CN107177030A - A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits - Google Patents

A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits Download PDF

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CN107177030A
CN107177030A CN201610137438.3A CN201610137438A CN107177030A CN 107177030 A CN107177030 A CN 107177030A CN 201610137438 A CN201610137438 A CN 201610137438A CN 107177030 A CN107177030 A CN 107177030A
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parts
weight
halogen
phenyl
substituted
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CN107177030B (en
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罗成
唐国坊
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN201610137438.3A priority Critical patent/CN107177030B/en
Priority to PCT/CN2016/098450 priority patent/WO2017152602A1/en
Priority to TW105131954A priority patent/TWI619766B/en
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    • 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
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    • 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
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    • 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
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • 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
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    • 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
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    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
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    • 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
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    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
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    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
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    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
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    • C08L2201/22—Halogen free composition

Abstract

The present invention relates to a kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits.The halogen-free thermosetting resin composite, Organic sulfides include the parts by weight of (A) cyanate ester resin 5~50 based on 100 parts by weight；(B) 5~40 parts of polyphenylene oxide resin；(C) the phosphorous parts by weight of bis-phenol polymer 5~30；(D) parts by weight of halogen-free epoxy resin 30~60.Prepreg and laminate for printed circuits that halogen-free thermosetting resin composite provided by the present invention is made, with high glass-transition temperature, excellent dielectric properties, low water absorption, high-fire resistance, high peel strength, excellent humidity resistance and good technique processability, and halogen-free flameproof can be realized, reach UL94 V 0.

Description

A kind of halogen-free thermosetting resin composite and prepreg and printed circuit use using it Laminate
Technical field
The present invention relates to a kind of halogen-free thermosetting resin composite, further relate to what the halogen-free thermosetting resin composite was made Prepreg and laminate for printed circuits.
Background technology
Traditional laminate for printed circuits generally realized using bromide fire retardant it is fire-retardant, especially with tetrabromobisphenol A type epoxy resin, this brominated epoxy resin has good anti-flammability, but it can produce 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 《On scrapping electric/electronic device instruction》With《ROHS》Just Formula is implemented, the focus for being developed into industry of halogen-free flameproof copper-clad laminate, and each copper-clad laminate producer all releases one after another The halogen-free flameproof copper-clad laminate of oneself.
Simultaneously with the high speed and multifunction of consumption electronic product information processing, applying frequency is improved constantly, except Outside the requirement more and more higher of environmental protection, it is desirable to which dielectric constant and dielectric loss value are more and more lower, therefore reduction Dk/Df turns into substrate Dealer's chases focus.
In addition, for copper clad foil substrate material, in order to meet the performance of PCB processing characteristicies 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 special Property, high peel strength, excellent humidity resistance and UL94V-0 halogen-free flameproof ranks.
Disclose and be blended using cyanate, epoxy resin, polyphenylene oxide resin and brominated flame-retardant in CN101796132A To heat resistance, dielectric properties are good, low CTE copper-clad plate, but it is brominated fire-retardant；Use is disclosed in patent CN103694642A Epoxy resin, cyanate esters or/and cyanate prepolymer, polyphosphonates or/and phosphonate ester-carbonate copolymer are prepared for The good Halogen UL94V-0 of dielectric properties, humidity resistance is fire-retardant, but its peel strength, interlayer adhesion and bending strength are relatively low.
It is well known that thering is multiple material to possess low dielectric constant, Dielectric loss tangent value characteristic at present, such as：Polyolefin, Fluororesin, polystyrene, polyphenylene oxide, Noryl, bismaleimide-triazine resin, polyvinyl benzene resin.Set above Although fat is with good dielectric properties, all there is technique difficult processing, poor heat resistance, the defect such as peel strength difference, it is impossible to Meet the requirement of high-frequency high-speed copper clad foil substrate.
The content of the invention
Through inventor study find, with cyanate, polyphenylene oxide, phosphorous bis-phenol polymer collectively as epoxy resin solidification Agent, respective advantage can be embodied in system and the effect of mutual catalyzing cooperation occurs.Cyanate can bring the high resistance to of system Hot and low dielectric loss value；Polyphenylene oxide can make system have excellent dielectric properties；Phosphorous bis-phenol polymer reaction group bag Two terminal hydroxy groups and phosphonate unit are included, phosphonate unit does not produce secondary hydroxyl, solidfied material glass transition temperature with epoxy reaction Degree is high, dielectric properties and excellent heat resistance.These three epoxy curing agent collective effects can also make system have excellent resist Peel strength.
In addition, the catalyst that cyanate can react as polyphenylene oxide and bis-phenol polyphosphoric acid with epoxy resin.Polyphenylene oxide and double The phenolic hydroxyl group reactivity of phenol polyphosphoric acid is very low, can just be reacted at very high temperatures with epoxy resin, and cyanate- OCN groups are just easy to react with the low activity hydroxyl of both of the above at 90~120 DEG C, then have hair more than 130 DEG C Solution estranged, can produce phenol negative oxygen ion in decomposable process.Phenol negative oxygen ion is easily reacted with epoxy resin, so as to reduce system Solidification temperature.The phenolic hydroxyl group in polyphenylene oxide and bis-phenol polyphosphoric acid can promote cyanate to solidify well simultaneously, reduce cyanate Solidification temperature, and cyanate is solidify to form the triazine ring that crosslink density is big, symmetry is high so that system have it is high The dielectric properties that glass transition temperature is become reconciled.There is more flexible chain ester chain in phosphorous bis-phenol polymer, system can be made Toughness improves a lot, and is embodied in peel strength.And phosphorus content is high in phosphorous bis-phenol polymer, as solidification There is effect of halogen-free flameproof while agent, can add on a small quantity or without can just reach sheet material in the other fire retardants of addition The effect of UL94V-0 halogen-free flameproofs.
Based on this, an object of the present invention is to provide a kind of halogen-free thermosetting resin composite, and uses its Prepreg and laminate for printed circuits.There is the laminate for printed circuits made using the resin combination high-vitrification to turn Temperature, excellent dielectric properties, high-fire resistance, excellent peel strength and good technique processability, and nothing can be realized Halogen is fire-retardant, reaches UL94V-0.
The present inventor to achieve the above object, has carried out in-depth study repeatedly, as a result found：By halogen-free epoxy resin, Cyanate ester resin, polyphenylene oxide resin, phosphorous bis-phenol polymer and composition that optionally other materials are suitably mixed to get, it is reachable To above-mentioned purpose.
That is, the present invention is adopted the following technical scheme that：A kind of halogen-free thermosetting resin composite, makees containing following four material For necessary component, organic solid content is based on 100 parts by weight, and it is included：
(A) cyanate ester resin：5~50 parts by weight；
(B) polyphenylene oxide resin：5~40 parts by weight；
(C) phosphorous bis-phenol polymer：5~30 parts by weight；
(D) halogen-free epoxy resin：30~60 parts by weight.
The halogen-free thermosetting resin composite of the present invention is cooperatively made with cyanate, polyphenylene oxide, phosphorous bis-phenol polymer For the curing agent of epoxy resin.Wherein cyanate ester resin can make co-curing system have high heat resistance and low dielectric loss Value；Polyphenylene oxide resin can make co-curing system have excellent dielectric properties and low water absorption rate；Phosphorous bis-phenol polymer architecture Symmetry is high, and the secondary hydroxyl reaction that the phosphonate unit in molecule can be with epoxy resin, can polarity in elimination system The shortcoming for the poor dielectric performance that big secondary hydroxyl is brought, makes dielectric properties excellent, and solidfied material Tg is high；In addition, this is phosphorous Bis-phenol polymer phosphorus content is high, there is halogen-free flameproof, only need on a small quantity add or can just be reached without additionally addition fire retardant It is fire-retardant to UL94V-0.The present invention utilizes the cooperative effect between cyanate, polyphenylene oxide, phosphorous bis-phenol polymer three, Ke Yixian The glass transition temperature and heat resistance for improving the prepreg made using the resin combination and laminate for printed circuits are write, and Make it have excellent dielectric properties, low water absorption, high peel strength, good humidity resistance and good technique processing Property, and halogen-free flameproof is realized, reach UL94V-0.In addition, the curing reaction of cyanate, phosphorous bis-phenol polymer and epoxy resin Speed is fast, and the curing reaction speed of polyphenylene oxide resin and epoxy resin is slow, while with cyanate, polyphenylene oxide, phosphorous bis-phenol Polymer composite curing epoxy resin causes curing reaction speed is moderate to be easily controlled, and greatly reduces production and processing technology Difficulty.
Each component is described in detail below.
Component (A) in the present invention, as cyanate ester resin, usage amount are 5 to 50 parts by weight, for example, 5 parts by weight, 10 Parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 weight Part.
The component (A) of the present invention, cyanate ester resin has following structure：
Wherein, R1For-CH2-、 In any one or at least two mixture；R2、R3、R4、R5、R6、R7、R8、R9It is each independently selected from hydrogen atom, C1-C4 Substituted or unsubstituted straight chained alkyl or C1-C4 (such as C1, C2, C3, C4) substitution or unsubstituted of (such as C1, C2, C3, C4) Branched alkyl in any one.
Preferably, the component (A) be double (the 4- cyanato-s phenyl) propane of 2,2-, it is double (4- cyanato-s phenyl) ethane, double (3,5- dimethyl -4- cyanato-s phenyl) methane, 2,2- couples of (4- cyanato-s phenyl) -1,1,1,3,3,3- HFC-236fas, α, α ' - Double (4- cyanato-s phenyl)-diisopropyl benzene, Cyclopeutadiene type cyanate, phenol novolak type cyanate, cresol novolak type cyanogen Double (4- cyanato-s phenyl) the propane prepolymers of acid esters, 2,2-, double (4- cyanato-s phenyl) ethane prepolymers, it is double (3,5- dimethyl- 4- cyanato-s phenyl) methane prepolymer, 2,2- double (4- cyanato-s phenyl) -1,1,1,3,3,3- HFC-236fas prepolymer, α, α ' - Double (4- cyanato-s phenyl)-diisopropyl benzene prepolymer, Cyclopeutadiene type cyanate prepolymer, phenol novolak type cyanate are pre- In polymers or cresol novolak type cyanate prepolymer any one or at least two mixture, double (the 4- cyanogen of preferably 2,2- Phenyl) propane, α, α '-bis- (4- cyanato-s phenyl)-diisopropyl benzene, double (3,5- dimethyl -4- cyanato-s phenyl) Methane, 2,2- couples of (4- cyanato-s phenyl) propane prepolymers, α, α '-bis- (4- cyanato-s phenyl)-diisopropyl benzene prepolymer In double (3,5- dimethyl -4- cyanato-s phenyl) methane prepolymers any one or at least two mixture.
Component (B) in the present invention, as polyphenylene oxide resin, usage amount are 5 to 40 parts by weight, for example, 5 parts by weight, 8 Parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 weight Part, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight or 40 parts by weight.
The component (B), polyphenylene oxide resin has following structure：
Wherein, R10For
In any one or at least two mixture.
Wherein, R11The substituted or unsubstituted straight chained alkyl or branched alkyl that are 1~4 for H, carbon number, substitution or not Any one in substituted phenyl.
Wherein, R12、R13、R14、R15、R16、R17、R18、R19It is identical or different, taken selected from H, F, carbon number for 1~4 Generation or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substitution or not Any one in substituted cyclohexyl or pi-allyl.
Preferably, n1、n2、n3、n40~40 positive integer is stood alone as, and meets 8≤n1+n2+n3+n4≤40。
The present invention component (C), as phosphorous bis-phenol polymer, usage amount be 5~30 parts by weight, for example, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 weight Part, 19 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 28 parts by weight or 30 parts by weight.
The component (C), phosphorous bis-phenol polymer has following structure：
Wherein R20、R21To be identical or different, it is selected from
In any one or at least two mixture.
Wherein, R11The substituted or unsubstituted straight chained alkyl or branched alkyl that are 1~4 for H, carbon number, substitution or not Any one in substituted phenyl.
Wherein, R12、R13、R14、R15、R16、R17、R18、R19、R23、R24It is identical or different, selected from H, F, carbon number be 1~ The substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted benzene of 4 (such as carbon number is 1,2,3 or 4) Any one in base, substituted or unsubstituted naphthyl, substituted or unsubstituted cyclohexyl.
Wherein, R22Substitution for C1~C20 (such as C1, C2, C3, C4, C6, C8, C10, C12, C15, C18 or C20) or Unsubstituted straight chained alkyl, C1~C20 (such as C1, C2, C3, C4, C6, C8, C10, C12, C15, C18 or C20) substitution or Unsubstituted branched alkyl, C2~C20 (such as C2, C3, C4, C6, C8, C10, C12, C15, C18 or C20) substitution do not take The linear alkene base in generation, C2~C20 (such as C2, C3, C4, C6, C8, C10, C12, C15, C18 or C20) substitution or unsubstituted Branched-chain alkene base, C2~C20 (such as C2, C3, C4, C6, C8, C10, C12, C15, C18 or C20) it is substituted or unsubstituted The substituted or unsubstituted branch of straight-chain alkyl-sub, C2~C20 (such as C2, C3, C4, C6, C8, C10, C12, C15, C18 or C20) Chain alkylidene, C5~C20 (such as C5, C6, C8, C10, C12, C15, C18 or C20) substituted or unsubstituted cycloalkyl or C6 Any one in~C20 (such as C6, C8, C10, C12, C15, C18 or C20) substituted or unsubstituted aryl.
Wherein, n2For 3~75 arbitrary integer, such as 3,4,6,8,9,10,11,13,15,17,18,19,20,23,26, 28th, 30,40,45,50,55,67,68,70 or 75.Preferably, n2For 4~60 arbitrary integer；Preferably n2For 5~50 times Meaning integer；Preferably n2 is 5~40 arbitrary integer；Preferably n2For 8~30 arbitrary integer；Preferably n2For 10~25 Arbitrary integer.
Wherein, n3、n4Integer that is identical or different, being 0~4.
Wherein, k, j are 0 or 1, but can not be 0 simultaneously.
The component (D) of the present invention, as halogen-free epoxy resin, usage amount is 30~60 parts by weight, for example, 30 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 45 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 weights Measure part, 56 parts by weight, 58 parts by weight or 60 parts by weight.
Component (D) halogen-free epoxy resin refers to the ring in 1 molecule with two or more epoxide groups Oxygen tree fat, selected from glycidol ethers, glycidol esters, glycidol amine, cycloaliphatic epoxy resin, epoxidation of olefins In class, glycolylurea epoxide resin or acid imide epoxy resin any one or at least two mixture.
Preferably, the glycidol ethers includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, orthoresol 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 is selected from the epoxy resin with following structure：
Wherein, Z1、Z2And Z3It is each independently selected fromR25For 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 singly-bound ,-CH2-、 In any one, n3 is 1 ~10 arbitrary integer, such as 2,3,4,5,6,7,8 or 9, R26Selected from hydrogen atom, substituted or unsubstituted containing the straight of carbon number 1~5 Any one in alkyl group or branched alkyl.
Preferably, the glycidol amine is different selected from triglycidyl group-p- amino-phenols, triglycidyl group trimerization Cyanate, four glycidyl group diaminourea dimethylene benzene, the amido diphenyl-methanes of four glycidyl group -4,4`- two, four shrink 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, and it has Higher degree of functionality and good dielectric properties, its solidfied material Tg are higher, and water absorption rate is low.
The halogen-free thermosetting resin composite of the present invention can also include component (E), as phosphonium flame retardant, with component (A), component (B), component (C), component (D) addition sum are 100 parts by weight meters, the addition of component (E) phosphonium flame retardant For 0~5 parts by weight.
Preferably, the phosphonium flame retardant is three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- Miscellaneous -10- phosphines phenanthrene -10- the oxides of dihydro-9-oxy, 2,6- bis- (2,6- 3,5-dimethylphenyls) phosphino- benzene, 10- phenyl -9,10- dihydros - In 9- oxa- -10- phosphine phenanthrene -10- oxides, phenoxy phosphazene compound, phosphate or polyphosphate any one or extremely Few two kinds mixture.
The halogen-free thermosetting resin composite of the present invention can also include component (F), as curing accelerator.
Preferably, the curing accelerator includes organic metal salt and selected from glyoxaline compound, glyoxaline compound In derivative, piperidines, pyridines, lewis acid or triphenylphosphine any one or at least two mixture.
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 it is mixed Compound, 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- diaminourea 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 DMAP, PA, 3- aminopyridines or 4- amino Any one in pyridine or at least two mixtures.
Preferably, using the gross weight of component (A), component (B), component (C) and component (D) as 100 parts by weight meters, the component (F) addition of curing accelerator is 0.01~1 parts by weight, preferably 0.025~0.85 parts by weight.
The halogen-free thermosetting resin composite of the present invention can also include component (G), as filler.
Preferably, the filler is selected from organic filler or inorganic filler, preferably inorganic filler, further preferably by surface The inorganic filler of processing, most preferably surface treated silica.
Preferably, the surface conditioning agent of the surface treatment is selected from silane coupler, silicone oligomer or titanate esters idol Join agent in any one or at least two mixture.
Preferably, counted by 100 parts by weight of inorganic filler, the consumption of the surface conditioning agent is 0.1~5.0 parts by weight, It is preferred that 0.5~3.0 parts by weight, more preferably 0.75~2.0 parts by weight.
Preferably, the inorganic filler is selected from nonmetal oxide, metal nitride, non-metal nitride, inorganic hydration In thing, inorganic salts, metal hydrate or Phos any one or at least two mixture, preferred molten titanium dioxide Silicon, powdered quartz, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminum oxide, talcum powder, aluminium nitride, nitrogen Change boron, carborundum, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates or one kind in mica or at least two mixing Thing.
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, using the addition sum of component (A), component (B), component (C) and component (D) as 100 parts by weight meters, institute The addition for stating component (G) 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, " comprising " of the present invention, can also be replaced For enclosed " being " or " by ... constitute ".
For example, the halogen-free thermosetting resin composite can also contain various additives, as concrete example, it can enumerate Phosphonium flame retardant, antioxidant, heat stabilizer, antistatic additive, ultra-violet absorber, pigment, colouring agent or lubricant etc..These are each Kind of additive can be used alone, and two kinds or two or more can also be used in mixed way.
The present invention halogen-free thermosetting resin composite customary preparation methods be：First solid content is put into, liquid is then added State solvent, after stirring is completely dissolved to solid content, adds liquid resin and accelerator, continues to stir.
As the solvent in the present invention, there is no particular limitation, as concrete example, can include methanol, ethanol, butanol Deng 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.Above solvent can be used alone, also can be two kinds Or two or more be used in mixed way.It is preferred that the ketone such as acetone, butanone, methyl ethyl ketone, cyclohexanone.The addition of the solvent by Those skilled in the art select according to oneself experience so that resin adhesive liquid reaches the viscosity for being adapted to use.
The prepreg of the present invention is attached to the nothing as described above on reinforcing material after being dried including reinforcing material and impregnation Halogen compositions of thermosetting resin, used reinforcing material, without special restriction, can be organic fiber, inorfil woven cloth Or non-woven fabrics.Described organic fiber can select aramid fiber non-woven fabrics, described inorfil woven cloth can for 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 consideration of good dimensional stability, woven cloth and the nonwoven thickness preferably 0.01~0.2mm, and is preferably It is surface-treated by fibrillation processing and silane coupler, 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 the reinforcing material halogen-free thermosetting resin composite above-mentioned by being impregnated with, 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 includes by heating and pressurization, glues prepreg more than a piece of or two panels The laminate for being combined and being made, and it is bonded in metal foils more than laminate one or both sides.Described laminate is Solidify in hot press and be made, solidification temperature is 150 DEG C~250 DEG C, solidifying pressure is 10~60Kg/cm2.Described metal foil For copper foil, nickel foil, aluminium foil and SUS paper tinsels etc., its material is not limited.
Compared with prior art, the present invention at least has the advantages that：
The present invention with cyanate, polyphenylene oxide, phosphorous bis-phenol polymer collectively as epoxy resin curing agent, in system Respective advantage and the effect with mutual catalyzing cooperation can be embodied；Cyanate can bring the high-fire resistance and low medium of system to damage Consumption value；Polyphenylene oxide can make system have excellent dielectric properties；Phosphorous bis-phenol polymer reaction group includes two terminal hydroxy groups and phosphine Acid esters unit, phosphonate unit and epoxy reaction do not produce secondary hydroxyl, and solidfied material glass transition temperature is high, dielectric properties and Excellent heat resistance.These three epoxy curing agent collective effects can also make system have excellent peel strength.
In addition, the catalyst that cyanate can react as polyphenylene oxide and bis-phenol polyphosphoric acid with epoxy resin.Polyphenylene oxide and contain The phenolic hydroxyl group reactivity of phosphorus bis-phenol polymer is very low, can just be reacted at very high temperatures with epoxy resin, and cyanic acid - OCN the groups of ester are just easy to react with the low activity hydroxyl of both of the above at 90~120 DEG C, then more than 130 DEG C Decompose, phenol negative oxygen ion can be produced in decomposable process.Phenol negative oxygen ion is easily reacted with epoxy resin, so as to reduce The solidification temperature of system.The phenolic hydroxyl group in polyphenylene oxide and bis-phenol polyphosphoric acid can promote cyanate to solidify well simultaneously, reduce cyanogen The solidification temperature of acid esters, and cyanate is solidify to form the triazine ring that crosslink density is big, symmetry is high, so that system has The dielectric properties that high glass transition temperature is become reconciled.There is more flexible chain ester chain in phosphorous bis-phenol polymer, body can be made The toughness of system improves a lot, and is embodied in peel strength.And phosphorus content is high in phosphorous bis-phenol polymer, as There is effect of halogen-free flameproof while curing agent, can add on a small quantity or without can just reach sheet material in the other fire retardants of addition To the effect of UL94V-0 halogen-free flameproofs.
Prepreg and laminate for printed circuits that halogen-free thermosetting resin composite provided by the present invention is made, have Up to 245 DEG C of glass transition temperature；Excellent dielectric properties, water absorption rate is controlled in the range of 0.07-0.11%；It is high heat-resisting Property；Peel strength is 0.9-1.2N/mm；Excellent humidity resistance and good technique processability, and can realize halogen-free flameproof, Reach UL94V-0.
Embodiment
Technical scheme is further illustrated below by embodiment.
As described below is the 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, some 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, carry out change implementation that can be appropriate.
1st, polyphenylene oxide is reallocated
4000g toluene is stirred and heated to 100 DEG C in equipped with agitator, condensing reflux pipe, the three-necked bottle of thermometer, so The PPO resins that 2000g number-average molecular weights are 20000 are added afterwards, and 250g 3,5,3', 5'- tetramethyls are added after homogeneous phase is changed into Base -4,4'- dihydroxybiphenyl, stirs 30min, then adds the 150g benzoyl peroxides (BPO) being dissolved in toluene, and keep Temperature is 92 DEG C, reacts 240min.Then product is cooled to room temperature and then adds 4000ml methanol, and be stirred vigorously, filtering, Dry, obtain difunctionality base PPO resins (PPO-2) 2100g of small molecule, its Mn=2118 is tested by GPC.
4000g toluene is stirred and heated to 100 DEG C in equipped with agitator, condensing reflux pipe, the three-necked bottle of thermometer, so The PPO resins that 2000g number-average molecular weights are 20000 are added afterwards, and 120g bisphenol-As (BPA), stirring are added after homogeneous phase is changed into 30min, then adds the 60g benzoyl peroxides (BPO) being dissolved in toluene, and keeping temperature is 92 DEG C, reacts 360min.So Product is cooled to room temperature afterwards and then 4000ml methanol is added, and is stirred vigorously, filters, dry, obtain double officials of small molecule Energy base PPO resins (PPO-3) 2000g, its Mn=4088 is tested by GPC.
4000g toluene is stirred and heated to 100 DEG C in equipped with agitator, condensing reflux pipe, the three-necked bottle of thermometer, so The PPO resins that 2000g number-average molecular weights are 20000 are added afterwards, and 120g TrisP-PA (Honshu is added after homogeneous phase is changed into Learn)
30min is stirred, the 60g being dissolved in toluene is then added Benzoyl peroxide (BPO), and keeping temperature is 92 DEG C, reacts 360min.Then product is cooled to room temperature and then addition 4000ml methanol, and be stirred vigorously, filter, dry, obtain difunctionality base PPO resins (PPO-4) 2000g of small molecule, lead to Cross GPC and test its Mn=3120.
4000g toluene is stirred and heated to 100 DEG C in equipped with agitator, condensing reflux pipe, the three-necked bottle of thermometer, so The PPO resins that 2000g number-average molecular weights are 20000 are added afterwards, and 120g TekP-4HBPA (Honshu is added after homogeneous phase is changed into Chemistry)30min is stirred, the 60g being dissolved in toluene is then added Benzoyl peroxide (BPO), and keeping temperature is 92 DEG C, reacts 360min.Then product is cooled to room temperature and then addition 4000ml methanol, and be stirred vigorously, filter, dry, obtain difunctionality base PPO resins (PPO-5) 2000g of small molecule, lead to Cross GPC and test its Mn=2480.
2nd, the preparation of phosphorous bis-phenol polymer
In N2Under the conditions of, add 77g hydroquinones (0.70mol) and 130.5g diphenyl methylphosphonates (DPP, 0.526mol) and catalyst tetraphenylphosphoniphenolate phenates (TPPP (30% phenol), 0.051g, 0.083mol), vacuum is reduced To 10mmHg, while heating the mixture to 240 DEG C, react 10 hours.By-product phenol is boiled off, 0.255g catalyst is added, And keep 210 DEG C/10mmHg conditions 4 hours.Post processing purification, it is the phosphorous of the phenolic hydroxyl group of reactivity to obtain two ends of chain Bis-phenol polymer C-1.Its Mn=8510 is tested by GPC.
In N2Under the conditions of, add 147g4,4`- '-biphenyl diphenols (Biphenol, 0.79mol) and 130.5g diphenyl methyls Phosphonate ester (DPP, 0.526mol) and catalyst tetraphenylphosphoniphenolate phenates (TPPP (30% phenol), 0.051g, 0.083mol), will Vacuum is reduced to 10mmHg, while heating the mixture to 265 DEG C, reacts 5 hours.By-product phenol is boiled off, is added 0.255g catalyst, and keep 265 DEG C/10mmHg conditions 2 hours.Post processing purification, it is reactivity to obtain two ends of chain Phenolic hydroxyl group phosphorous bis-phenol polymer C-2.Its Mn=2600 is tested by GPC.
In N2Under the conditions of, add 232.8g BisP-TMC (Honshu chemistry) (0.75mol) and 130.5g diphenyl methyls Phosphonate ester (DPP, 0.526mol) and catalyst tetraphenylphosphoniphenolate phenates (TPPP (30% phenol), 0.051g, 0.083mol), will Vacuum is reduced to 10mmHg, while heating the mixture to 265 DEG C, reacts 5 hours.By-product phenol is boiled off, is added 0.255g catalyst, and keep 265 DEG C/10mmHg conditions 2 hours.Post processing purification, it is reactivity to obtain two ends of chain Phenolic hydroxyl group phosphorous bis-phenol polymer C-3.Its Mn=4960 is tested by GPC.
By cyanate ester resin, polyphenylene oxide resin, phosphorous bis-phenol polymer, halogen-free epoxy resin and curing accelerator, nothing Halogen fire retardant, filler are well mixed in solvent by a certain percentage, and it is 65% to control glue solid content, is impregnated with 2116 glass-fiber-fabrics Above-mentioned glue, controls suitable thickness, and 2~15min is then toasted in 115~175 DEG C of baking oven is made prepreg, then by number Prepreg is stacked, and is 170~250 DEG C in solidification temperature in the stacked on 18 μ RTF copper foils in its both sides, and solidifying pressure is 25~ 60kg/cm2, hardening time be 60~300min under the conditions of copper-clad plate is made.
Embodiment 1-8 and comparative example 1-13 are related to material and trade mark information is as follows：
(A) cyanate
CY-40：Wuqiao resin factory, DCPD type cyanate ester resins
PT30S：LONCZ, Novolac Cyanate Ester Resins
CE01PS：Jiangsu apocalypse, bisphenol A cyanate ester resin
CE01MO：Jiangsu apocalypse, bisphenol A cyanate ester resin
(B)PPO
PPO-1：SA90, Sha Baiji, small molecule difunctionality base polyphenylene oxide, hydroxyl equivalent 850
PPO-2：Make small molecule PPO resins, Mn=2118 by oneself
PPO-3：Make small molecule PPO resins, Mn=4088 by oneself
PPO-4：Make small molecule PPO resins, Mn=3120 by oneself
PPO-5：Make small molecule PPO resins, Mn=2480 by oneself
(C) phosphorous bis-phenol polymer
C1, self-control, phosphorous bis-phenol polymer, phosphorus content 18%, Mn=8510
C2, self-control, phosphorous bis-phenol polymer, phosphorus content 11.7%, Mn=2600
C3, self-control, phosphorous bis-phenol polymer, phosphorus content 7.8%, Mn=4960
OL-1001：Phosphorous bis-phenol polymer, FRX OL1001 (U.S.'s FRX Polymers trade names, phosphorus content 8.5%)
OL-3001：Phosphorous bis-phenol polymer, (U.S.'s FRX Polymers trade names, phosphorus content 10%)
FYROL PMP：Supresta halogen-free phosphorus-containing fire retardant agent, phosphorus content 17.5%
(D) 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
(E) phosphonium flame retardant
SPB-100:Great mound chemistry, phosphine nitrile fire retardant, phosphorus content 13.4%
(F) accelerator
2E4MZ：2-ethyl-4-methylimidazole, four countries' chemical conversion
Zinc Isoocatanoate：BICAT Z, The Shepherd Chemical Company
(G) filler
Fused silica (average grain diameter is 1 to 10 μm, purity more than 99%)
Table 1-3 is embodiment 1-8 and comparative example 1-13 formula composition and its physical data.
Table 1
Table 2
Table 3
The method of testing of above characteristic is as follows：
(1) glass transition temperature (Tg)：Tested, surveyed according to the DMA of IPC-TM-650 2.4.24 defineds using DMA Method for testing is measured.
(2) dielectric constant and dielectric loss factor：Tested according to SPDR methods.
(3) humidity resistance (PCT) is evaluated：After the copper foil etching on copper-clad plate surface, 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 does not have also appearance to bubble or be layered in tin stove more than 5min, PCT/6h performance maps Target remarks additionally：× to be layered plate bursting, O is not stratified plate bursting, and every block of sheet material chooses three samples and does three experiments.
(4) humidity resistance is (hot and humid) evaluates：After the copper foil etching on copper-clad plate surface, substrate is evaluated；By substrate temperature In the climatic chamber that degree is 85 DEG C, humidity is 85% after 192 hours, it is immersed in 288 DEG C of tin stove, when substrate de-lamination plate bursting The Shi Jilu corresponding times；It can terminate to evaluate when substrate does not have also appearance to bubble or be layered in tin stove more than 5min, high temperature is high Wet/192h performance maps target supplementary notes：× to be layered plate bursting, O is not stratified plate bursting, and every block of sheet material chooses three samples and does three Secondary experiment.
(5) water imbibition：Water imbibition method of testing according to IPC-TM-650 2.6.2.1 defineds is measured.
(6) peel strength：Peel strength method of testing according to IPC-TM-650 2.4.8 defineds is measured.
(7)T300：TMA instrument is used, is measured according to the T300 method of testings of IPC-TM-650 2.4.24.1 defineds.
(8) anti-flammability：Carried out according to the standard methods of UL 94.
Comparative example 1 is can be seen that from table 1-3 physical data to contrast with embodiment 1, cyanate ester resin in resin combination Consumption is few, and the copper-clad plate dielectric properties being made are poor, and heat resistance is general；Comparative example 2 is contrasted with embodiment 4, resin combination Middle polyphenylene oxide consumption is few, causes rigid structure in system few, so that its heat resistance is decreased obviously, is embodied in T300 and only has 5.6min；Comparative example 3 is contrasted with embodiment 8, with the addition of curing agent excess in very few epoxy resin, system, and epoxy amount is not enough, System can not solidify well, and glass transition temperature declines；And PPO and phosphorous bis-phenol elder generation and polyisocyanate reactant in system It can also decompose afterwards, cause PPO and phosphorous bis-phenol to serve as the effect of plasticizer in system, also make under system glass transition temperature Drop；And cyanate consumption is excessive, humidity resistance (PCT, hot and humid) degradation is also resulted in；Comparative example 4 and embodiment 2 Compare, phosphorous bis-phenol polymer volume is very few, the copper-clad plate dielectric properties being made are poor；Cyanate resin is not added with comparative example 5 Copper-clad plate heat resistance made by fat is poor；It is not added with being not added with phosphorous bis-phenol in polyphenylene oxide resin and comparative example 7 in comparative example 6 The copper-clad plate dielectric properties and peel strength being not added with polymer and comparative example 8 made by halogen-free epoxy resin are poor； Compared with Example 7, cyanate ester resin consumption is excessive, and content of epoxy resin is less, made copper-clad plate dielectricity for comparative example 9 Can be poor；Compared with Example 2, polyphenylene oxide consumption is excessive, copper-clad plate humidity resistance, heat resistance and the stripping being made for comparative example 10 Intensity is poor；Compared with Example 4, phosphorous bis-phenol polymer volume is excessive, and the copper-clad plate Tg being made drastically declines for comparative example 11, Humidity resistance and water absorption rate are deteriorated；Compared with Example 1, content of epoxy resin is excessive, and curing agent is substantially not enough, leads for comparative example 12 The combination properties such as the copper-clad plate electrical property, heat resistance, the peel strength that are made are caused substantially to be deteriorated；Comparative example 13 compared with Example 4, The halogen-free phosphorus-containing fire retardant agent used, is single phenolic phosphonates, its only one of which curing activity point, causes its one end to participate in solid Change, the free end that the other end can be disturbed when heated causes its Tg, T300, dielectric properties, humidity resistance etc. to be all deteriorated；Implement Example 1-8 is with made by the cyanate ester resin of certain content and polyphenylene oxide resin, phosphorous bis-phenol polymer and halogen-free epoxy resin Copper-clad plate has high glass-transition temperature, excellent dielectric properties, low water absorption, high-fire resistance, high peel strength, excellent Different humidity resistance and good technique processability, and halogen-free flameproof can be realized, reach UL94V-0.
As described above, compared with general laminate, what halogen-free thermosetting resin composite provided by the present invention was made Prepreg and laminate for printed circuits are heat-resisting with high glass-transition temperature, excellent dielectric properties, low water absorption, height Property, high peel strength, excellent humidity resistance and good technique processability, and halogen-free flameproof can be realized, reach UL94V-0。
Described above, only presently preferred embodiments of the present invention for the person of ordinary skill of 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 (10)

1. a kind of halogen-free thermosetting resin composite, organic solid content is based on 100 parts by weight, and it is included：
(A) parts by weight of cyanate ester resin 5~50；
(B) parts by weight of polyphenylene oxide resin 5~40；
(C) the phosphorous parts by weight of bis-phenol polymer 5~30；
(D) parts by weight of halogen-free epoxy resin 30~60.
2. halogen-free thermosetting resin composite as claimed in claim 1, it is characterised in that the cyanate ester resin has as follows Structure：
Wherein, R1For-CH2-、In Any one or at least two mixture；R2、R3、R4、R5、R6、R7、R8、R9Hydrogen atom, C1-C4 is each independently selected to take Any one in generation or unsubstituted straight chained alkyl or the substituted or unsubstituted branched alkyls of C1-C4；
Preferably, the cyanate ester resin be double (the 4- cyanato-s phenyl) propane of 2,2-, it is double (4- cyanato-s phenyl) ethane, double (3,5- dimethyl -4- cyanato-s phenyl) methane, 2,2- couples of (4- cyanato-s phenyl) -1,1,1,3,3,3- HFC-236fas, α, α ' - Double (4- cyanato-s phenyl)-diisopropyl benzene, Cyclopeutadiene type cyanate, phenol novolak type cyanate, cresol novolak type cyanogen Double (4- cyanato-s phenyl) the propane prepolymers of acid esters, 2,2-, double (4- cyanato-s phenyl) ethane prepolymers, it is double (3,5- dimethyl- 4- cyanato-s phenyl) methane prepolymer, 2,2- double (4- cyanato-s phenyl) -1,1,1,3,3,3- HFC-236fas prepolymer, α, α ' - Double (4- cyanato-s phenyl)-diisopropyl benzene prepolymer, dicyclopentadiene type ethylene rhodanate prepolymer, phenol novolak type cyanate In prepolymer or cresol novolak type cyanate prepolymer any one or at least two mixture, the double (4- of preferably 2,2- Cyanato- phenyl) propane, α, α '-bis- (4- cyanato-s phenyl)-diisopropyl benzene, double (3,5- dimethyl -4- cyanato- benzene Base) methane, 2,2- double (4- cyanato-s phenyl) propane prepolymer, α, α '-bis- (4- cyanato-s phenyl)-diisopropyl benzene pre-polymerization In thing or double (3,5- dimethyl -4- cyanato-s phenyl) methane prepolymers any one or at least two mixture.
3. halogen-free thermosetting resin composite as claimed in claim 1 or 2, it is characterised in that the polyphenylene oxide resin has Following structure：
Wherein, R10For
In any one or at least two mixture；
Wherein, R11The substituted or unsubstituted straight chained alkyl or branched alkyl that are 1~4 for H, carbon number, substitution or unsubstituted Phenyl in any one；
Wherein, R12、R13、R14、R15、R16、R17、R18、R19It is identical or different, selected from H, F, carbon number for 1~4 substitution or not It is substituted straight chained alkyl or branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted Any one in cyclohexyl or pi-allyl；
Preferably, n1、n2、n3、n40~40 positive integer is stood alone as, and meets 8≤n1+n2+n3+n4≤40
4. the halogen-free thermosetting resin composite as described in one of claim 1-3, it is characterised in that the phosphorous bis-phenol polymerization Thing has following structure：
Wherein, R20、R21To be identical or different, it is selected from
In appoint Meaning it is a kind of or at least two mixtures；
Wherein, R11The substituted or unsubstituted straight chained alkyl or branched alkyl that are 1~4 for H, carbon number, substitution or unsubstituted Phenyl in any one；
Wherein, R12、R13、R14、R15、R16、R17、R18、R19、R23、R24It is identical or different, it is 1~4 selected from H, F, carbon number Substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substitution or Any one in unsubstituted cyclohexyl or pi-allyl；
Wherein, R22For C1~C20 substituted or unsubstituted straight chained alkyl, C1~C20 substituted or unsubstituted branched alkyl, C2~C20 substituted or unsubstituted linear alkene base, C2~C20 substituted or unsubstituted branched-chain alkene base, C2~C20 Substituted or unsubstituted straight-chain alkyl-sub, C2~C20 substituted or unsubstituted branched alkylidene, C5~C20 substitution or not Any one in substituted cycloalkyl or C6~C20 substituted or unsubstituted aryl；
Wherein, n2For 3~75 arbitrary integer；It is preferred that n2For 4~60 arbitrary integer；Further preferred n2For 5~50 it is any Integer；Still further preferably n2For 5~40 arbitrary integer；Still more preferably n2For 8~30 arbitrary integer；Further It is preferred that n2For 10~25 arbitrary integer；
Wherein, n3、n4It is identical or different, selected from 0~4 integer；
Wherein, k, j are 0 or 1, but can not be 0 simultaneously.
5. the halogen-free thermosetting resin composite as described in one of claim 1-4, it is characterised in that the halogen-free epoxy resin For glycidol ethers, glycidol esters, glycidol amine, cycloaliphatic epoxy resin, epoxidation of olefins class, hydantoin epoxy In resin or acid imide epoxy resin any one or at least two mixture；
Preferably, the glycidol ethers is bisphenol A type epoxy resin, bisphenol f type epoxy resin, orthoresol phenolic aldehyde asphalt mixtures modified by epoxy resin Fat, bisphenol A-type novolac epoxy resin, three phenolic novolac epoxy resins, dicyclopentadiene novolac epoxy resin, biphenyl type phenolic aldehyde ring In oxygen tree fat, alkyl benzene-type novolac epoxy resin or naphthol type novolac epoxy resin any one or at least two mixing Thing；
Preferably, the glycidol ethers is the epoxy resin with following structure：
Wherein, Z1、Z2And Z3It is each independently selected fromR27Selected from hydrogen atom, substitution or not Any one in the straight chained alkyl containing carbon number 1~5 or branched alkyl of substitution；
Y1And Y2It is each independently selected from singly-bound ,-CH2-、 In any one, R28It is selected from Any one in hydrogen atom, substituted or unsubstituted straight chained alkyl or branched alkyl containing carbon number 1~5；
n8For 1~10 arbitrary integer；
Preferably, the glycidol amine is selected from triglycidyl group-p- amino-phenols, triglycidyl group cyamelide Ester, four glycidyl group diaminourea dimethylene benzene, the amido diphenyl-methanes of four glycidyl group -4,4`- two, four glycidols Base -3,4`- diaminodiphenyl ethers, four glycidyl group -4,4`- diaminodiphenyl ethers or four glycidyl group -1,3- diaminourea In hexahydrotoluene any one or at least two mixture.
6. the halogen-free thermosetting resin composite as described in one of claim 1-5, it is characterised in that the halogen-free thermosetting tree Oil/fat composition also includes component (E) phosphonium flame retardant；
Preferably, the phosphonium flame retardant is three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- bis- Hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxides, 2,6- bis- (2,6- 3,5-dimethylphenyls) phosphino- benzene, 10- phenyl -9,10- dihydros -9- Any one in oxa- -10- phosphine phenanthrene -10- oxides, phenoxy phosphazene compound, phosphate or polyphosphate or at least two The mixture planted；
Preferably, using component (A), component (B), component (C), component (D) addition sum as 100 parts by weight meters, component (E) contains The addition of phosphorus fire retardant is 0~5 parts by weight；
Preferably, the halogen-free thermosetting resin composite also includes component (F) curing accelerator；
Preferably, the curing accelerator is organic metal salt, glyoxaline compound, the derivative of glyoxaline compound, piperidines In class compound, pyridines, lewis acid or triphenylphosphine any one or at least two mixture；
Preferably, the organic metal salt is sad metal salt, isooctyl acid metal salt, acetyl acetone salt, aphthenic acids metal In salt, salicylic acid metal salt or Metallic stearates any one or at least two mixture, wherein, the metal is 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- 11 In alkyl imidazole any one or at least two mixture；
Preferably, the piperidines is 2,3- diaminos phenylpiperidines, 2,5- diaminos phenylpiperidines, 2,6- diaminos phenylpiperidines, 2- Amino -3- methyl piperidines, 2- amino -4- methyl piperidines, 2- amino -3- nitros piperidines, 2- amino -5- nitros piperidines or 2- ammonia In base -4,4- lupetidines any one or at least two mixture；
Preferably, the pyridine compounds and their is DMAP, PA, 3- aminopyridines or 4-aminopyridine In any one or at least two mixture；
Preferably, using the addition sum of component (A), component (B), component (C) and component (D) as 100 parts by weight meters, described group The addition of part (F) curing accelerator is 0.01~1 parts by weight, preferably 0.025~0.85 parts by weight.
7. the halogen-free thermosetting resin composite as described in one of claim 1-6, it is characterised in that the halogen-free thermosetting tree Oil/fat composition also includes component (G) filler；
Preferably, the filler is selected from organic filler or inorganic filler, preferably inorganic filler, more preferably by surface The inorganic filler of processing, more preferably surface treated silica；
Preferably, the surface conditioning agent of the surface treatment is selected from silane coupler, silicone oligomer or titanate coupling agent In any one or at least two mixture；
Preferably, counted by 100 parts by weight of inorganic filler, the consumption of the surface conditioning agent is 0.1~5.0 parts by weight, preferably For 0.5~3.0 parts by weight, more preferably 0.75~2.0 parts by weight；
Preferably, the inorganic filler is selected from nonmetal oxide, metal nitride, non-metal nitride, inorganic hydrate, nothing In machine salt, metal hydrate or Phos any one or at least two mixture, preferably fused silica, crystallization Type silica, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminum oxide, talcum powder, aluminium nitride, boron nitride, carbon One kind or at least two mixture in SiClx, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates or mica；
Preferably, the organic filler in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder any one or At least two mixture；
Preferably, the median of the filler be 0.01~50 μm, preferably 0.01~20 μm, more preferably 0.1~ 10μm；
Preferably, using the addition sum of component (A), component (B), component (C) and component (D) as 100 parts by weight meters, described group The addition for dividing (G) filler is 5~300 parts by weight, more preferably preferably 5~200 parts by weight, 5~150 parts by weight.
8. a kind of prepreg, it includes reinforcing material and by attached thereto such as one of claim 1-7 after impregnation drying Described halogen-free thermosetting resin composite.
9. a kind of laminate, the laminate contains at least one prepreg as claimed in claim 8.
10. a kind of halogen-less high frequency circuit substrate, the substrate contains at least one prepreg as claimed in claim 8 and covered Metal foil in the prepreg one or both sides after overlapping.
CN201610137438.3A 2016-03-10 2016-03-10 A kind of halogen-free thermosetting resin composite and prepreg and laminate for printed circuits using it Expired - Fee Related CN107177030B (en)

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PCT/CN2016/098450 WO2017152602A1 (en) 2016-03-10 2016-09-08 Halogen-free thermosetting resin composition, and prepreg and laminate for printed circuits using same
TW105131954A TWI619766B (en) 2016-03-10 2016-10-03 Halogen-free thermosetting resin composition and laminate for use thereof and prepreg and printed circuit board

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CN108102594A (en) * 2017-12-14 2018-06-01 南亚新材料科技股份有限公司 It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive and preparation method thereof
CN108263068A (en) * 2017-12-14 2018-07-10 南亚新材料科技股份有限公司 A kind of method that copper coated foil plate is prepared using polyphenyl ether resin composition
CN109971131A (en) * 2017-12-28 2019-07-05 广东生益科技股份有限公司 Polyphenyl ether resin composition and application thereof
CN110452546A (en) * 2018-05-07 2019-11-15 广东生益科技股份有限公司 Resin combination, preliminary-dip piece used for printed circuit and metal-coated laminated board
CN110524985A (en) * 2019-08-06 2019-12-03 衢州艾科科技有限公司 A kind of epoxy earth material and preparation method thereof of three fiber composites enhancing
CN114685800A (en) * 2020-12-29 2022-07-01 洛阳尖端技术研究院 Phosphorus-containing hyperbranched polyol, phosphorus-containing hyperbranched epoxy resin, preparation method thereof, composition thereof and cyanate ester resin

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CN115073786A (en) * 2022-06-15 2022-09-20 航天特种材料及工艺技术研究所 Modified cyanate ester-based wave-transparent composite material and preparation method thereof

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CN108102594A (en) * 2017-12-14 2018-06-01 南亚新材料科技股份有限公司 It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive and preparation method thereof
CN108263068A (en) * 2017-12-14 2018-07-10 南亚新材料科技股份有限公司 A kind of method that copper coated foil plate is prepared using polyphenyl ether resin composition
CN109971131A (en) * 2017-12-28 2019-07-05 广东生益科技股份有限公司 Polyphenyl ether resin composition and application thereof
CN110452546A (en) * 2018-05-07 2019-11-15 广东生益科技股份有限公司 Resin combination, preliminary-dip piece used for printed circuit and metal-coated laminated board
CN110452546B (en) * 2018-05-07 2021-12-17 广东生益科技股份有限公司 Resin composition, prepreg for printed circuit, and metal-clad laminate
CN110524985A (en) * 2019-08-06 2019-12-03 衢州艾科科技有限公司 A kind of epoxy earth material and preparation method thereof of three fiber composites enhancing
CN114685800A (en) * 2020-12-29 2022-07-01 洛阳尖端技术研究院 Phosphorus-containing hyperbranched polyol, phosphorus-containing hyperbranched epoxy resin, preparation method thereof, composition thereof and cyanate ester resin

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