CN1333014C - Halogen-free resin composition - Google Patents
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- CN1333014C CN1333014C CNB031531725A CN03153172A CN1333014C CN 1333014 C CN1333014 C CN 1333014C CN B031531725 A CNB031531725 A CN B031531725A CN 03153172 A CN03153172 A CN 03153172A CN 1333014 C CN1333014 C CN 1333014C
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Abstract
The present invention provides a halogen-free resin composition which comprises a kind of or various kinds of phosphorus containing epoxy resin, a curing agent, a curing catalyst, polyphenylene oxide resin and a filling material, wherein the curing agent is in the structure which is disclosed in the formula (I), and the definition of each symbol in the formula is disclosed in the specification. The halogen-free resin composition of the present invention has the advantages of excellent heat resisting properties, flame resisting propertied and admirable dielectric properties without adding halogen. The halogen-free resin composition is particularly applicable to binding sheets, composite materials, laminose boards, printed circuit boards, copper foil adhesives, printing ink, a sealing material of semiconductors, etc., and the printing ink is used in a layer-increasing method.
Description
Technical field
The invention relates to a kind of not halogen-containing resin combination.Need not add halogenic ingredient in the said composition and can reach the difficulty combustion standard of UL94V-0, and have excellent thermotolerance and dielectric characteristics.
Background technology
Resins, epoxy has been widely used in as fields such as application, electric insulation, building building materials, solid and lamination product with the security of its easy processibility, height, excellent mechanical properties and chemical property.Wherein, laminated plates with the Resins, epoxy manufacturing, because Resins, epoxy is 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, makes the Resins, epoxy laminated plates be used in large quantities among electric and the electronic product.
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 system), use halogen contained compound, particularly bromated Resins, epoxy and stiffening agent, and cooperation can make the required requirement (as the UL94V-0 grade) of difficulty combustion characteristic conforms 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 UL94V-0.For example United States Patent (USP) the 5th, 262, No. 491 a kind of compositions that comprise polyphenylene oxide, Resins, epoxy, metal-salt and solidifying agent of announcement, and said composition meets flame retardancy and stable on heating standard, and at high temperature has excellent dielectric characteristics; But the composition that this patent discloses is by the bromine that contains 10% to 30%, and reaches required difficulty combustion and heat-resistant standard, yet, use the incombustible agent or the antimonous oxide of halogen-containing composition, will bring serious harm to the mankind far and away.
On the other hand, 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 processing procedure of printed circuit board (PCB), even welding sequence more than 270 ℃, this kind laminated plates material might break or plate bursting in the manufacturing and the course of processing; And, about 12 to 17ppm/ ℃ of this FR4 laminated plates dilation dimension in the plane, for the printed circuit board (PCB) of the existing development trend less than 100 μ m of live width/line-spacing, this laminated plates will be not suitable for using the field at HDI.Therefore, develop energetically at the various laminated plates materials of high heat-resistant quality, high glass tansition temperature of emphasizing.
Therefore, in the not halogen-containing resin combination of the present invention, be to use a kind of phosphorous epoxy resin (particularly side chain type phosphorous epoxy resin), and a kind of stiffening agent with benzoxazine ring-type structure, can be under the condition that need not use the compound that contains halogen or resin, make this resin combination reach the difficulty combustion standard of UL94V-0, and make this resin combination use the resin combination of solidifying agent commonly used to have preferable thermotolerance compared to other; On the other hand, in the not halogen-containing resin combination of the present invention, also comprise polyphenylene oxide resin, make said composition, also have splendid dielectric characteristics except that taking into account simultaneously flame retardancy and the thermotolerance.
Generally speaking, the compound with benzoxazine ring-type structure is to react and make via phenolic compound, amine compound and aldehyde compound.But, the patent of the method for making of multinomial compound with benzoxazine ring-type structure all is to utilize aniline and phenolic compound to react, as United States Patent (USP) the 6th, 005, promptly utilize for No. 064 resol, formaldehyde and aniline to form thermosetting resin with benzoxazine ring-type structure; And the flat 11-50123 patent of Japanese Patent Application also is a kind of method of utilizing bis-phenol, aniline, formalin and making the thermosetting resin of dihydrobenzo oxazines with methyl ethyl ketone as solvent.Yet employed aniline has toxicity and is the chemical substance of decree forbidding in this method for making, so this method for making does not meet the mass-produced demand of industrial community.
The inventor is through extensively and after the further investigation finding, use varsol to react with phenolic compound, aromatic diamine compound and aldehyde compound, can make this reactive system have advantages of higher stability, have toxic aniline reacts except that avoiding using, it is improper also can to reduce Yin Wendu control, make the compound Yin Gaowen that forms benzoxazine ring-type structure and open loop and carry out polymerization once more, gel of avoiding using high polar solvent or protonic solvent to react simultaneously and being produced or caking situation are suitable for industrial mass production.
Summary of the invention
For overcoming the shortcoming of above-mentioned prior art, the invention provides a kind of not halogen-containing resin combination, this resin combination comprises: (A) one or more phosphorous epoxy resin; (B) stiffening agent; (C) hardening accelerator; (D) polyphenylene oxide resin; And (E) packing material, wherein, the stiffening agent of composition (B) has the structure shown in the formula (I):
In the formula, R
1Be selected from the cohort that alkyl, thiazolinyl, alkoxyl group, hydroxyl and amido constitute; R
2Be selected from chemical bond, alkylidene group, O, S or SO
2The cohort that is constituted; R
3Be H or alkyl; And m and n are 0 to 4 integer independently.
Shown in the above-mentioned formula (I) in the structure, R
1With R
3Shown alkyl is meant straight chain, branch or the cyclic alkyl with 1 to 6 carbon atom, the example comprises, but non-being limited to: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, 2-amyl group, 3-amyl group, 2-methyl-1-butene base, isopentyl, sec.-amyl sec-pentyl secondary amyl, 3-methyl-2-butyl, neo-pentyl, hexyl, 4-methyl-2-amyl group, cyclopentyl and cyclohexyl etc.; This alkoxyl group is meant straight chain, branch or the cyclic alkoxy with 1 to 6 carbon atom, the example comprises, but non-being limited to: methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy, isopentyloxy, neopentyl oxygen, hexyloxy and cyclohexyloxy etc.; And this alkylidene group is meant the straight or branched alkylidene group with 1 to 6 carbon atom, the example comprises, but non-being limited to: methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, 2-methyl propylidene, 2,2 '-dimethyl propylidene and 2,3-dimethyl butylidene etc.
In the structure shown in the above-mentioned formula (I), R
1Be preferably alkyl, more preferably the tertiary butyl; R
2Be preferably alkylidene group, more preferably methylene radical; M is preferably 0; N is preferably 1 to 4 integer, and more preferably 1 or 2.In the structure shown in the one preferred formula (I), R
2Be methylene radical; And m and n are 0.
Having can be under the condition that solvent exists suc as formula the nitrogen oxygen helerocyclics of structure shown in (I), and use phenolic compound, aromatic diamine compound and aldehyde compound react and make.This phenolic compound can be the phenolic compound that is substituted or is unsubstituted; Wherein, this substituent example comprises, but non-being limited to: substituting groups such as alkyl, thiazolinyl, alkoxyl group, hydroxyl, halogen and amido.
The above-mentioned phenols bonded example that is substituted or is unsubstituted comprises, but non-being limited to: phenol, neighbour-cresols, p-Cresol, between-cresols, ethyl phenol, propyl phenoxy, isopropyl-phenol, butylphenol, sec-butyl phenol, tert-butyl phenol, amylic phenol, isopentyl phenol, hexyl phenol, cyclohexyl phenol, allyl phenol, 4-methoxyl group phenol, 3-methoxyl group phenol, 2-methoxyl group phenol, the 4-vinyl phenol, the 3-vinyl phenol, the 2-vinyl phenol, 4-hydroxyl phenol, 3-hydroxyl phenol, 2-hydroxyl phenol, 4-amido phenol, 3-amido phenol, 2-amido phenol, the 4-hydroxymethyl phenol, the 3-hydroxymethyl phenol, the 2-hydroxymethyl phenol, 4-methylol-2-methoxyl group phenol, 4-methylol-3-methoxyl group phenol, 4-sec.-propyl-2-methoxyl group phenol, 4-sec.-propyl-3-methoxyl group phenol, 2-hydroxyl-4-isopropyl-phenol, 3-hydroxyl 4-isopropyl-phenol, 4-vinyl-2-methoxyl group phenol, 4-vinyl-3-methoxyl group phenol, 4-vinyl-2-hydroxyl phenol, 4-vinyl-3-hydroxyl phenol etc.
There is no particular restriction suc as formula the phenolic compound of the nitrogen oxygen helerocyclics shown in (I) to be used for preparation, this phenolic compound can be simple function phenolic compound, difunctionality phenolic compound or multi-functional phenolic compound, as long as at least one ortho position of relative this hydroxyl is to be unsubstituted in this phenolic compound.
Be used for preparation suc as formula the aromatic diamine compound of the nitrogen oxygen helerocyclics shown in (I) suc as formula shown in (II):
In the formula, R
2, R
3And the m definition as above.
The example of the aromatic diamine compound shown in the formula (II) comprises, but non-being limited to: benzidine compounds, as 4,4 '-benzidine, 4,4 '-two amidos-2,2 '-dimethyl diphenyl, 4,4 '-two amidos-2-butyl-3-methyl diphenyl, 4,4 '-two amidos-2-ethyl-3-isopropyl biphenyl, 4,4 '-two amidos-2-methyl-3-propyl group biphenyl, 4,4 '-two amidos-2-methyl diphenyl, 4,4 '-two amidos-3-isopropyl biphenyl etc.; Two amido phenylbenzene alkyl compounds, as 4,4 '-two amido ditans, 4,4 '-two amido diphenylethanes, 4,4 '-two amido diphenyl propanes, 4,4 '-methylene-bis (2-aminotoluene), 4,4 '-ethylenebis (3-isopropyl aniline), 4,4 '-methylene-bis (2,6-dipropyl aniline), 4,4 '-ethylenebis (2, the 5-dibutyl aniline), 4,4 '-methylene-bis (2-ethyl-6-propyl group aniline), 4,4 '-methylene-bis (2-sec.-propyl-6-monomethylaniline) etc.; Two amido diphenylether compounds, as 4,4 '-two amido diphenyl ethers, two (4-amido-3-ethylphenyl) ether, two (4-amido-3-hexyl phenyl) ethers, two (4-amido-3,5-3,5-dimethylphenyl) ether etc.; Two amido diphenylsulfide compounds, as 4,4 '-two amido diphenylsulfide, two (4-amido-3-propyl group phenyl) thioethers, two (4-amido-3-tert-butyl-phenyl) thioether, two (4-amido-3,5-diethyl phenyl) thioether etc.; And two amido sulfobenzide compounds, as 4,4 '-two amido sulfobenzides, two (4-amido-3-isopropyl phenyl) sulfone, two (4-amido-3,5-diamyl phenyl) sulfone.
There is no particular restriction suc as formula the aldehyde compound of the nitrogen oxygen helerocyclics shown in (I) to be used for preparation, and the aldehyde compound that generally is used to prepare the nitrogen oxygen helerocyclics with benzoxazine ring-type structure all can use.The example of this aldehyde compound includes, but are not limited to: formaldehyde (or its steam), Paraformaldehyde 96 and polyoxymethylene etc.
Suc as formula the nitrogen oxygen helerocyclics shown in (I) is that to carry out polyreaction by phenolic compound, aromatic diamine compound and aldehyde compound obtained.Wherein, employed phenolic compound, aromatic diamine compound are 2: 1: 4 with the equivalents ratio of aldehyde compound.
There is no particular restriction in order to the solvent for preparing the nitrogen oxygen helerocyclics shown in this formula (I), as long as can suitably dissolve each reactant.The example of this solvent comprises, but non-being limited to: alcoholic solvent such as methyl alcohol, ethanol, propyl alcohol, Virahol and ethylene glycol etc.; Ether solvent is as 1,2-glycol dimethyl ether, tetrahydrofuran (THF) and dioxan etc.; Ketones solvent such as acetone, methyl ethyl ketone and methyl isopropyl Ketone etc.; Esters solvent such as methyl acetate and ethyl acetate etc.; And varsol, as aromatic hydrocarbon solvents such as toluene and dimethylbenzene.In this solvent, because the polarity of varsol is relatively low, it is only with phenolic compound in the reactant and aromatic diamine compound dissolving, aldehyde compound only had the dispersive effect, so be difficult for caking when dissolving each other, can improve the stability of system, avoid Yin Wendu control improper, make the too high further again open loop of the nitrogen oxygen helerocyclics Yin Wendu that forms benzoxazine ring-type structure carry out polymerization, so preferable in this solvent with varsol.
In the not halogen-containing resin combination of the present invention, the phosphorous epoxy resin of composition (A) is not limited to them, and it can be any phosphorous epoxy resin; Wherein, the phosphorous epoxy resin of this composition (A) is preferable with the side chain type phosphorous epoxy resin.The preferred embodiments of this side chain type phosphorous epoxy resin comprises, but non-being limited to:
(1) directly with organic ring-type phosphorus compound (as, 9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound (being designated hereinafter simply as HCA)) import formed side chain type phosphorous epoxy resin in the structure of Resins, epoxy, shown in (III):
In the formula, Epoxy is the Resins, epoxy of one of them epoxy group(ing) through open loop; And
(2) carry out addition reaction with this organic ring-type phosphorus compound HCA and aromatic aldehyde compounds earlier, carry out condensation reaction with aromatics again with active hydrogen, formation has the P contained compound of multiple functional radical, and (this P contained compound has the structure of similar bis-phenol, its difference is that the hydrogen atom or the organism of the structure central authorities of this P contained compound are to replace with HCA), P contained compound and Resins, epoxy with this multiple functional radical carries out addition reaction again, this P contained compound is imported in the structure of Resins, epoxy, and form the side chain type phosphorous epoxy resin, shown in (IV):
In the formula, Epoxy defines as above; And Ar
1With Ar
2Be independently selected from:
Wherein, R
4Be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
7And the cohort that constitutes of group such as acid anhydrides; R
5Be selected from the cohort that hydrogen, alkyl, alkoxyl group, nitro and aryl constitute; R
6Be chemical bond or alkylidene group; R
7Be hydrogen or alkyl; R
8Be selected from chemical bond ,-CR
5R
7-,-O-,-CO-,-S-,-SO-and-SO
2-the cohort that constituted; A and b are to be 0 to 6 integer and a+b≤6 independently; C and d are to be 0 to 4 integer and c+d≤4 independently; And z is 1 to 20 integer.
Above-mentioned R
5, R
6And R
7The example of shown alkyl, alkylidene group and alkoxyl group as defined above.R
5Shown aryl comprises: phenyl, tolyl, xylyl, phenmethyl and naphthyl etc.
The example of above-mentioned aromatic aldehyde compounds has the phenyl aldehyde compounds, for example the 4-hydroxy benzaldehyde.Above-mentioned example with aromatics of active hydrogen has phenolic compound.
In the not halogen-containing resin combination of the present invention, can use any Resins, epoxy and this organic ring-type phosphorus compound HCA, or carry out addition reaction with P contained compound that this HCA makes, to prepare suc as formula the side chain type phosphorous epoxy resin shown in (III) or the formula (IV), with one or more phosphorous epoxy resin as composition (A).The example of this Resins, epoxy comprises, but non-being limited to: difunctionality Resins, epoxy.So-called " difunctionality Resins, epoxy " is meant in a part of this resin to 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, hexamethylene-diamine, 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 not halogen-containing resin combination of the present invention, preferable with the Racemic glycidol ethers in order to the Resins, epoxy that forms the side chain type phosphorous epoxy resin.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: phenol formaldehyde polyglycidyl ether, cresoform polyglycidyl ether, dihydroxyphenyl propane formaldehyde polyglycidyl ether etc.
The example of phenyl polyhydroxy phenol polyglycidyl ether comprises: three (4-hydroxyphenyl) methane polyglycidyl ether, three (4-hydroxyphenyl) ethane polyglycidyl ether, three (4-hydroxyphenyl) propane polyglycidyl ether, three (4-hydroxyphenyl) butane polyglycidyl ether, three (3-methyl-4-hydroxyphenyl) methane polyglycidyl ether, three (3,5-dimethyl-4-hydroxyphenyl) methane polyglycidyl ether, four (4-hydroxyphenyl) ethane polyglycidyl ether, four (3,5-dimethyl-4-hydroxyphenyl) ethane polyglycidyl ether, dicyclo amylene-phenolic aldehyde polyglycidyl ether etc.
The addition reaction for preparing the side chain type phosphorous epoxy resin shown in above-mentioned formula (III) or the formula (IV) can be carried out the fusion addition reaction under the condition of solvent-free existence, or carries out back flow reaction under the condition that solvent exists.Wherein, the example of the solvent that uses in this back flow reaction comprises, but non-being limited to: ketones solvent, as acetone, methyl ethyl ketone, mibk etc.; Ether solvent is as glycol monomethyl methyl ether, propylene glycol monomethyl ether etc.; Esters solvent is as ethyl acetate, isopropyl acid ethyl ester, propylene glycol monomethyl ether ethyl ester etc.; Varsol is as toluene, dimethylbenzene etc.; And other aprotic solvent, as N, dinethylformamide, N, N-diethylformamide, dimethyl sulfoxide (DMSO) etc.
The temperature of reaction for preparing this side chain type phosphorous epoxy resin generally is between 50 to 350 ℃; Be preferably between 50 to 300 ℃; Be more preferred between 100 to 250 ℃; And be more preferred from again between 100 to 200 ℃.If when the temperature of this reaction is higher than 350 ℃, be easy to generate side reaction, and the wayward speed of response that should react, speeding up of this resin deterioration may be impelled; On the other hand, if when the temperature of this reaction is lower than 50 ℃, can makes the deterioration of efficiency of this reaction, and make the resin that is produced to be applicable to hot environment.
In the not halogen-containing resin combination of the present invention, phosphorous epoxy resin can use or make up two or more forms with mixture separately and use.The consumption of one or more phosphorous epoxy resin of this composition (A) in the total amount of the stiffening agent of the phosphorous epoxy resin of this composition (A) and composition (B), generally is in the scope of 40 to 80 weight %; Be preferably in the scope of 50 to 80 weight %; And better be in the scope of 60 to 80 weight %.If the consumption of one or more phosphorous epoxy resin of this composition (A) is lower than 40 weight %, then can makes thermotolerance and the flame retardancy deficiency of the product after the sclerosis, and be unfavorable for use.
In the not halogen-containing resin combination 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, 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 three (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, the butyl triphenyl 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 or its mixture.
In the not halogen-containing resin combination of the present invention, the consumption of this hardening accelerator is 0.01 to 1 weight % with respect to the total amount of this resin combination, is preferably 0.01 to 0.5 weight %, is more preferred from 0.02 to 0.1 weight %.
In the resin combination of the present invention, the polyphenylene oxide resin of this composition (D) has the structural unit shown in the formula V:
Wherein, R
9Be selected from the cohort that alkyl, alkoxyl group, aryl, amido, hydroxyl constitute; And x is 0 to 4 integer.
In the structural unit shown in the above-mentioned formula V, R
9Be preferably alkyl, more preferably methyl; X is preferably 2.
The monomeric example that is used to make the polyphenylene oxide resin of this composition (D) comprises, but non-being limited to: 2,6-dimethyl phenol, 2,6-diethyl phenol, 2,6-dipropyl phenol, 2,6-dibutyl phenol, 2,6-phenylbenzene phenol, 2,6-dimethoxy phenol, 2,6-diethoxy phenol, 2-methoxyl group-6-oxyethyl group phenol, 2,3,6-trimethylammonium phenol, 2,3,5,6-tetramethyl-phenol, 2-methyl-6-isobutyl-phenol, 2-methyl-6-phenyl phenol, 2,6-phenylbenzene phenol and 2,6-xylyl phenol etc.This monomer institute deutero-homopolymer, multipolymer or other sex change polyphenylene oxide resin all can be used as the polyphenylene oxide resin in the resin combination of the present invention.
Can use various known methods to make this polyphenylene oxide resin; For example, use at least one corresponding monohydroxy aromatic series chemical combination to carry out polyreaction with oxidation coupling (oxidative coupling) catalysis system.The example of this monohydroxy aromatics comprises, but non-being limited to: xylenol and 2,3,6-trimethylammonium phenol etc.
The molecular weight that is used as the polyphenylene oxide resin of composition (D) generally is in 10,000 to 100,000 scope, is preferably in 20,000 to 80,000 scope, and better is in 35,000 to 65,000 scope; And generally be the particle diameter with 1 to 200 μ m, be preferably particle diameter with 5 to 100 μ m, better is the particle diameter with 5 to 50 μ m.In the not halogen-containing resin combination of the present invention, the consumption of the polyphenylene oxide resin of this composition (D), solid amount in the stiffening agent of the phosphorous epoxy resin of this composition (A) and composition (B) is 10 to 50 weight %, is preferably 20 to 40 weight %, more is preferably 25 to 35 weight %.
In the resin combination of the present invention, the example of the packing material of composition (E) comprising: silicon dioxide powder (comprising ball-type and angle type fused silica, crystalline silica etc.), fused silica powder, talcum powder, aluminium hydrate powder, magnesium hydroxide powder, Paris white, aluminium nitrogen compound, boron-nitrogen compound, zinc borate etc., it can use or make up two or more forms with mixture separately and use.The median size of this weighting agent is preferably 1 to 40 μ m, if median size less than 1 μ m, can increase the viscosity of this resin combination, makes its mobile decline; If surpass the uneven distribution that 40 μ m then can cause resin and weighting agent in the composition.
In the not halogen-containing resin combination of the present invention, this fills the addition of agent material, is 20 to 150 weight % with composition (A), (B) and the total restatement of solid (D) of this resin combination, is preferably 30 to 100 weight %, is more preferred from 40 to 80 weight %.
The not halogen-containing resin combination 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.
The not halogen-containing resin combination of the present invention also can optionally add additive or modification agent, for example thermal stabilizer, light stabilizer, ultraviolet absorbers and plasticizer etc.
The suitable substrate preparation laminate of varnish (varnish) impregnation that can use the not halogen-containing resin combination of the present invention to be modulated into makes this base material heat drying again, can make dried prepreg (prepreg).The example of this base material includes, but are not limited to: fiber base material, as glass fibre, steel fiber, carbon fiber, Kevlar, pbo fiber, LCP fiber, Kelvar fiber, aromatic ester, boron and Mierocrystalline cellulose etc.; Cloth (mat) base material is as glasscloth; And paper base material, as aramid paper and LCP paper etc.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 present invention not sclerous reaction temperature of halogen-containing resin combination 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.
Use the not halogen-containing resin combination of the present invention, do not need to add other processing aid and difficult combustion additive, particularly halogen, can reach the difficulty combustion standard of UL94-V0 and have splendid heat-resisting character and dielectric characteristics.
The not halogen-containing resin combination of the present invention can be used for 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 ends material.
The specific embodiment mode
Details are as follows for each used in embodiment and synthesis example composition:
Resins, epoxy 1Represent 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 ℃.
Stiffening agent ARepresent Dyhard RU 100 (DICY), 10% is dissolved in DMF.
Stiffening agent BRepresent Changchun artificial resin factory to produce, with the resol that trade(brand)name BEH510A70 sells, its Ahew is between 105 to 110g/eq,
Catalyst (hardening accelerator) ARepresent glyoxal ethyline (2MI), 10% is dissolved in methyl ethyl ketone.
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 ASTMD1652, wherein indicator is a Viola crystallina.
(2) viscosity: epoxy resin varnish was placed 25 ℃ of thermostatic baths 4 hours, use Brookfield (Brookfield) viscometer in 25 ℃ of measurement persons.
(3) solid content: get the varnish sample that 1 gram contains Resins, epoxy, in 60 minutes non-volatile part measured weight percents of 150 ℃ of bakings.
Synthesis example 1
In the 3000 milliliter of five neck glass reaction still that is equipped with electrically heated cover, temperature regulator, electric blender and stirring rod, thermopair, water cooled condenser, feed hopper, insert 9 of 216 gram dryings processing, the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound (being designated hereinafter simply as organic ring-type phosphorus compound HCA), heating for dissolving and stirring in the glass reaction still, when treating that temperature reaches 110 ℃, add the 4-hydroxy benzaldehyde of 112 grams and the phenol of 940 grams, reaction was carried out more than 3 hours.Reclaim the superfluous phenol of reaction, the reactant of reaction being finished with methyl alcohol washes out, the reactant of finishing to this reaction of room temperature after-filtration to be cooled also carries out drying, get final product (9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound-10-yl)-two (4-hydroxy phenyl) methyl alcohol (being designated hereinafter simply as P contained compound HPP).
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, insert the Resins, epoxy 1 of 1000 grams and the P contained compound HPP of 550 grams, feed nitrogen and be heated to 120 ℃.After treating that Resins, epoxy 1 and P contained compound HPP dissolve fully, vacuumize and make reactants dry, feed nitrogen again and vacuumize, repeat twice of above-mentioned drying step.When question response still temperature is reduced to 85 to 90 ℃, add the triphenylphosphine of 6.0 grams, utilize stirrer to stir this Resins, epoxy and triphenylphosphine, and feed nitrogen.Heat this mixture to 160 and ℃ kept 10 minutes, treat this reaction heat release and be warming up to 180 ℃ and keep this temperature after 3 hours slowly, can get phosphorous epoxy resin A.The theoretical value of the epoxy equivalent (weight) of this phosphorous epoxy resin A is 582, and measured value is 605; Theoretical phosphorus content is 2.66 weight %.Propylene glycol monomethyl ether is added among the prepared phosphorous epoxy resin A,, obtain solid content and be 60% phosphorous epoxy resin A to dissolve this phosphorous epoxy resin.
Synthesis example 2
In being equipped with 1 liter of reaction vessel of agitator, thermometer, depressurized system, condensation heat packs and four opening for feeds, smart in regular turn scale adds 4,4 '-two amido ditans of 240 grams, the phenol of 228 grams, the Paraformaldehyde 96 of 156.8 grams 92% and the toluene of 300 grams.Close heating power supply after making this reactive system heat temperature raising to 50 ℃, treat that this system's heat release heats up, make temperature remain in 85 to 90 ℃ and react, last 2.5 hours.The person of connecing begins decompression, heating to reclaim toluene, treats that temperature arrives 130 ℃ and vacuum and presses greater than 650mmHg, and after confirming that toluene has reclaimed fully, adds methyl ethyl ketone to dissolve prepared product, obtains solid content and be 60% synthetic resins B.
Synthesis example 3
In 50 liters of stainless steels (SS316) reactor, insert 2 of 4000 grams (32.7 not ear), the N of the dibutylamine of the sodium hydroxide of 6-dimethyl phenol, 66 grams (1.6 not ear), 429 grams (3.3 not ear), 816 grams (8.1 not ear), N '-dimethylbutyl amine, 20 liters the cupric bromide of toluene, 78.5 grams (0.35 not ear).Make this reactive system under 38 ℃ and 1 atmospheric condition,, and stir to carry out polyreaction, last 2 hours with the speed of 300RPM with 1 liter/minute speed aerating oxygen.After polyreaction is finished, stop to stir, use the oxygen in this reactive system of nitrogen replacement, and the hydrochloric acid soln of 1600 milliliters of 1N is added in this reaction soln, to stop this reaction.The Na that in this reaction soln, adds 20 liter 1%
3EDTA, and stirred 10 minutes.Make its standing demix, behind the removal water layer solution, 20 liters deionized waters are added in the organic layer restir 10 minutes.Make its standing demix, behind the removal water layer solution, 25 liters methyl alcohol are added in the organic layer slowly, separate out the synthetic resins C1 of 3620 grams.Productive rate: 92%, intrinsic viscosity: 0.21dl./gram.
Synthesis example 4
In 50 liters of stainless steels (SS316) reactor, insert 2 of 4000 grams (32.7 not ear), the pyridine of the sodium hydroxide of 6-dimethyl phenol, 73 grams (1.8 not ear), 950 grams (12.0 not ear), 3.2 liters methyl alcohol, 18 liters the cupric chloride of toluene, 32.5 grams (0.35 not ear).Make this reactive system under 40 ℃ and 1 atmospheric condition,, and stir to carry out polyreaction, last 2 hours with the speed of 300RPM with 1 liter/minute speed aerating oxygen.After polyreaction is finished, stop to stir, use the oxygen in this reactive system of nitrogen replacement, and the hydrochloric acid soln of 1600 milliliters of 1N is added in this reaction soln, to stop this reaction.The Na that in this reaction soln, adds 20 liter 1%
3EDTA, and stirred 10 minutes.Make its standing demix, behind the removal water layer solution, 20 liters deionized waters are added in the organic layer restir 10 minutes.Make its standing demix, behind the removal water layer solution, 25 liters methyl alcohol are added in the organic layer slowly, separate out the synthetic resins C2 of 3040 grams.Productive rate: 77%, intrinsic viscosity: 0.23dl./gram.
Synthesis example 5
In 50 liters of stainless steels (SS316) reactor, insert 2 of 4000 grams (32.7 not ear), the Manganous chloride tetrahydrate (MnCl of the dibutylamine of the sodium hydroxide of 6-dimethyl phenol, 73 grams (1.8 not ear), 105 grams (0.18 not ear), 20 liters toluene, 10.2 grams (0.018 not ear)
2).Make this reactive system under 30 ℃ and 1 atmospheric condition,, and stir to carry out polyreaction, last 2 hours with the speed of 300RPM with 1 liter/minute speed aerating oxygen.After polyreaction is finished, stop to stir, use the oxygen in this reactive system of nitrogen replacement, and the hydrochloric acid soln of 1600 milliliters of 1N is added in this reaction soln, with termination reaction.The Na that in this reaction soln, adds 20 liter 1%
3EDTA, and stirred 10 minutes.Make its standing demix, behind the removal water layer solution, 20 liters deionized waters are added in the organic layer restir 10 minutes.Make its standing demix, behind the removal water layer solution, 25 liters methyl alcohol are added in the organic layer slowly, separate out the synthetic resins C3 of 3748 grams.Productive rate: 93%, intrinsic viscosity: 0.42dl./gram.
Synthesis example 6
In 50 liters of stainless steels (SS316) reactor, insert 2 of 4000 grams (32.7 not ear), the dibutylamine of the sodium hydroxide of 6-dimethyl phenol, 73 grams (1.8 not ear), 85 grams (0.66 not ear), 20 liters toluene; 12.5 the Manganous chloride tetrahydrate (MnCl of gram (0.096 not ear)
2).Make this reactive system under 25 ℃ and 1 atmospheric condition,, and stir to carry out polyreaction, last 3.5 hours with the speed of 300RPM with 1 liter/minute speed aerating oxygen.After polyreaction is finished, stop to stir, use the oxygen in this reactive system of nitrogen replacement, and the hydrochloric acid soln of 1600 milliliters of 1N is added in this reaction soln, with termination reaction.The Na that in this reaction soln, adds 20 liter 1%
3EDTA, and stirred 10 minutes.Make its standing demix, behind the removal water layer solution, 20 liters deionized waters are added in the organic layer restir 10 minutes.Make its standing demix, behind the removal water layer solution, 25 liters methyl alcohol are added in the organic layer slowly, separate out the synthetic resins C4 of 3808 grams.Productive rate: 95%, intrinsic viscosity: 0.62dl./gram.
Embodiment 1 to 4 and comparative example 1 to 3
According to composition shown in the table 1 and ratio, in the container that is being equipped with agitator and condenser under the room temperature, make epoxy resin varnish.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Resins, epoxy A (gram) | 48 | 48 | 48 | 48 | 48 | 48 | 48 |
| Synthetic resins B (gram) | 18 | 18 | 18 | 18 | 18 | ||
| Stiffening agent A | 5.0 | ||||||
| Stiffening agent B | 64 | ||||||
| Synthetic resins C1 (gram) | 12 | ||||||
| Synthetic resins C2 (gram) | 12 | ||||||
| Synthetic resins C3 (gram) | 12 | ||||||
| Synthetic resins C4 (gram) | 12 | ||||||
| Catalyst A | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 0.3 | 0.4 |
| SiO 2(5μm) | 77 | 77 | 77 | 77 | 77 | 77 | 77 |
| Toluene | 18 | 18 | 18 | 18 | |||
| Propylene glycol monomethyl ether | 7 | ||||||
| Dimethyl formamide | 48 |
With above-mentioned phosphorous epoxy resin varnish that is modulated into and glasscloth impregnation, after drying becomes prepreg under 170 ℃ the condition, superimposed with eight prepregs, it respectively places the Copper Foil of a slice 35 μ m up and down, becomes the laminate of phosphorous epoxy resin and glasscloth through 200 ℃, 25 kilograms/square centimeter pressure pressings.Respectively according to the glass tansition temperature and the stripping strength of the laminate of standard testing after pressing of IPC-TM-650-2.4.25 and IPC-TM-650-2.4.8; Standard testing surface resistivity and volume impedance according to IPC-TM-650-2.5.17; Standard testing circle electrostrictive coefficient and dissipation factor according to IPC-TM-650-2.5.5.4.The result is as shown in table 2:
Table 2
| Analysis project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Combustion testing | 94-V0 | 94-V0 | 94-V0 | 94-V0 | 94-V0 | 94-V0 | 94-V0 |
| Soldering resistance (288 ℃) | ＞180sec | ＞180sec | ＞180sec | ＞180sec | ＞180sec | ＞180sec | ＞180sec |
| Tg(DSC) | 162℃ | 161℃ | 162℃ | 164℃ | 163℃ | 138℃ | 144℃ |
| Stripping strength | 10.2 | 9.95 | 10.04 | 9.96 | 9.45 | 9.87 | 9.1 |
| Surface resistivity | 3.8*10 14 | 9.4*10 14 | 2.5*10 14 | 4.1*10 14 | 2.3*10 14 | 3.6*10 14 | 1.3*10 14 |
| The volume impedance | 4.7*10 15 | 7.6*10 15 | 6.6*10 15 | 7.7*10 15 | 5.8*10 15 | 4.3*10 15 | 5.7*10 15 |
| Boundary's electrostrictive coefficient | 3.89 | 3.94 | 3.92 | 3.92 | 4.43 | 4.73 | 4.62 |
| Dissipation factor | 0.008 | 0.009 | 0.008 | 0.008 | 0.011 | 0.021 | 0.016 |
By the test result of table 2 as can be known, the not halogen-containing resin combination of the present invention, need not add the composition that contains halogen, can reach the flame retardancy standard of UL94V-0, and the not halogen-containing resin combination of the present invention has preferable heat-resistant quality compared to other resin combination that uses existing solidifying agent; Moreover the not halogen-containing resin combination of the present invention has lower dielectric coefficient compared to the resin combination that does not contain polyphenylene oxide resin.
Embodiment 5 to 8
According to composition shown in the table 3 and ratio, in the container that is being equipped with agitator and condenser under the room temperature, make epoxy resin varnish.
Table 3
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Resins, epoxy A (gram) | 600 | 600 | 600 | 600 |
| Synthetic resins B (gram) | 240 | 240 | 240 | 240 |
| Synthetic resins C1 (gram) | 100 | |||
| Synthetic resins C2 (gram) | 100 |
| Synthetic resins C3 (gram) | 100 | |||
| Synthetic resins C4 (gram) | 100 | |||
| Catalyst A | 1.21 | 1.21 | 1.21 | 1.21 |
| SiO 2(5μm) | 20 | 20 | 20 | 20 |
| Toluene | 100 | 100 | 100 | 100 |
The phosphorous epoxy resin varnish that above-mentioned table 3 is modulated into is coated the uneven surface of 18 microns Copper Foil, and coating thickness is 80 microns, and is dry under 150 ℃ condition, makes the Copper Foil sample.The Copper Foil sample that makes is placed the upper and lower layer of the laminated plates of embodiment 1, become multi-ply wood through 185 ℃, 25 kilograms/square centimeter pressure pressings.According to this multiple-plate rerum natura of above-mentioned standard testing, the result is as shown in table 4:
Table 4
| Analysis project | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Combustion testing | 94-V0 | 94-V0 | 94-V0 | 94-V0 |
| Soldering resistance (288 ℃) | ＞180sec | ＞180sec | ＞180sec | ＞180sec |
| Tg(DSC) | 162℃ | 163℃ | 166℃ | 165℃ |
| Stripping strength (IPC specification＞61b/in (18 microns)) | 7.21 | 7.15 | 7.44 | 7.32 |
| Surface resistivity | 4.1*10 14 | 5.2*10 14 | 4.9*10 14 | 3.3*10 14 |
| The volume impedance | 2.6*10 15 | 4.1*10 15 | 5.6*10 15 | 6.3*10 15 |
| Boundary's electrostrictive coefficient | 3.77 | 3.76 | 3.74 | 3.7 |
| Dissipation factor | 0.008 | 0.008 | 0.009 | 0.008 |
By the test result of table 4 as can be known, when increasing layer material, has lower dielectric coefficient with the prescription of embodiment 5 to 8.
Claims (28)
1. not halogen-containing resin combination is characterized in that said composition comprises:
(A) one or more phosphorous epoxy resin, it is selected from
(1) have the side chain type phosphorous epoxy resin of the structure shown in the formula (III):
In the formula, Epoxy is the Resins, epoxy of one of them epoxy group(ing) through open loop, or
(2) have the side chain type phosphorous epoxy resin of the structure shown in the formula (IV):
In the formula, Epoxy as above defines; And Ar
1With Ar
2Be independently selected from:
Wherein, R
4Be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
7And the cohort that anhydride group constituted; R
5Be selected from the cohort that hydrogen, alkyl, alkoxyl group, nitro and aryl constitute; R
6Be chemical bond or alkylidene group; R
7Be hydrogen or alkyl; R
8Be selected from chemical bond ,-CR
5R
7-,-O-,-CO-,-S-,-SO-and-SO
2The cohort of-formation; A and b are to be 0 to 6 integer and a+b≤6 independently; C and d are to be 0 to 4 integer and c+d≤4 independently; And z is 1 to 20 integer;
(B) stiffening agent;
(C) hardening accelerator;
(D) polyphenylene oxide resin; And
(E) packing material, wherein, the stiffening agent of composition (B) has the structure shown in the formula (I):
In the formula, R
1Be selected from the cohort that alkyl, thiazolinyl, alkoxyl group, hydroxyl and amido constitute; R
2Be alkylidene group; R
3Be H or alkyl; And m and n are to be 0 to 4 integer independently.
2. composition as claimed in claim 1 is characterized in that R
2Be methylene radical; And m and n are 0.
3. composition as claimed in claim 1 is characterized in that, n is 1 to 4 integer.
4. composition as claimed in claim 1 is characterized in that R
1Be alkyl; And R
2Be alkylidene group.
5. composition as claimed in claim 4 is characterized in that R
1Be the tertiary butyl; And R
2Be methylene radical.
6. composition as claimed in claim 1 is characterized in that, the stiffening agent that has suc as formula the structure shown in (I) is under the condition that solvent exists, and is reacted by phenolic compound, aromatic diamine compound and aldehyde compound to make.
7. composition as claimed in claim 6 is characterized in that, this phenolic compound is a phenol; This aromatic diamine compound is 4,4 '-two amido ditans; And this aldehyde compound is a Paraformaldehyde 96.
8. composition as claimed in claim 6 is characterized in that, this solvent is an aromatic hydrocarbon solvent.
9. composition as claimed in claim 8 is characterized in that, this aromatic hydrocarbon solvent is a toluene.
10. composition as claimed in claim 8 is characterized in that, this aromatic hydrocarbon solvent is a dimethylbenzene.
11. composition as claimed in claim 1 is characterized in that, this side chain type phosphorous epoxy resin with the structure shown in the formula (III) is with 9, and the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide compound imports in the structure of Resins, epoxy obtained.
12. composition as claimed in claim 1 is characterized in that, this side chain type phosphorous epoxy resin with the structure shown in the formula (IV) is to import in the structure of Resins, epoxy P contained compound obtained.
13. composition as claimed in claim 12, it is characterized in that, this P contained compound is by 9, and the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide compound and aromatic aldehyde compounds carry out addition reaction, carry out condensation reaction with the aromatics with active hydrogen again and form.
14. composition as claimed in claim 13 is characterized in that, this aromatic aldehyde compounds is the phenyl aldehyde compounds, and this aromatics with active hydrogen is a phenol.
15. composition as claimed in claim 14 is characterized in that, this phenyl aldehyde compounds is the 4-hydroxy benzaldehyde.
16., it is characterized in that this Resins, epoxy is glycidyl ether resin as claim 11 or 12 described compositions.
17. composition as claimed in claim 16, it is characterized in that this glycidyl ether resin is selected from the cohort that glycidyl ether, phenolic aldehyde polyglycidyl ether and the polyhydroxy phenol poly epihydric alcohol ether monomer institute deutero-resin of bis-phenol glycidyl ether, xenol glycidyl ether, dihydroxy-benzene glycidyl ether, the glycidyl ether that contains azo-cycle, dihydroxy naphthlene are constituted.
18. composition as claimed in claim 1 is characterized in that, the consumption of one or more phosphorous epoxy resin of this composition (A) in the total amount of the stiffening agent of the phosphorous epoxy resin of this composition (A) and composition (B), is in the scope of 40 to 80 weight %.
19. 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, lithiumation thing, imidazolium compounds and composition thereof constitute.
20. composition as claimed in claim 19 is characterized in that, this hardening accelerator is a glyoxal ethyline.
21. composition as claimed in claim 19 is characterized in that, the hardening accelerator of this composition (C) is in the scope of 0.01 to 1 weight % with respect to the total amount of this resin combination.
22. composition as claimed in claim 1 is characterized in that, the polyphenylene oxide resin of this composition (D) has the structural unit shown in the formula V:
Wherein, R
9Be selected from the cohort that alkyl, alkoxyl group, aryl, amido, hydroxyl constitute; And x is 0 to 4 integer.
23. composition as claimed in claim 22 is characterized in that, this R
9For methyl and x are 2.
24. composition as claimed in claim 22 is characterized in that, the consumption of the polyphenylene oxide resin of this composition (D) in the solid amount of the stiffening agent of the phosphorous epoxy resin of this composition (A) and composition (B), is in the scope of 10 to 50 weight %.
25. composition as claimed in claim 1, it is characterized in that the packing material of this composition (E) is selected from the cohort that silicon dioxide powder, fused silica powder, talcum powder, aluminum oxide powder, aluminium hydrate powder, magnesium hydroxide powder, Paris white, zinc borate, aluminium nitrogen compound, boron-nitrogen compound or its mixture are constituted.
26. composition as claimed in claim 25 is characterized in that, the packing material of this composition (E) is a silicon dioxide powder.
27. composition as claimed in claim 26 is characterized in that, the consumption of the packing material of this composition (E) with composition (A), (B) and the total restatement of solid (D) of said composition, is in the scope of 20 to 150 weight %.
28. composition as claimed in claim 1 is characterized in that, said composition is to be used for 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 to end material.
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|---|---|---|---|
| CNB031531725A CN1333014C (en) | 2003-08-08 | 2003-08-08 | Halogen-free resin composition |
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|---|---|---|---|
| CNB031531725A CN1333014C (en) | 2003-08-08 | 2003-08-08 | Halogen-free resin composition |
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| CN1333014C true CN1333014C (en) | 2007-08-22 |
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| WO2012083728A1 (en) | 2010-12-23 | 2012-06-28 | 广东生益科技股份有限公司 | Halogen-free resin composition and method for fabricating halogen-free copper clad laminate using the same |
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| CN101580626B (en) * | 2009-01-24 | 2012-02-08 | 南亚塑胶工业股份有限公司 | Resin composition with high thermal conductivity, no halogen and difficult fire retardance and pre-impregnated body and coating material thereof |
| CN102206415A (en) * | 2010-03-30 | 2011-10-05 | 台光电子材料股份有限公司 | Resin composition, and prepreg, laminate and circuit board containing the composition |
| CN103113711B (en) * | 2013-01-28 | 2015-04-08 | 北京化工大学常州先进材料研究院 | Preparation method for low-dielectric halogen-free flame retardant glass fiber pre-impregnation material |
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| KR100850928B1 (en) | 2007-01-10 | 2008-08-07 | 광덕신약 주식회사 | Composition for coloring hair containing natural extracts and Method of manufacturing the same |
| WO2012083728A1 (en) | 2010-12-23 | 2012-06-28 | 广东生益科技股份有限公司 | Halogen-free resin composition and method for fabricating halogen-free copper clad laminate using the same |
| US9076573B2 (en) | 2010-12-23 | 2015-07-07 | Guangdong Shengyi Sci. Tech Co., Ltd. | Halogen-free resin composition and method for fabricating halogen-free copper clad laminate using the same |
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| CN1580127A (en) | 2005-02-16 |
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