CN108117633A - A kind of compositions of thermosetting resin - Google Patents

A kind of compositions of thermosetting resin Download PDF

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Publication number
CN108117633A
CN108117633A CN201611080924.2A CN201611080924A CN108117633A CN 108117633 A CN108117633 A CN 108117633A CN 201611080924 A CN201611080924 A CN 201611080924A CN 108117633 A CN108117633 A CN 108117633A
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resin
compositions
thermosetting resin
curing agent
epoxy resin
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CN108117633B (en
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罗成
唐国坊
许永静
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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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • 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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The present invention provides a kind of compositions of thermosetting resin, it includes phosphorous acid anhydrides, the compositions of thermosetting resin has good thermal stability, humidity resistance, toughness, dielectric constant and dielectric loss angle tangent is low, water absorption rate is low and the advantages that 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 and UL94 V-0 halogen-free flameproof ranks.
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 UL94 V-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 with phosphorous acid anhydrides, i.e., double hydroxyl fragrance oxygroup alkyl phosphine oxides of acid anhydrides sealing end are as ring The curing agent of oxygen resin will not generate polarity big secondary hydroxyl when being reacted with epoxy resin, the dielectric properties for making system are preferable, Simultaneously because itself being phosphorous active curing agent, there is the effect of halogen-free flameproof while as curing agent, need to only lack Amount is added or need not add other fire retardants can just make plate achieve the effect that UL94 V-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 good technique processability, and can realize halogen-free flameproof, reach UL94 V-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, Double hydroxyl fragrance oxygroup alkyl phosphine oxides of acid anhydrides sealing end and the composition that optionally other curing agent are suitably mixed to get, can reach Above-mentioned purpose.
That is, the present invention adopts the following technical scheme that：A kind of compositions of thermosetting resin, it includes epoxy resin and curings Agent, wherein curing agent include at least double hydroxyl fragrance oxygroup alkyl phosphine oxides of a kind of phosphorous acid anhydrides, i.e. acid anhydrides sealing end.
The compositions of thermosetting resin of the present invention is using double hydroxyl fragrance oxygroup alkyl phosphine oxides of acid anhydrides as epoxy resin Curing agent.Active ester groups content wherein as active group is high, can with to obtain crosslink density after epoxy resin cure big Solidfied material, heat-resist, Tg high material can be obtained；And double hydroxyl fragrance oxygroup alkyl phosphine oxide structures pair of acid anhydrides Title property is high, and the active ester units in molecule can be eliminated with that will not generate the big secondary hydroxyl of polarity after epoxy resin reaction The shortcomings that poor dielectric performance that the big secondary hydroxyl of polarity is brought, make dielectric properties excellent；Double hydroxyl fragrance oxygen of the acid anhydrides Base alkyl phosphine oxide is active ester, and ester bond its water absorption rate generated after being reacted with epoxy resin is low, makes to which improve phosphorous chemical combination The shortcomings that object humidity resistance is poor.In addition, double hydroxyl fragrance oxygroup alkyl phosphine oxides of acid anhydrides can have the effect of halogen-free flameproof, only It need to add on a small quantity or without additionally can to reach UL94 V-0 fire-retardant for addition fire retardant.
The present invention, can be notable using the active ester group of double hydroxyl fragrance oxygroup alkyl phosphine oxides of high symmetrical acid anhydrides 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 UL94 V-0.Each component is described in detail below.
According to the present invention, shown in the structural formula such as formula (I) of the phosphorous acid anhydrides：
Wherein, R1ForNaphthalene, containing carbon number be 1~4 straight or branched alkyl in any one；Its In the straight or branched alkyl containing carbon number 1~4 for example can be methyl, ethyl, propyl, butyl, isopropyl, isobutyl group or tertiary fourth Any one in base；
Wherein, n1For 0~5 integer, such as 0,1,2,3,4 or 5；
Wherein, R3For be 1~4 containing carbon number straight or branched alkyl in any one；Wherein containing the straight of carbon number 1~4 Chain or branched alkyl for example can be any one in methyl, ethyl, propyl, butyl, isopropyl, isobutyl group or tertiary butyl；
Wherein, R2Any one in following group：
Wherein, any one of Ar in following group：
Double hydroxyl fragrance oxygroup alkyl phosphine oxides of acid anhydrides sealing end in the present invention, structural formula can be such as lower structure：
According to the present invention, the phosphorous acid anhydrides accounts for the compositions of thermosetting resin epoxy resin and curing agent total weight 20%~60%, such as 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%th, the specific point value between 48%, 50%, 52%, 55%, 58% or 60% and above-mentioned numerical value, as space is limited and for The considerations of concise, the present invention specific point value that no longer scope described in exclusive list includes.
In the present invention, the phosphorous acid anhydrides preferably accounts for the compositions of thermosetting resin epoxy resin and curing agent gross weight The 20%~45% of amount, 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 fromR4Selected 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, third Any one in base, butyl, amyl, isopropyl, isobutyl group, tertiary butyl or isopentyl；
Wherein, Y1And Y2It is each independently selected from-CH2-、 In any one；R5It is former selected from hydrogen Any one in sub, substituted or unsubstituted straight chained alkyl or branched alkyl containing carbon number 1~5；Such as can be methyl, second Any one in base, propyl, butyl, amyl, isopropyl, isobutyl group, tertiary butyl or isopentyl；
Wherein, n2For 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 thermal curing agents can also include cyanate ester resin and/or bismaleimide-triazine tree Fat；Wherein, the cyanate ester resin has such as lower structure：
Wherein, R14For-CH2-、 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, 0%, 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 0%, 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 0%, 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：Acid anhydrides Double hydroxyl fragrance oxygroup alkyl phosphine oxides of sealing end：20~60 parts by weight；Halogen-free epoxy resin：30~60 parts by weight；Cyanate resin Fat and/or bismaleimide-triazine resin：0~50 parts by weight；SMA resins：0~40 parts by weight；Phenolic resin：0~20 weight Measure part.
" 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 play the role of the acid anhydrides sealing end of cured epoxy resin Double hydroxyl fragrance oxygroup alkyl phosphine oxides and optionally cyanate ester resin and/or bismaleimide-triazine resin, SMA resins Or phenolic resin, do not 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, can specifically be selected from phosphor-containing flame-proof Agent.
According to the present invention, the phosphonium flame retardant is selected from 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 In 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 is aoxidized by double hydroxyl fragrance oxygroup alkyl of acid anhydrides sealing end Phosphine, epoxy resin and the cyanate ester resin that may be added, SMA resins, the sum of the additive amount of phenolic resin are 100 parts by weight meters, The additive amount of organic halogen-free agent 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 weight Tool between part, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight or 15 parts by weight and above-mentioned numerical value Body point 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 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, added with phosphorous acid anhydrides, epoxy resin and the cyanate ester resin that may be added, SMA resins, phenolic resin The sum of dosage 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 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, added with phosphorous acid anhydrides, epoxy resin and the cyanate ester resin that may be added, SMA resins, phenolic resin The sum of dosage is 100 parts by weight meters, and the additive amount of the filler is 5~300 parts by weight, preferably 5~200 parts by weight, further It is preferred that 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, have made of halogen-free thermosetting resin composite provided by the present invention Up to 215 DEG C of glass transition temperature；Excellent dielectric properties, water absorption rate are controlled in the range of 0.06~0.1%；It is high heat-resisting Property；Excellent humidity resistance and good technique processability；Excellent flame retarding efficiency, P content 1.98% can reach UL94 V-0。
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 synthesis of phosphorous acid anhydrides P-A1
By double (4- oxybenzenes oxygroup) the methyl oxidation phosphines of 280g, the 1,2,4- Trimellitic Anhydride Chlorides of 425g 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, herein At a temperature of react 4h.Product is cooled to room temperature and then adds in 5% sodium carbonate liquor, and is vigorously stirred, filters, wash, dry, Obtain product, number P-A1.
2nd, the synthesis of phosphorous acid anhydrides P-A2
By double (the 4- hydroxyls biphenylyloxy) phenyl phosphine oxides of 494g, the 1,2,4- Trimellitic Anhydride Chlorides of 425g and 1500g pyrroles Pyridine 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, 4h is reacted at a temperature of this.Product is cooled to room temperature and then adds in 5% sodium carbonate liquor, and is vigorously stirred, filters, wash, do It is dry, obtain product, number P-A2.
3rd, the synthesis of phosphorous acid anhydrides P-A3
By double -2 (the 7- hydroxyls naphthoxy) phenyl phosphine oxides of 442g, the 1,2,4- Trimellitic Anhydride Chlorides of 425g and 1500g pyrroles Pyridine 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, 4h is reacted at a temperature of this.Product is cooled to room temperature and then adds in 5% sodium carbonate liquor, and is vigorously stirred, filters, wash, do It is dry, obtain product, number P-A3.
4th, the synthesis of phosphorous acid anhydrides P-A4
By double (the hydroxyl fluorenes oxygroup) phenyl phosphine oxides of 830g, the 1,2,4- Trimellitic Anhydride Chlorides of 425g 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, it is warm herein The lower reaction 4h of degree.Product is cooled to room temperature and then adds in 5% sodium carbonate liquor, and is vigorously stirred, filters, wash, dry, obtain To product, number P-A4.
5th, the synthesis of phosphorous acid anhydrides P-A5
By double (3- oxybenzenes the oxygroup) -4- aminomethyl phenyls phosphine oxides of 356g, 520g 7- formyl chloro -2,3- naphthoic acids acid anhydrides 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, 4h is reacted at this temperature.Product is cooled to room temperature and then adds in 5% sodium carbonate liquor, and is vigorously stirred, filtering, Washing, drying, obtain product, number P-A5.
By above-mentioned phosphorous acid anhydrides P-A, halogen-free epoxy resin and curing accelerator, halogen-free flame retardants, filler by certain ratio Example is uniformly mixed in solvent, and it is 65% to control glue solid content, impregnates above-mentioned glue with 2116 glass-fiber-fabrics, is controlled suitable thick Then degree toasts 2~15min in 115~175 DEG C of baking oven and prepreg is made, then stacks several prepregs, The stacked on 18 μ RTF copper foils in its both sides are 170~250 DEG C in solidification temperature, and solidifying pressure is 25~60kg/cm2, hardening time is Copper-clad plate is made under the conditions of 60~300min.
Embodiment 1~17 and comparative example 1~7 are related to material and trade mark information is as follows：
(A) phosphorous acid anhydrides P-A
P-A1：Make phosphorous acid anhydrides P-A by oneself
P-A2：Make phosphorous acid anhydrides P-A by oneself
P-A3：Make phosphorous acid anhydrides P-A by oneself
P-A4：Make phosphorous acid anhydrides P-A by oneself
P-A5：Make phosphorous acid anhydrides P-A by oneself
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
SEB-0904PM60：Phosphorus-containing phenolic aldehyde, SHIN-A
SHN-1655TM65：Phosphorus-containing phenolic aldehyde, SHIN-A
2812：Linear phenolic resin, MOMENTIVE (South Korea)
(E) phosphonium flame retardant
SPB-100：Great mound chemistry, phosphine nitrile fire retardant, phosphorus content 13.4%
(F)SMA
1000P：SMA, Sartomer
EF40：SMA, Sartomer
EF60：SMA, Sartomer
EF80：SMA, Sartomer
(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 1-4 is embodiment 1~17, and table 5 is the formula composition and its physical data of comparative example 1~7.
Table 1
Table 2
Table 3
Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13
P-A1 40
P-A2 50
P-A3
P-A4 60
P-A5 20
DOW92741 10
SEB-0904PM60 15
SHN-1655TM65 20
2812 5
HP-6000 55
HP-9900
NC-3000H 60
SKE-1 30
SKE-3 35
2E4MZ 0.1
Ball silicon 0 50 100 300
P% 2.58% 3.34% 2.17% 1.98%
Tg(DMA)/℃ 190 188 180 178
Dk(10GHz) 3.8 3.8 3.8 3.8
Df(10GHz) 0.0072 0.0072 0.0078 0.0072
Water imbibition/% 0.08 0.08 0.075 0.08
PCT/6h OOO OOO OOO OOO
T288/min ＞ 60 ＞ 60 ＞ 60 ＞ 60
Difficult to burn V-0 V-0 V-0 V-0
Table 4
Table 5
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 table 1-5：
Comparative example 1 and embodiment 2 compare, and are situated between in comparative example 1 using the copper-clad plate made by BHPPO and halogen-free epoxy resin Electrical property is poor, heat resistance and humidity resistance are poor, Tg is low, and water absorption rate is high；Comparative example 2 and embodiment 6 compare, and make in comparative example 2 With the copper-clad plate dielectric properties made by BHPPO and cyanate ester resin and halogen-free epoxy resin are poor, water absorption rate is high, heat resistance and Humidity resistance difference and Tg are low；Comparative example 3 and embodiment 2 compare, and cure halogen-free epoxy resin, phase using FRX3001 in comparative example 3 With under the conditions of, since FRX3001 reactivities are weak, OH-Content is low, and copper-clad plate can not be made；Comparative example 4 and embodiment 6 compare, In comparative example 4 using FRX3001 and the copper-clad plate dielectric properties made by the co-curing halogen-free epoxy resin of cyanate ester resin compared with Difference, Tg is low, humidity resistance is poor, poor fire；Comparative example 5 and embodiment 14 compare, and are total in comparative example 5 with FRX-3001 and SMA Same cured epoxy resin, under the same terms, since FRX3001 reactivities are weak, OH-Content is low, and copper-clad plate can not be made.
In addition, comparative example 6 is understood compared with embodiment 1, using content higher than in embodiment 1 in comparative example 6 Acid anhydrides sealing end double hydroxyl fragrance oxygroup alkyl phosphine oxides when, made by copper-clad plate heat resistance and humidity resistance it is poor, Tg is low；It will Comparative example 7 is understood compared with embodiment 1, using content less than double hydroxyls virtue that the acid anhydrides in embodiment 1 blocks in comparative example 7 During fragrant oxygroup alkyl phosphine oxide, made by copper-clad plate humidity resistance is poor, poor fire.
By the above results as can be seen that the double hydroxyls fragrance blocked by the way that BHPPO and FRX to be replaced with to the acid anhydrides of the present invention Oxygroup alkyl phosphine oxide, with halogen-free epoxy resin etc. made of prepreg and laminate for printed circuits, there are up to 215 DEG C Glass transition temperature；Excellent dielectric properties, water absorption rate are controlled in the range of 0.06~0.1%；High-fire resistance；Excellent Humidity resistance and good technique processability；Excellent flame retarding efficiency, P content 1.98% can reach UL94 V-0.
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 UL94 V-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, wherein curing agent at least wraps Containing a kind of phosphorous acid anhydrides, structural formula such as formula (I) is shown；
Wherein, R1ForAny one in naphthalene, the straight or branched alkyl containing carbon number 1~4；
Wherein, n1For 0~5 integer；
Wherein, R3For any one in the straight or branched alkyl containing carbon number 1~4；
Wherein, R2Any one in following group：
Wherein, any one of Ar in following group：
The phosphorous acid anhydrides accounts for the 20%~60% of the compositions of thermosetting resin epoxy resin and curing agent total weight；
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 phosphorous acid anhydrides accounts for the thermosetting property tree The 20%~45% of oil/fat composition 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.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114605779A (en) * 2020-12-09 2022-06-10 广东生益科技股份有限公司 Thermosetting resin composition, prepreg containing thermosetting resin composition, circuit substrate and printed circuit board

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114605779A (en) * 2020-12-09 2022-06-10 广东生益科技股份有限公司 Thermosetting resin composition, prepreg containing thermosetting resin composition, circuit substrate and printed circuit board
CN114605779B (en) * 2020-12-09 2023-09-12 广东生益科技股份有限公司 Thermosetting resin composition, prepreg comprising thermosetting resin composition, circuit substrate and printed circuit board

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