CN108219367A - A kind of halogen-free thermosetting resin composite, prepreg, laminate and printed wiring board containing it - Google Patents

A kind of halogen-free thermosetting resin composite, prepreg, laminate and printed wiring board containing it Download PDF

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Publication number
CN108219367A
CN108219367A CN201611199216.0A CN201611199216A CN108219367A CN 108219367 A CN108219367 A CN 108219367A CN 201611199216 A CN201611199216 A CN 201611199216A CN 108219367 A CN108219367 A CN 108219367A
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halogen
free
epoxy resin
weight
resin
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CN108219367B (en
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罗成
唐国坊
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • 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
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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

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

Abstract

The present invention provides a kind of halogen-free thermosetting resin composites,Contain its prepreg,Laminate and printed wiring board,The halogen-free thermosetting resin composite includes halogen-free epoxy resin and phosphorous cyanate,The phosphorous cyanate has structure shown in Formulas I,The phosphorous cyanate causes the compositions of thermosetting resin to have good thermal stability,Humidity resistance,Toughness,Dielectric constant and dielectric loss angle tangent are low,Water absorption rate is low and the advantages that halogen-free flameproof effect,There is up to 265 DEG C of glass transition temperature by the laminate that it is prepared,Excellent dielectric properties,Water absorption rate is controlled in 0.07 0.13% relatively low range,And with high-fire resistance,Excellent humidity resistance and good technique processability,Excellent flame retarding efficiency,P content 1.5% can reach 0 fire-retardant ranks of UL94 V.

Description

A kind of halogen-free thermosetting resin composite, prepreg, laminate and print containing it Wiring board processed
Technical field
The invention belongs to laminate technical field, be related to a kind of halogen-free thermosetting resin composite, containing it prepreg, Laminate and printed wiring board.
Background technology
Traditional laminate for printed circuits generally use bromide fire retardant is fire-retardant to realize, especially with tetrabromobisphenol A type epoxy resin, this brominated epoxy resin has good anti-flammability, but it can generate bromination hydrogen in burning.This Outside, bioxin, dibenzo have been detected in the combustion product of the waste electrical and electronic equipment of the halogens such as brominated, chlorine in recent years The carcinogens such as furans, therefore the application of brominated epoxy resin is restricted.On July 1st, 2006, two parts of environmental protection instructions of European Union 《It is instructed about electric/electronic device is scrapped》With《Restriction on the Use of Certain Hazardous Substances in Electrical and Electronic Equipment》Just Formula is implemented, and the hot spot for being developed into industry of halogen-free flameproof copper-clad laminate, each copper-clad laminate producer all releases one after another The halogen-free flameproof copper-clad laminate of oneself.
Phosphorus-containing compound is introduced in the resin matrix of copper-clad plate, becomes the main technological route of copper-clad plate halogen-free flameproof. Phosphorus flame retardant widely used on copper-clad plate field is broadly divided into two kinds of response type and addition type at present.Response type is mainly DOPO class compounds, based on phosphorous epoxy resin, phosphorus containing phenolic resin, phosphorus content is between 2~10%.However, practical should With middle discovery, DOPO classes compound has larger water absorption rate and poor dielectric properties and the plank humidity resistance poor.Addition type Predominantly phosphonitrile and phosphonate ester compound, the flame retarding efficiency of additive flame retardant is relatively low, and needing to add more amount could reach To flame-retardancy requirements.It is easy to migrate to plank in laminate process simultaneously because of its relatively low fusing point (generally below 150 DEG C) Surface influences plate property.The phosphonium flame retardant of response type includes phosphorus-containing phenolic aldehyde, phosphonic acid ester cyanate.It is wherein simple with containing Phosphorus phenolic aldehyde come cure with it is fire-retardant, lead to that plank Tg is low, humidity resistance is poor；And phosphonic acid ester cyanate is since there are phosphonate ester knots Structure causes its heat resistance, humidity resistance poor.
In addition, for copper clad foil substrate material, in order to meet the performance of PCB processing performances and terminal electronic product It is required that, it is necessary to have good dielectric properties, heat resistance and mechanical performance, while should also have good technique processing spy Property, high peel strength, excellent humidity resistance.
It is mentioned in CN102181143A and is used as epoxy with the phosphorous cyanate or phenylate type phosphine oxide cyanate of DOPO types Contain ether type structural unit in the curing agent of resin and the halogen-free flame retardants of system, wherein phenylate type phosphine oxide cyanic acid ester structure, Cause its heat resistance insufficient.
CN102199351A discloses a kind of compositions of thermosetting resin, by weight, including：Pi-allyl, which is modified span, to be come 10~65 parts of imide resin performed polymer；Compound 5~60 parts of cyanate ester resin；5~65 parts of halogen-free epoxy resin；Above-mentioned resin Total amount is 100 parts, and the dielectric constant for the copper-clad plate being prepared by the compositions of thermosetting resin is still within more than 4.2 Higher level, it is desirable to access the copper-clad plate of lower dielectric constant.
Therefore, in this field, it is expected to obtain a kind of thermosetting with good thermal stability, humidity resistance and dielectric properties Property resin combination.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of halogen-free thermosetting resin composite, contain Its prepreg, laminate and printed wiring board has height using the laminate for printed circuits that the resin combination makes Glass transition temperature, excellent dielectric properties, high-fire resistance, excellent peel strength and good technique processability, and It can realize halogen-free flameproof, reach the fire-retardant rank of UL94V-0.
For this purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of halogen-free thermosetting resin composite, the halogen-free thermosetting resin composite packet Halogen-free epoxy resin and curing agent are included, the curing agent includes at least a kind of phosphorous cyanate, and the phosphorous cyanate has Formulas I Shown structure：
Wherein, Ar1Selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene or substituted or unsubstituted fluorenes Base, substituted or unsubstituted xenyl or or the group of the structure containing DOPO in any one；Ar2For substituted or unsubstituted benzene Base, substituted or unsubstituted naphthalene, substituted or unsubstituted C1~C4 straight chained alkyl or branched alkyl；A be 1 or 2, b be 0 or 1, and meet a+b=2；
It is total that the phosphorous cyanate ester resin accounts for halogen-free epoxy resin and curing agent in the halogen-free thermosetting resin composite Weight 10%~50% (such as 10%, 12%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 33%, 35%, 38%th, 40%, 42%, 45%, 48% or 50%)；The halogen-free epoxy resin is accounted in the halogen-free thermosetting resin composite Halogen-free epoxy resin and curing agent total weight 30%~60% (such as 30%, 33%, 35%, 38%, 40%, 42%, 45%th, 48%, 50%, 53%, 55%, 58% or 60%).
Using phosphorous cyanate as the curing agent of epoxy resin, when being reacted with epoxy resin system can have and greatly hand over Join density, so as to make the Tg of system and heat resistance fine, and cyanate cure in itself generation triazine ring dielectric properties it is preferable, Itself it is simultaneously phosphorous cyanate curing agent, also has the effect of halogen-free flameproof while as curing agent, can add on a small quantity Add or without that just plank can be made to achieve the effect that UL94V-0 halogen-free flameproofs in the other fire retardants of addition.
The group containing DOPO structures described in the present invention, can be DOPO groups, the phenyl containing DOPO substituent groups, Naphthalene containing DOPO substituent groups, xenyl containing DOPO substituent groups etc..
Preferably, the Ar1It is selected from In any one, Ar4It is selected from
Preferably, Ar2ForR1And R2It independently is phenyl, naphthalene Base, C1~C4 straight chained alkyl or branched alkyl in any one or at least two combination, n1For 0~5 integer (such as 0th, 1,2,3,4 or 5), n2For 0~7 integer (such as 0,1,2,3,4,5,6 or 7).
In the present invention, the Ar2Straight chained alkyl or branched alkyl for C1~C4 refer to Ar2Can be C1, C2, C3 or The straight chained alkyl or branched alkyl of C4, such as methyl, ethyl, n-propyl, isopropyl or normal-butyl.
Preferably, the phosphorous cyanate can be any one in the compound with formula a-i structures or at least two The combination of kind：
The present invention is to provide a kind of halogen-free thermosetting resin composite, and halogen-free thermosetting resin combination of the present invention Object is for its purposes copper-clad plate, and the Halogen refers to not contain chlorine and/or bromo element, therefore group of the present invention Substituent group in do not contain chlorine and/or bromine, but F elements can be contained in its group or substituent group.
Halogen-free epoxy resin of the present invention refers to the epoxy in 1 molecule with two or more epoxy groups Resin.
Preferably, the halogen-free epoxy resin be selected from glycidyl ether type epoxy resin, glycidyl ester epoxy resin, Glycidyl amine epoxy resin, cycloaliphatic epoxy resin, epoxidation of olefins based epoxy resin, glycolylurea epoxide resin or acid imide In epoxy resin any one or at least two mixture.
Preferably, the glycidyl ether type epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, neighbour Cresol novolak epoxy, bisphenol A-type novolac epoxy resin, three phenolic novolac epoxy resins, dicyclopentadiene phenolic aldehyde asphalt mixtures modified by epoxy resin In fat, biphenyl type novolac epoxy resin, alkyl benzene-type novolac epoxy resin or naphthol type novolac epoxy resin any one or At least two mixture.
Heretofore described epoxy resin is halogen-free epoxy resin.
Preferably, the glycidol ethers are selected from the epoxy resin having the following structure：
Wherein, Z1、Z2And Z3It is each independently selected fromR3For hydrogen atom, substituted or unsubstituted C1 Any one in the straight chained alkyl or branched alkyl of~C5 (such as C1, C2, C3, C4 or C5)；Y1And Y2It is each independently selected from list Key ,-CH2-、 In any one, R4Straight chained alkyl selected from hydrogen atom, substituted or unsubstituted C1~C5 (such as C1, C2, C3, C4 or C5) Or any one in branched alkyl；n3For 1~10 arbitrary integer, such as 2,3,4,5,6,7,8 or 9.
Preferably, the glycidyl amine epoxy resin is selected from triglycidyl group para-aminophenol, three-glycidyl Base isocyanuric acid ester, four glycidyl group diamino dimethylene benzene, two amido diphenyl-methanes of four glycidyl group -4,4'-, Four glycidyl group -3,4'- diaminodiphenyl ethers, four glycidyl group -4,4'- diaminodiphenyl ethers or four glycidyl group - In 1,3- bis aminomethyl hexamethylenes any one or at least two mixture.
The halogen-free thermosetting resin composite of the present invention uses the halogen-free epoxy resin of above-mentioned specific molecular structure, has Higher degree of functionality and good dielectric properties, solidfied material Tg higher, water absorption rate are low.
Preferably, the halogen-free thermosetting resin composite also includes polyphenylene oxide resin.
Preferably, the polyphenylene oxide resin accounts for halogen-free epoxy resin and curing agent in the halogen-free thermosetting resin composite Total weight 0~40% and not include 0, such as 0.1%, 0.5%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%th, 22%, 25%, 28%, 30%, 33%, 35%, 38% or 40%.
Preferably, the polyphenylene oxide resin number-average molecular weight be 1000~5000, such as 1000,1200,1500,1800, 2000th, 2300,2500,2800,3000,3500,3800,4000,4500,4800 or 5000.
Preferably, the curing agent also includes active ester resin.
Preferably, the active ester resin accounts for halogen-free epoxy resin and curing agent in the halogen-free thermosetting resin composite Total weight 0~40% and not include 0, such as 0.1%, 0.5%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%th, 22%, 25%, 28%, 30%, 33%, 35%, 38% or 40%.
Preferably, the curing agent also includes SMA resins.
Preferably, the SMA resins are styrene and maleic anhydride by the ratio between amount of substance 1:1~8:1 (such as 1:1、 1.5:1、2:1、2.5:1、3:1、3.5:1、4:1、4.5:1、5:1、5.5:1、6:1、6.5:1、7:1、7.5:1 or 8:1) ratio Copolymerization obtains.
Preferably, it is total to account for halogen-free epoxy resin and curing agent in the halogen-free thermosetting resin composite for the SMA resins Weight 0~40% and not include 0, such as 0.1%, 0.5%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%th, 22%, 25%, 28%, 30%, 33%, 35%, 38% or 40%.
Preferably, the halogen-free thermosetting resin composite is also comprising phenolic resin, and the phenolic resin is phosphorous or not Phosphorous phenolic resin.
Preferably, it is total to account for halogen-free epoxy resin and curing agent in the halogen-free thermosetting resin composite for the phenolic resin Weight 0~20% and not include 0, such as 0.1%, 0.5%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18% or 20%.
Heretofore described compositions of thermosetting resin, including halogen-free epoxy resin and curing agent, with halogen-free epoxy resin It is 100 parts by weight meters with curing agent total weight, wherein halogen-free epoxy resin accounts for 30%~60%, and phosphorous cyanate ester resin accounts for 10% ~50%, polyphenylene oxide resin accounts for 0~40%, and active ester resin accounts for 0~40%, SMA resins and accounts for 0~40%, and phenolic resin accounts for 0~ 20%.
Preferably, the halogen-free thermosetting resin composite also includes organic halogen-free flame retardants.
Preferably, the organic halogen-free agent is the organic halogen-free agent of phosphorus system.
Preferably, by the sum of additive amount of halogen-free epoxy resin and curing agent in terms of 100 parts by weight, organic Halogen hinders The additive amount of agent is fired for 0~10 parts by weight and not including 0.
Preferably, the phosphorus system organic halogen-free agent is three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy benzenes Base) miscellaneous -10- phosphines phenanthrene -10- oxides of -9,10- dihydro-9-oxies, 2,6- bis- (2,6- 3,5-dimethylphenyls) phosphino- benzene, 10- phenyl - Miscellaneous -10- phosphines phenanthrene -10- the oxides of 9,10- dihydro-9-oxies, phenoxy phosphazene compound, phosphate, polyphosphate, polyphosphonates Or in phosphonate ester-carbonate copolymer any one or at least two mixture.
Preferably, the halogen-free thermosetting resin composite also includes curing accelerator.
Preferably, the curing accelerator includes organic metal salt, glyoxaline compound and its derivative, piperidines chemical combination In object, pyridine compounds and their, lewis acid or triphenylphosphine any one or at least two mixture.
Preferably, the organic metal salt for organic zinc salt, organic copper salt, organic molysite, organic tin salt, organic cobalt salt or In organic aluminium salt any one or at least two mixture.
Preferably, the glyoxaline compound is 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazoles or 2- In undecyl imidazole any one or at least two mixture.
Preferably, the piperidines are 2,3- diaminos phenylpiperidines, 2,5- diaminos phenylpiperidines, 2,6- diamino piperazines Pyridine, 2- amino -3- methyl piperidines, 2- amino -4- methyl piperidines, 2- amino -3- nitros piperidines, 2- amino -5- nitros piperidines or In 2- amino -4,4- lupetidines any one or at least two mixture.
Preferably, the pyridine compounds and their is 4-dimethylaminopyridine, 2-aminopyridine, 3- aminopyridines or 4- amino Any one in pyridine or at least two mixtures.
Preferably, it is counted by 100 parts by weight of the total amount of halogen-free epoxy resin and curing agent, the addition of the curing accelerator Measure as 0.01~1 parts by weight, for example, 0.01 parts by weight, 0.03 parts by weight, 0.05 parts by weight, 0.08 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, 0.9 weight Part or 1 parts by weight, preferably 0.025~0.85 parts by weight.
Preferably, the halogen-free thermosetting resin composite further includes filler.
Preferably, the filler is selected from organic filler or inorganic filler, preferably inorganic filler, further preferably by surface The inorganic filler of processing, most preferably surface treated silica.
Preferably, the surface conditioning agent used that is surface-treated is selected from silane coupling agent, silicone oligomer or metatitanic acid In ester coupling agent any one or at least two mixture.
Preferably, it is counted by 100 parts by weight of inorganic filler, the dosage of the surface conditioning agent is 0.1~5.0 parts by weight, Such as 0.1 parts by weight, 0.5 parts by weight, 0.75 parts by weight, 1 parts by weight, 1.3 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 weights Measure part, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, preferably 0.5~3.0 weight Part, more preferable 0.75~2.0 parts by weight.
Preferably, the inorganic filler is selected from nonmetal oxide, metal nitride, non-metal nitride, inorganic hydration In object, inorganic salts, metal hydrate or Phos any one or at least two mixture, preferred molten titanium dioxide Silicon, powdered quartz, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, nitrogen Change boron, silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates or one kind in mica or at least two mixing Object.
Preferably, the organic filler is any one in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder Kind or at least two mixture.
Preferably, the median of the filler be 0.01~50 μm, such as 0.05 μm, 0.08 μm, 0.1 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 13 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μ M, preferably 0.01~20 μm, further preferred 0.1~10 μm.
Preferably, it is counted by 100 parts by weight of the total amount of halogen-free epoxy resin and curing agent, the additive amount of the filler is 5 ~300 parts by weight, for example, 6 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 70 parts by weight, 90 parts by weight, 110 parts by weight, 130 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, 230 parts by weight, 250 parts by weight, 280 parts by weight or 300 parts by weight, preferably 5~200 parts by weight, further preferred 5~150 weight Measure part.
" comprising " of the present invention, it is intended that it can also include other components, these other components in addition to the component Assign the halogen-free thermosetting resin composite different characteristics.In addition to this, " comprising " of the present invention can also replace For enclosed " for " or " by ... form ".
For example, the halogen-free thermosetting resin composite can also contain various additives, as concrete example, can enumerate Phosphonium flame retardant, antioxidant, heat stabilizer, antistatic agent, ultra-violet absorber, pigment, colorant or lubricant etc..These are each Kind of additive can be used alone, and two kinds or two or more can also be used in mixed way.
On the other hand, the present invention provides a kind of resin adhesive liquid, and the resin adhesive liquid is by halogen-free thermosetting as described above Resin combination is dissolved or dispersed in solvent and obtains.
Preferably, the solvent is one kind or at least two in ketone, hydro carbons, ethers, esters or aprotic solvent Combination, preferably acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, methanol, ethyl alcohol, primary alconol, ethylene glycol list first Ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide or N, N- diethylformamide In it is a kind of or at least two mixture.The solvent can be used alone, and can also be used in mixed way.The additive amount of solvent can be by Those skilled in the art determine according to the viscosity of selected resin, so as to get the modest viscosity of resin adhesive liquid, convenient for curing, this Invention is not construed as limiting this.
On the other hand, the present invention provides a kind of prepreg, and the prepreg includes reinforcing material and by being impregnated with drying Adhere to halogen-free thermosetting resin composite as described above thereon afterwards.
Reinforcing material used in the present invention is limited without special, can be organic fiber, inorfil woven cloth or nothing Woven fabric.The organic fiber can select aramid nonwoven, and the inorfil woven cloth can be E- glass-fiber-fabrics, D- glass Fine cloth, S- glass-fiber-fabrics, T glass-fiber-fabrics, NE- glass-fiber-fabrics or quartz fabric.The thickness of the reinforcing material is not particularly limited, in lamination Plate has the considerations of good dimensional stability, the woven cloth and nonwoven thickness preferably 0.01~0.2mm, and preferably passes through What fibrillation processing and silane coupling agent were surface-treated, in order to provide good water resistance and heat resistance, the silane coupling agent is excellent Be selected as in epoxy silane coupling agent, amino silicane coupling agent or vinyl silicane coupling agent any one or at least two it is mixed Close object.By reinforcing material by being impregnated with above-mentioned halogen-free thermosetting resin composite, 100~250 DEG C (such as 110 DEG C, 130 DEG C, 150 DEG C, 180 DEG C, 200 DEG C, 220 DEG C or 240 DEG C) under the conditions of, toast (2 minutes, 4 minutes, 6 minutes, 8 points 1~15 minute Clock, 10 minutes, 12 minutes or 14 minutes) obtain the prepreg.
On the other hand, the present invention provides a kind of laminate, and the laminate includes an at least prepreg as described above.
On the other hand, the present invention provides a kind of metal-clad laminate, and the metal-clad laminate is including one or extremely The prepreg as described above of few two overlappings and the metal foil of the one or both sides of the prepreg after overlapping.
The metal-clad laminate of the present invention is included by being heated and pressurizeed, bonding prepreg more than a piece of or two panels Manufactured laminate and the metal foil being bonded in more than laminate one or both sides together.The laminate be In hot press cure be made, solidification temperature for 150 DEG C~250 DEG C (such as 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C or 240 DEG C), solidifying pressure be 10~60kg/cm2(such as 12kg/cm2、15kg/cm2、18kg/cm2、 20kg/cm2、25kg/cm2、30kg/cm2、35kg/cm2、40kg/cm2、45kg/cm2、50kg/cm2、55kg/cm2Or 58kg/ cm2).The metal foil is copper foil, nickel foil, aluminium foil and stainless steel (SUS) foil etc., and material is unlimited.
On the other hand, the present invention provides a kind of printed wiring board, and the printed wiring board includes at least one as described above Prepreg.
Compared with prior art, the invention has the advantages that：
Prepreg and laminate for printed circuits, have made of halogen-free thermosetting resin composite provided by the present invention Up to 265 DEG C of glass transition temperature, excellent dielectric properties, water absorption rate are controlled in the relatively low range of 0.07-0.13%, With high-fire resistance, excellent humidity resistance and good technique processability, excellent flame retarding efficiency, P content 1.5% Reach UL94V-0 fire-retardant ranks.
Specific embodiment
The technical solution further illustrated the present invention below by specific embodiment.Those skilled in the art should be bright , the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.
Preparation example 1
Equipped with condenser pipe, blender, thermometer 1000mL flasks in add in 106.4g (0.8mol) anhydrous Aluminum chloride, 170g 4- methoxy benzophenones (0.8mol) and 210mL phosphorus trichlorides (2.4mol) are warming up to 65~68 DEG C of reaction 7h.Subtract Pressure steams extra phosphorus trichloride, and 26g sulphur powders (0.8mol) are then added portionwise into flask, and control temperature adds less than 80 DEG C After complete 4h is reacted at 80~82 DEG C.510g 4- methoxy benzophenones (2.4mol) are added in after cooling, slowly it is warming up to 110~ 120 DEG C, 8.5h is reacted, 4- methoxy benzophenones is then steamed, is cooled to room temperature, be poured slowly into ice water, agitation and filtration, Washing, drying, with ethyl alcohol recrystallization, are dried to obtain three (4- methoxy benzophenones base) phosphine sulfides.
By above-mentioned three (4- methoxy benzophenones base) phosphine sulfides and toluene in flask, controlled at 25~30 DEG C, 2.5 the H of 170g 30% is added dropwise in~4h2O2, 4h is reacted after dripping, boils off water and toluene, obtains three (4- methoxy benzophenones Base) phosphine oxide.
By 1000g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxides in N2Under the conditions of be heated to 125 DEG C, so Three (4- methoxy benzophenones base) phosphine oxides of above-mentioned synthesis are added in afterwards, when being warming up to 180 DEG C after mixing, react 5h.
Then 380g alchlors and 285g pyridines, 300mL methylene chloride reflux 5h are added in.After cooling, add water, filter, Filter residue is washed 3 times with dichloromethane, and washing lotion merges with filtrate, separates organic phase.After organic phase is boiled off solvent, with 1000mL Dichloromethane dissolves the substance, adds in 190g triethylamines, and with ice-water bath controlled at 0~-5 DEG C.Then 0~-5 DEG C are instilled 120g ClCN, 400mL dichloromethane solutions.After dripping, then reactant is distinguished alkali cleaning, water by 0~-5 DEG C of heat preservation 5h It washes, pickling and repeatedly washing, then detaches organic phase, and boil off solvent, recrystallized after dry, obtain phosphorous cyanate A1.
Preparation example 2
Sequentially added into 500mL autoclaves alchlor 137.0g (1.0mol), phosphorus trichloride 178.0g (1.3mol), Tetrachloroethanes 275.0g after vacuumizing, is slowly filled with chloromethanes 75.0g (1.5mol).Stirring, heating are warming up to 80 DEG C, reaction 6h, cooling, filtering, dry white sand shape object.White sand shape object is transferred in 1L four-hole bottles, weighs dry sodium chloride 93.6g (1.6mol), aluminium powder 18.0g (0.65mol) mixing for standby use add in 15.0g aluminium/sodium chloride mixture in four-hole bottle, Stirred under nitrogen atmosphere, heating, white sand shape object fusing.After white sand shape object is completely melt, residual Al/chlorination is added portionwise Sodium mixture, within 160 DEG C of reaction temperature, side border ring steams product methyl dichloro phosphorus, until no product distillates, obtains Colourless transparent liquid methyl dichloro phosphorus.
Heating is equipped with 93.6g methyl dichloros phosphorus and 106.4g (0.8mol) AlCl3The four-hole bottle of mixture, is warming up to 60 DEG C, 26g sulphur powders (0.8mol) are added portionwise, control temperature is no more than 80 DEG C, reacts 3h at 80~84 DEG C after adding, be cooled to room Temperature.259.5g methyl phenyl ethers anisoles (2.4mol) are added in into above-mentioned four-hole boiling flask, are slowly warming up to 110~125 DEG C, react 7h, are treated anti- After answering, it is evaporated under reduced pressure out excessive methyl phenyl ethers anisole.Room temperature is cooled to, is poured slowly into ice water, agitation and filtration, is done washing It is dry, with ethyl alcohol recrystallization, it is dried to obtain two (4- methoxyphenyls) methyl phosphine sulfides.
By above-mentioned two (4- methoxyphenyls) methyl phosphine sulfides and toluene in flask, controlled at 25~30 DEG C, The H of 113g 30% is added dropwise in 2.5~4h2O2, 4h is reacted after dripping, boils off water and toluene, obtains two (4- methoxyphenyls) Methyl oxidation phosphine.Add in 253g alchlors and 190g pyridines, 300mL methylene chloride reflux 5h.After cooling, add water, filter, filter Slag is washed 3 times with dichloromethane, and washing lotion merges with filtrate, separates organic phase.Organic phase is boiled off into solvent and obtains two (4- hydroxy benzenes Base) methyl oxidation phosphine.
90g ClCN, 400mL dichloromethane under the conditions of 0~-5 DEG C are stirred into 30min, (the 4- hydroxyls of 124g bis- are then added dropwise Base phenyl) methyl oxidation phosphine, 127g triethylamines, 500mL dichloroethanes mixed liquor.After dripping, 0~-5 DEG C of heat preservation 5h, so Reactant is distinguished into alkali cleaning, washing, pickling and repeatedly washing afterwards, organic phase is then detached, and boil off solvent, is tied again after dry Crystalline substance obtains phosphorous cyanate A2.
Preparation example 3
Heating is equipped with 143.2g phenyl dichloros phosphorus and 106.4g (0.8mol) AlCl3The four-hole bottle of mixture, is warming up to 60 DEG C, 26g sulphur powders (0.8mol) are added portionwise, control temperature is no more than 80 DEG C, reacts 3h at 80~84 DEG C after adding, be cooled to Room temperature.432.2g2 is added in into above-mentioned four-hole boiling flask, 3,5,6- tetrafluoro methyl phenyl ethers anisoles (2.4mol) are slowly warming up to 110~125 DEG C, 7h is reacted, treats after reaction, to be evaporated under reduced pressure out excessive 2,3,5,6- tetrafluoro methyl phenyl ethers anisoles.Room temperature is cooled to, is poured slowly into Into ice water, agitation and filtration, washing, drying with ethyl alcohol recrystallization, are dried to obtain two (2,3,5,6- tetra- fluoro- 4- methoxybenzenes Base) phenyl phosphine sulfide.
By above-mentioned two (tetra- fluoro- 4- methoxyphenyls of 2,3,5,6-) phenyl phosphine sulfides and toluene in flask, control temperature It is 25~30 DEG C, the H of 113g 30% is added dropwise in 2.5~4h2O2, 4h is reacted after dripping, boils off water and toluene, obtains two (tetra- fluoro- 4- methoxyphenyls of 2,3,5,6-) phenyl phosphine oxide.Add in 253g alchlors and 190g pyridines, 300mL dichloromethanes Alkane reflux 5h.After cooling, add water, filter, filter residue is washed 3 times with dichloromethane, and washing lotion merges with filtrate, separates organic phase.It will Organic phase boils off solvent and obtains two (tetra- fluoro- 4- hydroxy phenyls of 2,3,5,6-) phenyl phosphine oxides.
90g ClCN, 400mL dichloromethane are stirred into 30min under the conditions of 0~-5 DEG C, then be added dropwise 155g bis- (2,3, 5,6- tetra- fluoro- 4- hydroxy phenyls) phenyl phosphine oxide, 127g triethylamines, 500mL dichloroethanes mixed liquor.After dripping, 0~- Then reactant is distinguished alkali cleaning, washing, pickling and repeatedly washing, then detaches organic phase, and boil off solvent by 5 DEG C of heat preservation 5h, It is recrystallized after drying, obtains phosphorous cyanate A3.
Preparation example 4
Equipped with condenser pipe, blender, thermometer 1000mL flasks in add in 106.4g (0.8mol) anhydrous Aluminum chloride, 86.5g methyl phenyl ethers anisoles (0.8mol) and 210mL phosphorus trichlorides (2.4mol) are warming up to 65~68 DEG C of reaction 7h.It is extra that decompression steams Phosphorus trichloride, be then added portionwise 26g sulphur powders (0.8mol) into flask, control temperature less than 80 DEG C, after adding 80~ 82 DEG C of reaction 4h.259.5g methyl phenyl ethers anisoles (2.4mol) are added in after cooling, are slowly warming up to 110~120 DEG C, react 8.5h, then Methyl phenyl ethers anisole is steamed, is cooled to room temperature, is poured slowly into ice water, agitation and filtration, washing, drying, with ethyl alcohol recrystallization, dry To three (4- methoxyphenyls) phosphine sulfides.
By above-mentioned three (4- methoxyphenyls) phosphine sulfides and toluene in flask, controlled at 25~30 DEG C, 2.5~ The H of 170g 30% is added dropwise in 4h2O2, 4h is reacted after dripping, boils off water and toluene, obtains three (4- methoxyphenyls) oxidation Phosphine.Add in 380g alchlors and 285g pyridines, 300mL methylene chloride reflux 5h.After cooling, add water, filter, filter residue dichloro Methane wash 3 times, washing lotion merges with filtrate, separates organic phase.Organic phase is boiled off into solvent and obtains three (4- hydroxy phenyls) oxidation Phosphine.110g ClCN, 400mL dichloromethane under the conditions of 0~-5 DEG C are stirred into 30min, (the 4- hydroxy benzenes of 324g tri- is then added dropwise Base) phosphine oxide, 190g triethylamines, 500mL dichloroethanes mixed liquor.After dripping, 0~-5 DEG C of heat preservation 5h then will reaction The alkali cleaning of object difference, washing, pickling and repeatedly washing, then detach organic phase, and boil off solvent, recrystallize, contained after dry Phosphorus cyanate A4.
Preparation example 5
Heating is equipped with 154.4g (4- methyl) phenyl dichloro phosphorus and 106.4g (0.8mol) AlCl3Four mouthfuls of mixture Bottle, is warming up to 60 DEG C, and 26g sulphur powders (0.8mol) are added portionwise, and control temperature is no more than 80 DEG C, in 80~84 DEG C of reactions after adding 3h is cooled to room temperature.456g β-naphthol methyl ethers (2.4mol) are added in into above-mentioned four-hole boiling flask, are slowly warming up to 110~125 DEG C, 7h is reacted, treats after reaction, to isolate excessive β-naphthol methyl ether.Room temperature is cooled to, is poured slowly into ice water, it is stirred Filter, washing, drying, with ethyl alcohol recrystallization, are dried to obtain two (5- methoxyl groups naphthalene) (4- aminomethyl phenyls) phosphine sulfides.
By above-mentioned two (5- methoxyl groups naphthalene) (4- aminomethyl phenyls) phosphine sulfides and toluene in flask, controlled at 25~ 30 DEG C, the H of 113g 30% is added dropwise in 2.5~4h2O2, 4h is reacted after dripping, boils off water and toluene, obtains two (5- methoxies Base naphthalene) (4- aminomethyl phenyls) phosphine oxide.Add in 253g alchlors and 190g pyridines, 300mL methylene chloride reflux 5h.Cooling Afterwards, add water, filter, filter residue is washed 3 times with dichloromethane, and washing lotion merges with filtrate, separates organic phase.Organic phase is boiled off into solvent Obtain two (5- hydroxynaphenyls) (4- aminomethyl phenyls) phosphine oxides.
80g ClCN, 400mL dichloromethane under the conditions of 0~-5 DEG C are stirred into 30min, (the 5- hydroxyls of 205g bis- are then added dropwise Base naphthalene) (4- aminomethyl phenyls) phosphine oxide, 127g triethylamines, 500mL dichloroethanes mixed liquor.After dripping, 0~-5 DEG C of guarantors Then reactant is distinguished alkali cleaning, washing, pickling and repeatedly washing, then detaches organic phase, and boil off solvent by warm 5h, dry After recrystallize, obtain phosphorous cyanate A5.
Preparation example 6
Heating is equipped with 143.2g phenyl dichloros phosphorus and 106.4g (0.8mol) AlCl3The four-hole bottle of mixture, is warming up to 60 DEG C, 26g sulphur powders (0.8mol) are added portionwise, control temperature is no more than 80 DEG C, reacts 3h at 80~84 DEG C after adding, be cooled to Room temperature.441g 4- methoxyl biphenyls (2.4mol) are added in into above-mentioned four-hole boiling flask, are slowly warming up to 110~125 DEG C, reaction 7h treats after reaction, to isolate excessive 4- methoxyl biphenyls.Room temperature is cooled to, is poured slowly into ice water, it is stirred It is filter, washing, dry, with ethyl alcohol recrystallization, [4- (4- methoxyphenyls) phenyl)] the phenyl phosphine sulfide that is dried to obtain two.
By above-mentioned two [4- (4- methoxyphenyls) phenyl)] phenyl phosphine sulfide and toluene in flask, controlled at 25 ~30 DEG C, the H of 113g 30% is added dropwise in 2.5~4h2O2, 4h is reacted after dripping, boils off water and toluene, obtains two [4- (4- Methoxyphenyl) phenyl)] phenyl phosphine oxide.Add in 253g alchlors and 190g pyridines, 300mL methylene chloride reflux 5h.It is cold But after, add water, filter, filter residue is washed 3 times with dichloromethane, and washing lotion merges with filtrate, separates organic phase.Organic phase is boiled off molten Agent obtains two [4- (4- hydroxy phenyls) phenyl)] phenyl phosphine oxide.
80g ClCN, 400mL dichloromethane under the conditions of 0~-5 DEG C are stirred into 30min, the [4- (4- of 231g bis- are then added dropwise Hydroxy phenyl) phenyl)] phenyl phosphine oxide, 127g triethylamines, 500mL dichloroethanes mixed liquor.After dripping, 0~-5 DEG C of guarantors Then reactant is distinguished alkali cleaning, washing, pickling and repeatedly washing, then detaches organic phase, and boil off solvent by warm 5h, dry After recrystallize, obtain phosphorous cyanate A6.
Embodiment 1-26 and comparative example 1-7
The component of resin combination is added to according to parts by weight dosage shown in table 1-5 in solvent and is uniformly mixed, control tree Fat glue solid content is 65%, impregnates above-mentioned resin adhesive liquid with 2116 glass-fiber-fabrics, suitable thickness is controlled, then at 115~175 DEG C Baking oven in baking 2~15min prepreg is made, then several prepregs are stacked, in the stacked on 18 μ RTF copper in its both sides Foil is 170~250 DEG C in solidification temperature, and solidifying pressure is 25~60kg/cm2, hardening time is makes under the conditions of 60~300min Into copper-clad plate, embodiment 1-26 and with the composition of the resin combination of comparative example 1-7 and the property of its copper-clad plate being prepared It can be as shown in table 1-5.
Embodiment 1-26 and comparative example 1-7 is related to material and trade mark information is as follows：
(A) phosphorous cyanate
A1：Phosphorous cyanate prepared by preparation example 1
A2：Phosphorous cyanate prepared by preparation example 2
A3：Phosphorous cyanate prepared by preparation example 3
A4：Phosphorous cyanate prepared by preparation example 4
A5：Phosphorous cyanate prepared by preparation example 5
A6：Phosphorous cyanate prepared by preparation example 6
A7：The phosphorous cyanate having the following structure：
(B) epoxy resin
HP-7200HHH：DIC, DCPD type epoxy resin, epoxide equivalent 288
HP-7200H-75M：DIC, DCPD type epoxy resin, epoxide equivalent 280
HP-6000：DIC, epoxy resin, epoxide equivalent 250
HP-9900：DIC, naphthol type epoxy resin, epoxide equivalent 274
NC-3000H：Japanese chemical drug, biphenyl epoxy resin, epoxide equivalent 294
SKE-1：Shang Kete, special epoxy resin, epoxide equivalent 120
(C) polyphenylene oxide resin：
SA90:Sha Baiji, phenol polyphenylene oxide resin, molecular weight 1800
(D) phenolic resin
DOW92741：Phosphorus-containing phenolic aldehyde, DOW Chemical
2812：Linear phenolic resin, MOMENTIVE (South Korea)
(E) active ester resin
HPC-8000-65T：DCPD type active esters, Japanese DIC
(F) phosphonium flame retardant
SPB-100：Great mound chemistry, phosphine nitrile fire retardant, phosphorus content 13.4%
(G) SMA resins
EF40：SMA, styrene-maleic anhydride copolymer, Sartomer
(H) curing accelerator
2E4MZ：2-ethyl-4-methylimidazole, four countries' chemical conversion
DMAP：4-dimethylaminopyridine, wide Rong Huaxue
BICAT Z：Zinc Isoocatanoate, The Shepherd Chemical Company
(I) filler
Fused silica (average grain diameter is 0.2 to 10 μm, more than 99% purity)
Table 1
Table 2
Table 3
Table 4
Table 5
Note：In PCT/6h, × to be layered plate bursting, O is not stratified plate bursting.
The test method of more than characteristic is as follows：
(1) glass transition temperature (Tg)：It is tested using DMA, is surveyed according to the DMA of IPC-TM-650 2.4.24 defineds Method for testing is measured.
(2) dielectric constant and dielectric loss factor：It is tested according to SPDR methods.
(3) humidity resistance (PCT) is evaluated：After the copper foil on copper-clad plate surface is etched, substrate is evaluated；By substrate placement force In pot, after being handled 6 hours under the conditions of 120 DEG C, 105KPa, it is immersed in 288 DEG C of tin stove, is recorded when substrate de-lamination plate bursting The corresponding time；It can terminate to evaluate when substrate also does not occur blistering or being layered in tin stove more than 5min.
(4)T288：With TMA instrument, it is measured according to the T300 test methods of IPC-TM-650 2.4.24.1 defineds.
(5) water imbibition：Water imbibition test method according to IPC-TM-650 2.6.2.1 defineds is measured.
(6) anti-flammability：It is carried out according to 94 standard methods of UL.
It can be seen that the glass for the copper-clad plate being prepared using halogen-free resin composition of the present invention from table 1-5 Change transition temperature and be up to 195 DEG C or more, dielectric constant is down to 3.8, and dielectric loss factor is 0.008 hereinafter, water absorption rate exists 0.13% hereinafter, T288 ＞ 60min, do not occur to be layered plate bursting, and flame retardant property can reach V-0 grades, have good resistance to Thermal stability, humidity resistance and good technique processability and excellent flame retarding efficiency, low water absorption rate and good Jie Electrical property.
Comparative example 1 and embodiment 5 compare, and the NC-3000H of 70 parts by weight are used in comparative example 1 so that Halogen in composition The dosage of epoxy resin is excessive, and made copper-clad plate dielectric properties are poor, poor heat resistance；Comparative example 2 and embodiment 6 compare, 25 parts by weight SKE-1 and 55 parts by weight cyanate ester resins are used in comparative example 2 so that the dosage of halogen-free epoxy resin in composition It is very few, and the dosage of phosphorous cyanate is excessive, water absorption rate height, the humidity resistance of made copper-clad plate are poor, are easily delaminated plate bursting, And heat resistance is poor；Comparative example 3 and embodiment 10 compare, and using 45 parts by weight SA90 and 5 parts by weight A2 in comparative example 3, make Polyphenylene oxide resin dosage is excessive in composition, phosphorous cyanate dosage is very few, and the heat resistance of made copper-clad plate is poor, resistance to Humid is poor, is easily delaminated plate bursting, and anti-flammability is also poor；Comparative example 4 and embodiment 16 compare, and 45 weights are used in comparative example 4 Measure part HPC-8000-65T so that the dosage of active ester resin is excessive in composition, and the heat resistance of made copper-clad plate is poor； Comparative example 5 is compared with embodiment 19, with 45 parts by weight EF40 in comparative example 5 so that the dosage mistake of SMA resins in resin combination More, the heat resistance for the copper-clad plate being prepared decreases, dielectric constant increases.Comparative example 6 is relative to embodiment 25, wherein containing 92741 dosage of phosphorus phenolic aldehyde is excessive, causes its heat resistance, humidity resistance poor.Comparative example 7 is relative to embodiment 5, in phosphorous cyanate Containing phenylate structure, lead to that its Tg is low, dielectric properties are slightly worse, water absorption rate is high, humidity resistance is unstable.
As described above, compared with general laminate, made of halogen-free thermosetting resin composite provided by the present invention Prepreg and laminate for printed circuits are heat-resisting with high glass-transition temperature, excellent dielectric properties, low water absorption, height Property, excellent humidity resistance and good technique processability, and can realize halogen-free flameproof, reach UL94V-0.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.

Claims (10)

1. a kind of halogen-free thermosetting resin composite, which is characterized in that the halogen-free thermosetting resin composite includes Halogen ring Oxygen resin and curing agent, wherein curing agent include at least a kind of phosphorous cyanate, and the phosphorous cyanate has to be tied shown in Formulas I Structure：
Wherein, Ar1Selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted fluorenyl, substitution Or any one in unsubstituted xenyl or the group of the structure containing DOPO；Ar2For substituted or unsubstituted phenyl, substitution or The straight chained alkyl or branched alkyl of unsubstituted naphthalene, substituted or unsubstituted C1~C4；A is 1 or 2, b are 0 or 1, and meet a + b=2；
The phosphorous cyanate ester resin accounts for halogen-free epoxy resin and curing agent total weight in the halogen-free thermosetting resin composite 10%~50%；
The halogen-free epoxy resin accounts for halogen-free epoxy resin and curing agent total weight in the halogen-free thermosetting resin composite 30%~60%.
2. halogen-free thermosetting resin composite according to claim 1, which is characterized in that
The Ar1It is selected from In any one, Ar4It is selected from
Preferably, Ar2ForR1And R2It independently is phenyl, naphthalene, C1 In the straight chained alkyl or branched alkyl of~C4 any one or at least two combination, n1For 0~5 integer, n2It is 0~7 Integer；
Preferably, the phosphorous cyanate is any one in the compound with formula a-i structures or at least two combination：
3. halogen-free thermosetting resin composite according to claim 1 or 2, which is characterized in that the halogen-free epoxy resin Selected from glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy Any one in resin, epoxidation of olefins based epoxy resin, glycolylurea epoxide resin or acid imide epoxy resin or at least two Mixture；
Preferably, the glycidyl ether type epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, o-cresol Novolac epoxy resin, bisphenol A-type novolac epoxy resin, three phenolic novolac epoxy resins, dicyclopentadiene novolac epoxy resin, connection Any one in benzene-type novolac epoxy resin, alkyl benzene-type novolac epoxy resin or naphthol type novolac epoxy resin or at least two The mixture of kind；
Preferably, the glycidyl amine epoxy resin is selected from triglycidyl group para-aminophenol, triglycidyl group three Polyisocyanate, four glycidyl group diamino dimethylene benzene, two amido diphenyl-methanes of four glycidyl group -4,4'-, four contractings Water glyceryl -3,4'- diaminodiphenyl ethers, four glycidyl group -4,4'- diaminodiphenyl ethers or four glycidyl group -1,3- In bis aminomethyl hexamethylene any one or at least two mixture.
4. halogen-free thermosetting resin composite according to any one of claim 1-3, which is characterized in that the curing agent Also include polyphenylene oxide resin；
Preferably, the polyphenylene oxide resin accounts for halogen-free epoxy resin and curing agent gross weight in the halogen-free thermosetting resin composite Amount 0~40% and not include 0；
Preferably, the polyphenylene oxide resin number-average molecular weight is 1000~5000；
Preferably, the curing agent also includes active ester resin；
Preferably, the active ester resin accounts for halogen-free epoxy resin and curing agent gross weight in the halogen-free thermosetting resin composite Amount 0~40% and not include 0；
Preferably, the curing agent also includes SMA resins；
Preferably, the SMA resins are styrene and maleic anhydride by the ratio between amount of substance 1:1~8:1 ratio is copolymerized to obtain；
Preferably, the SMA resins account for halogen-free epoxy resin and curing agent total weight in the halogen-free thermosetting resin composite 0~40% and not include 0；
Preferably, for the curing agent also comprising phenolic resin, the phenolic resin is phosphorous or not phosphorous phenolic resin；
Preferably, the phenolic resin accounts for halogen-free epoxy resin and curing agent total weight in the halogen-free thermosetting resin composite 0~20% and not include 0.
5. according to the halogen-free thermosetting resin composite described in any one of claim 1-4, which is characterized in that the Halogen heat Thermosetting resin composition also includes the organic halogen-free agent of addition type；
Preferably, the organic halogen-free agent is the organic halogen-free agent of phosphorus system；
Preferably, by the sum of additive amount of halogen-free epoxy resin and curing agent in terms of 100 parts by weight, the organic halogen-free agent Additive amount for 0~10 parts by weight and not include 0；
Preferably, the phosphorus system organic halogen-free agent for three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl)- Miscellaneous -10- phosphines phenanthrene -10- the oxides of 9,10- dihydro-9-oxies, 2,6- bis- (2,6- 3,5-dimethylphenyls) phosphino- benzene, 10- phenyl -9,10- Miscellaneous -10- phosphines phenanthrene -10- the oxides of dihydro-9-oxy, phenoxy phosphazene compound, phosphate, polyphosphate, polyphosphonates or phosphonic acids In ester-carbonate copolymer any one or at least two mixture；
Preferably, the halogen-free thermosetting resin composite also includes curing accelerator；
Preferably, the curing accelerator include organic metal salt, glyoxaline compound and its derivative, piperidines, In pyridine compounds and their, lewis acid or triphenylphosphine any one or at least two mixture；
Preferably, the organic metal salt is organic zinc salt, organic copper salt, organic molysite, organic tin salt, organic cobalt salt or organic In aluminium salt any one or at least two mixture；
Preferably, the glyoxaline compound is 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazoles or 2- 11 In alkyl imidazole any one or at least two mixture；
Preferably, the pyridine compounds and their is 4-dimethylaminopyridine, 2-aminopyridine, 3- aminopyridines or 4-aminopyridine In any one or at least two mixtures；
Preferably, it is counted by 100 parts by weight of the total amount of halogen-free epoxy resin and curing agent, the additive amount of the curing accelerator is 0.01~1 parts by weight, preferably 0.025~0.85 parts by weight；
Preferably, the halogen-free thermosetting resin composite further includes filler；
Preferably, the filler is selected from organic filler or inorganic filler, preferably inorganic filler, further preferably by surface treatment Inorganic filler, most preferably surface treated silica；
Preferably, the surface conditioning agent used that is surface-treated is selected from silane coupling agent, silicone oligomer or titanate esters idol Join agent in any one or at least two mixture；
Preferably, it is counted by 100 parts by weight of inorganic filler, the dosage of the surface conditioning agent is 0.1~5.0 parts by weight, preferably 0.5~3.0 parts by weight, more preferable 0.75~2.0 parts by weight；
Preferably, the inorganic filler is selected from nonmetal oxide, metal nitride, non-metal nitride, inorganic hydrate, nothing In machine salt, metal hydrate or Phos any one or at least two mixture, preferred molten silica, crystallization Type silica, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride, carbon One kind or at least two mixture in SiClx, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates or mica；
Preferably, the organic filler in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder any one or At least two mixture；
Preferably, the median of the filler is 0.01~50 μm, preferably 0.01~20 μm, further preferred 0.1~10 μm；
Preferably, it is counted by 100 parts by weight of the total amount of halogen-free epoxy resin and curing agent, the additive amount of the filler is 5~300 Parts by weight, preferably 5~200 parts by weight, further preferred 5~150 parts by weight.
6. a kind of resin adhesive liquid, which is characterized in that the resin adhesive liquid is by the Halogen as described in any one of claim 1-5 Compositions of thermosetting resin is dissolved or dispersed in solvent and obtains；
Preferably, the solvent is a kind of in ketone, hydro carbons, ethers, esters or aprotic solvent or at least two group Close, preferably acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, methanol, ethyl alcohol, primary alconol, glycol monoethyl ether, In propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide or N, N- diethylformamide It is a kind of or at least two mixture.
7. a kind of prepreg, which is characterized in that the prepreg includes reinforcing material and by adhering to thereon after being impregnated with drying The halogen-free thermosetting resin composite as described in any one of claim 1-5.
8. a kind of laminate, which is characterized in that the laminate includes an at least prepreg as claimed in claim 7.
9. a kind of metal-clad laminate, which is characterized in that the metal-clad laminate includes one or at least two overlapping Prepreg as claimed in claim 7 and the prepreg after overlapping one or both sides metal foil.
10. a kind of printed wiring board, which is characterized in that the printed wiring board includes at least one as claimed in claim 7 Prepreg.
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CN111662328A (en) * 2020-06-12 2020-09-15 万华节能科技集团股份有限公司 Derivative of flame-retardant environment-friendly toluene diisocyanate and synthetic method thereof
US11326015B1 (en) * 2019-02-01 2022-05-10 The United States Of America, As Represented By The Secretary Of The Navy Cyanate ester resin
CN115558334A (en) * 2022-09-21 2023-01-03 深圳市容大感光科技股份有限公司 Ink composition, circuit board containing ink composition, application of ink composition and method for electroplating through hole

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CN102181143A (en) * 2011-04-08 2011-09-14 苏州生益科技有限公司 High-frequency thermosetting resin composition, prepreg and laminated sheet
JP2015108154A (en) * 2015-02-13 2015-06-11 パナソニックＩｐマネジメント株式会社 Epoxy resin composition for printed wiring board, prepreg for printed wiring board using the epoxy resin composition for printed wiring board, and metal-clad laminate for printed wiring board

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CN1300301A (en) * 1999-03-23 2001-06-20 洛克泰特公司 Reworkable thermosetting resin composition
CN102181143A (en) * 2011-04-08 2011-09-14 苏州生益科技有限公司 High-frequency thermosetting resin composition, prepreg and laminated sheet
JP2015108154A (en) * 2015-02-13 2015-06-11 パナソニックＩｐマネジメント株式会社 Epoxy resin composition for printed wiring board, prepreg for printed wiring board using the epoxy resin composition for printed wiring board, and metal-clad laminate for printed wiring board

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Publication number Priority date Publication date Assignee Title
US11326015B1 (en) * 2019-02-01 2022-05-10 The United States Of America, As Represented By The Secretary Of The Navy Cyanate ester resin
CN111662328A (en) * 2020-06-12 2020-09-15 万华节能科技集团股份有限公司 Derivative of flame-retardant environment-friendly toluene diisocyanate and synthetic method thereof
CN115558334A (en) * 2022-09-21 2023-01-03 深圳市容大感光科技股份有限公司 Ink composition, circuit board containing ink composition, application of ink composition and method for electroplating through hole
CN115558334B (en) * 2022-09-21 2023-10-10 深圳市容大感光科技股份有限公司 Ink composition, circuit board containing same, application of ink composition and method for electroplating through holes

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