CN104583263B - Cyanuric acid is modified the manufacture method of phosphorous epoxy resin, the resin combination and its solidfied material of phosphorous epoxy resin is modified containing cyanuric acid - Google Patents
Cyanuric acid is modified the manufacture method of phosphorous epoxy resin, the resin combination and its solidfied material of phosphorous epoxy resin is modified containing cyanuric acid Download PDFInfo
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- CN104583263B CN104583263B CN201380044287.1A CN201380044287A CN104583263B CN 104583263 B CN104583263 B CN 104583263B CN 201380044287 A CN201380044287 A CN 201380044287A CN 104583263 B CN104583263 B CN 104583263B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
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Abstract
The manufacture method that a kind of cyanuric acid is modified phosphorous epoxy resin is provided, the cyanuric acid of anti-flammability of the manufacture using cyanuric acid and phosphorus compound by epoxy resin modification is modified phosphorous epoxy resin, pass through this method, it can be manufactured in a short time, and the residual of cyanuric acid is considerably less, the epoxy resin cured product with excellent physical property can be obtained.A kind of cyanuric acid is modified the manufacture method of phosphorous epoxy resin, it is using phosphorus compound, cyanuric acid and epoxy resin as must be obtained from composition reacted that the cyanuric acid, which is modified phosphorous epoxy resin, relative to 1 mole of cyanuric acid, it is 2.5~50 moles to make the phosphorus compound, and the resin combination and its solidfied material of phosphorous epoxy resin and curing agent are modified containing the cyanuric acid that the phosphorous rate obtained by this method is 1.0~5.0 mass %, Nitrogen content is 0.1~2.0 mass % and phosphorous rate and the summation of Nitrogen content is 2.5~5.5 mass %.
Description
Technical field
Contain the manufacturer of the non-halogen fire-retardancy epoxy resin of phosphorus atoms and nitrogen-atoms the present invention relates to a kind of molecular skeleton
Method, containing the epoxy resin obtained by the manufacture method and the composition epoxy resin of other epoxy resin, containing the asphalt mixtures modified by epoxy resin
The curable epoxy resin composition of oil/fat composition and curing agent and curable epoxy resin composition solidification formed
Epoxy resin cured product.
Background technology
Epoxy resin it is flame-retarded, the past as representated by tetrabromobisphenol A as the brominated epoxy resin of raw material,
Carried out by halogenation.But in the case of using halogenated epoxy resin, exist and find to pass through thermal decomposition during solidfied material burning
The problem of halide of reaction generation strong toxicity is such.In contrast, in recent years, it have studied the non-halogen fire-retardant using phosphorus compound
Technology, it is proposed that using the scheme of the phosphorus compound disclosed in 1~patent document of patent document 4.But these phosphorus compounds
It is low with the dissolubility of epoxy resin, solvent, it is difficult to be coupled in epoxy resin or dissolve and use in a solvent, therefore, such as specially
As disclosed in sharp 5~patent document of document 10, by being reacted in advance with epoxy resin, to form phosphorous asphalt mixtures modified by epoxy resin
Fat, phosphorous phenol resin, are used so as to assign solvent solubility.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Application 47-016436 publications
Patent document 2:Japanese Unexamined Patent Application 60-126293 publications
Patent document 3:Japanese Unexamined Patent Application 61-236787 publications
Patent document 4:Japanese Unexamined Patent Publication 05-331179 publications
Patent document 5:Japanese Unexamined Patent Publication 04-11662 publications
Patent document 6:Japanese Unexamined Patent Publication 2000-309623 publications
Patent document 7:Japanese Unexamined Patent Publication 11-166035 publications
Patent document 8:Japanese Unexamined Patent Publication 11-279258 publications
Patent document 9:Japanese Unexamined Patent Publication 2001-123049 publications
Patent document 10:Japanese Unexamined Patent Publication 2003-040969 publications
Patent document 11:Japanese Unexamined Patent Publication 2012-229364 publications
Non-patent literature
Non-patent literature 1:Western damp benevolence writes " polymer flame-retarded " P60, the row of the row of right column 22~27, P166,6-8-3 items,
1992, great achievement society
The content of the invention
The invention problem to be solved
For flame-retarded caused by phosphorus compound, if further to improve anti-flammability, phosphorous rate, molecular weight meeting are only improved
Become big, crosslink density can reduce, or must use the phosphorus-containing compound of high price.In contrast, the present inventors be conceived to it is non-specially
The synergy of described phosphorus and nitrogen to anti-flammability in sharp document 1, it is proposed that by using cyanuric acid as nitrogen compound
Improve the scheme (patent document 11) of anti-flammability.It has however been found that：According to manufacture method, epoxy resin and cyanuric acid are deficiently
Reaction, unreacted cyanuric acid easily left behind.The cyanuric acid remained in reaction system with slowly speed only with
Epoxy resin reacts, in addition, unreacted cyanuric acid is poor to the dissolubility of solvent, thereby further requires that reduction to solidifying physical property
Produce dysgenic unreacted cyanuric acid.
Means for solving the problems
In order to solve above-mentioned problem, the inventors discovered that, in the reaction of epoxy resin and cyanuric acid, by relative to
Cyanuric acid makes a certain proportion of specific phosphorus compound coexist and react, and the residual of cyanuric acid is considerably less, it is not necessary to prolonged
Reaction, the reaction with epoxy resin is easily carried out, so as to complete the present invention.
That is, the present invention relates to following aspect：
(1) a kind of cyanuric acid is modified the manufacture method of phosphorous epoxy resin, and the cyanuric acid, which is modified phosphorous epoxy resin, is
Using phosphorus compound, cyanuric acid and epoxy resin as must be obtained from composition reacted, the feature of the manufacture method exists
In, the phosphorus compound be following formulas (1) or phosphorus compound shown in following formulas (2) or containing both,
In formula (1), n represents 0 or 1, moreover, R1And R2Separately represent the alkyl of carbon number 1~6, R1And R2Can
With it is identical can also be different, or ring-type can be formed together with phosphorus atoms,
In formula (2), m represents 0 or 1, moreover, R3And R4Separately represent the alkyl of carbon number 1~6, R3And R4Can
With it is identical can also be different, or ring-type can be formed together with phosphorus atoms,
Coordinate 2.5~50 moles of phosphorus compounds relative to 1 mole of cyanuric acid, in phosphorus compound and cyanuric acid with such
Ratio coexist it is lower first mix the epoxy resin, then reacted, the cyanuric acid is modified the phosphorous rate of phosphorous epoxy resin
For 1.0~5.0 mass %, Nitrogen content is 0.1~2.0 mass %, and phosphorous rate and the summation of Nitrogen content are 2.5~5.5 matter
Measure %；
(2) a kind of composition epoxy resin, it is modified in the cyanuric acid obtained by the manufacture method described in above-mentioned (1) phosphorous
Coordinate in epoxy resin into other epoxy resin；
(3) a kind of curable epoxy resin composition, change in the cyanuric acid obtained by the manufacture method described in above-mentioned (1)
Property phosphorous epoxy resin in, relative to the cyanuric acid be modified phosphorous epoxy resin the equivalent of epoxy radicals 1, contained in terms of functional group's ratio
The curing agent of 0.4~2.0 equivalent；
(4) a kind of curable epoxy resin composition, in the composition epoxy resin described in above-mentioned (2), relative to this
The equivalent of epoxy radicals 1 of composition epoxy resin, by curing agent of the functional group containing 0.4~2.0 equivalent than in terms of；
(5) a kind of epoxy resin cured product, it is to solidify the curable epoxy resin composition described in above-mentioned (3) or (4)
Form.
Invention effect
The present invention is by relative to 1 mole of cyanuric acid, making specific phosphorus compound be total to 2.5~50 moles of mol ratio
Deposit, cyanuric acid is modified phosphorous epoxy resin obtained from then being reacted with epoxy resin, can manufacture in a short time, and cyanogen is urinated
The residual of acid is considerably less, can obtain the epoxy resin cured product with excellent physical property.
Embodiment
Hereinafter, embodiments of the present invention are described in detail.Phosphatization shown in the formula (1) of the present invention or (2) is closed
Thing, it can specifically enumerate：Miscellaneous -10- phospho hetero phenanthrenes -10- the oxygen of dimethyl phosphine, diethyl phosphine, diphenylphosphine, 9,10- dihydro-9-oxies
Compound (DOPO), dimethyl phosphine, diethyl phosphine oxide, dibutyl phosphine oxide, diphenyl phosphine oxide, 1,4- cyclooctylene oxygen
Change phosphine, 1,5- cyclooctylenes phosphine oxide (CPHO, Nippon Chemical Ind's system) etc..These phosphorus compounds can individually make
With can also mix two or more use, be not limited to these compounds.
In the present invention, cyanuric acid refers to the s- triazines -2,4 for being denoted as dynamic isomer, 6- triols and s- triazine -2,
4,6- triketones, there is no special provision to its ratio.
Although the technology as nitrogenated flame retardant addition cyanuric acid is disclosed, because cyanuric acid is to the dissolubility of solvent
It is bad, bad to the intermiscibility of epoxy resin or curing agent, therefore, it is difficult to obtain uniform resin combination, in terms of anti-flammability
Produce deviation.The cyanuric acid obtained by the manufacture method of the present invention is modified phosphorous epoxy resin, by making cyanuric acid and asphalt mixtures modified by epoxy resin
Fat reacts, and becomes uniform in resin combination, therefore, can obtain stable anti-flammability.In addition, referring to the resin of the present invention
During composition, as long as no specified otherwise, with composition epoxy resin, curable epoxy resin composition and comprising both
Meaning uses, and in the case of clear on context, represents any one.
For that in order to manufacture the epoxy resin that the cyanuric acid of the present invention is modified phosphorous epoxy resin and used, can enumerate：エ
ポ ト ー ト YD-128, エ ポ ト ー ト YD-8125 (Nippon Steel ＆ Sumitomo Metal Corporation's system, bisphenol A type epoxy resin), エ Port ト
ー ト YDF-170, エ ポ ト ー ト YDF-8170 (Nippon Steel ＆ Sumitomo Metal Corporation's system, bisphenol f type epoxy resin), YSLV-
80XY (Nippon Steel ＆ Sumitomo Metal Corporation's system, tetramethyl bisphenol f type epoxy resin), エ ポ ト ー ト YDC-1312 are (to benzene two
Phenol-type epoxy resin), jER YX-4000H (Mitsubishi chemical Co., Ltd's system, biphenyl type epoxy resin), エ ポ ト ー ト YDPN-
638th, エ ポ ト ー ト YDPN-63X (Nippon Steel's Co. Ltd. system, phenolic resin varnish type epoxy resin), エ ポ ト ー ト YDCN-701 are (new
Day iron lives aurification Co. Ltd. system, cresol novolak type epoxy resin), エ ポ ト ー ト GK-5855, エ ポ ト ー ト TX-
(aurification is lived to 1210 (Nippon Steel ＆ Sumitomo Metal Corporation's system, substituted benzene phenol-type epoxy resin) エ Port ト ー ト ZX-1201 by Nippon Steel
Learn Co. Ltd. system, bisphenol fluorene type epoxy resin), TX-0710 (Nippon Steel ＆ Sumitomo Metal Corporation's system, bisphenol S type epoxy tree
Fat), NC-3000 (Nippon Kayaku K. K's system, biphenyl aralkylphenol type epoxy resin), エ Port ト ー ト ZX-1355, エ Port
ト ー ト ZX-1711 (Nippon Steel ＆ Sumitomo Metal Corporation's system, naphthalene diol type epoxy resin), エ ポ ト ー ト ESN-155 (Nippon Steel
Firmly aurification Co. Ltd. system, betanaphthol aralkyl-type epoxy resin), エ ポ ト ー ト ESN-355, エ ポ ト ー ト ESN-375 it is (new
Day iron lives aurification Co. Ltd. system, bisnaphthol aralkyl-type epoxy resin), エ ポ ト ー ト ESN-475V, エ ポ ト ー ト ESN-
485 (Nippon Steel ＆ Sumitomo Metal Corporation's system, alpha-Naphthol aralkyl-type epoxy resins), EPPN-501H (Japanese chemical drug strain formula meetings
Society's system, triphenylmethane type epoxy resin), YSLV-120TE (Nippon Steel ＆ Sumitomo Metal Corporation's system, double thioether type ring oxygen tree
Fat), エ Port ト ー ト ZX-1684 (Nippon Steel ＆ Sumitomo Metal Corporation's system, resorcinol type epoxy resin), エ ピ Network ロ Application
HP-7200H (Dainippon Ink Chemicals's system, dicyclopentadiene-type epoxy resin), (aurification strain is lived to エ ポ ト ー ト YDG-414 by Nippon Steel
Formula commercial firm system, tetrafunctional epoxy resin) etc. by multivalence phenol resin phenolic compounds and epihalohydrins manufacture epoxy resin, TX-
0929th, TX-0934, ZX-1542, TX-1032 (Nippon Steel ＆ Sumitomo Metal Corporation's system, aklylene glycol type epoxy resin) etc.
The epoxy resin manufactured by alcoholic compound and epihalohydrins, セ ロ キ サ イ De 2021 (ダ イ セ Le chemical industry Co. Ltd. systems,
Aliphatic cyclic epoxy resin), エ ポ ト ー ト YH-434, (Nippon Steel ＆ Sumitomo Metal Corporation's system, diaminodiphenyl-methane
Four glycidyl group amine), jER 630 (Mitsubishi chemical Co., Ltd's system, aminobenzene phenol-type epoxy resin) etc. by amines and
The epoxy resin of epihalohydrins manufacture, エ ポ ト ー ト FX-289B, エ ポ ト ー ト FX-305, (aurification strain is lived to TX-0940 by Nippon Steel
Formula commercial firm system, phosphorous epoxy resin), urethane-modified epoxy resin, containEpoxy resin of oxazoline ketone ring etc., but simultaneously
It is not limited to these epoxy resin.
In addition, these epoxy resin can be used alone, can also and with two or more, bisphenol type can be used well
Epoxy resin, phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin.
The reaction of phosphorus compound, cyanuric acid and epoxy resin shown in formula (1) or (2), in phosphorus compound and cyanuric acid
Coexisting under reacted with epoxy resin, but 2.5~50 moles of phosphorus compounds are needed relative to 1 mole of cyanuric acid, relative to 1 mole
Cyanuric acid, the mol ratio of preferable phosphorus compound is 2.7~25 moles, preferably 3~10 moles.Urinated relative to 1 mole of cyanogen
Acid, in the case that phosphorus compound is less than 2.5 moles, the carrying out of the reaction of cyanuric acid and epoxy resin becomes insufficient, cyanuric acid
Residual quantity increase.If relative to 1 mole of cyanuric acid, phosphorus compound is more than 50 moles, although then cyanuric acid and epoxy resin
Reaction fully carry out, but cyanuric acid importing effect, i.e. phosphorus and the nitrogen of the nitrogen-atoms that bring to the synergy of anti-flammability almost
Disappear.In addition, if meet the concurrent conditions of phosphorus compound and cyanuric acid, then can epoxy resin and cyanuric acid reaction it
It is preceding or afterwards react epoxy resin and phosphorus compound.
Cyanuric acid for obtaining the present invention is modified the reaction temperature of phosphorous epoxy resin, can be the synthesis of epoxy resin
In generally set temperature, be 100~250 DEG C, preferably 120~200 DEG C.
In reaction, in order to shorten the time, reduce reaction temperature, catalyst can also be used.The catalyst that can be used does not have
There is special limitation, commonly used catalyst in the synthesis of epoxy resin can be used.It can use for example：Benzyl dimethyl
The phosphine such as the quaternary ammonium salts such as the tertiary amines such as amine, tetramethyl ammonium chloride, triphenylphosphine, three (2,6- Dimethoxyphenyl) phosphines, ethyl
Triphenyl phosphonium bromideDengThe various catalyst such as the imidazoles such as salt, 2-methylimidazole, 2-ethyl-4-methylimidazole, Ke Yidan
Solely use, can also and with two or more, be not limited to these catalyst.Alternatively, it is also possible to be split and be divided into makes for several times
With.
The catalytic amount used in reaction is not particularly limited, but relative to the epoxy resin used, preferably 5 mass %
Hereinafter, more preferably below 1 mass %, further preferred below 0.5 mass %.In the case where catalytic amount is more than 5 mass %,
The auto polymerization reaction that epoxy radicals be present becomes easily progress, the elevated tendency of resin viscosity, so it is not preferred.
In addition, atent solvent can also be used in reaction.Specifically, can use：Hexane, heptane, octane, decane,
The various hydrocarbon such as dimethylbutane, amylene, hexamethylene, hexahydrotoluene, benzene,toluene,xylene, ethylo benzene, ether, isopropyl ether,
Butyl ether, diisoamyl ether, methyl phenyl ether, ethylphenyl ether, amyl group phenyl ether, ethyl benzyl ether, twoAlkane, methylfuran,
The ethers such as tetrahydrofuran, methyl cellosolve, methylcellosolve acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl
Ether, diethylene glycol dimethyl ether, Methylethyl carbitol, propylene glycol monomethyl ether, dimethylformamide, dimethyl sulfoxide (DMSO) etc., but simultaneously
These solvents are not limited to, can be used alone, two or more use can also be mixed.
The epoxide equivalent that the cyanuric acid obtained in the present invention is modified phosphorous epoxy resin is preferably 100~700g/eq, more
Preferably 200~600g/eq.In the case where epoxide equivalent is less than 100g/eq, the cementability of solidfied material is easily deteriorated,
In the case of 700g/eq, the glass transition temperature (Tg) of solidfied material reduces, and resin combination turns into high viscosity, operates
Property is easily deteriorated.
The phosphorous rate that the cyanuric acid obtained in the present invention is modified phosphorous epoxy resin is 1.0~5.0 mass %, is preferably
1.5~4.0 mass %, more preferably 2.0~3.5 mass %.Nitrogen content is 0.1~2.0 mass %, preferably 0.5~1.0 matter
Measure %.In addition, phosphorous rate and the summation of Nitrogen content are 2.5~5.5 mass %, preferably 3.0~4.5 mass %, more preferably 3.0
~4.0 mass %.The cyanuric acid obtained in the present invention is modified the anti-flammability of phosphorous epoxy resin, due to the collaboration effect in phosphorus and nitrogen
Played under fruit, so even if providing that any one scope is also nonsensical, it is necessary to provide the scope of phosphorous rate and the summation of Nitrogen content.
If phosphorous rate and the summation of Nitrogen content are less than 2.5 mass %, it is likely that can not be given full play to because of resin combination fire-retardant
Property.In addition, if phosphorous rate and the summation of Nitrogen content be more than 5.5 mass %, although can then give full play to anti-flammability, resin
Composition turns into high viscosity, it is possible to produces harmful effect to solvent solubility.It is therefore preferable that make the total of phosphorous rate and Nitrogen content
The scope of sum is 2.5~5.5 mass %.
Other epoxy resin used in composition epoxy resin as the present invention, do not damaging the characteristic of the present invention
In the range of, it can will be modified phosphorous epoxy resin with cyanuric acid with above-mentioned epoxy resin identical epoxy resin and be used in combination.
The cyanuric acid of the present invention is modified phosphorous epoxy resin or composition epoxy resin, can be with shape by coordinating curing agent
Into curable epoxy resin composition.As curing agent, various phenolic compounds, anhydrides, amine, hydrazides class, acid can be used
Property the commonly used hardener for epoxy resin such as polyesters, these curing agent can use only a kind, can also and with 2 kinds
More than.Wherein, the curing agent contained as the curable epoxy resin composition of the present invention, preferably dicyanodiamide or phenolate
Compound.
In the curable epoxy resin composition of the present invention, for the usage amount of curing agent, relative to as asphalt mixtures modified by epoxy resin
The equivalent of epoxy radicals 1 of the functional group of fat, the functional group of curing agent is preferably 0.4~2.0 equivalent, more preferably 0.5~1.5 equivalent,
Particularly preferred 0.5~1.0 equivalent.Relative to the equivalent of epoxy radicals 1, curing agent is less than in the case of 0.4 equivalent or more than 2.0
In the case of equivalent, it is possible to which solidification becomes incomplete, it is impossible to obtains good solidification physical property.
As the concrete example for the phenolic compounds that can be used in the curable epoxy resin composition of the present invention, can illustrate
Go out：Bisphenol-A, Bisphenol F, bisphenol-c, bis-phenol K, bisphenol Z, bisphenol S, bisphenol-A, tetramethyl Bisphenol F, tetramethyl bisphenol S, four
The bisphenols such as methyl bisphenol Z, dihydroxydiphenyl thioether, 4,4 '-thiobis (3 methy 6 tert butyl phenol), catechol,
Resorcinol, methylresorcinol, hydroquinones, monomethyl hydroquinones, dimethyl hydroquinones, Trimethyl Hydroquinone,
The dihydroxy benzenes class such as single TBHQ, di-tert-butyl hydroquinone, 4, the biphenyl such as 4 '-xenol, tetramethyl biphenyl phenol
Polyhydroxy naphthalenes, the phenolic aldehyde such as 2 yuan of phenols such as phenols, dihydroxy naphthlene, bishydroxymethyl naphthalene, bishydroxymethyl naphthalene, trihydroxynaphthalene are clear
The phenols such as coating resins, DC-5 (Nippon Steel ＆ Sumitomo Metal Corporation's system, cresol novolac resin), naphthol novolac varnish gum
Or the phenols such as the condensation product of aphthols and aldehydes, SN-160, SN-395, SN-485 (Nippon Steel ＆ Sumitomo Metal Corporation's system) or
The condensation product of aphthols and xylylene glycol, GK-5855P (Nippon Steel ＆ Sumitomo Metal Corporation's system, substituting phenol resin),
The condensation product of phenols or aphthols and isopropenyl acetophenone, phenols or the reaction product of aphthols and bicyclopentadiene, phenol
The phenolic compounds with the phenolic hydroxyl group of more than 2 in a molecule such as condensation product of class or aphthols and biphenyl system condensing agent
Deng.
In addition, as above-mentioned phenols, can enumerate：Phenol, cresols, xylenols, butylphenol, amyl phenol, nonyl benzene
Phenol, butyl methyl phenol, pseudocuminol, phenylphenol etc., as above-mentioned aphthols, it can enumerate：1- naphthols, beta naphthal etc..
In addition, as above-mentioned aldehydes, can enumerate：Formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, benzaldehyde, chloroacetaldehyde, bromoacetaldehyde,
Glyoxal, MDA, butanedial, glutaraldehyde, hexandial, dialdehyde in heptan, decanedial, methacrylaldehyde, crotonaldehyde, salicylide, adjacent benzene two
Formaldehyde, hydroxy benzaldehyde etc., as above-mentioned biphenyl system condensing agent, it can enumerate：Double (methylol) biphenyl, double (methoxies) connection
Benzene, double (ethoxyl methyl) biphenyl, double (chloromethyl) biphenyl etc., but it is not limited to these.
As the other well known curing agent that can be used in the curable epoxy resin composition of the present invention, can lift
Go out：Methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, phthalic anhydride, trimellitic acid
The anhydrides such as acid anhydride, methylnadic anhydride, dicyanodiamide, diethylenetriamines, trien, four ethylidene five
The aliphatic amine such as amine, m-xylene diamine, IPD, diaminodiphenyl-methane, diamino diphenyl sulfone, diamino
The aromatic amines such as base diphenyl ether, diamino ethyl benzene, benzyldimethylamine, 2,4,2,4,6- tri- (dimethylaminomethyl) phenol
Deng amine, 2-methylimidazole, 2- phenylimidazoles, 2-ethyl-4-methylimidazole, 2- undecyl imidazoles, 1- cyano ethyl -2- first
The imidazoles such as base imidazoles and the salt of the formation such as they and trimellitic acid, isocyanuric acid, boron are the acid such as imidazole salt, dimer acids
The condensation product of class and polyamine class is the hydrazides class such as amine compound, adipic dihydrazide, sebacic dihydrazide such as daiamid, ammonia
The phosphine compounds such as yl benzoic acid esters, triphenylphosphine, tetraphenylphosphonibromide bromideDengThe quaternary ammonium salts such as salt, trimethyl ammonium chloride, two
Azabicyclic compounds and the salt of the formation such as they and phenols, novolac resin, boron trifluoride and amine, ether compound etc.
The complex compound of formation, aromatic seriesOr iodineSalt etc., but it is not limited to these.Furthermore it is possible to and these are changed with two or more
Compound.
In the curable epoxy resin composition of the present invention, organic solvent can also be used to be adjusted as viscosity and used.Make
For the organic solvent that can be used, can enumerate：The ethers such as the amide-types such as DMF, glycol monoethyl ether, acetone,
The alcohols such as the ketones such as butanone, methanol, ethanol, benzene, toluene etc. are aromatic hydrocarbon etc..Relative to the epoxy resin in resin combination
The mass parts of composition 100, with one kind in the range fit of 25~250 mass parts these solvents or it can be mixed with a variety of molten
Agent.
In the curable epoxy resin composition of the present invention, curing accelerator can be used as needed.As can be with
The example of the curing accelerator used, it can enumerate：The imidazoles such as 2-methylimidazole, 2- ethyl imidazol(e)s, 2-ethyl-4-methylimidazole
The tertiary amines such as class, 2- (dimethylaminomethyl) phenol, the carbon -7- alkene of 1,8- diazas-bicyclic (5,4,0) 11, triphenylphosphine,
The metallic compound such as phosphine, tin octoate of tricyclohexyl phosphine, triphenylphosphine triphenylborane etc.Using curing accelerator
In the case of, its usage amount, relative to the present invention resin combination in the mass parts of epoxy resin ingredient 100, preferably 0.02
~5.0 mass parts.By using curing accelerator, solidification temperature can be reduced, shortens hardening time.
In the curable epoxy resin composition of the present invention, filler can be used as needed.Specifically, can lift
Go out：Aluminium hydroxide, magnesium hydroxide, talcum, burn till talcum, clay, kaolin, titanium oxide, glass powder, boehmite, titanium dioxide
The inorganic fillers such as silicon ball, but pigment etc. can also be coordinated.The reasons why as using in general inorganic filling material, raising can be enumerated
Impact resistance.In addition, in the case of using the metal hydroxides such as aluminium hydroxide, magnesium hydroxide, worked as flame retardant,
Even if the phosphorous rate in resin combination is few, anti-flammability is also ensured that.Especially with respect to the mass of epoxy resin ingredient 100
Part, if use level, not more than 10 mass parts, the effect of impact resistance is few.But if use level is more than 150 mass
Part, then the cementability of the project needed as laminate purposes reduces.In addition, glass can also be contained in above-mentioned resin combination
The cellulosic such as glass fiber, paper pulp fiber, synthetic fibers, ceramic fibre packing material, particulate rubber, thermoplastic elastomer etc. have
Machine packing material.
By solidifying the curable epoxy resin composition of the present invention, phosphorous and nitrogen epoxy resin cure can be obtained
Thing.Solidification when, by make the form such as resin sheet, the copper foil of resin, prepreg and be laminated, carry out heating plus
It is cured, the phosphorous epoxy resin solidfied material as laminate can be obtained.
The curable epoxy resin composition that phosphorous epoxy resin is modified using the cyanuric acid for having the present invention is made, as logical
Laminate obtained from being heating and curing is crossed, evaluates the phosphorous and characteristic of the epoxy resin cured product of nitrogen, as a result, with using the present invention
Mol ratio scope outside phosphorus compound and cyanuric acid make the cyanuric acid that epoxy resin reacted be modified phosphorous epoxy resin,
And compared by phosphorus compound with the existing known phosphorous epoxy resin that epoxy resin obtains, show high bonding force, anti-flammability.
Embodiment
Although enumerating embodiment and comparative example, the present invention is specifically illustrated, the present invention is not limited to these
Embodiment.In embodiment and comparative example, as long as no specified otherwise, " part " represents mass parts, and " % " represents quality %.
The epoxide equivalent of the epoxy resin determined in embodiment and comparative example is measured according to JIS K 7236.
As for Nitrogen content, calculated by the Nitrogen content and use level of cyanuric acid and be modified phosphorous epoxy resin relative to cyanuric acid
Percentage.
The phosphorous rate of synthesized epoxy resin is measured with following method in embodiment and comparative example.That is, trying
Sulfuric acid 3mL is added in sample 150mg, and is heated 30 minutes.Room temperature is returned to, adds nitric acid 3.5mL and perchloric acid 0.5mL, heating
Decomposing to content turns into transparent or yellow.The liquid is diluted in 100mL pear-shaped flasks with pure water.By test liquid 10mL
It is put into 50mL pear-shaped flasks, adds 1 drop phenolphthalein indicator, adding 2mol/L ammoniacal liquor extremely turns into light red.Add 50% sulfuric acid
Liquid 2mL, and add pure water.2.5g/L ammonium metavanadate aqueous solution 5mL and 50g/L ammonium molybdate aqueous solution 5mL is added, then with pure
Water constant volume.After placing 40 minutes at room temperature, using spectrophotometer, using pure water as to shining under conditions of wavelength 440nm
Row measure, phosphorous rate is obtained by absorbance.
Phosphorous epoxy resin is modified to obtained cyanuric acid, outward appearance whether there is muddiness to confirm to remain cyanuric acid by visual observation
Whether there is.Noresidue cyanuric acid (zero) will be set to without muddiness, there will be muddiness to be set to residual cyanuric acid (×).
For the glass transition temperature of solidfied material, セ イ コ ー イ Application ス Star Le メ Application Star Co. Ltd. systems are used
Exster 6000, in the case of DSC, the value of initial flex point is set to glass transition temperature, will in the case of TMA
Flex point is set to glass transition temperature.
For peel strength of copper foil, it is measured according to JIS C 64815.7, for layers cementing power, according to JIS C
64815.7,1 prepreg and it is remaining 3 between peeled off and determined.
For anti-flammability, it is measured according to UL (Underwriter Laboratorics) specification.In addition, for residual flame
Time, 5 test film having flame inflammation firing duration total are represented.
For the reactivity of cyanuric acid, it is modified using initial epoxy base equivalent, theoretical epoxy base equivalent and cyanuric acid phosphorous
The value of the epoxide equivalent (final epoxide equivalent) of epoxy resin, is obtained by following formula
[(final epoxide equivalent-initial epoxy base equivalent)/(theoretical epoxy base equivalent-initial epoxy base equivalent)] ×
100
Wherein, in the case where final epoxide equivalent is more than theoretical epoxy base equivalent, reactivity is set to 100%.
Embodiment 1.
Added in 4 mouthfuls of removable flasks of glass system for possessing agitating device, thermometer, cooling tube, nitrogen gatherer
エ ポ ト ー ト YDPN-638 (Nippon Steel ＆ Sumitomo Metal Corporation's system, phenolic resin varnish type epoxy resin：Epoxide equivalent 177g/
Eq) 850 parts, HCA (Sanko Co., Ltd.'s system, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorous rate
14.2%) 127 parts, 23 parts of cyanuric acid (Tokyo HuaCheng Industry Co., Ltd's system), while importing nitrogen, while being stirred, enter
Go and heat and be warming up to 130 DEG C.Initial epoxy base equivalent under admixture is 207g/eq, after initial epoxy base determination of equivalent,
0.14 part of the triphenylphosphine as catalyst is added, carries out reacting for 4 hours at 160 DEG C.Obtained cyanuric acid is modified phosphorous ring
The phosphorous rate of oxygen tree fat (A-1) is 1.8%, and theoretical epoxy base equivalent is 270g/eq, and final epoxide equivalent is 272g/eq, cyanogen
The reactivity of uric acid is 100%.Show the result in table 1.
Embodiment 2.
エ ポ ト ー ト YDPN-638 are changed to 758 parts, cyanuric acid is changed to 3 parts, HCA is changed to 239 parts, except this
Outside, carry out operation similarly to Example 1.The phosphorous rate that obtained cyanuric acid is modified phosphorous epoxy resin (A-2) is
3.4%, initial epoxy base equivalent is 232g/eq, and theoretical epoxy base equivalent is 320g/eq, and final epoxide equivalent is 332g/
Eq, the reactivity of cyanuric acid is 100%.Show the result in table 1.
Embodiment 3.
Added in 4 mouthfuls of removable flasks of glass system for possessing agitating device, thermometer, cooling tube, nitrogen gatherer
エ ポ ト ー ト YDPN-63X (Nippon Steel ＆ Sumitomo Metal Corporation's system, narrow dispersed phenolic type epoxy resin：Epoxide equivalent
176g/eq) 692 parts, 250 parts of HCA, 58 parts of cyanuric acid, while import nitrogen, while being stirred, heated and be warming up to
130℃.Initial epoxy base equivalent under admixture is 254g/eq, and after initial epoxy base determination of equivalent, addition is used as catalyst
0.33 part of triphenylphosphine, carried out at 160 DEG C 4 hours react.Obtained cyanuric acid is modified containing for phosphorous epoxy resin (A-3)
Phosphorus rate is 3.6%, and theoretical epoxy base equivalent is 701g/eq, and final epoxide equivalent is 669g/eq, and the reactivity of cyanuric acid is
93%.Show the result in table 1.
Embodiment 4.
エ ポ ト ー ト YDPN-63X are changed to 640 parts, cyanuric acid is changed to 15 parts, HCA is changed to 345 parts, removed
Outside this, operation similarly to Example 3 is carried out.The phosphorous rate that obtained cyanuric acid is modified phosphorous epoxy resin (A-4) is
4.9%, initial epoxy base equivalent is 275g/eq, and theoretical epoxy base equivalent is 592g/eq, and final epoxide equivalent is 594g/
Eq, the reactivity of cyanuric acid is 100%.Show the result in table 1.
Embodiment 5.
Added in 4 mouthfuls of removable flasks of glass system for possessing agitating device, thermometer, cooling tube, nitrogen gatherer
507 parts of エ ポ ト ー ト YDPN-638, エ ポ ト ー ト YD-128 (Nippon Steel ＆ Sumitomo Metal Corporation's system, bisphenol A-type liquid epoxy
Resin：Epoxide equivalent 186g/eq) 300 parts, 162 parts of HCA, 31 parts of cyanuric acid, while nitrogen is imported, while be stirred,
Heated and be warming up to 130 DEG C.Initial epoxy base equivalent under admixture is 223g/eq, initial epoxy base determination of equivalent
Afterwards, triphenylphosphine 0.25 part of the addition as catalyst, carries out reacting for 4 hours at 160 DEG C.Obtained cyanuric acid is modified phosphorous
The phosphorous rate of epoxy resin (A-5) is 2.3%, and theoretical epoxy base equivalent is 333g/eq, and final epoxide equivalent is 330g/eq,
The reactivity of cyanuric acid is 97%.Show the result in table 1.
Embodiment 6.
Added in 4 mouthfuls of removable flasks of glass system for possessing agitating device, thermometer, cooling tube, nitrogen gatherer
433 parts of エ ポ ト ー ト YDPN-638, エ ポ ト ー ト YDCN-704 (Nippon Steel ＆ Sumitomo Metal Corporation's system, cresol novolak
Type epoxy resin：Epoxide equivalent 209g/eq) 300 parts, 250 parts of HCA, 17 parts of cyanuric acid, while nitrogen is imported, progress on one side
Stirring, heated and be warming up to 130 DEG C.Initial epoxy base equivalent under admixture is 258g/eq, initial epoxy base equivalent
After measure, 0.25 part of the triphenylphosphine as catalyst is added, carries out reacting for 4 hours at 160 DEG C.Obtained cyanuric acid is modified
The phosphorous rate of phosphorous epoxy resin (A-6) is 3.6%, and theoretical epoxy base equivalent is 429g/eq, and final epoxide equivalent is
428g/eq, the reactivity of cyanuric acid is 99%.Show the result in table 1.
Embodiment 7.
Added in 4 mouthfuls of removable flasks of glass system for possessing agitating device, thermometer, cooling tube, nitrogen gatherer
442 parts of エ ポ ト ー ト YDPN-638, YSLV-80XY (Nippon Steel ＆ Sumitomo Metal Corporation's system, tetramethyl bisphenol F type epoxy tree
Fat：Epoxide equivalent 190g/eq) 300 parts, 250 parts of HCA, 6 parts of cyanuric acid, while importing nitrogen, while being stirred, carry out
Heat and be warming up to 130 DEG C.Initial epoxy base equivalent under admixture is 245g/eq, after initial epoxy base determination of equivalent, is added
Add 0.25 part of the triphenylphosphine as catalyst, carry out reacting for 4 hours at 160 DEG C.Obtained cyanuric acid is modified phosphorous epoxy
The phosphorous rate of resin (A-7) is 3.6%, and theoretical epoxy base equivalent is 360g/eq, and final epoxide equivalent is 360/eq, and cyanogen is urinated
The reactivity of acid is 100%.Show the result in table 1.
Embodiment 8.
Added in 4 mouthfuls of removable flasks of glass system for possessing agitating device, thermometer, cooling tube, nitrogen gatherer
860 parts of エ ポ ト ー ト YDPN-638, CPHO (Nippon Chemical Ind's system, 1,5- cyclooctylene phosphine oxide, phosphorous rate
19.6%) 110 parts, 30 parts of cyanuric acid, while import nitrogen, while be stirred, heated and be warming up to 130 DEG C.Mixing
Initial epoxy base equivalent under state is 206g/eq, after initial epoxy base determination of equivalent, adds the triphenylphosphine as catalyst
0.14 part, carry out reacting for 4 hours at 160 DEG C.The phosphorous rate that obtained cyanuric acid is modified phosphorous epoxy resin (A-8) is
2.2%, theoretical epoxy base equivalent is 289g/eq, and final epoxide equivalent is 290/eq, and the reactivity of cyanuric acid is 100%.Will
As a result it is shown in table 1.
Comparative example 1.
Added in 4 mouthfuls of removable flasks of glass system for possessing agitating device, thermometer, cooling tube, nitrogen gatherer
954 parts of エ ポ ト ー ト YDPN-638,46 parts of cyanuric acids, while importing nitrogen, while being stirred, heated and heated up.Rise
Temperature is to 130 DEG C.Initial epoxy base equivalent under admixture is 185g/eq, and after initial epoxy base determination of equivalent, addition is as urging
0.05 part of the triphenylphosphine of agent, carries out reacting for 4 hours at 160 DEG C.Obtained cyanuric acid modified epoxy (A-9) is most
Whole epoxide equivalent is 194g/eq, and phosphorous rate is 0%.Theoretical epoxy base equivalent is 230g/eq, and the reactivity of cyanuric acid is
20%.Show the result in table 1.
Comparative example 2.
エ ポ ト ー ト YDPN-638 are changed to 843 parts, cyanuric acid is changed to 31 parts, in addition, carries out and implements
The same operation of example 1.The phosphorous rate that obtained cyanuric acid is modified phosphorous epoxy resin (A-10) is 1.8%, and initial epoxy base is worked as
It is 287g/eq to measure as 209g/eq, theoretical epoxy base equivalent, and final epoxide equivalent is 263g/eq, and the reactivity of cyanuric acid is
69%.Show the result in table 1.
Comparative example 3.
エ ポ ト ー ト YDPN-638 are changed to 882 parts, cyanuric acid is changed to 23 parts, HCA is changed to 95 parts, except this
Outside, carry out operation similarly to Example 1.The phosphorous rate that obtained cyanuric acid is modified phosphorous epoxy resin (A-11) is
1.35%, initial epoxy base equivalent is 200g/eq, and theoretical epoxy base equivalent is 248g/eq, and final epoxide equivalent is 231g/
Eq, the reactivity of cyanuric acid is 65%.Show the result in table 1.
Comparative example 4.
Added in 4 mouthfuls of removable flasks of glass system for possessing agitating device, thermometer, cooling tube, nitrogen gatherer
788 parts of エ ポ ト ー ト YDPN-638,23 parts of cyanuric acid, HCA-HQ (Sanko Co., Ltd.'s system, 10- (2,5- dihydroxy phenyl)-
10H-9- oxa- -10- phospho hetero phenanthrene -10- oxides, phosphorous rate 9.6%) 189 parts, while importing nitrogen, while being stirred, enter
Row is heated and heated up.It is warming up to 130 DEG C.If determine the initial epoxy base equivalent under admixture, if be 223g/eq, initially
After epoxide equivalent measure, 0.2 part of the triphenylphosphine as catalyst is added, carries out reacting for 4 hours at 160 DEG C, as a result, hair
Raw gelation, does not obtain epoxy resin.In addition, in gel compound, cyanuric acid is with solid residue.
Comparative example 5.
エ ポ ト ー ト YDPN-638 are changed to 855 parts, cyanuric acid is changed to 15 parts, HCA-HQ is changed to 130 parts,
In addition, carry out and the same operation of comparative example 4.The phosphorous rate that obtained cyanuric acid is modified phosphorous epoxy resin (A-12) is
1.2%, initial epoxy base equivalent is 206g/eq, and theoretical epoxy base equivalent is 271g/eq, and final epoxide equivalent is 224g/
Eq, the reactivity of cyanuric acid is 28%.Show the result in table 1.
Comparative example 6.
Added in 4 mouthfuls of removable flasks of glass system for possessing agitating device, thermometer, cooling tube, nitrogen gatherer
683 parts of エ ポ ト ー ト YDPN-638, エ ポ ト ー ト YDF-2001 (Nippon Steel ＆ Sumitomo Metal Corporation's system, bisphenol-f type solid ring
Oxygen tree fat：Epoxide equivalent 469g/eq) 190 parts, 127 parts of HCA, while importing nitrogen, while being stirred, are heated simultaneously
Heating.It is warming up to 130 DEG C.Initial epoxy base equivalent under admixture is 235g/eq, after initial epoxy base determination of equivalent, is added
Add 0.13 part of the triphenylphosphine as catalyst, carry out reacting for 4 hours at 160 DEG C.Obtained phosphorous epoxy resin (A-13)
Final epoxide equivalent be 272g/eq, phosphorous rate is 1.8%.Theoretical epoxy base equivalent is 272g/eq.Show the result in table 1.
Table 1
Embodiment 9~12 and 14~16 and comparative example 7~11.
Phosphorous epoxy resin is modified using the cyanuric acid of embodiment 1~5, comparative example 1~3 and comparative example 5 and is compared
The phosphorous epoxy resin of example 6 and the DICY (Japanese カ ー バ イ ト Co. Ltd. systems, dicyanodiamide) as curing agent, system
Make curable epoxy resin composition.Cooperation formula in solid constituent is shown in table 2.When coordinating, epoxy resin is dissolved in
Butanone and use.DICY be dissolved in methoxypropanol, N,N-dimethylformamide and use.2E4MZ (four countries' chemical conversion industry strain formulas
Commercial firm's system, 2-ethyl-4-methylimidazole) it is dissolved in methoxypropanol and uses.After cooperation, carried out with butanone, methoxypropanol
Regulation, so that nonvolatile component turns into 50%, obtain the lacquer type organic coating of homogeneous solution.
Obtained lacquer type organic coating is impregnated in into glass cloth WEA 7628XS13, and (Nitto Boseki Co. Ltd's system, 0.18mm are thick
Degree).The glass cloth of impregnation is subjected to drying in 8 minutes in 150 DEG C of recirculation furnaces, obtains prepreg.The preimpregnation that 4 are obtained
Expect it is overlapping, in upper and lower overlapping copper foil (Mitsu Mining ＆ Smelting Co., Ltd's system, 3EC), carry out 130 DEG C × 15 minutes and 170 DEG C ×
20kg/cm2The heating of × 70 minutes, pressurize, obtain laminate.The physical property of obtained laminate is shown in table 2.
In addition, TX-1210-90 in table represent エ ポ ト ー ト TX-1210-90 (Nippon Steel ＆ Sumitomo Metal Corporation's system,
Substituted benzene phenol-type epoxy resin:Epoxide equivalent 293g/eq).
Embodiment 13 and 17.
The cyanuric acid that is obtained using in embodiment 2 and 8 is modified phosphorous epoxy resin and (clear as the BRG-557 of curing agent
With electrician's Co. Ltd. system, novolac resin), make composition epoxy resin.Cooperation formula in solid constituent is shown in
Table 2.When coordinating, epoxy resin and BRG-557 are dissolved in butanone and used.2E4MZ is dissolved in methoxypropanol and used.Match somebody with somebody
After conjunction, it is adjusted with butanone, methoxypropanol, so that nonvolatile component turns into 50%, obtains the lacquer type organic coating of homogeneous solution.
Obtained lacquer type organic coating is impregnated in into glass cloth WEA 7628XS13, and (Nitto Boseki Co. Ltd's system, 0.18mm are thick
Degree).The glass cloth of impregnation is subjected to drying in 8 minutes in 150 DEG C of recirculation furnaces, obtains prepreg.Overlapping 4 obtain it is pre-
Leaching material, in upper and lower overlapping copper foil (Mitsu Mining ＆ Smelting Co., Ltd's system, 3EC), carry out 130 DEG C × 15 minutes and 190 DEG C ×
20kg/cm2The heating of × 80 minutes, pressurize, obtain laminate.The physical property of obtained laminate is shown in table 2.
Table 2
Distinguished by embodiment：By relative to 1 mole of phosphorus compound and epoxy for making defined molar ratio range of cyanuric acid
Resin is reacted, and by the reaction of short time cyanuric acid can be made fully to react, and obtains containing without the cyanuric acid modification of muddiness
Phosphorus epoxy resin.In addition, the cyanuric acid without muddiness fully reacted using cyanuric acid, which is modified phosphorous epoxy resin, carries out layer
Pressing plate is evaluated, as a result, aobvious with using unreacted and compared with having a case that the cyanuric acid modified epoxy of the comparative example of muddiness
Show high heat resistance, cementability, anti-flammability.
Industrial applicability
The present invention is specific phosphorus compound and cyanuric acid is coexisted with specific mol ratio and is reacted with epoxy resin
Manufacture method, the cyanuric acid obtained by the manufacture method, which is modified phosphorous epoxy resin, can be used as anti-flammability, heat resistance, cementability
Excellent electronic circuit board epoxy resin and utilize.
Claims (5)
1. a kind of cyanuric acid is modified the manufacture method of phosphorous epoxy resin, it is with phosphatization that the cyanuric acid, which is modified phosphorous epoxy resin,
As must be obtained from composition reacted, the manufacture method be characterised by, described for compound, cyanuric acid and epoxy resin
Phosphorus compound be following formulas (1) or phosphorus compound shown in following formulas (2) or containing both,
In formula (1), n represents 0 or 1, moreover, R1And R2Separately represent the alkyl of carbon number 1~6, R1And R2Can phase
Together can also be different, or ring-type can be formed together with phosphorus atoms,
In formula (2), m represents 0 or 1, moreover, R3And R4Separately represent the alkyl of carbon number 1~6, R3And R4Can phase
Together can also be different, or ring-type can be formed together with phosphorus atoms,
Relative to 1 mole of cyanuric acid, it is 13.7~50 moles to make the phosphorus compound, in phosphorus compound and cyanuric acid with such ratio
Coexist it is lower first mix above-mentioned epoxy resin, then reacted,
The phosphorous rate that the cyanuric acid is modified phosphorous epoxy resin is 1.0~5.0 mass %, and Nitrogen content is 0.1~2.0 matter
% is measured, and phosphorous rate and the summation of Nitrogen content are 2.5~5.5 mass %.
2. a kind of composition epoxy resin, it is phosphorous in the cyanuric acid modification obtained by the manufacture method described in claim 1
Coordinate in epoxy resin into obtained by other epoxy resin.
3. a kind of curable epoxy resin composition, it is modified in the cyanuric acid obtained by the manufacture method described in claim 1
In phosphorous epoxy resin, the equivalent of epoxy radicals 1 of phosphorous epoxy resin is modified relative to the cyanuric acid, is contained in terms of functional group's ratio
The curing agent of 0.4~2.0 equivalent.
A kind of 4. curable epoxy resin composition, in the composition epoxy resin described in claim 2, relative to the epoxy
The equivalent of epoxy radicals 1 of resin combination, by curing agent of the functional group containing 0.4~2.0 equivalent than in terms of.
5. a kind of epoxy resin cured product, it is to solidify the curable epoxy resin composition described in claim 3 or 4 to form
's.
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| PCT/JP2013/072894 WO2014034675A1 (en) | 2012-08-28 | 2013-08-27 | Method for producing cyanuric acid-modified phosphorus-containing epoxy resin, resin composition containing cyanuric acid-modified phosphorus-containing epoxy resin, and cured product of same |
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| WO2011096588A1 (en) * | 2010-02-08 | 2011-08-11 | 新日鐵化学株式会社 | Method for producing a phosphorus-containing epoxy resin, epoxy resin composition, and cured product thereof |
| CN102757547A (en) * | 2011-04-27 | 2012-10-31 | 新日铁化学株式会社 | Epoxy resin containing phosphor and nitrogen |
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| EP0825217A1 (en) * | 1996-08-23 | 1998-02-25 | Akzo Nobel N.V. | Adduct of bisepoxy compound and P-guanamine |
| JP2002284850A (en) * | 2001-03-26 | 2002-10-03 | Sanko Kk | Phosphorus and nitrogen modified flame-retardant epoxy resin composition, prepreg and laminate |
| JP4036011B2 (en) * | 2002-02-26 | 2008-01-23 | 日立化成工業株式会社 | Flame-retardant thermosetting resin composition, prepreg using the same, and laminate for electric wiring board |
| JP2006143850A (en) * | 2004-11-18 | 2006-06-08 | Hitachi Chem Co Ltd | Flame-retardant resin composition, prepreg and metal-clad laminated sheet |
| KR101571084B1 (en) * | 2007-05-18 | 2015-11-23 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Novel flame-retardant epoxy resin epoxy resin composition essentially containing the epoxy resin and cured product thereof |
| JP5153000B2 (en) * | 2009-04-01 | 2013-02-27 | 新日鉄住金化学株式会社 | Epoxy resin, production method thereof, epoxy resin composition and cured product |
| JP5591176B2 (en) * | 2011-04-27 | 2014-09-17 | 新日鉄住金化学株式会社 | Phosphorus and nitrogen containing epoxy resin |
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| WO2011096588A1 (en) * | 2010-02-08 | 2011-08-11 | 新日鐵化学株式会社 | Method for producing a phosphorus-containing epoxy resin, epoxy resin composition, and cured product thereof |
| CN102757547A (en) * | 2011-04-27 | 2012-10-31 | 新日铁化学株式会社 | Epoxy resin containing phosphor and nitrogen |
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Effective date of registration: 20191212 Address after: No.13-1, No.1, No.1, No Patentee after: Nippon Iron Chemical Materials Co., Ltd. Address before: Tokyo, Japan Patentee before: Nippon Steel Chemical Co. |