CN108164684A - A kind of compositions of thermosetting resin - Google Patents

A kind of compositions of thermosetting resin Download PDF

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Publication number
CN108164684A
CN108164684A CN201611114924.XA CN201611114924A CN108164684A CN 108164684 A CN108164684 A CN 108164684A CN 201611114924 A CN201611114924 A CN 201611114924A CN 108164684 A CN108164684 A CN 108164684A
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resin
compositions
thermosetting resin
epoxy resin
curing agent
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CN108164684B (en
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罗成
唐国坊
张江陵
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
    • 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
    • C08G59/62—Alcohols or phenols
    • 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

Abstract

The present invention provides a kind of compositions of thermosetting resin, it includes ester terminated phosphorous polymers, the compositions of thermosetting resin has many advantages, such as good thermal stability, humidity resistance, toughness, dielectric constant and dielectric loss angle tangent is low, water absorption rate is low and high halogen-free flameproof efficiency, and with excellent technique processability；The present invention also provides application of the compositions of thermosetting resin in resin sheet, resin laminated metal foil, 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 on July 1st, 2006, two parts of environmental protection instructions of European Union《It is instructed about electric/electronic device is scrapped》With《About In the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment》It is formal to implement, the exploitation of halogen-free flameproof copper-clad laminate As the hot spot of industry, each copper-clad laminate producer all releases the halogen-free flameproof copper-clad laminate of oneself one after another.
Phosphorus-containing compound is introduced in the resin matrix of copper-clad plate, becomes the main technological route of copper-clad plate halogen-free flameproof. Phosphorus flame retardant widely used on copper-clad plate field is broadly divided into two kinds of response type and addition type at present.Response type is mainly DOPO class compounds, based on phosphorous epoxy resin, phosphorus containing phenolic resin, phosphorus content is between 2~10%.However, practical should With middle discovery, DOPO classes compound has larger water absorption rate and poor dielectric properties and the plank humidity resistance poor.Addition type Predominantly phosphonitrile and phosphonate ester compound, the flame retarding efficiency of additive flame retardant is relatively low, and needing to add more amount could reach To flame-retardancy requirements.It is easy to migrate to plank in laminate process simultaneously because of its relatively low fusing point (generally below 150 DEG C) Surface influences plate property.
In addition, for copper clad foil substrate material, in order to meet the performance of PCB processing performances and terminal electronic product It is required that, it is necessary to have good dielectric properties, heat resistance and mechanical performance, while should also have good technique processing spy Property, high peel strength, excellent humidity resistance.
DOPO-HQ is the phosphorus curing agent of reactivity, can be cured and react with epoxy resin, but due to its activity Group is phenolic hydroxyl group, and the larger secondary hydroxyl of polarity can be generated after being reacted with epoxy resin, leads to the dielectric properties of solidfied material It is poor.The preparation method and its purposes of the active ester with the connection alkyl containing phospho hetero phenanthrene are disclosed in CN103965249A, but containing phospha Phenanthrene connection alkyl causes it slightly lower with Tg during epoxy resin cure, make its on High Tg CCL with being restricted. It is disclosed in CN105669760A using phenanthrene derivative containing phospha and the inactive ester type compound of glycerine synthesis, it can be to add The form added is fire-retardant to engineering material progress, and equally the Tg of reinforcing material is not contributed.It is mentioned in CN103694642A with poly- Phosphonate ester or/and phosphonate ester-carbonic ester and epoxy resin, cyanate ester resin blending prepare copper-clad plate.Polyphosphonates in this system Or/and phosphonate ester-carbonic ester has the heat resistance of system negative effect, and because of its phosphorus content as additive flame retardant Relatively low, flame retarding efficiency is low.
Invention content
Through inventor the study found that can be formed using ester terminated phosphorous polymer as epoxy resin and its curing agent Curing system addition fire retardant, but its higher fusing point and higher phosphorus content, relative to the phosphonic acids of common addition type Ester fire retardant has unrivaled advantage.More than feature is based on, without adding or only needing to add other fire retardants on a small quantity Plank is made to 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.There is high glass transition temperature using the laminate for printed circuits that the resin combination makes Degree, excellent dielectric properties, high-fire 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, as a result, it has been found that：By halogen-free epoxy resin, SMA resins and ester terminated phosphorous polymer 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, curing agent And ester terminated phosphorous polymer, wherein curing agent include at least SMA resins.
The compositions of thermosetting resin of the present invention is halogen-free thermosetting resin composite, with ester terminated phosphorous polymerization Halogen-free flame retardants of the object as the curing system of epoxy resin.Its phosphorus content is high, fusing point is high, is added in epoxy curing systems, Heat-resist, Tg high bittern-free flame-proof material can be obtained, need to only add on a small quantity or need not additionally add other fire retardants can It is fire-retardant to reach UL94V-0.
The present invention is by the use of high content of phosphorus, dystectic ester terminated phosphorous polymer as the fire-retardant of epoxy curing systems Agent can significantly improve the anti-flammability of the prepreg made using the resin combination and laminate for printed circuits, and The glass transition temperature and heat resistance of plank will not be reduced, and makes it have good technique processability, and realize halogen-free flameproof, is reached To UL94V-0.Each component is described in detail below.
According to the present invention, the ester terminated phosphorous polymer, shown in structural formula such as formula (I)：
Wherein, n1For 1~20 integer, for example, 1,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18, 19 or 20；
Wherein, R1For any one in phenyl, naphthalene, xenyl, the linear or branched alkyl group containing carbon number 1~4；Wherein Linear or branched alkyl group containing carbon number 1~4 for example can be methyl, ethyl, propyl, butyl, isopropyl, isobutyl group or tertiary butyl In any one；
Wherein, Ar1For In any one；
Wherein, Ar2ForIn any one；
Wherein, n2For 0~5 integer, such as 0,1,2,3,4 or 5；n3For 0~7 integer, such as 0,1,2,3,4,5,6 Or 7；
Wherein, R2For any one in the linear or branched alkyl group containing carbon number 1~4；The straight chain containing carbon number 1~4 Or branched alkyl for example can be any one in methyl, ethyl, propyl, butyl, isopropyl, isobutyl group or tertiary butyl.
Heretofore described ester terminated phosphorous polymer, structural formula can be such as lower structure：
Wherein, n1For 1~20 integer.
According to the present invention, the ester terminated phosphorous polymer account for the compositions of thermosetting resin epoxy resin, The 10%~35% of curing agent and ester terminated phosphorous polymer total weight, for example, 10%, 12%, 14%, 15%, 16%th, the specific point value between 18%, 20%, 22%, 25%, 28%, 30%, 32% or 35% and above-mentioned numerical value, is limited to Length and for it is concise the considerations of, the present invention specific point value that no longer range described in exclusive list includes.
According to the present invention, the epoxy resin accounts for the compositions of thermosetting resin epoxy resin, curing agent and ester Base sealing end phosphorous polymer total weight 30%~55%, such as 30%, 32%, 34%, 35%, 36%, 38%, 40%, 42%th, the specific point value between 45%, 48%, 50%, 52% or 55% and above-mentioned numerical value, as space is limited and for simplicity The considerations of, the present invention specific point value that no longer range described in exclusive list includes.
In the present invention, the epoxy resin is halogen-free epoxy resin, refer in 1 molecule tool there are two or two with The epoxy resin of upper epoxy group, selected from glycidol ethers, glycidol esters, glycidol amine, alicyclic epoxy tree In fat, epoxidation of olefins class, glycolylurea epoxide resin or acid imide epoxy resin any one or at least two mixture.
Preferably, the glycidol ethers include 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.Above-mentioned epoxy resin is the epoxy resin of Halogen.
Preferably, the glycidol ethers are selected from the epoxy resin having the following structure：
Wherein, Z1、Z2And Z3It is each independently selected fromR3For hydrogen atom, substitution or Any one in unsubstituted straight chained alkyl or branched alkyl containing carbon number 1~5.
Y1And Y2It is each independently selected from-CH2-、 In any one, n4It is 1~10 Arbitrary integer, such as 1,2,3,4,5,6,7,8,9 or 10, R4Straight chained alkyl or branch selected from hydrogen atom, containing carbon number 1~5 Any one in alkyl；Such as can be methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl group, tertiary butyl or different Any one in amyl.
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, two amido diphenyl-methanes of four glycidyl group -4,4`-, four shrinks are sweet Oil base -3,4`- diaminodiphenyl ethers, four glycidyl group -4,4`- diaminodiphenyl ethers 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 SMA resins may be used by styrene and maleic anhydride by 1:1~8:1 ratio copolymerization It obtains, preferably has the following structure：
Wherein a is 1~8 integer, such as 1,2,3,4,5,6,7 or 8；B be 5~40 integer, such as 5,8,10,12, 15th, 18,25,28,30,35 or 40.
According to the present invention, the SMA resins account for the compositions of thermosetting resin epoxy resin, curing agent and ester group The 35%~60% of the phosphorous polymer total weight of sealing end, for example, 35%, 37%, 38%, 40%, 42%, 45%, 48%, 50%th, the specific point value between 52%, 55%, 57%, 58% or 60% and above-mentioned numerical value, as space is limited and for simplicity The considerations of, the present invention specific point value that no longer range described in exclusive list includes.
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 the following structure：
Wherein, R13For-CH2-、 In any one or at least two mixture；R5、R6、R7、R8、R9、R10、R11Or R12It 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 bis- (the 4- cyanato-s phenyl) propane of 2,2-, bis- (4- cyanato-s phenyl) second Alkane, bis- (3,5- dimethyl -4- cyanato-s phenyl) methane, bis- (4- cyanato-s the phenyl) -1,1,1,3,3,3- hexafluoropropane of 2,2-, α, α '-bis- (4- cyanato-s phenyl)-diisopropyl benzene, Cyclopeutadiene type cyanate, phenol novolak type cyanate, cresol novolac Bis- (4- cyanato-s phenyl) the propane prepolymers of type cyanate, 2,2-, bis- (4- cyanato-s phenyl) ethane prepolymers, bis- (3,5- bis- Methyl -4- cyanato-s phenyl) methane prepolymer, bis- (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, preferably 2,2- Bis- (4- cyanato-s phenyl) propane, α, α '-bis- (4- cyanato-s phenyl)-diisopropyl benzene, bis- (3,5- dimethyl -4- cyanogen oxygen Base phenyl) methane, bis- (4- cyanato-s phenyl) the propane prepolymers of 2,2-, α, α '-bis- (4- cyanato-s phenyl)-diisopropyl benzene In prepolymer or bis- (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%~20% of object epoxy resin and curing agent total weight, for example, 0%, 2%, 4%, 5%, 8%, 10%, 12%, 14%th, the specific point value between 15%, 17% or 20% and above-mentioned numerical value, as space is limited and for it is concise the considerations of, this hair The specific point value that range described in bright no longer 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 range 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：Halogen Epoxy resin：30~55 parts by weight；35~60 parts by weight of SMA resins；Ester terminated phosphorous polymer：10~35 parts by weight； Cyanate ester resin and/or bismaleimide-triazine resin：0~20 parts by weight；Phenolic resin：0~20 parts by weight.
" the compositions of thermosetting resin epoxy resin, curing agent and ester terminated mentioned in the present invention In phosphorous polymer total weight ", curing agent refers to play the role of the SMA resins and optionally cyanate resin of cured epoxy resin Fat and/or bismaleimide-triazine resin and phenolic resin.
The compositions of thermosetting resin of the present invention can also include 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.
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 are 2,3- diaminos phenylpiperidines, 2,5- diaminos phenylpiperidines, 2,6- diamino piperazines Pyridine, 2- amino -3- methyl piperidines, 2- amino -4- methyl piperidines, 2- amino -3- nitros piperidines, 2- amino -5- nitros piperidines or In 2- amino -4,4- lupetidines any one or at least two mixture.
Preferably, the pyridine compounds and their is 4-dimethylaminopyridine, 2-aminopyridine, 3- aminopyridines or 4- amino Any one in pyridine or at least two mixtures.
Preferably, with ester terminated phosphorous polymer, epoxy resin and SMA resins and the cyanate resin that may be added Fat, phenolic resin the sum of additive amount be 100 parts by weight meters, the additive amount of the curing accelerator is 0.01~1 parts by weight, example 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 weight Part, 0.5 parts by weight, 0.8 parts by weight, 0.9 parts by weight or 1 parts by weight, 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, it is 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, silicon carbide, 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 ester terminated phosphorous polymer, epoxy resin and SMA resins and the cyanate resin that may be added Fat, phenolic resin the sum of additive amount be 100 parts by weight meters, the additive amount of the filler is 5~300 parts by weight, preferably 5~ 200 parts by weight, further preferred 5~150 parts by weight.
"comprising" of the present invention, it is intended that it can also include other components, these other components in addition to the component Assign the halogen-free thermosetting resin composite different characteristics.In addition to this, "comprising" of the present invention can also replace For enclosed " for " or " by ... form ".
For example, the halogen-free thermosetting resin composite can also contain various additives, as concrete example, can enumerate 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 enumerate 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 foils etc., material is unlimited.
Compared with prior art, the present invention at least has the advantages that：
The present invention is by the use of high content of phosphorus, dystectic ester terminated phosphorous polymer as the fire-retardant of epoxy curing systems Agent can significantly improve the flame retarding efficiency of the prepreg made using the resin combination and laminate for printed circuits, and And the glass transition temperature and heat resistance of plank will not be reduced, using made of halogen-free thermosetting resin composite provided by the invention Prepreg and laminate for printed circuits have up to 245 DEG C of glass transition temperature；Excellent dielectric properties, water absorption rate Control is in the range of 0.06-0.09%；High-fire resistance；Excellent humidity resistance and good technique processability；Excellent is fire-retardant Efficiency can reach UL94V-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, under 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.Do not changing in the scope of the claims, can suitably change implementation.
1st, the synthesis of phosphorous polymer P-AE1
By 320g ODOPB and 185g diphenylphosphoryl dichloros and 1.11g calcium chloride add in equipped with blender, condensing reflux pipe, It is stirred in the four-necked bottle of thermometer, while is passed through nitrogen, be then warming up to 160 DEG C, react 1.5h at this temperature.It then will be anti- Temperature rise is answered to 230 DEG C, and reacts 5h at this temperature.Then room temperature is reduced the temperature to, and adds in dichloromethane dissolving tree Fat, then 13.7g chlorobenzoyl chlorides are added in reaction system, 1.5h is reacted at this temperature.Then 5% sodium carbonate liquor is added in, and It is vigorously stirred, filters, washes, dries, obtain product, number P-AE1.
Wherein n1=20
2nd, the synthesis of phosphorous polymer P-AE2
By 370g 10- (2,5- dihydroxy naphthalene) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, 175g phenyl Phosphinylidyne dichloro and 1.11g calcium chloride in equipped with blender, condensing reflux pipe, thermometer four-necked bottle in stir, while be passed through nitrogen Then gas is warming up to 160 DEG C, reacts 1.5h at this temperature.Then 230 DEG C are warming up to, and 5h is reacted under logical condition of nitrogen gas. It is then cooled to room temperature, and adding in dichloromethane dissolves resin, then 2,4,6- trimethylbenzenes of 36.6g is added in reaction system Phenol equally reacts 2h at this temperature.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 synthesis of phosphorous polymer P-AE3
By 370g 10- (2,5- dihydroxy naphthalene) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, 195.6g naphthalenes Base phosphinylidyne dichloro and 1.11g calcium chloride in equipped with blender, condensing reflux pipe, thermometer four-necked bottle in stir, be passed through simultaneously Then nitrogen is warming up to 160 DEG C, reacts 2h at this temperature.Under logical condition of nitrogen gas, 230 DEG C are warming up to, and at this temperature React 5h.It is then cooled to room temperature, and adds in dichloromethane and dissolve resin.78.7g is added in tertiary butyl to reaction system again Chlorobenzoyl chloride equally reacts 2h at this temperature.Then 5% sodium carbonate liquor is added in, and is vigorously stirred, filters, wash, do It is dry, obtain product, number P-AE3.
Wherein n1=5
4th, the synthesis of phosphorous polymer P-AE4
By 320g ODOPB, 93.1g methyl phosphinylidyne dichloros and 1.11g calcium chloride in equipped with blender, condensing reflux pipe, temperature It spends in the four-necked bottle of meter and stirs, while be passed through nitrogen, be then warming up to 160 DEG C, react 1h at this temperature.In logical condition of nitrogen gas Under, 230 DEG C are warming up to, and react 5h at this temperature.It is then cooled to room temperature, adds in dichloromethane, dissolve resin, then to Reaction system adds in 92.76g to methyl benzoyl chloride, reacts 1h at this temperature.Then 5% sodium carbonate liquor is added in, and acute Strong stirring, filtering, washing, drying, obtains product, number P-AE4.
Wherein n1=3
5th, the synthesis of phosphorous polymer P-AE5
By 370g 10- (2,5- dihydroxy naphthalene) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, 79.8g methyl Phosphinylidyne dichloro and 1.11g calcium chloride in equipped with blender, condensing reflux pipe, thermometer four-necked bottle in stir, while be passed through nitrogen Then gas is warming up to 160 DEG C, reacts 1h at this temperature.Under logical condition of nitrogen gas, 230 DEG C are warming up to, and anti-at this temperature Answer 5h.It is then cooled to room temperature, and adds in dichloromethane and dissolve resin, then 152.5g 2- naphthalene formyls are added in reaction system Chlorine equally reacts 1h at this temperature.Product is cooled to room temperature and then adds in 5% sodium carbonate liquor, and be vigorously stirred, mistake Filter, washing, drying, obtain product, number P-AE5.
Wherein n1=1
By ester terminated phosphorous polymer P-AE, halogen-free epoxy resin, curing agent and curing accelerator, halogen-free flameproof Agent, filler are uniformly mixed in solvent by a certain percentage, and control glue solid content is 65%, impregnate above-mentioned glue with 2116 glass-fiber-fabrics Liquid controls suitable thickness, and 2~15min is then toasted in 115~175 DEG C of baking oven is made prepreg, then by several preimpregnation Material stacks, and is 170~250 DEG C in solidification temperature, solidifying pressure is 25~60kg/ in the stacked on 18 μ RTF copper foils in its both sides cm2, is copper-clad plate is made under the conditions of 60~300min in hardening time.
Embodiment 1~14 and comparative example 1~8 are related to material and trade mark information is as follows：
(A) phosphorous polymer P-AE fire retardants are made by oneself
P-AE1：Make phosphorous polymer P-AE1 fire retardants by oneself
Wherein n1=20.
P-AE2：Make phosphorous polymer P-AE2 fire retardants by oneself
Wherein n1=10.
P-AE3：Make phosphorous polymer P-AE3 fire retardants by oneself
Wherein n1=5.
P-AE4：Make phosphorous polymer P-AE4 fire retardants by oneself
Wherein n1=3.
P-AE5：Make phosphorous polymer P-AE5 fire retardants by oneself
Wherein n1=1.
ODOPB：10- (2,5- dihydroxy phenyls) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides
FRX-3001：
(B) epoxy resin
HP-7200HHH：DIC, DCPD type epoxy resin, epoxide equivalent 288
HP-7200H-75M：DIC, DCPD type epoxy resin, epoxide equivalent 280
HP-6000：DIC, epoxy resin, epoxide equivalent 250
HP-9900：DIC, naphthol type epoxy resin, epoxide equivalent 274
NC-3000H：Japanese chemical drug, biphenyl epoxy resin, epoxide equivalent 294
SKE-1：Shang Kete, special epoxy resin, epoxide equivalent 120
SKE-3：Shang Kete, special epoxy resin, epoxide equivalent 120
(C) SMA resins
EF1000：SMA, styrene-maleic anhydride copolymer, Sartomer
EF40：SMA, styrene-maleic anhydride copolymer, Sartomer
EF60：SMA, styrene-maleic anhydride copolymer, Sartomer
EF80：SMA, styrene-maleic anhydride copolymer, Sartomer
(D) cyanate
CY-40：Wuqiao resin factory, DCPD type cyanate ester resins
PT60S：LONCZ, Novolac Cyanate Ester Resins
CE01PS：Jiangsu apocalypse, bisphenol A cyanate ester resin
CE01MO：Jiangsu apocalypse, bisphenol A cyanate ester resin
(E) 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)
(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 0.2 to 10 μm, more than 99% purity)
Table 1-3 is embodiment 1~14, the formula composition and its physical data of 4 comparative example 1~8 of table.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
P-AE1 10
P-AE2 20
P-AE3 35
P-AE4 10 10
P-AE5 10
EF1000 35 35
EF40 40
EF60 50
EF80 60
HP-9900 55
NC-3000H 30 40 30
SKE-1 30
SPB-100 10 10
2E4MZ
DMAP 0.01 0.05 0.1 0.2 0.5
Ball silicon 0 25 25 25 300
P% 3.49% 2.31% 2.10% 2.37% 2.44%
Tg(DMA)/℃ 185 190 185 190 185
Dk(10GHz) 4 4 3.9 3.8 4.2
Df(10GHz) 0.008 0.0075 0.0075 0.0075 0.0071
Water imbibition/% 0.08 0.07 0.07 0.07 0.05
PCT/6h OOO OOO OOO OOO OOO
T288/min ＞ 60 ＞ 60 ＞ 60 ＞ 60 ＞ 60
Difficult to burn V-0 V-0 V-0 V-0 V-0
Table 2
Table 3
Table 4
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 In pot, after being handled 6 hours under the conditions of 120 DEG C, 105KPa, it is immersed in 288 DEG C of tin stove, is recorded when substrate de-lamination plate bursting The corresponding time；It can terminate to evaluate when substrate also does not occur blistering or being layered in tin stove more than 5min.
(4)T288：With TMA instrument, it is measured according to the T300 test methods of IPC-TM-650 2.4.24.1 defineds.
(5) water imbibition：Water imbibition test method according to IPC-TM-650 2.6.2.1 defineds is measured.
(6) anti-flammability：It is carried out according to 94 standard methods of UL.
The following is can be seen that from the data comparison of table 1-4：
Comparative example 1 and embodiment 3 compare, using made by ODOPB, SMA resin and halogen-free epoxy resin in comparative example 1 Copper-clad plate dielectric properties are poor, heat resistance and humidity resistance are poor, water absorption rate is high and poor fire；Comparative example 2 and embodiment 7 Compare, in comparative example 2 using the copper-clad plate Tg made by ODOPB, SMA resin and cyanate ester resin and halogen-free epoxy resin it is low, Water absorption rate is high, heat resistance and humidity resistance are poor, and poor fire；Comparative example 3 and embodiment 12 compare, and make in comparative example 3 With copper-clad plate water absorption rate height, heat resistance and the wet-heat resisting made by ODOPB, SMA resin and phenolic resin and halogen-free epoxy resin Property is poor；Comparative example 4 and embodiment 3 compare, using made by FRX3001 and SMA resins and halogen-free epoxy resin in comparative example 4 Copper-clad plate dielectric properties are poor, water absorption rate is high, heat resistance and humidity resistance are poor, and Tg is low, and poor fire；Comparative example 5 and reality It applies example 7 to compare, covers copper using made by FRX3001, SMA resin and cyanate ester resin and halogen-free epoxy resin in comparative example 5 Plate Tg is low, water absorption rate is high, heat resistance and humidity resistance are poor, and poor fire；Comparative example 6 and embodiment 12 compare, comparison FRX3001, SMA resin and copper-clad plate water absorption rate made by phenolic resin and halogen-free epoxy resin is high, heat resistance and resistance in example 6 Humid is poor.
In addition, comparative example 7 and embodiment 5 are compared it is found that using content less than in embodiment 5 in comparative example 7 During ester terminated phosphorous polymer, made by copper-clad plate dielectric properties it is poor；Comparative example 8 and embodiment 1 are compared Compared with it is found that in comparative example 8 using content higher than ester terminated phosphorous polymer in embodiment 1 when, made by cover copper Plate Tg is low, heat resistance and humidity resistance are poor.
By the above results as can be seen that by the way that ODOPB and FRX to be replaced with to ester terminated phosphorous polymerization of the invention Object, with SMA resins and halogen-free epoxy resin etc. made of prepreg and laminate for printed circuits, there are up to 245 DEG C Glass transition temperature；Excellent dielectric properties, water absorption rate are controlled in the range of 0.06-0.09%；High-fire resistance；Excellent is resistance to Humid and good technique processability；Excellent flame retarding efficiency can reach UL94 V-0.
As described above, compared with general laminate, made of halogen-free thermosetting resin composite provided by the present invention Prepreg and laminate for printed circuits are heat-resisting with high glass-transition temperature, excellent dielectric properties, low water absorption, height Property, excellent humidity resistance and good technique processability, and can realize halogen-free flameproof, reach UL94 V-0.
The above, only presently preferred embodiments of the present invention, for those of ordinary skill in the art, can basis Technical scheme of the present invention and technical concept make other various corresponding changes and deformation, and all these changes and deformation are all The range 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 include epoxy resin, curing agent and ester terminated phosphorous poly- Close object；
The curing agent includes at least SMA resins；
Shown in the ester terminated phosphorous polymer structural formula such as formula (I)；
Wherein, n1For 1~20 integer；
Wherein, R1For any one in phenyl, naphthalene, xenyl, the linear or branched alkyl group containing carbon number 1~4；
Wherein, Ar1For In any one；
Wherein, Ar2ForIn any one；
Wherein, n2For 0~5 integer；n3For 0~7 integer；
Wherein, R2For any one in the linear or branched alkyl group containing carbon number 1~4；
The epoxy resin accounts for the compositions of thermosetting resin epoxy resin, curing agent and ester terminated phosphorous polymerization The 30%~55% of object total weight；
The SMA resins account for the compositions of thermosetting resin epoxy resin, curing agent and ester terminated phosphorous polymerization The 35%~60% of object total weight；
The ester terminated phosphorous polymer accounts for the compositions of thermosetting resin epoxy resin, curing agent and ester group envelope The 10%~35% of the phosphorous polymer total weight at end.
2. compositions of thermosetting resin as described in claim 1, which is characterized in that the SMA resins are styrene and Malaysia Acid anhydrides presses 1:1~8:1 ratio is copolymerized to obtain.
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.
4. compositions of thermosetting resin as claimed in claim 3, which is characterized in that the cyanate ester resin and/or span come Acid imide-cyanate resin accounts for the 0%~20% of the compositions of thermosetting resin epoxy resin and curing agent total weight.
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.
6. compositions of thermosetting resin as claimed in claim 5, which is characterized in that the phenolic resin accounts for the thermosetting property tree The 0%~20% of oil/fat composition epoxy resin and curing agent total 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 foil, preimpregnation Application in material, laminate, metal-clad laminate or printed wiring board.
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