CN1249128C - Phosphorous resin and fire retarded resin composition containing said resin - Google Patents
Phosphorous resin and fire retarded resin composition containing said resin Download PDFInfo
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- CN1249128C CN1249128C CNB001235281A CN00123528A CN1249128C CN 1249128 C CN1249128 C CN 1249128C CN B001235281 A CNB001235281 A CN B001235281A CN 00123528 A CN00123528 A CN 00123528A CN 1249128 C CN1249128 C CN 1249128C
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Abstract
The present invention relates to phosphorus-containing resin and a fire retardant resin composite containing the resin. The fire retardant resin composite comprises the phosphorus-containing resin, a nitrogen-containing resin solidifying agent and a solidification reaction accelerating agent. Not containing halogen and not needing to be added with other fire retardants, the fire retardant resin composite has the properties of fine fire-retardance and high heat-resistance, and can be applied to the manufacture of adhesive bonding sheets, composite materials, laminated boards, printed circuit boards, copper foil binders and semiconductor packing materials.
Description
The present invention relates to a kind of phosphorous resin and contain the fire-proof resin composition of this resin.
Matrix material, especially epoxy resin composite material, with the security of its easy processibility, height, excellent mechanical properties and chemical property, be applied to widely in the every field as application, electric insulation, building building materials, tackiness agent and laminated product etc.Wherein, veneer sheet with the Resins, epoxy manufacturing, strong because of Resins, epoxy to the bounding force of strongtheners such as glasscloth, do not produce fugitive constituent when solidifying, mould shrinkage is little, therefore resulting veneer sheet has advantages such as use range is wide, physical strength is excellent, electric insulating quality is good, chemical proofing is good, improved the reliability of laminated plate material greatly, make epoxy laminate be used in a large number electrical equipment and electronic product in.
Yet,, also require veneer sheet need have more excellent electrical properties, mechanical properties and heat-resisting processibility in order to adapt in the printed circuit board (PCB) to accurate day by day fine rule road and highdensity requirement.With present common FR4 veneer sheet, second-order transition temperature after it solidifies is mostly 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 ℃, so laminate sheet material might break or plate bursting in the manufacturing and the course of processing.Therefore, people develop the laminate sheet material of various high thermal stabilities, high glass-transition temperature energetically.In addition, for veneer sheet, another critical nature is its flame-retarding characteristic.In the occasion of some use, for example in the vehicles such as aircraft, automobile and public transportation, because of directly threatening, so the flame-retarding characteristic of printed circuit board (PCB) is absolute necessary for the person and life security.
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.Veneer sheet for Resins, epoxy/glass fibre class (or organic fibre), use halogen contained compound, particularly bromated Resins, epoxy and solidifying agent, and cooperation requires (as UL 94V-0 grade) as the flame retardant of antimonous oxide class in the hope of the harshness that can reach the veneer sheet flame-retarding characteristic.Usually, Resins, epoxy need contain the bromine content up to 17%～21%, and is used antimonous oxide or other fire retardant, just can reach the level of UL 94V-0.Yet, use high bromine content Resins, epoxy or antimonous oxide, will bring some danger to the mankind undoubtedly.
At first, antimonous oxide has been listed in carcinogenic substance; On the other hand, bromine not only can produce mordant bromine free radical and hydrogen bromide in the incendiary process, the aromatics of high bromine content more can produce the bromination furans and Xiuization dioxin (dioxin) compounds of severe toxicity, badly influences people's health and environment.Therefore, seeking a kind of new fire retardant material and fire-retardantization method, improve the pollution and the environmental issue of present veneer sheet because of using brominated epoxy resin to cause, is instant thing.Especially, the epoxy fiberglass layer pressing plate usage quantity of FR-4 class is big, and then demand is stronger.
The fire retardant that Phosphorus compound has the environmental protection notion as a new generation is studied widely and is used.For example directly use the organic compound (for example triphenylphosphine acid esters, trityl phosphonic acid ester, carbonic acid etc.) of red phosphorus or phosphorus to wait to replace halogen compounds and be used as fire retardant, to improve the combustioncharacteristics of macromolecular material or gel-type resin.Yet, directly add these compounds among resin, not only because of the flame retarding efficiency that is subject to these compounds needs bigger addition, and will directly have influence on the characteristic of resin base material because of its lower molecular weight, high transport property:, cause practical difficulty as electrical properties, bond strength etc.
In recent years, cooperate the consideration of environmental protection and safety with the idea of reactive flame retardant, phosphatization Resins, epoxy has been used to replace the prescription of brominated epoxy resin as non-combustible high pressure laminate, for example No. 5376453, United States Patent (USP), use the phosphoric acid ester of band epoxy group(ing) to cooperate nitrogenous ring-type solidifying agent to make veneer sheet, but be difficult to reach the shortcoming that UL 94V-0 requires, and added multiple phosphoric acid ester epoxide in order to remedy the phosphorus content deficiency; United States Patent (USP) then utilizes for No. 5458978 epoxy phosphate ester to cooperate nitrogenous Resins, epoxy and metal composite as solidifying agent, and its finished glass transition temperature is about 175 ℃, and flame-retardant nature then reaches UL 94V-0 edge (42 seconds with respect to threshold value 50 seconds).No. 5086156, No. 4973631, United States Patent (USP) and United States Patent (USP) use have active hydrogen substituting group (as amino) the trihydrocarbyl phosphine muriate separately or cooperate other amine curing agents, be used for the curing of Resins, epoxy; Be used for resin the low shortcoming of phosphorus content is arranged yet solidifying agent is imported phosphorus, also do not have the measurement of actual flame retardant effect in these two parts of patents.
The present invention is target to improve electric and mechanical essential property with reducing cost, thereby has finished the present invention promptly at the shortcoming in the above-mentioned existing technology.
An object of the present invention is to provide a kind of phosphorous resin, have good flame retardant resistance, electric property and mechanical property based on the fire-proof resin composition of this phosphorous resin;
Another purpose of the present invention provides the fire-proof resin composition of described phosphorous resin.
A kind of phosphorous resin of the present invention, this phosphorous resin be characterized as the functional group that contains following formula (A):
The represented functional group of phosphorous resin Chinese style of the present invention (A) is by 9 of the epoxide group of Resins, epoxy and following formula (B), and the 10-dihydro-9-oxy is assorted-and 10-phosphorus anthracene-10-oxide compound reaction obtains:
Phosphorous resin of the present invention can be by known Resins, epoxy and 9, the 10-dihydro-9-oxy is assorted-10-phosphorus anthracene-10-oxide compound and depend on the circumstances other contain that the compound bearing active hydrogen reaction makes.
The Resins, epoxy of making phosphorous resin of the present invention can be any Resins, epoxy, and its specific examples comprises glycidyl ether, phenolic aldehyde polyglycidyl ether and the polyhydroxy phenol polyglycidyl ether etc. of bis-phenol glycidyl ether, two diphenol glycidyl ether, dihydroxy-benzene glycidyl ether, the glycidyl ether that contains azo-cycle, dihydroxy naphthlene.
The bis-phenol glycidyl ether comprises for example 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.
Two diphenol glycidyl ethers for example comprise 4,4 '-diphenol glycidyl ether, 3,3 '-dimethyl-4,4 '-diphenol glycidyl ether, 3,3 ', 5,5 '-tetramethyl--4,4 '-diphenol glycidyl ether.
The dihydroxy-benzene glycidyl ether comprises for example Resorcinol glycidyl ether, Resorcinol glycidyl ether, isobutyl-Resorcinol glycidyl ether.
The phenolic aldehyde polyglycidyl ether comprises for example phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether, bisphenol-A phenolic polyglycidyl ether.
The polyhydroxy phenol polyglycidyl ether comprises for example 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, dicyclo amylene-phenolic aldehyde polyglycidyl ether.
The glycidyl ether that contains azo-cycle comprises for example triglycidyl ether of chlorinated isocyanurates and the triglycidyl ether of cyanurate.
The glycidyl ether of dihydroxy naphthlene for example comprises 1,6-dihydroxy naphthlene diglycidylether and 2,6-dihydroxy naphthlene diglycidylether.
The above Resins, epoxy can be that a kind of independent use or two or more mixing are used.
Wherein be preferably four (phenyl-4-hydroxyl) ethane polyglycidyl ether of polymer with bis phenol A glycidyl ether, phenolic aldehyde polyglycidyl ether, three (4-hydroxy phenyl) methane polyglycidyl ether, dicyclo amylene-phenolic aldehyde polyglycidyl ether and four functional groups, or its mixture.
Make phosphorous resin of the present invention depend on the circumstances other contain compound bearing active hydrogen and comprise amine, bis-phenol resin, dihydroxy-benzene, polyhydroxy phenol resin and phenolic etc.
Amine comprises for example dicyan diamide, diaminodiphenyl-methane.
Bisphenol resin for example comprises formula HO-Ph-X-Ph-OH, and (wherein Ph represents phenyl, X=-CH
2-C (CH
3)
2-,-O-,-S-,-CO-,-SO
2-) represented compound, for example: dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, 4,4 ' diphenol, 3,3 '-dimethyl-4,4 ' diphenol, 3,3 ', 5,5 '-tetramethyl--4,4 ' diphenol.
Dihydroxy-benzene comprises for example Resorcinol, Resorcinol, isobutyl-Resorcinol.
The polyhydroxy phenol resin comprises for example 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.
The phenolic that is fit to is for example: phenol formaldehyde condensate, cresols phenolic condensation compound, bisphenol-A phenolic condenses, dicyclo amylene-phenolic condensation compound.
Make in the phosphorous resin of the present invention, the usage ratio of mentioned component is the Resins, epoxy epoxy equivalent (weight): formula (B) compound activity hydrogen equivalent: other contain Ahew=100 of compound bearing active hydrogen: (5～50): (0～45), be preferably 100: (10～50): (0～45), more preferably 100: (15～40): (0～45).The too high resin solution viscosity that will cause of formula (B) compounds content uprises, and formula (B) compounds content is crossed the low product flame retardant resistance variation that will cause after the curing.Other contain the compound bearing active hydrogen too high levels and will cause the molecular weight of resin excessive, even can cause phosphorous epoxy resin to solidify and can't use.
Make in the phosphorous resin of the present invention, except that mentioned component, can add catalyzer again and be beneficial to the carrying out that react.Catalyst system therefor comprises tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt, boron trifluoride complex, lithiumation thing and imidazolium compoundss and composition thereof.
Tertiary amine is triethylamine, tributylamine, dimethyl amine ethanol, 3,5-dimethylphenyl amine, three (N, N-dimethyl-amino methyl) phenol, N for example, N-dimethyl-amino methyl phenol.
Three grades of phosphines are triphenylphosphine for example.
Quaternary ammonium salt is tetramethyl-ammonium muriate, tetramethyl-ammonium bromide, tetramethyl-ammonium iodide, triethylbenzene ammonium methyl muriate, triethylbenzene ammonium methyl bromide, triethylbenzene ammonium methyl iodide for example.
Quaternary alkylphosphonium salt is the 4-butyl-phosphonium muriate for example, the 4-butyl-phosphonium bromide, the 4-butyl-phosphonium iodide, 4-butyl-phosphonium acid ester salt acetic acid title complex (tetrabutylphosphonium acetate 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 is glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole etc. for example.
The above catalyzer can be separately or two or more be used in combination.
Preferred catalyzer is tertiary amine and imidazolium compounds, especially xylidine, glyoxal ethyline, 2-phenylimidazole and 2-ethyl-4-methylimidazole etc.
The usage quantity of catalyzer is 50～50 of an initiator gross weight, and 000ppm is preferably 100～30,000ppm, and more preferably 200～10,000ppm also has more preferably 500～2,000ppm.If the amount of catalyzer surpasses 50,000ppm, though can shorten the reaction times, to by product generate and to electrical properties, moisture resistance, the suction character of subsequently application such as board layer zoarium etc. detrimentally affect is arranged, if addition is too little, then speed of reaction is crossed slow and inefficiency.
The reaction of the phosphorous resin of preparation the present invention can be carried out the fusion addition reaction in the presence of solvent-free, or carries out back flow reaction in the presence of solvent.
Used suitable solvent comprises organic aromatic series class, ketone, protonic solvent, ethers, ester class etc.
The organic fragrant same clan that is fit to is for example: toluene, dimethylbenzene.
The ketone that is fit to is for example: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK).
The protonic solvent that is fit to is for example: N, dinethylformamide, N, N-diethylformamide, dimethyl sulfoxide (DMSO).
The ethers that is fit to is for example: ethylene glycol monomethyl ether, propylene glycol monomethyl ether.
The ester class that is fit to is for example: ethyl acetate, isopropyl acid ethyl ester, propylene glycol monomethyl ether ethyl ester.
The temperature of reaction for preparing phosphorous resin of the present invention is generally 50～350 ℃, is preferably 50～300 ℃, more preferably 100～250 ℃, most preferably is 100～200 ℃.The too high easy generation side reaction of temperature makes speed of response be difficult to control, and will impel the resin degradation speed to speed; Temperature is crossed low except that the efficient difference, and the resin properties that is produced difficulty meets the high temperature user demand.
The invention still further relates to a kind of fire-proof resin composition, it comprises that (a) phosphorous resin of the present invention, the represented solidifying agent of (b) following formula (C) reach (c) curing catalyst.
R in the formula
2Expression-[CH
2-R
3]
nH (n is 0～20 integer) or hydrogen atom; But at least one R
2Be not hydrogen atom:
R
1Expression NHR
2, C
1-6Alkyl or phenyl,
R
3Expression phenylene, naphthylidene or group with following formula structure:
In the formula A represent-O-,-S-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-or group with following formula structure:
Above-mentioned R
3Reach in the represented group of A, aromatic group can be selected from hydroxyl, amino, carboxyl, C through one or more again
1-6The substituting group of alkyl replaces.
Curing catalyst in the fire-proof resin composition of the present invention comprises tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt, boron trifluoride complex, lithiumation thing and imidazolium compoundss and composition thereof.
Tertiary amine is triethylamine, tributylamine, dimethyl amine ethanol, 3,5-dimethylphenyl amine, three (N, N-dimethyl-amino methyl) phenol, N for example, N-dimethyl-amino methyl phenol.
Three grades of phosphines are triphenylphosphine for example.
Quaternary ammonium salt is tetramethyl-ammonium muriate, tetramethyl-ammonium bromide, tetramethyl-ammonium iodide, triethylbenzene ammonium methyl muriate, triethylbenzene ammonium methyl bromide, triethylbenzene ammonium methyl iodide for example.
Quaternary alkylphosphonium salt is the 4-butyl-phosphonium muriate for example, 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 is glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole etc. for example.
The above curing catalyst can be separately or two or more be used in combination.
Preferred curing catalyst is tertiary amine and imidazolium compounds, especially xylidine, glyoxal ethyline, 2-phenylimidazole and 2-ethyl-4-methylimidazole etc.
The usage quantity of curing catalyst is 50～50 of fire-proof resin composition gross weight, and 000ppm is preferably 100～30,000ppm, and more preferably 200～10,000ppm most preferably is 500～2,000ppm.If the amount of curing catalyst surpasses 50,000ppm, though can shorten the reaction times, to by product generate and to electrical properties, moisture resistance, the suction character of subsequently application such as board layer zoarium etc. exert an adverse impact, if addition is too little, then speed of reaction is crossed slow and inefficiency.
Fire-proof resin composition of the present invention except phosphorous resin of the present invention, also can contain other not phosphorated Resins, epoxy.
Phosphorated Resins, epoxy not can be any Resins, epoxy, and its specific examples comprises glycidyl ether, phenolic aldehyde polyglycidyl ether and the polyhydroxy phenol polyglycidyl ether etc. of bis-phenol glycidyl ether, two diphenol glycidyl ether, dihydroxy-benzene glycidyl ether, the glycidyl ether that contains azo-cycle, dihydroxy naphthlene.
The bis-phenol glycidyl ether comprises for example 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.
Two diphenol glycidyl ethers for example comprise 4,4 '-diphenol glycidyl ether, 3,3 '-dimethyl-4,4 '-diphenol glycidyl ether, 3,3 ', 5,5 '-tetramethyl--4,4 '-diphenol glycidyl ether.
The dihydroxy-benzene glycidyl ether comprises for example Resorcinol glycidyl ether, Resorcinol glycidyl ether, isobutyl-Resorcinol glycidyl ether.
The phenolic aldehyde polyglycidyl ether comprises for example phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether, bisphenol-A phenolic polyglycidyl ether.
The polyhydroxy phenol polyglycidyl ether comprises for example 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, dicyclo amylene-phenolic aldehyde polyglycidyl ether.
The glycidyl ether that contains azo-cycle comprises for example triglycidyl ether of chlorinated isocyanurates and the triglycidyl ether of cyanurate.
The glycidyl ether of dihydroxy naphthlene for example comprises 1,6-dihydroxy naphthlene diglycidylether and 2,6-dihydroxy naphthlene diglycidylether.
In fire-proof resin composition of the present invention, can be used more than one described not phosphorous epoxy resins or be used the mixture of two or more above-described not phosphorous epoxy resins.Wherein be preferably four (phenyl-4-hydroxyl) ethane polyglycidyl ether of polymer with bis phenol A glycidyl ether, phenolic aldehyde polyglycidyl ether, three (4-hydroxy phenyl) methane polyglycidyl ether, dicyclo amylene-phenolic aldehyde polyglycidyl ether and four functional groups, or its mixture.
When being used not phosphorated Resins, epoxy, the ratio of phosphorous resin of the present invention accounts for 5～100% of Resins, epoxy gross weight, is preferably 20～100%, and more preferably 25～100%.This ratio is low excessively, easily causes flame retardant resistance and thermotolerance deficiency.
In the fire-proof resin composition of the present invention, except aforementioned formula (C) compound, also other solidifying agent be can comprise, amine, bis-phenol resin, dihydroxy-benzene, polyhydroxy phenol resin and phenolic etc. for example comprised.
Amine comprises for example dicyan diamide, diaminodiphenyl-methane.
Bisphenol resin for example comprises formula HO-Ph-X-Ph-OH, and (wherein Ph represents phenyl, X=-CH
2-C (CH
3)
2-,-O-,-S-,-CO-,-SO
2-) represented compound, for example: dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, 4,4 ' diphenol, 3,3 '-dimethyl-4,4 ' diphenol, 3,3 ', 5,5 '-tetramethyl--4,4 ' diphenol.
Dihydroxy-benzene comprises for example Resorcinol, Resorcinol, isobutyl-Resorcinol.
The polyhydroxy phenol resin comprises for example 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.
The phenolic that is fit to is for example: phenol formaldehyde condensate, cresols phenolic condensation compound, bisphenol-A phenolic condenses, dicyclo amylene-phenolic condensation compound.
Use in the example of other solidifying agent, the solidifying agent ratio of formula (C) compound accounts for 5～100% of solidifying agent gross weight, is preferably 20～100%, most preferably is 25～100%.Ratio is crossed low easily cause flame retardant resistance and thermotolerance deficiency.
In the fire-proof resin composition of the present invention, the addition of solidifying agent is decided according to the epoxy equivalent (weight) of the reactive behavior hydrogen equivalent of each solidifying agent and Resins, epoxy, the equivalence ratio that is fit to is the epoxy equivalent (weight) 100% to Resins, epoxy, the reactive behavior hydrogen equivalent of solidifying agent is 20～140%, preferred equivalence ratio is the epoxy equivalent (weight) 100% to Resins, epoxy, the reactive behavior hydrogen equivalent of solidifying agent is 40～95%, preferred equivalence ratio is the epoxy equivalent (weight) 100% to Resins, epoxy, the reactive behavior hydrogen equivalent 50～95% of solidifying agent.
When fire-proof resin composition of the present invention is modulated into varnish (varnish), can add solvent to adjust viscosity.The suitable solvent comprises organic aromatic series class, ketone, protonic solvent, ethers, ester class etc.
The organic fragrant same clan that is fit to is for example: toluene, dimethylbenzene.
The ketone that is fit to is for example: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK).
The protonic solvent that is fit to is for example: N, dinethylformamide, N, N-diethylformamide, dimethyl sulfoxide (DMSO).
The ethers that is fit to is for example: ethylene glycol monomethyl ether, propylene glycol monomethyl ether.
The ester class that is fit to is for example: ethyl acetate, isopropyl acid ethyl ester, propylene glycol monomethyl ether ethyl ester.
Viscosity is adjusted to 20～500cps/25 ℃ usually.
Decide according to end-use, also can in fire-proof resin composition of the present invention, add general additive or properties-correcting agent, as thermo-stabilizer, photostabilizer, ultraviolet absorbers and softening agent etc.
Fire-proof resin composition of the present invention can utilize the known method of general industrial community, and fire-proof resin composition of the present invention is made laminate with platinum foil, fiber support thing.
Use fire-proof resin composition of the present invention to be modulated into varnish (varnish), with this varnish impregnation fiber base material such as organic or inorganic fibre base material (for example glass fibre, steel fiber, carbon fiber, aramid fiber, boron and Mierocrystalline cellulose etc.), with impregnated fiber base material heat drying, the prepreg that obtains doing (prepreg).The further moulding of this prepreg can be made composite material laminated board, maybe this prepreg is used bonding coat separately as other film, or with one or more these prepreg combinations, thereon the one side or its on, Copper Foil is placed on following two sides, depress heating this prepreg or its composition and obtain the veneer sheet matrix material adding, resulting veneer sheet matrix material is in dimensional stability, chemical proofing, erosion resistance, the standard that has all surpassed present product on water absorbability and the electrical properties, be suitable for making and be used in electronics, space, the electric product of traffic etc., as be used to make printed circuit board (PCB) and multilayer circuit board etc.
Also fire-proof resin composition of the present invention can be modulated into varnish, coat on the Copper Foil, heat drying, and the Copper Foil that is coated with resin that obtains doing (RCC, Resin Coated Copper).This Copper Foil that is coated with resin at room temperature keeping quality can reach the several months long, has good storage stability.This Copper Foil that is coated with resin moulding is further made composite material laminated board, or the independent bonding coat that uses as other film, or one or more this be coated with the Copper Foils combination of resin, thereon the one side or its on, following two sides in layer adds lamination one by one and closes (build-up) and obtain the veneer sheet matrix material, resulting veneer sheet matrix material is in dimensional stability, chemical proofing, erosion resistance, the standard that has all surpassed present product on water absorbability and the electrical properties is suitable for manufacturing and is used in electronics, space, the multilayer printed circuit board of traffic etc.
The suitable curing reaction temperature of fire-proof resin composition of the present invention is 20～350 ℃, is preferably 50～300 ℃, more preferably 100～250 ℃, also has more preferably 120～220 ℃.The too high easy generation side reaction of temperature and difficult its speed of response of control, and may impel the speed of resin deterioration to speed; Temperature is crossed low except that the efficient difference, the difficult requirement that meets the high temperature use of the resin properties that is produced.
According to the fire-proof resin composition that the present invention formed, 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.
The present invention will further specify with following synthesis example and embodiment, but therefore not limit the scope of the invention.
Details are as follows for used each composition among synthesis example and the embodiment:
Resins, epoxy 1Be to produce by Changchun artificial resin factory, the polyglycidyl ether of cresols-phenolic condensation compound of selling with trade(brand)name CNE200ELB, its epoxy equivalent (weight) is 200～220g/eq, hydrolyzable chlorine is 700ppm following (an ASTM method).
Resins, epoxy 2Be to be produced by Changchun artificial resin factory, with the phenolic aldehyde polyglycidyl ether that trade(brand)name PNE177 sells, its epoxy equivalent (weight) is 170～190g/eq, and hydrolyzable chlorine is 1000ppm following (an ASTM method).
Resins, epoxy 3Be to produce by Changchun artificial resin factory, the diglycidylether of the dihydroxyphenyl propane of selling with trade(brand)name BE188EL, its epoxy equivalent (weight) is 185～195g/eq, and hydrolyzable chlorine is below the 200ppm, and viscosity is 11000～15000cps/25 ℃.
Resins, epoxy 4Be to be produced by Changchun artificial resin factory, commodity are called BE501, and its epoxy equivalent (weight) is 490～510g/eq.
Resins, epoxy 5Be to produce by Changchun artificial resin factory, the diglycidylether of the tetrabromo-bisphenol of selling with trade(brand)name BEB530A80, its epoxy equivalent (weight) is 430～450g/eq, bromine content is 18.5～20.5wt%.
HCA(FORTE CHEMICAL CO. LTD) produces, and commodity are called 9 of DOPO, and the 10-dihydro-9-oxy is mixed-10-phosphorus anthracene-10-oxide compound along dimerization in representative.
Catalyzer (curing catalyst) ARepresent second base triphenyl phosphonium salt acetic ester acetate title complex, 10% is dissolved in methyl alcohol.
Catalyzer (curing catalyst) BRepresent glyoxal ethyline (2MI), 10% is dissolved in methyl ethyl ketone.
Nitrogen-containing hardener ARepresent the dicyan diamide, 10% is dissolved in dimethyl formamide.
Nitrogen-containing hardener BChange into production by FDAC, commodity are called melan 9000
TM70
Nitrogen-containing hardener CBe synthesis example 5 prepared nitrogen-containing hardeners.
Solidifying agent DProduced by Changchun artificial resin factory, trade(brand)name BEH510, Ahew are 105～110g/eq.
Relevant epoxy equivalent (weight) used herein (EEW, Epoxy Equivalent Weight), varnish viscosity, solids content record 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 according to ASTM D1652 method, wherein indicator is a Viola crystallina.
(2) viscosity: phosphorous epoxy resin varnish was placed 25 ℃ of thermostatic baths 4 hours, measure in 25 ℃ with Brookfield (Brookfield) viscometer.
(3) solids content: get the varnish sample that 1 gram contains phosphorous epoxy resin of the present invention, in 60 minutes non-volatile part measured weight percents of 150 ℃ of bakings.
Below, will do illustrating in greater detail by following synthesis example and embodiment to the present invention, but scope of the present invention is not limited in the following synthesis example and embodiment.
Synthesis example 1: phosphorous Resin A synthetic
In the 3000ml five neck glass reaction stills that are equipped with electrically heated cover, temperature regulator, electric blender and stirring rod, nitrogen inlet, thermopair, water cooled condenser, feed hopper, insert Resins, epoxy 1 (1000 gram) and HCA (400g), feed nitrogen and be heated to 120 ℃, after Resins, epoxy 1 and HCA are fused fully, vacuumize and make above raw material drying, feed nitrogen again and vacuumize repetition above-mentioned steps 2 times.Temperature of reaction kettle is reduced to 85～90 ℃ then, add catalyst A (6.0g).The startup stirrer stirs resin and catalyzer and feeds nitrogen.With gained mixture heating up to 160 ℃ and kept 10 minutes.Find reactant blow slowly heat release, continue heat release and be warming up to 180 ℃, under this temperature, keep then obtaining phosphorous Resin A in 3 hours, its epoxy equivalent (weight) is 453g/eq, theoretical phosphorus content is 4.1wt%.
Synthesis example 2～4
Use following table 1 listed composition and listed weight, react according to the similar approach of synthesis example 1, but after reaction finishes, the listed solvent of adding table 1 obtains the phosphorous resin of solution state to the Resins, epoxy that obtains.The epoxy equivalent (weight) of the phosphorous resin of synthesis example 2～4 gained, solids content and theoretical phosphorus content are as shown in table 2.
Table 1 synthesis example 2～4 synthesizing formulas
| Synthesis example 2 | Synthesis example 3 | Synthesis example 4 | |
| Phosphorous resin B | Phosphorous resin C | Phosphorous resin D | |
| Resins, epoxy 1 (gram) | 1000 | ||
| Resins, epoxy 2 (gram) | 1000 | 454.5 | |
| Resins, epoxy 3 (gram) | 448.8 | ||
| HCA (gram) | 320 | 320 | 145.5 |
| Bisphenol-A (gram) | 139.3 | ||
| Curing catalyst A (gram) | 6.0 | 6.0 | 5.4 |
| Propylene glycol monoether ethyl ester (milliliter) | 450 | 300 | 520.0 |
| Acetone (milliliter) | 450 | 595 |
Table 2 phosphorous epoxy resin property analysis
| Phosphorous resin B | Phosphorous resin C | Phosphorous resin D | |
| Epoxy equivalent (weight) (g/eq) | 403 | 378 | 451 |
| Solids content | 59.8％ | 60.1％ | 59.7％ |
| Theoretical phosphorus content | 3.48％ | 3.48％ | 1.76％ |
Synthesis example 5: nitrogen-containing hardener C's is synthetic
In the 3000ml five neck vials that are equipped with electrically heated cover, temperature regulator, electric blender and stirring rod, nitrogen inlet, thermopair, water cooled condenser, feed hopper, insert phenol 1269 grams, 37.4% formaldehyde, 541.5 grams, trimeric cyanamide 204 grams, triethylamine 10.2 grams.Be warming up to 80～85 ℃, reacted 3 hours.Add trimeric cyanamide 204 grams, reacted again 1 hour.After reaction is finished, be warming up to 100 ℃ gradually and dewater, be warming up to 120～125 ℃ of reactions 2 hours again.After reaction finishes, slowly unreacted phenol is steamed with normal pressure with the reaction condensation water and remove, under 180 ℃ of vacuum, kept 1 hour at last.Products therefrom is nitrogen-containing hardener C totally 984 grams.Theoretical nitrogen content is 13.4wt%, and Ahew is 125g/eq.
Embodiment 1～7 and comparative example 1
In being equipped with under the room temperature in the container of agitator and condenser, synthesis example 2～4 the phosphorous resin B of synthetic, C and D, solidifying agent, curing catalyst and solvents are modulated into epoxy resin varnish according to ratio shown in the table 3.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | |
| Lacquer formulation | ||||||||
| Phosphorous resin B (gram) | 150 | |||||||
| Phosphorous resin C (gram) | 150 | 150 | 150 | |||||
| Phosphorous resin D (gram) | 200 | 200 | 200 | |||||
| Resins, epoxy 4 (gram) | 153 | 147 | 147 | 147 | ||||
| Resins, epoxy 5 (gram) | 125 | |||||||
| Solidifying agent A | 26.5 | |||||||
| Solidifying agent B | 65 | 50 | 58 | |||||
| Solidifying agent C | 65 | 50 | ||||||
| Solidifying agent D | 65 | 50 | ||||||
| Curing catalyst B | 1.8 | 2.4 | 0.9 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
With the modulated epoxy resin varnish impregnated glass fiber cloth of making, 150 ℃ of dryings through impregnated fiberglass cloth after 120 minutes, obtain prepreg, then by DSC (Differential ScanCalorimeter, TA2910) (temperature range is 50～250 ℃, heat-up rate is 20 ℃/minute) second-order transition temperature of prepreg of test gained, (it is the method according to UL746 to measure its flame retardant resistance by combustion test, the prepreg test piece is cut into 5 of the prints of 12.5mm * 1.3mm size, every burns 2 times, 10 times the burning summation is no more than 50 seconds, and single is the highest to be no more than 10 seconds, represents that promptly combustion test passes through).The result is as shown in table 4:
Table 4 is through film flame retardant resistance and the second-order transition temperature of 150 ℃ of bakings after 120 minutes
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | |
| Average burning time (second) | 2～3 | 0～1 | Burning | 2～3 | 2～3 | Burning | 5～6 | 2～3 |
| Tg(℃) | 191.8 | 195.3 | 195.5 | 195.3 | 193.5 | 192.6 | 189.1 | 134.8 |
Eight prepregs are superimposed, and it respectively places the Copper Foil of a slice 35 μ m up and down, through 185 ℃, 25kg/cm
2The physical properties of each veneer sheet is analyzed in pressure pressing and become the veneer sheet of Resins, epoxy and glasscloth, and its result is as shown in table 5:
Table 5
| Analysis project | Condition and specification | Embodiment 1 | Embodiment 4 | Embodiment 7 | Comparative example 1 |
| Combustion testing | UL94-VO | By | By | By | By |
| Soldering resistance | 288 ℃ of specification＞300 second | By | By | By | Failure |
| Stripping strength | IPC specification＞8 lb/in | 8.9 | 8.6 | 8.7 | 9.3 |
| Surface resistivity | IPC specification＞10 10Ω | 2.68×10 15 | 1.98×10 15 | 2.63×10 15 | 3.57×10 15 |
| The volume impedance | IPC specification＜10 10Ω | 0.89×10 13 | 1.81×10 13 | 1.16×10 14 | 1.06×10 14 |
| Specific inductivity | IPC specification＜5.4 | 4.7 | 4.8 | 4.7 | 4.7 |
| Dissipation factor | - | 0.022 | 0.021 | 0.020 | 0.020 |
Embodiment 8～11 and comparative example 2
In being equipped with under the room temperature in the container of agitator and condenser, be modulated into epoxy resin varnish according to composition shown in the general of ratio shown in the table 6.
Table 6
| Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Comparative example 2 | |
| Phosphorous Resin A (gram) | 105 | ||||
| Phosphorous resin B (gram) | 150 | ||||
| Phosphorous resin C (gram) | 150 | ||||
| Phosphorous resin D (gram) | 200 | ||||
| Resins, epoxy 4 (gram) | 153 | 147 | 147 | ||
| Resins, epoxy 5 (gram) | 125 | ||||
| Solidifying agent A (gram) | 26.5 | ||||
| Solidifying agent C (gram) | 68 | 65 | 68 | 96 | |
| Curing catalyst B (gram) | 2.4 | 0.9 | 0.6 | 0.6 | 0.65 |
With the foregoing description 8,10 and 11 and the composition epoxy resin of comparative example 2 gained coat on the 18 micron copper foil uneven surfaces with 80 micron thickness, in 150 ℃ of oven dry.The Copper Foil that is coated with Resins, epoxy of gained is added in the aforementioned prepreg of being made by the composition epoxy resin of embodiment 1 both sides up and down, through 185 ℃ of temperature and 25kg/cm
2The pressure pressing makes multi-ply wood.Analyze this multiple-plate physical properties, the result is as shown in table 7.
Table 7
| Analysis project | Condition and specification | Embodiment 8 | Embodiment 10 | Embodiment 11 | Comparative example 2 |
| Combustion testing | UL 94-VO | By | By | By | By |
| Soldering resistance | IPC260 ℃ of specification＞30 second | By | By | By | By |
| Stripping strength | IPC specification＞6 lb/in (18 μ m) | 7.6 | 7.4 | 8.0 | 8.4 |
By The above results can find out phosphorous epoxy resin of the present invention more not phosphorated Resins, epoxy demonstrate more excellent combustion testing performance and soldering resistance, but stripping strength is not seen reduction.
Claims (4)
1. fire-proof resin composition, it comprises:
(a) phosphorous resin is characterized in that, it contains the functional group as shown in the formula (A):
This functional group is by 9 of the epoxide group of Resins, epoxy and following formula (B), and the 10-dihydro-9-oxy is mixed-10-phosphorus anthracene-10-oxide compound
Reaction makes, or by the epoxide group and 9 of following formula (B) of Resins, epoxy, and mix-10 phosphorus anthracene-10-oxide compound and other of 10-dihydro-9-oxy contains compound bearing active hydrogen and react and make;
The Resins, epoxy of the phosphorous resin of wherein said manufacturing is selected from glycidyl ether, phenolic aldehyde polyglycidyl ether and the polyhydroxy phenol polyglycidyl ether of bis-phenol glycidyl ether, two diphenol glycidyl ether, dihydroxy-benzene glycidyl ether, the glycidyl ether that contains azo-cycle, dihydroxy naphthlene;
Described other contain compound bearing active hydrogen and are selected from amine, bisphenol resin, dihydroxy-benzene, polyhydroxy phenol resin and phenolic material;
The Resins, epoxy and 9 of the phosphorous resin of described manufacturing, the 10-dihydro-9-oxy is assorted-and 10-phosphorus anthracene-10-oxide compound and other contain the epoxide group equivalent of the reaction ratio of compound bearing active hydrogen for this Resins, epoxy: 9, the 10-dihydro-9-oxy is assorted-10-phosphorus anthracene-10-oxide compound Ahew: the Ahew of other active hydrogen-contg compounds is 100: (5～50): (0～45);
(b) solidifying agent shown in the following formula (C):
R in the formula
2Be hydrogen atom or [CH
2-R
3]
nH, [CH
2-R
3]
nN among the H is 0～20 integer; But at least one R
2It is not hydrogen atom;
R ' is NHR
2, C
1-6Alkyl or phenyl,
R
3Be phenylene, naphthylidene or group with following formula structure:
In the formula A be-O-,-S-,-SO
2-, CO-,-CH
2-,-C (CH
3)
2-or group with following formula structure:
Above-mentioned R
3Reach in the represented group of A, described aromatic group again can be by one or more hydroxyl, amino, carboxyl, C of being selected from
1-6The substituting group of alkyl replaces; And
(c) curing catalyst is selected from tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt, boron trifluoride complex, lithiumation thing and imidazolium compoundss and composition thereof;
The ratio of the epoxide group of the Resins, epoxy of the phosphorous resin of wherein said manufacturing and the Ahew of solidifying agent is: when the epoxide group equivalent of Resins, epoxy is 100%, the Ahew of solidifying agent is 20～140%, and the ratio of curing catalyst is 50～50 of a fire-proof resin composition gross weight, 000ppm.
2. according to the fire-proof resin composition of claim 1, wherein can comprise the Resins, epoxy that is selected from following cohort again: glycidyl ether, phenolic aldehyde polyglycidyl ether and the polyhydroxy phenol polyglycidyl ether of bis-phenol glycidyl ether, two diphenol glycidyl ether, dihydroxy-benzene glycidyl ether, the glycidyl ether that contains azo-cycle, dihydroxy naphthlene.
3. according to the fire-proof resin composition of claim 1, wherein can comprise the solidifying agent that is selected from amine, bisphenol resin, dihydroxy-benzene, polyhydroxy phenol resin and phenolic again.
4. the fire-proof resin composition of claim 1 is in order to make substrate or the semiconductor sealing material that adhesive sheet, matrix material, veneer sheet, printed circuit board (PCB), Layer increasing method are used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001235281A CN1249128C (en) | 2000-08-18 | 2000-08-18 | Phosphorous resin and fire retarded resin composition containing said resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001235281A CN1249128C (en) | 2000-08-18 | 2000-08-18 | Phosphorous resin and fire retarded resin composition containing said resin |
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| Publication Number | Publication Date |
|---|---|
| CN1339519A CN1339519A (en) | 2002-03-13 |
| CN1249128C true CN1249128C (en) | 2006-04-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1333014C (en) * | 2003-08-08 | 2007-08-22 | 长春人造树脂厂股份有限公司 | Halogen-free resin composition |
| CN100445320C (en) * | 2006-07-26 | 2008-12-24 | 华南师范大学 | Prepn of polyphosphate |
| CN101679602B (en) * | 2007-05-18 | 2013-04-17 | 新日铁住金化学株式会社 | Novel flame-retardant epoxy resin, epoxy resin composition essentially containing the epoxy resin, and cured product thereof |
| CN101195676B (en) * | 2007-12-27 | 2012-08-22 | 东莞理工学院 | Phosphor A containing novolac epoxy and method for producing the same |
| CN102134304B (en) * | 2011-03-03 | 2012-08-29 | 沈阳化工大学 | Reactive type phosphoric epoxy resin flame retardant and preparation method thereof |
| CN116496469B (en) * | 2023-03-13 | 2024-01-26 | 广州光通科技有限公司 | Phosphorus-containing flame-retardant resin, and preparation method and application thereof |
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