CN1580120A - Flame-retarded epoxy resin composition and phosphorous compound - Google Patents
Flame-retarded epoxy resin composition and phosphorous compound Download PDFInfo
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- CN1580120A CN1580120A CN 03153171 CN03153171A CN1580120A CN 1580120 A CN1580120 A CN 1580120A CN 03153171 CN03153171 CN 03153171 CN 03153171 A CN03153171 A CN 03153171A CN 1580120 A CN1580120 A CN 1580120A
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Abstract
This invention provides a kind of fire resistance epoxy resin copolymer and is composed of (A) one or two epoxy resins, (B) hardener and (C) hardening accelerant. The hardener of the (B) is a kind of phosphorus-containing compound demonstrated by the figure (1) and the definitions of the symbols in figure (1) are explained in the specification. The fire resistance epoxy resin copolymer in this invention already has good fire resistance properties and thermal endurance without being added halogen or other fire resisting agent. It can be applied to thermohardening rosin, thermoplastic resin, binding sheets, composites, laminose boards, printed circuit board, copper foil adhesive, printing ink used in layer-increasing method, blocking material of semi-conductors and so on.
Description
Technical field
The invention relates to a kind of with the flame-retardant resin composition of P contained compound as stiffening agent.This P contained compound also can improve the thermotolerance of composition simultaneously except that increasing effectively the flame retardancy of resin combination.
Background technology
Matrix material, especially epoxy resin composite material with the security of its easy processibility, height, excellent mechanical properties and chemical property, are used in widely as fields such as application, electric insulation, building building materials, solid and lamination product.Wherein, laminated plates with the Resins, epoxy manufacturing, because of Resins, epoxy strong to the adhesion of supporting materials such as glasscloth, fugitive constituent does not take place during sclerosis, mould shrinkage is little, therefore resulting laminated plates has advantages such as use range is wide, physical strength is excellent, electric insulating quality is good, chemical proofing is good, has improved the reliability of lamination sheet material greatly, and the Resins, epoxy laminated plates is used among electric and the electronic product in large quantities.
Yet in order to satisfy fine rule road and the highdensity requirement that progresses greatly day by day in the printed circuit board (PCB), laminated plates also needs to have more excellent electrical properties, mechanical properties and heat-resisting processibility.With present common FR4 laminated plates, glass tansition temperature after the sclerosis is greatly about about 130 ℃, for the cutting and the boring processing that surpass 200 ℃ in the printed circuit board (PCB) processing procedure, even welding sequence more than 270 ℃, this kind laminated plates material might break or plate bursting in the manufacturing and the course of processing.Therefore, develop energetically at the various laminated plates materials of high heat-resistant quality, high glass tansition temperature of emphasizing.In addition, for laminated plates, another important properties is its difficult combustion characteristic.In some Application Areas, for example be used for the vehicles such as aircraft, automobile and public transportation, because of directly threatening for the person and life security.Therefore, the difficulty of printed circuit board (PCB) combustion characteristic is absolute necessary.
For improving the difficulty combustion characteristic of laminated plates material, must use some to have and isolate the material that flame reduces ignition quality.For the laminated plates that Resins, epoxy/glass fibers is maintained (or organic fibre is), use halogen contained compound, particularly bromated Resins, epoxy and stiffening agent, and cooperation can make the difficulty combustion characteristic conforms necessary requirement (as UL 94V-0 grade) of this laminated plates as the difficulty combustion auxiliary agent of the class of antimonous oxide.Usually, Resins, epoxy must contain the bromine content up to 17% to 21%, and is used antimonous oxide or other incombustible agent, just can reach the level of UL 94V-0.Yet the Resins, epoxy or the antimonous oxide of use high bromine content will bring serious harm to the mankind undoubtedly.
At first, antimonous oxide has been listed in carcinogenic substance; On the other hand, bromine not only can produce in the incendiary process has corrosive bromine free radical and hydrogen bromide, and the aromatics that bromine content is high more can produce the bromination furans and the bromination Dioxins compound of severe toxicity, has a strong impact on the health and the environment of human body.Therefore, seeking a kind of new nonflammable material to improve pollution and the environmental issue of present laminated plates because of using brominated epoxy resin to cause, is instant thing.Especially, with the development of person's electronic product, the usage quantity of the epoxy glass laminated plates of FR-4 class increases gradually, to the also increase thereupon of demand of this flame retardant material.
At present, with the incombustible agent that phosphorus series compound has the environmental protection notion as a new generation, studied widely and used.For example replace halogen compounds and be used as incombustible agent, to improve the combustioncharacteristics of macromolecular material or hardening resin with the organic compound (for example triphenylphosphine acid esters, trityl phosphonic acid ester etc.) that directly uses red phosphorus or phosphorus.Yet, directly in resin, add these compounds, not only be subject to the difficulty combustion efficient of these compounds, need bigger addition, and because of its molecular weight is low, high drift will directly have influence on the characteristic of resin base material: as electrical properties, then intensity etc., cause the difficulty in the practicality.
In recent years, idea with the response type incombustible agent cooperates considering of environmental protection and safety, contain phosphatization Resins, epoxy and be used to replace brominated epoxy resin, as the prescription of difficulty combustion laminated plates, for example United States Patent (USP) the 5th, 376, No. 453, use the phosphoric acid ester of band epoxy group(ing) to cooperate nitrogenous annular sclerosis agent to make laminated plates, but be difficult to reach the shortcoming that UL 94V-0 requires, added multiple phosphoric acid ester epoxide in order to remedy the phosphorus content deficiency; United States Patent (USP) the 5th, 458 then utilizes for No. 978 epoxy phosphate ester to cooperate nitrogenous Resins, epoxy and metal composite as stiffening agent, about 175 ℃ of the glass tansition temperature of its finished product, and flame retardancy matter then only reaches UL 94V-0 edge (42 seconds with respect to threshold value 50 seconds).On the other hand, the trihydrocarbyl phosphine muriate that United States Patent (USP) the 4th, 973, No. 631 and United States Patent (USP) make apparatus active hydrogen substituting group (as, amido) for the 5th, 086, No. 156 separately or cooperate other amine type hardeners is used for the sclerosis of Resins, epoxy; Yet use stiffening agent that phosphorus is imported in the resin, may produce the insufficient shortcoming of phosphorus content, moreover, there is not the measurement of actual difficulty combustion effect in these two parts of patents yet, can't prove that its flame retardancy can reach UL 94V-0 grade.
Therefore, the inventor studies widely at above-mentioned shortcoming, finds to use a kind of specific P contained compound in resin combination, except that increasing effectively the flame retardancy of this resin combination, also can improve the thermotolerance of said composition simultaneously.
Summary of the invention
For overcoming the shortcoming of above-mentioned prior art, a purpose of the present invention is to provide the P contained compound shown in a kind of formula (I):
In the formula, each symbol definition is as follows.
Another object of the present invention provides a kind of flame-retardant resin composition, and said composition comprises: (A) one or more Resins, epoxy; (B) stiffening agent; And (C) hardening accelerator, wherein, the stiffening agent of composition (B) is suc as formula the P contained compound shown in (I)
Another purpose of the present invention provides a kind of flame-retardant resin composition, comprising: (A) one or more Resins, epoxy; (B) stiffening agent; And (C) hardening accelerator; Wherein, the stiffening agent of composition (B) comprises that also other has the compound that can carry out reactive activity hydrogen with epoxy group(ing) except that comprising the P contained compound shown in the formula (I).
Flame-retardant resin composition of the present invention comprises: (A) one or more Resins, epoxy; (B) stiffening agent; And (C) hardening accelerator, wherein, the stiffening agent of composition (B) is suc as formula the P contained compound shown in (I):
In the formula, R
1Be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4And the cohort that group constituted such as acid anhydrides, wherein R
4Be hydrogen or alkyl; And Ar
1With Ar
2Be independently selected from:
Wherein, R
2Be selected from the cohort that alkyl, alkoxyl group, nitro and aryl constitute; R
3For chemical bond or stretch alkyl; R
5Be selected from chemical bond ,-CR
2R
4-,-O-,-CO-,-S-,-SO-and-SO
2-the cohort that constituted; R
1With R
4Definition as above; A and b independently are 0 to 6 integer and a+b≤6; C and d independently are 0 to 4 integer and c+d≤4; And z is 1 to 20 integer.
Above-mentioned R
2With R
4Shown alkyl is meant straight chain, side chain or cyclic alkyl, comprising: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, second butyl, tributyl, amyl group, 2-amyl group, 3-amyl group, 2-methyl-1-butene base, isopentyl, second amyl group, 3-methyl-2-butyl, neo-pentyl, hexyl, 4-methyl-2-amyl group, cyclopentyl and cyclohexyl etc.R
3The shown alkyl of stretching comprises: stretch methyl, stretch ethyl, stretch propyl group, stretch butyl, stretch amyl group and stretch hexyl etc.R
2Shown alkoxyl group comprises: methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, second butoxy, the 3rd butoxy, pentyloxy, isopentyloxy, neopentyl oxygen, hexyloxy and cyclohexyloxy etc.R
2Shown aryl comprises: phenyl, tolyl, xylyl, phenmethyl and naphthyl etc.
P contained compound shown in the formula (I) is to carry out addition reaction by reactive organic ring-type phosphorus compound and aromatic aldehyde compounds with monofunctional, formation has the P contained compound of alcohol radical, utilize organic acid as catalyst again, make have one-OH at least ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4Or the substituent aromatics of acid anhydrides and this P contained compound with alcohol radical carry out condensation reaction and form.
Above-mentioned example with reactive organic ring-type phosphorus compound of monofunctional is 9 shown in the formula (II), and the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound:
The aromatic aldehyde compounds that is used to make this P contained compound has a substituting group at least, be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4And the cohort that constitutes of group such as acid anhydrides, comprise the benzaldehyde compounds or the naphthaldehyde compounds that are substituted or are unsubstituted.
The example of this benzaldehyde compounds comprises, but non-being limited to: through alkyl, alkoxyl group, the hydroxy benzaldehyde that nitro or aryl are substituted or are unsubstituted, the hydroxymethyl phenyl aldehyde, the hydroxyethyl phenyl aldehyde, hydroxyl isopropyl benzene formaldehyde, carboxyl benzaldehyde, the carboxyl tolyl aldehyde, the carboxy ethyl phenyl aldehyde, carboxyl isopropyl benzene formaldehyde, the amido phenyl aldehyde, the amine tolyl aldehyde, amine ethylbenzene formaldehyde, amido isopropyl benzene formaldehyde, phthalaldehyde, the hydroxybenzene dialdehyde, the carboxyl phthalaldehyde, the amido phthalaldehyde, and the thiophenol that on phenyl ring, has an aldehyde radical at least, hydroxythiophenol, the carboxyl thiophenol, the amido thiophenol, the benzyl thiophenol, hydroxyl benzyl thiophenol, carboxyl benzyl thiophenol, the aminocarbonyl phenylmethyl thiophenol, Phenylsulfonic acid, hydroxy benzenesulfonic acid, the carboxyl Phenylsulfonic acid, the amido Phenylsulfonic acid, benzamide, hydroxybenzamide, the carboxyl benzamide, the amido benzamide, the anilino methyl-formiate, the anilino ethyl formate, isopropyl N-phenyl carbamate, benzene methanamine base methyl-formiate, benzene methanamine base ethyl formate, phthalate anhydride, dihydroxy-benzene, benzene dicarboxylic acid, benzene disulfonic acid, benzene diamide etc.
Also can use the naphthaldehyde compounds to prepare this P contained compound, the example of this naphthaldehyde compounds comprises, but non-being limited to: through alkyl, alkoxyl group, the naphthaldehyde that nitro or aryl replace or be unsubstituted, the hydroxyl naphthaldehyde, the methylol naphthaldehyde, the hydroxyethyl naphthaldehyde, hydroxyl isopropyl naphthalene formaldehyde, the carboxyl naphthaldehyde, the carboxymethyl naphthaldehyde, the propyloic naphthaldehyde, carboxyl isopropyl naphthalene formaldehyde, the amido naphthaldehyde, amine methylnaphthalene formaldehyde, amine ethyl naphthalene formaldehyde, amido isopropyl naphthalene formaldehyde, the naphthalene dialdehyde, hydroxyl naphthalene dialdehyde, carboxyl naphthalene dialdehyde, amido naphthalene dialdehyde, and the thionaphthol that on naphthalene nucleus, has an aldehyde radical at least, the hydroxyl thionaphthol, the carboxyl thionaphthol, the amido thionaphthol, the naphthalene methylthio phenol, hydroxyl naphthalene methylthio phenol, carboxyl naphthalene methylthio phenol, amido naphthalene methylthio phenol, naphthene sulfonic acid, croceine acid, the carboxyl naphthene sulfonic acid, the amido naphthene sulfonic acid, naphthoamide, the hydroxyl naphthoamide, the carboxyl naphthoamide, the amido naphthoamide, the naphthylamine base methyl-formiate, the naphthylamine base ethyl formate, the naphthylamine base isopropyl formate, naphthalene methylamino methyl-formiate, the naphthalene methylurethane, naphthalic anhydride, naphthalenediol, naphthalene dicarboxylic acids, naphthalene disulfonic acid, naphthalene diamide etc.
Except that above-mentioned benzaldehyde compounds and naphthaldehyde compounds, other aromatic aldehyde compounds that on phenyl ring, has an aldehyde radical at least, also can be used for making this P contained compound, the example of this aromatic aldehyde compounds comprises, but non-being limited to: biphenyl compound, phenylbenzene alkyl compound, diphenylether compound, diphenylmethyl ketone compounds, diphenylsulfide compounds, diphenyl sulfoxide compounds and the sulfobenzide compounds etc. that on phenyl ring, have an aldehyde radical at least.
The aromatics that can carry out condensation reaction with above-mentioned P contained compound with alcohol radical be have at least one-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4Or the substituent aromatics of acid anhydrides, biphenyl compound, phenylbenzene alkyl compound, diphenylether compound, diphenylmethyl ketone compounds, diphenylsulfide compounds, diphenyl sulfoxide compounds or sulfobenzide compounds.
Can carry out the aromatics of condensation reaction to have hydroxyl with P contained compound with alcohol radical, carboxyl or amido person are preferable, the example comprises, but non-being limited to: phenol, phenylcarbinol, phenylethyl alcohol, phenylformic acid, toluylic acid, phthalandione, hydroxy-benzoic acid, aniline, benzene methanamine, amido phenol, the amido Phenylsulfonic acid, amido phenol sulfonic acid, hydroxymethyl aniline, Qiang Yijibenan, the amido phenylformic acid, naphthols, 2, the 6-dihydroxy naphthlene, naphthoic acid, naphthalic acid, naphthylamines, naphthylene diamine, the amido naphthols, the amido naphthene sulfonic acid, the amido sulfonaphthol, the methylol naphthylamines, the hydroxyethyl naphthylamines, the amido naphthoic acid.
Except that above-mentioned aromatics, the 4-xenol, 4,4 '-dihydroxybiphenyl, the 4-carboxyl biphenyl, 4,4 '-dicarboxylate biphenyl, 2, two (4-hydroxy phenyl) propane of 2-, 2-(3-hydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, two (4-hydroxy phenyl) methane, 2, two (4-carboxyl phenyl) propane of 2-, 2-(3-carboxyl phenyl)-2-(4 '-carboxyl phenyl) propane, two (4-carboxyl phenyl) methane, 4-hydroxyl phenylate, two (2-hydroxybenzene) ether, two (3-hydroxybenzene) ether, two (4-hydroxybenzene) ether, 4-carboxyl phenylate, two (2-carboxyl benzene) ether, two (3-carboxyl benzene) ether, two (4-carboxyl benzene) ether, the 4-dihydroxy benaophenonel, two (2-hydroxybenzene) ketone, two (3-hydroxybenzene) ketone, two (4-hydroxybenzene) ketone, the 4-carboxyl benzophenone, two (2-carboxyl benzene) ketone, two (3-carboxyl benzene) ketone, two (4-carboxyl benzene) ketone, 2-hydroxy-4-methyl benzophenone, 2-hydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethyl benzophenone, 4-carboxyl-2 methyl benzophenone, the 4-aminobenzophenone, 4-hydroxyl diphenyl sulfide, two (2-hydroxybenzene) thioether, two (3-hydroxybenzene) thioether, two (4-hydroxybenzene) thioether, 4-carboxyl diphenyl sulfide, two (2-carboxyl benzene) thioether, two (3-carboxyl benzene) thioether, two (4-carboxyl benzene) thioether, 2-hydroxy-4-methyl diphenyl sulfide, 2-hydroxyl-4-methoxyl group diphenyl sulfide, 2,2 '-dihydroxyl-4,4 '-dimethyl diphenyl sulfide, 4-carboxyl-2-methyldiphenyl thioether, 4-amido diphenyl sulfide, two (2-hydroxybenzene) sulfoxide, two (3-hydroxybenzene) sulfoxide, two (4-hydroxybenzene) sulfoxide, two (2-carboxyl benzene) sulfoxide, two (3-carboxyl benzene) sulfoxide, two (4-carboxyl benzene) sulfoxide, two (2, the 3-dihydroxy-benzene) sulfoxide, two (2, the 4-dihydroxy-benzene) sulfoxide, two (2,4-dihydroxyl-6-methylbenzene) sulfoxide, two (2, the 5-dihydroxy-benzene) sulfoxide, two (3, the 4-dihydroxy-benzene) sulfoxide, two (3, the 5-dihydroxy-benzene) sulfoxide, two (2,3, the 4-trihydroxybenzene) sulfoxide, two (2,3,4-trihydroxy--6-methylbenzene) sulfoxide, two (2,4, the 6-trihydroxybenzene) sulfoxide, two (2-hydroxybenzene) sulfone, two (3-hydroxybenzene) sulfone, two (4-hydroxybenzene) sulfone, two (2-carboxyl benzene) sulfone, two (3-carboxyl benzene) sulfone, two (4-carboxyl benzene) sulfone, two (2, the 4-dihydroxy-benzene) sulfone, two (3, the 4-dihydroxy-benzene) sulfone, two (3, the 5-dihydroxy-benzene) sulfone, two (3, the 6-dihydroxy-benzene) aromatics such as sulfone and two (3,5-dimethyl-4-hydroxybenzene) sulfone also is suitable for making this P contained compound.
Organic acid as the catalyst for preparing this P contained compound can be carboxylic acid or the sulfonic acid that is substituted or is unsubstituted.This organic acid example comprises, but non-being limited to: formic acid, acetate, propionic acid, butyric acid, 2 Methylpropionic acid, valeric acid, 3 Methylbutanoic acid, 2-Methyl Butyric Acid, caproic acid, enanthic acid, sad, oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, sebacic acid, hydroxyethanoic acid, lactic acid, tartrate, citric acid, oxysuccinic acid, ethylenediamine tetraacetic acid (EDTA), the salicylic acid hexahydrobenzoic acid, 1, the 4-cyclohexane dicarboxylic acid, phenylformic acid, phthalandione, the benzene tricarbonic acid, trifluoromethayl sulfonic acid, ethane sulfonic acid, propane sulfonic acid, Phenylsulfonic acid, benzene disulfonic acid, naphthene sulfonic acid, naphthalene disulfonic acid, right-toluenesulphonic acids.
In the flame-retardant resin composition of the present invention, the Resins, epoxy of composition (A) can be phosphorous or phosphorated Resins, epoxy not, this not phosphorated Resins, epoxy comprise difunctionality Resins, epoxy.So-called " difunctionality Resins, epoxy " is meant in a part of this resin, have two or more epoxide groups, for example the epoxide group that forms via the glycidyl esterification reaction of the glycidyl amination reaction of the reaction of glycidyl etherificate, one-level or the secondary amine of the oxidizing reaction of alkene, oh group or carboxylic acid.
The compound that can be used for carrying out this kind epoxidation reaction comprises: dihydroxy-benzene class, for example catechol, Resorcinol and Resorcinol etc.; Bisphenols, for example 2, the 6-dihydroxy naphthlene, 2, two (4-hydroxyphenyl) propane (being called dihydroxyphenyl propane again) of 2-, 2-(3-hydroxyphenyl)-2-(4 '-hydroxyphenyl) propane, two (4-hydroxyphenyl) methane (being called Bisphenol F again), two (4-hydroxyphenyl) sulfone (being called bisphenol S again), two (4-hydroxyphenyl) thioether, two (4-hydroxyphenyl) methylbenzene, two (4-hydroxyphenyl) methylcyclohexane, 4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxyl-3,3 ', 5,5 '-tetramethyl biphenyl, 4,4 '-dihydroxybiphenyl ether, 6,6 '-dihydroxyl-3,3,3 ', 3 '-tetramethyl--1, the 1-spirobindene completely reaches 1,3,3-trimethylammonium-1-(4-hydroxyphenyl)-1-indane-6-alcohol etc.; Oligomerization phenols, for example four phenolic group ethane and naphthols-cresols resol etc.; Phenol resins class, for example resol, phenol aralkyl, naphthols aralkyl and phenol-dicyclopentadiene copolymer resin etc.; Aliphatics and aromatic amine, for example quadrol, propylene diamine, six are stretched methanediamine, aniline, 4,4 '-two amido ditans (MDA), 4,4 '-two amido diphenyl ethers, 4,4 '-two amido sulfobenzides, 2,2 '-two (4,4 '-diamines phenyl) propane ,-benzene two methanediamines, right-benzene two methanediamines, 1,2-diamines basic ring hexane and aniline aralkyl resin etc.; The amido phenols, for example between-amido phenol, right-amido phenol, 2-(4-amine phenyl)-2-(4 '-hydroxyphenyl) propane and 4-amine phenyl-4-hydroxyphenyl methane etc.; Carboxylic-acid, for example phthalandione, m-phthalic acid, terephthalic acid, tetrahydrochysene phthalandione, six hydrogen phthalandiones, dimeracid and 1,3-dicarboxyl hexanaphthene etc.; And hydroxyl carboxylic-acid etc., for example Whitfield's ointment and 4-oxybenzene formic acid.
In the flame-retardant resin composition of the present invention, the Resins, epoxy of composition (A) is preferable with the Racemic glycidol ethers.The monomer whose example comprises: the glycidyl ether of bis-phenol glycidyl ether, xenol glycidyl ether, dihydroxy-benzene glycidyl ether, the glycidyl ether that contains azo-cycle, dihydroxy naphthlene, phenolic aldehyde polyglycidyl ether and polyhydroxy phenol polyglycidyl ether etc.
The example of bis-phenol glycidyl ether comprises: dihydroxyphenyl propane glycidyl ether, Bisphenol F glycidyl ether, dihydroxyphenyl propane D glycidyl ether, bisphenol S glycidyl ether, tetramethyl-dihydroxyphenyl propane glycidyl ether, tetramethyl-Bisphenol F glycidyl ether, tetramethyl-dihydroxyphenyl propane D glycidyl ether, tetramethyl-bisphenol S glycidyl ether etc.
The example of xenol glycidyl ether comprises: 4, and 4 '-xenol glycidyl ether, 3,3 '-dimethyl-4,4 ' xenol glycidyl ether, 3,3 ' 5,5 '-tetramethyl--4,4 ' xenol glycidyl ether etc.
The example of dihydroxy-benzene glycidyl ether comprises: Resorcinol glycidyl ether, Resorcinol glycidyl ether, isobutyl-Resorcinol glycidyl ether etc.
The example that contains the glycidyl ether of azo-cycle comprises: the triglycidyl ether of chlorinated isocyanurates, the triglycidyl ether of cyanurate etc.
The example of the glycidyl ether of dihydroxy naphthlene comprises: 1, and 6-dihydroxy naphthlene diglycidylether, 2,6-dihydroxy naphthlene diglycidylether etc.
The example of phenolic aldehyde polyglycidyl ether comprises: phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether, bisphenol-A phenolic polyglycidyl ether etc.
The example of phenyl polyhydroxy phenol polyglycidyl ether comprises: ginseng (4-hydroxyphenyl) methane polyglycidyl ether, ginseng (4-hydroxyphenyl) ethane polyglycidyl ether, ginseng (4-hydroxyphenyl) propane polyglycidyl ether, ginseng (4-hydroxyphenyl) butane polyglycidyl ether, ginseng (3-methyl-4-hydroxyphenyl) methane polyglycidyl ether, ginseng (3,5-dimethyl-4-hydroxyphenyl) methane polyglycidyl ether, four (4-hydroxyphenyl) ethane polyglycidyl ethers, four (3,5-dimethyl-4-hydroxyphenyl) ethane polyglycidyl ethers, dicyclo amylene-phenolic aldehyde polyglycidyl ether etc.
This Resins, epoxy can use or make up two or more forms with mixture separately and use.Wherein, the preferably is dihydroxyphenyl propane glycidyl ether, phenolic aldehyde polyglycidyl ether, ginseng (4-hydroxyphenyl) methane polyglycidyl ether, dicyclo amylene-phenolic aldehyde polyglycidyl ether and four (4-hydroxyphenyl) ethane polyglycidyl ethers, or its mixture.
In the flame-retardant resin composition of the present invention, composition (A) also can be not halogen-containing phosphorous epoxy resin or other not halogen-containing Resins, epoxy except that can be above-mentioned not phosphorated Resins, epoxy.Wherein, this not halogen-containing phosphorous epoxy resin can utilize organic ring-type phosphorus compound (as, 9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound) or with the formed P contained compound of this organic ring-type phosphorus compound (as, (9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound-10-yl) and-two (4-hydroxybenzene) methane) carry out addition reaction with the Resins, epoxy of multiple functional radical with catalyst catalysis, this organic ring-type phosphorus compound or this P contained compound are imported in the structure of Resins, epoxy of this multiple functional radical, form not halogen-containing phosphorous epoxy resin; Or make this P contained compound and epoxy chloropropane under the condition that sodium hydroxide exists, carry out the epoxidation processing procedure, also can form not halogen-containing phosphorous epoxy resin.
In the flame-retardant resin composition of the present invention, the stiffening agent of composition (B) is suc as formula the P contained compound shown in (I):
In the formula, R
1, Ar
1And Ar
2Definition as above.
The stiffening agent of this composition (B) can comprise further that other has the compound that can carry out reactive activity hydrogen with epoxy group(ing) except that can be the P contained compound shown in the formula (I).
Above-mentioned example with compound bearing active hydrogen comprises, but non-being limited to: aminated compounds, anhydrides compound, dihydroxy-benzene compounds, bisphenol resin, polyhydroxy phenol resin and phenolic condensation body etc.
The example of this aminated compounds comprises: the fatty amine compounds, as Diethylenetriaminee (DETA) (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), diethylin propyl group amine (DEAPA), methylene diamines, N-amido ethyl piperazidine (AEP) and m-xylylenediamine (MXDA) etc.; The aromatic amine compounds, as-phenylenediamine (MPDA), 4,4 '-two amido ditans (MDA), two amido sulfobenzides (DADPS) and two amido diphenyl ethers etc.; And secondary or tertiary amine compounds, as benzyl dimethyl amine (BDMA), dimethylamine sylvan (DMP-10), ginseng (dimethylamine methyl) phenol (DMP-30) and piperidines etc.
This anhydrides examples for compounds comprises: MALEIC ANHYDRIDE (MA), phthalate anhydride (PA), hexahydrophthalic anhydride (HHPA), tetrahydrochysene phthalate anhydride (THPA), pyromellitic acid dianhydride (PMDA) and benzene tricarboxylic acid acid anhydride (TMA).
The example of this dihydroxy-benzene compounds comprises: Resorcinol, Resorcinol, isobutyl-Resorcinol.
The example of this bisphenol resin comprises: (wherein, Ph is a phenyl to formula HO-Ph-X-Ph-OH those shown, and X is-C (CH
3)
2-,-O-,-S-,-CO-or-SO
2-), as 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.
The example of this polyhydroxy phenol resin comprises: ginseng (4-hydroxyphenyl) methane, ginseng (4-hydroxyphenyl) ethane, ginseng (4-hydroxyphenyl) propane, ginseng (4-hydroxyphenyl) butane, ginseng (3-methyl-4-hydroxyphenyl) methane, ginseng (3,5-dimethyl-4-hydroxyphenyl) methane, four (4-hydroxyphenyl) ethane, four (3,5-dimethyl-4-hydroxyphenyl) ethane.
The example of this phenolic condensation body comprises: phenol formaldehyde condensation body, cresoform condensation body, bisphenol-A phenolic condensation body, dicyclopentadiene-phenol formaldehyde condensation body.
The stiffening agent person that other can be used as Resins, epoxy comprises: urea resin, melamine resin, polyamide resin, dicyan diamide and boron fluoride amine compound etc.
This stiffening agent can use or make up two or more forms with mixture separately and use.
In the flame-retardant resin composition of the present invention,, the flame retardancy variation of the product after the sclerosis will be made if the content of P contained compound shown in the formula (I) is low excessively; Therefore, the usage ratio scope of the stiffening agent of this composition (B) is, the epoxy equivalent (weight) number of the Resins, epoxy of composition (A): the Ahew number of the P contained compound of formula (I): other has Ahew number=100 of compound bearing active hydrogen: (5 to 95): (85 to 0), be preferably 100: (25 to 95): (70 to 0) are more preferred from 100: (35 to 95): (60 to 0).
In the flame-retardant resin composition of the present invention, the example of the hardening accelerator of composition (C) comprising: tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt, boron trifluoride complex salt, lithiumation thing, imidazolium compounds or its mixtures.
The example of tertiary amine comprises: triethylamine, tributylamine, 3,5-dimethylphenyl amine, diethyl phenyl amine, Alpha-Methyl benzyl dimethyl amine, dimethyl amine ethanol, N, N-dimethyl-aminomethyl phenol and ginseng (N, N-dimethyl-aminomethyl) phenol etc.
The example of three grades of phosphines comprises: triphenylphosphine etc.
The example of quaternary ammonium salt comprises: tetramethyl ammonium chloride, 4 bromide, Tetramethylammonium iodide, etamon chloride, tetraethylammonium bromide, tetraethyl ammonium iodide, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, triethylbenzene ammonio methacrylate, triethylbenzene methyl brometo de amonio, triethylbenzene methyl ammonium iodide, triethylbenzene ethyl ammonium chloride, triethylbenzene ethyl brometo de amonio and triethylbenzene ethyl ammonium iodide etc.
The example of quaternary alkylphosphonium salt comprises: 4-butyl phosphonium chloride, four butyl phosphonium bromides, four butyl phosphonium iodides, 4-butyl-phosphonium acetate, the tetraphenyl phosphonium chloride, 4-phenyl phosphonium bromide, the tetraphenyl phosphonium iodide, ethyl triphenyl phosphonium chloride, the ethyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, Yi base triphenyl phosphonium acetate, Yi base triphenyl phosphonium phosphoric acid salt, the propyl group triphenyl phosphonium chloride, propyl group three phenyl phosphonium bromides, propyl group triphenyl phosphonium iodide, Ding base triphenyl phosphonium phosphonium chloride, butyl triphenyl phosphonium bromide and butyl triphenyl phosphonium iodide etc.
The example of imidazolium compounds comprises: glyoxal ethyline, 2-ethyl imidazol(e), 2-dodecyl imidazoles, 2-heptadecyl imidazoles, 2-phenylimidazole, 4-methylimidazole, 4-ethyl imidazol(e), 4-dodecyl imidazoles, 4-heptadecyl imidazoles, 2-phenyl-4-methylimidazole, 2-phenyl 4-hydroxy methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-hydroxy methylimidazole, 1-cyanoethyl-4-methylimidazole and 2-phenyl-4,5-dihydroxyl Methylimidazole etc.
This hardening accelerator can use or make up two or more forms with mixture separately and use.Wherein, the preferably is that imidazolium compounds is Yu quaternary alkylphosphonium salt, particularly glyoxal ethyline, 2-phenylimidazole, Yi base triphenyl phosphonium acetate, butyl triphenyl phosphonium bromide or its mixture.
In the flame-retardant resin composition of the present invention, the consumption of this hardening accelerator is 50 to 50000ppm with respect to the total amount of composition (A) and composition (B), is preferably 100 to 30000ppm, is more preferred from 200 to 10000ppm, is more preferred from 500 again to 2000ppm.
Suitable temperature of reaction is 20 to 300 ℃, is preferably 50 to 250 ℃, is more preferred from 100 to 220 ℃, is more preferred from 120 to 200 ℃ again.
Flame-retardant resin composition of the present invention also can be modulated into varnish and use.When desire is modulated into the varnish use with resin combination of the present invention, can add the viscosity that appropriate solvent is adjusted said composition; Usually, the viscosity of this resin combination is preferable with 20 to 500cps/25 ℃ scope.
The solvent that is suitable for adjusting the viscosity of said composition comprises: organic aromatic species solvent, protonic solvent, ketones solvent, ether solvent and esters solvent etc.
The example of this organic aromatic species solvent comprises: toluene and dimethylbenzene etc.; The example of this protonic solvent comprises: N, dinethylformamide, N, N-diethylformamide and dimethyl sulfoxide (DMSO) etc.; The example of this ketones solvent comprises: acetone, methyl ethyl ketone and methyl iso-butyl ketone (MIBK) etc.; The example of this ether solvent comprises: ethylene glycol monomethyl ether, propylene glycol monomethyl ether etc.; And the example of this esters solvent comprises: ethyl acetate, isopropyl acid ethyl ester and propylene glycol monomethyl ether ethyl ester etc.
Flame-retardant resin composition of the present invention also can optionally add additive or modification agent, for example thermal stabilizer, light stabilizer, ultraviolet absorbers and plasticizer etc.
Flame-retardant resin composition of the present invention can utilize oneself method of knowing of general industry, makes laminate with Copper Foil, fiber support thing and flame-retardant resin composition of the present invention.
Varnish (varnish) the impregnation fiber base material that uses flame-retardant resin composition of the present invention to be modulated into, organic or inorganic fiber base material (as glass fibre, steel fiber, carbon fiber, aramid fiber, Aromatic polyester, boron and Mierocrystalline cellulose etc.) for example, make this fiber base material heat drying again, can make dried prepreg (prepreg).This prepreg can further be made the matrix material laminated plates, be used in the bonding coat of other film or made up with one or more prepregs separately, one side or upper and lower faces are placed Copper Foil thereon, depress heating this prepreg or its composition adding, resulting laminated plates matrix material all surpasses the standard of present product on dimensional stability, chemical proof, erosion resistance, water absorbability and electrical properties, suitable manufacturing is used for the electric product of electronics, space, traffic etc., for example is used to make printed circuit board (PCB) and multilayer circuit board etc.
The sclerous reaction temperature of flame-retardant resin composition of the present invention is generally 20 to 350 ℃, is preferably 50 to 300 ℃, is more preferred from 100 to 250 ℃, is more preferred from 120 to 220 ℃ again.If the temperature of sclerous reaction is too high, then is easy to generate the speed of side reaction and difficult this sclerous reaction of control, and may impels the speed of resin deterioration to speed; If the temperature of sclerous reaction is low excessively, except the efficient that reduces this sclerous reaction, the also difficult demand that meets the high temperature use of the resin properties that is produced.
P contained compound shown in a kind of formula of the present invention (I):
In the formula, R
1Be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH-,-SO
3H ,-CONH
2,-NHCOOR
4And the cohort that constitutes of group such as acid anhydrides, wherein R
4Be hydrogen or C
1-6Alkyl; And Ar
1With Ar
2Be independently selected from:
Its first, R
2Be selected from C
1-6Alkyl, C
1-6The cohort that alkoxyl group, nitro and aryl constitute; R
3Be chemical bond or C
1-6Stretch alkyl; R
5Be selected from chemical bond ,-CR
2R
4-,-O-,-CO-,-S-,-SO-and-SO
2The cohort of-formation; R
1With R
4Definition as above; A and b independently are that 0 to 6 integer and a+b are in 0 to 6 scope; C and d independently are that 0 to 4 integer and c+d are in 0 to 4 scope; And z is 1 to 20 integer.Wherein, Ar
1With Ar
2For stretching phenyl, R
1Be selected from-OH ,-COOH and-NH
2The cohort that is constituted.
Use flame-retardant resin composition of the present invention, do not need to add other processing aid and difficult combustion additive, can improve the flame retardancy and the heat-resisting character of this composition epoxy resin simultaneously.
Embodiment
Details are as follows for each used in embodiment and synthesis example composition:
Resins, epoxy 1Represent Changchun artificial resin factory to produce, with the phenolic aldehyde polyglycidyl ether that trade(brand)name PNE177 sells, its epoxy equivalent (weight) is between 170 to 190g/eq, and hydrolyzable chlorine is 1000ppm following (an ASTM method).
Resins, epoxy 2Represent Changchun artificial resin factory to produce, the polyglycidyl ether of the ortho-cresol formaldehyde condensation body of selling with trade(brand)name CNE200ELB, its epoxy equivalent (weight) are between 200 to 220g/eq, and hydrolyzable chlorine is 700ppm following (an ASTM method).
Resins, epoxy 3Represent Changchun artificial resin factory to produce, with the bisphenol-A phenolic polyglycidyl ether that trade(brand)name BNE210 sells, its epoxy equivalent (weight) is between 180 to 200g/eq, and hydrolyzable chlorine is 300ppm following (an ASTM method).
Resins, epoxy 4Represent Changchun artificial resin factory to produce, the polyglycidyl ether of the four phenolic group ethane of selling with trade(brand)name TNE190A70, its epoxy equivalent (weight) are between 190 to 210g/eq, and hydrolyzable chlorine is 1000ppm following (an ASTM method).
Resins, epoxy 5Represent Changchun artificial resin factory to produce, the diglycidylether of the dihydroxyphenyl propane of selling with trade(brand)name BE188EL, its epoxy equivalent (weight) are between 185 to 195g/eq, and hydrolyzable chlorine is below the 200ppm, and viscosity is between 11000 to 15000cps/25 ℃.
Resins, epoxy 6Represent Yuka Shell Epoxy Co to produce, 3,3 ', 5,5 ' tetramethyl--4,4 ' xenol glycidyl ether, its epoxy equivalent (weight) of selling with trade(brand)name YX4000 between 180 to 200g/eq.
Resins, epoxy 7Represent Changchun artificial resin factory to produce, 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%.
Catalyst (hardening accelerator) ARepresent Yi base triphenyl phosphonium acetate, 10% is dissolved in methyl alcohol.
Catalyst (hardening accelerator) BRepresent glyoxal ethyline (2MI), 10% is dissolved in methyl ethyl ketone.
Stiffening agent ARepresent Dyhard RU 100 (DICY).
Stiffening agent BRepresent Changchun artificial resin factory to produce, trade(brand)name BEH510, Ahew between 105 to 110g/eq.
Relevant epoxy equivalent (weight) used herein (EEW, Epoxy Equivalent Weight), varnish viscosity (Viscosity), solid content (Solid content), test according to following method of testing:
(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: epoxy resin varnish was placed 25 ℃ of thermostatic baths 4 hours, use Brookfield (Brookfield) viscometer 25 ℃ of measurement persons.
(3) solid content: get the varnish sample that contains Resins, epoxy of 1 gram, at 60 minutes non-volatile part measured weight percents of 150 ℃ of bakings.
Synthesis example 1: synthetic P contained compound
The electrically heated cover is equipped with, temperature regulator, electric blender and stirring rod, nitrogen inlet, thermopair, water cooled condenser, insert 9 of 600 toluene that restrain and 600 grams in 3000 milliliter of five neck glass reaction still of feed hopper, the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound, vacuumize and be heated to 120 ℃, make 9, the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide compound dissolves and dry 30 minutes fully, feed the nitrogen decompress(ion) again and add the 4-hydroxy benzaldehyde of 320 grams and the phenol of 1570 grams, the oxalic acid that adds 16 grams again continues reaction at 110 ℃ and can obtain throw out in 5 hours; The question response system cools to room temperature, with the resultant of reaction filtration drying, get final product the P contained compound shown in the formula (I), be 291 ℃ through the fusing point of this P contained compound of dsc analysis.
Embodiment 1 to 3 and comparative example 1
Embodiment 1 to 3 for the P contained compound that uses synthesis example 1 separately and make as stiffening agent; In the container that is being equipped with agitator and condenser under the room temperature, P contained compound, hardening accelerator and the solvent of Resins, epoxy, synthesis example 1 are modulated into epoxy resin varnish according to the ratio shown in the table 1.
Table 1
Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
Lacquer formulation | ||||
Resins, epoxy 1 | ??200 | ???- | ???- | |
Resins, epoxy 2 | ??- | ???200 | ???- | |
Resins, epoxy 3 | ??- | ???- | ???200 | ???- |
Resins, epoxy 4 | ??7 | ???7 | ???7 | ???7 |
Resins, epoxy 5 | ||||
Resins, epoxy 6 | ??- | ???- | ???- | |
Resins, epoxy 7 | ??- | ???- | ??250 | |
Stiffening agent A | ??- | ???- | ??5.2 | |
P contained compound (synthesis example 1) | ??235 | ???205 | ???215 | ??- |
Dimethyl formamide (DMF) | ??210 | ???200 | ???215 | ??55 |
Hardening accelerator A | ???0.66 | ????0.62 | ???0.58 | ????1.2 |
Hardening accelerator B | ???1.1 | ????1.1 | ???1.1 | ????0 |
With glasscloth contain be dipped in the institute synthetic epoxy resin varnish in, through 160 ℃ of dryings 8 to 10 minutes, after becoming prepreg, superimposed with eight prepregs, it respectively places the Copper Foil of 35 microns of a slices up and down, through 185 ℃, 25 kilograms/square centimeter pressure pressing and become the laminate of Resins, epoxy and glasscloth, through DSC (Differential Scan Calorimeter, TA2910) (temperature range is 50 to 250 ℃, heat-up rate is 20 ℃/minute) test its glass transition point, and, 5 of specimen that are of a size of 12.5 millimeters * 1.3 millimeters being cut in the prepreg test piece according to the method for UL746, combustion test is surveyed its flame retardancy, 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 rerum natura result who analyzes each laminate is as shown in table 2:
Table 2
Analysis project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
Combustion testing | By | By | By | By |
Tg(℃) | ???155.5℃ | ???158.3℃ | ??161.6℃ | ??137.8℃ |
Soldering resistance (288 ℃) | ??>180sec | ???>180sec | ??>180sec | ??>180sec |
Stripping strength | ???8.4 | ???8.3 | ??8.4 | ??10.8 |
Surface resistivity | ???2.3×10 14 | ??4.6×10 14 | ??1.9×10 14 | ??3.57×10 15 |
The volume impedance | ???5.8×10 15 | ??9.2×10 15 | ??1.08×10 15 | ??1.06×10 15 |
Specific inductivity | ???4.7 | ??4.6 | ??4.6 | ??4.7 |
Dissipation factor | ???0.016 | ??0.016 | ??0.015 | ??0.020 |
Embodiment 4 to 9
Embodiment 4 to 9 is that the difunctionality base mixes use with the Resins, epoxy of multiple functional radical, the P contained compound that makes with synthesis example 1 is modulated into epoxy resin varnish with P contained compound, hardening accelerator and solvent that Resins, epoxy, synthesis example 1 make according to the ratio shown in the table 3 as stiffening agent in the container that is being equipped with agitator and condenser under the room temperature again.
Table 3
Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
Lacquer formulation | ||||||
Resins, epoxy 1 (gram) | ???150 | ???150 | ||||
Resins, epoxy 2 (gram) | ???- | ???150 | ???150 | |||
Resins, epoxy 3 (gram) | ???- | ???- | ???150 | ???- | ???- | ???150 |
Resins, epoxy 4 (gram) | ????7 | ????7 | ????7 | ????7 | ????7 | ????7 |
Resins, epoxy 5 (gram) | ????50 | ????50 | ????50 | |||
Resins, epoxy 6 (gram) | ????50 | ????50 | ????50 | |||
P contained compound (synthesis example 1) | ????226 | ????207 | ????213 | ????225 | ????206 | ????212 |
Dimethyl formamide (DMF) | ????219 | ????210 | ????210 | ????219 | ????210 | ????212 |
Hardening accelerator A | ????0.66 | ????0.58 | ????0.61 | ????0.70 | ????0.72 | ????0.77 |
Hardening accelerator B | ????0.75 | ????0.70 | ????0.73 | ????0.75 | ????0.70 | ????0.73 |
With glasscloth contain be dipped in the institute synthetic epoxy resin varnish in, through 160 ℃ of dryings 8 to 10 minutes, after becoming prepreg, superimposed with eight prepregs, it respectively places the Copper Foil of 35 microns of a slices up and down, through 185 ℃, 25 kilograms/square centimeter pressure pressings and become the laminate of Resins, epoxy and glasscloth.The rerum natura result who analyzes each laminate is as shown in table 4:
Table 4
Analysis project | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
Combustion testing | By | By | By | By | By | By |
Tg(℃) | 145.2℃ | 146.1℃ | 151.2℃ | 145.3℃ | 144.2℃ | 148.7℃ |
Soldering resistance | >180sec | >180sec | >180sec | >180sec | >180sec | >180sec |
Stripping strength | 10.1 | 9.9 | 9.9 | 9.7 | 9.4 | 9.8 |
Surface resistivity | 1.7×10 13 | 2.6×10 13 | 1.6×10 13 | 3.1×10 13 | 1.8×10 13 | 1.1×10 13 |
The volume impedance | 5.8×10 14 | 7.7×10 14 | 7.1×10 14 | 1.02×10 14 | 1.06×10 14 | 1.02×10 14 |
Specific inductivity | 4.7 | 4.6 | 4.7 | 4.6 | 4.5 | 4.6 |
Dissipation factor | 0.021 | 0.019 | 0.02 | 0.019 | 0.017 | 0.017 |
Embodiment 10 to 15
Embodiment 10 to 15 is the Resins, epoxy of difunctionality base or multiple functional radical, mixing use with synthesis example 1 prepared P contained compound and other stiffening agent hardens, according to the ratio shown in the table 5, the P contained compound, stiffening agent, hardening accelerator and the solvent that in the container that is being equipped with agitator and condenser under the room temperature Resins, epoxy, synthesis example 1 are made are modulated into epoxy resin varnish.
Table 5
Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | |
Lacquer formulation |
Resins, epoxy 2 (gram) | ???200 | ???200 | ???200 | |||
Resins, epoxy 4 (gram) | ???7 | ???7 | ???7 | ????7 | ???7 | ??7 |
Resins, epoxy 5 (gram) | ????200 | ???200 | ??200 | |||
P contained compound (synthesis example 1) | ???130 | ???144 | ???140 | ????140 | ???150 | ??140 |
Stiffening agent A | ???4 | ???2 | ????4.1 | ??2 | ||
Stiffening agent B | ???45 | ???27 | ???40 | ??30 | ||
Dimethyl formamide (DMF) | ???170 | ???180 | ???175 | ????175 | ???180 | ??175 |
Hardening accelerator A | ???0.42 | ???0.47 | ???0.43 | ????0.68 | ???0.66 | ??0.61 |
Hardening accelerator B | ???0.65 | ???0.72 | ???0.7 | ????0.73 | ???0.75 | ??0.73 |
With glasscloth contain be immersed in the institute synthetic epoxy resin varnish in, through 160 ℃ of dryings 8 to 10 minutes, after becoming prepreg, superimposed with eight prepregs, it respectively places the Copper Foil of 35 microns of a slices up and down, through 185 ℃, 25 kilograms/square centimeter pressure pressings and become the laminate of Resins, epoxy and glasscloth.The rerum natura result who analyzes each laminate is as shown in table 6:
Table 6
Analysis project | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 |
Combustion testing | By | By | By | By | By | By |
Tg(℃) | 181℃ | 188℃ | 182℃ | 128℃ | 138℃ | 137℃ |
Soldering resistance | >180sec | >180sec | >180sec | 122sec | >180sec | >180sec |
Stripping strength | 10.1 | 9.9 | 9.9 | 9.7 | 9.4 | 9.8 |
Surface resistivity | 1.7×10 13 | 2.6×10 13 | 1.6×10 13 | 3.1×10 13 | 1.8×10 13 | 1.1×10 13 |
The volume impedance | 5.8×10 14 | 7.7×10 14 | 7.1×10 14 | 1.02×10 14 | 1.06×10 14 | 1.02×10 14 |
Specific inductivity | 4.7 | 4.6 | 4.7 | 4.6 | 4.5 | 4.6 |
Dissipation factor | 0.015 | 0.017 | 0.15 | 0.019 | 0.019 | 0.019 |
The thermotolerance deficiency of embodiment 13 prepared laminaties, the rerum natura of the prepared laminate of all the other each embodiment all can meet demand.
Use the foregoing description 1,4,10 and 11 and comparative example 3 prepared composition epoxy resins be coated on 80 micron thickness on the uneven surface of 18 micron copper foils, 150 ℃ of oven dry.The Copper Foil of Resins, epoxy coating is added in the above-mentioned prepreg of being made by the composition epoxy resin of embodiment 10 both sides up and down, and the pressure pressing through 185 ℃ of temperature and 25 kilograms/square centimeter makes multi-ply wood.Analyze this multiple-plate rerum natura, the result is as shown in table 7:
Table 7
Analysis project | Condition and specification | Embodiment 1 | Embodiment 4 | Embodiment 10 | Embodiment 11 | Comparative example 1 |
Combustion testing | UL94-V0 | By | By | By | By | By |
Soldering resistance | IPC260 ℃ of specification>3 second | By | By | By | By | By |
Stripping strength | IPC specification>6 lb/in (18 μ m) | ??7.1 | ??7.5 | ??7.7 | ??7.6 | ??8.2 |
Can find out compared to bromated Resins, epoxy by The above results, use flame-retardant resin composition of the present invention need not add halogen or other incombustible agent, also can have suitable combustion testing result and soldering resistance, and do not reduce stripping strength, be fit to be applied in thermosetting resin, thermoplastic resin, adhesive sheet, matrix material, laminated plates, printed circuit board (PCB), Copper Foil solid, the printing ink that is used for Layer increasing method and semiconductor package and end material.
Claims (13)
1. difficult combustible epoxy resin composition is characterized in that said composition comprises:
(A) one or more Resins, epoxy;
(B) stiffening agent; And
(C) hardening accelerator; Wherein, the stiffening agent of composition (B) is the P contained compound shown in the formula (I):
In the formula, R
1Be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4And the cohort that constitutes of group such as acid anhydrides, wherein R
4Be hydrogen or C
1-6Alkyl; And Ar
1With Ar
2Be independently selected from:
Wherein, R
2Be selected from C
1-6Alkyl, C
1-6The cohort that alkoxyl group, nitro and aryl constitute; R
3Be chemical bond or C
1-6Stretch alkyl; R
5Be selected from chemical bond ,-CR
2R
4-,-O-,-CO-,-S-,-SO-and-SO
2-the cohort that constituted; R
1With R
4Definition as above; A and b independently are that 0 to 6 integer and a+b are in 0 to 6 scope; C and d independently are that 0 to 4 integer and c+d are in 0 to 4 scope; And z is 1 to 20 integer.
2. composition as claimed in claim 1 is characterized in that, this composition (A) Resins, epoxy is glycidyl ether resin.
3. composition as claimed in claim 1 is characterized in that, the usage ratio scope of the stiffening agent of this composition (B) is the epoxy equivalent (weight) number of the Resins, epoxy of composition (A): Ahew number=100 of the stiffening agent of this composition (B): (5 to 95).
4. composition as claimed in claim 1 is characterized in that, the stiffening agent of this composition (B) also comprises having compound bearing active hydrogen, and this active hydrogen can react with the stiffening agent as Resins, epoxy with epoxy group(ing).
5. composition as claimed in claim 4, it is characterized in that this has compound bearing active hydrogen and is selected from the cohort that aminated compounds, anhydrides compound, dihydroxy-benzene compounds, bisphenol resin, polyhydroxy phenol resin, phenolic condensation body, urea resin, melamine resin, polyamide resin, dicyan diamide and boron fluoride amine compound constitute.
6. composition as claimed in claim 4 is characterized in that, is the Resins, epoxy of 100 composition (A) with respect to the epoxy equivalent (weight) number, and the Ahew number with compound bearing active hydrogen is 5 to 85.
7. composition as claimed in claim 1 is characterized in that, the hardening accelerator of this composition (C) is selected from the cohort that tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt, boron trifluoride complex salt, lithiumation thing, imidazolium compounds and composition thereof are constituted.
8. composition as claimed in claim 7 is characterized in that this hardening accelerator is a glyoxal ethyline.
9. composition as claimed in claim 7 is characterized in that, this hardening accelerator is a Yi base triphenyl phosphonium acetate.
10. composition as claimed in claim 7 is characterized in that, the hardening accelerator of this composition (C) is 50 to 50000ppm with respect to the total amount of composition (A) and composition (B).
11. the P contained compound shown in the formula (I):
In the formula, R
1Be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4And the cohort that constitutes of group such as acid anhydrides, wherein R
4Be hydrogen or C
1-6Alkyl; And Ar
1With Ar
2Be independently selected from:
Wherein, R
2Be selected from C
1-6Alkyl, C
1-6The cohort that alkoxyl group, nitro and aryl constitute; R
3Be chemical bond or C
1-6Stretch alkyl; R
5Be selected from chemical bond ,-CR
2R
4-,-O-,-CO-,-S-,-SO-and-SO
2The cohort of-formation; R
1With R
4Definition as above; A and b independently are that 0 to 6 integer and a+b are in 0 to 6 scope; C and d independently are that 0 to 4 integer and c+d are in 0 to 4 scope; And z is 1 to 20 integer.
12. P contained compound as claimed in claim 11 is characterized in that, Ar
1With Ar
2For stretching phenyl.
13. P contained compound as claimed in claim 11 is characterized in that, R
1Be selected from-OH ,-COOH and-NH
2The group that is constituted.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101405342B (en) * | 2006-04-24 | 2011-01-05 | 东丽株式会社 | Epoxy resin composition, fiber-reinforced composite material and method for producing the same |
CN102382420A (en) * | 2010-09-06 | 2012-03-21 | 宏昌电子材料股份有限公司 | High CTI (Comparative Tracking Index) epoxy resin composition for printed circuit copper-clad plate |
CN112266576A (en) * | 2020-11-04 | 2021-01-26 | 纽宝力精化(广州)有限公司 | Brominated epoxy resin composition for paper substrate |
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2003
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101405342B (en) * | 2006-04-24 | 2011-01-05 | 东丽株式会社 | Epoxy resin composition, fiber-reinforced composite material and method for producing the same |
CN102382420A (en) * | 2010-09-06 | 2012-03-21 | 宏昌电子材料股份有限公司 | High CTI (Comparative Tracking Index) epoxy resin composition for printed circuit copper-clad plate |
CN102382420B (en) * | 2010-09-06 | 2013-01-16 | 宏昌电子材料股份有限公司 | High CTI (Comparative Tracking Index) epoxy resin composition for printed circuit copper-clad plate |
CN112266576A (en) * | 2020-11-04 | 2021-01-26 | 纽宝力精化(广州)有限公司 | Brominated epoxy resin composition for paper substrate |
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