WO2013056411A1 - 环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板 - Google Patents

环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板 Download PDF

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Publication number
WO2013056411A1
WO2013056411A1 PCT/CN2011/080891 CN2011080891W WO2013056411A1 WO 2013056411 A1 WO2013056411 A1 WO 2013056411A1 CN 2011080891 W CN2011080891 W CN 2011080891W WO 2013056411 A1 WO2013056411 A1 WO 2013056411A1
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epoxy resin
resin composition
flame retardant
compound
component
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PCT/CN2011/080891
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English (en)
French (fr)
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曾宪平
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广东生益科技股份有限公司
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Priority to PCT/CN2011/080891 priority Critical patent/WO2013056411A1/zh
Priority to US14/352,893 priority patent/US20140342161A1/en
Priority to EP11874126.3A priority patent/EP2770024A4/en
Publication of WO2013056411A1 publication Critical patent/WO2013056411A1/zh

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    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • C08G59/4276—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • 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
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0183—Dielectric layers
    • H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0212—Resin particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer
    • Y10T428/31522—Next to metal

Definitions

  • the present invention relates to a resin composition, and more particularly to an epoxy resin composition and a prepreg and a copper clad laminate produced using the same. Background technique
  • the existing traditional FR-4 is difficult to meet the high-frequency and high-speed development needs of electronic products, and the substrate material is no longer a mechanical support role in the traditional sense, but will become a PCB and terminal manufacturer together with electronic components. An important way to improve product performance. Because high DK slows the signal transmission rate, high Df converts the signal portion into thermal energy loss in the substrate material, so reducing DK/Df has become a hot pursuit for substrate manufacturers.
  • the traditional FR-4 material uses dicyandiamide as a curing agent.
  • This kind of curing agent has good process operability due to its tertiary amine. However, due to its weak carbon-nitrogen bond, it is easily cracked at high temperature.
  • the cured product has a low heat-resistant decomposition temperature and cannot be adapted to the heat resistance requirements of the lead-free process.
  • the industry began to use phenolic resin as a curing agent for epoxy.
  • the phenolic resin has a high-density benzene ring heat-resistant structure, so the epoxy curing system The heat resistance is excellent, but at the same time, the dielectric properties of the cured product tend to deteriorate.
  • Japanese Patent Laid-Open No. 2002-012650, 2003-082063 proposes the synthesis of a series of active ester curing agents containing a benzene ring, a naphthalene ring or a biphenyl structure as a curing agent for an epoxy resin such as IAAN, IABN, TriABN, TAAN. Compared with conventional phenolic products, the products can significantly reduce their dielectric constant and dielectric loss values.
  • Japanese Patent Laid-Open No. 2003-252958 proposes a biphenyl type epoxy resin and an active ester as a curing agent, which can obtain a cured product which lowers the dielectric constant and the dielectric loss value, but the epoxy resin used is bifunctional and active.
  • the curing density of the ester is low, the heat resistance of the cured product is low, and the temperature of the glass flower is low.
  • Japanese Patent Laid-Open No. 2004-155990 which uses an aromatic carboxylic acid to react with an aromatic phenol to obtain a polyfunctional active ester curing agent, and the use of the active ester curing agent to cure the phenolic epoxy can obtain higher heat resistance.
  • Japanese Patent Laid-Open No. 2009-235165 proposes a new polyfunctional active ester curing agent. Curing an epoxy containing an aliphatic structure gives a cured product having a high glass transition temperature and a low dielectric constant and dielectric loss.
  • thermosetting resin composition having a stable dielectric constant and excellent electrical continuity.
  • the main components include an epoxy resin, an active ester hardener, a hardening accelerator, and an organic solvent.
  • the obtained cured product has good copper foil adhesion, dielectric constant and dielectric loss.
  • the amount of epoxy resin and active ester was studied. The relationship between the structure and properties of epoxy resin and active ester was not studied. .
  • Japanese Patent Laid-Open No. 2009-242559, JP-A-2009-242560, JP-A-2010-077344, JP-A-2010-077343, respectively, discloses the use of alkylated phenol or alkylated naphthol novolac type epoxy resin, biphenyl.
  • the phenolic epoxy resin which uses an active ester as a curing agent, can obtain a cured product having low hygroscopicity, low dielectric constant, and dielectric loss tangent.
  • An object of the present invention is to provide an epoxy resin composition which can provide excellent dielectric properties, moist heat resistance and high glass transition temperature required for a copper clad laminate.
  • Another object of the present invention is to provide a prepreg and a copper-clad laminate which are prepared by using the above epoxy resin composition, which have excellent dielectric properties, heat and humidity resistance, and high glass transition temperature. Low water absorption.
  • an epoxy resin composition comprising the following essential components:
  • the epoxy resin containing the naphthol structure of the component (A) includes at least one epoxy resin having the following structural formula:
  • n and n are each 1 or 2
  • q is an integer of 1 to 10
  • R is H or an alkyl group having 1 to 5 carbon atoms.
  • the component (B) active ester curing agent is prepared by reacting a phenolic compound, a difunctional carboxylic acid aromatic compound or an acidic compound and a monohydroxy compound which are linked by an aliphatic cyclic hydrocarbon structure.
  • the amount of the difunctional carboxylic acid aromatic compound or the acid compound is 1 mol, the amount of the phenol compound linked by the aliphatic cyclic hydrocarbon structure is 0.05 to 0.75 mol, and the amount of the monohydroxy compound is 0.25 to 0.95 mol.
  • the active ester of the component (B) includes an active ester of the following structural formula:
  • X is a benzene or naphthalene ring
  • j is 0 or 1
  • k is 0 or 1
  • n represents an average repeating unit of 0.25-1.25.
  • the curing accelerator is one or a mixture of an imidazole compound and a piperidine compound.
  • the blending amount of the flame retardant is preferably from 5 to 100 parts by weight, based on 100 parts by weight of the total of the component (A), the component (B) and the component (C); a bromine-containing or halogen-free flame retardant, which is decabromodiphenyl ether, decabromodiphenylethane, brominated styrene, ethylene bis-tetrabromophthalimide or bromination Polycarbonate;
  • the [3 ⁇ 4 flame retardant is tris(2,6-dimercaptophenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxygen Hetero-10-phosphinophen-10-oxide, 2,6-bis(2,6-diamidinophenyl)phosphinobenzene or 10-phenyl-9, 10-dihydro-9-oxa-10 - phosphaphenanthrene-10-oxide, phenoxypho
  • the organic or inorganic filler is further contained, and the compounding amount of the filler is 5 to 500 parts by weight, preferably 5 to 300 parts by weight, based on 100 parts by weight of the total of the component (A), the component (B) and the component (C).
  • the inorganic filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, and hollow dioxide.
  • the organic filler is one or more selected from the group consisting of polytetrafluoroethylene powder, polyphenylene sulfide, and polyethersulfone powder.
  • the present invention provides a prepreg prepared by using the above epoxy resin composition, comprising a reinforcing material and an epoxy resin composition adhered thereto by impregnation and drying.
  • the present invention provides a copper-clad laminate produced using the above epoxy resin composition, comprising a plurality of laminated prepregs, and a copper foil pressed on one side or both sides of the laminated prepreg,
  • the prepreg is made of the epoxy resin composition.
  • the epoxy resin composition of the present invention has an epoxy resin having at least one naphthol structure in a molecular structure, which has a high functionality and a high glass transition temperature;
  • the naphthol group structure is introduced into the structure, the cured product has low water absorption rate and the coefficient of swelling;
  • the epoxy resin composition of the invention uses the active ester as a curing agent, and fully exerts the reaction of the active ester with the epoxy without generating a pole a group of groups, thereby having excellent dielectric properties and good heat and humidity resistance, and an epoxy resin having a specific naphthol structure, further reducing the water absorption of the cured resin and reducing the dielectric loss value of the cured product;
  • the prepreg and the copper-clad laminate thereof produced using the above epoxy resin composition have excellent dielectric properties, moist heat resistance, and high glass transition temperature.
  • the epoxy resin composition of the present invention contains the following essential components:
  • the component (A) contains an epoxy resin having a naphthol structure and a component (B).
  • the active ester curing agent is used in an amount equivalent to a molar equivalent ratio of 0.9 to 1.2, based on the weight of the solid component.
  • the epoxy resin containing the naphthol structure of the component (A) includes at least one epoxy resin having the following structural formula:
  • n and n are each 1 or 2
  • q is an integer of 1 to 10
  • R is H or an alkyl group having 1 to 5 carbon atoms.
  • the above epoxy resin containing a naphthol structure may more specifically have the following structural formula:
  • q is an integer from 1 to 10;
  • q is an integer from 1 to 10;
  • q is an integer from 1 to 10.
  • the component (B) active ester curing agent is obtained by reacting a phenolic compound linked by an aliphatic cyclic hydrocarbon structure, a difunctional carboxylic acid aromatic compound or an acidic compound and a monohydroxy compound.
  • the amount of the difunctional carboxylic acid aromatic compound or the acid compound is 1 mol
  • the amount of the phenol compound linked by the aliphatic cyclic hydrocarbon structure is 0.05 to 0.75 mol
  • the amount of the monohydroxy compound is 0.25 to 0.95 mol.
  • the active ester of component (B) includes an active ester of the formula:
  • X is a benzene or naphthalene ring
  • j is 0 or 1
  • k is 0 or 1
  • n represents an average repeating unit of 0.25-1.25.
  • the curing accelerator is one or a mixture of an imidazole compound and a piperidine compound.
  • the amount of the accelerator is calculated as the relative component (A) of the epoxy resin having at least one naphthol structure in the molecular structure and the component (B) active ester curing agent in a total weight of 100 parts, and the parts by weight are 0.05 to 1.0 part by weight.
  • the present invention may further contain a flame retardant, and the cured resin is provided with flame retardant properties and meets UL 94 V-0 requirements.
  • the flame retardant added as needed is not particularly limited, and may be a bromine-containing or halogen-free flame retardant, a halogen flame retardant, a flame retardant containing a silicon oxide, a silicon-containing flame retardant, a nitrogen-containing flame retardant, etc. It does not affect the dielectric properties.
  • the bromine-containing flame retardant may be decabromodiphenyl ether, decabromodiphenylethane, brominated styrene, ethylene bistetrabromophthalimide or brominated polycarbonate; the halogen-free
  • the flame retardant is tris(2,6-dimercaptophenyl)phosphine, 10-(2,5-dihydroxyphenyl)-lO-dihydro-9-oxa-10-phosphinophen-10-oxide , 2,6-bis(2,6-diamidinophenyl)phosphinobenzene or 10-phenyl-9, 10-dihydro-9-oxa-10-phosphinophen-10-oxide, phenoxy
  • a phosphinium compound a zinc borate, a phosphate, a polyester, a flame retardant, a silicon-containing flame retardant, or a nitrogen-containing flame retardant.
  • Optional commercial materials such as bromine-based flame retardant BT-93, BT-93W, HP-8010, HP-3010; Halogen-free flame retardants are SP-100, PX-200, PX-202, FR-700, OP-930, OP-935 are not limited to the above materials.
  • the amount of the flame retardant is determined according to the UL 94 V-0 level of the cured product, and is not particularly limited, and is 100 parts by weight relative to the total of the component (A), the component (B), and the component (C). It is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight.
  • the present invention may further contain an organic or inorganic filler.
  • the filler to be added as needed is not particularly limited, and the inorganic filler may be selected from the group consisting of crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, boron nitride, and carbonization.
  • the organic filler may be selected from polytetrafluoroethylene One or more of ethylene powder, polyphenylene sulfide, polyethersulfone powder, and the like.
  • the shape, particle diameter, and the like of the inorganic filler are not particularly limited, and usually have a particle diameter of 0.01 to 50 ⁇ m, preferably 0.01 to 20 ⁇ m, particularly preferably 0.1 to 10 ⁇ m, and an inorganic filler having such a particle size range. It is more easily dispersed in the resin liquid.
  • the mixing amount of the filler is also not particularly limited, and is based on the total of the components ( ⁇ ), the components ( ⁇ ), and the component (C). 100 parts by weight, from 5 to 1000 parts by weight, preferably from 5 to 300 parts by weight, more preferably from 5 to 200 parts by weight, particularly preferably from 5 to 150 parts by weight.
  • the prepreg prepared by using the above epoxy resin composition includes a reinforcing material and an epoxy resin composition adhered thereto by impregnation and drying, and the reinforcing material is a prior art reinforcing material such as a fiberglass cloth or the like.
  • a copper-clad laminate produced using the above epoxy resin composition comprising a plurality of laminated prepregs, and a copper foil pressed on one side or both sides of the laminated prepreg, the epoxy resin being used for the prepreg Composition preparation.
  • the epoxy resin composition of the present invention is made into a certain concentration of a glue, and the prepreg is obtained by impregnating the reinforcing material, then drying at a certain temperature, removing the solvent and semi-curing the resin composition. Then, one or more of the prepregs described above are stacked in a certain order, and the copper foil is respectively pressed on both sides of the prepreg which are superposed on each other, and cured in a hot press to obtain a copper clad laminate.
  • the curing temperature is 150-250 ° C and the curing pressure is 25-60 Kg/cm 2 .
  • the dielectric constant and dielectric loss factor, glass transition temperature and moisture heat resistance of the copper clad laminate produced above were measured and described and described in detail in the following examples.
  • Tg(DMA)/°C 180 190 210 165 160 200
  • NC-7300L naphthol type novolac epoxy resin, epoxy equivalent: 214g/eq;
  • NC-7000L naphthol type novolac epoxy resin, epoxy equivalent: 232g/eq;
  • NC-7700L naphthol type novolac epoxy resin, epoxy equivalent: 233 g/eq;
  • HP-7200-H biscyclopentadiene type novolac epoxy resin, epoxy equivalent: 280 g/eq;
  • N-690 Linfen phenol novolac epoxy resin, epoxy equivalent: 215g/eq;
  • HPC-8000-65T active ester curing agent, active ester equivalent: 223g / eq;
  • TD-2090 linear phenolic curing agent, hydroxyl equivalent: 105g/eq;
  • Glass transition temperature (Tg) Determined by DMA test according to the DMA test method specified in IPC-TM-650 2.4.24.
  • the copper-clad laminate of the present invention has superior dielectric properties, high glass transition temperature, and high heat and humidity resistance as compared with a general copper foil substrate, and is suitable for high frequency applications.

Abstract

一种环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板。该环氧树脂组合物包括以下必要组分：（A）含有萘酚结构的环氧树脂；（B）活性酯固化剂；（C）固化促进剂。使用本发明的环氧树脂组合物可以制备低吸水性和低介电损耗值的环氧树脂固化物。所制备的半固化片及其覆铜箔层压板具有良好的介电性能、耐湿热性能和高的玻璃化转变温度。

Description

环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板 技术领域
本发明涉及一种树脂组合物， 尤其涉及一种环氧树脂组合物以及使用 其制作的半固化片与覆铜箔层压板。 背景技术
随着电子产品信息处理的高速化和多功能化， 应用频率不断提高， 3- 6GHz将成为主流， 除了保持对层压板材料的耐热性有更高的要求外， 对 其介电常数和介质损耗值要求会越来越低。 现有的传统 FR-4很难满足电 子产品的高频及高速发展的使用需求， 同时基板材料不再是扮演传统意义 下的机械支撑角色， 而将与电子组件一起成为 PCB和终端厂商设计者提升 产品性能的一个重要途径 。 因为高 DK会使信号传递速率变慢， 高 Df会 使信号部分转化为热能损耗在基板材料中， 因而降低 DK/Df 已成为基板业 者的追逐热点。 传统的 FR-4 材料多釆用双氰胺作为固化剂， 这种固化剂 由于具有三级反应胺， 具有良好工艺操作性， 但是由于其碳 -氮键较弱， 在 高温下容易裂解， 导致固化物的耐热分解温度较低， 无法适应无铅工艺的 耐热要求。 在此背景下， 随着 2006 年无铅工艺的大范围实施， 行业内开 始釆用酚醛树脂作为环氧的固化剂， 酚醛树脂具有高密度的苯环耐热结 构， 所以和环氧固化后体系的耐热性非常优异， 但是同时出现固化产物的 介电性能被恶化的趋势。
日本专利特开 2002-012650 , 2003-082063 提出了合成一系列含有苯 环、 萘环或联苯结构的活性酯固化剂作为环氧树脂的固化剂如 IAAN, IABN, TriABN, TAAN, 得到的固化产物和传统酚醛相比， 可以明显的降 低其介电常数和介质损耗值。
日本专利特开 2003-252958 提出了釆用联苯型环氧树脂和活性酯作为 固化剂， 可以得到降低介电常数和介质损耗值固化产物， 但是由于釆用的 环氧树脂为双官能及活性酯的固化交密度低， 固化物的耐热性较低， 玻璃 花温度低。
日本专利特开 2004-155990, 釆用芳香族羧酸与芳香族酚反应得到一 种多官能度活性酯固化剂， 使用该活性酯固化剂固化酚醛型环氧可以得到 较高耐热性、 较好介电常数和介质损耗值的固化产物。
日本专利特开 2009-235165 提出了一种新的多官能度活性酯固化剂， 固化一种含有脂肪族结构的环氧， 可以得到同时具有较高玻璃花转变温度 和较低介电常数和介质损耗的固化产物。
日本专利特开 2009-040919提出了一种介电常数稳定， 导电层接着性 优异的热固性树脂组合物， 主要组分包括环氧树脂、 活性酯硬化剂、 硬化 促进剂、 有机溶剂。 得到的固化产物具有很好的铜箔结着性， 介电常数和 介质损耗， 对环氧树脂和活性酯的用量做了研究， 对于环氧树脂和活性酯 结构和性能的关系并未做研究。
另外， 日本专利特开 2009-242559 , 特开 2009-242560 , 特开 2010- 077344, 特开 2010-077343 分别提出了釆用烷基化苯酚或烷基化萘酚酚醛 型环氧树脂、 联苯型酚醛环氧树脂， 以活性酯作为固化剂， 可以得到低吸 湿性、 低介电常数和介质损耗正切的固化产物。
以上现有专利技术中， 虽然都提出了使用活性酯作为环氧树脂可以改 善固化产物的耐湿性， 降低吸水率， 降低固化产物的介电常数和介质损耗 值， 但是其缺点是很难在耐热性和介电性能之间取得一个很好的平衡， 使 固化产物同时具有高的玻璃化转变温度和低的介质损耗正切值， 且使其介 电性能随频率的变化比较稳定， 吸水率更低。 发明内容
本发明的目的在于提供一种环氧树脂组合物， 能够提供覆铜箔层压板 所需的优良的介电性能、 耐湿热性能及高的玻璃化转变温度。
本发明的另一目的在于， 提供一种使用上述环氧树脂组合物制作的半 固化片及覆铜箔层压板， 具有优异的介电性能、 耐湿热性能， 同时还具有 高的玻璃化转变温度， 更低的吸水率。
为实现上述目的， 本发明提供一种环氧树脂组合物， 包含以下必要组 分：
(A)含有萘酚结构的环氧树脂；
(B)活性酯固化剂；
(C)固化促进剂。
所述组分 (A)含有萘酚结构的环氧树脂包括至少一种具有下述结构式的 环氧树脂：
式一：
Figure imgf000004_0001
其中 m、 n分别为 1或 2, q为 1〜10的整数， R为 H、 或碳原子数为 1〜5的烷基。
所述组分 (B)活性酯固化剂是由一种通过脂肪环烃结构连接的酚类化合 物、 二官能度羧酸芳香族化合物或酸性 1¾化物及一种单羟基化合物反应而 付。
所述二官能度羧酸芳香族化合物或酸性! ¾化物用量为 lmol, 通过脂肪 环烃结构连接的酚类化合物用量为 0.05〜0.75mol , 单羟基化合物用量为 0.25〜0.95mol。
所述组分 (B)活性酯包括下述结构式的活性酯：
二：
Figure imgf000004_0002
式中 X为苯环或萘环， j为 0或 1 , k为 0或 1 , n表示平均重复单元 为 0.25-1.25。
所述固化促进剂为咪唑类化合物、 哌啶类化合物中的一种或多种混合 物。
还包括阻燃剂， 阻燃剂的混合量相对于组分 (A)、 组分 (B)及组分 (C)的 合计 100重量份， 优选为 5-100重量份； 该阻燃剂为含溴或无卤阻燃剂， 所述含溴阻燃剂为十溴二苯醚、 十溴二苯乙烷、 溴化苯乙烯、 乙撑双四溴 邻苯二曱酰亚胺或溴化聚碳酸酯； 所述无 [¾阻燃剂为三 （2 , 6-二曱基苯 基） 膦、 10- ( 2 , 5-二羟基苯基） -9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物、 2 , 6-二（2 , 6-二曱基苯基） 膦基苯或 10-苯基 -9 , 10-二氢 -9-氧杂 -10-膦 菲 -10-氧化物、 苯氧基膦氰化合物、 硼酸锌、 磷酸酯、 聚磷酸酯、 含碑阻 燃剂、 含硅阻燃剂、 或含氮阻燃剂。
进一步还包括有机或无机填料， 填料的混合量相对于组分 (A)、 组分 (B) 及组分 (C)的合计 100重量份为 5-500重量份， 优选为 5-300重量份； 无机 填料选自结晶型二氧化硅、 熔融二氧化硅、 球形二氧化硅、 空心二氧化 硅、 玻璃粉、 氮化铝、 氮化硼、 碳化硅、 氢氧化铝、 二氧化钛、 钛酸锶、 钛酸钡、 氧化铝、 硫酸钡、 滑石粉、 硅酸鈣、 碳酸鈣、 云母中的一种或多 种； 有机填料选自聚四氟乙烯粉末、 聚苯硫醚、 聚醚砜粉末中的一种或多 种。
同时， 本发明提供一种使用上述环氧树脂组合物制作的半固化片， 包 括增强材料及通过含浸干燥后附着其上的环氧树脂组合物。
进一步， 本发明还提供一种使用上述环氧树脂组合物制作的覆铜箔层 压板， 包括数张叠合的半固化片、 及压覆在叠合的半固化片一侧或两侧的 铜箔， 所述半固化片釆用所述环氧树脂组合物制成。
本发明的有益效果： ①本发明的环氧树脂组合物釆用分子结构中至少 含有一种萘酚结构的环氧树脂， 其具有较高的官能度， 具有高的玻璃化转 变温度； 同时分子结构中引入萘酚基团结构， 固化物具有低的吸水率， 地 膨胀系数； ②本发明的环氧树脂组合物以活性酯作为固化剂， 充分发挥了 活性酯在和环氧反应不生成极性基团基团， 从而介电性能优异耐湿热性能 好的优势， 另外含有特定萘酚结构的环氧树脂， 进一步降低了树脂固化物 的吸水性， 降低固化物的介质损耗值； ③本发明的使用上述环氧树脂组合 物制作的半固化片及其覆铜箔层压板， 具有优异的介电性能、 耐湿热性 能， 同时还具有高的玻璃化转变温度。 具体实施方式
本发明的环氧树脂组合物包含以下必要组分：
(A)含有萘酚结构的环氧树脂；
(B)活性酯固化剂；
(C)固化促进剂。
按固体组分重量份计算， 组分 (A)含有萘酚结构的环氧树脂与组分 (B) 活性酯固化剂的用量为按照摩尔当量比计算而得， 其当量比为 0.9〜1.2。
所述组分 (A)含有萘酚结构的环氧树脂包括至少一种具有下述结构式 的环氧树脂：
Figure imgf000005_0001
其中 m、 n分别为 1或 2, q为 1〜10的整数， R为 H、 或碳原子数为 1〜5的烷基。
上述含萘酚结构的环氧树脂， 更具体可以为如下结构式：
Figure imgf000006_0001
式中 q为 1〜10的整数;
四：
Figure imgf000006_0002
式中 q为 1〜10的整数;
Figure imgf000006_0003
式中 q为 1〜10的整数。
所述组分 (B)活性酯固化剂是由一种通过脂肪环烃结构连接的酚类化合 物、 二官能度羧酸芳香族化合物或酸性 1¾化物及一种单羟基化合物反应而 得。 所述二官能度羧酸芳香族化合物或酸性 1¾化物用量为 Imol, 通过脂肪 环烃结构连接的酚类化合物用量为 0.05〜0.75mol , 单羟基化合物用量为 0.25〜0.95mol。 所述组分 (B)活性酯包括下述结构式的活性酯:
二：
Figure imgf000007_0001
式中 X为苯环或萘环， j为 0或 1 , k为 0或 1 , n表示平均重复单元 为 0.25-1.25。
所述固化促进剂为咪唑类化合物、 哌啶类化合物中的一种或多种混合 物。 促进剂用量为相对组分 (A) 分子结构中至少含有一种萘酚结构的环氧 树脂与组分 (B)活性酯固化剂总重量 100份计算， 其重量份为 0.05〜1.0份。
如有需要， 本发明中还可以含有阻燃剂， 提供树脂固化物具有阻燃特 性， 符合 UL 94 V-0要求。 对视需要而添加的阻燃剂并无特别限定， 可以 为含溴或无卤阻燃剂、 卤素阻燃剂、 含碑阻燃剂、 含硅阻燃剂、 含氮阻燃 剂等， 以不影响介电性能为佳。 所述含溴阻燃剂可为十溴二苯醚、 十溴二 苯乙烷、 溴化苯乙烯、 乙撑双四溴邻苯二曱酰亚胺或溴化聚碳酸酯； 所述 无卤阻燃剂为三 （2 , 6-二曱基苯基） 膦、 10- ( 2 , 5-二羟基苯基） - lO- 二氢 -9-氧杂 -10-膦菲 -10-氧化物、 2 , 6-二（2 , 6-二曱基苯基） 膦基苯或 10-苯基 -9, 10-二氢 -9-氧杂 -10-膦菲 -10-氧化物、 苯氧基膦氰化合物、 硼酸 锌、 磷酸酯、 聚碑酸酯、 含碑阻燃剂、 含硅阻燃剂、 或含氮阻燃剂。 可选 的商品化材料如溴系阻燃剂雅宝公司的 BT-93,BT-93W,HP-8010,HP-3010; 无卤阻燃剂有 SP-100, PX-200, PX-202, FR-700 , OP-930,OP-935但并不 限于以上材料。 阻燃剂的用量根据固化产物达到 UL 94 V-0 级别要求而 定， 并没有特别的限制， 相对于组分 (A)、 组分 (B)及组分 (C)的合计 100重 量份， 优选为 5-100重量份， 更优选为 10〜50重量份。
如有需要， 本发明中还可以进一步含有有机或无机填料。 对视需要而 添加的填料并无特别限定， 无机填料可选自结晶型二氧化硅、 熔融二氧化 硅、 球形二氧化硅、 空心二氧化硅、 玻璃粉、 氮化铝、 氮化硼、 碳化硅、 氢氧化铝、 二氧化钛、 钛酸锶、 钛酸钡、 氧化铝、 硫酸钡、 滑石粉、 硅酸 钙、 碳酸钙、 云母等中的一种或多种； 有机填料可以选自聚四氟乙烯粉 末、 聚苯硫醚、 聚醚砜粉末等中的一种或多种。 另外， 无机填料的形状、 粒径等也无特别限定， 通常粒径为 0.01-50 μ ιη, 优选为 0.01-20 μ ιη, 特优 选为 0.1-10 μ ηι, 这种粒径范围的无机填料在树脂液中更易分散。 再者， 填料的混合量也无特别限定， 相对于组分 (Α)、 组分 (Β)及组分 (C)的合计 100重量份， 为 5-1000重量份， 优选为 5-300重量份， 更优选为 5-200重 量份， 特优选为 5-150重量份。
使用上述环氧树脂组合物制作的半固化片， 包括增强材料及通过含浸 干燥后附着其上的环氧树脂组合物， 增强材料使用现有技术的增强材料， 如玻纤布等。 使用上述环氧树脂组合物制作的覆铜箔层压板， 包括数张叠 合的半固化片、 及压覆在叠合的半固化片一侧或两侧的铜箔， 所述半固化 片釆用所述环氧树脂组合物制作。
将本发明的环氧树脂组合物制成一定浓度的胶液， 通过浸渍增强材 料， 然后在一定的温度下烘干， 赶走溶剂及使树脂组合物进行半固化， 得 到半固化片。 然后将上述所述的半固化片一张或多张按照一定顺序叠合在 一起， 将铜箔分别压覆在相互叠合的半固化片两侧， 在热压机中固化制得 覆铜箔层压板， 其固化温度为 150-250 °C , 固化压力为 25-60 Kg/cm2。
针对上述制成的覆铜箔层压板， 测其介电常数和介电损耗因子、 玻璃 化转变温度及耐湿热性能， 如下述实施例进一步给予详加说明与描述。
实施例 1 :
取一容器， 加入 100 重量份的萘酚型酚醛环氧树脂 NC-7300L, 然后 加入等当量重量份活性酯固化剂 HPC-8000-65T , 搅拌， 加入适量 DMAP , 以及溶剂曱苯， 继续搅拌均匀即成胶液。 用玻璃纤维布 (型号为 2116, 厚度为 0.08mm)浸渍上述胶液， 并控制至合适厚度， 然后烘干除去 溶剂制得半固化片。 使用数张所制得的半固化片相互叠合， 在其两侧上各 压覆一张铜箔， 放进热压机中固化制成所述覆铜箔层压板。 物性数据如表 1所示。
实施例 2〜3：
制作工艺和实施例 1相同， 配方组成及其物性数据如表 1所示。
比较例 1-3:
制作工艺和实施例 1相同， 配方组成及其物性数据如表 1所示。
表 1.各实施例及比较例的配方组成及其物性数据
Figure imgf000008_0001
HPC-8000- leq leq leq leq leq ― 65T
TD-2090 —- ― ― —- —- leq
DMAP 0.15 0.15 0.15 0.15 0.15 ―
2E4MZ —- —- ― ― —- 0.075
Tg(DMA)/°C 180 190 210 165 160 200
Dk(5G) 3.7 3.8 3.7 3.9 3.9 4.4
Df(5G) 0.007 0.0075 0.007 0.011 0.014 0.019 吸水率％ 0.12 0.13 0.13 0.13 0.18 0.30 耐湿热 '1 "生 3/3 3/3 3/3 3/3 3/3 2/3 表中列举的材料具体如下：
NC-7300L:萘酚型酚醛环氧树脂， 环氧当量： 214g/eq;
NC-7000L:萘酚型酚醛环氧树脂， 环氧当量： 232g/eq;
NC-7700L:萘酚型酚醛环氧树脂， 环氧当量： 233g/eq;
HP-7200-H:双环戊二烯型酚醛环氧树脂， 环氧当量： 280g/eq;
N-690: 临曱酚酚醛环氧树脂， 环氧当量： 215g/eq;
HPC-8000-65T:活性酯固化剂， 活性酯当量： 223g/eq;
TD-2090: 线性酚醛固化剂， 羟基当量： 105g/eq;
DMAP:4-二曱氨基吡啶；
2E4MZ: 2-乙基 -4-曱基咪唑。
以上特性的测试方法如下：
( 1 ) 玻璃化转变温度 ( Tg ) ： 使用 DMA 测试， 按照 IPC-TM-650 2.4.24所规定的 DMA测试方法进行测定。
( 2 )介电常数和介电损耗因子： 按照 SPDR方法测试。
( 3 ) 耐湿热性评价： 将覆铜板表面的铜箔蚀刻后， 评价基板； 将基 板放置压力锅中， 在 120°C、 105KPa条件下处理 2h; 后浸渍在 288°C的锡 炉中， 当基板分层爆板时记录相应时间； 当基板在锡炉中超过 5min还没 出现气泡或分层时即可结束评价。
物性分析
从表 1 的物性数据可知比较例 1-2中使用现有酚醛环氧树脂和活性酯 固化时， 玻璃化转变温度一般， 介电性能和吸水率较一般环氧有改善， 同 时耐湿热性能好； 比较例 3 中同样结构的环氧树脂在用酚醛固化的时候， 虽然可以得到较高的玻璃化转变温度， 但是介电性能， 耐湿热性能都较 差， 实施例 1-3 使用萘酚型酚醛环氧树脂活性酯共同固化， 由于萘酚结构 的存在， 得到的层压板材料的吸水率低， 介电性能和耐湿热性能优异， 且 玻璃化转变温度高。
如上所述， 与一般的铜箔基板相比， 本发明的覆铜箔层压板拥有更加 优异的介电性能、 高的玻璃化转变温度， 同时耐湿热性能好， 适用高频领 域。
以上所述， 仅为本发明的较佳实施例， 对于本领域的普通技术人员来 说， 可以根据本发明的技术方案和技术构思作出其他各种相应的改变和变 形， 而所有这些改变和变形都应属于本发明权利要求的保护范围。

Claims

权 利 要 求
1、 一种环氧树脂组合物， 包含以下必要组分：
(A)含有萘酚结构的环氧树脂；
(B)活性酯固化剂；
(C)固化促进剂。
2、 如权利要求 1 所述的环氧树脂组合物， 其中， 所述组分 (A)含有萘 酚结构的环氧树脂包括至少一种具有下述结构式的环氧树脂：
Figure imgf000011_0001
其中 m、 n分别为 1或 2, q为 1〜10的整数， R为 H、 或碳原子数为 1〜5的烷基。
3、 如权利要求 1 所述的环氧树脂组合物， 其中， 所述组分 (B)活性酯 固化剂是由一种通过脂肪环烃结构连接的酚类化合物、 二官能度羧酸芳香 族化合物或酸性 1¾化物及一种单羟基化合物反应而得。
4、 如权利要求 3 所述的环氧树脂组合物， 其中， 所述二官能度羧酸 芳香族化合物或酸性 1¾化物用量为 lmol, 通过脂肪环烃结构连接的酚类化 合物用量为 0.05〜0.75mol, 单羟基化合物用量为 0.25〜0.95mol。
5、 如权利要求 1 所述的环氧树脂组合物， 其中， 所述组分 (B)活性酯 包括下述结构式的活性酯：
二：
Figure imgf000011_0002
式中 X为苯环或萘环， j为 0或 1 , k为 0或 1 , n表示平均重复单元 为 0.25-1.25。
6、 如权利要求 1 所述的环氧树脂组合物， 其中， 所述固化促进剂为 咪唑类化合物、 哌啶类化合物中的一种或多种混合物。
7、 如权利要求 1 所述的环氧树脂组合物， 其中， 还包括阻燃剂， 阻 燃剂的混合量相对于组分 (A)、 组分 (B)及组分 (C)的合计 100重量份， 优选 为 5-100 重量份； 该阻燃剂为含溴或无卤阻燃剂， 所述含溴阻燃剂为十溴 二苯醚、 十溴二苯乙烷、 溴化苯乙烯、 乙撑双四溴邻苯二曱酰亚胺或溴化 聚碳酸酯； 所述无卤阻燃剂为三 （2, 6-二曱基苯基）膦、 10- ( 2, 5-二羟 基苯基） -9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物、 2 , 6-二（2 , 6-二曱基苯 基）膦基苯或 10-苯基 -9, 10-二氢 -9-氧杂 -10-膦菲 -10-氧化物、 苯氧基膦氰 化合物、 硼酸锌、 磷酸酯、 聚碑酸酯、 含碑阻燃剂、 含硅阻燃剂、 或含氮 阻燃剂。
8、 如权利要求 1 所述的环氧树脂组合物， 其中， 进一步还包括有机 或无机填料， 填料的混合量相对于组分 (A)、 组分 (B)及组分 (C)的合计 100 重量份， 优选为 5-500 重量份； 无机填料选自结晶型二氧化硅、 熔融二氧 化硅、 球形二氧化硅、 空心二氧化硅、 玻璃粉、 氮化铝、 氮化硼、 碳化 硅、 氢氧化铝、 二氧化钛、 钛酸锶、 钛酸钡、 氧化铝、 硫酸钡、 滑石粉、 硅酸鈣、 碳酸鈣、 云母中的一种或多种； 有机填料选自聚四氟乙烯粉末、 聚苯硫醚、 聚酸砜粉末中的一种或多种。
9、 一种使用如权利要求 1 所述的环氧树脂组合物制作的半固化片， 包括增强材料及通过含浸干燥后附着其上的环氧树脂组合物。
10、 一种使用如权利要求 1 所述环氧树脂组合物制作的覆铜箔层压 板， 包括数张叠合的半固化片、 及压覆在叠合的半固化片一侧或两侧的铜 箔， 所述半固化片釆用所述环氧树脂组合物制成。
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