by weight of the silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.
表2Table 2
Figure PCTCN2017092371-appb-000008
Figure PCTCN2017092371-appb-000008
Figure PCTCN2017092371-appb-000009
Figure PCTCN2017092371-appb-000009
通过表2可以看出，将实施例1～3分别与比较例1～3相比，实施例1～3所制备的基材层间结合力为0.4～0.6，而比较例1～3制备的基材层间结合力仅为0.1～0.2，说明本发明通过采用乙烯基有机硅树脂作为主体树脂，乙烯基改性聚苯醚作为基板层间粘合力改性剂，相对于纯乙烯基有机硅体系，其所制备的基材层间粘合力大幅度提高；另外，实施例1～3所制备的基材介质常数和介质损耗性能基本与比较例1～3一致，说明本发明采用乙烯基改性聚苯醚作为层间粘合力改性剂，没有损害基材的介质常数和介质损耗性能。将实施例1～3分别与比较例4～6相比，实施例1～3所制备的基材在没有使用阻燃剂的条件下，能够实现无卤无磷V-0级阻燃，而比较例4～6却不能实现V-0级阻燃；另外，相对于比较例4～6，实施例1～3所制备的基材具有更低的介质常数和介质损耗，说明本发明通过采用乙烯基有机硅树脂作为主体树脂，乙烯基改性聚苯醚作为基板层间粘合力改性剂，相对于采用乙烯基改性聚苯醚树脂作为主体树脂，乙烯基有机硅树脂作为交联剂，其所制备的基材具有更优异的介电常数和介质损耗性 能，并能实现无卤无磷V-0级阻燃。As can be seen from Table 2, in Examples 1 to 3, compared with Comparative Examples 1 to 3, the adhesion between the substrates prepared in Examples 1 to 3 was 0.4 to 0.6, and Comparative Examples 1 to 3 were prepared. The adhesion between the substrate layers is only 0.1 to 0.2, indicating that the present invention uses a vinyl silicone resin as a host resin, and a vinyl modified polyphenylene ether as a substrate interlayer adhesion modifier relative to a pure vinyl organic In the silicon system, the adhesion between the substrates prepared by the substrate is greatly improved; in addition, the dielectric constants and dielectric loss properties of the substrates prepared in Examples 1 to 3 are substantially the same as those in Comparative Examples 1 to 3, indicating that the present invention uses ethylene. The modified polyphenylene ether as an interlayer adhesion modifier does not impair the dielectric constant and dielectric loss properties of the substrate. Comparing Examples 1 to 3 with Comparative Examples 4 to 6, respectively, the substrates prepared in Examples 1 to 3 were able to achieve halogen-free and phosphorus-free V-0 flame retardant without using a flame retardant. Comparative Examples 4 to 6 failed to achieve V-0 flame retardancy; in addition, the substrates prepared in Examples 1 to 3 had lower dielectric constants and dielectric loss than Comparative Examples 4 to 6, indicating that the present invention was adopted. Vinyl silicone resin as the main resin, vinyl modified polyphenylene ether as the interlaminar adhesion modifier, compared with vinyl modified polyphenylene ether resin as the main resin, vinyl silicone resin as crosslinking Agent, the substrate prepared thereof has more excellent dielectric constant and dielectric loss Can, and can achieve halogen-free and phosphorus-free V-0 flame retardant.
实施例4Example 4
将90.0重量份的三维无规网状结构MQ乙烯基有机硅树脂DY-VMQ102，10.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表3所示。90.0 parts by weight of a three-dimensional random network structure MQ vinyl silicone resin DY-VMQ102, 10.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of silicon The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.
实施例5Example 5
将90.0重量份的线性乙烯基有机硅树脂DMS-V05，10.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表3所示。90.0 parts by weight of a linear vinyl silicone resin DMS-V05, 10.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.
实施例6Example 6
将90.0重量份的环形乙烯基有机硅树脂WD-V4，10.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化 90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表3所示。90.0 parts by weight of the cyclic vinyl silicone resin WD-V4, 10.0 parts by weight of the vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of the radical initiator DCP, 233.0 parts by weight of the silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.
比较例7Comparative Example 7
将10.0重量份的三维无规网状结构MQ乙烯基有机硅树脂DY-VMQ102，90.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高频电路基板。基材综合性能如表3所示。10.0 parts by weight of a three-dimensional random network structure MQ vinyl silicone resin DY-VMQ102, 90.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of silicon The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.
比较例8Comparative Example 8
将10.0重量份的线性乙烯基有机硅树脂DMS-V05，90.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高频电路基板。基材综合性能如表3所示。10.0 parts by weight of a linear vinyl silicone resin DMS-V05, 90.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.
比较例9Comparative Example 9
将10.0重量份的环型乙烯基有机硅树脂WD-V4，90.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将 4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高频电路基板。基材综合性能如表3所示。10.0 parts by weight of a cyclic vinyl silicone resin WD-V4, 90.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, and 233.0 parts by weight of a silica fine powder 525 were dissolved in In a toluene solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.
表3table 3
原料和性能Raw materials and properties 实施例4Example 4 实施例5Example 5 实施例6Example 6 比较例7Comparative Example 7 比较例8Comparative Example 8 比较例9Comparative Example 9
DY-VMQ102DY-VMQ102 9090 00 00 1010 00 00
DMS-V05DMS-V05 00 9090 00 00 1010 00
WD-V4WD-V4 00 00 9090 00 00 1010
SA9000SA9000 1010 1010 1010 9090 9090 9090
DCPDCP 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0
525525 233233 233233 233233 233233 233233 233233
21162116 155155 155155 155155 155155 155155 155155
层间粘合力(N/mm)Interlayer adhesion (N/mm) 0.4～0.60.4 to 0.6 0.4～0.60.4 to 0.6 0.4～0.60.4 to 0.6 0.7～0.80.7 to 0.8 0.7～0.80.7 to 0.8 0.7～0.80.7 to 0.8
Tg-DMA(℃)Tg-DMA (°C) 181.0181.0 180.9180.9 180.6180.6 201.2201.2 210.8210.8 222.6222.6
吸水率(％)Water absorption rate (%) 0.140.14 0.120.12 0.150.15 0.140.14 0.120.12 0.150.15
阻燃性能Flame retardant performance V-0V-0 V-0V-0 V-0V-0 非V-0non-V-0 非V-0non-V-0 非V-0non-V-0
介电常数(10GHz)Dielectric constant (10GHz) 3.813.81 3.833.83 3.803.80 4.284.28 4.304.30 4.284.28
介质损耗(10GHz)Dielectric loss (10GHz) 0.00410.0041 0.00400.0040 0.00430.0043 0.00690.0069 0.00680.0068 0.00670.0067
通过表3可以看出，将实施例4～5分别与比较例7～9相比，实施例4～6所制备的基材在没有使用阻燃剂的条件下，能够实现无卤无磷V-0级阻燃，而比较例7～9却不能实现V-0级阻燃；另外，相对于比较例7～9，实施例4～6所制备的基材具有更低的介质常数和介质损耗，说明本发明通过采用乙烯基有机硅树脂作为主体树脂，乙烯基改性聚苯醚作为基板层间粘合力改性剂，相对于采用乙烯基改性聚苯醚树脂作为主体树脂，乙烯基有机硅树脂作为交联剂，其所制备的基材具有更优异的介电常数和介质损耗性能，并能实现无卤无磷V-0级阻燃。As can be seen from Table 3, in Examples 4 to 5, compared with Comparative Examples 7 to 9, the substrates prepared in Examples 4 to 6 were able to realize halogen-free and phosphorus-free V without using a flame retardant. -0 grade flame retardant, while Comparative Examples 7-9 failed to achieve V-0 grade flame retardant; in addition, the substrates prepared in Examples 4 to 6 had lower dielectric constants and media than Comparative Examples 7-9. Loss, indicating that the present invention uses a vinyl silicone resin as a host resin, a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier, and a vinyl-modified polyphenylene ether resin as a host resin, ethylene. The base silicone resin is used as a crosslinking agent, and the prepared substrate has better dielectric constant and dielectric loss performance, and can realize halogen-free and phosphorus-free V-0 flame retardant.
实施例7Example 7
将85.0重量份的三维无规网状结构MQ乙烯基有机硅树脂DY-VMQ102， 15.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表4所示。85.0 parts by weight of a three-dimensional random network structure MQ vinyl silicone resin DY-VMQ102, 15.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of silicon The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.
实施例8Example 8
将85.0重量份的线性乙烯基有机硅树脂DMS-V05，15.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表4所示。85.0 parts by weight of a linear vinyl silicone resin DMS-V05, 15.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.
实施例9Example 9
将85.0重量份的环形乙烯基有机硅树脂WD-V4，15.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表4所示。85.0 parts by weight of the cyclic vinyl silicone resin WD-V4, 15.0 parts by weight of the vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of the radical initiator DCP, 233.0 parts by weight of the silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.
比较例10 Comparative Example 10
将15.0重量份的三维无规网状结构MQ乙烯基有机硅树脂DY-VMQ102，85.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表4所示。15.0 parts by weight of a three-dimensional random network structure MQ vinyl silicone resin DY-VMQ102, 85.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of silicon The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.
比较例11Comparative Example 11
将15.0重量份的线性乙烯基有机硅树脂DMS-V05，85.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表4所示。15.0 parts by weight of a linear vinyl silicone resin DMS-V05, 85.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of a silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.
比较例12Comparative Example 12
将15.0重量份的环形乙烯基有机硅树脂WD-V4，85.0重量份的乙烯基改性聚苯醚树脂SA9000，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表4所示。 15.0 parts by weight of the cyclic vinyl silicone resin WD-V4, 85.0 parts by weight of the vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of the radical initiator DCP, 233.0 parts by weight of the silica fine powder 525, dissolved in toluene In a solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.
表4Table 4
原料和性能Raw materials and properties 实施例7Example 7 实施例8Example 8 实施例9Example 9 比较例10Comparative Example 10 比较例11Comparative Example 11 比较例12Comparative Example 12
DY-VMQ102DY-VMQ102 8585 00 00 1515 00 00
DMS-V05DMS-V05 00 8585 00 00 1515 00
WD-V4WD-V4 00 00 8585 00 00 1515
SA9000SA9000 1515 1515 1515 8585 8585 8585
DCPDCP 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0 3.03.0
525525 233233 233233 233233 233233 233233 233233
21162116 155155 155155 155155 155155 155155 155155
层间粘合力(N/mm)Interlayer adhesion (N/mm) 0.4-0.60.4-0.6 0.4-0.60.4-0.6 0.4-0.60.4-0.6 0.7-0.80.7-0.8 0.7-0.80.7-0.8 0.7-0.80.7-0.8
Tg-DMA(℃)Tg-DMA (°C) 182.5182.5 182.6182.6 180.7180.7 205.2205.2 214.8214.8 225.6225.6
吸水率(％)Water absorption rate (%) 0.110.11 0.100.10 0.100.10 0.130.13 0.140.14 0.120.12
阻燃性能Flame retardant performance V-0V-0 V-0V-0 V-0V-0 非V-0non-V-0 非V-0non-V-0 非V-0non-V-0
介电常数(10GHz)Dielectric constant (10GHz) 3.803.80 3.833.83 3.843.84 4.254.25 4.274.27 4.264.26
介质损耗(10GHz)Dielectric loss (10GHz) 0.00430.0043 0.00440.0044 0.00450.0045 0.00650.0065 0.00660.0066 0.00650.0065
通过表4可以看出，将实施例7～9分别与比较例10～12相比，实施例7～9所制备的基材在没有使用阻燃剂的条件下，能够实现无卤无磷V-0级阻燃，而比较例10～12却不能实现V-0级阻燃；另外，相对于比较例10～12，实施例7～9所制备的基材具有更低的介质常数和介质损耗，说明本发明通过采用乙烯基有机硅树脂作为主体树脂，乙烯基改性聚苯醚作为基板层间粘合力改性剂，相对于采用乙烯基改性聚苯醚树脂作为主体树脂，乙烯基有机硅树脂作为交联剂，其所制备的基材具有更优异的介电常数和介质损耗性能，并能实现无卤无磷V-0级阻燃。As can be seen from Table 4, in Examples 7 to 9 and Comparative Examples 10 to 12, the substrates prepared in Examples 7 to 9 were able to realize halogen-free and phosphorus-free V without using a flame retardant. -0 grade flame retardant, while Comparative Examples 10-12 did not achieve V-0 flame retardant; in addition, the substrates prepared in Examples 7-9 had lower dielectric constants and media than Comparative Examples 10-12. Loss, indicating that the present invention uses a vinyl silicone resin as a host resin, a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier, and a vinyl-modified polyphenylene ether resin as a host resin, ethylene. The base silicone resin is used as a crosslinking agent, and the prepared substrate has better dielectric constant and dielectric loss performance, and can realize halogen-free and phosphorus-free V-0 flame retardant.
实施例10Example 10
将90.0重量份的三维无规网状结构MQ乙烯基有机硅树脂DY-VMQ102，10.0重量份的乙烯基改性聚苯醚树脂OPE-2ST，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂， 制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表5所示。90.0 parts by weight of a three-dimensional random network structure MQ vinyl silicone resin DY-VMQ102, 10.0 parts by weight of a vinyl modified polyphenylene ether resin OPE-2ST, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight The silicon micropowder 525 is dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, and drying in an oven to remove the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.
实施例11Example 11
将80.0重量份的线性乙烯基有机硅树脂DMS-V05，20.0重量份的乙烯基改性聚苯醚树脂OPE-2ST，2.0重量份的自由基引发剂DCP，185.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表5所示。80.0 parts by weight of linear vinyl silicone resin DMS-V05, 20.0 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST, 2.0 parts by weight of free radical initiator DCP, 185.0 parts by weight of silicon micropowder 525, dissolved In a toluene solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.
实施例12Example 12
将70.0重量份的环型乙烯基有机硅树脂WD-V4，30.0重量份的乙烯基改性聚苯醚树脂OPE-2ST，1.0重量份的自由基引发剂DCP，155.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表5所示。70.0 parts by weight of a cyclic vinyl silicone resin WD-V4, 30.0 parts by weight of a vinyl modified polyphenylene ether resin OPE-2ST, 1.0 part by weight of a radical initiator DCP, and 155.0 parts by weight of a silica fine powder 525, Dissolved in toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.
实施例13Example 13
将85.0重量份的三维无规网状结构MQ乙烯基有机硅树脂DY-VMQ102，15.0重量份的乙烯基改性聚苯醚树脂OPE-2ST，3.0重量份的自由基引发剂DCP，233.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻 纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表5所示。85.0 parts by weight of a three-dimensional random network structure MQ vinyl silicone resin DY-VMQ102, 15.0 parts by weight of a vinyl modified polyphenylene ether resin OPE-2ST, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight The silicon micropowder 525 is dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass cloth, controlling the single weight by the clamp shaft, and drying in an oven to remove the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.
实施例14Example 14
将85.0重量份的线性乙烯基有机硅树脂DMS-V05，15.0重量份的乙烯基改性聚苯醚树脂OPE-2ST，2.0重量份的自由基引发剂DCP，185.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表5所示。85.0 parts by weight of linear vinyl silicone resin DMS-V05, 15.0 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST, 2.0 parts by weight of free radical initiator DCP, 185.0 parts by weight of silicon micropowder 525, dissolved In a toluene solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.
实施例15Example 15
将85.0重量份的环型乙烯基有机硅树脂WD-V4，15.0重量份的乙烯基改性聚苯醚树脂OPE-2ST，1.0重量份的自由基引发剂DCP，155.0重量份的硅微粉525，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表5所示。85.0 parts by weight of a cyclic vinyl silicone resin WD-V4, 15.0 parts by weight of a vinyl-modified polyphenylene ether resin OPE-2ST, 1.0 part by weight of a radical initiator DCP, and 155.0 parts by weight of a silica fine powder 525, Dissolved in toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.
实施例16Example 16
将80.0重量份的三维无规网状结构MQ乙烯基有机硅树脂DY-VMQ102，20.0重量份的乙烯基改性聚苯醚树脂OPE-2ST，3.0重量份的自由基引发剂DCP， 233.0重量份的硅微粉SC-2300SVJ，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表5所示。80.0 parts by weight of a three-dimensional random network structure MQ vinyl silicone resin DY-VMQ102, 20.0 parts by weight of a vinyl modified polyphenylene ether resin OPE-2ST, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight The silicon micropowder SC-2300SVJ is dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.
实施例17Example 17
将80.0重量份的线性乙烯基有机硅树脂DMS-V05，20.0重量份的乙烯基改性聚苯醚树脂OPE-2ST，2.0重量份的自由基引发剂DCP，185.0重量份的硅微粉SC-2300SVJ，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表5所示。80.0 parts by weight of linear vinyl silicone resin DMS-V05, 20.0 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST, 2.0 parts by weight of radical initiator DCP, 185.0 parts by weight of silicon micropowder SC-2300SVJ , dissolved in toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.
实施例18Example 18
将80.0重量份的环型乙烯基有机硅树脂WD-V4，20.0重量份的乙烯基改性聚苯醚树脂OPE-2ST，1.0重量份的自由基引发剂DCP，155.0重量份的硅微粉SC-2300SVJ，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力为50kg/cm2，固化温度为200℃，制得高频电路基板。基材综合性能如表5所示。80.0 parts by weight of a cyclic vinyl silicone resin WD-V4, 20.0 parts by weight of a vinyl-modified polyphenylene ether resin OPE-2ST, 1.0 part by weight of a radical initiator DCP, and 155.0 parts by weight of a silicon micropowder SC- 2300SVJ, dissolved in toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.
表5table 5
Figure PCTCN2017092371-appb-000010
Figure PCTCN2017092371-appb-000010
Figure PCTCN2017092371-appb-000011
Figure PCTCN2017092371-appb-000011
通过表5可以看出，本发明通过采用乙烯基有机硅树脂作为主体树脂，乙烯基改性聚苯醚作为基板层间粘合力改性剂，其所制备的基材具有好的基材层间粘合力，能够满足覆铜板层间粘合力的要求，并具有低介质常数和低介质损耗，同时能够实现无卤无磷V-0级阻燃，非常适合制备高频电子设备的电路基板。As can be seen from Table 5, the present invention adopts a vinyl silicone resin as a host resin and a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier, and the prepared substrate has a good substrate layer. Inter-adhesive force, can meet the requirements of adhesion between layers of CCL, and has low dielectric constant and low dielectric loss, and can achieve halogen-free and phosphorus-free V-0 flame retardant, which is very suitable for the circuit of high-frequency electronic equipment. Substrate.
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。 The Applicant declares that the present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must be implemented by the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims (10)

  1. 一种热固性乙烯基有机硅树脂组合物，其特征在于，包括：A thermosetting vinyl silicone resin composition, comprising:
    (1)乙烯基有机硅树脂；(1) a vinyl silicone resin;
    该乙烯基有机硅树脂为线性乙烯基有机硅树脂、环形乙烯基有机硅树脂、三维无规网状结构MQ乙烯基有机硅树脂中的任意一种或至少两种的混合物；The vinyl silicone resin is any one or a mixture of at least two of a linear vinyl silicone resin, a cyclic vinyl silicone resin, a three-dimensional random network structure MQ vinyl silicone resin;
    (2)乙烯基改性聚苯醚树脂；(2) a vinyl modified polyphenylene ether resin;
    (3)自由基引发剂；(3) a free radical initiator;
    以乙烯基有机硅树脂的重量为100份计，乙烯基改性聚苯醚树脂的重量为10～30份。The weight of the vinyl-modified polyphenylene ether resin is from 10 to 30 parts by weight based on 100 parts by weight of the vinyl silicone resin.
  2. 如权利要求1所述的树脂组合物，其特征在于，所述线性乙烯基有机硅树脂的结构为：The resin composition according to claim 1, wherein the linear vinyl silicone resin has a structure of:
    Figure PCTCN2017092371-appb-100001
    Figure PCTCN2017092371-appb-100001
    其中，R1、R2、R3三者至少有一个为取代或未取代的C2～C10含C＝C的基团；其余两者均独立地选自取代或未取代的C1～C8直链烷基、取代或未取代的C1～C8支链烷基、取代或未取代的苯基、取代或未取代的C2～C10含C＝C的基团中的任意一种，且5≤m≤100，m为自然数；Wherein at least one of R 1 , R 2 and R 3 is a substituted or unsubstituted C 2 -C 10 C=C-containing group; the other two are independently selected from substituted or unsubstituted C1 to C8 straight chain An alkyl group, a substituted or unsubstituted C1-C8 branched alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C2-C10 group containing C=C, and 5≤m≤ 100, m is a natural number;
    优选地，所述环形乙烯基有机硅树脂的结构为：Preferably, the structure of the cyclic vinyl silicone resin is:
    Figure PCTCN2017092371-appb-100002
    Figure PCTCN2017092371-appb-100002
    其中，R4选自取代或未取代的C1～C12直链烷基或取代或未取代的C1～C12支链烷基；2≤n≤10，n为自然数；Wherein R 4 is selected from a substituted or unsubstituted C1-C12 linear alkyl group or a substituted or unsubstituted C1-C12 branched alkyl group; 2≤n≤10, n is a natural number;
    优选地，所述三维无规网状结构MQ乙烯基有机硅树脂的结构为： Preferably, the structure of the three-dimensional random network structure MQ vinyl silicone resin is:
    (R5R6R7SiO1/2)x(5iO4/2)y (R 5 R 6 R 7 SiO 1/2 ) x (5iO 4/2 ) y
    其中，3≤x≤100，6≤y≤100，9≤x+y≤200，且0.1≤x/y≤4；Wherein, 3≤x≤100, 6≤y≤100, 9≤x+y≤200, and 0.1≤x/y≤4;
    R5、R6、R7三者至少有一个为含不饱和双键的基团，其余两者均独立地选自取代或未取代的C1～C8直链烷基、取代或未取代的C1～C8支链烷基、取代或未取代的苯基、取代或未取代的含C＝C的基团中的任意一种。At least one of R 5 , R 6 and R 7 is a group containing an unsaturated double bond, and the other two are independently selected from a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1 group. Any one of a C8 branched alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C=C-containing group.
  3. 如权利要求1或2所述的树脂组合物，其特征在于，所述乙烯基改性聚苯醚树脂具有如下结构：The resin composition according to claim 1 or 2, wherein the vinyl-modified polyphenylene ether resin has the following structure:
    Figure PCTCN2017092371-appb-100003
    Figure PCTCN2017092371-appb-100003
    其中，1≤e≤100，1≤f≤100，2≤e+f≤100；并且M选自：Wherein, 1≤e≤100, 1≤f≤100, 2≤e+f≤100; and M is selected from:
    Figure PCTCN2017092371-appb-100004
    Figure PCTCN2017092371-appb-100004
    其中，N选自-O-、-CO-、-SO-、-SC-、-SO2-、-C(CH3)2-中的任意一种或至少两种的组合；Wherein N is selected from any one of -O-, -CO-, -SO-, -SC-, -SO 2 -, -C(CH 3 ) 2 - or a combination of at least two;
    R8、R10、R12、R14、R17、R19、R21和R23均独立地选自取代或未取代的C1～C8直链烷基、取代或未取代的C1～C8支链烷基、取代或未取代的苯基中的任意一种或至少两种的组合； R 8 , R 10 , R 12 , R 14 , R 17 , R 19 , R 21 and R 23 are each independently selected from a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1-C8 branch. Any one or a combination of at least two of an alkyl group, a substituted or unsubstituted phenyl group;
    R9、R11、R13、R15、R18、R20、R22和R24均独立地选自氢原子、取代或未取代的C1～C8直链烷基、取代或未取代的C1～C8支链烷基、取代或未取代的苯基中的任意一种或至少两种的组合；R 9 , R 11 , R 13 , R 15 , R 18 , R 20 , R 22 and R 24 are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1. Any one or a combination of at least two of a C8 branched alkyl group, a substituted or unsubstituted phenyl group;
    R16选自：R 16 is selected from:
    Figure PCTCN2017092371-appb-100005
    Figure PCTCN2017092371-appb-100005
    其中，B为亚芳香基、羰基或碳原子数为1～10的亚烷基中的任意一种；R25、R26和R27均独自地选自氢原子或碳原子数为1～10的烷基中的任意一种；Wherein B is a arylene group, a carbonyl group or an alkylene group having 1 to 10 carbon atoms; and R 25 , R 26 and R 27 are each independently selected from a hydrogen atom or have 1 to 10 carbon atoms. Any of the alkyl groups;
    优选地，所述乙烯基改性聚苯醚树脂的数均分子量为500～10000g/mol，优选800～8000g/mol，进一步优选1000～4000g/mol。Preferably, the vinyl-modified polyphenylene ether resin has a number average molecular weight of 500 to 10,000 g/mol, preferably 800 to 8000 g/mol, and more preferably 1,000 to 4,000 g/mol.
  4. 如权利要求1-3之一所述的树脂组合物，其特征在于，所述自由基引发剂为过氧化物自由基引发剂；The resin composition according to any one of claims 1 to 3, wherein the radical initiator is a peroxide radical initiator;
    优选地，所述自由基引发剂选自过氧化二异丙苯、过氧化二苯甲酰、过氧化苯甲酰、过氧化苯甲酸叔丁酯或4，4-二(叔丁基过氧化)戊酸正丁酯中的任意一种或至少两种的混合物；Preferably, the free radical initiator is selected from the group consisting of dicumyl peroxide, dibenzoyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate or 4,4-di(tert-butylperoxide) Any one or a mixture of at least two of n-butyl valerate;
    优选地，以乙烯基有机硅树脂和乙烯基改性聚苯醚树脂的重量份之和为100份计，自由基引发剂的重量为1～3份。Preferably, the weight of the radical initiator is from 1 to 3 parts by weight based on 100 parts by weight of the vinyl silicone resin and the vinyl modified polyphenylene ether resin.
  5. 如权利要求1-4之一所述的树脂组合物，其特征在于，所述树脂组合物还包括粉末填料；The resin composition according to any one of claims 1 to 4, wherein the resin composition further comprises a powder filler;
    优选地，所述粉末填料选自结晶型二氧化硅、无定形二氧化硅、球形二氧 化硅、熔融二氧化硅、二氧化钛、碳化硅、玻璃纤维、氧化铝、氮化铝、氮化硼、钛酸钡或钛酸锶中的任意一种或至少两种的混合物；Preferably, the powder filler is selected from the group consisting of crystalline silica, amorphous silica, spherical dioxygen Any one or a mixture of at least two of silicon, fused silica, titania, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, barium titanate or barium titanate;
    优选地，所述粉末填料的粒径为0.2～10μm；Preferably, the powder filler has a particle size of 0.2 to 10 μm;
    优选地，以乙烯基有机硅树脂和乙烯基改性聚苯醚树脂的重量份之和为100份计，粉末填料的重量为100～300份。Preferably, the weight of the powder filler is from 100 to 300 parts by weight based on 100 parts by weight of the vinyl silicone resin and the vinyl modified polyphenylene ether resin.
  6. 一种树脂胶液，其特征在于，其是将如权利要求1-5之一所述的树脂组合物溶解或分散在溶剂中得到。A resin glue obtained by dissolving or dispersing a resin composition according to any one of claims 1 to 5 in a solvent.
  7. 一种预浸料，其特征在于，其是将玻璃纤维布浸润在如权利要求6所述的树脂胶液后，干燥得到。A prepreg obtained by infiltrating a glass fiber cloth in the resin glue according to claim 6 and drying.
  8. 如权利要求7所述的预浸料，其特征在于，以乙烯基有机硅树脂、乙烯基改性聚苯醚树脂和粉末填料的重量之和为100重量份计，玻璃纤维布的重量为40～150份。The prepreg according to claim 7, wherein the weight of the glass fiber cloth is 40 parts by weight based on 100 parts by weight of the sum of the weight of the vinyl silicone resin, the vinyl modified polyphenylene ether resin and the powder filler. ~150 copies.
  9. 一种高频电路基板，其特征在于，所述高频电路基板由如权利要求7或8所述的预浸料制成；A high frequency circuit substrate, characterized in that the high frequency circuit substrate is made of the prepreg according to claim 7 or 8;
    优选地，所述高频电路基板是通过以下方法制得的：重叠至少一张所述的预浸料，在预浸料的两侧放置铜箔，进行层压成型制备得到。Preferably, the high-frequency circuit substrate is obtained by laminating at least one of the prepregs, placing copper foil on both sides of the prepreg, and performing lamination molding.
  10. 如权利要求1-5之一所述的树脂组合物在制备树脂胶液、预浸料和高频电路基板中的应用。 Use of the resin composition according to any one of claims 1 to 5 for preparing a resin glue, a prepreg, and a high frequency circuit substrate.
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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112795169B (en) * 2020-12-31 2022-07-19 广东生益科技股份有限公司 Resin composition, resin film containing resin composition, prepreg, laminated board, copper-clad plate and printed circuit board
CN113185751A (en) * 2021-04-23 2021-07-30 艾蒙特成都新材料科技有限公司 Halogen-free silicon flame-retardant vinyl resin, preparation method thereof and application thereof in copper-clad plate
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5571609A (en) * 1994-10-13 1996-11-05 Rogers Corporation Polybutadiene and polyisoprene based thermosetting compositions and method of manufacture thereof
US20020040104A1 (en) * 1998-11-02 2002-04-04 Gil Technologies Vinyl-terminated polybutadiene and butadiene-styrene copolymers containing urethane and/or ester residues, and the electrical laminates obtained therefrom
CN101370866A (en) * 2006-02-17 2009-02-18 日立化成工业株式会社 Thermocurable resin composition comprising semi-ipn-type complex, and varnish, prepreg and metal-clad laminate sheet using the same
CN102161823A (en) * 2010-07-14 2011-08-24 广东生益科技股份有限公司 Composite material, high-frequency circuit substrate therefrom and manufacture method thereof
CN102993683A (en) * 2012-11-27 2013-03-27 广东生益科技股份有限公司 Resin composition and use thereof
CN105086417A (en) * 2014-05-06 2015-11-25 广东生益科技股份有限公司 Resin composition and application of resin composition in high frequency circuit board

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6352782B2 (en) * 1999-12-01 2002-03-05 General Electric Company Poly(phenylene ether)-polyvinyl thermosetting resin
US6306963B1 (en) * 2000-05-08 2001-10-23 General Electric Co. Thermosetting resins and laminates
JP2003012820A (en) * 2001-06-28 2003-01-15 Asahi Kasei Corp Cross-linking composite material and its laminate
DE10321555A1 (en) * 2003-05-14 2004-12-02 Degussa Ag Transparent masterbatches for thermoplastic materials
JP2005281673A (en) * 2004-03-02 2005-10-13 Tamura Kaken Co Ltd Thermosetting resin composition, resin film and product
CN101423658B (en) * 2008-11-27 2011-07-20 中国蓝星（集团）股份有限公司 Polyphenylene oxide resin composition and method for inhibiting discoloration of polyphenylene oxide resin
KR101911571B1 (en) * 2011-03-24 2018-10-24 미츠비시 가스 가가쿠 가부시키가이샤 Resin composition, prepreg and resin sheet, and metal foil-clad laminate
CN102807658B (en) * 2012-08-09 2014-06-11 广东生益科技股份有限公司 Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite
CN104650574B (en) * 2015-02-10 2017-02-22 郴州功田电子陶瓷技术有限公司 Polyphenyl ether copper-clad laminate composition
CN104725828B (en) * 2015-03-04 2017-11-21 广东生益科技股份有限公司 A kind of resin combination and use its prepreg and laminate
WO2017002319A1 (en) * 2015-06-30 2017-01-05 パナソニックＩｐマネジメント株式会社 Curable composition, prepreg, metal foil with composition, metal-clad laminate and wiring board

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5571609A (en) * 1994-10-13 1996-11-05 Rogers Corporation Polybutadiene and polyisoprene based thermosetting compositions and method of manufacture thereof
US20020040104A1 (en) * 1998-11-02 2002-04-04 Gil Technologies Vinyl-terminated polybutadiene and butadiene-styrene copolymers containing urethane and/or ester residues, and the electrical laminates obtained therefrom
CN101370866A (en) * 2006-02-17 2009-02-18 日立化成工业株式会社 Thermocurable resin composition comprising semi-ipn-type complex, and varnish, prepreg and metal-clad laminate sheet using the same
CN102161823A (en) * 2010-07-14 2011-08-24 广东生益科技股份有限公司 Composite material, high-frequency circuit substrate therefrom and manufacture method thereof
CN102993683A (en) * 2012-11-27 2013-03-27 广东生益科技股份有限公司 Resin composition and use thereof
CN105086417A (en) * 2014-05-06 2015-11-25 广东生益科技股份有限公司 Resin composition and application of resin composition in high frequency circuit board

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