CN1156539C - Fire-retarded resin and fire-retardedresin composition containing said resin - Google Patents
Fire-retarded resin and fire-retardedresin composition containing said resin Download PDFInfo
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- CN1156539C CN1156539C CNB001235265A CN00123526A CN1156539C CN 1156539 C CN1156539 C CN 1156539C CN B001235265 A CNB001235265 A CN B001235265A CN 00123526 A CN00123526 A CN 00123526A CN 1156539 C CN1156539 C CN 1156539C
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Abstract
The present invention relates to fire-retardant resin, a side chain of which comprises epoxy resin modified by a reactive phosphorus containing compound, particularly to a fire-retardant resin composition which comprises epoxy resin, a curing agent and a curing catalyst, wherein the side chain of the fire-retardant resin composition contains the epoxy resin which is modified by a reactive phosphorus containing compound; the curing agent which does not contain halogen can react with an epoxy group in the epoxy resin. The fire-retardant resin composition which has the characteristics of excellent heat resisting properties and improved fire-retardant properties is particularly suitable to be used as a sticky material for bonding layer sheets, composite materials, printed circuit boards and copper foils, and as a sealing material of semiconductors, etc.
Description
Technical field
The present invention relates to a kind of Resins, epoxy, particularly relate to a kind of difficult combustible epoxy resin, it is to utilize the epoxy reaction that has on side chain in reactive P contained compound and the Resins, epoxy, obtains to have improved heat-resistant resin.The invention still further relates to a kind of difficult combustible epoxy resin composition, it comprises that side chain contains the Resins, epoxy flame retardancy composition of reactive P contained compound modification, objectionable impuritiess such as the not halogen-containing or antimonous oxide of said composition, and do not need to add in addition the flame retardant resistance material, promptly have heat-resisting and difficult combustion effect, and can reach the flame retardancy standard of UL94V-0.
Background technology
The flame retardancy composition of Shi Yonging generally is the flame retardant resistance material that adds halogen-containing compound or contain the class of oxidizing substances such as antimony, vanadium in it is formed traditionally, to form the high composition of thermotolerance, the use of these materials tends to produce the serious environmental pollution problem.
Application facet at matrix material, for example: application, electric insulation, the building building materials, purposes such as tackiness agent and lamination product, more often use at present the matrix material of epoxy resin, itself has easy processibility by what Resins, epoxy, the security of height, excellent mechanical properties and chemical property etc., be widely used in every field, the most normal Resins, epoxy that utilizes is made laminated plates, again because Resins, epoxy is strong to the clinging power of supporting materials such as glasscloth, do not produce fugitive constituent during curing and mould shrinkage is less, therefore the laminated plates that is made by Resins, epoxy is applied to the product and the parts of aspects such as electric and electronic product in large quantities, yet make its quality variation in making processes or when using because of the rising of temperature for fear of product or parts, often need to add the additive that can improve the heat-resisting character of Resins, epoxy, often directly add for example halogen compounds traditionally, P contained compound or antimony, metal oxides such as vanadium are to improve the heat-resisting character of Resins, epoxy.
Making with the printed circuit board (PCB) that attracts attention at present, except the line pattern on the circuit card is needed the refinement carefully, laminated plates also requires to have electrical properties, mechanical properties and the processing thermotolerance of excellence, for example common FR4 laminated plates, most second-order transition temperatures that solidify the resin of Hou are about 130 ℃, to surpassing 200 ℃ the cutting and the processing of holing in the what printed circuit board (PCB) processing procedure, even the welding sequence more than 270 ℃, make and may break in the laminated plates manufacturing and the course of processing or the plate bursting situation.In addition, be difficult combustion characteristic for another important properties of laminated plates of printed circuit board (PCB), in the scope of some application, for example aircraft, automobile and public transportation vehicle etc., the difficulty combustion characteristic of printed circuit board (PCB) is absolute necessary.
Introduce in the laminated plates material for difficulty being fired characteristic, must use some to have and isolate the material that flame reduces ignition quality.Laminated plates for Resins, epoxy/glass fibre class (or organic fibre), generally be to add halogen contained compound, particularly bromated Resins, epoxy and solidifying agent, and cooperation is as the difficulty combustion auxiliary agent of antimonous oxide and so on, in the hope of reaching the harsh requirement (as the UL94V-0 grade) to the difficult combustion of laminated plates characteristic.Usually the firing-difficult matter matter in the Resins, epoxy need contain the bromine content up to 17% to 21%, and is used antimonous oxide or other incombustible agent, just can reach the standard of UL94V-0.Yet, the health of use high bromine content Resins, epoxy or antimonous oxide meeting harm humans.On the other hand, bromine can produce mordant bromine free radical and hydrogen bromide in the incendiary process, and the aromatics of high bromine content more can produce hypertoxic bromination furans and Xiuization dioxin-like compound etc., badly influences people's health and environment.Therefore; seek a kind of new nonflammable material and difficult burning method; to improve pollution and the environmental issue that product such as present laminated plates or parts cause because of the Resins, epoxy that uses bromine-containing compound or bromination; be instant thing; especially; in order to adapt to the electric epoxy glass laminated plates that waits product and parts to use the FR-4 class in large quantities, more must active development can harm humans and the difficult combustible epoxy resin material of environment protection.
In recent years, for safeguarding human beings'health and reducing environomental pollution source, developed a kind of flame retardant material of response style, wherein again to use P contained compound to replace the technology of the flame retardant resistance material that bromine-containing compound etc. uses traditionally extensively to be accepted, at present study and use the flame retardancy 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 incombustible agent, and the ignition quality of improvement macromolecular material or curable resin material, yet directly add this compounds to resin, often need directly to add a large amount of such flame retardancy material ability combustion effects in distress, and because the molecular weight of compound is lower, produce higher transport property (migration) and will directly influence the character of resin base material, electrical properties for example, character such as adhesion strength are understood variation, and cause the difficulty in the application.
Known, replace the technology of the Resins, epoxy of general employed brominated or bromination with the phosphorous epoxy resin of reaction formation as the flame retardancy composition, for example: at United States Patent (USP) the 5th, 376, in No. 453, use has the laminated plates that the composition of the phosphoric acid ester of epoxy group(ing) and nitrogen-containing hardener makes, and it must add the multiple composition that contains phosphoric acid ester Resins, epoxy and increase phosphorus content in order to remedy the combustion standard that is difficult for reaching UL94V-0; United States Patent (USP) the 5th, 458 is in No. 978, the composition that it is to use epoxy phosphate ester, nitrogen-containing epoxy thermoset and metal composite solidifying agent to form, it has second-order transition temperature is about 175 ℃, has the flame retardancy matter (40 seconds, the what threshold value is 50 seconds relatively) near what UL94V-0; United States Patent (USP) the 4th, 973,631 and 5, in 086, No. 156, use has the trihydrocarbyl phosphine oxide compound of active hydrogen substituting group (for example amino) or cooperates other amine curing agents in order to cured epoxy resin separately, borrow this curing mode that phosphorus is introduced in the resin, the content of phosphorus is lower, can't reach the effect of difficult combustion, the flame retardancy effect of not surveying in these two parts of patents.
The technology that above-mentioned known patent discloses often need be added the standard that multiple P contained compound just can reach flame retardancy, but the processing conditions that multiple extra additive adding regular meeting makes product is wayward or the quality of product is reduced.
Therefore, the method that improves flame retardancy at present is to use the nitrogenous materials such as brominated or antimony that use traditionally with the replacement of phosphorated material, and the most frequently used material of nitrogenous material is trimeric cyanamide, DICY and the cyanate ester class that contains triazine ring (triazine ring) etc.; The general the most frequently used material of phosphorated compound is non-reacted P contained compound or P contained compound with reactive functional group, wherein because the thermotolerance of non-reacted P contained compound than the poor heat resistance of reactive P contained compound, and reactive P contained compound combines with other molecules has advantages of higher stability, therefore present flame retardant material is to use reactive P contained compound, reactive P contained compound form commonly used is a straight chain type, reactive P contained compound is because of having on main chain-the O-P-O-key, and general heat-resisting character is poorer than halogen-containing or not halogen-containing composition epoxy resin.
Goal of the invention
The present invention discloses a kind of Resins, epoxy that contains reactive phosphorus compound modification on side chain, can be a what phosphorus compound side chain position with the reactivity of epoxy reaction in the Resins, epoxy in the primary structure, have than general P contained compound or the better heat-resisting character of Resins, epoxy, be suitable as the flame retardancy composition, and under the situation that does not influence working properties, can replace the material that contains halogen compounds, and reach environmental requirement.
Primary and foremost purpose of the present invention is to provide a kind of difficult combustible epoxy resin;
Another object of the present invention is to provide a kind of difficult combustible epoxy resin composition that contains this difficult combustible epoxy resin;
A further object of the present invention is to provide a kind of cured article and its preparation method of being made by difficult combustible epoxy resin composition of the present invention.
Further purpose of the present invention is to provide described difficult combustible epoxy resin composition in the application that is used for making substrate, Copper Foil tackiness agent and semiconductor sealing material that adhesive sheet, matrix material, laminated plates, printed circuit board (PCB), Layer increasing method use.
The present invention discloses Resins, epoxy and the composition thereof that a kind of side chain has reactive P contained compound modification, disclosed is and to have simple function reactive 9, the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, hereinafter referred is HCA) with contain reactive aldehydes and carry out addition reaction, generation has the P contained compound of alcohol radical, its Hou again with phenols, the compound that organic acid etc. contain the functional group carries out condensation reaction, and the what side chain that so can put in place has reactive P contained compound.This kind P contained compound can be directly used in the difficult combustible epoxy resin constituent, also can be applicable in thermoplastic plastic or the thermohardening type resin combination.
Generally, copper (the RCC of copper plate pressing plate (copper clad laminate), Layer increasing method (build-up), coated with resins, Resin Coated Copper) Resins, epoxy of used low bromine content is by the reaction of bisphenol-type epoxy resin and tetrabromobisphenol and get, the disclosed difunctionality base or the P contained compound of multiple functional radical can replace tetrabromobisphenol or other bromine-containing compound and P contained compound, directly add in the what resin combination, or carry out addition reaction with Resins, epoxy and obtain the Resins, epoxy of P contained compound.
The resin combination of the P contained compound that the employed phosphorous flame retardant resin composition of common processing is a straight chain type or the P contained compound of non-response type, its working properties has bigger difference.The phosphorus containg substances that the Resins, epoxy of the P contained compound modification that the present invention discloses has flame retardancy, have on the side chain of this P contained compound can with the group of epoxy reaction in the Resins, epoxy, the difference of its working properties can be less.On the other hand, can reduce the flowability of Resins, epoxy by what side chain HCA molecular grouping, stability of molecule is higher during what high temperature, and thermotolerance is also higher.
The P contained compound Resins, epoxy of the position what side chain that the present invention discloses can replace the cured resin of the bromine-containing compound of present use, for example the epoxy resin mold compound in the semiconductor sealing material (EMC ' s, Epoxy Molding Compounds) and matrix material etc.
The Resins, epoxy of P contained compound of the present invention can directly add in the thermoplastic resin, for example polynary ester, polyethers, polyolefine, PEEK, PPE, POM etc., also can directly add in the composition of such resin formation of what, or react with this resin and obtain the P contained compound resin combination.
P contained compound Resins, epoxy that the present invention discloses and composition thereof have excellent thermotolerance and flame retardancy, can improve the shortcoming of known technology, and improve electric and mechanical properties and reducing cost.The composition epoxy resin of the P contained compound modification of the novelty that the present invention discloses, can be applicable to make preimpregnation thing (prepreg), laminated plates and the printed circuit board (PCB) etc. that need have difficult combustion effect, and cooperate the use of this constituent, make laminated plates have high second-order transition temperature and excellent thermotolerance simultaneously.
The present invention relates to a kind of difficult combustible epoxy resin, it contains the Resins, epoxy of reactive P contained compound for side chain.Do not influence can replace halogen contained compound or bromination under the working properties situation resin as the flame retardancy composition.
The present invention relates to a kind of difficult combustible epoxy resin composition again, it comprises
(1) side chain contains the Resins, epoxy of reactive P contained compound,
(2) not halogen-containing solidifying agent, its have active hydrogen can with the epoxy reaction in the Resins, epoxy,
(3) curing catalyst,
Above-mentioned difficult combustible epoxy resin composition has the excellent thermotolerance and the improved characteristics of flame retardancy, and said composition is not halogen-containing and do not need to add in addition the flame retardant resistance material and promptly have excellent heat-resisting character, flame retardancy; Above-mentioned again not halogen-containing solidifying agent can be phosphorous or nitrogen compound.
The present invention discloses the Resins, epoxy of the reactive P contained compound modification of having of a kind of what side chain and contains the composition of this resin, wherein P contained compound is by HCA and reactive aldehydes addition reaction, generate organic ring-type phosphorus compound, thereafter the compound that contains the functional group with phenols, organic acid etc. again carries out condensation reaction, so can obtain being positioned at side chain and have reactive organic ring-type phosphorus compound.For example: HCA and hydroxy benzaldehyde carry out addition reaction, carry out condensation reaction with phenols again and must have the P contained compound of multiple functional radical; HCA and glyoxal reaction carry out condensation reaction with phenols again and must have the P contained compound of multiple functional radical; The similar bis-phenol of the P contained compound of this multiple functional radical, just hydrogen or the organism with structure central authorities replaces with HCA; Organic ring-type phosphorus compound of this multiple functional radical can react with Resins, epoxy, with the Resins, epoxy (abbreviating the flame retardancy phosphorous epoxy resin hereinafter sometimes as) that makes the P contained compound modification.
The difficult combustible epoxy resin of the P contained compound modification that the present invention discloses is by shown in the following formula (A),
R in the formula
5 'Be selected from-O-,-NH-,-S-,-COO-,-SO
3-,-CO-, CH
3CON＜group; Ar
1And Ar
2Be selected from following radicals:
R
6Be H, C
1-10Alkyl or aryl; R
7For-CH
2-,-(CH
3)
2C-,-SO
2-,-CO-,-O-; R
8For-OH ,-NH
2,-SH ,-COOH ,-SO
3H ,-COH ,-NHCOCH
3M, n are the integer of 0-4; Z is the integer of 1-20; Epoxy-is the Resins, epoxy of one of them epoxy group(ing) through open loop.
R in the following formula
6Shown C
1-10Alkyl means the straight or branched alkyl that contains 1 to 10 carbon atom, and it comprises methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, heptyl, octyl group, nonyl, decyl etc.
R in the following formula
6Shown aryl means the aryl that contains 6 to 10 carbon atoms, and it comprises phenyl, naphthyl etc.
Being characterized as of above-mentioned Resins, epoxy contains the reactive phosphorus compound of side chain in the Resins, epoxy, this side chain P contained compound, shown in (B):
In the formula, R
5For be selected from-OH ,-NH
2,-SH ,-COOH ,-SO
3H ,-COH ,-NHCOCH
3Group; Ar
1And Ar
2Be selected from following radicals separately:
R
6Be H, C
1-10Alkyl or aryl; R
7For-CH
2-,-(CH
3)
2C-,-SO
2-,-CO-,-O-; R
8For-OH ,-NH
2,-SH ,-COOH ,-SO
3H ,-COH ,-NHCOCH
3M, n are the integer of 0-4; Z is the integer of 1-20.
Above-mentioned P contained compound (A) is by HCA, shown in (C):
Carry out addition reaction with the compound that contains the C=O reactive group (for example aldehydes etc.), generate the P contained compound with alcohol radical, right Hou is carried out condensation reaction with compounds such as phenols, organic acids again and is obtained P contained compound suc as formula (B).Prepared formula (B) P contained compound again with the Resins, epoxy that contains at least two terminal epoxy groups on an epoxy reaction, form the difficult combustible epoxy resin of formula (A).
The kind that is used to make Resins, epoxy of the present invention can be any Resins, epoxy with at least two terminal epoxy groups, and specific examples comprises: based epoxy resins such as bis-phenol glycidyl ether, two diphenol glycidyl ether, dihydroxy-benzene glycidyl ether, the glycidyl ether that contains azo-cycle, dihydroxy naphthlene glycidyl ether, phenolic aldehyde polyglycidyl ether and poly-hydroxy glycidyl ether.
Bis-phenol glycidyl ether specific examples 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 and tetramethyl-bisphenol S glycidyl ether etc.
Two diphenol glycidyl ether specific exampless comprise: 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.
Dihydroxy-benzene glycidyl ether specific examples comprises: Resorcinol glycidyl ether, Resorcinol glycidyl ether and isobutyl-benzene diphenol glycidyl ether etc.
Phenolic aldehyde polyglycidyl ether specific examples comprises: phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether and bisphenol-A phenolic polyglycidyl ether etc.
Phenyl polyhydroxy phenol polyglycidyl ether specific examples 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 ethers and dicyclo amylene-phenolic aldehyde polyglycidyl ether etc.
The glycidyl ether specific examples that contains azo-cycle comprises: the triglycidyl ether of chlorinated isocyanurates and the triglycidyl ether of cyanurate etc.
The glycidyl ether specific examples of dihydroxy naphthlene comprises: 1, and 6-dihydroxy naphthlene diglycidylether and 2,6-dihydroxy naphthlene diglycidylether etc.
Above-mentioned Resins, epoxy can use separately or use with two kinds or multiple form of mixtures.Wherein be preferably dihydroxyphenyl propane glycidyl ether, phenolic aldehyde polyglycidyl ether, three (4-hydroxy phenyl) methane polyglycidyl ether, dicyclo amylene-phenolic aldehyde polyglycidyl ether and four (4-hydroxy phenyl) ethane polyglycidyl ether, or its mixture.
Make difficult combustible epoxy resin of the present invention, comprise that according to circumstances other contains compound bearing active hydrogen, for example: amine, bisphenol resin, dihydroxy-benzene, polyhydroxy phenol resin and phenolic etc.
The amine specific examples comprises: dicyan diamide, diaminodiphenyl-methane etc.
The bisphenol resin specific examples comprises: (wherein Ph represents phenylene, and X is-CH to contain formula-Ph-X-Ph-
2-,-C (CH
3)
2-,-O-,-S-,-CO-,-SO
2-) shown in 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 etc.
The dihydroxy-benzene specific examples comprises: Resorcinol, Resorcinol, isobutyl-Resorcinol etc.
Many (hydroxyl phenol) resin specific examples 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 phenolic specific examples comprises: phenol formaldehyde condensate, cresols phenolic condensation compound, bisphenol-A phenolic condenses, dicyclo amylene-phenolic condensation compound etc.
Difficult combustible epoxy resin of the present invention comprises that according to circumstances other contains compound bearing active hydrogen, is preferably dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane and Resorcinol.
Make difficult combustible epoxy resin of the present invention, the equivalent ratio of mentioned component is a Resins, epoxy: the equivalent ratio of P contained compound is 100: 5 to 100: 150, is preferably 100: 10 to 100: 50, preferred 100: 15 to 100: 40.And when the high what 150 of the relative proportion of P contained compound, will cause the viscosity of resin solvent solubleness variation and resin solution to uprise; If the relative proportion of P contained compound is lower than at 5 o'clock, with the product flame retardancy variation that causes after the curing.
The reactive mode of making flame retardancy phosphorous epoxy resin of the present invention can be fusion addition reaction (advancement reaction) or back flow reaction mode (reflux reaction); Wherein, back flow reaction is and the back flow reaction mode of solvent that suitable solvent is ketone, organic aromatic species, aprotic solvent, ethers or ester class etc.Organic aromatic species is preferable with toluene, dimethylbenzene, ketone is preferable with acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), aprotic solvent is with N, dinethylformamide, N, N-diethylformamide, dimethyl sulfoxide (DMSO) are preferable, ethers is preferable with ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and the ester class is preferable with ethyl acetate, isopropyl acid ethyl ester, propylene glycol monomethyl ether ethyl ester.
The temperature of reaction of making flame retardancy phosphorous epoxy resin of the present invention is generally 50 to 350 ℃, is preferably 50 to 300 ℃, more preferably 100 to 250 ℃, most preferably is 100 to 200 ℃.And when 350 ℃ of high whats of temperature of reaction, be easy to generate side reaction and more difficult controls reaction speed, and may impel the speed of resin deterioration to speed; When 50 ℃ of low whats of temperature of reaction, efficient difference and the resin properties that is produced be difficult to meet the requirement that high temperature uses.
The invention still further relates to a kind of difficult combustible epoxy resin composition, it comprises:
(1) difficult combustible epoxy resin of above-mentioned formula (A), the Resins, epoxy of its reactive P contained compound modification for side chain contains,
(2) not halogen-containing solidifying agent, its have active hydrogen can with the epoxy reaction in the Resins, epoxy,
(3) curing catalyst.
Flame retardant resin composition of the present invention except the Resins, epoxy that contains the side chain type P contained compound of the present invention, also can further comprise other not phosphorated Resins, epoxy.It is selected from Resins, epoxy, resol, vibrin, carbamide resin, polyamide resin, polychlorostyrene polyimide resin and composition thereof.
Phosphorated Resins, epoxy not can be any Resins, epoxy, and it is selected from: 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.
Bis-phenol glycidyl ether specific examples 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.
Two diphenol glycidyl ether specific exampless comprise: (4,4 '-diphenol) glycidyl ether, 3,3 '-dimethyl-(4,4 '-diphenol) glycidyl ether, 3,3 ', 5,5 '-tetramethyl--(4,4 '-diphenol) glycidyl ether etc.
Dihydroxy-benzene glycidyl ether specific examples comprises: Resorcinol glycidyl ether, Resorcinol glycidyl ether, isobutyl-Resorcinol glycidyl ether etc.
Phenolic aldehyde polyglycidyl ether specific examples comprises: phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether, bisphenol-A phenolic polyglycidyl ether etc.
Phenyl polyhydroxy phenol polyglycidyl ether specific examples 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, dicyclo amylene-phenolic aldehyde polyglycidyl ether etc.
The glycidyl ether specific examples that contains azo-cycle comprises the triglycidyl ether of chlorinated isocyanurates, the triglycidyl ether of cyanurate etc.
The glycidyl ether specific examples of dihydroxy naphthlene comprises 1,6-dihydroxy naphthlene diglycidylether and 2,6-dihydroxy naphthlene diglycidylether.
These Resins, epoxy can use separately or use with two or more form of mixtures.
Preferred specific examples is polymer with bis phenol A glycidyl ether, phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether, three (4-hydroxy phenyl) methane polyglycidyl ether, dicyclo amylene-phenolic aldehyde polyglycidyl ether and four (4-hydroxy phenyl) ethane polyglycidyl ether, or its mixture.
The flame retardancy phosphorous epoxy resin of the invention described above with the content ratio of phosphorated Resins, epoxy not is: the flame retardancy phosphorous epoxy resin accounts for 5 to 100% of Resins, epoxy gross weight, is preferably 20 to 100%, and more preferably 25 to 100%.And, cause flame retardancy and stable on heating deficiency easily if during the low what 5% of content ratio.
The solidifying agent that has in the stable on heating composition epoxy resin of difficult combustion of the present invention, comprise contain compound bearing active hydrogen can with solidifying agent and other not halogen-containing solidifying agent of phosphorous, the nitrogen of epoxy reaction.
The spendable resin curing agent that contains nitrogen and phosphorus in the difficult combustible epoxy resin composition of the present invention has the structure shown in the following formula (D):
R in the formula
1Be selected from hydrogen atom or following formula (E
1) or (E
2) arbitrary structure, but R
1At least one is not a hydrogen atom:
(E
1) R
1=-[CH
2-R
3]
nH; R wherein
3Group for phenylene, naphthylidene or following formula:
In the formula A be-O-,-S-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-or the group of following formula:
Or
R
4Be H, C
1-10Alkyl or aryl; Y is-OH ,-NH
2,-COOH; A is the integer of 0-2; X is the integer of 0-4; Above-mentioned R
3And in the base shown in the A, aryl can be by one or more hydroxyl, amino, carboxyl, C of being selected from
1-6The substituting group of alkyl replaces; N is 0 to 20 integer;
(E
2) R in the formula
3, n separately with following formula (E
1) definition identical;
R
2For-NHR
1, C
1-6Alkyl or aryl; But at least one R
1It is not hydrogen atom.
In the difficult combustible epoxy resin composition of the present invention contained other not halogen-containing and can with the solidifying agent of epoxy reaction, comprise amine, bisphenol resin, dihydroxy-benzene, polyhydroxy phenol resin and phenolic.
The amine specific examples comprises dicyan diamide, diaminodiphenyl-methane etc.
The bisphenol resin specific examples comprises and contains formula-Ph-X-Ph-(wherein Ph represents phenylene, and X is-CH
2-,-C (CH
3)
2-,-O-,-S-,-CO-,-SO
2-) shown in 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 '-'-biphenyl diphenol), 3,3 '-dimethyl-4,4 '-'-biphenyl diphenol, 3,3 ', 5,5 '-tetramethyl--(4,4 '-'-biphenyl diphenol) etc.
The dihydroxy-benzene specific examples comprises Resorcinol, Resorcinol, isobutyl-Resorcinol etc.
Many (hydroxyl 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 etc.
The phenolic specific examples comprises phenol formaldehyde condensate, cresols phenolic condensation compound, bisphenol-A phenolic condenses, dicyclo amylene-phenolic condensation compound etc.
Contained solidifying agent is selected from amine, bisphenol resin, dihydroxy-benzene, polyhydroxy phenol resin, phenolic and anhydrides in the difficult combustible epoxy resin composition of the present invention.
Contained curing agent content is according to the epoxy equivalent (weight) of the reactive behavior hydrogen equivalent of solidifying agent and Resins, epoxy and decide in the difficult combustible epoxy resin composition of the present invention, the epoxy equivalent (weight) of Resins, epoxy is 1 00% o'clock, the equivalent of the reactive hydrogens of solidifying agent is 20 to 140%, with 40 to 95 is preferable, again with 50 to 95% for better.
Contained 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 in the difficult combustible epoxy resin composition of the present invention; With its mixture etc.
The tertiary amine specific examples comprises: triethylamine, tributylamine, dimethyl amine ethanol, 3,5-dimethylphenyl amine, three (N, N-dimethyl-amino methyl) phenol, N, N-dimethyl-amino methyl phenol etc.
Three grades of phosphine specific exampless comprise: 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 quaternary alkylphosphonium salt specific examples 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 for example glyoxal ethyline (2MI), 2-phenylimidazole (2PI), 2-ethyl-4-methylimidazole (2E4MZ), C11MI, C17MI etc.Such curing catalyst can use separately or use with two kinds or multiple form of mixtures.
Preferred curing catalyst is tertiary amine, San Ji Phosphonium or imidazolium compounds, more preferably xylidine, glyoxal ethyline (2MI), 2-phenylimidazole (2PI), 2-ethyl-4-methylimidazole (2E4MZ).
The usage quantity of curing catalyst is 50 to 50 of a composition total weight, and 000ppm is preferably 100 to 30,000ppm, and more preferably 200 to 10,000ppm most preferably is 500 to 2,000ppm.If the high what 50000ppm of addition of curing catalyst though can shorten the reaction times, can influence the character of application because of the generation of by product, for example be used for the fit aspect of board layer, can make the character variation such as electrical properties, moisture resistance, water-absorbent of generation; And if during the low what 50ppm of addition, speed of response is slowly than inefficiency.
Difficult combustible epoxy resin composition of the present invention has excellent thermotolerance and flame retardancy matter, after solidifying, solidifying agent is suitable as high heat-stable material, for example: the Copper Foil tackiness agent (RCC) of adhesive sheet or prepreg, matrix material, laminated plates, printed circuit board (PCB), coated with resins Copper Foil, the epoxy resin mold compound in the semiconductor sealing material (EMC ' s), high heat-resisting powder body coating, engineering plastics etc., can be according to each composition in the different purposes allotment compositions.
The composition epoxy resin of P contained compound modification of the present invention in addition can add solvent and adjust viscosity to be deployed into varnish (varnish) form, and suitable solvent comprises 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 for example N, dinethylformamide, N, N-diethylformamide, dimethyl sulfoxide (DMSO); Ethers comprises ethylene glycol monomethyl ether, propylene glycol monomethyl ether; The ester class comprises ethyl acetate, isopropyl acid ethyl ester, propylene glycol monomethyl ether ethyl ester.Be mainly during allotment the scope of viscosity controller at 20 to 500cps/25 ℃.
General for the interpolation and choice of Solvent interpolation of curing catalyst, the gel time that is preferably this difficulty combustion resinous varnish is controlled at 30 to 500 seconds/171 ℃ scope, the preferable scope that is controlled at 20 to 500cps/25 ℃ of viscosity.
Decide according to the scope of using, the phosphorous resin combination of flame retardancy of the present invention also can add general additive or properties-correcting agent, for example thermo-stabilizer, photostabilizer, ultraviolet absorbers and plasticizer etc.
The invention further relates to described difficult combustible epoxy resin composition in the application that is used for making substrate that adhesive sheet, matrix material, laminated plates, printed circuit board (PCB), Layer increasing method use, Copper Foil tackiness agent, semiconductor sealing material.
Composition epoxy resin with P contained compound modification of thermotolerance and flame retardancy of the present invention can be in order to make laminated plates or adhesive sheet, it can use the impregnation fiber base material of organic or inorganic material, for example glass, metal, carbon fiber, aromatic poly (aramid), boride, Mierocrystalline cellulose (cellulose) etc.
Difficult combustible epoxy resin composition of the present invention can utilize the known method of general industry to make the laminate of Copper Foil, fiber support thing and difficult combustible epoxy resin composition of the present invention.
Can use phosphorated Resins, epoxy flame retardancy composition of the present invention and nitrogenous Resins, epoxy to be modulated into varnish, impregnation glasscloth or organic fibre, the heating universe is dry, and obtain the prepreg (prepreg) of the universe, this prepreg moulding is further made the matrix material laminated plates, or be used for the bonding coat of other films separately, or with one or more combinations, what on it one side or on, Copper Foil is placed on following two sides, depress heating this prepreg or its composition adding, resulting laminated plates matrix material is in dimensional stability, chemical proof, erosion resistance, the standard that all surpasses present product on water absorbability and the electrical properties, be suitable for making electronics, space, electric products such as traffic are as making printed circuit board (PCB) and multilayer circuit board etc. with what.Its spendable impregnation fiber base material is the organic or inorganic fiber base material, and it comprises, for example: glass fibre, steel fiber, carbon fiber, Kevlar, boron and Mierocrystalline cellulose etc.
Also difficult combustion heat-resistant resin composition of the present invention can be modulated into varnish, on the coating what Copper Foil, the heating universe is dry and obtain the gum Copper Foil of the universe.This gum Copper Foil is at room temperature preserved and can be reached the several months long, has good storage stability.This gum Copper Foil further moulding is made into the matrix material laminated plates, or be used in the bonding coat of other film separately, or with one or more combinations, what on it one side or upper and lower faces in layer add lamination one by one and close (build-up), resulting laminated plates matrix material all surpasses the standard of present product on dimensional stability, chemical proof, erosion resistance, water absorbability and electrical properties, be fit to make the multilayer printed circuit board of electronics, space, traffic etc. with what.
Other the invention still further relates to a kind of cured article and its preparation method of being made by difficult combustible epoxy resin composition of the present invention, this cured article makes the curing under temperature of reaction is 20 to 350 ℃ of this difficult combustible epoxy resin composition, described temperature is preferably 50 to 300 ℃, more preferably 100 to 250 ℃, most preferably be 120 to 220 ℃.Above-mentioned curing reaction temperature must carefully be controlled, if 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 demand that meets the high temperature use of the resin properties that is produced.
According to difficult combustion heat-resistant resin composition of the present invention, do not need to add other processing aids and difficult combustion additive, can improve the flame retardancy and the heat-resisting character of Resins, epoxy equally.
Embodiment
To explain the present invention 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 1: the Resins, epoxy that artificial resin factory in Changchun produces, trade(brand)name CNE200ELB,
Be the polyglycidyl ether of cresols-aldehyde condensate, its epoxy equivalent (weight) is between 200 to 220g/eq, and hydrolyzable chlorine is below the 200ppm.
Resins, epoxy 2: the Resins, epoxy that artificial resin factory in Changchun produces, trade(brand)name PNE177 is the phenolic aldehyde polyglycidyl ether, and its epoxy equivalent (weight) is between 170 to 190g/eq, and hydrolyzable chlorine is below the 1000ppm.
Resins, epoxy 3: the Resins, epoxy that artificial resin factory in Changchun produces, trade(brand)name BE188EL is the diglycidylether of dihydroxyphenyl propane, and its epoxy equivalent (weight) is between 180 to 195g/eq, and hydrolyzable chlorine is below the 200ppm.
On behalf of Changchun artificial resin factory, Resins, epoxy 4 produce, and the diglycidylether of the tetrabromo-bisphenol of selling with trade(brand)name BEB530A80, its epoxy equivalent (weight) be between 430 to 450g/eq, bromine content between 18.5 to 20.5wt%.
HCA: 9, the 10-dihydro-9-oxy is mixed-10-phosphorus-Fei-10-oxide compound.
Catalyst (claiming curing catalyst again) A: triphenylphosphine, in the 10% molten what methyl ethyl ketone.
Catalyst (claiming curing catalyst again) B: glyoxal ethyline (2MI), in the 10% molten what methyl ethyl ketone.
Solidifying agent A: the dicyan diamide, in the 10% molten what dimethyl formamide.
Solidifying agent B: FDAC changes into production, and commodity are called melan 9000
TM70
Solidifying agent C: artificial resin factory in Changchun produces, and commodity are called BEH510, Ahew between 105 to 110g/eq.
Relevant epoxy equivalent (weight) used herein (EEW, Epoxy Equivalent Weight), varnish viscosity (Viscosity), solid composition (Solid content), be according to following method of testing test:
(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 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, use Brookfield (Brookfield) viscometer in 25 ℃ of measurements.
(3) solid composition: get the varnish sample that contains phosphorous epoxy resin of the present invention of 1 gram, in the weight percent of 60 minutes measured nonvolatile component of 150 ℃ of bakings.
Synthesis example 1: P contained compound HCP's is synthetic
Organic ring-type phosphorus compound HCA (9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound) and 216 grams insert in the glass reaction still dissolving and stir, when temperature arrives 110 ℃, add polyoxymethylene 32.6 gram (Changchun artificial resin systems, Para 92%), elevated temperature to 150 ℃ also reacts more than 3 hours.Be decompressed to 20mmHg and kept 1 hour, generate organic ring-type phosphorus compound HCAL246 gram, add toluene 246 grams thereafter again.Heating for dissolving stirs in the what glass reaction still, adds phenol 94 grams and right-toluene sulfonic acide 2.5 grams when temperature arrives 110 ℃, and reacts more than 3 hours.It is dry to be cooled to room temperature, filtering reaction thing and the universe then, and generates the organic ring-type phosphorus compound of title.
Organic ring-type phosphorus compound HCP that above-mentioned reaction generates, its fusing point is 146 ℃.Ultimate analysis
As shown in the formula:
(C
19H
15O
2P molecular weight=306)
| C％ | H％ | P％ | |
| Measured value | 74.3％ | 4.9％ | 10.2％ |
| Calculated value | 74.51％ | 4.9％ | 10.13％ |
Synthesis example 2: P contained compound HDP's is synthetic
Organic ring-type phosphorus compound HCA (216 gram) places glass reaction still heating for dissolving to stir, and adds 40% oxalic dialdehyde, 72.5 grams when temperature reaches 110 ℃, and reacts more than 3 hours.It is dry to be cooled to room temperature, filtering reaction thing and the universe then, generates organic ring-type phosphorus compound HCAG.
Organic ring-type phosphorus compound HCAG that above-mentioned reaction generates, its fusing point is 243 ℃.Ultimate analysis as shown in the formula:
(C
26H
20O
6P
2Molecular weight=490)
| C％ | H％ | P％ | |
| Measured value | 63.9％ | 4.1％ | 12.5％ |
| Calculated value | 63.67％ | 4.08％ | 12.65％ |
Place glass reaction still heating for dissolving to stir organic ring-type phosphorus compound HCAG245 gram and toluene 245 grams, when temperature reaches 110 ℃, add phenol 94 grams and right-toluene sulfonic acide 2.5 grams, and react more than 3 hours.It is dry to be cooled to room temperature, filtering reaction thing and the universe then, generates organic ring-type phosphorus compound HDP.
Organic ring-type phosphorus compound HDP that above-mentioned reaction generates, its fusing point is 260 ℃.Ultimate analysis as shown in the formula:
(C
38H
28O
6P
2Molecular weight=642)
| C％ | H％ | P％ | |
| Measured value | 71.2％ | 4.4％ | 9.6％ |
| Calculated value | 71.03％ | 4.36％ | 9.66％ |
Synthesis example 3: P contained compound HPP's is synthetic
Organic ring-type phosphorus compound HCA (216 gram) places glass reaction still heating for dissolving to stir, and adds p-hydroxybenzaldehyde (4-Hydroxybenzaldehyde) 112 grams when temperature reaches 110 ℃, and reacts more than 3 hours.Be cooled to room temperature then, the filtering reaction thing and the universe are dry, generate organic ring-type phosphorus compound HPP.
Organic ring-type phosphorus compound HPP that above-mentioned reaction generates, its fusing point is 286 ℃.Ultimate analysis as shown in the formula:
| C％ | H％ | P％ | |
| Measured value | 72.7％ | 4.6％ | 7.4％ |
| Calculated value | 72.46％ | 4.59％ | 7.49％ |
(C
25H
19O
4P molecular weight=414)
Synthesis example 4: phosphorous epoxy resin A's is synthetic
Be equipped with and add Resins, epoxy 3 (1000 gram) and organic ring-type phosphorus compound HPP (380.5 gram) in 3000 milliliter of five neck glass reaction still of electrically heated cover, temperature regulator, electric blender and stirring rod, nitrogen inlet, thermopair, water cooled condenser, feed hopper, feed nitrogen and be heated to 120 ℃, after Resins, epoxy 3 and HCA are fused fully, vacuumize and make the above raw material universe dry, feed nitrogen again and vacuumize repetition above-mentioned steps 2 times.Temperature of reaction kettle is reduced to 85 to 90 ℃, adds catalyst A (6.0 gram).The startup stirrer stirs resin and catalyst and feeds nitrogen.Gained mixture heating up to 160 ℃ also kept 10 minutes.Can find the slow heat release of reactant, lasting heat release is warming up to 180 ℃, and kept this temperature 3 hours and phosphorous epoxy resin A, its epoxy equivalent (weight) is 396, theoretical phosphorus content is 2.0wt%.
Synthesis example 5 to 7: phosphorous epoxy resin B, C and D's is synthetic
This synthesis example is reacted according to the similar approach of synthesis example 1, but after the what reaction end, adds the listed solvent of table 1 to gained Resins, epoxy, gets the phosphorous resin of solution state.The epoxy equivalent (weight) of the phosphorous resin of synthesis example 4 to 7 gained, solid composition and theoretical phosphorus content are shown in following table 2.
Table 1: synthesis example 4 to 7 prescriptions
| Synthesis example four | Synthesis example five | Synthesis example six | Synthesis example seven | |
| Phosphorous epoxy resin A | Phosphorous epoxy resin B | Phosphorous epoxy resin C | Phosphorous epoxy resin D | |
| Resins, epoxy 1 (gram) | 362 | |||
| Resins, epoxy 2 (gram) | 360 | |||
| Resins, epoxy 3 (gram) | 1000 | 640 | 1000 | 625 |
| HPP (gram) | 380.5 | 380.5 | 454 | 380.5 |
| Bisphenol-A (gram) | 13 | |||
| Catalyst A (gram) | 6.0 | 6.0 | 6.0 | 5.9 |
| Propylene glycol methyl ether acetate (milliliter) | 230 | 230 | 242.3 | 230 |
| Acetone (milliliter) | 230 | 230 | 242.3 | 230 |
Table 2: the phosphorous epoxy resin property analysis
| Phosphorous epoxy resin A | Phosphorous epoxy resin B | Phosphorous epoxy resin C | Phosphorous epoxy resin D | |
| Epoxy equivalent (weight) (g/eq) | 396 | 389 | 472 | 438 |
| Gu composition | 74.9％ | 74.7％ | 75.1％ | 75.0％ |
Synthesis example 8: the solidifying agent D's of phosphorous and nitrogen is synthetic
In the 3000 milliliter of five neck glass reaction still that is equipped with electrically heated cover, temperature regulator, electric blender and stirring rod, nitrogen inlet, thermopair, water cooled condenser, feed hopper, add phenol 1410 grams (15 moles), 92% polyoxymethylene, 244.7 grams (7.5 moles), benzoquinones guanamines (benzoguanamine) 337 grams (1.8 moles), HCA259 gram (1.2 moles) and oxalic acid 11.2 grams, vacuumize after the fusion and make the above raw material universe dry, feed nitrogen again and vacuumize repetition above-mentioned steps 2 times.Be warming up to 100 to 110 ℃, reacted 3 hours, be warming up to 120 to 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 phosphorous and solidifying agent D nitrogen.Softening temperature is 161 ℃ by analysis.Theoretical nitrogen content is 10.0wt%, and phosphorus content is 2.93wt%, and Ahew is 210g/eq.
Embodiment 1 to 7 and comparative example 1
In being equipped with under the room temperature in the container of agitator and condenser, above-mentioned institute synthetic phosphorous epoxy resin, solidifying agent, curing catalyst and solvent 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 epoxy resin A (gram) | 125 | |||||||
| Phosphorous epoxy resin B (gram) | 125 | |||||||
| Phosphorous epoxy resin C (gram) | 125 | 125 | 125 | |||||
| Phosphorous epoxy resin D (gram) | 125 | 125 | ||||||
| Resins, epoxy 4 (gram) | 125 | |||||||
| Solidifying agent A | 28.2 | 28.0 | 26.5 | 26.5 | ||||
| Solidifying agent B | 31.8 | |||||||
| Solidifying agent C | 28.3 | 29.5 | ||||||
| Solidifying agent D | 53.1 | |||||||
| Curing catalyst B | 1.8 | 1.2 | 1.0 | 0.6 | 0.8 | 0.5 | 0.6 | 0.6 |
With modulated phosphorous epoxy resin varnish of making and glasscloth impregnation, through 190 ℃ of universes after dry 120 minutes, after becoming prepreg, the prepreg of gained is through DSC (Differential ScanCalorimeter, TA2910) (temperature range is 50 to 250 ℃ to record its second-order transition temperature, heat-up rate is 20 ℃/minute), survey its flame retardancy through combustion test.It is the method according to UL746, and 5 of 12.5mm * 1.3mm size are cut in the prepreg test piece, every burning 2 times, and 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
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | |
| Average burning time (second) | 2 to 3 | 0 to 1 | 0 to 1 | 2 to 3 | 2 to 3 | 1 to 2 | 2 to 3 | 1 to 2 |
| Tg(℃) | 157 | 165 | 173 | 147 | 155 | 151 | 151 | 135 |
Superimposed with eight prepregs, it respectively places the Copper Foil of a slice 35 μ m up and down, and through 185 ℃, the pressing of 25kg/cm2 pressure and become the laminate of phosphorous epoxy resin and glasscloth, the rerum natura result who analyzes each laminate 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-V0 | + | + | + | + |
| Soldering resistance | 288 ℃ of specification＞120 second | + | + | + | + |
| Stripping strength | IPC specification＞8lb/in | 11.2 | 11.2 | 10.9 | 11.1 |
| The surface resistance | Specification＞10 12 | 2.88×10 15 | 1.25×10 15 | 1.22×10 15 | 3.57×10 15 |
| The volume resistance | Specification＞10 10 | 1.25×10 14 | 0.97×10 14 | 0.88×10 14 | 1.06×10 14 |
| Specific inductivity | IPC specification＜5.4 | 4.7 | 4.7 | 4.8 | 4.7 |
| The loss factor | - | 0.020 | 0.024 | 0.019 | 0.020 |
("+" means: by)
Embodiment 8 to 11 and comparative example 2
In being equipped with under the room temperature in the container of agitator and condenser, all compositions are modulated into epoxy resin varnish according to ratio shown in the table 6.
Table 6
| Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Comparative example 2 | |
| Phosphorous epoxy resin A (gram) | 105 | ||||
| Phosphorous epoxy resin B (gram) | 150 | ||||
| Phosphorous epoxy resin C (gram) | 150 | ||||
| Phosphorous epoxy resin D (gram) | 150 | ||||
| Resins, epoxy 4 | 125 | ||||
| Solidifying agent A | 32.4 | 32.4 | 27.5 | 29.9 | 26.5 |
| Curing catalyst B | 2.4 | 0.9 | 0.6 | 0.6 | 0.65 |
The foregoing description 3,7 and 8 and the epoxy resin component of comparative example 2 gained with on 80 micron thickness coating what, the 18 micron copper foil uneven surfaces, 170 ℃ of bakings of what universe.The Copper Foil of the epoxy resin coating 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 the pressing of 25kg/cm2 pressure, makes multi-ply wood.Analyze this multiple-plate rerum natura, the result is as shown in table 7.
Table 7
| Analysis project | Repair part and specification | Embodiment 8 | Embodiment 3 | Embodiment 7 | Comparative example 2 |
| Combustion testing | UL94-V0 | + | + | + | + |
| Soldering resistance | IPC260 ℃ of specification＞30 second | + | + | + | + |
| Stripping strength | IPC specification＞6lb/in (18 μ m) | 7.6 | 7.4 | 8.0 | 8.4 |
("+" means: by)
Claims (21)
1. difficult combustible epoxy resin, it has suc as formula the tectonic element shown in (A):
R in the formula
5 'Be selected from-O-,-NH-,-S-,-COO-; Ar
1And Ar
2Be selected from following radicals separately:
R
6Be H, C
1-10Alkyl or aryl; R
7For-CH
2-,-(CH
3)
2C-,-SO
2-,-CO-,-O-; R
8For-OH ,-NH
2,-SH ,-COOH ,-SO
3H ,-COH ,-NHCOCH
3M, n are the integer of 0-4; Z is the integer of 1-20; Epoxy-is the Resins, epoxy of one of them epoxy group(ing) through open loop.
2. difficult combustible epoxy resin as claimed in claim 1, the Resins, epoxy of wherein said formula (A) are by 9 shown in the following formula (C), and the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound:
Carry out addition reaction with the compound that contains the C=O reactive group, generate P contained compound, and then carry out condensation reaction with compounds such as phenols, organic acids and obtain the P contained compound of following formula (B) with alcohol radical:
In the formula, R
5Be selected from-OH ,-NH
2,-SH ,-COOH; Ar
1And Ar
2As the defined group of above-mentioned claim 1; Prepared again formula (B) P contained compound again with the Resins, epoxy that contains at least two terminal epoxy groups on an epoxy reaction, form the difficult combustible epoxy resin of formula (A).
3. difficult combustible epoxy resin as claimed in claim 2, wherein Resins, epoxy: the equivalent ratio of P contained compound is 100: 5 to 100: 150.
4. difficult combustible epoxy resin as claimed in claim 3, wherein Resins, epoxy: the equivalent ratio of P contained compound is 100: 10 to 100: 50.
5. difficult combustible epoxy resin as claimed in claim 4, wherein Resins, epoxy: the equivalent ratio of P contained compound is 100: 15 to 100: 40.
6. difficult combustible epoxy resin composition, it comprises:
(1) the described difficult combustible epoxy resin of each of claim 1 to 5, the Resins, epoxy of its reactive P contained compound modification for side chain contains,
(2) not halogen-containing epoxy curing agent, its have active hydrogen can with the epoxy reaction in the Resins, epoxy,
(3) curing catalyst.
7. difficult combustible epoxy resin composition as claimed in claim 6, the not halogen-containing epoxy curing agent of composition (2) compound that is nitrogenous or phosphorus wherein has the structure shown in the following formula (D):
R in the formula
1Be selected from hydrogen atom or following formula (E
1) or (E
2) arbitrary structure, but R
1At least one is not a hydrogen atom:
(E
1) R
1=-[CH
2-R
3]
nH; R wherein
3Group for phenylene, naphthylidene or following formula:
In the formula A be-O-,-S-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-or the group of following formula:
Or
R
4Be H or aryl; Y is-OH ,-NH
2,-COOH; A is the integer of 0-2; X is the integer of 0-4; Above-mentioned R
3And in the base shown in the A, the hydrogen atom of aryl is by one or more hydroxyl, amino, carboxyl, C of being selected from
1-6The substituting group of alkyl replaces or is not substituted; N is 0 to 20 integer;
(E
2) R in the formula
3, n separately with following formula (E
1) definition identical;
R
2For-NHR1, C
1-6Alkyl or aryl; But at least one R
1It is not hydrogen atom;
8. difficult combustible epoxy resin composition, it comprises:
(1) the described difficult combustible epoxy resin of each of claim 1 to 5,
(2) phosphorated Resins, epoxy not,
(3) not halogen-containing epoxy curing agent, its have active hydrogen can with the epoxy reaction in the Resins, epoxy,
(4) curing catalyst.
9. difficult combustible epoxy resin composition as claimed in claim 8, wherein said not phosphorated Resins, epoxy 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.
10. the content of the Resins, epoxy of P contained compound modification is 5 to 100% of Resins, epoxy gross weight in the difficult combustible epoxy resin composition as claimed in claim 8, wherein said composition (1).
11. the content of the Resins, epoxy of P contained compound modification is 20 to 100% of Resins, epoxy gross weight in the difficult combustible epoxy resin composition as claimed in claim 10, wherein said composition (1).
12. the content of the Resins, epoxy of P contained compound modification is 25 to 100% of Resins, epoxy gross weight in the difficult combustible epoxy resin composition as claimed in claim 11, wherein said composition (1).
13. difficult combustible epoxy resin composition as claimed in claim 6, wherein said solidifying agent are selected from amine, bisphenol resin, dihydroxy-benzene, polyhydroxy phenol resin, phenolic and anhydrides.
14. difficult combustible epoxy resin composition as claimed in claim 6, wherein composition (3) curing catalyst is selected from tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt, boron trifluoride complex, lithiumation thing, imidazolium compounds and composition thereof.
15. difficult combustible epoxy resin composition as claimed in claim 6 is 100 in the Resins, epoxy epoxy equivalent (weight) wherein, this hardener dose counts 20 to 140 with its reactive behavior hydrogen equivalent.
16. difficult combustible epoxy resin composition as claimed in claim 15 is 100 in the Resins, epoxy epoxy equivalent (weight) wherein, this hardener dose is 50 to 95 with its reactive behavior hydrogen equivalent.
17. difficult combustible epoxy resin composition as claimed in claim 6, wherein said curing catalyst consumption are to account for 50 to 50 of composition epoxy resin gross weight, 000ppm.
18. difficult combustible epoxy resin composition as claimed in claim 17, wherein said curing catalyst consumption are 100 to 30 of composition epoxy resin gross weight, 000ppm.
19. difficult combustible epoxy resin composition as claimed in claim 18, wherein said curing catalyst consumption are 500 to 2 of composition epoxy resin gross weight, 000ppm.
20. as claim 6 or 8 described difficult combustible epoxy resin compositions, said composition is in the application that is used for making substrate that adhesive sheet, matrix material, laminated plates, printed circuit board (PCB), Layer increasing method use, Copper Foil tackiness agent, semiconductor sealing material.
21. a cured article is characterized in that, it is solidified under 20 to 350 ℃ by claim 6 or 8 described difficult combustible epoxy resin compositions and makes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001235265A CN1156539C (en) | 2000-08-18 | 2000-08-18 | Fire-retarded resin and fire-retardedresin composition containing said resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001235265A CN1156539C (en) | 2000-08-18 | 2000-08-18 | Fire-retarded resin and fire-retardedresin composition containing said resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1339538A CN1339538A (en) | 2002-03-13 |
| CN1156539C true CN1156539C (en) | 2004-07-07 |
Family
ID=4589932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001235265A Expired - Fee Related CN1156539C (en) | 2000-08-18 | 2000-08-18 | Fire-retarded resin and fire-retardedresin composition containing said resin |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004113355A1 (en) * | 2003-06-18 | 2004-12-29 | Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. | Method for producing organic compounds containing poly-dopo, and the use of the same |
| 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 |
| CN100384932C (en) * | 2004-10-11 | 2008-04-30 | 广东生益科技股份有限公司 | Thermosetting resin composition, presoaking materials and laminated sheet for printed circuit using same |
| DE102005015605B4 (en) * | 2005-04-05 | 2008-04-17 | Schill + Seilacher "Struktol" Aktiengesellschaft | Organophosphorus-containing prepolymers and uses therefor |
| CN101457012B (en) * | 2008-12-31 | 2011-06-15 | 广东生益科技股份有限公司 | Resin composition and copper clad laminate prepared by metal foil coated with resin composition |
| EP3540000A1 (en) | 2018-03-16 | 2019-09-18 | Stutz, Felix Benjamin | Flame retardant polyamide 6 master batch and fibers made thereof |
| CN114350024B (en) * | 2021-12-28 | 2023-06-23 | 福建新安科技有限责任公司 | Compound containing phosphorus and sulfonate as well as preparation method and application thereof |
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2000
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1339538A (en) | 2002-03-13 |
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