WO2014040262A1 - 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
WO2014040262A1
WO2014040262A1 PCT/CN2012/081368 CN2012081368W WO2014040262A1 WO 2014040262 A1 WO2014040262 A1 WO 2014040262A1 CN 2012081368 W CN2012081368 W CN 2012081368W WO 2014040262 A1 WO2014040262 A1 WO 2014040262A1
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Prior art keywords
epoxy resin
compound
resin composition
active ester
flame retardant
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PCT/CN2012/081368
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English (en)
French (fr)
Inventor
曾宪平
任娜娜
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广东生益科技股份有限公司
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Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to KR1020157009585A priority Critical patent/KR101849833B1/ko
Priority to EP12884451.1A priority patent/EP2896653B1/en
Priority to US14/420,517 priority patent/US20150189745A1/en
Priority to PCT/CN2012/081368 priority patent/WO2014040262A1/zh
Publication of WO2014040262A1 publication Critical patent/WO2014040262A1/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
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
    • 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
    • C08G59/3227—Compounds containing acyclic nitrogen atoms
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • 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
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2475—Coating or impregnation is electrical insulation-providing, -improving, or -increasing, or conductivity-reducing

Definitions

  • This invention relates to the field of printed circuit boards, and more particularly to a non-epoxy resin composition and a prepreg and copper clad laminate produced therefrom. Background technique
  • the high dielectric loss value (Df) causes the signal portion to be converted into thermal energy loss in the substrate material, thus reducing the dielectric constant/dielectric loss value has become a substrate manufacturer. Chasing hot spots.
  • the traditional epoxy fiberglass cloth laminate material uses dicyandiamide as a curing agent. This curing agent has good process operability due to its tertiary reaction amine, but its carbon-nitrogen bond is weak, at high temperature. It is easy to crack, resulting in a low heat-resistant decomposition temperature of the cured product, which cannot meet the heat resistance requirements of the lead-free process.
  • Phenolic resins have been used as curing agents for epoxy resins in the industry. Phenolic resins have a high-density benzene ring heat-resistant structure, so after epoxy curing The heat resistance of the system is extremely 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 curing agents for epoxy resins, such as IAAN, IABN, TriABN and TAAN.
  • the cured product can significantly reduce its dielectric constant and dielectric loss value compared to conventional phenolic resins.
  • 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 cured crosslink density of the ester is low, the heat resistance of the cured product is low, and the glass transition temperature is low.
  • the invention discloses a polyfunctional active ester curing agent by reacting an aromatic carboxylic acid with an aromatic phenol, and curing the phenolic epoxy using the active ester curing agent can obtain higher heat resistance.
  • Japanese Patent Laid-Open No. 2009-235165 proposes a new polyfunctional active ester curing agent which cures an epoxy resin containing an aliphatic structure and can simultaneously have a high glass transition temperature and a low dielectric constant. The cured product of the dielectric loss value.
  • 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, low dielectric constant and dielectric loss value, and the amount of epoxy resin and active ester is studied, and the relationship between the structure and properties of epoxy resin and active ester is studied. Not # ⁇ .
  • 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, with the active ester as a curing agent, can obtain a cured product having low hygroscopicity, low dielectric constant and dielectric loss tangent.
  • the 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, and the amount of the phenolic 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 structural formula of the active ester curing agent is as follows:
  • X is a benzene or naphthalene ring
  • j is 0 or 1
  • k is 0 or 1
  • n is 0.25-2.5.
  • the flame retardant compound containing the trace is a phosphate compound, a phosphate compound, a phosphazene compound, a phosphorus phenanthrene compound and a derivative thereof, a phenolic resin, and a daunting polycarbonate.
  • the phosphorus-containing [3 ⁇ 4 flame retardant compound has a phosphorus content of 5 to 30% by weight.
  • the epoxy resin composition further contains a curing accelerator which is one or a mixture of imidazoles and derivatives thereof, piperidine compounds, Lewis acids, and triphenylphosphine.
  • a curing accelerator which is one or a mixture of imidazoles and derivatives thereof, piperidine compounds, Lewis acids, and triphenylphosphine.
  • the epoxy resin composition further includes an organic filler, an inorganic filler, or a mixture of an organic filler and an inorganic filler, the filler being used in an amount relative to the epoxy resin, the active ester curing agent, and the
  • the total amount of the halogen-free flame retardant compound is from 5 to 500 parts by weight based on 100 parts by weight.
  • the inorganic filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, Hollow silica, glass powder, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, barium titanate, barium titanate, aluminum oxide, barium sulfate, talc, calcium silicate, calcium carbonate, and One or more of mica; the organic filler is selected from one or more of polytetrafluoroethylene powder, polyphenylene sulfide, and polyacid present powder.
  • the present invention also 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 prepreg, comprising a plurality of laminated prepregs, and a copper foil laminated on one side or both sides of the laminated prepreg.
  • the epoxy resin composition of the present invention uses an epoxy resin containing a nitrogen element in a molecular chain, which has a high functionality, and may contain an active ester curing agent due to a nitrogen element.
  • the phosphorus element plays a synergistic flame retardant effect, and while providing high heat resistance, the flame retardant requirement can be achieved with as little phosphorus flame retardant as possible;
  • the epoxy resin composition of the present invention is active Ester as a curing agent, fully exerts the advantage that the active ester and epoxy do not form polar groups, and thus has excellent dielectric properties and good heat and humidity resistance. The specific structure of the flame retardant is not sacrificed at the expense of the original cured product.
  • the present invention is produced using the above epoxy resin composition.
  • Prepreg and its copper clad laminate have excellent dielectric properties, moisture and heat resistance, and flame retardancy up to UL94 V-0. detailed description
  • the present invention provides an epoxy resin composition
  • an epoxy resin composition comprising the following components: an epoxy resin having 3 or more epoxy groups in a molecular chain and containing a nitrogen element, and a flame retardant compound and an active ester Hardener.
  • the epoxy resin having three or more epoxy groups in the molecular chain and containing a nitrogen element is at least one of epoxy resins having the following structural formula:
  • the structural formula of the nitrogen-containing epoxy resin described in the present invention may specifically be as follows
  • the structural formula of the nitrogen-containing epoxy resin described in the present invention may specifically be as follows:
  • the structural formula of the nitrogen-containing epoxy resin described in the present invention may specifically be as follows
  • the structural formula of the nitrogen-containing epoxy resin described in the present invention may specifically be as follows
  • the structural formula of the nitrogen-containing epoxy resin described in the present invention may specifically be as follows
  • the active ester curing agent is a phenolic compound linked by an aliphatic cyclic hydrocarbon structure, a difunctional carboxylic acid aromatic compound or an acidic compound and a monohydroxy group.
  • the compound is obtained by reaction.
  • the active ester mainly functions to cure the epoxy resin. Since it does not have secondary hydroxyl groups after curing, the epoxy resin has no hydroxyl group in the cured product, and has good dielectric properties and low Water absorption, good resistance to heat and humidity.
  • the difunctional carboxylic acid aromatic compound or the acid compound is used in an amount of 1 mol, and the amount of the phenolic compound linked by the aliphatic cyclic hydrocarbon structure is 0.05 to 0.75 mol, and the monohydroxy compound is used. The amount used is 0.25 to 0.95 mol.
  • the structure of the phenolic compound linked by an aliphatic cyclic hydrocarbon structure is as follows:
  • X is a benzene or naphthalene ring
  • j is 0 or 1
  • k is 0 or 1
  • n is 0.25-2.5.
  • the active ester curing agent is used in an amount of 100 parts by weight of the epoxy resin containing 3 or more epoxy groups and containing a nitrogen element, and is calculated based on the epoxy equivalent and the active ester equivalent ratio.
  • the equivalent ratio is from 0.85 to 1.2, preferably from 0.9 to 1.1, and most preferably from 0.95 to 1.05.
  • the phosphate compound may be selected from an aromatic phosphate compound, specifically resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol-bis(phosphoric acid- 2,6-dimercaptophenyl ester), or biphenyldiol-bis(phosphoric acid-2,6-didecylphenyl ester).
  • aromatic phosphate compound specifically resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol-bis(phosphoric acid- 2,6-dimercaptophenyl ester), or biphenyldiol-bis(phosphoric acid-2,6-didecylphenyl ester).
  • the phosphazene compound may be selected from tripolyphosphazene or tetraphosphazene, and the commercially available product may be SPB-100;
  • the phenanthrene compound and its derivative may be 9,10-dihydro-9-oxa-10-phosphinophen-10-oxide, tris(2,6-dimercaptophenyl)phosphine, 10-(2, 5 -dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphinophen-10-oxide, 2,6-di(2,6-diamidinophenyl)phosphinobenzene or 10 -phenyl-9, 10-dihydro-9-oxa-10-phosphinophen-10-oxide;
  • the brick-containing phenolic resin may be 9,10-dihydro-9-oxa-10-phosphine -10-Oxide (DOPO)
  • the purpose of the monument-containing halogen-free flame retardant compound described in the present invention is flame retardant, and in order to ensure better comprehensive properties of the cured product, such as heat resistance and hydrolysis resistance, the flame retardant compound containing the trace is not included.
  • the amount of addition is 10 to 150 parts by weight, more preferably 20, based on 100 parts by weight of the total of the epoxy resin, the active ester curing agent, and the above-mentioned flame retardant compound. - 120 parts by weight.
  • the curing accelerator is not particularly limited as long as it can catalyze the reaction of the epoxy functional group and lower the reaction temperature of the curing system, and is preferably an imidazole compound and a derivative compound thereof, a piperidine compound, a Lewis acid, and a triphenylphosphine.
  • the imidazole compound may, for example, be 2-mercaptoimidazole, 2-phenylimidazole or 2-ethyl-4-mercaptoimidazole
  • the piperidine compound may be exemplified by 2,3-diaminopiperidine.
  • 2,5-diaminopiperidine 2,6-diaminopiperidine 2,5-Diamino, 2-amino-3-indolylpiperidine, 2-amino-4-4hydrazinopiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitroperidine Pyridine, 4-didecylaminopiperidine.
  • the amount of the accelerator is 0.05 to 1.0 part by weight based on 100 parts by weight of the total of the epoxy resin, the active ester curing agent, and the monument-free halogen-free flame retardant compound.
  • the organic filler may be selected from polytetrafluoroethylene One or more of ethylene powder, polyphenylene sulfide, and polyethersulfone powder. Further, the shape, particle diameter, and the like of the inorganic filler are not particularly limited, and the usual particle diameter is
  • the prepreg prepared by using the above epoxy resin composition comprises a reinforcing material and an epoxy resin composition adhered thereto by impregnation and drying, and a reinforcing material such as a glass fiber cloth or the like is used as the reinforcing material.
  • 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.
  • the prepreg obtained by using a plurality of sheets was laminated on each other, and a copper foil was laminated on both sides thereof, and placed in a heat press to be cured to form the copper-clad laminate. Curing in a hot press to obtain a copper clad laminate having a curing temperature of 200 ° C, a curing pressure of 30 Kg/cm 2 and a curing time of 90 min.
  • the above glue is impregnated with a glass fiber cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent is dried to obtain a prepreg.
  • the prepregs obtained by using a plurality of sheets are stacked one on another.
  • the copper foil is laminated on each of the two sides and cured in a hot press to form the copper clad laminate.
  • the copper foil laminate is cured in a hot press, and the curing temperature is At 200 ° C, the curing pressure is 30 Kg/cm 2 and the curing time is 90 min.
  • a prepreg is obtained by laminating a plurality of prepregs obtained by laminating a plurality of copper foils on both sides thereof and being cured in a hot press to form the copper clad laminate. Curing to obtain a copper clad laminate with a curing temperature of 200 ° C, a curing pressure of 30 Kg / cm 2 , and a curing time of 90 min
  • KES-224 Kelon KOLON, EEW is 125g/mol, then add 178.4 parts by weight of active ester curing agent HPC-8000-65T (Japan DIC company, active ester equivalent is 223g/mol), stir and hook, then add phosphate Flame retardant compound PX-202 (Japan DAIHACHI, phosphorus content 8%) 119.3 parts by weight, stir evenly, then add appropriate amount DMAP, and the solvent benzene, continue to stir and form a glue.
  • active ester curing agent HPC-8000-65T Japanese DIC company, active ester equivalent is 223g/mol
  • PX-202 Japanese DAIHACHI, phosphorus content 8%
  • a thickness of 0.08 mm is impregnated with the above-mentioned glue, and controlled to a suitable thickness, and then dried to remove the solvent to obtain a prepreg.
  • the prepreg obtained by using a plurality of sheets was laminated on each other, and a copper foil was laminated on both sides thereof, and placed in a heat press to be cured to form the copper-clad laminate. Curing in a hot press to obtain a copper clad laminate having a curing temperature of 200 ° C, a curing pressure of 30 Kg/cm 2 and a curing time of 90 min.
  • the prepregs obtained by using a plurality of sheets are laminated on each other.
  • a copper foil is laminated on both sides thereof and cured in a hot press to form the copper clad laminate.
  • the copper foil laminate is cured in a hot press, and the curing temperature is 200. °C, curing pressure is 30 Kg/cm 2 , curing time is 90min.
  • the prepreg obtained by using a plurality of sheets is laminated on each other, and a copper foil is laminated on both sides thereof, and placed in a hot press to be cured to form the copper-clad laminate.
  • Curing in a hot press A copper clad laminate having a curing temperature of 200 ° C, a curing pressure of 30 Kg/cm 2 and a curing time of 90 min was obtained.
  • Tg Glass transition temperature
  • the DMA test method specified in 2.4.24 is measured.
  • Examples 1-4 compared with the curing of the novolac epoxy resin and the active ester in Comparative Example 1, are co-cured by using a nitrogen-containing polyfunctional epoxy resin active ester, nitrogen element
  • the presence of synergistic flame retardant with the phosphorus flame retardant, good flame retardancy, and the resulting laminate material has low water absorption, excellent dielectric properties and heat and humidity resistance, and a glass transition temperature surface.
  • the epoxy resin composition of the present invention comprises a nitrogen-containing epoxy resin in the molecular chain, an active ester curing agent, and a halogen-free flame retardant compound; and a general copper foil substrate Compared with the epoxy resin composition prepared by using the epoxy resin composition of the invention, the copper-clad laminate has better dielectric properties, high glass transition temperature, and good heat and humidity resistance, and realizes halogen-free flame retardant V-0. Class, applicable to no high frequency field.

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Abstract

本发明涉及一种树脂组合物以及使用其制作的半固化片与覆铜箔层压板，该树脂组合物包含组分如下：分子链中含有3个或3个以上环氧基、且含有氮元素的环氧树脂，含磷无卤阻燃剂化合物及活性酯固化剂；所述分子链中含有3个或3个以上环氧基、且含有氮元素的环氧树脂的用量为100重量份，所述含碑无卤阻燃剂化合物的用量为10〜150重量份，所述活性酯固化剂的用量当量比，以环氧当量与活性酯当量比计算，为0.85-1.2。使用该环氧树脂组合物制作的半固化片与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，同时实现无卤阻燃，达到UL 94V-0。

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
本发明涉及印制电路板领域， 尤其涉及一种无 [¾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。 现有的传统环氧玻璃纤维布层 压板（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印 制电路板 ( PCB )和终端厂商设计者提升产品性能的一个重要途径。 因为 高介电常数（DK )会使信号传递速率变慢， 高介质损耗值 ( Df )会使信 号部分转化为热能损耗在基板材料中， 因而降低介电常数 /介质损耗值已成 为基板业者的追逐热点。 传统的环氧玻璃纤维布层压板材料多釆用双氰胺 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树脂的固化剂， 酚醛树 脂具有高密度的苯环耐热结构， 所以环氧固化后的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 和 TAAN, 得到的固化产物和传统的酚醛树脂相比， 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联密度低， 固化物的耐热性较低， 玻 璃化温度氐。
曰本专利特开 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、 较低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树脂， 可以得到同时具有较高玻璃化转变 温度和较低介电常数和介质损耗值的固化产物。
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。 其得到的固化产物具有很好的铜箔结着性， 较低介电 常数和介质损耗值， 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 #丈研究。
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值的固化产物。
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。 同时对如何实现固化产物的 无卤阻燃性并没有做研究。 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， 并实现无卤阻燃， 达到 UL 94 V- 0。
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， 同时实现无! ¾阻燃， 达到 UL 94 V- 0。
为实现上述目的， 本发明提供一种环氧树脂组合物， 包含组分如下： 分子链中含有 3个或 3个以上环氧基、 且含有氮元素的环氧树脂， 含碑无 1¾阻燃剂化合物及活性酯固化剂； 所述分子链中含有 3个或 3个以上环氧 基、 且含有氮元素的环氧树脂的用量为 100重量份， 所述含碑无卤阻燃剂 化合物的用量为 10〜150 重量份， 所述活性酯固化剂的用量当量比， 以环 氧当量与活性酯当量比计算， 为 0.85〜1.2。
所述分子链中含有 3个或 3个以上环氧基、 且含有氮元素的环氧树脂 
Figure imgf000004_0001
Figure imgf000005_0001
所述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! ¾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! ¾化物用量为 lmol, 该种通过 脂肪环烃结构连接的酚类化合物用量为 0.05〜0.75mol, 该种单羟基化合物 用量为 0.25〜0.95mol。
所述)活性酯固化剂的结构式如下：
Figure imgf000005_0002
式中， X为苯环或萘环， j为 0或 1 , k为 0或 1 , n为 0.25-2.5。
所述含碑无 1¾阻燃剂化合物为磷酸酯化合物、 磷酸酯盐化合物、 磷腈 化合物、 磷菲化合物及其衍生物、 含碑酚醛树脂、 及碑化聚碳酸酯中的一 种或几种的混合物； 所述含磷无 [¾阻燃剂化合物的磷含量为 5〜30%重量 比。
进一步所述环氧树脂组合物还包含固化促进剂， 所述固化促进剂为咪 唑类及其衍生化合物、 哌啶类化合物、 路易斯酸、 及三苯基膦中的一种或 多种混合物。
再进一步所述环氧树脂组合物还包括有机填料、 无机填料、 或有机填 料和无机填料的混合物， 所述填料的用量相对于 所述环氧树脂、 所述活 性酯固化剂、 及所述含碑无卤阻燃剂化合物的合计 100重量份计算， 为 5- 500重量份。
所述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、 硅酸钙、 碳酸钙、 及云 母中的一种或多种； 所述有机填料选自聚四氟乙烯粉末、 聚苯硫醚、 及聚 酸现粉末中的一种或多种。
同时， 本发明还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半固化片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。
本发明的有益效果： 首先， 本发明所述的环氧树脂组合物釆用分子链 中含有氮元素的环氧树脂， 其具有较高的官能度， 由于含有氮元素， 可以 和活性酯固化剂中的磷元素发挥协同阻燃作用， 在提供高耐热性的同时， 可以在尽量少用磷阻燃剂的前提下达到阻燃要求； 其次， 本发明所述的环 氧树脂组合物以活性酯作为固化剂， 充分发挥了活性酯和环氧反应不生成 极性基团， 从而介电性能优异耐湿热性能好的优势， 釆用特定结构的含碑 阻燃剂在不牺牲原有固化产物的耐热性、 低吸水性、 优异介电性能的同 时， 实现了无! ¾阻燃， 固化产物的阻燃性达到 UL94 V-0 级； 最后， 本发 明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， 阻燃性达到 UL94 V-0级。 具体实施方式
为更进一步阐述本发明所釆取的技术手段及其效果， 以下结合本发明 的优选实施例进行详细描述。
本发明提供一种环氧树脂组合物， 包含组分如下： 分子链中含有 3 个 或 3 个以上环氧基、 且含有氮元素的环氧树脂， 含碑无 1¾阻燃剂化合物及 活性酯固化剂。
所述分子链中含有 3个或 3个以上环氧基、 且含有氮元素的环氧树脂 为具有下述结构式的环氧树脂中的至少一种：
式 I
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000008_0001
本发明中所述的含有氮元素的环氧树脂的结构式具体还可以如下所
Figure imgf000008_0002
下
Figure imgf000008_0003
本发明中所述的含有氮元素的环氧树脂的结构式具体还可以如 下所示:
Figure imgf000008_0004
本发明中所述的含有氮元素的环氧树脂的结构式具体还可以如下所
Figure imgf000009_0001
本发明中所述的含有氮元素的环氧树脂的结构式具体还可以如下
Figure imgf000009_0002
本发明中所述的含有氮元素的环氧树脂的结构式具体还可以如下
Figure imgf000009_0003
本发明所述的环氧树脂组合物中， 所述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。 该活性酯主要起到固化环氧树脂的作用， 由于其和环氧树脂固化后没有二次羟基的产生， 所以固化产物中基本不存 在羟基极性基团， 具有良好的介电性能和低的吸水率， 良好的耐湿热性。
所述二官能度羧酸芳香族化合物或酸性! ¾化物用量为 lmol, 该种通过 脂肪环烃结构连接的酚类化合物用量为 0.05〜0.75mol, 该种单羟基化合物 用量为 0.25〜0.95mol。
式的化合物:
Figure imgf000010_0001
所述一种通过脂肪环烃结构连接的酚类化合物的结构如下:
Figure imgf000010_0002
Figure imgf000011_0001
式中， X为苯环或萘环， j为 0或 1 , k为 0或 1 , n为 0.25-2.5。
所述活性酯固化剂的用量， 以所述含有 3个或 3个以上的环氧基、 且 含有氮元素的环氧树脂 100重量份计算， 且根据环氧当量与活性酯当量比 计算， 该当量比为 0.85〜1.2, 优选为 0.9〜1.1 , 最优选为 0.95〜1.05。
本发明所述的环氧树脂组合物中， 所述含碑无 1¾阻燃剂化合物为磷酸 酯化合物、 磷酸酯盐化合物、 磷腈化合物、 磷菲化合物及其衍生物、 含碑 酚醛树脂、 及碑化聚碳酸酯中的一种或几种的混合物； 所述含碑无 [¾阻燃 剂化合物的磷含量为 5〜30%重量比。
所述磷酸酯化合物可选为芳香族磷酸酯化合物， 具体为间苯二酚-双 (磷酸二苯酯） 、 双酚 A-双（磷酸二苯酯） 、 间苯二酚-双（磷酸 -2,6-二 曱基苯酯） 、 或联苯二酚-双（磷酸 -2,6-二曱基苯酯） 。 可用的商品化产品 如 CR-741 , PX-200, PX-202 等； 所述磷腈化合物可选为三聚磷腈或四聚 磷腈， 可选商品化产品有 SPB-100; 所述磷菲化合物及其衍生物可以为 9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物、 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； 所述含磚酚醛树脂可以为 9,10-二氢 -9-氧杂 -10-膦菲 -10-氧化物 （DOPO ) 改性酚醛， 所述酚醛可选为线形酚醛、 临曱酚酚醛、 双酚 A型酚醛、 联苯 酚醛、 芳烷基酚醛或多官能酚醛。 可选商品化产品有 XZ92741。
本发明中所述的含碑无卤阻燃剂化合物的目的是阻燃， 为了保证固化 产物有更好的综合性能， 如耐热性、 耐水解性， 所述含碑无 1¾阻燃剂化合 物的添加量， 以所述环氧树脂、 所述活性酯固化剂、 及所述含碑无 [¾阻燃 剂化合物的合计 100 重量份算， 添加量为 10〜150重量份， 进一步优选为 20-120重量份。
所述固化促进剂， 没有特别限定， 只要能催化环氧官能团反应、 降低 固化体系的反应温度即可， 优选为咪唑类化合物及其衍生化合物 、 哌啶 类化合物、 路易斯酸、 及三苯基膦中的一种或多种混合物。 所述的咪唑类 化合物可以列举有 2-曱基咪唑， 2-苯基咪唑， 2-乙基 -4-曱基咪唑， 所述的 哌啶化合物可以列举有 2,3-二氨基哌啶， 2,5-二氨基哌啶 2,6-二氨基哌啶， 2,5-二氨基， 2-氨基 -3-曱基哌啶， 2-氨基 -4-4 曱基哌啶， 2-氨基 -3-硝基哌 啶， 2-氨基 -5-硝基哌啶， 4-二曱基氨基哌啶。 促进剂用量， 以所述环氧树 月旨、 所述活性酯固化剂、 及所述含碑无卤阻燃剂化合物的合计 100重量份 算， 为 0.05〜1.0重量份。
如有需要， 本发明中还可以进一步含有有机填料、 无机填料、 或有机 填料和无机填料的混合物。 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、 硅酸鈣、 碳酸鈣、 及云母中的一种或 多种； 有机填料可以选自聚四氟乙烯粉末、 聚苯硫醚、 及聚醚砜粉末中的 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 ιη, 这种粒径范围的 无机填料在树脂液中更易分散。 再者， 所述填料的用量也无特别限定， 相 对于所述环氧树脂、 所述活性酯固化剂、 及所述含碑无 1¾阻燃剂化合物的 合计 100重量份计算， 为 5-500重量份， 优选为 5-300重量份， 更优选为 5-200重量份， 特优选为 15-100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， 如玻璃纤维布等。
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。
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， 挥发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 4，4-二氨基二苯曱烷四缩水甘油氨树脂
KES-224 (韩国 KOLON公司， EEW为 125g/mol, 然后加入 178.4重量份 活性酯固化剂 HPC-8000-65T ( 日 本 DIC 公司 ， 活性酯当量为 223g/mol ) , 搅拌均匀， 再加入阻燃剂磷酸酯铝盐 OP935 ( Clariant公司， 磷含量为 23% ) 30 重量份再加入适量 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。 在热压机中固化制得覆铜箔层压板， 其固化温度 为 200 °C , 固化压力为 30 Kg/cm2 , 固化时间为 90min。
实施例 2:
取一容器， 加入 100 重量份对胺苯三缩水甘油氨树脂 MY0500 ( Hunstman公司， EEW为 110g/mol, 然后加入 192.6重量份活性酯固化 剂 HPC-8000-65T (日本 DIC 公司， 活性酯当量为 223g/mol ) , 搅拌均 匀， 再加入阻燃剂 DOPO改性酚酸树脂 XZ92741 ( DOW公司， 磷含量为 9% ) 87.5 重量份， 搅拌均匀后， 再加入适量 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。 在热压机中固化制得覆铜箔层压板， 其固 化温度为 200 °C , 固化压力为 30 Kg/cm2 , 固化时间为 90min。
实施例 3:
取一容器， 加入 100 重量份 4，4-二氨基二苯曱烷四缩水甘油氨树脂 KES-224 (韩国 KOLON公司， EEW为 125g/mol, 然后加入 178.4重量份 活性酯固化剂 HPC-8000-65T ( 日 本 DIC 公司 ， 活性酯当量为 223g/mol ) , 搅拌均匀， 再加入阻燃剂苯氧碑腈化合物 SPB-100 (日本大 冢公司， 磷含量为 12% ) 69.6重量份， 搅拌均匀后， 再加入适量 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。 在热压机中固化制得覆 铜箔层压板， 其固化温度为 200°C , 固化压力为 30 Kg/cm2, 固化时间为 90min„
实施例 4:
取一容器， 加入 100 重量份 4，4-二氨基二苯曱烷四缩水甘油氨树脂
KES-224 (韩国 KOLON公司， EEW为 125g/mol, 然后加入 178.4重量份 活性酯固化剂 HPC-8000-65T ( 日 本 DIC 公司 ， 活性酯当量为 223g/mol ) , 搅拌均勾， 再加入磷酸酯阻燃剂化合物 PX-202 ( 日本 DAIHACHI , 磷含量为 8% ) 119.3 重量份， 搅拌均匀后， 再加入适量 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。 在热压机中固 化制得覆铜箔层压板， 其固化温度为 200°C , 固化压力为 30 Kg/cm2, 固化 时间为 90min。
比较例 1 :
取一容器， 加入 100重量份临曱酚酚醛环氧树脂 N690 (日本 DIC公 司， EEW 为 205g/mol, 然后加入 108.8 重量份活性酯固化剂 HPC-8000- 65T (日本 DIC公司， 活性酯当量为 223g/mol ) , 搅拌均匀， 再加入阻燃 剂碑酸酯铝盐 OP930 ( Clariant公司， 磷含量为 23% ) 32.5 重量份， 搅拌 均匀后， 再加入适量 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。 在热压机中固化制得覆铜箔层压板， 其固化温度为 200°C , 固化压 力为 30 Kg/cm2 , 固化时间为 90min。
比较例 2:
取一容器， 加入 100 重量份 4，4-二氨基二苯曱烷四缩水甘油氨树脂 KES-224 (韩国 KOLON公司， EEW为 125g/mol, 然后加入 178.4重量份 活性酯固化剂 HPC-8000-65T ( 日 本 DIC 公司 ， 活性酯当量为 223g/mol ) , 搅拌均勾， 再加入乙撑双四溴邻苯二曱酰亚胺 BT-93W (雅 宝化工， 溴含量： 67.2% ) 69.6 重量份再加入适量 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。 在热压机中固化制得覆铜箔层压板， 其固化温度为 200 °C , 固化压力为 30 Kg/cm2, 固化时间为 90min。
上述实施例和比较例制成的覆铜板的各种物性数据如表 1所示。
表 1.各实施例及比较例制成的覆铜板的物性数据
实施例 实施例 实施例 实施例 比较例 比较例 组分名称
1 2 3 4 1 2
Tg ( °c ) 210 215 215 205 175 185
Dk(lOGHz) 3.8 3.9 3.7 3.9 3.9 3.9 Df(10GHz) 0.0095 0.0010 0.009 0.010 0.015 0.010 耐湿热 '1 "生 3/3 3/3 3/3 3/3 2/3 3/3 阻燃性 V-0 V-0 V-0 V-0 V-l V-0 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。
( 4 ) 阻燃性： 按照 UL 94 标准方法进行。 物性分析
从表 1 的物性数据可知， 实施例 1-4, 相较于比较例 1 中使用线性酚 醛环氧树脂和活性酯固化而言， 由于使用含氮多官能环氧树脂活性酯共同 固化， 氮元素的存在可以和磷阻燃剂发挥协同阻燃， 阻燃性良好， 同时得 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 温度面。
综上所述， 本发明所述的环氧树脂组合物包括分子链中含氮的环氧树 月旨、 活性酯固化剂、 及含碑无卤阻燃剂化合物； 与一般的铜箔基板相比， 使用本发明所述的环氧树脂组合物制得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， 实现无卤阻燃 V-0 级， 适用无 1¾高频领域。
以上实施例， 并非对本发明的组合物的含量作任何限制， 凡是依据本 发明的技术实质或组合物成份或含量对以上实施例所作的任何细微修改、 等同变化与修饰， 均仍属于本发明技术方案的范围内。

Claims

权 利 要 求
1、 一种环氧树脂组合物， 包含组分如下： 分子链中含有 3 个或 3 个 以上环氧基、 且含有氮元素的环氧树脂， 含碑无卤阻燃剂化合物及活性酯 固化剂； 所述分子链中含有 3个或 3个以上环氧基、 且含有氮元素的环氧 树脂的用量为 100 重量份， 所述含磚无卤阻燃剂化合物的用量为 10〜150 重量份， 所述活性酯固化剂的用量当量比， 以环氧当量与活性酯当量比计 算， 为 0.85〜1.2。
2、 如权利要求 1所述的环氧树脂组合物， 其中， 所述分子链中含有 3 个或 3 个以上环氧基、 且含有氮元素的环氧树脂为具有下述结构式的环氧 树脂中的至少一种：
式 I
Figure imgf000016_0001
其中， η为 1〜3的整数值； Ar为:
Figure imgf000016_0002
Figure imgf000017_0001
3、 如权利要求 1 所述的环氧树脂组合物， 其中， 所述含碑无 1¾阻燃 剂化合物为磷酸酯化合物、 磷酸酯盐化合物、 磷腈化合物、 磷菲化合物及 其衍生物、 含碑酚醛树脂、 及碑化聚碳酸酯中的一种或几种的混合物； 所 述含碑无卤阻燃剂化合物的磷含量为 5〜30%重量比。
4、 如权利要求 1 所述的环氧树脂组合物， 其中， 所述活性酯固化剂 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制得。
5、 如权利要求 4 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, 该种通过脂肪环烃结构连接的酚 类化合物用量为 0.05〜0.75mol, 该种单羟基化合物用量为 0.25〜0.95mol。
6、 如权利要求 1 所述的环氧树脂组合物， 其中， 所述活性酯固化剂 的结构式如下：
式 III 0 0
式中， X为苯环或萘环， j为 0或 1 , k为 0或 1 , n为 0.25-2.5。
7、 如权利要求 1 所述的环氧树脂组合物， 还包括固化促进剂， 所述 固化促进剂为咪唑类化合物及其衍生物、 哌啶类化合物、 路易斯酸、 及三 苯基膦中的一种或多种混合物。
8、 如权利要求 1 所述的环氧树脂组合物， 还包括有机填料、 无机填 料或有机填料和无机填料的混合物， 所述填料的用量， 相对于所述环氧树 月旨、 所述活性酯固化剂、 及所述含碑无卤阻燃剂化合物的合计 100重量份 计算， 为 5-500重量份。
9、 如权利要求 8 所述的环氧树脂组合物， 其中， 所述无机填料选自 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、 及云母中的一种或多种； 所 述有机填料选自聚四氟乙烯粉末、 聚苯硫醚、 及聚醚砜粉末中的一种或多 种。
10、 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。
11、 一种使用如权利要求 10 所述的半固化片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。
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