CN108117632A - A kind of compositions of thermosetting resin - Google Patents

A kind of compositions of thermosetting resin Download PDF

Info

Publication number
CN108117632A
CN108117632A CN201611081915.5A CN201611081915A CN108117632A CN 108117632 A CN108117632 A CN 108117632A CN 201611081915 A CN201611081915 A CN 201611081915A CN 108117632 A CN108117632 A CN 108117632A
Authority
CN
China
Prior art keywords
resin
compositions
thermosetting resin
curing agent
epoxy resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201611081915.5A
Other languages
Chinese (zh)
Other versions
CN108117632B (en
Inventor
罗成
唐国坊
许永静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shengyi Technology Co Ltd
Original Assignee
Shengyi Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shengyi Technology Co Ltd filed Critical Shengyi Technology Co Ltd
Priority to CN201611081915.5A priority Critical patent/CN108117632B/en
Publication of CN108117632A publication Critical patent/CN108117632A/en
Application granted granted Critical
Publication of CN108117632B publication Critical patent/CN108117632B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • 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
    • 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
    • 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
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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 present invention provides a kind of compositions of thermosetting resin, it includes active ester phosphonate resins, the compositions of thermosetting resin has many advantages, such as good thermal stability, humidity resistance, dielectric constant and dielectric loss angle tangent is low, water absorption rate is low and halogen-free flameproof effect, and with excellent technique processability；The present invention also provides application of the compositions of thermosetting resin in resin sheet, resin laminated metal paper tinsel, prepreg, laminate, metal-clad laminate and printed wiring board.

Description

A kind of compositions of thermosetting resin
Technical field
The present invention relates to technical field of polymer materials more particularly to a kind of compositions of thermosetting resin and use the pre- of it Leaching material and laminate for printed circuits.
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 on 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. Phosphonium 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%.It is however, actual It is found in, DOPO classes compound is poor with larger water absorption rate and poor dielectric properties and plate humidity resistance.Addition Type is mainly phosphonitrile and phosphonate ester compound, and the flame retarding efficiency of additive flame retardant is relatively low, it is necessary to add more amount ability Reach flame-retardancy requirements.It is easy to migrate to plate in laminate process simultaneously because of its relatively low fusing point (generally below 150 DEG C) Material surface, influences plate property.
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 possess 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 the phosphorus curing agent with reactivity to hold oxybenzene oxygroup alkyl phosphine oxide, can be cured with epoxy resin instead Should, but since its active group is phenolic hydroxyl group, can generate the larger secondary hydroxyl of polarity after being reacted with epoxy resin, cause The dielectric properties of solidfied material are poor.Polyphosphonates or/and phosphonate ester-carbonic ester of the selection with hydroxyl are common in CN103384674A Polymers forms composition with epoxy, and active group is phenolic hydroxyl group, equally exists the problem of dielectric properties are poor； Disclosed in CN103694642A using epoxy resin, cyanate esters or/and cyanate prepolymer, polyphosphonates or/and Phosphonate ester-carbonate copolymer is prepared for the fire-retardant prepregs of the good Halogen UL94V-0 of dielectric properties, humidity resistance and covers copper foil Laminate, but its peel strength, interlayer adhesion and bending strength are relatively low.
The content of the invention
Through inventor the study found that using the end oxybenzene oxygroup alkyl phosphine oxide of esterification modification as the curing of epoxy resin Agent will not generate polarity big secondary hydroxyl when being reacted with epoxy resin, the dielectric properties for making system are preferable, simultaneously because its Body is phosphorous active curing agent, also has the effect of halogen-free flameproof while as curing agent, need to only be added on a small quantity or need not Adding other fire retardants just can make plate achieve the effect that UL94V-0 halogen-free flameproofs.
Based on this, one of the objects of the present invention is to provide a kind of compositions of thermosetting resin and its preimpregnation is used Material and laminate for printed circuits.The laminate for printed circuits made using the resin combination has high glass transition temperature Degree, excellent dielectric properties, high-fire resistance and humidity resistance and good technique processability, and can realize halogen-free flameproof, reach UL94V-0。
The present inventor to achieve the above object, has carried out in-depth study repeatedly, it turns out that：By halogen-free epoxy resin, The end oxybenzene oxygroup alkyl phosphine oxide of esterification modification and the composition that optionally other curing agent are suitably mixed to get, can reach State purpose.
That is, the present invention adopts the following technical scheme that：A kind of compositions of thermosetting resin, it includes epoxy resin and epoxies Resin curing agent, wherein curing agent include at least a kind of active ester phosphonate resin.
The compositions of thermosetting resin of the present invention is a kind of halogen-free thermosetting resin composite, with the end hydroxyl of esterification modification Curing agent of the phenoxy group alkyl phosphine oxide as epoxy resin.Active ester groups content wherein as active group is high, Ke Yiyu The big solidfied material of crosslink density is obtained after epoxy resin cure, heat-resist, Tg high material can be obtained；And esterification modification End oxybenzene oxygroup alkyl phosphine oxide structures symmetry it is high, and the active ester units in molecule after epoxy resin reaction with that will not give birth to Polarity big secondary hydroxyl, makes dielectricity at the shortcomings that can eliminating the poor dielectric performance that the big secondary hydroxyl of polarity is brought It can be excellent；The end oxybenzene oxygroup alkyl phosphine oxide of the esterification modification is active ester, with the ester bond generated after epoxy resin reaction Water absorption rate is low, makes to which improve the shortcomings that phosphorus-containing compound humidity resistance is poor.In addition, the end oxybenzene oxygroup alkyl oxygen of esterification modification Changing phosphine has effects that halogen-free flameproof, need to only add on a small quantity or can to reach UL94V-0 fire-retardant without additionally add fire retardant.
The present invention, can be notable using the active ester group of the end oxybenzene oxygroup alkyl phosphine oxide of high symmetrical esterification modification The glass transition temperature and heat resistance of the prepreg that the resin combination is used to make and laminate for printed circuits are improved, And excellent dielectric properties, low water absorption, good humidity resistance and good technique processability are made it have, and realize Halogen It is fire-retardant, reach UL94V-0.Each component is described in detail below.
According to the present invention, the active ester phosphonate resin, shown in structural formula such as formula (I)：
Wherein, n1For 3~20 integer, such as 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 Or 20；
Wherein, n2For 0~5 integer, such as 0,1,2,3,4 or 5；
Wherein, R1For any one in phenyl, naphthalene, the straight or branched alkyl containing carbon number 1~4；It is wherein described to contain The straight or branched alkyl of carbon number 1~4 for example can be in methyl, ethyl, propyl, butyl, isopropyl, isobutyl group or tertiary butyl Any one；
Wherein, R2For be 1~4 containing carbon number straight or branched alkyl in any one；Wherein described carbon containing number 1~4 Straight or branched alkyl for example can be any one in methyl, ethyl, propyl, butyl, isopropyl, isobutyl group or tertiary butyl Kind；
Wherein, Ar1、Ar2It is each independently selected from any one in following group：
Heretofore described active ester phosphonate resin, structural formula can be specifically structure shown below：
According to the present invention, the active ester phosphonate resin accounts for the compositions of thermosetting resin epoxy resin and consolidates The 20%~50% of agent total weight, for example, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 35%, 38%, 40%th, the specific point value between 42%, 45%, 48% or 50% and above-mentioned numerical value is examined as space is limited and for concise Consider, the present invention specific point value that no longer scope described in exclusive list includes.
In the present invention, the active ester phosphonate resin preferably account for the compositions of thermosetting resin epoxy resin and The 20%~45% of curing agent total weight, further preferred 25%~40%, still more preferably 25%~30%.
According to the present invention, the epoxy resin accounts for the compositions of thermosetting resin epoxy resin and curing agent total weight 30%~60%, such as 30%, 32%, 34%, 35%, 36%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%th, the specific point value between 58% or 60% and above-mentioned numerical value, as space is limited and for it is concise the considerations of, the present invention not The specific point value that scope described in exclusive list includes again.
Present invention preferably employs halogen-free epoxy resin, the halogen-free epoxy resin refer in 1 molecule tool there are two or The epoxy resin of more than two epoxide groups can specifically be selected from glycidol ethers, glycidol esters, glycidyl amine In class, cycloaliphatic epoxy resin, epoxidation of olefins class, glycolylurea epoxide resin or acid imide epoxy resin any one or at least Two kinds of mixture, wherein typical but non-limiting mixture is：Glycidol ethers and glycidol esters, aliphatic ring Oxygen resin and epoxidation of olefins class, glycidol amine and glycolylurea epoxide resin.
Preferably, the glycidol ethers includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, o-cresol phenolic aldehyde Epoxy resin, bisphenol A-type novolac epoxy resin, three phenolic novolac epoxy resins, dicyclopentadiene novolac epoxy resin, biphenyl type Any one in novolac epoxy resin, alkyl benzene-type novolac epoxy resin or naphthol type novolac epoxy resin or at least two Mixture.
It is further preferred that the glycidol ethers is selected from the epoxy resin such as lower structure：
Wherein, Z1、Z2And Z3It is each independently selected fromOrR3Selected from hydrogen atom, substitution or Any one in unsubstituted straight chained alkyl or branched alkyl containing carbon number 1~5；Such as can be methyl, ethyl, propyl, Any one in butyl, amyl, isopropyl, isobutyl group, tertiary butyl or isopentyl；
Wherein, Y1And Y2It is each independently selected from-CH2-、 OrIn any one；R4 Any one in hydrogen atom, substituted or unsubstituted straight chained alkyl or branched alkyl containing carbon number 1~5；It such as can be with It is any one in methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl group, tertiary butyl or isopentyl；
Wherein, n3For 1~10 arbitrary integer, such as 1,2,3,4,5,6,7,8,9 or 10.
Preferably, it is different to be selected from triglycidyl group-p- amino-phenols, triglycidyl group trimerization for the glycidol amine Cyanate, four glycidyl group diamino dimethylene benzene, four glycidyl group -4,4 '-diaminodiphenylmethane, four shrinks are sweet Oil base -3,4 '-diaminodiphenyl ether, four glycidyl group -4,4 '-diaminodiphenyl ether or four glycidyl group -1,3- diaminos In ylmethyl hexamethylene 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.
According to the present invention, the curing agent can also include cyanate ester resin and/or bismaleimide-triazine resin； Wherein, the cyanate ester resin has such as lower structure：
Wherein, R5For-CH2-、Or In any one or at least two mixture；R6、R7、R8、R9、R10、R11、R12、R13It is each independently selected from hydrogen atom, takes Any one in generation or unsubstituted straight chained alkyl or branched alkyl containing carbon number 1~4, such as can be methyl, ethyl, third Any one in base, butyl, isopropyl, isobutyl group or tertiary butyl.
Preferably, the cyanate ester resin is selected from 2,2- double (4- cyanato-s phenyl) propane, double (4- cyanato-s phenyl) second Double (4- cyanato-s the phenyl) -1,1,1,3,3,3- hexafluoropropane of alkane, double (3,5- dimethyl -4- cyanato-s phenyl) methane, 2,2-, α, α '-bis- (4- cyanato-s phenyl)-diisopropyl benzene, Cyclopeutadiene type cyanate, phenol novolak type cyanate, cresol novolac Type cyanate, 2,2- double (4- cyanato-s phenyl) propane prepolymer, double (4- cyanato-s phenyl) ethane prepolymers, double (3,5- bis- Methyl -4- cyanato-s phenyl) methane prepolymer, double (4- cyanato-s the phenyl) -1,1,1,3,3,3- hexafluoropropane prepolymers of 2,2-, α, α '-bis- (4- cyanato-s phenyl)-diisopropyl benzene prepolymers, dicyclopentadiene type ethylene rhodanate prepolymer, phenol novolak type In cyanate prepolymer or cresol novolak type cyanate prepolymer any one or at least two mixture, be preferably 2,2- Double (4- cyanato-s phenyl) propane, α, α '-bis- (4- cyanato-s phenyl)-diisopropyl benzene, double (3,5- dimethyl -4- cyanogen oxygen Base phenyl) methane, 2,2- double (4- cyanato-s phenyl) propane prepolymer, α, α '-bis- (4- cyanato-s phenyl)-diisopropyl benzenes In prepolymer or double (3,5- dimethyl -4- cyanato-s phenyl) methane prepolymers any one or at least two mixture.
According to the present invention, the cyanate ester resin and/or bismaleimide-triazine resin account for the thermosetting resin group Close the 0%~50% of object epoxy resin and curing agent total weight, for example, 1%, 2%, 4%, 5%, 8%, 10%, 12%, 14%th, 15%, 17%, 20%, 22%, 25%, 30%, 32%, 35%, 37%, 39%, 40%, 42%, 45%, 48% or Specific point value between 50% and above-mentioned numerical value, as space is limited and for it is concise the considerations of, the present invention no longer exclusive list institute State the specific point value that scope includes.
According to the present invention, the curing agent can also include SMA resins；The SMA resins mean phenylethylene-maleic anhydride Resin may be employed by styrene and maleic anhydride by 1:1~8:1 ratio is copolymerized to obtain.
According to the present invention, the SMA resins account for the compositions of thermosetting resin epoxy resin and curing agent total weight 0%~40%, such as 1%, 2%, 4%, 5%, 8%, 10%, 12%, 14%, 15%, 17%, 20%, 22%, 25%, 30%th, the specific point value between 32%, 35%, 37%, 39% or 40% and above-mentioned numerical value, as space is limited and for simplicity The considerations of, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, the curing agent can also include phenolic resin；The phenolic resin is phosphorous or not phosphorous Phenolic resin, the phenolic resin being known in the art, the present invention do not do particular determination.
According to the present invention, the phenolic resin accounts for the compositions of thermosetting resin epoxy resin and curing agent total weight 0%~20%, such as 1%, 2%, 4%, 5%, 8%, 10%, 12%, 14%, 15%, 17% or 20% and above-mentioned number Specific point value between value, as space is limited and for it is concise the considerations of, present invention tool that no longer scope described in exclusive list includes Body point value.
Heretofore described compositions of thermosetting resin, organic solid content specifically include based on 100 parts by weight：Activity Esters phosphonate resins：20~50 parts by weight；Halogen-free epoxy resin：30~60 parts by weight；Cyanate ester resin and/or span carry out acyl Imines-cyanate resin：0~50 parts by weight；SMA resins：0~40 parts by weight；Phenolic resin：0~20 parts by weight.
" the compositions of thermosetting resin epoxy resin and curing agent total weight " mentioned in the present invention refers to join With the total weight of the component of cross-linking polymerization, wherein, curing agent refers to the active esters phosphine for playing the role of cured epoxy resin Acid ester resin and optionally cyanate ester resin and/or bismaleimide-triazine resin, SMA resins or phenolic resin, no Include the components such as filler, accelerating agent and fire retardant.
The compositions of thermosetting resin of the present invention can also include organic halogen-free flame retardants, the organic halogen-free agent tool Body can be selected from phosphonium flame retardant.
According to the present invention, the phosphonium flame retardant can be selected from three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy Phenyl) miscellaneous -10- phosphines phenanthrene -10- oxides of -9,10- dihydro-9-oxies, 2,6- bis- (2,6- 3,5-dimethylphenyls) phosphino- benzene, 10- benzene Miscellaneous -10- phosphines phenanthrene -10- the oxides of base -9,10- dihydro-9-oxies, phenoxy phosphazene compound, phosphate, polyphosphate, polyphosphonic acid In ester or phosphonate ester-carbonate copolymer any one or at least two mixture.
In the present invention, epoxy resin and curing agent total amount in the compositions of thermosetting resin have based on 100 parts by weight The additive amount of machine halogen-free flame retardants is 0~15 parts by weight, that is to say, that by active ester phosphonate resin, epoxy resin and can Can cyanate ester resin, SMA resins, the sum of the additive amount of phenolic resin of addition be 100 parts by weight meters, organic halogen-free agent Additive amount is 0~15 parts by weight, such as 1 parts by weight, 3 parts by weight, 5 parts by weight, 6 parts by weight, 8 parts by weight, 9 parts by weight, 10 weights Specific point value between amount part, 11 parts by weight, 12 parts by weight, 13 parts by weight or 15 parts by weight and above-mentioned numerical value, as space is limited And for it is concise the considerations of, the present invention specific point value that no longer scope described in exclusive list includes.
The halogen-free thermosetting resin composite of the present invention can also further include curing accelerator.
Preferably, the curing accelerator includes organic metal salt and selected from glyoxaline compound, glyoxaline compound In derivative, piperidines, pyridine compounds and their, lewis acid or triphenylphosphine any one or at least two it is mixed Close object.
Preferably, the organic metal salt in the curing accelerator includes sad metal salt, isooctyl acid metal salt, levulinic In ketone metal salt, metal naphthenate, salicylic acid metal salt or Metallic stearates any one or at least two mixing Object, wherein, the metal in zinc, copper, iron, tin, cobalt or aluminium 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 is 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, with active ester phosphonate resin, epoxy resin and the cyanate ester resin that may be added, SMA resins, phenol The sum of additive amount of urea formaldehyde is 100 parts by weight meters, and the additive amount of the curing accelerator is 0.01~1 parts by weight, such as 0.01 parts by weight, 0.025 parts by weight, 0.05 parts by weight, 0.07 parts by weight, 0.085 parts by weight, 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 0.9 parts by weight or 1 parts by weight are preferably 0.025~0.85 parts by weight.
The halogen-free thermosetting resin composite of the present invention can also further include 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, it is even to be selected from silane coupling agent, silicone oligomer or titanate esters for the surface conditioning agent of the surface treatment Join agent in any one or at least two mixture.
Preferably, counted by 100 parts by weight of inorganic filler, the dosage of the surface conditioning agent is 0.1~5 parts by weight, excellent Select 0.5~3 parts by weight, more preferable 0.75~2 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 silica, Powdered quartz, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, nitridation In boron, carborundum, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates or mica any one or at least two it is mixed Close 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, preferably 0.01~20 μm, further preferred 0.1~ 10μm。
Preferably, with active ester phosphonate resin, epoxy resin and the cyanate ester resin that may be added, SMA resins, phenol The sum of additive amount of urea formaldehyde is 100 parts by weight meters, and the additive amount of the filler is 5~300 parts by weight, preferably 5~200 weight Part, further preferred 5~150 parts by weight.
"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, "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 Antioxidant, heat stabilizer, antistatic agent, ultra-violet absorber, pigment, colorant or lubricant etc..These additives can be single It solely uses, two kinds or two or more can also be used in mixed way.
The preparation method of the halogen-free thermosetting resin composite of the present invention is ordinary skill in the art means, specific side Method is：First solid content is put into, then adds in liquid solvent, is stirred to solid content after being completely dissolved, add liquid resin and Accelerating agent continues to stir evenly.
As the solvent in the present invention, there is no particular limitation, as concrete example, can include methanol, ethyl alcohol, butanol Wait alcohols, the ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol, acetone, butanone, first The ketones such as methyl ethyl ketone methyl ketone, cyclohexanone；The arenes such as toluene, dimethylbenzene；The esters such as ethyl acetate, ethoxyethyl acetate Class；The nitrogen-containing solvents such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide.More than solvent can be used alone, also can be two kinds Or it two or more is used in mixed way.It is preferred that the ketones such as acetone, butanone, methyl ethyl ketone, cyclohexanone.The additive amount of the solvent by Those skilled in the art select according to oneself experience so that resin adhesive liquid reaches the viscosity for being suitble to use.
The prepreg of the present invention is attached to the nothing as described above on reinforcing material including reinforcing material and impregnation after dry Halogen compositions of thermosetting resin, used reinforcing material are limited without special, can be organic fiber, inorfil woven cloth Or non-woven fabrics.The organic fiber can select aramid nonwoven, the inorfil woven cloth can be E- glass-fiber-fabrics, D- glass-fiber-fabrics, 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, and is in Laminate has the considerations of good dimensional stability, the woven cloth and nonwoven thickness preferably 0.01~0.2mm, and preferably It is surface-treated by fibrillation processing and silane coupling agent, it is described silane coupled in order to provide good water resistance and heat resistance Agent is preferably any one or at least two in epoxy silane coupling agent, amino silicane coupling agent or vinyl silicane coupling agent Mixture.By reinforcing material by being impregnated with above-mentioned halogen-free thermosetting resin composite, under the conditions of 100~250 DEG C, baking Obtain the prepreg within 1~15 minute.
The laminate for printed circuits of the present invention is included by being heated and pressurizeed, gluing prepreg more than a piece of or two panels Be combined and manufactured laminate and the metal foil that is bonded in more than laminate one or both sides.The laminate is Cure in hot press and be made, solidification temperature is 150~250 DEG C, and solidifying pressure is 10~60kg/cm2.The metal foil is Copper foil, nickel foil, aluminium foil and SUS paper tinsels etc., material is unlimited.
Compared with prior art, the present invention at least has the advantages that：
Prepreg and laminate for printed circuits made of compositions of thermosetting resin provided by the present invention have up to 235 DEG C of glass transition temperature；Excellent dielectric properties, water absorption rate are can be controlled in the range of 0.07%~0.13%；Have High-fire resistance, excellent humidity resistance and good technique processability；Excellent flame retarding efficiency, phosphorus content is 1.5% Achieve the effect that UL94V-0 halogen-free flameproofs.
Specific embodiment
The technical solution further illustrated the present invention below by specific embodiment.
As described below is the specific embodiment of the embodiment of the present invention, it is noted that for the common skill of the art For art personnel, on the premise of principle of the embodiment of the present invention is not departed from, several improvements and modifications can also be made, these improvement The protection domain of the embodiment of the present invention is also considered as with retouching.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.The embodiment of the present invention be not limited to Under specific embodiment.In the range of claim is not changed, implementation can be suitably changed.
1st, the fat polymerization reaction of double (4- hydroxyls naphthoxy) phenyl phosphine oxides
Equipped with agitating paddle, thermometer, nitrogen ingress pipe and reflux condensing tube, on be terminated with HCl device for absorbing tail gas 374.5g 1,4- bisnaphthols and 70.8g xylene solvents are added in 2000ml three-necked flasks.It is slowly added dropwise under stiring 162.4g phenylphosphonyl dichlorides, then pass to nitrogen, 6h liquid separations while hot after reaction are reacted at 130 DEG C, then with 50 DEG C Excessive Isosorbide-5-Nitrae-the bisnaphthol of hot water washing three times, then is positioned over drying in 80 DEG C of vacuum drying chambers and obtains white powder for 24 hours, after grinding Double (the 4- hydroxyls naphthoxy) phenyl phosphine oxides of last shape solid.
By double (4- hydroxyls naphthoxy) phenyl phosphine oxide, 213g paraphthaloyl chlorides and the 1500g pyridines of 350g in equipped with stirring Device, condensing reflux pipe, thermometer four-necked bottle in stir, while be passed through nitrogen, be then warming up to 30 DEG C, react at this temperature 4h.Then 15g phenol is added in reaction system again, equally reacts 2h at this temperature.Product is cooled to room temperature and then is added in 5% sodium carbonate liquor, and be vigorously stirred, it filters, wash, dry, obtain product, number P-AE1.
Wherein n1=20.
2nd, the fat polymerization reaction of double (3- oxybenzenes oxygroup) phenyl phosphine oxides
By double (3- oxybenzenes oxygroup) phenyl phosphine oxide, 243.6g m-phthaloyl chlorides and the 1500g pyridines of 342g in equipped with stirring It mixes and is stirred in the four-necked bottle of device, condensing reflux pipe, thermometer, while be passed through nitrogen, be then warming up to 30 DEG C, at this temperature instead Answer 4h.Then 2, the 6- xylenols of 50g are added in reaction system again, equally react 2h at this temperature.Product is cooled down To room temperature and then 5% sodium carbonate liquor is added in, and is vigorously stirred, filters, wash, dry, obtain product, number P-AE2.
Wherein n1=10.
3rd, the fat polymerization reaction of double (4- oxybenzenes oxygroup) naphthalene phosphine oxides
By double (4- oxybenzenes oxygroup) naphthalene phosphine oxide, 285g paraphthaloyl chlorides and the 1500g pyridines of 392g in equipped with stirring Device, condensing reflux pipe, thermometer four-necked bottle in stir, while be passed through nitrogen, be then warming up to 30 DEG C, react at this temperature 4h.Then 120g p-t-butyl phenols are added in reaction system again, equally reacts 2h at this temperature.Product is cooled to room temperature Then 5% sodium carbonate liquor is added in, and is vigorously stirred, filters, wash, dry, obtains product, number P-AE3.
Wherein n1=5.
4th, the fat polymerization reaction of double (4- oxybenzenes oxygroup) methyl oxidation phosphines
By double (4- oxybenzenes oxygroup) methyl oxidation phosphine, 418g biphenyl dimethyl chloride and the 1500g pyridines of 280g in equipped with stirring Device, condensing reflux pipe, thermometer four-necked bottle in stir, while be passed through nitrogen, be then warming up to 30 DEG C, react at this temperature 4h.Then 216g p-methyl phenols are added in reaction system again, equally reacts 2h at this temperature.It is right that product is cooled to room temperature After add in 5% sodium carbonate liquor, and be vigorously stirred, filter, wash, dry, obtain product, number P-AE4.
Wherein n1=3.
5th, the fat polymerization reaction of double (4- oxybenzenes oxygroup) naphthalene phosphine oxides
By double (4- oxybenzenes oxygroup) the naphthalene phosphine oxides of 392g, the 2,6- naphthalenes dimethyl chloride of 506g and 1500g pyridines in equipped with Blender, condensing reflux pipe, thermometer four-necked bottle in stir, while be passed through nitrogen, be then warming up to 30 DEG C, at this temperature React 4h.Then 2, the 6- xylenols of 244g are added in reaction system again, equally react 2h at this temperature.Product is cold But arrive room temperature and then add in 5% sodium carbonate liquor, and be vigorously stirred, filter, wash, dry, obtain product, number P-AE5.
Wherein n1=1.
Above-mentioned active ester phosphonate resin, halogen-free epoxy resin and curing accelerator, halogen-free flame retardants, filler are pressed Certain proportion is uniformly mixed in solvent, and it is 65% to control glue solid content, impregnates above-mentioned glue with 2116 glass-fiber-fabrics, control is closed Then suitable thickness toasts 2~15min in 115~175 DEG C of baking oven and prepreg is made, several prepregs then are stacked in one It rises, is 170~250 DEG C in solidification temperature, solidifying pressure is 25~60kg/cm in the stacked on 18 μ RTF copper foils in its both sides2, cure Copper-clad plate is made under the conditions of being 60~300min in time.
Examples 1 to 9 and comparative example 1~8 are related to material and trade mark information is as follows：
(A) active ester phosphonate resin and reactive phosphonium flame retardant are made by oneself
P-AE1：Make double (4- hydroxyls naphthoxy) phenyl phosphine oxide resins of esterification modification by oneself
Wherein n1=20；
P-AE2：Make double (3- oxybenzenes oxygroup) phenyl phosphine oxide resins of esterification modification by oneself
Wherein n1=10；
P-AE3：Make double (4- oxybenzenes oxygroup) naphthalene phosphine oxide resins of esterification modification by oneself
Wherein n1=5；
P-AE4：Make double (4- oxybenzenes oxygroup) methyl oxidation phosphine resins of esterification modification by oneself
Wherein n1=3；
P-AE5：Make double (4- oxybenzenes oxygroup) naphthalene phosphine oxide resins of esterification modification by oneself
Wherein n1=1；
BHPPO：Double (4- oxybenzenes oxygroup) phenyl phosphine oxides
FRX-3001：
(B) cyanate
CY-40：Wuqiao resin factory, DCPD type cyanate ester resins
PT-60S：LONCZ, Novolac Cyanate Ester Resins
CE01PS：Jiangsu apocalypse, bisphenol A cyanate ester resin
CE01MO：Jiangsu apocalypse, bisphenol A cyanate ester resin
(C) 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
SKE-3：Shang Kete, special epoxy resin, epoxide equivalent 120
(D) phenolic resin
DOW92741：Phosphorus-containing phenolic aldehyde, DOW Chemical
2812：Linear phenolic resin, MOMENTIVE (South Korea)
(E)SMA
EF60：SMA, Sartomer
(F) phosphonium flame retardant
SPB-100：Great mound chemistry, phosphine nitrile fire retardant, phosphorus content 13.4%
(G) accelerating agent
2E4MZ：2-ethyl-4-methylimidazole, four countries' chemical conversion
DMAP：4-dimethylaminopyridine, wide Rong Huaxue
BICAT Z：Zinc Isoocatanoate, The Shepherd Chemical Company
(H) filler
Fused silica (average grain diameter is 1 to 10 μm, purity more than 99%)
Table 1 is Examples 1 to 9, and table 2 is the formula composition and its physical data of comparative example 1~8.
Table 1
Table 2
PCT/6h performance maps target remarks additionally：× 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 Pot in, under the conditions of 120 DEG C, 105KPa processing 6 it is small when after, be immersed in 288 DEG C of tin stove, 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 from the data comparison of Tables 1 and 2：
Comparative example 1 and embodiment 6 are compared and understood, using made by BHPPO and halogen-free epoxy resin in comparative example 1 Copper-clad plate dielectric properties are poor, poor heat resistance, water absorption rate are high and Tg is low, and the additive amount of phosphorus is higher；By comparative example 2 and in fact Apply example 5 and be compared and understand, in comparative example 2 using BHPPO and cyanate ester resin and halogen-free epoxy resin made by copper-clad plate Dielectric properties are poor, water absorption rate is high, humidity resistance is poor and Tg is low, and the additive amount of phosphorus is also higher；By comparative example 3 and embodiment 6 into Row is relatively understood, cures halogen-free epoxy resin using FRX3001 in comparative example 3, under the same terms, is lived since FRX3001 reacts The poor, OH of property-Content is low, and copper-clad plate can not be made；Comparative example 4 and embodiment 2 are compared and understood, is used in comparative example 4 FRX3001 and copper-clad plate dielectric properties made by the co-curing halogen-free epoxy resin of cyanate ester resin are poor, Tg is low, wet-heat resisting The poor, poor fire of property；Comparative example 5 and embodiment 9 are compared and understood, is total in comparative example 5 using FRX-3001 and SMA resins Same cured epoxy resin, heat resistance, humidity resistance, anti-flammability are all than the difference in embodiment 9, and Tg is low.
In addition, comparative example 6-7 is understood compared with embodiment 6, using content less than in embodiment 6 in comparative example 6 Active ester phosphonate resin when, due to curing agent deficiency, lead to not to be made plate, and high using content in comparative example 7 Made copper-clad plate Tg is low during active ester phosphonate resin in embodiment 6, heat resistance and humidity resistance are poor.
Further more, comparative example 8 is understood compared with embodiment 6, the active esters phosphine of low polymerization degree is used in comparative example 8 Acid ester resin, heat resistance are poorer than embodiment 6, and Tg is low.
By the above results as can be seen that by the way that BHPPO and FRX to be replaced with to active ester phosphonate tree of the invention Fat, and the control of its content is being accounted for the 20%~50% of epoxy resin and curing agent total weight, with the systems such as halogen-free epoxy resin Into prepreg and laminate for printed circuits, there is up to 235 DEG C of glass transition temperature；Excellent dielectric properties are inhaled Water rate is can be controlled in the range of 0.07%~0.13%；With high-fire resistance, excellent humidity resistance and the processing of good technique Property；Excellent flame retarding efficiency, phosphorus content can achieve the effect that UL94V-0 halogen-free flameproofs 1.5%.
In conclusion 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 halogen-free flameproofs.
The above is only presently preferred embodiments of the present invention, for those of ordinary skill in the art, can basis Technical scheme and technical concept make other various corresponding changes and deformation, and all these changes and deformation are all The scope of the claims in the present invention should be belonged to.

Claims (8)

1. a kind of compositions of thermosetting resin, which is characterized in that comprising epoxy resin and curing agent, the curing agent at least wraps Containing a kind of active ester phosphonate resin, structural formula such as formula (I) is shown；
Wherein, n1For 3~20 integer；
Wherein, n2For 0~5 integer；
Wherein, R1For any one in phenyl, naphthalene, the straight or branched alkyl containing carbon number 1~4；
Wherein, R2For any one in the straight or branched alkyl containing carbon number 1~4；
Wherein, Ar1、Ar2It is each independently selected from any one in following group：
The active ester phosphonate resin accounts for the compositions of thermosetting resin epoxy resin and curing agent total weight 20%~50%；
The epoxy resin accounts for the 30%~60% of the compositions of thermosetting resin epoxy resin and curing agent total weight.
2. compositions of thermosetting resin as described in claim 1, which is characterized in that the active ester phosphonate resin accounts for institute State the 20%~45% of compositions of thermosetting resin epoxy resin and curing agent total weight, preferably 25%~40%.
3. compositions of thermosetting resin as claimed in claim 1 or 2, which is characterized in that the curing agent also includes cyanate Resin and/or bismaleimide-triazine resin；
Preferably, the cyanate ester resin and/or bismaleimide-triazine resin account for the compositions of thermosetting resin middle ring The 0%~50% of oxygen resin and curing agent total weight.
4. the compositions of thermosetting resin as described in one of claims 1 to 3, which is characterized in that the curing agent also includes SMA Resin；
Preferably, the SMA resins account for the compositions of thermosetting resin epoxy resin and curing agent total weight 0%~ 40%.
5. the compositions of thermosetting resin as described in one of Claims 1 to 4, which is characterized in that the curing agent also includes phenol Urea formaldehyde；
Preferably, the phenolic resin account for the compositions of thermosetting resin epoxy resin and curing agent total weight 0%~ 20%.
6. the compositions of thermosetting resin as described in one of Claims 1 to 5, which is characterized in that the thermosetting resin combination Object also includes organic halogen-free flame retardants；
Preferably, the organic halogen-free agent is phosphonium flame retardant；
Preferably, the epoxy resin in the compositions of thermosetting resin and curing agent total amount are based on 100 parts by weight, organic Halogen The content of fire retardant is 0~15 parts by weight.
7. the compositions of thermosetting resin as described in one of claim 1~6, which is characterized in that the thermosetting resin combination Object also includes filler and/or accelerating agent.
8. the compositions of thermosetting resin as described in one of claim 1~7 is in resin sheet, resin laminated metal paper tinsel, preimpregnation Application in material, laminate, metal-clad laminate or printed wiring board.
CN201611081915.5A 2016-11-30 2016-11-30 A kind of compositions of thermosetting resin Expired - Fee Related CN108117632B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611081915.5A CN108117632B (en) 2016-11-30 2016-11-30 A kind of compositions of thermosetting resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611081915.5A CN108117632B (en) 2016-11-30 2016-11-30 A kind of compositions of thermosetting resin

Publications (2)

Publication Number Publication Date
CN108117632A true CN108117632A (en) 2018-06-05
CN108117632B CN108117632B (en) 2019-08-23

Family

ID=62226141

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611081915.5A Expired - Fee Related CN108117632B (en) 2016-11-30 2016-11-30 A kind of compositions of thermosetting resin

Country Status (1)

Country Link
CN (1) CN108117632B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1723243A (en) * 2002-11-08 2006-01-18 阿克苏诺贝尔公司 Epoxy resin composition containing reactive flame retardant phosphonate oligomer and filler
JP2015054868A (en) * 2013-09-10 2015-03-23 Dic株式会社 Phosphorus atom-containing active ester resin, epoxy resin composition, cured product of the same, prepreg, circuit board, and build-up film
WO2015096141A1 (en) * 2013-12-27 2015-07-02 广东生益科技股份有限公司 Thermosetting epoxy resin composition and use thereof
CN105153234A (en) * 2014-06-13 2015-12-16 广东生益科技股份有限公司 Phenoxy cyclotriphosphazene active ester, halogen free resin composition and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1723243A (en) * 2002-11-08 2006-01-18 阿克苏诺贝尔公司 Epoxy resin composition containing reactive flame retardant phosphonate oligomer and filler
JP2015054868A (en) * 2013-09-10 2015-03-23 Dic株式会社 Phosphorus atom-containing active ester resin, epoxy resin composition, cured product of the same, prepreg, circuit board, and build-up film
WO2015096141A1 (en) * 2013-12-27 2015-07-02 广东生益科技股份有限公司 Thermosetting epoxy resin composition and use thereof
CN105153234A (en) * 2014-06-13 2015-12-16 广东生益科技股份有限公司 Phenoxy cyclotriphosphazene active ester, halogen free resin composition and application thereof

Also Published As

Publication number Publication date
CN108117632B (en) 2019-08-23

Similar Documents

Publication Publication Date Title
JP7232915B2 (en) Thermosetting resin composition, and prepreg, metal foil clad laminate and printed circuit board containing the same
CN108164685B (en) A kind of compositions of thermosetting resin
CN107177030B (en) A kind of halogen-free thermosetting resin composite and prepreg and laminate for printed circuits using it
EP3093315B1 (en) Halogen-free epoxy resin composition, prepreg and laminate using same
CN105331053B (en) A kind of halogen-free resin composition and use its prepreg and laminate for printed circuits
CN105315615B (en) A kind of composition epoxy resin and the prepreg and copper-clad laminate using its making
CN103992622B (en) A kind of halogen-free resin composition and the prepreg using it and laminate for printed circuits
CN103013046B (en) Halogen-free flame retardant resin composition and use thereof
CN108250675A (en) A kind of phosphorous active ester and its halogen-free composition and copper clad foil substrate
CN105348742B (en) Compositions of thermosetting resin, prepreg and the laminate of the benzoxazine colophony containing melamine-type
CN109337289A (en) Compositions of thermosetting resin and prepreg, laminate and high-frequency circuit board containing it
CN108219371A (en) Composition epoxy resin, prepreg, laminate and printed circuit board
CN109988298A (en) A kind of modified polyphenylene ether resin, compositions of thermosetting resin and application thereof
CN108148178A (en) A kind of compositions of thermosetting resin
CN107227001B (en) A kind of halogen-free thermosetting resin composite and prepreg, laminate and printed circuit board containing it
CN105801814B (en) A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits
CN106893258B (en) A kind of composition epoxy resin and prepreg, laminate and printed circuit board containing it
CN108117723A (en) A kind of compositions of thermosetting resin and use its prepreg and laminate for printed circuits
CN105802128B (en) A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits
CN108117634B (en) A kind of compositions of thermosetting resin
CN108164684B (en) A kind of compositions of thermosetting resin
CN108219367A (en) A kind of halogen-free thermosetting resin composite, prepreg, laminate and printed wiring board containing it
CN108117633B (en) A kind of compositions of thermosetting resin
CN108976705A (en) A kind of halogen-free epoxy resin composition and prepreg and laminate using it
CN108117632B (en) A kind of compositions of thermosetting resin

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20190823