CN1350030A - Fireproof epoxy resin composite and its application - Google Patents
Fireproof epoxy resin composite and its application Download PDFInfo
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- CN1350030A CN1350030A CN00130176A CN00130176A CN1350030A CN 1350030 A CN1350030 A CN 1350030A CN 00130176 A CN00130176 A CN 00130176A CN 00130176 A CN00130176 A CN 00130176A CN 1350030 A CN1350030 A CN 1350030A
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Abstract
The present invention relates to a flame retardant epoxy resin composite, which is characterized by that it contains (A) at least one kind of epoxy resin and (B) heterocyclic compound containing phosphorus and nitrogen, and said compound possesses the group capable of reacting with epoxy radical being in epoxy resin, and can be used as solidifying agent of epoxy resin. Said epoxy resin composite formed from said components of (A) and (B) possesses improved flame retardant property, suitable for flame retardant material, can be used for making composite material, laminated board, printed circuit board and electronic and electric products. Besides, the solidifying agent containing no phosphorus, solidification accelerant and other additives of solvent, etc. can be selectively added.
Description
The present invention relates to a kind of flame-retardant epoxy resin omposition, it is characterized by and comprise: (A) at least a Resins, epoxy; And (B) phosphorous, nitrogen heterocyclic, this compound have can with the group of epoxy reaction in the Resins, epoxy, can be used as epoxy curing agent.
Above-mentioned flame-retardant epoxy resin omposition does not contain flame retardant resistance material commonly used such as halogen compounds and antimonous oxide, and can reach the flame-retarding characteristic standard of UL94V-0, have excellent fire retardant character, be fit to be used as the material of parts required in the associated uses such as making electronic product, electric product and auto parts with heat-resisting or flame-retardant nature.
The epoxide of knowing commonly used is restricted the scope of its application owing to combustioncharacteristics itself, and the known resin that contains halogen or alkylhalide group group that adds in epoxide can improve the flame-retardant nature of epoxide.Traditionally, for the flame retardant resistance of improving polymkeric substance or its composition is used halogenated organic compound widely or is contained the flame retardant resistance material of oxidizing substances such as antimony, vanadium and so on, with the high composition of formation thermotolerance, yet often need to add high-load this class just can reach flame retardant resistance through halogenated resin or metal oxides such as polymkeric substance or antimony requirement.
Because Resins, epoxy itself has the security of easy processibility, height, excellent mechanical properties and chemical property etc., be widely used in every field, as the matrix material application facet, for example: purposes such as application, electric insulation, building building materials, tackiness agent and laminated products; Resins, epoxy is strong to the bounding force of strongtheners such as glasscloth again, so do not produce fugitive constituent during curing and the less Resins, epoxy that also uses at present of mould shrinkage is made veneer sheet; The veneer sheet that is made by Resins, epoxy has been used as the material of products such as electric and electronics and parts in large quantities on the other hand.
The making of quite valued printed circuit board (PCB) at present, except the line pattern on the circuit card is required the precision, veneer sheet also requires to have excellent electrical properties, mechanical properties and processing thermotolerance.Common FR4 veneer sheet or increase layer and use the gum Copper Foil, the second-order transition temperature of the resin behind most the curing is about 130 ℃, for the cutting and the boring processing that surpass 200 ℃ in the printed circuit board (PCB) processing procedure, even the welding sequence more than 270 ℃, make and may break in the veneer sheet manufacturing and the course of processing or the situation of plate bursting, therefore the various resins of high thermal stability, high glass-transition temperature of emphasizing are developed successively.In addition, for the veneer sheet of use in printed circuit board, another important properties is a flame-retarding characteristic, and to the scope of some application, for example aircraft, automobile and public transportation vehicle etc., the flame-retarding characteristic of printed circuit board (PCB) are absolute necessary.
For flame-retarding characteristic is introduced in the laminate sheet material, must use some to have and isolate the material that flame reduces ignition quality.For the veneer sheet of Resins, epoxy/glass fibre class (or organic fibre) or increase layer insulating material, generally be to add halogen contained compound, particularly bromated Resins, epoxy and solidifying agent, and cooperation requires (as the UL94V-0 grade) as the flame retardant of antimonous oxide and so in the hope of the harshness that can reach the veneer sheet flame-retarding characteristic.Usually the fire retardant matter in the Resins, epoxy need contain the bromine content up to 21%, and is used antimonous oxide or other fire retardant, just can reach the standard of UL94V-0, yet uses high bromine content Resins, epoxy or antimonous oxide, the health of meeting harm humans; On the other hand, bromine can produce toxic smokes such as mordant bromine free radical and hydrogen bromide in the incendiary process, the aromatics of high bromine content more can produce the bromination furans of severe toxicity and Xiuization dioxin or the like compound, badly influence people's health and environment.Therefore, seeking a kind of new fire retardant material and fire-retardantization method, to improve product such as present veneer sheet or parts because of pollution and environmental issue that the Resins, epoxy that uses bromine-containing compound or bromination causes, has been instant thing.Especially, in order to satisfy the electric needs that wait product and parts to use the epoxy fiberglass layer pressing plate of FR-4 class in a large number, more answer the active development can harm humans and the fire-retarded epoxy resin material of environment.
In recent years,, developed multiple new flame-retardant materials, the wherein extensively received technology that has the use P contained compound to replace traditional flame retardant resistance materials such as bromine-containing compound for safeguarding human beings'health and reducing environomental pollution source.At present study and use the flame retardant resistance material with environmental protection notion of Phosphorus compound widely as a new generation, for example directly add red phosphorus or phosphorated organic compound (such as triphenyl, trityl phosphoric acid ester etc.) etc. material is to replace halogen compounds as fire retardant, and improve the ignition quality of macromolecular material or curable resin material, yet, add this compounds to resin, often need directly to add such a large amount of flame retardant resistance materials and just flame retardant effect can be arranged, and because the molecular weight of compound is lower, the higher transport property (migration) that it has will directly influence the character of resin base material, electrical properties for example, bond strength, character such as thermotolerance are understood variation, thereby cause the difficulty in the application.
The phosphorous epoxy resin that had developed response type afterwards replaces the technology of the Resins, epoxy of general employed brominated or bromination as the flame retardant resistance composition, for example: United States Patent (USP) the 5th, 376, the veneer sheet that the composition that uses phosphoric acid ester with epoxy group(ing) and nitrogen-containing hardener makes is disclosed for No. 453, it must add the multiple Resins, epoxy of phosphoric acid ester that contains to increase phosphorus content in order to remedy the not combustion standard of readily accessible UL94V-0; At United States Patent (USP) the 5th, 458, in No. 978, its use be the composition that forms by epoxy phosphate ester, nitrogen-containing epoxy thermoset and metal composite solidifying agent, its second-order transition temperature is about 175 ℃, has the flame-retardant nature that approaches UL94V-0 (42 seconds, with respect to threshold value 50 seconds); At United States Patent (USP) the 4th, 973,631 and 5, in 086, No. 156, used separately have the active hydrogen substituting group (for example amido) the trihydrocarbyl phosphine oxide compound or cooperate other amine curing agent in order to cured epoxy resin, by this curing mode phosphorus is introduced in the resin, but the content of phosphorus is lower, can't reach fire-retardant effect, the flame retardant resistance effect of not surveying in these two parts of patents.Technology by above-mentioned patent disclosure can be recognized; for improving flame-retardant nature; often need to add the standard that multiple or high-load P contained compound just can reach flame retardant resistance, but the adding regular meeting of multiple additional additive makes the processing conditions of product wayward or the quality of product is descended.
Therefore, the method that improves flame retardant resistance at present is to use nitrogenous and phosphorated material to replace the materials such as brominated or antimony that use traditionally.
The environmental issue that the present inventor produces at the flame retardant resistance material that added objectionable impuritiess such as halogen-containing or antimony in the past, but developed a kind of fire-retardant compound of compliance with environmental protection requirements, it is a kind of phosphorous, nitrogen heterocyclic, textural have can with the group of the epoxy reaction of Resins, epoxy, can be used as the curing agent component of composition epoxy resin.
Main purpose of the present invention provides a kind of flame-retardant epoxy resin omposition, and it is to add a kind of phosphorous, the nitrogen heterocyclic of effective content in Resins, epoxy, thereby the flame resistivity matter of composition epoxy resin is improved;
Another purpose of the present invention provides another kind of composition epoxy resin, and it is except that a kind of phosphorous, the nitrogen heterocyclic that adds effective content in Resins, epoxy, also comprise not the phosphorated solidifying agent, and selectivity comprise curing catalyst and solvent;
A further object of the present invention provides described composition epoxy resin and is preparing film, laminate or plate, increasing layer application aspect veneer sheet with insulating material and printed circuit board (PCB) processing procedure.
A kind of flame-retardant epoxy resin omposition of the present invention is characterized by and comprises:
(A) at least a Resins, epoxy;
(B) phosphorous, nitrogen heterocyclic, this compound have can with the group of epoxy reaction in the Resins, epoxy, can be used as curing agent for epoxy resin, its structure is suc as formula shown in (I),
In the formula, m is 0～2 integer, and n is 3～7 integer, but wherein at least one m is not 2.
Reach the flame-retardant nature that the flame-retardant epoxy resin omposition of (B) being formed has improvement by mentioned component (A), be suitable as the required flame-retardant materials of parts such as matrix material, veneer sheet, printed circuit board (PCB) and electronics, electric product, and, optionally add not other additives such as phosphorated solidifying agent, curing catalyst and solvent according to applied scope.
For this reason, the present invention also provides another kind of flame-retardant epoxy resin omposition, it is characterized by to comprise:
(A) at least a Resins, epoxy;
(B) phosphorous, nitrogen heterocyclic, this compound have can with the group of epoxy reaction in the Resins, epoxy, can be used as curing agent for epoxy resin, its structure is suc as formula shown in (I),
In the formula, m is 0～2 integer, and n is 3～7 integer, but wherein at least one m is not 2;
(C) phosphorated solidifying agent not;
And optionally add
(D) curing catalyst;
(E) solvent.
In the present invention, (A) Resins, epoxy composition of composition can be general epoxide, and it can comprise the Resins, epoxy that one or more epoxide are formed, and its epoxy equivalent (weight) (EEW) that is characterized as of this Resins, epoxy is below 600.Can be used for Resins, epoxy of the present invention comprises: through bis-phenol, phenol, dihydroxy-benzene, two diphenol, naphthalene, alkyl, alkene alkane, nitrogen heterocyclic ring, cresols-aldehyde, resol, siloxanes or polysiloxane, and the group modified epoxide that contains epoxy group(ing) such as aryl phosphate ester.
In flame-retardant epoxy resin omposition of the present invention, Resins, epoxy with epoxy group(ing) comprises: glycidyl ether, glycidyl amine, epihydric alcohol sulfide and Racemic glycidol carbonic ether etc., and wherein preferably with through bis-phenol, two diphenol, dihydroxy-benzene, polyvalent alcohol, and the glycidyl ether that carries out modification such as silicone.
In the present invention, such specific examples through the glycidyl ether of special groups modification comprises: have-the Ph-X-Ph-group that (wherein X is CH
2, C (CH
3)
2, CH (CH
3), O, S, C=O, SO
2Deng) the diglycidylether through the bis-phenol modification, it comprises dihydroxyphenyl propane glycidyl ether, Bisphenol F glycidyl ether, dihydroxyphenyl propane D glycidyl ether, bisphenol S glycidyl ether, tetramethyl-dihydroxyphenyl propane glycidyl ether, tetramethyl-Bisphenol F glycidyl ether, tetramethyl-dihydroxyphenyl propane D glycidyl ether, tetramethyl-bisphenol S glycidyl ether etc.; The specific examples of the glycidyl ether of two diphenol modifications comprises: 4, and 4 '-diphenol glycidyl ether, 3,3 '-dimethyl-4,4 '-diphenol glycidyl ether, and 3,3 ', 5,5 '-tetramethyl--4,4 '-diphenol glycidyl ether etc.; The specific examples of dihydroxy-benzene glycidyl ether comprises: Resorcinol glycidyl ether, Resorcinol glycidyl ether, and isobutyl-Resorcinol glycidyl ether etc.; The specific examples of phenolic aldehyde polyglycidyl ether comprises: phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether, and bisphenol-A phenolic polyglycidyl ether etc.; The polyglycidyl ether specific examples of poly-hydroxy modification comprises: three (4-hydroxy phenyl) methane polyglycidyl ether, three (4-hydroxy phenyl) ethane polyglycidyl ether, three (4-hydroxy phenyl) propane polyglycidyl ether, three (4-hydroxy phenyl) butane polyglycidyl ether, three (3-methyl-4-hydroxy phenyl) methane polyglycidyl ether, three (3,5-dimethyl-4-hydroxy phenyl) methane polyglycidyl ether, four (4-hydroxy phenyl) ethane polyglycidyl ether, four (3,5-dimethyl-4-hydroxy phenyl) ethane polyglycidyl ether etc.; Above-mentioned Resins, epoxy can single form or the form of mixtures of multiple Resins, epoxy use.
In the present invention, three (4-hydroxy phenyl) methane polyglycidyl ether of the polymer with bis phenol A glycidyl ether of the preferred difunctionality base of above-mentioned Resins, epoxy composition, Resorcinol glycidyl ether, trifunctional base, four functional groups' four (4-hydroxy phenyl) ethane polyglycidyl ethers or cresols phenolic aldehyde polyglycidyl ether, its can single form or the form of mixtures of multiple Resins, epoxy use.
Resins, epoxy composition among the present invention also can use silicone or rubbery copolymer to carry out modification again.Described silicone compound is the end capped siloxanes of amido (trade(brand)name SF-8012 for example for example, available from Japan XINYUE), described rubbery copolymer is the multipolymer of the carboxy blocking of divinyl and vinyl cyanide (trade(brand)name CTBN for example for example, available from U.S. Goodrich company) or the end capped multipolymer of amido of divinyl and vinyl cyanide (for example trade(brand)name ATBN, available from U.S. Goodrich company).
In flame-retardant epoxy resin omposition of the present invention, in order to improve flame retardant resistance and stable on heating be (B) phosphorous, nitrogen heterocyclic, this compound have can with the group of epoxy reaction in the Resins, epoxy, it can be used as epoxy curing agent, its structure is suc as formula shown in (I)
In the formula, m is 0～2 integer, and n is 3～7 integer, but wherein at least one m is not 2.
In the present invention, contain can with the addition of the heterogeneous ring compound solidifying agent (B) of phosphorous, the nitrogen of the group of epoxy reaction, decide according to the epoxy equivalent (weight) of its reactive behavior hydrogen equivalent and Resins, epoxy (A).(A) Resins, epoxy in the flame-retardant epoxy resin omposition and (B) usage ratio of phosphorous, nitrogen heterocyclic, with epoxy equivalent (weight) 100% is benchmark, the reactive behavior hydrogen equivalent of solidifying agent (B) is 20～95%, the reactive behavior hydrogen equivalent of preferred solidifying agent is 40～90%, and the reactive behavior hydrogen equivalent of preferred solidifying agent is 50～90%.
In addition, phosphorated solidifying agent, (D) curing catalyst, (E) solvent do not reach (F) other additives can to add (C) in flame-retardant epoxy resin omposition of the present invention further, to be applicable to the requirement of various high heat-stable material Application Areass, purposes such as laminate, IC packaged material, high heat-resisting powder body coating for example.Can add solvent again, control viscosity is modulated into varnish with it, in order to manufacturing have the flame retardant resistance effect film, veneer sheet, increase layer with insulating material etc.
The not phosphorated solidifying agent that is fit to comprise contain bis-phenol, dihydroxy-benzene, phenol, naphthalene, alkene alkane, cyclic hydrocarbon, nitrogen heterocyclic ring, resol, siloxanes, polysiloxane and have-(wherein X is CH to the Ph-X-Ph-group
2, C (CH
3)
2, CH (CH
3), O, S, C=O, SO
2Deng) polyalcohols, polyamine, polythiol, and material such as poly-carbonic acid; The phosphorated solidifying agent does not comprise amine, polyhydroxy phenol and phenolic aldehyde again, and the specific examples of amine comprises: dicyan diamide (NH
2C (NH) is (NHCN)), two amido ditans (DDM) etc.; Polyhydroxy phenol comprises: three (4-hydroxy phenyl) methane, three (4-hydroxy phenyl) ethane, three (4-hydroxy phenyl) propane, three (4-hydroxy phenyl) butane, three (3-methyl-4-hydroxy phenyl) methane, three (3,5-dimethyl-4-hydroxy phenyl) methane, four (4-hydroxy phenyl) ethane, four (3,5-dimethyl-4-hydroxy phenyl) ethane etc.; The specific examples of phenolic aldehyde comprises: phenol formaldehyde condensate, cresols phenolic condensation compound, bisphenol-A phenolic condenses etc.
The normal not phosphorated solidifying agent that uses is the not phosphorus curing agent of dicyan diamide, two amido ditans, diethyl triamine (DETA), diamino diphenyl sulfone (DDS), mphenylenediamine (MPDA), methyldiphenylamine (MDA), maleic acid (MA), Tetra hydro Phthalic anhydride (PA), hexahydrophthalic anhydride (HHPA), Tetra Hydro Phthalic Anhydride (THPA) etc. for example.
The content of above-mentioned not phosphorated solidifying agent, decide according to the epoxy equivalent (weight) of the reactive behavior hydrogen equivalent of phosphorated solidifying agent not and Resins, epoxy, epoxy equivalent (weight) 100% with Resins, epoxy is a benchmark, the reactive behavior hydrogen equivalent of phosphorated solidifying agent is not 20～95%, be preferably 40～90%, more preferably 50～90%.
In flame-retardant epoxy resin omposition of the present invention, optionally also can add curing catalyst in addition, suitable curing catalyst comprises tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt and imidazolium compoundss, or its mixture.The specific examples of tertiary amine comprises: triethylamine, tributylamine, dimethyl amine ethanol, three (N, N-dimethyl-aminomethyl) phenol, N, N-dimethyl-aminomethyl phenol etc.; The specific examples of three grades of phosphines comprises: triphenylphosphine etc.; The quaternary ammonium salt specific examples comprises: tetramethyl-ammonium muriate, tetramethyl-ammonium bromide, tetramethyl-ammonium iodide, triethylbenzene ammonium methyl muriate, triethylbenzene ammonium methyl bromide, triethylbenzene ammonium methyl iodide etc.; The specific examples of quaternary alkylphosphonium salt comprises: the 4-butyl-phosphonium muriate, the 4-butyl-phosphonium bromide, the 4-butyl-phosphonium iodide, 4-butyl-phosphonium acid ester salt acetic acid title complex, the tetraphenylphosphoniphenolate muriate, the tetraphenylphosphoniphenolate bromide, the tetraphenylphosphoniphenolate iodide, Yi base triphenyl phosphonium muriate, Yi base triphenyl phosphonium bromide, Yi base triphenyl phosphonium iodide, Yi base triphenyl phosphonium acid ester salt acetic acid title complex, Yi base triphenyl phosphonium acid ester salt phosphorylated ligand compound, propyl group triphenyl phosphonium muriate, propyl group triphenyl phosphonium bromide, propyl group triphenyl phosphonium iodide, Ding base triphenyl phosphonium muriate, Ding base triphenyl phosphonium bromide, Ding base triphenyl phosphonium iodide etc.; Imidazolium compounds comprises: 2-methyl-imidazoles, 2-phenyl-imidazoles, 2-ethyl-4-methyl-imidazoles, 2-dodecyl-imidazoles, 2-heptadecyl-imidazoles etc.Preferred curing catalyst Wei quaternary alkylphosphonium salt and imidazolium compounds, more preferably 2-methyl-imidazoles, 2-phenyl-imidazoles, Yi base triphenyl phosphonium acid ester salt acetic acid title complex, Ding base triphenyl phosphonium bromide.Above-mentioned curing catalyst can single form or the use of its form of mixtures.
In flame-retardant epoxy resin omposition of the present invention, the curing catalyst content of Tian Jiaing optionally is with respect to the gross weight of composition, be 0.005～5.0wt%, be preferably 0.05～4.5wt%, more preferably 0.1～4.0wt% most preferably is 0.15～3.0wt%.
In the present composition,,, can exert an adverse impact to the generation of by product and to the homogeneity of the transformation efficiency of curing reaction though can shorten the reaction times if the curing catalyst content that added is higher than 5.0wt%; And if the content of the curing catalyst in the composition is lower than 0.005wt%, speed of response is then slow excessively, and inefficiency.
In flame-retardant epoxy resin omposition of the present invention, can add solvent to be modulated into varnish, adding solvent adjusts in 20～500cps/25 ℃ the viscosity of composition epoxy resin of the present invention, be beneficial to use preimpregnation again drying mode make film, or be coated with and become to increase layer with an insulation layer (dielectric layer forbuild-up process).
The solvent that is fit to of modulation varnish is organic benzene class, ketone, aprotic solvent, ethers, reaches ester class etc.Organic benzene class comprises: toluene, dimethylbenzene; Ketone comprises: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Aprotic solvent comprises: N, dinethylformamide, N, N-diethylformamide; Ethers comprises: ethylene glycol monomethyl ether, propylene glycol monomethyl ether; The ester class comprises: ethyl acetate, isopropyl acid ethyl ester.
Generally speaking, composition of the present invention is modulated into varnish, can adds curing catalyst and selectivity and add solvent, with the scope of viscosity controller at 20～500cps/25 ℃, gel time is controlled at 30～500 seconds/171 ℃ scope.
According to scope of using and purposes that some is special and decide, in flame-retardant epoxy resin omposition of the present invention, can add generally commercially available additive or properties-correcting agent, for example thermo-stabilizer, photostabilizer, ultraviolet absorbers, plasticizer or mineral filler etc.Though also can use the additive or the properties-correcting agent that contain halogen or antimonous oxide, based on prevention and cure of pollution and toxic problem, composition of the present invention does not advise using such additive.
After flame-retardant epoxy resin omposition disclosed in this invention is modulated into varnish, can utilizes the known method of general industry to make Copper Foil, fiber support thing and contain the laminate of the flame-retardant epoxy resin omposition of phosphorus-nitrogen compound.But flame-retardant epoxy resin omposition impregnation of fibers base material of the present invention, as use the material (for example glass, metal, carbon fiber, inorganic fibre (as boron fibre), match network spin, Mierocrystalline cellulose and organic polymer material etc.) of organic or inorganic, for example can use composition epoxy resin varnish impregnation glasscloth of the present invention, to flood the glasscloth heat drying of composition epoxy resin varnish of the present invention, and the film that obtains doing; Such film keeping quality at room temperature can reach the several months long, has excellent in storage stability.This film moulding is further made composite material laminated board, or be used in the bonding coat of other films separately, or use one or more array configurations, and one side that can be thereon or on, Copper Foil is placed on following two sides, depress heating this film or its molectron adding, resulting veneer sheet matrix material is in dimensional stability, chemical proofing, erosion resistance, all can obtain the significant standard that improves and surpass present product on water absorbability and the electrical properties, be suitable for making electronics, electric, space, product or its parts such as traffic for example are used to make printed circuit board (PCB) and multilayer circuit board etc.; Or utilizing accurate coating process to make on Copper Foil increases layer usefulness gum Copper Foil (as the Copper Foil of coated with resins; Or be coated on and make the insulating film that increases layer usefulness on the release film, for example with phosphorous epoxy resin composition varnish impregnation glasscloth, maybe this composition epoxy resin varnish is coated on the Copper Foil and in addition dry, and obtain doing increase layer gum Copper Foil.This class increase the layer with the gum Copper Foil at room temperature storage property can reach the several months long, it has good storage stability, utilizes the hot pressing processing procedure to can be used to make compact high-density printed circuit board product.
The manufacture method of phosphor-containing flame-proof epoxy resin composition of the present invention, for solidifying said composition down for 20～350 ℃ in temperature of reaction, preferably under 50～300 ℃ of temperature, solidify, more preferably under 100～250 ℃ of temperature, solidify, most preferably under 120～220 ℃ temperature, solidify.
Necessary careful control of above-mentioned curing reaction temperature if temperature surpasses 350 ℃, easily produces side reaction and controls its speed of response than difficult, and may impel the speed of resin deterioration to speed; If temperature is lower than 20 ℃, except that the efficient difference, the difficult satisfied desired character of at high temperature using of the characteristic of resulting resin.
In phosphor-containing flame-proof epoxy resin composition of the present invention, do not need to add other processing aids and flame-retardant additive, can improve the flame retardant resistance and the heat-resisting character of Resins, epoxy simultaneously.And the invention provides a kind of have can with the functional group's of epoxy reaction the phosphazene that contains, it makes the composition epoxy resin that contains phosphazene of the present invention have higher flame retardant resistance, thermostability and mechanical properties than other composition epoxy resin that contains phosphorus-nitrogen compound.
In sum, according to the present invention, phosphorous, the nitrogen heterocyclic that adds effective content can improve the flame resistivity matter of composition epoxy resin to Resins, epoxy.By above-mentioned phosphorous, nitrogen heterocyclic and the formed composition epoxy resin of Resins, epoxy, except that flame-retardant nature with improvement, also have the effect and the excellent working properties that improve electric and mechanical properties, and, therefore can reduce cost of manufacture owing to need not add a large amount of flame-retardant additives; This kind flame-retardant epoxy resin omposition is suitable for making film (prepreg), veneer sheet with flame-retardant nature, increases layer with insulating material and printed wiring material etc. in addition, and it has high second-order transition temperature and excellent thermotolerance.
Embodiment
The present invention will explain with following synthesis example and embodiment, but therefore not limit the scope of the invention.
Epoxy equivalent (weight) among the relevant embodiment (EEW, Epoxy Equivalent Weight), varnish viscosity, solid component content are tested according to following testing method:
(1) epoxy equivalent (weight): make Resins, epoxy be dissolved in chlorobenzene: in the solvent of chloroform=1: 1, carry out titration with the HBr/ Glacial acetic acid, record epoxy equivalent (weight) according to the method for ASTM D1652, wherein indicator is a Viola crystallina.
(2) viscosity: phosphorous epoxy resin varnish was placed 25 ℃ of thermostatic baths 4 hours, with Brookfield (Brookfield) viscometer in 25 ℃ of viscosity that measure varnish.
(3) solid component content: get the 1 gram varnish sample that contains the composition epoxy resin of phosphorus-nitrogen compound of the present invention, baking is 60 minutes under 150 ℃ of temperature, records the weight percent of non-volatile composition, thereby obtains the solid component content.
Details are as follows for used each composition among synthesis example and the embodiment:
Resins, epoxy 1: the Resins, epoxy that artificial resin factory in Changchun produces, it is the diglycidylether of the dihydroxyphenyl propane of commodity BE188EL by name, epoxy equivalent (weight) is 185～195 gram/equivalents, and hydrolyzable chlorine content is below the 200ppm, and viscosity is 11000～15000cps/25 ℃.
Resins, epoxy 2: the Resins, epoxy that artificial resin factory in Changchun produces, it is the polyglycidyl ether of cresols-aldehyde condensate of commodity CNE200A80 by name, and epoxy equivalent (weight) is 200～220 gram/equivalents, and solvent is an acetone, and the solid component content is 79.0～81.0wt%.
Resins, epoxy 3: the Resins, epoxy that artificial resin factory in Changchun produces, it is the diglycidylether of the tetrabromo-bisphenol of commodity BEB530A80 by name, and epoxy equivalent (weight) is 430～450 gram/equivalents, and bromine content is 18.5～20.5wt%.
Resins, epoxy 4: the Resins, epoxy that artificial resin factory in Changchun produces, it is the diglycidylether of the tetrabromo-bisphenol of commodity BEB526A80 by name, and epoxy equivalent (weight) is 410～430 gram/equivalents, and bromine content is 19.0～21.0wt%.
Solidifying agent A: the dicyan diamide is dissolved in the dimethyl formamide (DMF), and the concentration of formation is 10% solution.
Curing catalyst: glyoxal ethyline is dissolved among the DMF, and the concentration of formation is 10% solution.
Synthesis example: phosphorous, nitrogen heterocyclic synthetic
Use has 1 rising of temperature indicating device and condensation reflux unit and presses glass reactor, and the reflux end of this reactor is equipped with Glass tubing to be connected to the hydrochloric acid absorption cell; 300 milliliters chlorobenzenes, 150 milliliters phosphorus trichloride and the magnesium chloride of 0.5 gram are added in the glass reactor; 500 milliliters 50wt% aqueous sodium hydroxide solution is inserted in the hydrochloric acid absorption cell; Reactor is heated to 131 ℃, finds that chlorobenzene begins to reflux, and this moment, the speed with 20 ml/min began to feed ammonia, stopped to feed chlorine after 1 hour in stirring reaction; The speed that changes with 20 ml/min feeds ammonia, and finding this moment has hydrogen chloride gas slowly to enter in the hydrochloric acid absorption cell via glass piping; In stirring reaction after 3 hours, the control valve of closing volume pipeline, and open the control valve that distills pipeline, and remove chlorobenzene after 30 minutes in steaming, cool the temperature to 70 ℃, add 300 milliliters 1, the tetra-n-butyl ammonia chloride of the phenol of 4-dioxane (dioxane), 450 grams and 0.5 gram is closed the distillation pipe-line control valve and is opened the return line control valve, and temperature is risen to 101 ℃, this moment 1,4-dioxane solution begins to reflux; After reaction 2 hours, the closing volume pipe-line control valve, the ammonia that adds 4 kilograms/square centimeter then, pressurization stirring reaction were opened the distillation pipeline and are discharged unreacted ammonia after 1 hour, temperature is risen to 101 ℃ simultaneously, remove 1 to steam, the 4-dioxane finally makes phosphorous, nitrogen heterocyclic mixture of products, it has suc as formula the structure shown in (I)
Via P
31NMR analyzes, and the compound of n=3 accounts for 57.1% in the formula, and the compound of n=4 accounts for 21.6%, and the compound of n=5 accounts for 1.9%, and the compound of n=6 accounts for 13.9%, and the compound of n＞7 accounts for 5.5%.Get 200 gram Resins, epoxy 1 (EEW=188), the above-mentioned cyclic phosphines nitrile compounds that make of 200 grams and 2 and restrain triphenylphosphines and mix and be heated with stirring to 180 ℃, react after 2 hours, cool the temperature to room temperature, the EEW that records reaction product is 1228; By the EEW of this reaction product, can instead push away calculating NH phosphorous, nitrogen heterocyclic
2Equivalent is 271.
Embodiment 1
Under room temperature, in the container that is equipped with agitator and condenser, the Resins, epoxy 1 and 216.2 that mixes 150.0 grams restrains by the prepared cyclic phosphines nitrile compound of synthesis example (suc as formula the structure shown in (I)), add the 10%DMF solution (curing catalyst) of the glyoxal ethyline of 1.35 grams, and the methyl ethyl ketone that adds 370 grams mixes, be modulated into the composition epoxy resin varnish that contains phosphazene, its solid component content is about 40～50wt%, and viscosity controller is at about 500cps/25 ℃.
With the modulated epoxy resin varnish impregnated glass fiber cloth of making that contains phosphazene, after 150 ℃ of dryings become film, under 180 ℃ of temperature, dried by the fire 120 minutes then, obtain film, this film that makes is with dsc (DSC, Differential Scan Calorimeter TA2910) tests its second-order transition temperature, and carries out combustion test according to U.S. electric laboratory UL-94 combustion test method and detect its flame retardant resistance.The result is as shown in table 1.
Embodiment 2
Under room temperature, in the container that is equipped with agitator and condenser, the Resins, epoxy 1 and 132.8 that mixes 150.0 grams restrains by prepared phosphorous, the nitrogen heterocyclic (suc as formula the structure shown in (I)) of synthesis example, add the not phosphorated solidifying agent A of 12.6 grams, add the 10%DMF solution (curing catalyst) of the glyoxal ethyline of 0.89 gram, reach the methyl ethyl ketones that add 370 grams and mix, be modulated into the composition epoxy resin varnish that contains phosphazene.
With the detection method of the modulated epoxy resin varnish of making that contains phosphazene, record second-order transition temperature and flame-retardant nature according to embodiment 1.The result is as shown in table 1.
Embodiment 3
Under room temperature, in the container that is equipped with agitator and condenser, the Resins, epoxy 2 and 184.8 that mixes 150.0 grams restrains by prepared phosphorous, the nitrogen heterocyclic (suc as formula the structure shown in (I)) of synthesis example, add the 10%DMF solution (curing catalyst) of the glyoxal ethyline of 1.30 grams, reach the methyl ethyl ketones that add 370 grams and mix, be modulated into the composition epoxy resin varnish that contains phosphazene.
With the detection method of the modulated epoxy resin varnish of making that contains phosphazene, record second-order transition temperature and flame-retardant nature according to embodiment 1.The result is as shown in table 1.
Embodiment 4
Under room temperature, in the container that is equipped with agitator and condenser, the Resins, epoxy 2 and 130.6 that mixes 150.0 grams restrains by prepared phosphorous, the nitrogen heterocyclic (suc as formula the structure shown in (I)) of synthesis example, add the not phosphorated solidifying agent A of 30.8 grams, add the 10%DMF solution (curing catalyst) of the glyoxal ethyline of 2.1 grams, reach the methyl ethyl ketones that add 370 grams and mix, be modulated into the composition epoxy resin varnish that contains phosphazene.
With the detection method of the modulated epoxy resin varnish of making that contains phosphazene, record second-order transition temperature and flame-retardant nature according to embodiment 1.The result is as shown in table 1.
Comparative example 1
Under room temperature, in the container that is equipped with agitator and condenser, mix the Resins, epoxy 3 of 125.0 grams and the not phosphorated solidifying agent A of 250 grams, add the 10%DMF solution (curing catalyst) of the glyoxal ethyline of 0.625 gram, reach the methyl ethyl ketones that add 370 grams and mix, be modulated into composition epoxy resin varnish.
With the detection method of the modulated epoxy resin varnish of making, record second-order transition temperature and flame-retardant nature according to embodiment 1.The result is as shown in table 1.
Comparative example 2
Under room temperature, in the container that is equipped with agitator and condenser, mix the Resins, epoxy 4 of 125.0 grams and the not phosphorated solidifying agent A of 260 grams, add the 10%DMF solution (curing catalyst) of the glyoxal ethyline of 0.625 gram, reach the methyl ethyl ketones that add 370 grams and mix, be modulated into composition epoxy resin varnish.
With the detection method of the modulated epoxy resin varnish of making, record second-order transition temperature and flame-retardant nature according to embodiment 1.The result is as shown in table 1.
Table 1
| Lacquer formulation | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Resins, epoxy 1 (gram) | ??150.0 | ??150.0 | ???- | ???- | ??- | ????- |
| Resins, epoxy 2 (gram) | ??- | ??- | ???150 | ???150 | ??- | ????- |
| Resins, epoxy 3 (gram) | ??- | ??- | ???- | ???- | ??125 | ????- |
| Resins, epoxy 4 (gram) | ??- | ??- | ???- | ???- | ??- | ????125 |
| Cyclic phosphines nitrile compound (gram) | ??216.2 | ??132.8 | ???184.8 | ???130.6 | ??- | ????- |
| Solidifying agent A (gram) | ??- | ??12.6 | ???- | ???30.8 | ??250 | ????260 |
| Promotor (gram) | ??1.35 | ??0.89 | ???1.30 | ???2.1 | ??0.625 | ????0.625 |
| Film A | Film B | Film C | Film D | Film E | Film F | |
| ??Tg(℃) | ??169 | ??174 | ???187 | ???192 | ??132 | ????150 |
| Combustion test | By | By | By | By | By | By |
Embodiment 5,6 and comparative example 3,4
It is superimposed to carry out lamination by each eight film of film A (embodiment 1), film C (embodiment 3), film E (comparative example 1) and film F (comparative example 2), it respectively places the Copper Foil of 35 microns of a slices up and down, under 185 ℃ of temperature, impose 25 kilograms/square centimeter pressure, this laminate of pressing and Copper Foil, and form the glass fibre cloth laminated board; (veneer sheet A, C, E and F) carries out physical property measurement to each veneer sheet, and analytical results is as shown in table 2.
Table 2
| Analysis project | The condition specification | Embodiment 5 (veneer sheet A) | Embodiment 6 (veneer sheet C) | Comparative example 3 (veneer sheet E) | Comparative example 4 (veneer sheet F) |
| Soldering resistance | 260 ℃ of spec.＞30 of IPC second | By | By | By | By |
| Stripping strength | IPC spec.＞8 pound/inch | ????8.92 | ????8.56 | ????9.25 | ????8.90 |
| Surface resistivity | ????IPC?spec.＞10 12 | ??2.78×10 15 | ??2.36×10 15 | ??2.88×10 15 | ??3.57×10 15 |
| Volume resistance | ????IPC?spec.＞10 10 | ??2.10×10 13 | ??2.02×10 13 | ??1.16×10 14 | ??1.06×10 14 |
| Specific inductivity | ????IPC?spec.＜5.4 | ?????4.45 | ?????4.81 | ?????4.72 | ?????4.60 |
| Dissipation factor | ?????????-- | ?????0.021 | ?????0.023 | ?????0.022 | ?????0.020 |
Embodiment 7,8 and comparative example 5,6
According to embodiment 1, embodiment 3, the method modulating epoxy resin composition varnish of comparative example 1 and comparative example 2, wherein solvent is 170 gram methyl ethyl ketones, the solid component content of varnish is about 70～80wt%, viscosity controller is at about 2000cps/25 ℃, the varnish that is modulated into is coated on the 18 micron copper foil internal layers, the thickness of coating is 80 microns, and with 175 ℃ of dryings after 3 minutes, with aforesaid substrate (film A, C, E and F) carry out pressing, under 180 ℃ of temperature, impose 25 kilograms/square centimeter pressure, carried out pressing 2 hours, form and increase laminate (A, C, E and F), analyze its thermotolerance, electric property, bond strength, detected result is as shown in table 3.
Table 3
| Analysis project | The condition specification | Embodiment 7 (increasing laminate A) | Embodiment 8 (increasing laminate C) | Comparative example 5 (increasing laminate E) | Comparative example 6 (increasing laminate F) |
| Soldering resistance | 260 ℃ of spec.＞30 of IPC second | By | By | By | By |
| Stripping strength | IPC spec.＞8 pound/inch | ????8.43 | ????8.27 | ????8.97 | ????8.44 |
| Surface resistivity | ??IPC?spec.＞10 12 | ??1.07×10 15 | ??1.12×10 15 | ??1.11×10 15 | ??1.21×10 15 |
| Volume resistance | ??IPC?spec.＞10 10 | ??1.57×10 16 | ??1.37×10 16 | ??1.10×10 16 | ??1.11×10 16 |
| Path formation property | 10 μ s/3 shot (Laser drill) | ?????OK | ?????OK | ?????OK | ?????OK |
Claims (32)
1. flame-retardant epoxy resin omposition, it comprises:
(A) at least a Resins, epoxy;
(B) phosphorous, nitrogen heterocyclic, this compound have can with the group of epoxy reaction in the Resins, epoxy, can be used as curing agent for epoxy resin, its structure is suc as formula shown in (I),
In the formula, m is 0～2 integer, and n is 3～7 integer, but wherein at least one m is not 2.
2. flame-retardant epoxy resin omposition, it comprises:
(A) at least a Resins, epoxy;
(B) phosphorous, nitrogen heterocyclic, this compound have can with the group of epoxy reaction in the Resins, epoxy, can be used as curing agent for epoxy resin, its structure is suc as formula shown in (I),
In the formula, m is 0～2 integer, and n is 3～7 integer, but wherein at least one m is not 2;
(C) phosphorated solidifying agent not;
And optionally add
(D) curing catalyst;
(E) solvent.
3. as the flame-retardant epoxy resin omposition of claim 1 or 2, wherein the epoxy equivalent (weight) of (A) Resins, epoxy is below 600.
4. as the flame-retardant epoxy resin omposition of claim 1 or 2, wherein the kind of (A) Resins, epoxy comprises: through bis-phenol, phenol, dihydroxy-benzene, two diphenol, naphthalene, alkyl, alkene alkane, cyclic hydrocarbon, nitrogen heterocyclic ring, cresols-aldehyde, siloxanes or polysiloxane, and the group modified compound with epoxy group(ing) of aryl phosphate ester.
5. flame-retardant epoxy resin omposition as claimed in claim 4, the compound that wherein has epoxy group(ing) comprises glycidyl ether, glycidyl amine, Racemic glycidol mercaptan ether and Racemic glycidol carbonic ether.
6. as the flame-retardant epoxy resin omposition of claim 1 or 2, wherein (A) Resins, epoxy composition is through bis-phenol, two diphenol, dihydroxy-benzene, polyvalent alcohol, reaches the glycidyl ether that silicone carries out modification.
7. flame-retardant epoxy resin omposition as claimed in claim 6, wherein said glycidyl ether through modification comprises: have-diglycidylether of the bis-phenol modification of Ph-X-Ph-group, wherein X is CH
2, C (CH
3)
2, CH (CH
3), O, S, C=O, SO
2The glycidyl ether of two diphenol modifications is 4,4 '-diphenol glycidyl ether, 3,3 '-dimethyl-4,4 '-diphenol glycidyl ether, and 3,3 ', 5,5 '-tetramethyl--4,4 '-diphenol glycidyl ether; The dihydroxy-benzene glycidyl ether is Resorcinol glycidyl ether, Resorcinol glycidyl ether, and isobutyl-Resorcinol glycidyl ether; The phenolic aldehyde polyglycidyl ether is phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether, and bisphenol-A phenolic polyglycidyl ether; Poly-hydroxy phenyl phenol polyglycidyl ether is three (4-hydroxy phenyl) methane polyglycidyl ether, three (4-hydroxy phenyl) ethane polyglycidyl ether, three (4-hydroxy phenyl) propane polyglycidyl ether, three (4-hydroxy phenyl) butane polyglycidyl ether, three (3-methyl-4-hydroxy phenyl) methane polyglycidyl ether, three (3,5-dimethyl-4-hydroxy phenyl) methane polyglycidyl ether, four (4-hydroxy phenyl) ethane polyglycidyl ether, four (3,5-dimethyl-4-hydroxy phenyl) ethane polyglycidyl ether; Or their mixture.
8. flame-retardant epoxy resin omposition as claimed in claim 7, wherein (A) Resins, epoxy is polymer with bis phenol A glycidyl ether, Resorcinol glycidyl ether, three (4-hydroxy phenyl) methane polyglycidyl ether, four (4-hydroxy phenyl) ethane polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether or its mixture.
9. as the flame-retardant epoxy resin omposition of claim 1 or 2, wherein (A) Resins, epoxy is to use the Resins, epoxy that silicone or rubbery copolymer carry out modification.
10. flame-retardant epoxy resin omposition as claimed in claim 9, wherein silicone compound is the end capped siloxanes of amido, rubbery copolymer is the carboxyl or the end capped multipolymer of amido of divinyl and vinyl cyanide.
11. flame-retardant epoxy resin omposition as claim 1 or 2, the content of (B) phosphorous, nitrogen heterocyclic wherein, decide with the epoxy equivalent (weight) of (A) Resins, epoxy according to its reactive behavior hydrogen equivalent, with epoxy equivalent (weight) 100% is benchmark, and the reactive behavior hydrogen equivalent of solidifying agent (B) is 20～95%.
12. as the flame-retardant epoxy resin omposition of claim 11, wherein the content of (B) phosphorous, nitrogen heterocyclic is benchmark with epoxy equivalent (weight) 100%, the reactive behavior hydrogen equivalent of (B) of solidifying agent is 40～90%.
13. as the flame-retardant epoxy resin omposition of claim 12, wherein the content of (B) phosphorous, nitrogen heterocyclic is benchmark with epoxy equivalent (weight) 100%, the reactive behavior hydrogen equivalent of solidifying agent (B) is 50～90%.
14. flame-retardant epoxy resin omposition as claimed in claim 2, wherein (C) not the phosphorated solidifying agent be dicyan diamide, two amido ditans, diethyl triamine, diamino diphenyl sulfone, mphenylenediamine, methyldiphenylamine, maleic acid, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride.
15. flame-retardant epoxy resin omposition as claimed in claim 2, wherein (C) not the phosphorated solidifying agent be tertiary amine, quaternary ammonium salt, three grades of phosphine, quaternary alkylphosphonium salts, and imidazolium compounds.
16. flame-retardant epoxy resin omposition as claimed in claim 2, wherein (C) content of phosphorated solidifying agent is not decided according to the epoxy equivalent (weight) of its reactive behavior hydrogen equivalent and Resins, epoxy, is benchmark with epoxy equivalent (weight) 100%, and the reactive behavior hydrogen equivalent is 20～95%.
17. as the flame-retardant epoxy resin omposition of claim 16, wherein (C) content of phosphorated solidifying agent not is benchmark with epoxy equivalent (weight) 100%, the reactive behavior hydrogen equivalent is 40～90%.
18. as the flame-retardant epoxy resin omposition of claim 17, wherein (C) content of phosphorated solidifying agent not is benchmark with epoxy equivalent (weight) 100%, the reactive behavior hydrogen equivalent is 50～90%.
19. flame-retardant epoxy resin omposition as claimed in claim 2, wherein the content of (D) curing catalyst is 0.005～5.0wt% with respect to the gross weight of composition.
20. as the flame-retardant epoxy resin omposition of claim 19, wherein the content of (D) curing catalyst is 0.05～4.5wt% with respect to the gross weight of composition.
21. as the flame-retardant epoxy resin omposition of claim 20, wherein the content of curing catalyst is 0.1～4.0wt% with respect to the gross weight of composition.
22. as the flame-retardant epoxy resin omposition of claim 21, wherein the content of (D) curing catalyst is 0.15～3.0wt% with respect to the gross weight of composition.
23. flame-retardant epoxy resin omposition as claimed in claim 2, wherein (E) solvent is organic benzene class, ketone, aprotic solvent, ethers, reaches the ester class.
24. as the flame-retardant epoxy resin omposition of claim 1 or 2, it further comprises thermo-stabilizer, photostabilizer, ultraviolet absorbers, plasticizer or mineral filler.
25. the film that the flame-retardant epoxy resin omposition of claim 1 or 2 and reinforcement base material are made.
26. the application of the film of claim 25 aspect prepared layer zoarium or plate, wherein said laminate or plate are with the laminated formation of film.
27. the flame-retardant epoxy resin omposition of claim 1 or 2 increases the application of layer aspect insulating material in preparation, the wherein said layer that increases is made by composition is coated on the base material with insulating material.
28. for the application aspect the laminate sheet material of seal circuit board process use, wherein institute's laminate sheet material is by being formed by film and the Copper Foil hot pressing that composition is made to the flame-retardant epoxy resin omposition of claim 1 or 2 in preparation.
29. as the film of claim 25, wherein said reinforcement base material is a fibrous material.
30. as the application of claim 26, wherein said reinforcement base material is a fibrous material.
31. as the application of claim 27, wherein said base material is Copper Foil or release film.
32. a fire-retarded epoxy resin curing composition, it is the solidification compound that is made by the flame-retardant epoxy resin omposition that solidifies claim 1 or 2.
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| CNB001301764A CN100371376C (en) | 2000-10-19 | 2000-10-19 | Fireproof epoxy resin composite and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001301764A CN100371376C (en) | 2000-10-19 | 2000-10-19 | Fireproof epoxy resin composite and its application |
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| CN100371376C CN100371376C (en) | 2008-02-27 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005070990A1 (en) * | 2004-01-12 | 2005-08-04 | Taizhou Repow Chemical And Material Institute Co., Ltd | An epoxy resin curing agent containing elemental phosphorus and the method for preparing the same |
| CN102250317A (en) * | 2011-05-09 | 2011-11-23 | 复旦大学 | Rapid curable epoxy resin for electronic packaging, and application thereof |
| CN102276797A (en) * | 2011-06-22 | 2011-12-14 | 天津市凯华绝缘材料有限公司 | Epoxy resin composition with excellent temperature cycle performance and preparation method thereof |
| CN106564240A (en) * | 2016-11-07 | 2017-04-19 | 北京新福润达绝缘材料有限责任公司 | Manufacturing method of glass fiber mat laminated plate high in proof tracking index |
| CN110650997A (en) * | 2017-07-13 | 2020-01-03 | 东丽株式会社 | Molded article and method for producing same |
| CN111057217A (en) * | 2019-12-26 | 2020-04-24 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition and prepreg, laminated board and printed circuit board using same |
| CN115216019A (en) * | 2022-08-31 | 2022-10-21 | 北京化工大学 | Efficient flame-retardant phosphoramide polymer flame retardant and preparation method and application thereof |
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| DE1445352A1 (en) * | 1961-07-03 | 1969-08-07 | Akademie D Wissenschaften Zu B | Process for curing epoxy resins |
| US3280222A (en) * | 1965-11-15 | 1966-10-18 | Olin Mathieson | Aminophenoxy and nitrophenoxy phosphonitriles |
| JPS627723A (en) * | 1985-07-03 | 1987-01-14 | Shin Etsu Chem Co Ltd | Epoxy resin composition |
| FR2658199B1 (en) * | 1990-02-13 | 1992-05-15 | Atochem | PROCESS FOR THE PREPARATION OF POLYPHOSPHAZENES BY SUBSTITUTION OF POLYDICHLOROPHOSPHAZENE. |
| DE59310074D1 (en) * | 1992-07-09 | 2000-08-17 | Ciba Sc Holding Ag | Curable suspensions based on epoxy resins |
| CN1178230A (en) * | 1996-07-30 | 1998-04-08 | 日本化药株式会社 | Epoxy resin liquid composition for semiconductor encapsulation |
| BR9806712A (en) * | 1997-10-15 | 2000-04-04 | Otsuka Chemical Co Ltd | Compound of cross-linked phenoxyphosphazene, flame retardants, flame retardant resin compositions, flame retardant resin moldings |
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| WO2005070990A1 (en) * | 2004-01-12 | 2005-08-04 | Taizhou Repow Chemical And Material Institute Co., Ltd | An epoxy resin curing agent containing elemental phosphorus and the method for preparing the same |
| CN102250317A (en) * | 2011-05-09 | 2011-11-23 | 复旦大学 | Rapid curable epoxy resin for electronic packaging, and application thereof |
| CN102276797A (en) * | 2011-06-22 | 2011-12-14 | 天津市凯华绝缘材料有限公司 | Epoxy resin composition with excellent temperature cycle performance and preparation method thereof |
| CN102276797B (en) * | 2011-06-22 | 2013-02-13 | 天津市凯华绝缘材料有限公司 | Epoxy resin composition with excellent temperature cycle performance and preparation method thereof |
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| CN111057217A (en) * | 2019-12-26 | 2020-04-24 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition and prepreg, laminated board and printed circuit board using same |
| WO2021128630A1 (en) * | 2019-12-26 | 2021-07-01 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition and prepreg, laminated board and printed circuit board using thermosetting epoxy resin composition |
| CN111057217B (en) * | 2019-12-26 | 2021-08-27 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition and prepreg, laminated board and printed circuit board using same |
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