CN103724998A - Cyanate resin composition and application thereof - Google Patents
Cyanate resin composition and application thereof Download PDFInfo
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- CN103724998A CN103724998A CN201410004394.8A CN201410004394A CN103724998A CN 103724998 A CN103724998 A CN 103724998A CN 201410004394 A CN201410004394 A CN 201410004394A CN 103724998 A CN103724998 A CN 103724998A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
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- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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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
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
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- 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
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- 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
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- 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
- B32B2363/00—Epoxy resins
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- 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
- B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a cyanate resin composition, and a prepreg, laminated board, metal foil clad laminated board and printed circuit board prepared from the same. The cyanate resin composition comprises a cyanate resin (A) and an epoxy resin disclosed as Formula (I). The cyanate resin composition, and the prepreg, laminated board, metal foil clad laminated board and printed circuit board prepared from the cyanate resin composition have the advantages of favorable moisture resistance, favorable heat resistance, high flame retardancy, high reliability and low planar thermal expansion coefficient, and is suitable for substrate materials for manufacturing high-density printed circuit boards.
Description
Technical field
The present invention relates to a kind of resin combination, relate in particular to a kind of cyanate resin composition and use its prepreg of preparing, veneer sheet, metal-clad laminate and printed-wiring board (PWB).
Background technology
Along with the development of computer, electronics and information communication device miniaturization, high performance, multifunction, printed-wiring board (PWB) is also had higher requirement: miniaturization, slimming, highly integrated and high reliability.This just requires the metal-clad laminate for making printed-wiring board (PWB) to have more excellent wet fastness, thermotolerance and reliability etc.
Meanwhile, due to the raising of semiconductor packages density, in order to reduce the warpage issues producing in encapsulation process, strong request in recent years reduces the in-plane thermal expansivity of veneer sheet.
Cyanate ester resin has excellent dielectric properties, thermotolerance, mechanical property and processes, its make high-end printed-wiring board (PWB) with in metal-clad laminate being a kind of conventional matrix resin.But the humidity resistance of cyanate ester resin after due to its self cure is poor, therefore generally by epoxy resin etc., to after its modification, use again.
Conventional bisphenol-type epoxy resin at present, although processes excellence, Shortcomings aspect thermotolerance, wet fastness; Although linear phenol aldehyde type epoxy resin improves aspect thermotolerance, at still Shortcomings of the aspects such as wet fastness, processibility.
In addition, for the preparation of the resin combination of metal-clad laminate, conventionally need to there is flame retardant resistance, therefore also need with brominated fire retardant, to realize fire-retardant simultaneously.But, owing in recent years the concern of environmental problem being improved, need to halide-containing, not realize fire-retardantly, therefore this just requires resin itself to have more excellent flame retardant resistance.
Although phenol phenyl aralkyl-type epoxy resin, phenol naphthyl aralkyl-type epoxy resin have been improved wet fastness, Shortcomings aspect thermotolerance, flame retardant resistance, in-plane thermal expansivity.
Naphthols xenyl aralkyl-type epoxy resin, naphthols naphthyl aralkyl-type epoxy resin although flame retardant resistance is improved, are brought the rising of resin melting viscosity thereupon, and workability declines.
Summary of the invention
One of object of the present invention is to provide a kind of cyanate resin composition, and this cyanate resin composition has good wet fastness, thermotolerance, flame retardant resistance and reliability, and low in-plane thermal expansivity has good workability simultaneously.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of cyanate resin composition, comprises cyanate ester resin (A), has the epoxy resin (B) of formula I structure
Wherein, R
1be selected from phenyl and naphthyl, and R
1the mol ratio of middle naphthyl/(naphthyl+phenyl) is that 0.05～0.95, R is aryl, the integer that n is 1～20.
Described n is for example 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19.
The molar ratio of described naphthyl/(naphthyl+phenyl) is as being 0.08,0.12,0.15,0.21,0.26,0.32,0.38,0.45,0.51,0.56,0.62,0.67,0.71,0.76,0.81,0.88,0.92,0.94.
Preferably, the integer that n is 1～15, the integer that preferably n is 1～10, n is in 1～10 scope time, and the epoxy resin (B) with formula I structure is better to the wetting property of base material.
Preferably, the mol ratio of naphthyl/(naphthyl+phenyl) is 0.1～0.8, preferably 0.2～0.7.
Described R is phenyl, naphthyl or xenyl, and preferably R is naphthyl or xenyl.
Described naphthyl is Alpha-Naphthyl or betanaphthyl.
Preferably, described in, there is the melt viscosity≤1.0Pas at 150 ℃ of the epoxy resin (B) of formula I structure.
The epoxy resin with formula I structure (B) exemplary in the present invention is as follows:
Wherein, R
1be selected from phenyl and naphthyl, and R
1the mol ratio of middle naphthyl/(naphthyl+phenyl) is that 0.2～0.7, R is aryl, the integer that n is 1～10.
Melt viscosity≤1.0Pas at 150 ℃ of described epoxy resin (B) with formula I structure.This epoxy resin (B) with formula I structure can significantly improve humidity resistance, flame retardant resistance and the processes of cyanate resin composition, reduces in-plane thermal expansivity.
Contriver finds through research, can obtain a kind of resin combination with good wet fastness, thermotolerance, flame retardant resistance, reliability, processes and low in-plane thermal expansivity when cyanate ester resin (A) is used together with having the epoxy resin (B) of formula I structure.In molecular structure by the content control of naphthalene nucleus, phenyl ring within the specific limits, thereby reduced the melt viscosity of resin, processes is improved; Because the rigid structure of resin matrix has kept good thermotolerance, and there is good wet fastness, flame retardant resistance and reliability, low in-plane thermal expansivity.Based on above-mentioned discovery, contriver has completed the present invention.
The not special restriction of cyanate ester resin of the present invention (A), is selected from molecular structure and contains at least two cyanate ester based cyanate ester resins or cyanate prepolymer, preferably from bisphenol A cyanate ester resin, Bisphenol F type cyanate ester resin, tetramethyl bisphenol F cyanate resin, bis-phenol M type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol E-type cyanate resin, bis-phenol P type cyanate ester resin, linear Novolac Cyanate Ester Resins, cresols Novolac Cyanate Ester Resins, naphthol type cyanate ester resin, Naphthol phenolic cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, bisphenol A cyanate ester prepolymer, Bisphenol F type cyanate prepolymer, tetramethyl-Bisphenol F type cyanate prepolymer, bis-phenol M type cyanate prepolymer, bisphenol S type cyanate prepolymer, bisphenol E-type cyanate prepolymer, bis-phenol P type cyanate prepolymer, linear Novolac Cyanate Eater Resin prepolymer, cresols Novolac Cyanate Eater Resin prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, dicyclopentadiene type ethylene rhodanate prepolymer, phenolphthalein type cyanate prepolymer, the mixture of any one in aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer or at least two kinds, the mixture of for example bisphenol A cyanate ester resin of described mixture and Bisphenol F type cyanate ester resin, the mixture of tetramethyl bisphenol F cyanate resin and bis-phenol M type cyanate ester resin, the mixture of bisphenol S type cyanate ester resin and bisphenol E-type cyanate resin, the mixture of bis-phenol P type cyanate ester resin and linear Novolac Cyanate Ester Resins, the mixture of cresols Novolac Cyanate Ester Resins and Naphthol phenolic cyanate ester resin, the mixture of dicyclopentadiene type ethylene rhodanate resin and phenolphthalein type cyanate ester resin, the mixture of aralkyl-type cyanate ester resin and aralkyl Novolac Cyanate Ester Resins, the mixture of linear Novolac Cyanate Ester Resins and bisphenol A cyanate ester prepolymer, the mixture of bisphenol A cyanate ester prepolymer and Bisphenol F type cyanate prepolymer, the mixture of tetramethyl-Bisphenol F type cyanate prepolymer and bis-phenol M type cyanate prepolymer, the mixture of bisphenol S type cyanate prepolymer and bisphenol E-type cyanate prepolymer, the mixture of bis-phenol P type cyanate prepolymer and linear Novolac Cyanate Eater Resin prepolymer, the mixture of cresols Novolac Cyanate Eater Resin prepolymer and naphthol novolac type cyanate prepolymer, dicyclopentadiene type ethylene rhodanate prepolymer, phenolphthalein type cyanate prepolymer, the mixture of aralkyl-type cyanate prepolymer and aralkyl Novolac Cyanate Eater Resin prepolymer, in order to improve the thermotolerance of cyanate resin composition, flame retardant resistance, this cyanate ester resin (A) is preferred linear Novolac Cyanate Ester Resins further, naphthol type cyanate ester resin, Naphthol phenolic cyanate ester resin, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, linear Novolac Cyanate Eater Resin prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, phenolphthalein type cyanate prepolymer, the mixture of any one in aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer or at least two kinds, particularly preferably linear Novolac Cyanate Ester Resins, Naphthol phenolic cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, linear Novolac Cyanate Eater Resin prepolymer, the mixture of any one in naphthol novolac type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer or at least two kinds.Cyanate ester resin (A) can be used separately, also can mix as required use.
The consumption of described cyanate ester resin (A) has no particular limits, its preferably account for cyanate ester resin (A) and have formula I structure epoxy resin (B) gross weight 10～90%, for example 12%, 15%, 21%, 26%, 32%, 36%, 45%, 52%, 58%, 63%, 67%, 72%, 77%, 85%, 88%, further preferably 20～80%, particularly preferably 30～70%.
The epoxy resin (B) with formula I structure can be used separately, also can as required at least two kinds of epoxy resin (B) with formula I structure be mixed to use.
The consumption of the described epoxy resin (B) with formula I structure has no particular limits, its preferably account for cyanate ester resin (A) and have formula I structure epoxy resin (B) gross weight 10～90%, for example 12%, 15%, 21%, 26%, 32%, 36%, 45%, 52%, 58%, 63%, 67%, 72%, 77%, 85%, 88%, further preferably 20～80%, particularly preferably 30～70%.
The synthetic method of the described epoxy resin (B) with formula I structure has no particular limits, and those skilled in the art can select in conjunction with the expertise of oneself according to prior art.Particularly, for example can obtain in the following way the epoxy resin (B) with formula I structure: under the condition that has basic cpd, the aralkyl-type phenol resin of structure as shown in formula II is reacted in inert organic solvents with epoxy chloropropane, obtain having the epoxy resin (B) of formula I structure.
Wherein, R
1be selected from phenyl and naphthyl, and R
1the mol ratio of middle naphthyl/(naphthyl+phenyl) is that 0.05～0.95, R is aryl, the integer that n is 1～20.
This cyanate resin composition also includes mineral filler (C).In cyanate resin composition, add mineral filler (C), can obtain the resin combination of the halogen-free flameproof that flame retardant properties, in-plane thermal expansivity are more excellent.Mineral filler of the present invention (C) has no particular limits, and is selected from silicon-dioxide, metal hydrate, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, aluminium nitride, silicon carbide, aluminum oxide, zinc borate, zinc, clay, kaolin, talcum, mica, comprehensive silicon micro mist, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, fused silica powder, the mixture of any one in short glass fiber or hollow glass or at least two kinds, preferably powdered quartz, fused silica, soft silica, preparing spherical SiO 2, hollow silicon dioxide, aluminium hydroxide, boehmite, magnesium hydroxide, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, aluminium nitride, silicon carbide, aluminum oxide, zinc borate, zinc, clay, kaolin, talcum, mica, comprehensive silicon micro mist, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, fused silica powder, the mixture of any one in short glass fiber or hollow glass or at least two kinds, the mixture of for example powdered quartz of described mixture and fused silica, the mixture of soft silica and preparing spherical SiO 2, the mixture of hollow silicon dioxide and aluminium hydroxide, the mixture of boehmite and magnesium hydroxide, the mixture of molybdenum oxide and zinc molybdate, titanium oxide, zinc oxide, the mixture of strontium titanate and barium titanate, barium sulfate, the mixture of boron nitride and aluminium nitride, silicon carbide, aluminum oxide, the mixture of zinc borate and zinc, comprehensive silicon micro mist, E glass powder, D glass powder, the mixture of L glass powder and M glass powder, S glass powder, T glass powder, the mixture of NE glass powder and fused silica powder, clay, kaolin, the mixture of talcum and mica, the mixture of short glass fiber and hollow glass, further preferred molten silicon-dioxide is or/and boehmite.Wherein, fused silica has the characteristic of low thermal coefficient of expansion, the flame retardant resistance of boehmite and excellent heat resistance, therefore preferably it.
There is no particular limitation for the median size (d50) of mineral filler (C), but consider from dispersed angle, median size (d50) is preferably 0.1～10 micron, for example 0.2 micron, 0.8 micron, 1.5 microns, 2.1 microns, 2.6 microns, 3.5 microns, 4.5 microns, 5.2 microns, 5.5 microns, 6 microns, 6.5 microns, 7 microns, 7.5 microns, 8 microns, 8.5 microns, 9 microns, 9.5 microns, more preferably 0.2～5 micron.Can use separately as required or multiple combination is used the mineral filler (C) of dissimilar, variable grain size distribution or different median sizes.
The consumption of mineral filler of the present invention (C) has no particular limits, preferably take cyanate ester resin (A) and the gross weight of epoxy resin (B) with formula I structure as 100 parts of weight parts, the amount of described mineral filler (C) is 10～300 weight parts, for example 20 weight parts, 40 weight parts, 60 weight parts, 80 weight parts, 100 weight parts, 120 weight parts, 140 weight parts, 160 weight parts, 180 weight parts, 200 weight parts, 220 weight parts, 240 weight parts, 260 weight parts, 280 weight parts, 290 weight parts, be preferably 30～200 weight parts, more preferably 50～150 weight parts.
Mineral filler of the present invention (C) can mating surface treatment agent or wetting agent, dispersion agent use together.There is no particular limitation for effects on surface treatment agent, and it is selected from the conventional surface treatment agent of inorganics surface treatment.It is specially tetraethoxy compounds, organic acid compound, aluminate compound, titanate ester compound, silicone oligomer, macromole treatment agent, silane coupling agent etc.Silane coupling agent is had no particular limits, it is selected from the conventional silane coupling agent of inorganics surface treatment, and it is specially amino silicane coupling agent, epoxy silane coupling, vinyl silicane coupling agent, phenyl silane coupling agent, cationic silane coupling agent, mercaptosilane coupling agents etc.Wetting agent, dispersion agent are had no particular limits, and it is selected from the wetting agent, the dispersion agent that are usually used in coating.The surface treatment agent that the present invention can use separately as required or appropriately combined use is dissimilar or wetting agent, dispersion agent.
Cyanate resin composition of the present invention can also comprise organic filler (D).To organic filler (D), there is no particular limitation, be selected from the mixture of any one or at least two kinds in organosilicon, liquid crystalline polymers, thermosetting resin, thermoplastic resin, rubber or core shell rubbers, further preferably organosilicon powder or/and core shell rubbers.Described organic filler (D) can be powder or particle.Wherein, organosilicon powder has good flame-retarding characteristic, and core shell rubbers has good toughening effect, thus preferably it.
The consumption of organic filler of the present invention (D) has no particular limits, preferably take cyanate ester resin (A) and the gross weight of epoxy resin (B) with formula I structure as 100 parts of weight parts, the amount of described organic filler (D) is 1～30 weight part, for example 2 weight parts, 5 weight parts, 7 weight parts, 9 weight parts, 12 weight parts, 15 weight parts, 18 weight parts, 21 weight parts, 24 weight parts, 27 weight parts, 29 weight parts, be preferably 3～25 weight parts, more preferably 5～20 weight parts.
" comprising " of the present invention, mean it except described component, can also comprise other components, these other components give described resin combination different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... composition ".
Cyanate resin composition of the present invention can also be used together in conjunction with the epoxy resin in addition of the epoxy resin (B) with formula I structure, as long as it does not damage the proper property of cyanate resin composition, can be selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, linear phenol aldehyde type epoxy resin, cresols phenol aldehyde type epoxy resin, bisphenol-A phenolic type epoxy resin, tetramethyl-bisphenol f type epoxy resin, bis-phenol M type epoxy resin, bisphenol-s epoxy resin, bisphenol E-type epoxy resin, bis-phenol P type epoxy resin, trifunctional phenol-type epoxy resin, four sense phenol-type epoxy resins, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol novolac type epoxy resin, anthracene type epoxy resin, phenoxy group type epoxy resin, norbornene-type epoxy resin, diamantane type epoxy resin, Cong type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl-type epoxy resin, aralkyl phenol aldehyde type epoxy resin, in molecule, contain the epoxy resin of arylene ether structure, cycloaliphatic epoxy resin, polyvalent alcohol type epoxy resin, containing epoxy silicone, nitrogen-containing epoxy thermoset, phosphorous epoxy resin, glycidyl amine epoxy resin, ethylene oxidic ester epoxy resin etc.These epoxy resin can be used separately as required or multiple combination is used.
Cyanate resin composition of the present invention can also be used together in conjunction with various superpolymer, as long as it does not damage the proper property of cyanate resin composition.Concrete example is as being liquid crystalline polymers, thermosetting resin, thermoplastic resin, different flame-retardant compound or additive etc.They can use separately as required or multiple combination is used.
Cyanate resin composition of the present invention can also be used in conjunction with curing catalyst as required together, to control curing reaction speed.Described curing catalyst has no particular limits, and it can be selected from the curing catalyst that is usually used in promoting solidifying cyanate ester resin, epoxy resin, and it is specially the organic salt, imidazole and its derivants, tertiary amine etc. of the metal of copper, zinc, cobalt, nickel, manganese and so on.
In addition, described cyanate resin composition can also contain various additives, as concrete example, can enumerate oxidation inhibitor, thermo-stabilizer, static inhibitor, UV light absorber, pigment, tinting material, lubricant etc.
As the preparation method of one of resin combination of the present invention, can prepare by the epoxy resin with formula I structure (B) described in known method cooperation, stirring, mixing, cyanate ester resin (A) etc.
Another object of the present invention is to provide a kind of prepreg that uses above-mentioned cyanate resin composition to prepare, veneer sheet, metal-clad laminate and printed-wiring board (PWB), the veneer sheet and the metal-clad laminate that use this prepreg to make have good wet fastness, thermotolerance, flame retardant resistance and reliability, low in-plane thermal expansivity, there is good workability simultaneously, be suitable for preparing the baseplate material of high density printed circuit board.
The invention provides a kind of prepreg that uses above-mentioned cyanate resin composition to prepare, described prepreg comprises base material and is dried the cyanate resin composition as above on postadhesion base material by impregnation.Base material of the present invention has no particular limits, and it can be selected from known to making the base material of various printed wiring panel materials.Be specially inorganic fibre (glass fibre such as such as E glass, D glass, L glass, M glass, S glass, T glass, NE glass, quartz), organic fibre (such as polyimide, polymeric amide, polyester, polyphenylene oxide, liquid crystalline polymers etc.).The form of base material is yarn fabric, non-woven fabrics, rove, staple fibre, fibrous paper etc. normally.In above-mentioned base material, base material preferred glass fibers cloth of the present invention.
The preparation method of prepreg of the present invention does not have concrete restriction, as long as it is the method by cyanate resin composition of the present invention is combined to prepare prepreg with base material.
Can be as required with an organic solvent in the above-mentioned cyanate resin composition of preparing prepreg, to organic solvent, there is no particular limitation, as long as the solvent compatible with the mixture of cyanate ester resin (A) with thering is the epoxy resin (B) of formula I structure, described solvent, as concrete example, can enumerate: methyl alcohol, ethanol, the alcohols such as butanols, ethyl cellosolve, ethylene glycol butyl ether, ethylene glycol-methyl ether, diethylene glycol ether, the ethers such as Diethylene Glycol butyl ether, acetone, butanone, ethyl methyl ketone, hexone, the ketones such as pimelinketone, toluene, dimethylbenzene, sym-trimethylbenzene etc. are aromatic hydrocarbon based, ethoxyethyl group acetic ester, the ester classes such as vinyl acetic monomer, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, the nitrogenous kind solvent such as METHYLPYRROLIDONE.Above-mentioned solvent can be used separately, also can be as required by two kinds or two or more mixing use.
The present invention also provides a kind of veneer sheet and metal-clad laminate that uses above-mentioned prepreg to prepare.Described veneer sheet comprises at least one prepreg as above, and the prepreg lamination after superimposed is solidified and obtains veneer sheet.Described metal-clad laminate comprises at least one prepreg as above, and the one or both sides of the prepreg after superimposed are covered with tinsel, and lamination solidifies and obtains metal-clad laminate.Use veneer sheet and metal-clad laminate prepared by this prepreg to there is good wet fastness, thermotolerance, flame retardant resistance and reliability, low in-plane thermal expansivity, there is good workability simultaneously, be therefore suitable for preparing the baseplate material of high density printed circuit board.
The preparation method of veneer sheet of the present invention can be prepared by known method, for example: an above-mentioned prepreg is placed or by two or two above prepregs stacking, as required, tinsel is placed in a side or both sides at prepreg or stacking prepreg, and curing veneer sheet or the metal-clad laminate of obtaining of lamination.Described tinsel has no particular limits, and it is optional from the tinsel for printed-wiring board (PWB) material.Veneer sheet and multiple-plate general lamination that lamination can select printed-wiring board (PWB) to use.
The present invention also provides a kind of printed-wiring board (PWB), and described printed-wiring board (PWB) comprises at least one prepreg as above.The preparation method of printed-wiring board (PWB) of the present invention does not have concrete restriction, can prepare by known method.
Beneficial effect of the present invention: cyanate resin composition provided by the invention, there is good wet fastness, thermotolerance, flame retardant resistance and reliability, low in-plane thermal expansivity has good workability simultaneously.The prepreg, veneer sheet and the metal-clad laminate that use this cyanate resin composition to make, also there is good wet fastness, thermotolerance, flame retardant resistance and reliability, low in-plane thermal expansivity, there is good workability simultaneously, be suitable for making the baseplate material of high density printed circuit board.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
The metal-clad laminate of making for cyanate resin composition of the present invention, detect its thermotolerance (Tg), resistance to immersed solder, humidity resistance, flame retardant resistance and in-plane thermal expansivity (CTE), its test result further gives to illustrate in detail and describe as following embodiment.
Synthesis example 1: naphthyl aralkyl-type phenol resin synthetic
In flask, add 2-Naphthol 46g, phenol 271g, dichloromethyl naphthalene 215g and chlorobenzene 300g, rising temperature for dissolving slowly while stirring under nitrogen protection is reacted 2 hours at approximately 80 ℃.Then, limit distills chlorobenzene limit and is warmed up to 180 ℃, reacts 1 hour at 180 ℃.After reaction, by underpressure distillation, solvent and unreacted monomer are removed, obtained the naphthyl aralkyl-type phenol resin of brown.From the unreacted monomer reclaiming, analyzed, the mol ratio that enters 2-Naphthol/(2-Naphthol+phenol) in resin is 0.23.
Synthesis example 2: naphthyl aralkyl-type phenol resin synthetic
In flask, add 2-Naphthol 96g, phenol 251g, dichloromethyl naphthalene 150g and chlorobenzene 450g, rising temperature for dissolving slowly while stirring under nitrogen protection is reacted 2 hours at approximately 80 ℃.Then, limit distills chlorobenzene limit and is warmed up to 180 ℃, reacts 1 hour at 180 ℃.After reaction, by underpressure distillation, solvent and unreacted monomer are removed, obtained the naphthyl aralkyl-type phenol resin of brown.From the unreacted monomer reclaiming, analyzed, the mol ratio that enters 2-Naphthol/(2-Naphthol+phenol) in resin is 0.50.
Synthesis example 3: naphthyl aralkyl-type phenol resin synthetic
In flask, add 2-Naphthol 224g, phenol 272g, dichloromethyl naphthalene 100g and chlorobenzene 300g, rising temperature for dissolving slowly while stirring under nitrogen protection is reacted 2 hours at approximately 80 ℃.Then, limit distills chlorobenzene limit and is warmed up to 180 ℃, reacts 1 hour at 180 ℃.After reaction, by underpressure distillation, solvent and unreacted monomer are removed, obtained the naphthyl aralkyl-type phenol resin of brown.From the unreacted monomer reclaiming, analyzed, the mol ratio that enters 2-Naphthol/(2-Naphthol+phenol) in resin is 0.70.
Synthesis example 4: naphthyl aralkyl-type novolac epoxy synthetic
The naphthyl aralkyl-type phenol resin 100g obtaining in synthesis example 1 is dissolved in epoxy chloropropane 307g and diethylene glycol dimethyl ether 48g, decompression, at 60 ℃ with 4 hours dropping 48% aqueous sodium hydroxide solution 40g.During this by the water of generation by removing outside system with the azeotropic of epoxy chloropropane, the epoxy chloropropane distilling out turns back in system.After dropping finishes, then continue reaction 1 hour.Then by underpressure distillation, epoxy chloropropane and diethylene glycol dimethyl ether are removed, added 295g methyl iso-butyl ketone (MIBK) stirring and dissolving even, by washing, the salt of generation is removed.Then, add 48% aqueous sodium hydroxide solution 9g, at 80 ℃, react 2 hours.After reaction, wash with water until washing lotion is neutral, by underpressure distillation, methyl iso-butyl ketone (MIBK) is removed afterwards, obtained naphthyl aralkyl-type novolac epoxy, the melt viscosity at 150 ℃ is 0.4Pas.
Synthesis example 5: naphthyl aralkyl-type novolac epoxy synthetic
The naphthyl aralkyl-type phenol resin 100g obtaining in synthesis example 2 is dissolved in epoxy chloropropane 298g and diethylene glycol dimethyl ether 45g, decompression, at 60 ℃ with 4 hours dropping 48% aqueous sodium hydroxide solution 38g.During this by the water of generation by removing outside system with the azeotropic of epoxy chloropropane, the epoxy chloropropane distilling out turns back in system.After dropping finishes, then continue reaction 1 hour.Then by underpressure distillation, epoxy chloropropane and diethylene glycol dimethyl ether are removed, added 295g methyl iso-butyl ketone (MIBK) stirring and dissolving even, by washing, the salt of generation is removed.Then, add 48% aqueous sodium hydroxide solution 9g, at 80 ℃, react 2 hours.After reaction, wash with water until washing lotion is neutral, by underpressure distillation, methyl iso-butyl ketone (MIBK) is removed afterwards, obtained naphthyl aralkyl-type novolac epoxy, the melt viscosity at 150 ℃ is 0.5Pas.
Synthesis example 6: naphthyl aralkyl-type novolac epoxy synthetic
The naphthyl aralkyl-type phenol resin 100g obtaining in synthesis example 3 is dissolved in epoxy chloropropane 300g and diethylene glycol dimethyl ether 45g, decompression, at 60 ℃ with 4 hours dropping 48% aqueous sodium hydroxide solution 38.5g.During this by the water of generation by removing outside system with the azeotropic of epoxy chloropropane, the epoxy chloropropane distilling out turns back in system.After dropping finishes, then continue reaction 1 hour.Then by underpressure distillation, epoxy chloropropane and diethylene glycol dimethyl ether are removed, added 295g methyl iso-butyl ketone (MIBK) stirring and dissolving even, by washing, the salt of generation is removed.Then, add 48% aqueous sodium hydroxide solution 9g, at 80 ℃, react 2 hours.After reaction, wash with water until washing lotion is neutral, by underpressure distillation, methyl iso-butyl ketone (MIBK) is removed afterwards, obtained naphthyl aralkyl-type novolac epoxy, the melt viscosity at 150 ℃ is 0.6Pas.
Synthesis example 7: xenyl aralkyl-type novolac epoxy synthetic
By xenyl aralkyl-type phenol resin (by bright and change into Co., Ltd. and provide, the mol ratio of naphthyl alcohol/(naphthyl alcohol+phenol) is 0.70) 100g is dissolved in epoxy chloropropane 257g and diethylene glycol dimethyl ether 48g, at decompression, 60 ℃ with 4 hours dropping 48% aqueous sodium hydroxide solution 32.5g.During this by the water of generation by removing outside system with the azeotropic of epoxy chloropropane, the epoxy chloropropane distilling out turns back in system.After dropping finishes, then continue reaction 1 hour.Then by underpressure distillation, epoxy chloropropane and diethylene glycol dimethyl ether are removed, added 295g methyl iso-butyl ketone (MIBK) stirring and dissolving even, by washing, the salt of generation is removed.Then, add 48% aqueous sodium hydroxide solution 9g, at 80 ℃, react 2 hours.After reaction, wash with water until washing lotion is neutral, by underpressure distillation, methyl iso-butyl ketone (MIBK) is removed afterwards, obtained xenyl aralkyl-type novolac epoxy, the melt viscosity at 150 ℃ is 0.6Pas.
Embodiment 1
By linear 30 weight parts Novolac Cyanate Ester Resins (PT-30, by LONZA, provided), the naphthyl aralkyl-type novolac epoxy, the 0.02 weight part zinc octoate that obtain in 70 weight part synthesis examples 6 be dissolved in butanone and mix, add afterwards 150 weight part boehmite (APYRAL AOH 30, by Nabaltec, provided), 1.5 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), 1 weight part dispersion agent (BYK-W903, by BYK, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.The E glasscloth that is 0.1mm with thickness floods above glue, after then solvent is removed in oven dry, makes prepreg.Respectively the above-mentioned prepreg of 1,4,8 is superimposed, and at its electrolytic copper foil that both sides cover 18 μ m thickness separately, carries out solidifying for 2 hours in press, solidifying pressure is 45 Kg
/cm
2, solidification value is 220 ℃, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.
Embodiment 2
By 50 weight part naphthyl alcohol aralkyl-type cyanate ester resins (the naphthyl alcohol aralkyl resin SN485 being provided by Nippon Steel reacts and makes with mauguinite), the naphthyl aralkyl-type novolac epoxy obtaining in 45 weight part synthesis examples 6, 5 weight part naphthylidene ether type naphthols epoxy resin (EXA-7311, by Dainippon Ink Chemicals, provided), 0.02 weight part zinc octoate is dissolved in butanone and mixes, add afterwards 110 weight part spherical fused silica (SC2050, by Admatechs, provided), organosilicon powder (the KMP-605 of 5 weight part nucleocapsid structures, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.
Embodiment 3
By 10 weight part Naphthol phenolic cyanate ester resins (being made by the method reaction providing in Chinese patent CN102911502A synthesis example 2), 45 weight part naphthyl alcohol aralkyl-type cyanate ester resins (the naphthyl alcohol aralkyl resin SN485 being provided by Nippon Steel reacts and makes with mauguinite), the naphthyl aralkyl-type novolac epoxy obtaining in 5 weight part synthesis examples 4, the naphthyl aralkyl-type novolac epoxy obtaining in 40 weight part synthesis examples 5, 0.02 weight part zinc octoate is dissolved in butanone and mixes, add afterwards 50 weight part spherical fused silica (SC2050, by Admatechs, provided), 70 weight part boehmite (APYRAL AOH 30, by Nabaltec, provided), 10 weight part organosilicon powder (KMP-590, by SHIN-ETSU HANTOTAI's chemistry, provided), organosilicon powder (the KMP-605 of 5 weight part nucleocapsid structures, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), 1 weight part dispersion agent (BYK-W903, by BYK, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.
Embodiment 4
By 70 weight part naphthyl alcohol aralkyl-type cyanate ester resins (the naphthyl alcohol aralkyl resin SN485 being provided by Nippon Steel reacts and makes with mauguinite), the naphthyl aralkyl-type novolac epoxy obtaining in 20 weight part synthesis examples 6, 10 weight part phenol xenyl aralkyl-type epoxy resin (NC-3000-FH, by Nippon Kayaku K. K, provided), 0.02 weight part zinc octoate is dissolved in butanone and mixes, add afterwards 60 weight part boehmite (APYRAL AOH 30, by Nabaltec, provided), 20 weight part organosilicon powder (KMP-590, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), 1 weight part dispersion agent (BYK-W903, by BYK, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.
Embodiment 5
By linear 25 weight parts Novolac Cyanate Ester Resins (PT-30, by LONZA, provided), the naphthyl aralkyl-type novolac epoxy, the 0.02 weight part zinc octoate that obtain in 75 weight part synthesis examples 4 be dissolved in butanone and mix, add afterwards 220 weight part spherical fused silica (SC2050, by Admatechs, provided), 1.5 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), 1 weight part dispersion agent (BYK-W903, by BYK, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.
Embodiment 6
By 70 weight part naphthyl alcohol aralkyl-type cyanate ester resins (the naphthyl alcohol aralkyl resin SN485 being provided by Nippon Steel reacts and makes with mauguinite), the naphthyl aralkyl-type novolac epoxy obtaining in 30 weight part synthesis examples 6, 0.02 weight part zinc octoate is dissolved in butanone and mixes, add afterwards 15 weight part spherical fused silica (SC2050, by Admatechs, provided), 30 weight part organosilicon powder (KMP-590, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.
Embodiment 7
By 50 weight part naphthyl alcohol aralkyl-type cyanate ester resins (the naphthyl alcohol aralkyl resin SN485 being provided by Nippon Steel reacts and makes with mauguinite), the xenyl aralkyl-type novolac epoxy obtaining in 50 weight part synthesis examples 7, 0.02 weight part zinc octoate is dissolved in butanone and mixes, add afterwards 90 weight part spherical fused silica (SC2050, by Admatechs, provided), 10 weight part organosilicon powder (KMP-590, by SHIN-ETSU HANTOTAI's chemistry, provided), organosilicon powder (the KMP-600 of 15 weight part nucleocapsid structures, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.
Comparative example 1
With 70 weight part bisphenol A type epoxy resins (
1055, by Dainippon Ink Chemicals, provided) replacing the 70 weight part naphthyl aralkyl-type novolac epoxys that use in embodiment 1, other are the copper-clad laminate of 0.1,0.4,0.8 millimeter according to the method acquisition thickness identical with embodiment 1.
Comparative example 2
With 45 weight part phenol phenyl aralkyl-type epoxy resin (NC-2000, by Nippon Kayaku K. K, provided) replace the 45 weight part naphthyl aralkyl-type novolac epoxys that use in embodiment 2, other are the copper-clad laminate of 0.1,0.4,0.8 millimeter according to the method acquisition thickness identical with embodiment 2.
Comparative example 3
With 30 weight part bisphenol A type epoxy resins (
1055, by Dainippon Ink Chemicals, provided) replacing the 30 weight part naphthyl aralkyl-type novolac epoxys that use in embodiment 6, other are the copper-clad laminate of 0.1,0.4,0.8 millimeter according to the method acquisition thickness identical with embodiment 6.
Comparative example 4
By 39.2 weight part phenyl aralkyl-type phenol resin (MEH-7800H, by bright and change into Co., Ltd. and provide), the naphthyl aralkyl-type novolac epoxy obtaining in 60.8 weight part synthesis examples 6, 0.075 weight part diethyl tetramethyl-imidazoles is dissolved in butanone and mixes, add afterwards 110 weight part spherical fused silica (SC2050, by Admatechs, provided), organosilicon powder (the KMP-605 of 5 weight part nucleocapsid structures, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.
The physical property measurement data of the copper-clad laminate that above-described embodiment 1-7 and comparative example 1-4 make are as shown in table 1, table 2.
The physical property measurement data of the copper-clad laminate that table 1 embodiment 1-7 makes
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Tg,℃ | 245 | 245 | 250 | 260 | 240 | 260 | 243 |
| Resistance to immersed solder, S | ＞120 | ＞120 | ＞120 | ＞120 | ＞120 | ＞120 | ＞120 |
| Humidity resistance | 0/3 | 0/3 | 0/3 | 0/3 | 0/3 | 0/3 | 0/3 |
| Flame retardant resistance | V-0 | V-0 | V-0 | V-0 | V-0 | V-1 | V-0 |
| CTE,ppm/℃ | 10.6 | 9.3 | 10.2 | 12.3 | 8.4 | 12.9 | 9.4 |
The physical property measurement data of the copper-clad laminate that table 2 comparative example 1-4 makes
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Tg,℃ | 210 | 220 | 230 | 170 |
| Resistance to immersed solder, S | ＞120 | ＞120 | ＞120 | ＞120 |
| Humidity resistance | 3/3 | 0/3 | 3/3 | 0/3 |
| Flame retardant resistance | Burning | V-1 | Burning | V-1 |
| CTE,ppm/℃ | 12.7 | 11.3 | 14.8 | 13.4 |
In table 1 and table 2, the testing method of physical data is as follows:
Tg: testing tool and condition: DMA, 5 ℃/min of temperature rise rate, test sample specification: Copper Foil is removed in etching, 0.8 millimeter.
Resistance to immersed solder: by the tin stove of 288 ℃ of the sample immersions of 50 × 50 millimeters, observation layering foaming situation also records the corresponding time.Test sample specification: not etching Copper Foil, 0.4 millimeter.
Flame retardant resistance: pass judgment on according to UL94 testing vertical flammability standard.Test sample specification: Copper Foil is removed in etching, 0.4 millimeter.
Humidity resistance: the sample of 50 × 50 millimeters is dried to 2 hours at 105 ℃.Then, sample is processed 3 hours under 121 ℃ and two normal atmosphere with steam pressure pot machine, then by sample wicking 60 seconds in the tin stove of 260 ℃, whether layering (layering sample number/test sample number) of observing samples.Test sample specification: Copper Foil is removed in etching, 0.4 millimeter.
CTE: measurement direction is along glass-fiber-fabric warp thread direction; Testing tool and condition: TMA, is warmed up to 300 ℃ with the temperature rise rate of 10 ℃/min from 25 ℃ of room temperatures, measures the in-plane thermal expansivity from 50 ℃ to 130 ℃.Test sample specification: Copper Foil is removed in etching, 0.1 millimeter.
Physical Property Analysis:
Described embodiment is compared with comparative example, and the thermotolerance of embodiments of the invention 1～7, humidity resistance and flame retardant resistance are all better than using comparative example 1 and the comparative example 3 of bisphenol A type epoxy resin; The thermotolerance of embodiments of the invention 1～5, embodiment 7 and flame retardant resistance are all better than comparative example 4 and use the comparative example 2 of phenol phenyl aralkyl-type epoxy resin; Thermotolerance, flame retardant resistance and the in-plane thermal expansivity of embodiments of the invention 1,2,6 is all better than the comparative example 1 that uses bisphenol A type epoxy resin to replace naphthyl aralkyl-type novolac epoxy, the comparative example 2 that uses phenol phenyl aralkyl-type epoxy resin replacement naphthyl aralkyl-type novolac epoxy, uses bisphenol A type epoxy resin to replace the comparative example 3 of naphthyl aralkyl-type novolac epoxy.
Especially, comparative example 4 is owing to having used phenolic resin curing naphthyl aralkyl-type novolac epoxy, although its filling kind and content, manufacture craft are all identical with embodiment 2, thermotolerance, flame retardant resistance and the in-plane thermal expansivity of embodiment 2 are all better than comparative example 4.
In sum, cyanate resin composition of the present invention and use its prepreg making, veneer sheet and metal-clad laminate to there is good wet fastness, thermotolerance, flame retardant resistance and reliability, low in-plane thermal expansivity, is suitable for making the baseplate material of high density printed circuit board.
Above embodiment, not the content of composition of the present invention is imposed any restrictions, any trickle modification, equivalent variations and modification that the weight part of every foundation technical spirit of the present invention or composition or content are done above embodiment, all still belong in the scope of technical solution of the present invention.
Applicant's statement, the present invention illustrates detailed composition of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed composition, does not mean that the present invention must rely on above-mentioned detailed composition and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a cyanate resin composition, is characterized in that, described cyanate resin composition comprises cyanate ester resin (A), has the epoxy resin (B) of formula I structure
Wherein, R
1be selected from phenyl and naphthyl, and R
1the mol ratio of middle naphthyl/(naphthyl+phenyl) is that 0.05～0.95, R is aryl, the integer that n is 1～20.
2. cyanate resin composition as claimed in claim 1, is characterized in that, described in there is the integer that epoxy resin (B) n of formula I structure is 1～15, the integer that preferably n is 1～10;
Preferably, the mol ratio of naphthyl/(naphthyl+phenyl) is 0.1～0.8, preferably 0.2～0.7;
Preferably, R is phenyl, naphthyl or xenyl, preferably naphthyl or xenyl;
Preferably, described in, there is the melt viscosity≤1.0Pas at 150 ℃ of the epoxy resin (B) of formula I structure.
3. cyanate resin composition as claimed in claim 1 or 2, is characterized in that, described cyanate ester resin (A) is selected from molecular structure and contains at least two cyanate ester based cyanate ester resins or cyanate prepolymer, preferably from bisphenol A cyanate ester resin, Bisphenol F type cyanate ester resin, tetramethyl bisphenol F cyanate resin, bis-phenol M type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol E-type cyanate resin, bis-phenol P type cyanate ester resin, linear Novolac Cyanate Ester Resins, cresols Novolac Cyanate Ester Resins, naphthol type cyanate ester resin, Naphthol phenolic cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, bisphenol A cyanate ester prepolymer, Bisphenol F type cyanate prepolymer, tetramethyl-Bisphenol F type cyanate prepolymer, bis-phenol M type cyanate prepolymer, bisphenol S type cyanate prepolymer, bisphenol E-type cyanate prepolymer, bis-phenol P type cyanate prepolymer, linear Novolac Cyanate Eater Resin prepolymer, cresols Novolac Cyanate Eater Resin prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, dicyclopentadiene type ethylene rhodanate prepolymer, phenolphthalein type cyanate prepolymer, the mixture of any one in aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer or at least two kinds, further preferred linear Novolac Cyanate Ester Resins, naphthol type cyanate ester resin, Naphthol phenolic cyanate ester resin, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, linear Novolac Cyanate Eater Resin prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, phenolphthalein type cyanate prepolymer, the mixture of any one in aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer or at least two kinds,
Preferably, described cyanate ester resin (A) account for cyanate ester resin (A) and have formula I structure epoxy resin (B) gross weight 10～90%, further preferably 20～80%, particularly preferably 30～70%.
4. the cyanate resin composition as described in one of claim 1-3, it is characterized in that, the epoxy resin (B) with formula I structure account for cyanate ester resin (A) and have formula I structure epoxy resin (B) gross weight 10～90%, further preferably 20～80%, particularly preferably 30～70%.
5. the cyanate resin composition as described in one of claim 1-4, is characterized in that, described cyanate resin composition also includes mineral filler (C);
Preferably, described mineral filler (C) is selected from silicon-dioxide, metal hydrate, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, aluminium nitride, silicon carbide, aluminum oxide, zinc borate, zinc, clay, kaolin, talcum, mica, comprehensive silicon micro mist, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, fused silica powder, the mixture of any one in short glass fiber or hollow glass or at least two kinds, preferably powdered quartz, fused silica, soft silica, preparing spherical SiO 2, hollow silicon dioxide, aluminium hydroxide, boehmite, magnesium hydroxide, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, aluminium nitride, silicon carbide, aluminum oxide, zinc borate, zinc, clay, kaolin, talcum, mica, comprehensive silicon micro mist, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, fused silica powder, the mixture of any one in short glass fiber or hollow glass or at least two kinds, further preferred molten silicon-dioxide is or/and boehmite,
Preferably, the median size (d50) of mineral filler (C) is 0.1～10 micron, is preferably 0.2～5 micron;
Preferably, take cyanate ester resin (A) and the gross weight of epoxy resin (B) with formula I structure as 100 parts of weight parts, the amount of described mineral filler (C) is 10～300 weight parts, is preferably 30～200 weight parts, more preferably 50～150 weight parts.
6. the cyanate resin composition as described in one of claim 1-5, is characterized in that, described cyanate resin composition can also comprise organic filler (D);
Preferably, described organic filler (D) is selected from the mixture of a kind of in organosilicon, liquid crystalline polymers, thermosetting resin, thermoplastic resin, rubber or core shell rubbers or at least two kinds, further preferably organosilicon powder or/and core shell rubbers;
Preferably, take cyanate ester resin (A) and the gross weight of epoxy resin (B) with formula I structure as 100 parts of weight parts, the amount of described organic filler (D) is 1～30 weight part, is preferably 3～25 weight parts, more preferably 5～20 weight parts.
7. a prepreg, is characterized in that, described prepreg comprises base material and is dried the cyanate resin composition as described in one of claim 1-6 on postadhesion base material by impregnation.
8. a veneer sheet, is characterized in that, described veneer sheet comprises at least one prepreg as claimed in claim 7.
9. a metal-clad laminate, is characterized in that, described metal-clad laminate comprises at least one prepreg as claimed in claim 7 and is overlying on the tinsel of prepreg one or both sides.
10. a printed-wiring board (PWB), is characterized in that, described printed-wiring board (PWB) comprises at least one prepreg as claimed in claim 7.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410004394.8A CN103724998A (en) | 2013-05-30 | 2014-01-02 | Cyanate resin composition and application thereof |
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| CN201310210181 | 2013-05-30 | ||
| CN201310210181.6 | 2013-05-30 | ||
| CN201410004394.8A CN103724998A (en) | 2013-05-30 | 2014-01-02 | Cyanate resin composition and application thereof |
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| CN201410004394.8A Pending CN103724998A (en) | 2013-05-30 | 2014-01-02 | Cyanate resin composition and application thereof |
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| CN109486185A (en) * | 2018-12-10 | 2019-03-19 | 苏州大学 | Aramid fiber enhances cyanate composite material |
| CN110431187A (en) * | 2017-03-13 | 2019-11-08 | 横滨橡胶株式会社 | Cyanate resin composition and prepreg |
| CN111019298A (en) * | 2019-12-27 | 2020-04-17 | 广东全宝科技股份有限公司 | Resin composition and high-heat-resistant metal-based copper-clad plate |
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