CN107177030B - A kind of halogen-free thermosetting resin composite and prepreg and laminate for printed circuits using it - Google Patents
A kind of halogen-free thermosetting resin composite and prepreg and laminate for printed circuits using it Download PDFInfo
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- CN107177030B CN107177030B CN201610137438.3A CN201610137438A CN107177030B CN 107177030 B CN107177030 B CN 107177030B CN 201610137438 A CN201610137438 A CN 201610137438A CN 107177030 B CN107177030 B CN 107177030B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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 5~50 parts by weight of (A) cyanate ester resin based on 100 parts by weight；(B) 5~40 parts of polyphenylene oxide resin；(C) phosphorous 5~30 parts by weight of bis-phenol polymer；(D) 30~60 parts by weight of halogen-free epoxy resin.Prepreg made of halogen-free thermosetting resin composite provided by the present invention and laminate for printed circuits, 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 it is able to achieve halogen-free flameproof, reach UL94 V-0.
Description
Technical field
The present invention relates to a kind of halogen-free thermosetting resin composite, further relate to made of the halogen-free thermosetting resin composite
Prepreg and laminate for printed circuits.
Background technique
It is fire-retardant to realize that traditional laminate for printed circuits generallys use bromide fire retardant, especially with tetrabromobisphenol
A type epoxy resin, this brominated epoxy resin has good anti-flammability, but it can generate bromination hydrogen in burning.This
Outside, dioxin, 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
" about electric/electronic device instruction is scrapped " and " Restriction on the Use of Certain Hazardous Substances in Electrical and Electronic Equipment " is just
Formula is implemented, and the hot spot for being developed into industry of halogen-free flameproof copper-clad laminate, each copper-clad laminate producer all releases one after another
The halogen-free flameproof copper-clad laminate of oneself.
Simultaneously with the high speed and multifunction of consumption electronic product information processing, applying frequency is continuously improved, in addition to
The requirement of environmental protection is higher and higher outer, it is desirable that dielectric constant and dielectric loss value are lower and lower, therefore reduce Dk/Df and have become substrate
Dealer's chases hot spot.
In addition, for copper clad foil substrate material, in order to meet the performance of PCB processing performance 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 special
Property, high peel strength, excellent humidity resistance and UL94V-0 halogen-free flameproof rank.
It discloses in CN101796132A and is blended using cyanate, epoxy resin, polyphenylene oxide resin and brominated flame-retardant
To heat resistance, the copper-clad plate of good, the low CTE of dielectric properties, 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 lower.
It is well known that have low dielectric constant, Dielectric loss tangent value characteristic there are many material at present, such as: polyolefin,
Fluororesin, polystyrene, polyphenylene oxide, Noryl, bismaleimide-triazine resin, polyvinyl benzene resin.The above tree
Although the defects of rouge all has technique difficult processing, poor heat resistance with good dielectric properties, and peel strength is poor, can not
Meet the requirement of high-frequency high-speed copper clad foil substrate.
Summary of the invention
Through inventor the study found that with cyanate, polyphenylene oxide, phosphorous bis-phenol polymer collectively as epoxy resin solidification
Agent can embody respective advantage in system and the effect of mutual catalyzing cooperation occurs.Cyanate can bring the height of system resistance to
Hot and low dielectric loss value；Polyphenylene oxide can make system have excellent dielectric properties；Phosphorous bis-phenol polymer reaction group packet
Two terminal hydroxy groups and phosphonate unit are included, phosphonate unit and epoxy reaction do not generate secondary hydroxyl, solidfied material glass transition temperature
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 be reacted 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 react at very high temperatures with epoxy resin, and cyanate-
OCN group is just easy to react with the low activity hydroxyl of both of the above at 90~120 DEG C, then has hair at 130 DEG C or more
Solution estranged can generate phenol negative oxygen ion in decomposable process.Phenol negative oxygen ion is easy to react with epoxy resin, 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 made to be formed by curing the triazine ring that crosslink density is big, symmetry is high, so that it is high to have system
Glass transition temperature and good dielectric properties.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, is being used as solidification
The effect of there are also halogen-free flameproofs while agent can add on a small quantity or without can just plate be made to reach in the other fire retardants of addition
The effect of UL94V-0 halogen-free flameproof.
Based on this, one of the objects of the present invention is to provide a kind of halogen-free thermosetting resin composites, and use its
Prepreg and laminate for printed circuits.Turned using the laminate for printed circuits that the resin combination makes with high-vitrification
Temperature, excellent dielectric properties, high-fire resistance, excellent peel strength and good technique processability, and it is able to achieve nothing
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, it has been found that: by halogen-free epoxy resin,
Cyanate ester resin, polyphenylene oxide resin, phosphorous bis-phenol polymer and the optionally composition that properly mixes of other substances, it is reachable
To above-mentioned purpose.
That is, the present invention adopts the following technical scheme: a kind of halogen-free thermosetting resin composite, makees containing following four substance
For necessary component, organic solid content based on 100 parts by weight, it includes:
(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.
Halogen-free thermosetting resin composite of the 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 phosphonate unit in molecule can be reacted with the secondary hydroxyl of epoxy resin, can polarity in elimination system
The shortcomings that big secondary hydroxyl bring poor dielectric performance, keep dielectric properties excellent, and solidfied material Tg high；In addition, this is phosphorous
Bis-phenol polymer phosphorus content is high, there is the effect of halogen-free flameproof, only need to add or can reach on a small quantity without additionally adding fire retardant
It is fire-retardant to UL94V-0.The present invention utilizes the synergistic effect between cyanate, polyphenylene oxide, phosphorous bis-phenol polymer three, Ke Yixian
The glass transition temperature and heat resistance for improving the prepreg and laminate for printed circuits that make using the resin combination are write, and
Make it have excellent dielectric properties, low water absorption, high peel strength, good humidity resistance and the processing of good technique
Property, and realize halogen-free flameproof, reach UL94V-0.In addition, the curing reaction of cyanate, phosphorous bis-phenol polymer and epoxy resin
Rate is fast, and the curing reaction rate of polyphenylene oxide resin and epoxy resin is slow, while with cyanate, polyphenylene oxide, phosphorous bis-phenol
Polymer composite curing epoxy resin makes curing reaction rate is moderate to be easy to control, 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.
Component (A) of the invention, cyanate ester resin has the 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
The substituted or unsubstituted straight chained alkyl or C1-C4 (such as C1, C2, C3, C4) of (such as C1, C2, C3, C4) are substituted or unsubstituted
Branched alkyl in any one.
Preferably, the component (A) be bis- (the 4- cyanato- phenyl) propane of 2,2-, it is bis- (4- cyanato- phenyl) ethane, double
(3,5- dimethyl -4- cyanato- phenyl) methane, 2,2- bis- (4- cyanato- phenyl) -1,1,1,3,3,3- hexafluoropropane, α, α ' -
Bis- (4- cyanato- phenyl)-diisopropyl benzenes, Cyclopeutadiene type cyanate, phenol novolak type cyanate, cresol novolak type cyanogen
Bis- (4- cyanato- phenyl) the propane prepolymers of acid esters, 2,2-, bis- (4- cyanato- phenyl) ethane prepolymers, bis- (3,5- dimethyl-
4- cyanato- phenyl) methane prepolymer, 2,2- bis- (4- cyanato- phenyl) -1,1,1,3,3,3- hexafluoropropane prepolymers, α, α ' -
Bis- (4- cyanato- phenyl)-diisopropyl benzene prepolymers, 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, bis- (the 4- cyanogen of preferably 2,2-
Phenyl) propane, α, bis- (4- cyanato- the phenyl)-diisopropyl benzenes of α ' -, bis- (3,5- dimethyl -4- cyanato- phenyl)
Methane, 2,2- bis- (4- cyanato- phenyl) propane prepolymers, α, bis- (4- cyanato- the phenyl)-diisopropyl benzene prepolymers of α '-
In bis- (3,5- dimethyl -4- cyanato- 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 the following structure:
Wherein, R10For
In any one or at least two mixture.
Wherein, R11For H, carbon atom number be 1~4 substituted or unsubstituted straight chained alkyl or branched alkyl, replace or not
Any one in substituted phenyl.
Wherein, R12、R13、R14、R15、R16、R17、R18、R19It is identical or different, it is 1~4 to take selected from H, F, carbon atom number
Generation or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or not
Any one in substituted cyclohexyl or allyl.
Preferably, n1、n2、n3、n40~40 positive integer is stood alone as, and meets 8≤n1+n2+n3+n4≤40。
Component (C) of the invention, 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 have the following structure:
Wherein R20、R21Be it is identical or different, be selected from
In appoint
It anticipates a kind of or at least two mixtures.
Wherein, R11For H, carbon atom number be 1~4 substituted or unsubstituted straight chained alkyl or branched alkyl, replace 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 atom number be 1~
The substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted benzene of 4 (such as carbon atom number is 1,2,3 or 4)
Base, substituted or unsubstituted naphthalene, any one in substituted or unsubstituted cyclohexyl.
Wherein, R22For C1~C20 (such as C1, C2, C3, C4, C6, C8, C10, C12, C15, C18 or C20) substitution 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 or do not take
The linear alkene base in generation, C2~C20 (such as C2, C3, C4, C6, C8, C10, C12, C15, C18 or C20) it is substituted 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, the substituted or unsubstituted naphthenic base of C5~C20 (such as C5, C6, C8, C10, C12, C15, C18 or C20) or C6
Any one in the substituted or unsubstituted aryl of~C20 (such as C6, C8, C10, C12, C15, C18 or C20).
Wherein, n2For 3~75 arbitrary integer, for example, 3,4,6,8,9,10,11,13,15,17,18,19,20,23,26,
28,30,40,45,50,55,67,68,70 or 75.Preferably, n2For 4~60 arbitrary integer；Preferably n2For 5~50 times
Meaning integer；The arbitrary integer that preferably n2 is 5~40；Preferably n2For 8~30 arbitrary integer；Preferably n2It is 10~25
Arbitrary integer.
Wherein, n3、n4It is identical or different, it is 0~4 integer.
Wherein, k, j are 0 or 1, but cannot simultaneously be 0.
Component (D) of the invention, as halogen-free epoxy resin, usage amount be 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 epoxy groups
Oxygen resin is 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 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 fromR25For hydrogen atom, replace
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 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, it is different to be selected from triglycidyl group-p- amino-phenol, triglycidyl group trimerization for the glycidol amine
Cyanate, four glycidyl group diamino dimethylene benzene, two amido diphenyl-methane of four glycidyl group -4,4`-, four shrinks are sweet
Oil base -3,4`- diaminodiphenyl ether, four glycidyl group -4,4`- diaminodiphenyl ether or four glycidyl group -1,3- diamino
In ylmethyl hexamethylene any one or at least two mixture.
Halogen-free thermosetting resin composite of the 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.
Halogen-free thermosetting resin composite of the invention can also include component (E), as phosphonium flame retardant, with component
(A), the sum of component (B), component (C), component (D) additive amount are 100 parts by weight meters, the additive amount 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- phosphine phenanthrene -10- the oxide of dihydro-9-oxy, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, 10- phenyl -9,10- dihydro -
In 9- oxa- -10- phosphine phenanthrene -10- oxide, phenoxy phosphazene compound, phosphate or polyphosphate any one or extremely
Few two kinds of mixture.
Halogen-free thermosetting resin composite of the 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
Close 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- phenylimidazole or 2-
In undecyl imidazole any one or at least two mixture.
Preferably, the piperidines are 2,3- diamino phenylpiperidines, 2,5- diamino phenylpiperidines, 2,6- diamino piperazine
Pyridine, 2- amino -3- methyl piperidine, 2- amino -4- methyl piperidine, 2- amino -3- nitro piperidines, 2- amino -5- nitro piperidines or
In 2- amino -4,4- lupetidine any one or at least two mixture.
Preferably, the pyridine compounds and their is 4-dimethylaminopyridine, 2-aminopyridine, 3- aminopyridine or 4- amino
Any one in pyridine or at least two mixtures.
Preferably, in terms of by the gross weight of component (A), component (B), component (C) and component (D) for 100 parts by weight, the component
(F) additive amount of curing accelerator is 0.01~1 parts by weight, preferably 0.025~0.85 parts by weight.
Halogen-free thermosetting resin composite of the 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, it is even to be selected from silane coupling agent, silicone oligomer or titanate esters for the surface treating agent of the surface treatment
Join agent in any one or at least two mixture.
Preferably, in terms of by inorganic filler for 100 parts by weight, the dosage of the surface treating agent is 0.1~5.0 parts by weight,
It is preferred that 0.5~3.0 parts by weight, more preferable 0.75~2.0 parts by weight.
Preferably, the inorganic filler is selected from nonmetal oxide, metal nitride, non-metal nitride, inorganic hydration
In object, inorganic salts, metal hydrate or Phos any one or at least two mixture, preferred molten titanium dioxide
Silicon, crystalline sillica, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, nitrogen
Change the mixing of one of boron, silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates or mica or at least two
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, in terms of by the sum of additive amount of component (A), component (B), component (C) and component (D) for 100 parts by weight, institute
The additive amount 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 especially except described group
Assign the halogen-free thermosetting resin composite different characteristics.In addition to this, " comprising " of the present invention can also replace
For enclosed " for " or " by ... form ".
For example, the halogen-free thermosetting resin composite can also contain various additives, as concrete example, can enumerate
Phosphonium flame retardant, antioxidant, heat stabilizer, antistatic agent, ultraviolet absorbing agent, pigment, colorant or lubricant etc..These are each
Kind additive can be used alone, and two or more can also be used in mixed way.
Halogen-free thermosetting resin composite customary preparation methods of the invention are as follows: first solid content is put into, liquid is then added
State solvent adds liquid resin and promotor, continues to stir evenly after stirring is completely dissolved to solid content.
As the solvent in the present invention, there is no particular limitation, as concrete example, can enumerate methanol, ethyl alcohol, butanol
Equal 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.The above solvent can be used alone, can also 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.
Prepreg of the invention include reinforcing material and impregnation it is dry after be attached to nothing as described above on reinforcing material
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 choose aramid nonwoven, the inorfil woven cloth can for E- glass-fiber-fabric,
D- glass-fiber-fabric, S- glass-fiber-fabric, T glass-fiber-fabric, NE- glass-fiber-fabric 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.
Laminate for printed circuits of the invention includes by being heated and pressurizeed, making the prepreg of a piece of or two panels or more viscous
It is combined and manufactured laminate, and is bonded in the metal foil of laminate one or both sides or more.The laminate is
Solidify in hot press and be made, solidification temperature is 150 DEG C~250 DEG C, and solidifying pressure is 10~60Kg/cm2.The metal foil
For copper foil, nickel foil, aluminium foil and SUS foil etc., material is unlimited.
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 can be embodied and have the effect of mutual catalyzing cooperation；Cyanate can bring the high-fire resistance and low medium damage of system
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 generate 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 be reacted 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 react at very high temperatures with epoxy resin, and cyanic acid
- OCN the group of ester is just easy to react with the low activity hydroxyl of both of the above at 90~120 DEG C, then at 130 DEG C or more
It decomposes, phenol negative oxygen ion can be generated in decomposable process.Phenol negative oxygen ion is easy to react with epoxy resin, 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 made to be formed by curing the triazine ring that crosslink density is big, symmetry is high, so that system be made to have
High glass transition temperature and good dielectric properties.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, is being used as
The effect of there are also halogen-free flameproofs while curing agent can add on a small quantity or without can just plate be made to reach in the other fire retardants of addition
To the effect of UL94V-0 halogen-free flameproof.
Prepreg made of halogen-free thermosetting resin composite provided by the present invention and laminate for printed circuits, have
Up to 245 DEG C of glass transition temperature；Excellent dielectric properties, water absorption rate control within the scope of 0.07-0.11%；High heat resistance
Property；Peel strength is 0.9-1.2N/mm；Excellent humidity resistance and good technique processability, and it is able to achieve halogen-free flameproof,
Reach UL94V-0.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
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, without departing from the principles of the embodiments of the present invention, several improvements and modifications can also be made, these improvement
Also it is considered as the protection scope of the embodiment of the present invention 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, appropriate can change implementation.
1, polyphenylene oxide is reallocated
4000g toluene is stirred and heated to 100 DEG C in the three-necked bottle that blender, condensing reflux pipe, thermometer are housed, so
The PPO resin that 2000g number-average molecular weight is 20000 is added afterwards, 250g 3,5,3', 5'- tetramethyl are added after becoming homogeneous phase
Base -4,4'- dihydroxybiphenyl stirs 30min, the 150g benzoyl peroxide (BPO) being dissolved in toluene is then added, and keep
Temperature is 92 DEG C, reacts 240min.Then product is cooled to room temperature and 4000ml methanol is then added, and be vigorously stirred, filtering,
It is dry, bifunctional base PPO resin (PPO-2) 2100g of small molecule is obtained, its Mn=2118 is tested by GPC.
4000g toluene is stirred and heated to 100 DEG C in the three-necked bottle that blender, condensing reflux pipe, thermometer are housed, so
The PPO resin that 2000g number-average molecular weight is 20000 is added afterwards, 120g bisphenol-A (BPA) is added after becoming homogeneous phase, stirring
Then the 60g benzoyl peroxide (BPO) being dissolved in toluene is added in 30min, and keeping temperature is 92 DEG C, reacts 360min.So
Product is cooled to room temperature afterwards, 4000ml methanol is then added, and be vigorously stirred, filtered, dries, obtain double officials of small molecule
Energy base PPO resin (PPO-3) 2000g, tests its Mn=4088 by GPC.
4000g toluene is stirred and heated to 100 DEG C in the three-necked bottle that blender, condensing reflux pipe, thermometer are housed, so
The PPO resin that 2000g number-average molecular weight is 20000 is added afterwards, (the Honshu 120g TrisP-PA is added after becoming homogeneous phase
It learns)
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 room temperature is cooled to then to be added
4000ml methanol, and be vigorously stirred, it filters, dry, obtain bifunctional base PPO resin (PPO-4) 2000g of small molecule, lead to
It crosses GPC and tests its Mn=3120.
4000g toluene is stirred and heated to 100 DEG C in the three-necked bottle that blender, condensing reflux pipe, thermometer are housed, so
The PPO resin that 2000g number-average molecular weight is 20000 is added afterwards, (the Honshu 120g TekP-4HBPA is added after becoming homogeneous phase
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 room temperature is cooled to then to be added
4000ml methanol, and be vigorously stirred, it filters, dry, obtain bifunctional base PPO resin (PPO-5) 2000g of small molecule, lead to
It crosses GPC and tests its Mn=2480.
2, the preparation of phosphorous bis-phenol polymer
In N2Under the conditions of, be added 77g hydroquinone (0.70mol) and 130.5g diphenyl methylphosphonate (DPP,
0.526mol) and catalyst tetraphenylphosphoniphenolate phenates (TPPP (30% phenol), 0.051g, 0.083mol), vacuum degree is reduced
To 10mmHg, while 240 DEG C are heated the mixture to, reacted 10 hours.By-product phenol is boiled off, 0.255g catalyst is added,
And it is kept for 210 DEG C/10mmHg condition 4 hours.Post-processing purification, two ends for obtaining chain are the phosphorous of reactive phenolic hydroxyl group
Bis-phenol polymer C-1.Its Mn=8510 is tested by GPC.
In N2Under the conditions of, 147g4,4`- '-biphenyl diphenol (Biphenol, 0.79mol) and 130.5g diphenyl methyl is added
Phosphonate ester (DPP, 0.526mol) and catalyst tetraphenylphosphoniphenolate phenates (TPPP (30% phenol), 0.051g, 0.083mol), will
Vacuum degree 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 kept for 265 DEG C/10mmHg condition 2 hours.Post-processing purification obtains two ends of chain as reactivity
Phenolic hydroxyl group phosphorous bis-phenol polymer C-2.Its Mn=2600 is tested by GPC.
In N2Under the conditions of, 232.8g BisP-TMC (Honshu chemistry) (0.75mol) and 130.5g diphenyl methyl is added
Phosphonate ester (DPP, 0.526mol) and catalyst tetraphenylphosphoniphenolate phenates (TPPP (30% phenol), 0.051g, 0.083mol), will
Vacuum degree 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 kept for 265 DEG C/10mmHg condition 2 hours.Post-processing purification obtains two ends of chain as reactivity
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 uniformly mixed in solvent by a certain percentage, and control glue solid content is 65%, are impregnated with 2116 glass-fiber-fabrics
Above-mentioned glue controls suitable thickness, then toasts 2~15min in 115~175 DEG C of baking oven and prepreg is made, then will count
Prepreg stacks, and is 170~250 DEG C in solidification temperature in the stacked on 18 μ RTF copper foil in its two sides, and solidifying pressure is 25~
60kg/cm2, curing time be 60~300min under the conditions of copper-clad plate is made.
Embodiment 1-8 and comparative example 1-13 is related to material and trade mark information is as follows:
(A) cyanate
CY-40: Wuqiao resin factory, DCPD type cyanate ester resin
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: self-control small molecule PPO resin, Mn=2118
PPO-3: self-control small molecule PPO resin, Mn=4088
PPO-4: self-control small molecule PPO resin, Mn=3120
PPO-5: self-control small molecule PPO resin, Mn=2480
(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 name, phosphorus content 8.5%)
OL-3001: phosphorous bis-phenol polymer, (U.S.'s FRX Polymers trade name, 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: big tomb chemistry, phosphine nitrile fire retardant, phosphorus content 13.4%
(F) promotor
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, 99% or more purity)
Table 1-3 is the formula composition and its physical data of embodiment 1-8 and comparative example 1-13.
Table 1
Table 2
Table 3
The test method of the above 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 defined
Method for testing is measured.
(2) it dielectric constant and dielectric loss factor: is tested according to SPDR method.
(3) humidity resistance (PCT) is evaluated: after the copper foil on copper-clad plate surface is etched, evaluating substrate；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 furnace, 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 furnace more than 5min, PCT/6h performance map
Target supplementary explanation: × to be layered plate bursting, O is not stratified plate bursting, and every piece of plate three samples of selection do and test three times.
(4) humidity resistance (high temperature and humidity) is evaluated: after the copper foil on copper-clad plate surface is etched, evaluating substrate；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 furnace, when substrate de-lamination plate bursting
The Shi Jilu corresponding time；It can terminate to evaluate when substrate also does not occur blistering or being layered in tin furnace more than 5min, high temperature is high
Wet/192h performance map target supplementary explanation: × to be layered plate bursting, O is not stratified plate bursting, and every block of plate chooses three samples and does three
Secondary experiment.
(5) it water imbibition: is measured according to the water imbibition test method of IPC-TM-650 2.6.2.1 defined.
(6) it peel strength: is measured according to the peel strength test method of IPC-TM-650 2.4.8 defined.
(7) T300: TMA instrument is used, is measured according to the T300 test method of IPC-TM-650 2.4.24.1 defined.
(8) it anti-flammability: is carried out according to 94 standard method of UL.
It can be seen that comparative example 1 from the physical data of table 1-3 and embodiment 1 compare, cyanate ester resin in resin combination
Dosage is few, and manufactured copper-clad plate dielectric properties are poor, and heat resistance is general；Comparative example 2 and embodiment 4 compare, resin combination
Middle polyphenylene oxide dosage is few, causes rigid structure in system few, so that its heat resistance be made to be decreased obviously, is embodied in T300 and only has
5.6min；Comparative example 3 and embodiment 8 compare, and are added to very few epoxy resin, and curing agent is excessive in system, and epoxy amount is insufficient,
System cannot solidify well, glass transition temperature decline；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 dosage is excessive, also results in humidity resistance (PCT, high temperature and humidity) degradation；Comparative example 4 and embodiment 2
It compares, phosphorous bis-phenol polymer volume is very few, and manufactured copper-clad plate dielectric properties are poor；Cyanate resin is not added in comparative example 5
Copper-clad plate heat resistance made by rouge is poor；It is not added in comparative example 6 in polyphenylene oxide resin and comparative example 7 and is not added with phosphorous bis-phenol
It is poor that copper-clad plate dielectric properties and peel strength made by halogen-free epoxy resin are not added in polymer and comparative example 8；
Compared with Example 7, cyanate ester resin dosage is excessive, and content of epoxy resin is less for comparative example 9, made copper-clad plate dielectricity
It can be poor；Compared with Example 2, polyphenylene oxide dosage is excessive for comparative example 10, manufactured copper-clad plate humidity resistance, heat resistance and removing
Intensity is poor；Compared with Example 4, phosphorous bis-phenol polymer volume is excessive for comparative example 11, and manufactured copper-clad plate Tg sharply declines,
Humidity resistance and water absorption rate are deteriorated；Compared with Example 1, content of epoxy resin is excessive for comparative example 12, and curing agent is obviously insufficient, leads
The comprehensive performances such as copper-clad plate electrical property, heat resistance, peel strength made of causing obviously are deteriorated；Comparative example 13 compared with Example 4,
The halogen-free phosphorus-containing fire retardant agent used, is single phenol phosphonate, only one curing activity point causes one end that can participate in solid
Change, the free end that the other end can disturb when heated causes its Tg, T300, dielectric properties, humidity resistance etc. to be all deteriorated；Implement
Example 1-8 is 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 it is able to achieve halogen-free flameproof, reach UL94V-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 have high glass-transition temperature, excellent dielectric properties, low water absorption, high heat resistance
Property, high peel strength, excellent humidity resistance and good technique processability, and it is able to achieve halogen-free flameproof, reach
UL94V-0。
The above, only presently preferred embodiments of the present invention for those of ordinary skill in the art can bases
Technical solution of the present invention and technical concept make other various corresponding changes and modifications, and all these change and modification are all
It should belong to the range of the claims in the present invention.
Claims (46)
1. a kind of halogen-free thermosetting resin composite, organic solid content based on 100 parts by weight, it includes:
(A) 10~50 parts by weight of cyanate ester resin；
(B) 5~40 parts by weight of polyphenylene oxide resin；
(C) phosphorous 8~30 parts by weight of bis-phenol polymer；
(D) 30~58 parts by weight of halogen-free epoxy resin；
The phosphorous bis-phenol polymer has the following structure:
Wherein, R20、R21Be it is identical or different, be selected from In appoint
It anticipates a kind of or at least two mixtures；
Wherein, R11For H, the carbon atom number substituted or unsubstituted straight chained alkyl that is 1~4 or branched alkyl, substituted 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 atom number
Substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or
Any one in unsubstituted cyclohexyl or allyl；
Wherein, R22For the substituted or unsubstituted straight chained alkyl of C1~C20, C1~C20 substituted or unsubstituted branched alkyl,
The substituted or unsubstituted linear alkene base of C2~C20, the substituted or unsubstituted branched-chain alkene base of C2~C20, C2~C20
Substituted or unsubstituted straight-chain alkyl-sub, the substituted or unsubstituted branched alkylidene of C2~C20, the substitution of C5~C20 or not
Any one in the substituted or unsubstituted aryl of substituted naphthenic base or C6~C20；
Wherein, n2For 3~75 arbitrary integer；Wherein, n3、n4It is identical or different, selected from 0~4 integer；
Wherein, k, j are 0 or 1, but cannot simultaneously be 0.
2. halogen-free thermosetting resin composite as described in claim 1, which is characterized 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、R9It is each independently selected from hydrogen atom, C1-C4 takes
Any one in generation or unsubstituted straight chained alkyl or the substituted or unsubstituted branched alkyl of C1-C4.
3. halogen-free thermosetting resin composite as claimed in claim 2, which is characterized in that the cyanate ester resin is that 2,2- is bis-
(4- cyanato- phenyl) propane, bis- (4- cyanato- phenyl) ethane, bis- (3,5- dimethyl -4- cyanato- phenyl) methane, 2,2-
Bis- (4- cyanato- phenyl) -1,1,1,3,3,3- hexafluoropropane, α, α '-bis- (4- cyanato- phenyl)-diisopropyl benzenes, ring penta
Bis- (4- cyanato- phenyl) the propane pre-polymerizations of diene type cyanate, phenol novolak type cyanate, cresol novolak type cyanate, 2,2-
Object, bis- (4- cyanato- phenyl) ethane prepolymers, bis- (3,5- dimethyl -4- cyanato- phenyl) methane prepolymers, the bis- (4- of 2,2-
Cyanato- phenyl) -1,1,1,3,3,3- hexafluoropropane prepolymer, α, bis- (4- cyanato- the phenyl)-diisopropyl benzene pre-polymerizations of α ' -
In object, dicyclopentadiene type ethylene rhodanate prepolymer, phenol novolak type cyanate prepolymer or cresol novolak type cyanate prepolymer
Any one or at least two mixture.
4. halogen-free thermosetting resin composite as claimed in claim 3, which is characterized in that the cyanate ester resin is that 2,2- is bis-
(4- cyanato- phenyl) propane, α, bis- (4- cyanato- the phenyl)-diisopropyl benzenes of α ' -, bis- (3,5- dimethyl -4- cyanato-s
Phenyl) methane, 2,2- bis- (4- cyanato- phenyl) propane prepolymers, α, bis- (4- cyanato- the phenyl)-diisopropyl benzenes of α '-are pre-
In polymers or bis- (3,5- dimethyl -4- cyanato- phenyl) methane prepolymers any one or at least two mixture.
5. halogen-free thermosetting resin composite as claimed in claim 1 or 2, which is characterized in that the polyphenylene oxide resin has
Such as flowering structure:
Wherein, R10For
In any one or at least two mixture；
Wherein, R11For H, the carbon atom number substituted or unsubstituted straight chained alkyl that is 1~4 or branched alkyl, substituted or unsubstituted
Phenyl in any one；
Wherein, R12、R13、R14、R15、R16、R17、R18、R19It is identical or different, selected from H, F, the substitution or not that carbon atom number is 1~4
It is substituted straight chained alkyl or branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted
Any one in cyclohexyl or allyl；
n1、n2、n3、n40~40 positive integer is stood alone as, and meets 8≤n1+n2+n3+n4≤40。
6. halogen-free thermosetting resin composite as described in claim 1, which is characterized in that the knot of the phosphorous bis-phenol polymer
In structure, n2For 4~60 arbitrary integer.
7. halogen-free thermosetting resin composite as claimed in claim 6, which is characterized in that the knot of the phosphorous bis-phenol polymer
In structure, n2For 5~50 arbitrary integer.
8. halogen-free thermosetting resin composite as claimed in claim 7, which is characterized in that the knot of the phosphorous bis-phenol polymer
In structure, n2For 5~40 arbitrary integer.
9. halogen-free thermosetting resin composite as claimed in claim 8, which is characterized in that the knot of the phosphorous bis-phenol polymer
In structure, n2For 8~30 arbitrary integer.
10. halogen-free thermosetting resin composite as claimed in claim 9, which is characterized in that the phosphorous bis-phenol polymer
In structure, n2For 10~25 arbitrary integer.
11. halogen-free thermosetting resin composite as described in claim 1, which is characterized in that the halogen-free epoxy resin is contracting
Water glycerol ethers, glycidol esters, glycidol amine, cycloaliphatic epoxy resin, epoxidation of olefins class, glycolylurea epoxide resin
In acid imide epoxy resin any one or at least two mixture.
12. halogen-free thermosetting resin composite as claimed in claim 11, which is characterized in that the glycidol ethers are double
Phenol A type epoxy resin, bisphenol f type epoxy resin, Study On O-cresol Epoxy Resin, bisphenol A-type novolac epoxy resin, three phenolic phenol
Formaldehyde epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl type novolac epoxy resin, alkyl benzene-type novolac epoxy resin or naphthalene
In phenolic novolac epoxy resin any one or at least two mixture.
13. halogen-free thermosetting resin composite as claimed in claim 11, which is characterized in that the glycidol ethers are tool
Just like the epoxy resin of flowering structure:
Wherein, Z1、Z2And Z3It is each independently selected fromR27Selected from hydrogen atom, replace or not
Replace the straight chained alkyl or branched alkyl containing carbon number 1~5 in any one；
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.
14. halogen-free thermosetting resin composite as claimed in claim 11, which is characterized in that the glycidol amine is selected from
Triglycidyl group-p- amino-phenol, triglycidyl group isocyanuric acid ester, four glycidyl group diamino dimethylene
Benzene, two amido diphenyl-methane of four glycidyl group -4,4`-, four glycidyl group -3,4`- diaminodiphenyl ether, four glycidols
Any one in base -4,4`- diaminodiphenyl ether or four glycidyl group -1,3- bis aminomethyl hexamethylene or at least two
Mixture.
15. halogen-free thermosetting resin composite as described in claim 1, which is characterized in that the halogen-free thermosetting resin group
Closing object further includes component (E) phosphonium flame retardant.
16. halogen-free thermosetting resin composite as claimed in claim 15, which is characterized in that the phosphonium flame retardant is three
(2,6- 3,5-dimethylphenyl) phosphine, the miscellaneous -10- phosphine phenanthrene -10- oxide of 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy, 2,
6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, the miscellaneous -10- phosphine phenanthrene -10- oxide of 10- phenyl -9,10- dihydro-9-oxy, phenoxy group
In phosphazene compound, phosphate or polyphosphate any one or at least two mixture.
17. halogen-free thermosetting resin composite as claimed in claim 15, which is characterized in that with component (A), component (B), group
Dividing the sum of (C), component (D) additive amount is 100 parts by weight meters, and the additive amount of component (E) phosphonium flame retardant is 0~5 parts by weight.
18. halogen-free thermosetting resin composite as described in claim 1, which is characterized in that the halogen-free thermosetting resin group
Closing object further includes component (F) curing accelerator.
19. halogen-free thermosetting resin composite as claimed in claim 18, which is characterized in that the curing accelerator is organic
Metal salt, glyoxaline compound, the derivative of glyoxaline compound, piperidines, pyridines, lewis acid or triphenyl
In phosphine any one or at least two mixture.
20. halogen-free thermosetting resin composite as claimed in claim 19, which is characterized in that the organic metal salt is octanoic acid
In metal salt, isooctyl acid metal salt, acetyl acetone salt, metal naphthenate, salicylic acid metal salt or Metallic stearates
Any one or at least two mixture, wherein the metal be zinc, copper, iron, tin, cobalt or aluminium in any one or
At least two mixture.
21. halogen-free thermosetting resin composite as claimed in claim 19, which is characterized in that the glyoxaline compound is 2-
Any one in methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole or 2- undecyl imidazole or at least two
Mixture.
22. halogen-free thermosetting resin composite as claimed in claim 19, which is characterized in that the piperidines are 2,
3- diamino phenylpiperidines, 2,5- diamino phenylpiperidines, 2,6- diamino phenylpiperidines, 2- amino -3- methyl piperidine, 2- amino -4- methyl piperazine
In pyridine, 2- amino -3- nitro piperidines, 2- amino -5- nitro piperidines or 2- amino -4,4- lupetidine any one or extremely
Few two kinds of mixture.
23. halogen-free thermosetting resin composite as claimed in claim 19, which is characterized in that the pyridine compounds and their is 4-
In dimethylamino naphthyridine, 2-aminopyridine, 3- aminopyridine or 4-aminopyridine any one or at least two mixture.
24. halogen-free thermosetting resin composite as claimed in claim 18, which is characterized in that with component (A), component (B), group
The sum of additive amount of part (C) and component (D) is 100 parts by weight meters, the additive amount of component (F) curing accelerator for 0.01~
1 parts by weight.
25. halogen-free thermosetting resin composite as claimed in claim 24, which is characterized in that with component (A), component (B), group
The sum of additive amount of part (C) and component (D) is 100 parts by weight meters, and the additive amount of component (F) curing accelerator is 0.025
~0.85 parts by weight.
26. halogen-free thermosetting resin composite as described in claim 1, which is characterized in that the halogen-free thermosetting resin group
Closing object further includes component (G) filler.
27. halogen-free thermosetting resin composite as claimed in claim 26, which is characterized in that the filler is selected from organic filler
Or inorganic filler.
28. halogen-free thermosetting resin composite as claimed in claim 27, which is characterized in that the filler is inorganic filler.
29. halogen-free thermosetting resin composite as claimed in claim 26, which is characterized in that the filler be by surface at
The inorganic filler of reason.
30. halogen-free thermosetting resin composite as claimed in claim 26, which is characterized in that the filler be by surface at
The silica of reason.
31. halogen-free thermosetting resin composite as claimed in claim 29, which is characterized in that at the surface of the surface treatment
Manage agent in silane coupling agent, silicone oligomer or titanate coupling agent any one or at least two mixture.
32. halogen-free thermosetting resin composite as claimed in claim 31, which is characterized in that with inorganic filler for 100 weight
Part meter, the dosage of the surface treating agent are 0.1~5.0 parts by weight.
33. halogen-free thermosetting resin composite as claimed in claim 32, which is characterized in that with inorganic filler for 100 weight
Part meter, the dosage of the surface treating agent are 0.5~3.0 parts by weight.
34. halogen-free thermosetting resin composite as claimed in claim 33, which is characterized in that with inorganic filler for 100 weight
Part meter, the dosage of the surface treating agent are 0.75~2.0 parts by weight.
35. halogen-free thermosetting resin composite as claimed in claim 27, which is characterized in that the inorganic filler is selected from non-gold
Belong to any in oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salts, metal hydrate or Phos
It is a kind of or at least two mixture.
36. halogen-free thermosetting resin composite as claimed in claim 35, which is characterized in that the inorganic filler is melting two
Silica, crystalline sillica, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, talcum powder, nitridation
One of aluminium, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates or mica or at least two
Mixture.
37. halogen-free thermosetting resin composite as claimed in claim 27, which is characterized in that the organic filler is selected from poly- four
In vinyl fluoride powder, polyphenylene sulfide or polyether sulfone powder any one or at least two mixture.
38. halogen-free thermosetting resin composite as claimed in claim 27, which is characterized in that the median of the filler is
0.01~50 μm.
39. halogen-free thermosetting resin composite as claimed in claim 38, which is characterized in that the median of the filler is
0.01~20 μm.
40. halogen-free thermosetting resin composite as claimed in claim 39, which is characterized in that the median of the filler is
0.1~10 μm.
41. halogen-free thermosetting resin composite as claimed in claim 26, which is characterized in that with component (A), component (B), group
Dividing the sum of additive amount of (C) and component (D) is 100 parts by weight meters, and the additive amount of component (G) filler is 5~300 weight
Part.
42. halogen-free thermosetting resin composite as claimed in claim 41, which is characterized in that with component (A), component (B), group
Dividing the sum of additive amount of (C) and component (D) is 100 parts by weight meters, and the additive amount of component (G) filler is 5~200 weight
Part.
43. halogen-free thermosetting resin composite as claimed in claim 42, which is characterized in that with component (A), component (B), group
Dividing the sum of additive amount of (C) and component (D) is 100 parts by weight meters, and the additive amount of component (G) filler is 5~150 weight
Part.
44. a kind of prepreg comprising reinforcing material and by after impregnation drying it is attached thereto as claim 1-43 it
Halogen-free thermosetting resin composite described in one.
45. a kind of laminate, the laminate contains an at least prepreg as claimed in claim 44.
46. a kind of halogen-less high frequency circuit substrate, the substrate contain at least one prepreg as claimed in claim 44 and
The metal foil of prepreg one or both sides after being overlying on overlapping.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610137438.3A CN107177030B (en) | 2016-03-10 | 2016-03-10 | A kind of halogen-free thermosetting resin composite and prepreg and laminate for printed circuits using it |
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610137438.3A CN107177030B (en) | 2016-03-10 | 2016-03-10 | A kind of halogen-free thermosetting resin composite and prepreg and laminate for printed circuits using it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107177030A CN107177030A (en) | 2017-09-19 |
| CN107177030B true CN107177030B (en) | 2019-06-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610137438.3A Expired - Fee Related CN107177030B (en) | 2016-03-10 | 2016-03-10 | A kind of halogen-free thermosetting resin composite and prepreg and laminate for printed circuits using it |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN107177030B (en) |
| TW (1) | TWI619766B (en) |
| WO (1) | WO2017152602A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN110452545B (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 |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020830A (en) * | 2010-12-23 | 2011-04-20 | 广东生益科技股份有限公司 | Halogen-free fire resistance resin composite and application thereof |
| CN102181143A (en) * | 2011-04-08 | 2011-09-14 | 苏州生益科技有限公司 | High-frequency thermosetting resin composition, prepreg and laminated sheet |
| CN102585480A (en) * | 2011-12-29 | 2012-07-18 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg prepared from composition, and laminated board prepared from composition and used for printed circuit board |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103443159A (en) * | 2011-03-24 | 2013-12-11 | 三菱瓦斯化学株式会社 | Resin composition, prepreg and resin sheet, and metal foil-lad laminate |
| TW201313462A (en) * | 2011-06-03 | 2013-04-01 | Arisawa Seisakusho Kk | Flame-retardant resin composition and flexible printed wiring board metal-clad laminate, cover-lay, flexible printed wiring board adhesive sheet, and flexible printed wiring board, which use this resin composition |
| CN103396434A (en) * | 2013-07-22 | 2013-11-20 | 荆州市江汉精细化工有限公司 | Synthesis method of vinyltrimethoxysilane oligomer |
-
2016
- 2016-03-10 CN CN201610137438.3A patent/CN107177030B/en not_active Expired - Fee Related
- 2016-09-08 WO PCT/CN2016/098450 patent/WO2017152602A1/en active Application Filing
- 2016-10-03 TW TW105131954A patent/TWI619766B/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020830A (en) * | 2010-12-23 | 2011-04-20 | 广东生益科技股份有限公司 | Halogen-free fire resistance resin composite and application thereof |
| CN102181143A (en) * | 2011-04-08 | 2011-09-14 | 苏州生益科技有限公司 | High-frequency thermosetting resin composition, prepreg and laminated sheet |
| CN102585480A (en) * | 2011-12-29 | 2012-07-18 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg prepared from composition, and laminated board prepared from composition and used for printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201731955A (en) | 2017-09-16 |
| TWI619766B (en) | 2018-04-01 |
| WO2017152602A1 (en) | 2017-09-14 |
| CN107177030A (en) | 2017-09-19 |
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