WO2015096116A1 - Composition de résine thermodurcissable et son utilisation - Google Patents

Composition de résine thermodurcissable et son utilisation Download PDF

Info

Publication number
WO2015096116A1
WO2015096116A1 PCT/CN2013/090655 CN2013090655W WO2015096116A1 WO 2015096116 A1 WO2015096116 A1 WO 2015096116A1 CN 2013090655 W CN2013090655 W CN 2013090655W WO 2015096116 A1 WO2015096116 A1 WO 2015096116A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
group
substituted
unsubstituted
parts
Prior art date
Application number
PCT/CN2013/090655
Other languages
English (en)
Chinese (zh)
Inventor
曾宪平
任娜娜
Original Assignee
广东生益科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to PCT/CN2013/090655 priority Critical patent/WO2015096116A1/fr
Priority to KR1020167018084A priority patent/KR101814313B1/ko
Publication of WO2015096116A1 publication Critical patent/WO2015096116A1/fr

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • C08K5/0033—Additives activating the degradation of the macromolecular compound
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065—Preparatory processes
    • C08G73/0655—Preparatory processes from polycyanurates
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2485/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
    • C08J2485/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus
    • 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

Definitions

  • the present invention relates to a thermosetting resin composition, and more particularly to a halogen-free thermosetting resin composition, a prepreg and a laminate produced therewith, and a high-frequency circuit substrate.
  • the operating frequency of traditional communication equipment generally exceeds 500MHz, most of which is ⁇ 10GHz.
  • the operating frequency is also continuously increased, and as the frequency continues to increase, signal integrity is brought.
  • the dielectric properties of copper clad laminate materials are a major aspect of signal integrity.
  • the substrate how to reduce the dielectric constant and the dielectric loss tangent is a hot technical issue in recent years.
  • the copper clad substrate material in order to meet the processing performance of the PCB and the performance requirements of the terminal electronic product, it is necessary to have good dielectric properties, heat resistance and mechanical properties, and also have good processing characteristics, high Peel strength, low water absorption, excellent heat and humidity resistance, and UL94 V-0 flame retardant rating.
  • CN102597089A discloses a resin composition comprising a cyanate polymer and a condensed phosphate, a cured resin, a sheet-like cured resin, a laminate, a prepreg, an electronic component, a single layer and a multilayer circuit board, which are used for It is especially suitable for single-layer and multi-layer circuit boards in the high-frequency range higher than 100MHz.
  • a resin composition comprising a cyanate polymer and a condensed phosphate, a cured resin, a sheet-like cured resin, a laminate, a prepreg, an electronic component, a single layer and a multilayer circuit board, which are used for It is especially suitable for single-layer and multi-layer circuit boards in the high-frequency range higher than 100MHz.
  • due to the small molecular weight and large plasticity of the condensed phosphate ester it has great influence on the heat resistance of the curing system and cannot adapt to high heat resistance. Sexual requirements.
  • thermosetting resin composition capable of providing excellent dielectric properties, moist heat resistance, mechanical properties, and good processability required for a copper clad laminate. Characteristics, high peel strength, low water absorption, high T g , excellent heat and humidity resistance and halogen-free flame retardant, UL 94 V-0 flame retardant.
  • the present invention adopts the following scheme:
  • thermosetting resin composition comprising:
  • the invention adopts polyphosphonate or / and phosphonate-carbonate copolymer as flame retardant, and has the advantages of large molecular weight, good heat resistance and small plasticity.
  • polyphosphonate structural formula is as follows:
  • Ar is an aryl group
  • the -O-Ar-O- includes, but is not limited to, a resorcinol reactive group, a hydroquinone reactive group, a bisphenol A reactive group, a bisphenol F reactive group, 4 , 4'-diphenol, phenolphthalein reactive group, 4,4'-thiodiphenol reactive group, 4,4'-sulfonyl diphenol reactive group or 3,3,5-trimethylcyclohexyl Any one of phenols;
  • X is a substituted or unsubstituted linear fluorenyl group of C1 C20, a substitution or not taken of C1 C20 Substituted branched fluorenyl, C2 ⁇ C20 substituted or unsubstituted linear olefin group, C2 C20 substituted or unsubstituted branched olefin group, C2 C20 substituted or unsubstituted linear fluorenylene group, C2 C20 a substituted
  • the structural formula of the phosphonate-carbonate copolymer is as follows:
  • ⁇ Ar 2 and Ar 3 are each independently an aryl group, and the -0-Ar 3 -0- includes, but is not limited to, a resorcinol reactive group, a hydroquinone reactive group, a bisphenol A reactive group , bisphenol F reactive group, 4,4'-diphenol, phenolphthalein reactive group, 4,4'-thiodiphenol reactive group, 4,4'-sulfonyl diphenol reactive group or 3,3 Any one of 5-trimethylcyclohexyldiphenol;
  • X 1 and X 2 are each independently a substituted or unsubstituted linear fluorenyl group of C1 C20, a substituted or unsubstituted branched fluorenyl group of C1 C20 a substituted or unsubstituted linear olefin group of C2 C20, a substituted or unsubstituted branched olefin group of C2 C20, a substituted or unsubstituted linear flu
  • An aryl group means any functional group or substituent derived from an aromatic ring, and exemplary aromatic rings are toluene, ethylbenzene, n-propylbenzene, cumene, styrene, phenol, acetophenone, anisole, phenylethyl ether, Benzyl alcohol, benzaldehyde, benzoyl chloride, benzoic acid, benzonitrile, nitrobenzene, nitrosobenzene, aniline, fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, benzenesulfonic acid, diphenyl ketone, Diphenylethylenedione, phenylacetic acid, mandelic acid, cinnamic acid, acetanilide, phenethylamine, azobenzene, diazonium chloride, benzoyl peroxide, benzyl chloride, benz
  • the polyphosphonate or / and phosphonate-carbonate copolymers include, but are not limited to,
  • R 3 , R 4 are independently selected from substituted or unsubstituted aliphatic or aromatic hydrocarbon groups, preferably from unsubstituted aliphatic or aromatic hydrocarbon groups; 13 ⁇ 4 is any integer from 1 to 100, n 3 , n 4 and n 5 is independently an arbitrary integer from 1 to 75, and 1 is an arbitrary integer from 2 to 50.
  • the n 2 , n 3 , and n 5 are each independently an arbitrary integer of 5 to 75, and preferably ⁇ , n 2 , n 3 , n 4 , and n 5 are each independently an integer of 10 to 75. .
  • the p and P1 are each independently an arbitrary integer of 5 to 50, and preferably p and P1 are each independently an arbitrary integer of 10 to 50.
  • the 111 and 134 are each independently, for example, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95.
  • n 2 , n 3 , and n 5 are each independently 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 or 72, respectively. .
  • the p and Pi are each independently, for example, 3, 5, 10, 14, 18, 22, 26, 30, 34, 38, 42, 45 or 48.
  • the polyphosphonate or phosphonate-carbonate copolymer has a weight average molecular weight of from 1000 to 60,000, preferably from 2,000 to 50,000, further preferably from 2,500 to 10,000.
  • the weight average molecular weight is less than 1000, after adding to the cured resin, the heat resistance of the cured product is lowered, such as a decrease in glass transition temperature; but when the weight average molecular weight is more than 60,000, the polyphosphonate or phosphonic acid Ester-carbonate
  • the solubility of the polymer in an organic solvent is too poor to obtain a good and uniform resin glue, which satisfies the technical requirements of the copper clad laminate.
  • Cyanate ester, BP a tree containing two or more hydroxyl groups (an OCN) in its molecular structure
  • R 2 , R 3 , R 1Q , Ru are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C4 linear fluorenyl group or a substituted or unsubstituted C1-C4 branched fluorenyl group, R 2 , R 3 , R 1Q , Ru are the same or different; preferably, the cyanate prepolymer of the present invention has the following structure
  • R 12 and R 13 are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C4 linear fluorenyl group or a substituted or unsubstituted C1-C4 branched fluorenyl group, k is Any integer from 1 to 7.
  • the component (A) is selected from the group consisting of 2,2-bis(4-cyanooxyphenyl)propanthene, bis(4-cyanooxyphenyl)acetamidine, bis(3,5-dimethyl 4-cyanooxyphenyl) formamidine, 2,2-bis(4-cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropene, ⁇ , ⁇ '- Bis(4-cyanooxyphenyl)-m-isopropylidenebenzene, cyclopentadiene-type cyanate, phenol novolac cyanate, cresol novolac cyanate, 2,2-bis(4- Cyanooxyphenyl) Polymer, bis(4-cyanooxyphenyl)acetamethylene prepolymer, bis(3,5-dimethyl-4-cyanooxyphenyl)formamyl prepolymer, 2,2-dual (4 -cyanooxyphenyl)-1,1,1,3,3,3-hexafluoroprop
  • thermosetting resin composition comprising a (c) cyanate compound or/and a cyanate prepolymer: 50 to 90 parts by weight, ( ⁇ ) a polyphosphonate or/and a phosphonate- Carbonate copolymer: 10 to 50 parts by weight; preferably the resin composition comprises ( ⁇ ) cyanate compound or/and cyanate prepolymer: 60-80 parts by weight, ( ⁇ ) polyphosphonate or / And phosphonate-carbonate copolymer: 20 to 40 parts by weight; further preferably, the resin composition comprises ( ⁇ ) cyanate compound or/and cyanate ester prepolymer: 70-80 parts by weight, ( ⁇ Polyphosphonate or / and phosphonate-carbonate copolymer: 20 to 30 parts by weight.
  • the parts by weight of the ( ⁇ ) cyanate compound or/and the cyanate prepolymer are, for example, 52 parts by weight, 54 parts by weight, 57 parts by weight, 61. Parts by weight, 65 parts by weight, 68 parts by weight, 72 parts by weight, 76 parts by weight, 78 parts by weight, 82 parts by weight, 86 parts by weight, 88 parts by weight; the (B) polyphosphonate or/and phosphonate
  • the parts by weight of the carbonate copolymer are, for example, 12 parts by weight, 15 parts by weight, 18 parts by weight, 24 parts by weight, 27 parts by weight, 32 parts by weight, 38 parts by weight, 42 parts by weight, 46 parts by weight, 48 parts by weight. .
  • thermosetting resin composition of the present invention a suitable compounding component such as a curing agent, an accelerator or the like is selected, and the components (A) and (B) are blended to obtain the thermosetting resin composition of the present invention.
  • thermosetting resin composition of the present invention further comprises (C) a halogen-free epoxy resin, if necessary, preferably, the halogen-free epoxy resin is selected from the group consisting of a halogen-free bisphenol A-type cyclic bisphenol F-type epoxy resin. , o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, trisphenol novolac epoxy resin, nitrogen-containing epoxy resin, silicon-containing epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl type Any one or a mixture of at least two of a novolac epoxy resin, a nonylbenzene type novolac epoxy resin or a naphthol type novolac epoxy resin.
  • the mixture is, for example, a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin, a mixture of o-cresol novolac epoxy resin and bisphenol A type novolac epoxy resin, a trisphenol type novolac epoxy resin and Mixture of nitrogen epoxy resin, mixture of silicon-containing epoxy resin and dicyclopentadiene novolac epoxy resin, mixture of biphenyl type phenolic acid epoxy resin and nonylbenzene type novolac epoxy resin, naphthol type novolac epoxy a mixture of resin and bisphenol A type epoxy resin.
  • the component (C) halogen-free epoxy resin is selected from the group consisting of epoxy resins having the following structure:
  • Xi, x 2 , x 3 are each independently selected from R 5 is selected from a hydrogen atom, a substituted or unsubstituted C1-C5 linear fluorenyl group or a substituted or unsubstituted C1-C5 branched fluorenyl group.
  • ⁇ ⁇ 2 are each independently selected from a single bond, -CH:
  • R 6 is selected from a hydrogen atom, a substituted or unsubstituted C1-C5 linear fluorenyl group, or a substituted or unsubstituted One of the C1-C5 branched fluorenyl groups.
  • the halogen-free epoxy resin is selected from any one or a mixture of at least two epoxy resins having the following structure:
  • ⁇ is an arbitrary integer from 1 to 10, such as 2, 3, 4, 5, 6, 7, 8, or 9, and R 7 is selected from a hydrogen atom, a substituted or unsubstituted C1-C5 linear fluorenyl group or a substituent. Or an unsubstituted C1-C5 branched fluorenyl group;
  • a 2 is any integer from 1 to 10, such as 2, 3, 4- 6, 7, 8, or 9;
  • a 3 is any integer from 1 to 10, such as 2, 3, 4, 5, 6, 7, 8, or 9;
  • the halogen-free epoxy resin is selected from the group consisting of epoxy resins having the following structural formula:
  • a 5 is any integer from 2 to 10, such as 3, 4, 5, 6, 7, 8, or 9;
  • R 8 , R 9 are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C5 straight One of a chain fluorenyl group or a substituted or unsubstituted C1-C5 branched fluorenyl group.
  • the component (C) halogen-free epoxy resin is added in an amount of 10 to 50 parts by weight, for example, 12 parts by weight based on 100 parts by weight of the component (A) cyanate compound or/and cyanate prepolymer. Parts, 14 parts by weight, 18 parts by weight, 22 parts by weight, 24 parts by weight, 29 parts by weight, 32 parts by weight, 35 parts by weight, 38 parts by weight, 42 parts by weight, 46 parts by weight, 48 parts by weight, preferably 20 to 40 parts by weight Parts by weight.
  • thermosetting resin composition of the present invention further comprises a component (D) filler, and the filler to be added as needed is not particularly limited, and the filler is selected from the group consisting of an organic filler or/and an inorganic filler, preferably an inorganic filler. Further preferred are surface treated inorganic fillers, most preferably surface treated silica.
  • the surface treated surface treatment agent is selected from any one or a mixture of at least two of a silicon germanium coupling agent, a silicone oligomer, or a titanate coupling agent.
  • the silicon germanium coupling agent is selected from the group consisting of vinyl trimethoxysilane, vinyl triethoxysilane, 3-glycidylpropyltrimethoxysilane, 2-(3,4 epoxycyclohexyl) Ethyltrimethoxysilane, 3-glycidylpropyltriethoxysilane, 3-glycidylmethyldimethoxysilane, P-isobutylenetrimethoxysilane, 3-isobutylenepropyltriethoxy Silicon germanium, 3-isobutenylmethyldimethoxysilane, 3-isobutenylmethyldimethoxymethylsilane, 3-allyltrimethoxysilane, N-2 (aminoethyl)-3-aminopropylmethyldimethoxy
  • the amount of the silicon germanium coupling agent to be used is not particularly limited, and the amount of the surface treatment agent is usually 0.1 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight, based on 100 parts by weight of the inorganic filler.
  • One ⁇ is preferably 0.75 to 2.0 parts by weight.
  • the inorganic filler is selected from any one of a non-metal oxide, a metal nitride, a non-metal nitride, an inorganic hydrate, an inorganic salt, a metal hydrate or an inorganic phosphorus or a mixture of at least two, preferably a crystalline type of dioxide Silicon, 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 Any one or a mixture of at least two of talc, calcium silicate, calcium carbonate or mica.
  • the mixture is, for example, a mixture of crystalline silica and fused silica, a mixture of spherical silica and hollow silica, a mixture of glass powder and aluminum nitride, a mixture of boron nitride and silicon carbide, aluminum hydroxide. a mixture with titanium dioxide, a mixture of barium titanate, barium titanate and alumina, a mixture of barium sulfate, talc, calcium silicate, calcium carbonate and mica.
  • the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, organophosphorus salt compound or polyethersulfone powder.
  • the mixture is, for example, a mixture of a polytetrafluoroethylene powder and a polyphenylene sulfide, a mixture of an organic phosphorus salt compound and a polyethersulfone powder.
  • the shape, particle diameter, and the like of the filler are also not particularly limited, and it is preferable that the filler has a median diameter of 0.01 to 50 ⁇ m, for example, 1 ⁇ m, 3 ⁇ m, 7 ⁇ m, 12 ⁇ m, 25 ⁇ m, 28 ⁇ m, 32 ⁇ m, 37 ⁇ m, 43 ⁇ m, 47 ⁇ m 49 ⁇ , preferably 0.01 to 20 ⁇ m, further preferably 0.1 to 10 ⁇ m, and the inorganic filler having such a particle size range is more easily dispersed in the resin liquid.
  • the amount of the component (D) filler to be added is also not particularly limited, and the total weight of the component (A), the component (B), and the component (C) is 100 parts by weight, and the component (D)
  • the filler is added in an amount of 5 to 1000 parts by weight, for example, 10 parts by weight, 80 parts by weight, 120 parts by weight, 230 parts by weight, 350 parts by weight, 450 parts by weight, 520 parts by weight, 680 parts by weight, 740 parts by weight, 860 parts by weight
  • the parts by weight, 970 parts by weight preferably 5 to 300 parts by weight, more preferably 5 to 200 parts by weight, most preferably 15 to 150 parts by weight.
  • thermosetting resin composition of the present invention further comprises a component (E) catalyst, and the catalyst is not particularly limited as long as it can catalyze a curing reaction of a cyanate ester, a cyanate ester, and an epoxy resin, and may be selected. Any one or a mixture of at least two of an organic metal salt compound such as copper, zinc, cobalt, nickel, iron, an imidazole compound and a derivative thereof or tertiary ammonia.
  • an organic metal salt compound such as copper, zinc, cobalt, nickel, iron, an imidazole compound and a derivative thereof or tertiary ammonia.
  • An exemplary component (E) catalyst is selected from the group consisting of 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, tri-n-butylamine, triphenylphosphine, boron trifluoride complex Any one or a mixture of at least two of a metal salt of octanoic acid, a metal salt of acetylacetonate, a metal salt of cyclodecanoic acid, a metal salt of salicylic acid or a metal stearate, such as a metal stearate and a mixture of a metal salt of salicylic acid, a mixture of a metal salt of a cyclic phthalic acid and a metal acetylacetonate, a mixture of a metal octoate and a boron trifluoride complex, a mixture of triphenylphosphine and tri-n-butylamine, 2-B a mixture of benzyl-4
  • the component (E) catalyst is added in an amount of 100 parts by weight based on the total weight of the component (A), the component (B) and the component (C), and the filler is added in an amount of 0.01 1.0 part by weight. .
  • the addition amount is, for example, 0.02 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight or 0.9 parts by weight.
  • thermosetting resin composition comprising:
  • thermosetting resin composition comprising:
  • Halogen-free epoxy resin The halogen-free epoxy resin is added in an amount of 10 to 50 parts by weight based on 100 parts by weight of the component (A).
  • thermosetting resin composition comprising:
  • (C) a halogen-free epoxy resin the component of the halogen-free epoxy resin is 10 to 50 parts by weight based on 100 parts by weight of the component (A);
  • filler the total weight of the component (A), the component (B) and the component (C) is 100 parts by weight, the filler is added in an amount of 5 to 1000 parts by weight;
  • the filler is added in an amount of 0.01 to 1.0 part by weight based on 100 parts by weight based on the total weight of the component (A), the component (B) and the component (C).
  • thermosetting resin composition of the present invention may be added with a thermosetting resin.
  • a thermosetting resin include a polyphenylene ether resin, a phenol resin, a urethane resin, a melamine resin, and the like, and a curing agent of these thermosetting resins may be added or Curing agent accelerator.
  • thermosetting resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These thermosetting resins and various additives may be used singly or in combination of two or more kinds.
  • the component (A), the component (B), the component (C), the catalyst, the filler, and various thermosetting resins may be blended, stirred, and mixed by a known method. , various additives, to prepare.
  • the resin glue liquid can be obtained by dissolving or dispersing the thermosetting 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, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and mesitylene, ethoxylate
  • An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide or hydrazine-methyl-2-pyrrolidone.
  • solvents may be used singly or in combination of two or more.
  • aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, butanone, 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 those skilled in the art according to their 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.
  • Another object of the present invention is to provide a prepreg comprising a reinforcing material and a thermosetting resin composition as described above adhered to the reinforcing material by impregnation and drying.
  • the reinforcing material is not particularly limited and may be an organic fiber, an inorganic fiber woven fabric or a non-woven fabric, and the organic fiber may preferably be aramid nonwoven, and the inorganic fiber woven fabric may be ⁇ -glass fiber, D-glass fiber. , S-glass, ⁇ -glass, ⁇ -glass and quartz cloth.
  • the thickness of the reinforcing material is not particularly limited.
  • the thickness of the braided fabric or nonwoven fabric is preferably 0.01 to 0.2 mm, and preferably passes through the opening.
  • the silicon germanium coupling agent is preferably an epoxy silicon germanium coupling agent, an amino silicon germanium coupling agent or a vinyl silicon germanium coupler. Any one or a mixture of at least two of the agents.
  • the prepreg is obtained by drying the prepreg impregnated with the thermosetting resin composition at 100 to 200 ° C for 2 to 10 minutes.
  • a third object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • One or more prepregs as described above are stacked in a certain order and solidified in a hot press to obtain a laminate having a curing temperature of 150 250 ° C and a curing pressure of 25 to 60 kg/cm. 2 .
  • One or more prepregs as described above are stacked in a certain order, and the copper foil is respectively pressed on one side or both sides of the prepreg which are superposed on each other, and is solidified in a hot press.
  • the copper clad laminate has a curing temperature of 150 250 ° C and a curing pressure of 25 to 60 kg/cm 2 .
  • the prepreg, the laminate and the copper-clad laminate according to the invention have excellent dielectric properties, moisture and heat resistance, high glass transition temperature, lower water absorption, and halogen-free resistance. Burning, reaching UL 94 V-0.
  • a fourth object of the present invention is to provide a high-frequency circuit substrate comprising at least one prepreg as described above, and a copper foil covering both sides of the laminated prepreg.
  • thermosetting resin provided by the invention has low dielectric constant and dielectric loss tangent; 2 the invention further adopts polyphosphonate or/and phosphonate -carbonate copolymer as a flame retardant, without sacrificing the heat resistance of the original cured product, low water absorption, excellent dielectric properties, and achieving halogen-free flame retardant, the flame retardancy of the cured product reaches UL94 V- Grade 0; 3
  • the prepreg and the copper-clad laminate thereof produced by using the above thermosetting resin composition of the present invention have excellent dielectric properties, moist heat resistance, flame retardancy up to UL94 V-0 grade, and good process processing Sex. detailed description
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120 min.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • phenolic cyanate resin PT-30 (LONZA, cyano equivalent: 139 g/eq)
  • polyphosphonate HM1100 FRX Polymers, phosphorus content
  • 10.8% by weight 10 parts by weight was uniformly stirred, and then 0.035 parts by weight of the catalyst zinc octoate and the solvent methyl ethyl ketone were added, and stirring was continued to form a glue.
  • the prepreg was prepared by dipping the above-mentioned glue with a glass cloth (model 2116, thickness 0.08 mm) and controlling to a suitable thickness, followed by drying to remove the solvent.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • the prepreg was prepared by dipping the above-mentioned glue with a glass cloth (model 2116, thickness 0.08 mm) and controlling to a suitable thickness, followed by drying to remove the solvent.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • phenolic cyanate resin PT-30 (LONZA), 30 parts by weight of linalyl phenol novolac epoxy resin NC-2000L (Nippon Chemical Co., Ltd., EEW is 238 g/ Eq), then add polyphosphonate FRX OL5000 (FRX Polymers, phosphorus content of 10.8%) 15 parts by weight, stir evenly, then add 0.035 parts by weight of catalyst zinc octoate, and solvent butanone, continue to stir evenly into a glue .
  • the prepreg was prepared by dipping the above-mentioned glue with a glass cloth (model 2116, thickness 0.08 mm) and controlling to a suitable thickness, followed by drying to remove the solvent.
  • prepregs Use several prepregs They are laminated on each other, and a copper foil is laminated on both sides thereof to be cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 250 ° C and a curing pressure of 25 to 60 kg/cm 2 . , curing time is 90 ⁇ 120min.
  • the above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • the prepreg was prepared by dipping the above-mentioned glue with a glass cloth (model 2116, thickness 0.08 mm) and controlling to a suitable thickness, followed by drying to remove the solvent.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • Example 8 Take a container, add 60 parts by weight of phenolic cyanate resin PT-30 (L0NZA company), 15 parts by weight of phenol novolac type epoxy resin ⁇ 690 (Japan DIC company, EEW is 205 g/eq), and then add phosphine
  • the ester-carbonate copolymer FRX CO6000 (FRX Polymers, Inc., phosphorus content: 10.6%) was uniformly stirred under 25 parts by weight, and 0.035 parts by weight of the catalyst zinc octoate and the solvent methyl ethyl ketone were further added, and the mixture was continuously stirred to form a glue.
  • the above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • the above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • the above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper clad laminate having a curing temperature of 150-250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • phenolic cyanate resin PT-30 (LONZA), 12 parts by weight of linalyl phenol novolac epoxy resin NC-2000L (Nippon Chemical Co., Ltd., EEW is 238 g/ Eq), then add phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers, phosphorus content 10.6%) 40 parts by weight, stir evenly, add 15.6 parts by weight of silica, and solvent butanone, continue to stir evenly Serve as a glue.
  • the above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • the above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25-60 kg/cm 2 and the curing time is 90-120 min.
  • the above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25-60 kg/cm 2 and the curing time is 90-120 min.
  • the above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm) and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper clad laminate having a curing temperature of 150-250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • the above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 to 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120 min.
  • the above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg.
  • a glass cloth model 2116, thickness 0.08 mm
  • the dipping materials are superposed on each other, and a copper foil is pressed on both sides thereof to be cured in a hot press to obtain a copper clad laminate having a curing temperature of 150 to 250 ° C and a curing pressure of 25 to 60 kg. /cm 2 , curing time is 90 ⁇ 120min.
  • the prepreg obtained by using a plurality of sheets is superposed on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150 250 ° C.
  • the curing pressure is 25 ⁇ 60 kg/cm 2 and the curing time is 90 ⁇ 120min.
  • T g Glass transition temperature
  • the copper-clad laminate of the present invention has excellent dielectric properties, higher glass transition temperature, and good heat and humidity resistance, as compared with a general copper foil substrate. Suitable for lead-free high-speed communication applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine thermodurcissable comprenant : (A) un composé de cyanate et/ou un prépolymère de cyanate ; (B) un poly-phosphonate et/ou un copolymère phosphonate-carbonate. La composition de résine thermodurcissable selon l'invention présente une constante diélectrique et une tangente de perte diélectrique basses. Les préimprégnés et stratifiés plaqués cuivre à base de ladite composition de résine thermodurcissable présentent de remarquables propriétés diélectriques, ainsi qu'en matière de résistance à l'eau et à la chaleur, une tenue au feu V-0 selon la norme UL94 et une bonne aptitude à l'usinage.
PCT/CN2013/090655 2013-12-27 2013-12-27 Composition de résine thermodurcissable et son utilisation WO2015096116A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2013/090655 WO2015096116A1 (fr) 2013-12-27 2013-12-27 Composition de résine thermodurcissable et son utilisation
KR1020167018084A KR101814313B1 (ko) 2013-12-27 2013-12-27 열경화성 수지 조성물 및 그 용도

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2013/090655 WO2015096116A1 (fr) 2013-12-27 2013-12-27 Composition de résine thermodurcissable et son utilisation

Publications (1)

Publication Number Publication Date
WO2015096116A1 true WO2015096116A1 (fr) 2015-07-02

Family

ID=53477383

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/090655 WO2015096116A1 (fr) 2013-12-27 2013-12-27 Composition de résine thermodurcissable et son utilisation

Country Status (2)

Country Link
KR (1) KR101814313B1 (fr)
WO (1) WO2015096116A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111139021A (zh) * 2020-01-09 2020-05-12 西南科技大学 一种可低温固化高粘接耐热氰酸酯胶黏剂及其制备方法
WO2020115041A1 (fr) * 2018-12-04 2020-06-11 Hexcel Composites Limited Composition adhésive
WO2020186572A1 (fr) * 2019-03-18 2020-09-24 广东生益科技股份有限公司 Composition de résine, préimprégné la contenant, et carte stratifiée et carte de circuit imprimé
CN114479013A (zh) * 2020-10-27 2022-05-13 广东生益科技股份有限公司 一种氰基改性的活性酯及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030003305A1 (en) * 2001-03-27 2003-01-02 International Business Machines Corporation Halogen free triazines, bismaleimide/epoxy polymers, prepregs made therefrom for circuit boards and resin coated articles, and use
CN102020830A (zh) * 2010-12-23 2011-04-20 广东生益科技股份有限公司 无卤阻燃性树脂组合物及其应用
CN102504201A (zh) * 2011-10-18 2012-06-20 广东生益科技股份有限公司 环氧树脂组合物及使用其制作的高频电路基板
CN103328702A (zh) * 2010-11-17 2013-09-25 Frx聚合物股份有限公司 作为用于聚酯纤维的阻燃剂的膦酸酯聚合物、共聚物及其各自的寡聚物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030003305A1 (en) * 2001-03-27 2003-01-02 International Business Machines Corporation Halogen free triazines, bismaleimide/epoxy polymers, prepregs made therefrom for circuit boards and resin coated articles, and use
CN103328702A (zh) * 2010-11-17 2013-09-25 Frx聚合物股份有限公司 作为用于聚酯纤维的阻燃剂的膦酸酯聚合物、共聚物及其各自的寡聚物
CN102020830A (zh) * 2010-12-23 2011-04-20 广东生益科技股份有限公司 无卤阻燃性树脂组合物及其应用
CN102504201A (zh) * 2011-10-18 2012-06-20 广东生益科技股份有限公司 环氧树脂组合物及使用其制作的高频电路基板

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020115041A1 (fr) * 2018-12-04 2020-06-11 Hexcel Composites Limited Composition adhésive
CN113166615A (zh) * 2018-12-04 2021-07-23 赫克塞尔合成有限公司 粘合剂组合物
US11873422B2 (en) 2018-12-04 2024-01-16 Hexcel Composites Limited Adhesive composition
WO2020186572A1 (fr) * 2019-03-18 2020-09-24 广东生益科技股份有限公司 Composition de résine, préimprégné la contenant, et carte stratifiée et carte de circuit imprimé
CN111139021A (zh) * 2020-01-09 2020-05-12 西南科技大学 一种可低温固化高粘接耐热氰酸酯胶黏剂及其制备方法
CN111139021B (zh) * 2020-01-09 2021-09-21 西南科技大学 一种可低温固化高粘接耐热氰酸酯胶黏剂及其制备方法
CN114479013A (zh) * 2020-10-27 2022-05-13 广东生益科技股份有限公司 一种氰基改性的活性酯及其制备方法和应用
CN114479013B (zh) * 2020-10-27 2023-07-11 广东生益科技股份有限公司 一种氰基改性的活性酯及其制备方法和应用

Also Published As

Publication number Publication date
KR20160097258A (ko) 2016-08-17
KR101814313B1 (ko) 2018-01-04

Similar Documents

Publication Publication Date Title
CN107109049B (zh) 高频用热固性树脂组合物、利用其的预浸料、层叠片和印刷电路基板
JP6079930B2 (ja) Ｎ−置換マレイミド基を有するポリフェニレンエーテル誘導体、並びにそれを用いた熱硬化性樹脂組成物、樹脂ワニス、プリプレグ、金属張積層板、及び多層プリント配線板
JP6705446B2 (ja) 熱硬化性樹脂組成物、プリプレグ、積層板及び多層プリント配線板
JP6891279B2 (ja) 難燃性ポリフェニレンエーテル樹脂組成物
CN103694642B (zh) 一种热固性树脂组合物及其用途
US10029438B2 (en) Thermosetting resin composition and use thereof
TWI619766B (zh) Halogen-free thermosetting resin composition and laminate for use thereof and prepreg and printed circuit board
TW201116588A (en) Thermosetting resin compositions and articles
WO2016011705A1 (fr) Composition de résine exempte d'halogène ainsi que préimprégné et carte stratifiée utilisés pour un circuit imprimé qui sont fabriqués à partir de la composition de résine exempte d'halogène
JP6822268B2 (ja) 熱硬化性樹脂組成物、プリプレグ、銅張積層板、プリント配線板及び半導体パッケージ
TW201422673A (zh) 一種熱固性氰酸酯及其應用
WO2016074288A1 (fr) Composition de résine thermodurcissable et pré-imprégné et carte stratifiée préparés à partir de celle-ci
TW201823335A (zh) 環氧樹脂組合物、預浸料、層壓板和印刷電路板
JP6307236B2 (ja) 硬化性樹脂組成物、硬化物、電気・電子部品及び回路基板材料
WO2013097133A1 (fr) Composition de résine thermodurcie, imprégné et stratifié pour carte de circuit imprimé fabriquée à partir de ceux-ci
WO2015096116A1 (fr) Composition de résine thermodurcissable et son utilisation
JP7106819B2 (ja) 樹脂ワニス、樹脂組成物、プリプレグ、積層板、多層プリント配線板及び樹脂ワニスの保存方法
TWI636084B (zh) 印刷電路板用樹脂組成物、預浸體、覆金屬箔疊層板、樹脂複合片及印刷電路板
KR101708146B1 (ko) 저유전 손실 특성을 가진 고주파용 열경화성 수지 조성물, 이를 이용한 프리프레그, 및 동박적층판
WO2016107068A1 (fr) Composition de résine thermodurcissable sans halogène, ainsi que préimprégné et stratifié de circuit imprimé utilisant celle-ci
KR20150068181A (ko) 저유전 손실 특성을 가진 고주파용 열경화성 수지 조성물, 이를 이용한 프리프레그, 및 동박적층판
WO2015096141A1 (fr) Composition de résine époxyde thermodurcissable et ses applications
JPWO2020095422A1 (ja) 樹脂組成物、樹脂組成物の硬化物、プリプレグ、積層板、樹脂フィルム、多層プリント配線板、ミリ波レーダー用多層プリント配線板及びポリフェニレンエーテル誘導体
JP7415272B2 (ja) インダンビスフェノール化合物、硬化性樹脂組成物、及び、硬化物
KR101614581B1 (ko) 변성 폴리페닐렌 옥사이드를 이용한 동박적층판

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13900558

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20167018084

Country of ref document: KR

Kind code of ref document: A

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC

122 Ep: pct application non-entry in european phase

Ref document number: 13900558

Country of ref document: EP

Kind code of ref document: A1