CN104583276A - Curing agent for episulfide compounds, curable composition, cured product of episulfide compound, and method for curing episulfide compound - Google Patents
Curing agent for episulfide compounds, curable composition, cured product of episulfide compound, and method for curing episulfide compound Download PDFInfo
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- CN104583276A CN104583276A CN201380038095.XA CN201380038095A CN104583276A CN 104583276 A CN104583276 A CN 104583276A CN 201380038095 A CN201380038095 A CN 201380038095A CN 104583276 A CN104583276 A CN 104583276A
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- UDQDOJHLCISELU-YCRREMRBSA-M C/C=C1/c2c(C([O-])=O)c(OC)ccc2CCC1 Chemical compound C/C=C1/c2c(C([O-])=O)c(OC)ccc2CCC1 UDQDOJHLCISELU-YCRREMRBSA-M 0.000 description 2
- WDXWWMDFAPUXSL-UHFFFAOYSA-N C(C1)C[NH]=C2N1CCCCC2 Chemical compound C(C1)C[NH]=C2N1CCCCC2 WDXWWMDFAPUXSL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides a photobase-generating curing agent for episulfide compounds, which has excellent base generation efficiency, while generating no outgas. A curing agent for episulfide compounds of the present invention is composed of a compound represented by general formula (1). In general formula (1), X1 represents, for example, an oxygen atom; each of X2 and X3 represents, for example, a hydrogen atom; R1 represents, for example, a methyl group; both R2 and R3 are absent; each of R4, R5, R6, R7, R8 and R9 represents, for example, a hydrogen atom; R10 represents, for example, a methyl group; and B represents a base.
Description
Technical field
The present invention relates to the cured article of episulfide compounds solidifying agent, solidification compound and episulfide compounds, particularly light alkali generation type episulfide compounds solidifying agent, the solidification compound containing this solidifying agent and episulfide compounds, the cured article by the episulfide compounds of this solidifying agent solidification.Relate to the curing by this solidifying agent solidification episulfide compounds further.
Background technology
High and the wet fastness of the thermotolerance of resin cured matter episulfide compounds being solidified with solidifying agent is also good, and forms the resin cured matter of the transparency, specific refractory power also high excellence, therefore, it is possible to launch application in purposes widely.Particularly advantageously can use in the purposes of the optical materials such as the electric and electronic such as semiconductor-encapsulating material and electrically insulating material field, lens resin etc.
As episulfide compounds solidifying agent, such as 1 can be used, two (amino methyl) hexanaphthene, 1 of 3-, 8-diazabicyclo [5.4.0]-7-hendecene and so on, common alkali cpd is as anionic curing property compound solidifying agent, but its reactivity is very high, the problem that the package stability therefore having a solidification compound containing episulfide compounds and solidifying agent is poor, work-ing life is very short and so on.Therefore, propose that to use alkali to produce agent good and be cured rapidly the method for reaction by outside stimulus as the package stability of solidification compound.
Produce agent as alkali, the light alkali that include, for example out described in patent documentation 1 produces agent.But produce agent for the light alkali of patent documentation 1, the alkali that can produce is restricted, be difficult to adjust base strength.In addition, the shortcoming that the low and reaction producing alkali of alkali generation efficiency that light action causes is difficult to carry out rapidly and so on is also had.
In contrast, such as Patent Document 2 discloses the high alkali of alkali generation efficiency to produce agent.But this alkali produces agent when producing alkali by rayed, due to decarbonate reaction, therefore also can produce exhaust (outgas) simultaneously.Therefore, sometimes produced exhaust in cured film, in this case, has the anxiety causing the reduction of cured film intensity as gas bubbles left.
Therefore, such as Patent Document 3 discloses the light alkali not producing exhaust and produce agent.But this light alkali produces in agent, and alkali generation efficiency does not still meet for high request performance in recent years, seeking the further improvement that light alkali produces agent.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-264156 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-280785 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2009-80452 publication
Summary of the invention
the problem that invention will solve
The present invention under this background, its object is to provide, alkali generation efficiency be excellent, do not cause that exhaust produces and also make solidification compound time the light alkali generation type episulfide compounds solidifying agent of package stability excellence, solidification compound containing this solidifying agent and episulfide compounds, the cured article of episulfide compounds utilizing this solidifying agent to solidify and curing.
for the scheme of dealing with problems
Therefore, the present inventor etc. conduct in-depth research repeatedly in view of described truth, found that, by using the compound shown in following general formula (1), produce agent than existing smooth alkali and more efficiently can produce alkali, without exhaust when making episulfide compounds solidify in addition, and then, the package stability of the solidification compound containing this solidifying agent and episulfide compounds is good, thus completes the present invention.
That is, the present invention has the technical scheme of following [1] ~ [6].
A kind of episulfide compounds solidifying agent, it comprises [1] compound shown in following general formula (1).
In general formula (1),
X
1, X
2and X
3separately for being selected from any one atom in the group that is made up of the alkylidene group of hydrogen atom, Sauerstoffatom, carbonatoms 1 ~ 3, sulphur atom, alkylsulfonyl and silanol group or group.
R1, R2 and R3 is separately for being selected from by the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one group in the group of the Heterocyclylalkyl composition of two rings or three-ring type.Also can form ring texture for more than 2 group bondings being selected from the group that is made up of R1, R2 and R3, this ring texture can also have more than 1 or 2 heteroatoms in the group selecting free oxygen atom, nitrogen-atoms and sulphur atom to form in ring.Wherein, X
1, X
2and X
3during for hydrogen atom or silanol group, R1, R2 and R3 do not exist.
R4, R5, R6, R7, R8 and R9 is separately for being selected from by hydrogen atom, halogen atom, hydroxyl, sulfydryl, nitro, silanol group, the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one atom in the group of the Heterocyclylalkyl composition of two rings or three-ring type or group.Also can be that R4 and R6 or R6 and R9 forms unsaturated link(age) jointly with the C-C existed together.
R10 is for being selected from by hydrogen atom, the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one atom in the group of the Heterocyclylalkyl composition of two rings or three-ring type or group.
B is alkali.
[2] the episulfide compounds solidifying agent according to aforementioned [1], wherein, in general formula (1), R4, R5, R6, R7, R8 and R9 are hydrogen atom, and R10 is methyl.
[3] the episulfide compounds solidifying agent according to aforementioned [1] or [2], wherein, episulfide compounds is the episulfide compounds of epithio equivalent 50 ~ 2000.
[4] solidification compound, it contains the episulfide compounds solidifying agent described in any one in aforementioned [1] ~ [3] and episulfide compounds.
[5] cured article for episulfide compounds, it is the episulfide compounds solidifying agent solidification described in any one in episulfide compounds utilizes aforementioned [1] ~ [3].
[6] curing for episulfide compounds, it solidifies episulfide compounds by making the compound shown in following general formula (1) have an effect.
In general formula (1),
X
1, X
2and X
3separately for being selected from any one atom in the group that is made up of the alkylidene group of hydrogen atom, Sauerstoffatom, carbonatoms 1 ~ 3, sulphur atom, alkylsulfonyl and silanol group or group.
R1, R2 and R3 is separately for being selected from by the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one group in the group of the Heterocyclylalkyl composition of two rings or three-ring type.Also can form ring texture for more than 2 group bondings being selected from the group that is made up of R1, R2 and R3, this ring texture can also have more than 1 or 2 heteroatoms in the group selecting free oxygen atom, nitrogen-atoms and sulphur atom to form in ring.Wherein, X
1, X
2and X
3during for hydrogen atom or silanol group, R1, R2 and R3 do not exist.
R4, R5, R6, R7, R8 and R9 is separately for being selected from by hydrogen atom, halogen atom, hydroxyl, sulfydryl, nitro, silanol group, the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one atom in the group of the Heterocyclylalkyl composition of two rings or three-ring type or group.Also can be that R4 and R6 or R6 and R9 forms unsaturated link(age) jointly with the C-C existed together.
R10 is for being selected from by hydrogen atom, the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one atom in the group of the Heterocyclylalkyl composition of two rings or three-ring type or group.
B is alkali.
the effect of invention
According to episulfide compounds solidifying agent of the present invention, alkali generation efficiency is excellent, not causing exhaust to produce, therefore can carry out rapidly the solidification of episulfide compounds when making episulfide compounds solidify, and, the effect of not residual bubble in cured article can be obtained.In addition, the solidification compound containing solidifying agent of the present invention and episulfide compounds has the effect of package stability excellence, can guarantee the sufficient activity duration.
Embodiment
Below describe the present invention in detail.It should be noted that, in the present invention, episulfide compounds solidifying agent not only refers to as solidifying agent works, but also comprises the concept worked as curing catalyst (auxiliary curing agent).
(episulfide compounds solidifying agent)
The feature of episulfide compounds solidifying agent of the present invention is, comprises the compound shown in following general formula (1).
In chemical structure shown in above-mentioned general formula (1), contributing to the basic structure position that alkali (B) produces is following structure position, wherein, and carboxylic acid ester groups (-COO-) and olefinic double bond (C=CH
2) be the group directly contributing to cyclisation type alkali generation mechanism.
That is, the said structure position in general formula (1) is as follows, for producing spike and alkali (B) by rayed (h ν), makes the characteristic portion that episulfide compounds solidifies efficiently.
On the other hand, the R1 ~ R10 in formula (1) and X
1~ X
3for characteristic portion and the incidental any substituting group of basic framework, as long as hinder alkali generation mechanism of the present invention or hinder the substituting group that the possibility of the solidification of the episulfide compounds as solidification object is low, be then any substituting group originally.But, R1 ~ R10 and X in the present invention
1~ X
3for following specific atoms or group.
In anion structure part in above-mentioned general formula (1), X
1, X
2and X
3separately for being selected from any one atom in the group that is made up of the alkylidene group of hydrogen atom, Sauerstoffatom, carbonatoms 1 ~ 3, sulphur atom, alkylsulfonyl and silanol group or group.
X
1, X
2and X
3be not hydrogen atom or silanol group time, during in other words as any person in the alkylidene group of Sauerstoffatom, carbonatoms 1 ~ 3, sulphur atom and alkylsulfonyl, respectively with X
1, X
2and X
3corresponding R1, R2 and R3 is separately for being selected from by the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one group in the group of the Heterocyclylalkyl composition of two rings or three-ring type.In addition, X
1, X
2and X
3during for hydrogen atom or silanol group, R1, R2 and R3 do not exist.
Also can form ring texture for more than 2 group bondings being selected from the group that is made up of R1, R2 and R3, this ring texture can also have more than 1 or 2 heteroatoms in the group selecting free oxygen atom, nitrogen-atoms and sulphur atom to form in ring.
It should be noted that, in the present invention, aryl is finger ring type unsaturated compound, such as, also containing undersaturated triatomic ring, five-ring etc.
R4, R5, R6, R7, R8 and R9 is separately for being selected from by hydrogen atom, halogen atom, hydroxyl, sulfydryl, nitro, silanol group, the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one atom in the group of the Heterocyclylalkyl composition of two rings or three-ring type or group.Also can be that R4 and R6 or R6 and R9 forms unsaturated link(age) jointly with the C-C existed together.
R10 is for being selected from by hydrogen atom, the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing Sauerstoffatom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one atom in the group of the Heterocyclylalkyl composition of two rings or three-ring type or group.
As the alkyl of carbonatoms 1 ~ 20, can list the alkyl of the straight or brancheds such as methyl, ethyl, propyl group, sec.-propyl, carbonatoms is preferably 1 ~ 18, and more preferably 1 ~ 15.
As the monocyclic, bicyclic or tricyclic formula aryl of carbonatoms 3 ~ 20, can list phenyl, benzyl, tolyl, naphthyl, phenanthryl, anthryl etc., carbonatoms is preferably 4 ~ 18, and more preferably 6 ~ 15.
As the heteroaryl of the monocyclic, bicyclic or tricyclic formula containing the heteroatomic carbonatoms 3 ~ 15 of 1 ~ 5 in the group selecting free oxygen atom, nitrogen-atoms and sulphur atom to form, furyl, benzofuryl, thienyl, thioxanthene base, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, pyrazinyl, pyrimidyl, indolizinyl, pseudoindoyl, purine radicals, naphthyridinyl, carbazyl etc. can be listed, carbonatoms is preferably 3 ~ 14, and more preferably 3 ~ 13.Heteroatoms number is preferably 1 ~ 4, and can also containing heteroatoms not of the same race.
As the cycloalkyl of the monocyclic, bicyclic or tricyclic formula of carbonatoms 3 ~ 15, can list cyclopropyl, cyclopentyl, suberyl etc., carbonatoms is preferably 3 ~ 14, and more preferably 3 ~ 13.
As the Heterocyclylalkyl of the monocyclic, bicyclic or tricyclic formula containing the heteroatomic carbonatoms 3 ~ 15 of 1 ~ 5 in the group selecting free oxygen atom, nitrogen-atoms and sulphur atom to form, tetrahydrofuran base, THP trtrahydropyranyl, tetrahydro-thienyl, 1-methylpyrrole alkyl etc. can be listed, carbonatoms is preferably 3 ~ 14, and more preferably 3 ~ 13.Heteroatoms number is preferably 1 ~ 4, and can also containing heteroatoms not of the same race.
As halogen atom, atomic iodine, bromine atoms, chlorine atom, fluorine atom can be listed.
In cationic moiety in above-mentioned general formula (1), B is alkali, include, for example out following amine compound.
Can list: the Armeen compound such as methylamine, ethamine, propylamine, hexylamine, octylame, decyl amine, amino dodecane, cetylamine, stearylamine, ethylenediamine, 1,3-propylene diamine, 1,6-hexanediamine, diethylene triamine;
The ester ring type primary amines such as your ketone diamines of hexahydroaniline, 1,3-(two amino-ethyl) hexanaphthene, diamino-cyclohexane, different fluorine;
The primary aromatic amine compounds such as benzylamine, aniline, mphenylenediamine, m-xylene diamine;
The aliphatic secondary amine compound such as dimethylamine, diethylamine, dibutylamine, dihexylamine, Di-Octyl amine, didecylamine, ethyl dimethylamine;
The ester ring type secondary amine compounds such as aziridine, azetidine, tetramethyleneimine, piperidines, norbornane dimethylamine, 1,3-two (4-piperidyl) propane;
The aromatic amine compounds such as benzyl methylamine, pentanoic, dibenzylamine;
Triethylamine, Tributylamine, trihexylamine, trioctylamine, tridecylamine, ethyl diisopropylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0]-7-hendecene (DBU), 1,5, the aliphatic tertiary amine compounds such as 7-tri-azabicyclo [4.4.0] ten-5-alkene (TBD), Isosorbide-5-Nitrae-diazabicyclo [2.2.0] octane, phosphine nitrile alkali;
Pyridine, 2,4, the imidazole compounds such as pyridine based compound, imidazoles, glyoxal ethyline, 2-undecyl imidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole such as 6-trimethylpyridine, 2,6-bis-(tertiary butyl) pyridine; The aromatic uncle amine compounds such as triphenylamine, methyldiphenyl base amine, Diethyl Aniline, tribenzyl amine.
Among them, aliphatic tertiary amine compound or the aromatic uncle amine compound compounding amount when using as solidifying agent is also harmless less, preferred, wherein, preferably 1,8-diazabicyclo [5.4.0]-7-hendecene (DBU), 1,5,7-tri-azabicyclo [4.4.0] ten-5-alkene (TBD), phosphine nitrile alkali, imidazoles, glyoxal ethyline etc.
In general formula (1), preferably R4, R5, R6, R7, R8 and R9 are hydrogen atom, R10 is the compound of methyl, i.e. compound shown in following general formula (2).
X in above-mentioned general formula (2)
1, X
2, X
3, R1, R2 be identical with above-mentioned general formula (1) respectively with R3.
In anion structure part in compound shown in general formula (2), preferably, X
1for Sauerstoffatom, X
2and X
3be hydrogen atom, structure that R1 is the alkyl of carbonatoms 1 ~ 20, X in addition
1and X
2be hydrogen atom, X
3for the structure that Sauerstoffatom, R3 are the alkyl of carbonatoms 1 ~ 20, it is further preferred that X
1for Sauerstoffatom, X
2and X
3be hydrogen atom, R1 is the structure of methyl, in addition X
1and X
2be hydrogen atom, X
3for Sauerstoffatom, R3 are the structure of methyl.
In addition, in cationic moiety, alkali B is preferably 1,8-diazabicyclo [5.4.0]-7-hendecene (DBU), 1,5,7-tri-azabicyclo [4.4.0] ten-5-alkene (TBD), phosphine nitrile alkali, imidazoles, glyoxal ethyline etc.
Shown in general formula (1), compound can adopt known method to manufacture.Such as, can manufacture according to the method described in Japanese Unexamined Patent Publication 2012-250969 publication.
Using episulfide compounds solidifying agent of the present invention as the episulfide compounds of object for having the compound of more than 1 epithio base in simple function episulfide compounds or a part, the vulcanizing agents such as various known epoxy resin and thiocyanic acid salt, thio urea are reacted under the existence of appropriate solvent, the Sauerstoffatom of epoxy group(ing) is replaced into sulphur atom, can easily obtain thus.It should be noted that, when the Sauerstoffatom of epoxy group(ing) is replaced by sulphur atom, can be the Sauerstoffatom of all epoxy group(ing) replace by sulphur atom, also can be that the Sauerstoffatom of the epoxy group(ing) of a part is replaced by sulphur atom.
Wherein, representatively episulfide compounds, can exemplify following compound.
Can list: (1) is by by being undertaken glycidated by dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, tetrabromo-bisphenol etc., bisphenol-type epoxy resin that is that obtain carries out the glycidated bisphenol type episulfide resin of sulfo-further;
(2) by by being undertaken glycidated by the nuclear hydrogenation compound of the bisphenols such as dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, tetrabromo-bisphenol, A Hydrogenated Bisphenol A type epoxy resin that is that obtain carries out the glycidated A Hydrogenated Bisphenol A type episulfide resin of sulfo-further;
(3) will epoxy resin that is that obtain carries out the glycidated episulfide resin of sulfo-by being undertaken glycidated by other 2 yuan of phenols such as xenol, dihydroxy naphthlene, dihydroxy-anthracene, 9,9-two (4-hydroxyphenyl) fluorenes;
(4) will by by 1,1, the triphen phenols such as 1-tri-(4-hydroxyphenyl) methane, 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl) phenyl) ethylidene) bis-phenol carry out glycidated and epoxy resin that is that obtain carries out the glycidated episulfide resin of sulfo-further;
(5) will epoxy resin that is that obtain carries out the glycidated episulfide resin of sulfo-further by being undertaken glycidated by four phenol such as 1,1,2,2-tetra-(4-hydroxyphenyl) ethane;
(6) by by being undertaken glycidated by phenol novolacs, cresol novolak, bisphenol A novolac, brominated phenol phenolic varnish, brominated bisphenol A phenolic varnish etc., phenolic resin varnish type epoxy resin that is that obtain carries out the glycidated phenolic varnish type episulfide resin of sulfo-further;
(7) by by being undertaken glycidated by the polyvalent alcohol such as glycerine, polyoxyethylene glycol, aliphatics ether type epoxy that is that obtain carries out the glycidated aliphatics ether type episulfide resin of sulfo-further;
(8) by by being undertaken glycidated by hydroxycarboxylic acids such as p-hydroxybenzoic acid, β-carbonaphthoic acids, ether ester epoxy resin that is that obtain carries out the glycidated Etheric ester type episulfide resin of sulfo-further;
(9) by by being undertaken glycidated by the poly carboxylic acid of phthalic acid, terephthalic acid and so on, ester type epoxy resin that is that obtain carries out the glycidated ester type episulfide resin of sulfo-further;
(10) will that obtain amine type epoxy resin, triglycidyl isocyanurate etc. carry out the glycidated amine type episulfide resin of sulfo-further by being undertaken glycidated by amine compound such as 4,4-diaminodiphenyl-methane, meta-aminophenols;
(11) the sulfo-Racemic glycidol compound of the polymeric amide polyamine of the dicarboxylic acid such as the polyalkylene such as diethylenetriamine, Triethylenetetramine (TETA) polyamine and hexanodioic acid;
(12) 3,4-epithio cyclohexyl methyls-3 ', the ester ring type episulfide such as 4 '-epithio cyclohexane carboxylate, two-(3,4-epithio cyclohexyl) adipic acid ester, 1,2-epithio-4-vinyl cyclohexane;
(13) the silicone modified episulfide resin that obtains of the reaction of organopolysilane and episulfide resin, phenol novolak type episulfide resin;
(14) episulfide compounds and the polymkeric substance thereof such as methacrylic acid sulfo-glycidyl ester, methacrylic acid 3,4-epithio cyclohexylmethyl, propylene sulfide, sulfuration hexanaphthene;
(15) episulfide compounds such as two (2,3-epithiopropyl) sulfide, two (2,3-epithiopropyl sulfo-) ethane, two (5,6-epithio-3-sulfo-hexane) sulfide; Deng.
The mixture of the a kind of episulfide compounds be selected from these episulfide compounds or the episulfide compounds mixing two or more can be used.
In addition, these episulfide compounds are suitably selected according to the purposes of cured article.Such as, Polarizer caking agent preferably uses the episulfide compounds of above-mentioned (2), (10), (11) and (12); Semi-conductor resist layer preferably uses the episulfide compounds of above-mentioned (2), (10), (12), (14) and (15); Organic EL sealing agent preferably uses the episulfide compounds of above-mentioned (3) and (13); LED sealing agent preferably uses the episulfide compounds of above-mentioned (2), (10), (12) and (13); Insulating material for printed circuit board preferably uses the episulfide compounds of above-mentioned (1), (3) and (6).
Episulfide compounds preferably epithio equivalent (molecular-weight average of average 1 epithio base) is 50 ~ 2000, more preferably 50 ~ 1800.When epithio equivalent is too small, has the tendency becoming the reaction be difficult to when controlling solidification, on the other hand, when epithio equivalent is excessive, have the tendency declined with the consistency of episulfide compounds solidifying agent, solvent.
It should be noted that, the epithio equivalent of episulfide compounds can calculate according to the epithio functional group number of gel permeation chromatography and this compound.
(solidification compound)
The feature of solidification compound of the present invention is containing episulfide compounds solidifying agent of the present invention and above-mentioned episulfide compounds.
The content of the episulfide compounds solidifying agent in solidification compound of the present invention, relative to episulfide compounds 100 weight part, is preferably set to 0.1 ~ 60 weight part, is more preferably set to 0.5 ~ 50 weight part, be preferably set to 1 ~ 40 weight part further.When the content of solidifying agent is very few, have the tendency becoming and be difficult to episulfide compounds is reacted rapidly.On the other hand, when content is too much, have the tendency that solidifying agent itself makes the decreased solubility of episulfide compounds, and, have and become disadvantageous tendency on cost.
In solidification compound of the present invention, as required, relative to episulfide compounds 100 weight part, can containing being generally 1 ~ 40 weight part, be preferably 5 ~ 20 weight parts produce alkali proliferative alkali multiplication agent based on the effect of alkali.In addition, relative to episulfide compounds 100 weight part, containing being generally 1 ~ 30 weight part, being preferably 2 ~ 20 weight part sensitizing agents.
In addition, in solidification compound of the present invention, as required, solvent can be contained.As this solvent, include, for example out the aromatic hydrocarbon compounds such as toluene; Saturated or the unsaturated hydrocarbon compound of hexane, heptane etc.; The ethers such as Anaesthetie Ether, tetrahydrofuran (THF); The ketone such as acetone, methylethylketone; The ester classes such as ethyl acetate; The alcohols such as ethanol, Virahol; The halogen series solvents etc. such as chloroform.The a kind of solvent being selected from these solvents or the mixed solvent mixing two or more can be used.
In solidification compound of the present invention, the mode that the content of solvent such as evenly can apply being coated with solidification compound on regulation base material, when forming the layer of solidification compound is suitably selected.
In addition, also episulfide compounds solidifying agent of the present invention can be used as curing catalyst, in this case, known solidifying agent such as follows can be used as solidifying agent.
Anhydrides: the aromatic anhydride classes such as Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, PMA; The compound that the annular aliphatic anhydrides such as Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylene Tetra Hydro Phthalic Anhydride, dodecenylsuccinic anhydride, trialkyl Tetra Hydro Phthalic Anhydride and their Sauerstoffatom are replaced by sulphur atom.
Polyatomic phenol: the compound that the phenolic varnish compound class, three hydroxyphenyl methane classes, aralkyl Polyphenols, Dicyclopentadiene (DCPD) Polyphenols etc. of 2 yuan of phenol such as pyrocatechol, Resorcinol, quinhydrones, Bisphenol F, dihydroxyphenyl propane, bisphenol S, xenol, phenol novolacs class, cresol novolak class, dihydroxyphenyl propane and their Sauerstoffatom are replaced by sulphur atom.
These solidifying agent may be used singly or in combination of two or more.About the usage ratio of above-mentioned solidifying agent, relative to episulfide compounds 100 weight part, be generally 0.01 ~ 200 weight part, be preferably 10 ~ 100 weight parts.
In addition, the content of curing catalyst (solidifying agent of the present invention), relative to episulfide compounds 100 weight part, is generally 0.01 ~ 10 weight part, is preferably 0.1 ~ 5 weight part.
And then relative to above-mentioned known solidifying agent 100 weight part, curing catalyst (solidifying agent of the present invention) is preferably 0.1 ~ 10 weight part, more preferably 1 ~ 5 weight part.
In solidification compound of the present invention, and then, in the scope not hindering the object of the invention and effect, can be suitable for containing various additive.As this additive, include, for example out weighting agent, pigment, dyestuff, flow agent, defoamer, static inhibitor, UV light absorber, pH adjusting agent, dispersion agent, dispersing auxiliary, surface-modifying agent, softening agent, plasticising promotor, anti-dripping agent, curing catalyst, light acid producing agent etc.Can use and be selected from the one kind or two or more of these additives.
In solidification compound of the present invention, and then, for the purpose of the character improving the cured article in final film, adhesive linkage, molding etc., can compounding various solidified nature monomer, oligopolymer or synthetic resins.Such as, the one kind or two or more combination of the thinners used for epoxy resin such as monoepoxide, common aromatic series and alicyclic epoxy resin, resol, Synolac, melmac, fluoro-resin, vinyl chloride resin, acrylic resin, silicone resin, vibrin etc. can be listed.As long as these compounding ratio is the amount in the scope of the original character not damaging solidification compound of the present invention, is usually preferably below 100 weight parts relative to episulfide compounds 100 weight part, is particularly preferably below 50 weight parts.
Episulfide compounds solidifying agent of the present invention, episulfide compounds and any composition physically can mix according to known method, condition by solidification compound of the present invention, manufacture thus.
As the method by episulfide compounds solidifying agent of the present invention and episulfide compounds mixing, include, for example out use roller mixing roll, kneader or forcing machine etc. by the solidifying agent of specified amount and episulfide compounds and arbitrarily composition carry out mixing method.
(curing of episulfide compounds)
In the present invention, episulfide compounds can solidify by making the compound shown in above-mentioned general formula (1) have an effect.Such as, can by carrying out rayed to the solidification compound containing episulfide compounds solidifying agent of the present invention and above-mentioned episulfide compounds or heat solidifying.
By the effect of light or heat, in solidification compound of the present invention, produce alkali, episulfide compounds is cured by polymerization, thus forms the cured article of episulfide compounds.
When solidification compound of the present invention is solidified by irradiation ultraviolet radiation, can be 10 ~ 10000mJ/cm by irradiating cumulative exposure usually
2, be preferably 10 ~ 8000mJ/cm
2ultraviolet solidify.Below output wavelength optimal wavelength 400nm has the ultraviolet of luminescence distribution.
As the ultraviolet source that uviolizing uses, as long as the wavelength that can export about 256 ~ 365nm is just not particularly limited, such as, can use the various known lamps such as high voltage mercury lamp, metal halide lamp, high-energy metals halide lamp, xenon lamp, LED.Wherein, high voltage mercury lamp, metal halide lamp is preferably used.
The curing reaction that uviolizing causes easily is hindered because of oxygen, and therefore, as atmosphere during uviolizing, oxygen concentration is preferably less than 3%, and more preferably less than 0.5%, be particularly preferably less than 0.3%.
For solidification compound of the present invention, even if at room temperature also carry out polyreaction after uv irradiation, but solidify well in order to efficiency, preferably carry out heat treated.The condition of heat treated according to illumination, cumulative exposure, to be produced the various condition such as the kind of alkali, the kind of alkali solidified nature compound that agent produces by the light alkali used and suitablely to determine, but Heating temperature is generally 30 ~ 200 DEG C, preferably be set to 40 ~ 150 DEG C, be particularly preferably set to 50 ~ 130 DEG C.In addition, be generally 10 seconds ~ 1 day heat-up time, be preferably set to 60 seconds ~ 360 minutes, be particularly preferably set to 5 minutes ~ 120 minutes.
Solidification compound of the present invention contains episulfide compounds solidifying agent of the present invention and episulfide compounds, therefore generation efficiency carries out the reaction of the alkali and episulfide compounds etc. of self cure agent generation well continuously, and curing speed and reaction efficiency excellence, solidification is carried out rapidly.In addition, when episulfide compounds is solidified, do not produce exhaust, therefore can obtain the effect of not residual bubble in cured article.The solidification compound of the present invention playing this effect such as can be suitably used for highly sensitive photo-curing material, erosion resistant (pattern forming material) etc.
The cured article of the episulfide compounds utilizing episulfide compounds solidifying agent of the present invention to solidify can be widely used as thermotolerance, dimensional stability, the component etc. in the effective field of the characteristics such as insulativity, such as, coating or printing ink can be widely used as, organic EL, the sealing sealer and adhesive of LED, Polarizer caking agent, color printer, the light output layer of organic EL etc. and light output film, display base plate, flexible display substrates, Flexible Displays film, semiconductor device, electronic unit, interlayer dielectric, wiring mulch film, optical circuit, optical circuit parts, antireflection film, holography, the member of formation of optical component or material of construction, print can be provided thus, transparent sealant, color printer, display base plate, flexible display substrates, Flexible Displays film, semiconductor device, electronic unit, interlayer dielectric, wiring mulch film, optical circuit, optical circuit parts, antireflection film, holography, optical component or building slab etc.In addition, the patterns formed as cured article etc. possess thermotolerance, insulativity, such as, can be advantageously used for transparent sealant, color printer, display base plate, flexible display substrates, Flexible Displays film, electronic unit, semiconductor device, interlayer dielectric, wiring mulch film, optical circuit, optical circuit component, antireflection film, other opticses or electronic component.
Embodiment
Below, list embodiment and illustrate the present invention further, as long as but the present invention is no more than its main idea is just not limited to following examples.It should be noted that, in example, " % ", " part " refer to weight basis.
(synthesis example 1)
[synthesis of 8-bromo-7-methoxyl group-3,4-dihydro-2H-naphthalene-1-ketone (i)]
7-methoxyl group-3,4-dihydro-2H-naphthalene-1-ketone 20.00g (0.11mol), N-bromosuccinimide 23.14g (0.13mol), acetonitrile 200ml is added in 500ml reactor.Reactor monolith is carried out shading, at room temperature carries out reaction in 30 hours.After reaction terminates, reaction solution water 300ml is cleaned 3 times, then concentrates, obtain crude product thus.
Utilized by the crude product of acquisition silica gel column chromatography (ethyl acetate/hexane=1/7 (volume ratio)) to carry out purifying, obtain 8-bromo-7-methoxyl group-3,4-dihydro-2H-naphthalene-1-ketone (i) 23.28g thus.Yield is 83%.
(synthesis example 2)
[synthesis of the bromo-1-ethidine of 8--7-methoxyl group-1,2,3,4-naphthane (ii)]
Under nitrogen atmosphere, in 500ml reactor, add Ethyltriphenylphosphonium brimide 37.28g (0.10mol), potassium tert.-butoxide 8.64g (0.08mol), tetrahydrofuran (THF) 90ml, at room temperature stir 1 hour.Then, the tetrahydrofuran (THF) 40ml solution of the 8-bromo-7-methoxyl group-3,4-dihydro-2H-naphthalene-1-ketone (i) 20.15g (0.08mol) obtained in synthesis example 1 is added drop-wise in reaction mixture, drips after terminating and at room temperature react 16 hours.After reaction terminates, in reaction solution, add dilute hydrochloric acid, clean 3 times with methylene dichloride 200ml.The organic layer of acquisition is concentrated, stirs 30 minutes add hexane 700ml in concentrated solution after.Then, filter the crystal removed and separate out, the filtrate of acquisition is concentrated, obtains crude product thus.
Utilized by the crude product of acquisition silica gel column chromatography (ethyl acetate/hexane=1/5 (volume ratio)) to carry out purifying, obtain the bromo-1-ethidine of 8--7-methoxyl group-1,2,3,4-naphthane (ii) 16.36g thus.Yield is 79%.
(synthesis example 3)
[synthesis of 8-ethidine-2-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid (iii)]
Under nitrogen atmosphere, in 500ml reactor, add magnesium 1.46g (0.06mol), tetrahydrofuran (THF) 80ml, at room temperature stir 10 minutes.Then, by the bromo-1-ethidine of the 8--7-methoxyl group-1,2,3 obtained in synthesis example 2, the tetrahydrofuran (THF) 40ml solution of 4-naphthane (ii) 8.55g (0.03mol) is added drop-wise in reaction mixture, drips after terminating and makes its reflux 1 hour.After reflux terminates, reaction solution is injected in dry ice (about 500g) excessive greatly, till being placed into dry ice sublimation.Thereafter, in reaction solution, add dilute hydrochloric acid, clean 3 times with methylene dichloride 200ml.The organic layer of acquisition is concentrated, obtains crude product thus.
Utilized by the crude product of acquisition silica gel column chromatography (ethyl acetate/hexane=1/5 (volume ratio)) to carry out purifying, obtain 8-ethidine-2-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid (iii) 4.53g thus.Yield is 61%.
(Production Example 1)
[synthesis of 8-ethidine-2-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid diazabicycloundecene salt]
8-ethidine-2-the methoxyl group-5 obtained in synthesis example 3 is added in 500ml reactor, 6,7,8-naphthane-1-carboxylic acid (iii) 1.00g (4.3mmol), 1,8-diazabicyclo [5.4.0]-7-hendecene 0.66g (4.3mmol), diethyl ether 250ml, at room temperature react 1 hour.After reaction terminates, solvent is removed under reduced pressure distillation, obtains following shown 8-ethidine-2-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid diazabicycloundecene salt 1.38g thus.Yield is 83%.
(Production Example 2)
[synthesis of 8-ethidine-2-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid three azabicyclo decene salt]
8-ethidine-2-the methoxyl group-5 obtained in synthesis example 3 is added in 200ml reactor, 6,7,8-naphthane-1-carboxylic acid (iii) 1.00g (4.3mmol), 1,5,7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene 0.60g (4.3mmol), diethyl ether 100ml, at room temperature react 1 hour.After reaction terminates, by filtering the crystal extracting and separate out, obtain following shown 8-ethidine-2-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid three azabicyclo decene salt 1.47g thus.Yield is 92%.
(Production Example 3)
[synthesis of 8-ethidine-2-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid phosphine nitrile alkali salt]
8-ethidine-2-the methoxyl group-5 obtained in synthesis example 3 is added in 200ml reactor, 6,7,8-naphthane-1-carboxylic acid (iii) 0.80g (3.4mmol), phosphine nitrile alkali 0.61g (3.4mmol), diethyl ether 100ml, at room temperature react 1 hour.After reaction terminates, solvent is removed under reduced pressure distillation, obtains following shown 8-ethidine-2-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid phosphine nitrile alkali salt 1.41g thus.Yield is 100%.
(Production Example 4)
[synthesis of 8-ethidine-2-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid imidazole salts]
8-ethidine-2-the methoxyl group-5 obtained in synthesis example 3 is added in 1L reactor, 6,7,8-naphthane-1-carboxylic acid (iii) 1.96g (8.4mmol), imidazoles 0.57g (8.4mmol), diethyl ether 500ml, at room temperature react 1 hour.After reaction terminates, by filtering the crystal extracting and separate out, obtain following shown 8-ethylidene-2-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid imidazole salts 1.72g thus.Yield is 68%.
(synthesis example 4)
[synthesis of 8-bromo-5-methoxyl group-3,4-dihydro-2H-naphthalene-1-ketone (iv)]
5-methoxyl group-3,4-dihydro-2H-naphthalene-1-ketone 20.00g (0.11mol), N-bromosuccinimide 23.14g (0.13mol), acetonitrile 200ml is added in 500ml reactor.Reactor monolith is carried out shading, at room temperature carries out reaction in 48 hours.After reaction terminates, reaction solution water 300ml is cleaned 3 times, then concentrates, obtain crude product thus.
Utilized by the crude product of acquisition silica gel column chromatography (ethyl acetate/hexane=1/7 (volume ratio)) to carry out purifying, obtain 8-bromo-5-methoxyl group-3,4-dihydro-2H-naphthalene-1-ketone (iv) 25.98g thus.Yield is 89%.
(synthesis example 5)
[synthesis of the bromo-1-ethidine of 8--5-methoxyl group-1,2,3,4-naphthane (v)]
Under nitrogen atmosphere, in 500ml reactor, add Ethyltriphenylphosphonium brimide 37.28g (0.10mol), potassium tert.-butoxide 8.64g (0.08mol), tetrahydrofuran (THF) 90ml, at room temperature stir 1 hour.Then, by the bromo-5-methoxyl group-3 of 8-obtained in synthesis example 4, the tetrahydrofuran (THF) 40ml solution of 4-dihydro-2H-naphthalene-1-ketone (iv) 20.15g (0.08mol) is added drop-wise in reaction mixture, drips after terminating, at room temperature reacts 16 hours.After reaction terminates, in reaction solution, add dilute hydrochloric acid, clean 3 times with methylene dichloride 200ml.The organic layer of acquisition is concentrated, stirs 30 minutes add hexane 700ml in concentrated solution after.Then, filter the crystal removed and separate out, the filtrate of acquisition is concentrated, obtains crude product thus.
Utilized by the crude product of acquisition silica gel column chromatography (ethyl acetate/hexane=1/5 (volume ratio)) to carry out purifying, obtain the bromo-1-ethidine of 8--5-methoxyl group-1,2,3,4-naphthane (v) 13.78g thus.Yield is 65%.
(synthesis example 6)
[synthesis of 8-ethidine-4-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid (vi)]
Under nitrogen atmosphere, in 500ml reactor, add magnesium 1.46g (0.06mol), tetrahydrofuran (THF) 80ml, at room temperature stir 10 minutes.Then, by the bromo-1-ethidine of the 8--5-methoxyl group-1,2,3 obtained in synthesis example 5, the tetrahydrofuran (THF) 40ml solution of 4-naphthane (v) 8.55g (0.03mol) is added drop-wise in reaction mixture, drips after terminating and makes its reflux 1 hour.After reflux terminates, reaction solution is injected in dry ice (about 500g) excessive greatly, till being placed into dry ice sublimation.Thereafter, in reaction solution, add dilute hydrochloric acid, clean 3 times with methylene dichloride 200ml.The organic layer of acquisition is concentrated, obtains crude product thus.
Utilized by the crude product of acquisition silica gel column chromatography (ethyl acetate/hexane=1/5 (volume ratio)) to carry out purifying, obtain 8-ethidine-4-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid (vi) 4.00g thus.Yield is 54%.
(Production Example 5)
[synthesis of 8-ethidine-4-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid diazabicycloundecene salt]
8-ethidine-4-the methoxyl group-5 obtained in synthesis example 6 is added in 500ml reactor, 6,7,8-naphthane-1-carboxylic acid (vi) 1.00g (4.3mmol), 1,8-diazabicyclo [5.4.0]-7-hendecene 0.66g (4.3mmol), diethyl ether 250ml, at room temperature react 1 hour.After reaction terminates, solvent is removed under reduced pressure distillation, obtains following shown 8-ethidine-4-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid diazabicycloundecene salt 1.67g thus.Yield is 100%.
(Production Example 6)
[synthesis of 8-ethidine-4-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid three azabicyclo decene salt]
8-ethidine-4-the methoxyl group-5 obtained in synthesis example 6 is added in 200ml reactor, 6,7,8-naphthane-1-carboxylic acid (vi) 0.31g (1.3mmol), 1,5,7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene 0.19g (1.3mmol), diethyl ether 120ml, at room temperature react 1 hour.After reaction terminates, by filtering the crystal extracting and separate out, obtain following shown 8-ethidine-4-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid three azabicyclo decene salt 0.34g.Yield is 69%.
(Production Example 7)
[synthesis of 8-ethidine-4-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid phosphine nitrile alkali salt]
8-ethidine-4-the methoxyl group-5 obtained in synthesis example 6 is added in 200ml reactor, 6,7,8-naphthane-1-carboxylic acid (vi) 0.23g (1.0mmol), phosphine nitrile alkali 0.18g (1.0mmol), diethyl ether 50ml, at room temperature react 1 hour.After reaction terminates, solvent is removed under reduced pressure distillation, obtains following shown 8-ethidine-4-methoxyl group-5,6,7,8-naphthane-1-carboxylic acid three azabicyclo decene salt 0.40g thus.Yield is 97%.
(comparing Production Example 1)
[synthesis of 2-(3-benzoylphenyl) propionic acid diazabicycloundecene salt]
2-(3-benzoylphenyl) propionic acid 3.0g (11.8mmol), 1 is added in 100ml reactor; 8-diazabicyclo [5.4.0]-7-hendecene 1.80g (11.8mmol), diethyl ether 30ml, at room temperature react 1 hour.After reaction terminates, solvent is removed under reduced pressure distillation, obtains following shown 2-(3-benzoylphenyl) propionic acid diazabicycloundecene salt 4.96g thus.Yield is 100%.
(comparing Production Example 2)
[synthesis of 2-(3-benzoylphenyl) propionic acid three azabicyclo decene salt]
2-(3-benzoylphenyl) propionic acid 1.00g (3.9mmol), 1 is added in 100ml reactor; 5; 7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene 0.55g (3.9mmol), diethyl ether 150ml, at room temperature react 1 hour.After reaction terminates, solvent is removed under reduced pressure distillation, obtains following shown 2-(3-benzoylphenyl) propionic acid three azabicyclo decene salt 1.73g thus.Yield is 100%.
(embodiment 1 ~ 7, comparative example 1 ~ 2)
The compound manufactured in Production Example 1 ~ 7 is used as the solidifying agent of embodiment 1 ~ 7, compares the solidifying agent that the compound manufactured in Production Example 1 ~ 2 is used as comparative example 1 ~ 2, carry out following evaluation.
(assessment item)
(1) dissolution rate does not measure (alkali generation efficiency)
Relative to nuclear hydrogenation bisphenol A-type episulfide resin (Mitsubishi Chemical Corporation manufactures, YL-7007) 100 parts, mixed curing agent 8 parts, chloroform 100 parts, prepare homogeneous solution.This is prepared liquid uses bar coater (No.20) to carry out film on non-alkali glass, carries out preheating in 5 minutes at 50 DEG C.Use metal halide lamp, irradiate with the exposure of 365nm conversion for 928mJ/
cm
2ultraviolet after, at the temperature that table 1 is recorded, carry out 40 minutes heat treated, thus obtain cured film.After the cured film obtained is flooded 30 seconds in chloroform, take out in chloroform, and make it dry.Not dissolution rate is obtained according to the cured film weight difference before and after chloroform dipping.Show the result in table 1.
(2) confirm have bubble-free to occur
Relative to nuclear hydrogenation bisphenol A-type episulfide resin (Mitsubishi Chemical Corporation manufactures, YL-7007) 100 parts, mixed curing agent 8 parts.Mixed solution defoamer is carried out deaeration, thus prepares sample.By the mould that the insulate on Si thing of the sample loading thickness 2mm be prepared into is made, clamp across mould release film 2 non-alkali glasss, use metal halide lamp, irradiate with the exposure of 365nm conversion for 2145mJ/cm
2ultraviolet.Then, carry out 1 hour heat treated at the temperature that table 1 is recorded after, self-template takes out, and obtains the tabular cured article of about 2mm.For the cured article obtained, visual confirmation has bubble-free.Show the result in table 1.
[table 1]
(comparative example 3)
In embodiment 6, nuclear hydrogenation bisphenol A-type episulfide resin is become bisphenol A type epoxy resin (Mitsubishi Chemical Corporation manufactures, jER828), in addition, similarly carry out, but cannot cured film be obtained.
(comparative example 4)
In embodiment 6, nuclear hydrogenation bisphenol A-type episulfide resin is become nuclear hydrogenation bisphenol A type epoxy resin (Mitsubishi Chemical Corporation manufactures, YX8000), in addition, similarly carry out, but cannot cured film be obtained.
According to result shown in table 1, if use episulfide compounds solidifying agent of the present invention, the existing solidifying agent shown in alkali generation efficiency with comparative example 1,2 is identical, can carry out rapidly the solidification of episulfide compounds.In addition, also known episulfide compounds solidifying agent of the present invention is different from the existing solidifying agent shown in comparative example 1,2, does not cause the generation of exhaust when episulfide compounds is solidified, and therefore can obtain the effect of not residual bubble and so in cured film.And known compared with the result of comparative example 3,4, solidifying agent of the present invention is excellent especially for the solidified nature of episulfide compounds.
In addition, as following operation, carry out storage stability test.
(storage stability test)
Prepare following embodiment 8,9 and the solidification compound shown in comparative example 5,6 respectively, at 25 DEG C, using Brookfield viscometer, (Brookfield Asset Management Inc. manufactures, DV-II+Pro) measure the time reached till 2 times of viscosity of initial viscosity, its time is evaluated as package stability.
(embodiment 8)
Relative to nuclear hydrogenation bisphenol A-type episulfide resin 100 parts, 8 parts, solidifying agent, the chloroform 16 parts of mixing Production Example 5, thus prepare solidification compound.The time that the viscosity measuring this solidification compound is issued to till initial viscosity 2 times at 25 DEG C, evaluate package stability.Show the result in table 2.
(embodiment 9)
Relative to nuclear hydrogenation bisphenol A-type episulfide resin 100 parts, 8 parts, solidifying agent, the chloroform 16 parts of mixing Production Example 6, thus prepare solidification compound.The time that the viscosity measuring this solidification compound is issued to till initial viscosity 2 times at 25 DEG C, evaluate package stability.Show the result in table 2.
(comparative example 5)
Relative to nuclear hydrogenation bisphenol A-type episulfide resin 100 parts, mixing 1,8-diazabicyclo [5.4.0]-7-hendecene 3 parts, chloroform 16 parts, thus prepare solidification compound.The time that the viscosity measuring this solidification compound is issued to till initial viscosity 2 times at 25 DEG C, evaluate package stability.Show the result in table 2.
(comparative example 6)
Relative to nuclear hydrogenation bisphenol A-type episulfide resin 100 parts, 3 parts, mixing 1,5,7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene, chloroform 16 parts, thus prepare solidification compound.The time that the viscosity measuring this solidification compound is issued to till initial viscosity 2 times at 25 DEG C, evaluate package stability.Show the result in table 2.
[table 2]
According to result shown in table 2, with using as existing solidifying agent normally used basic cpd be used as solidifying agent situation compared with, the package stability employing the solidification compound of episulfide compounds solidifying agent of the present invention is very excellent.
In detail and describe the present invention with reference to specific embodiment, but can add various change, amendment without departing from the spirit and scope of the present invention, this is apparent to those skilled in the art.The Japanese patent application (Japanese Patent Application 2012-159536) that the application proposed based on July 18th, 2012, is incorporated in this using its content as reference.
utilizability in industry
The alkali generation efficiency of episulfide compounds solidifying agent of the present invention is excellent, does not cause the generation of exhaust, and the package stability especially when forming solidification compound is excellent, is therefore useful especially as the solidifying agent in field of electronic materials.In addition, the episulfide compounds utilizing episulfide compounds solidifying agent of the present invention to solidify is useful as component such as optical component, the electronic component in the field requiring the characteristics such as thermotolerance, dimensional stability, insulativity.
Claims (6)
1. an episulfide compounds solidifying agent, it comprises the compound shown in following general formula (1),
In general formula (1),
X
1, X
2and X
3separately for being selected from any one atom in the group that is made up of the alkylidene group of hydrogen atom, Sauerstoffatom, carbonatoms 1 ~ 3, sulphur atom, alkylsulfonyl and silanol group or group,
R1, R2 and R3 is separately for being selected from by the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one group in the group of the Heterocyclylalkyl composition of two rings or three-ring type, also can for being selected from by R1, R2 and R3 composition group in more than 2 group bondings thus formed ring texture, this ring texture can also have in ring selects free oxygen atom, more than 1 or 2 heteroatoms in the group of nitrogen-atoms and sulphur atom composition, wherein, X
1, X
2and X
3during for hydrogen atom or silanol group, R1, R2 and R3 do not exist,
R4, R5, R6, R7, R8 and R9 is separately for being selected from by hydrogen atom, halogen atom, hydroxyl, sulfydryl, nitro, silanol group, the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one atom in the group of the Heterocyclylalkyl composition of two rings or three-ring type or group, also can be that R4 and R6 or R6 and R9 forms unsaturated link(age) jointly with the C-C existed together,
R10 is for being selected from by hydrogen atom, the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one atom in the group of the Heterocyclylalkyl composition of two rings or three-ring type or group,
B is alkali.
2. episulfide compounds solidifying agent according to claim 1, wherein, in general formula (1), R4, R5, R6, R7, R8 and R9 are hydrogen atom, and R10 is methyl.
3. episulfide compounds solidifying agent according to claim 1 and 2, wherein, episulfide compounds is the episulfide compounds of epithio equivalent 50 ~ 2000.
4. a solidification compound, it contains episulfide compounds solidifying agent described in any one in claims 1 to 3 and episulfide compounds.
5. a cured article for episulfide compounds, it utilizes the episulfide compounds solidifying agent described in any one in claim 1 ~ 3 to solidify for episulfide compounds.
6. a curing for episulfide compounds, it solidifies episulfide compounds by making the compound shown in following general formula (1) have an effect,
In general formula (1),
X
1, X
2and X
3separately for being selected from any one atom in the group that is made up of the alkylidene group of hydrogen atom, Sauerstoffatom, carbonatoms 1 ~ 3, sulphur atom, alkylsulfonyl and silanol group or group,
R1, R2 and R3 is separately for being selected from by the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one group in the group of the Heterocyclylalkyl composition of two rings or three-ring type, also can for being selected from by R1, R2 and R3 composition group in more than 2 group bondings thus formed ring texture, this ring texture can also have in ring selects free oxygen atom, more than 1 or 2 heteroatoms in the group of nitrogen-atoms and sulphur atom composition, wherein, X
1, X
2and X
3during for hydrogen atom or silanol group, R1, R2 and R3 do not exist,
R4, R5, R6, R7, R8 and R9 is separately for being selected from by hydrogen atom, halogen atom, hydroxyl, sulfydryl, nitro, silanol group, the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one atom in the group of the Heterocyclylalkyl composition of two rings or three-ring type or group, also can be that R4 and R6 or R6 and R9 forms unsaturated link(age) jointly with the C-C existed together,
R10 is for being selected from by hydrogen atom, the alkyl of carbonatoms 1 ~ 20, the monocycle of carbonatoms 3 ~ 20, two rings or three-ring type aryl, containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, the heteroaryl of two rings or three-ring type, the monocycle of carbonatoms 3 ~ 15, the cycloalkyl of two rings or three-ring type, and containing selecting free oxygen atom, the monocycle of 1 ~ 5 heteroatomic carbonatoms 3 ~ 15 in the group of nitrogen-atoms and sulphur atom composition, any one atom in the group of the Heterocyclylalkyl composition of two rings or three-ring type or group,
B is alkali.3 -->
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-159536 | 2012-07-18 | ||
| JP2012159536 | 2012-07-18 | ||
| PCT/JP2013/069448 WO2014014037A1 (en) | 2012-07-18 | 2013-07-17 | Curing agent for episulfide compounds, curable composition, cured product of episulfide compound, and method for curing episulfide compound |
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|---|---|
| CN104583276A true CN104583276A (en) | 2015-04-29 |
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|---|---|---|---|
| CN201380038095.XA Pending CN104583276A (en) | 2012-07-18 | 2013-07-17 | Curing agent for episulfide compounds, curable composition, cured product of episulfide compound, and method for curing episulfide compound |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5566510B2 (en) |
| KR (1) | KR20150032746A (en) |
| CN (1) | CN104583276A (en) |
| WO (1) | WO2014014037A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503907A (en) * | 2016-01-18 | 2016-04-20 | 北京大学 | Method for enantioselectively synthesizing Vinca alkaloids |
| CN111234184A (en) * | 2020-03-19 | 2020-06-05 | 南京工业大学 | Preparation method of polyester |
| CN115135697A (en) * | 2020-02-19 | 2022-09-30 | 株式会社大赛璐 | Process for producing polythioether compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3918411B2 (en) * | 2000-08-01 | 2007-05-23 | 三菱化学株式会社 | Curable composition and cured product thereof |
| JP2003261648A (en) * | 2002-03-12 | 2003-09-19 | Mitsubishi Chemicals Corp | Heterocycle-containing compound and composition containing this |
| JP5765851B2 (en) * | 2011-05-09 | 2015-08-19 | 学校法人東京理科大学 | Carboxylic acid compound, base generator and photosensitive resin composition containing the base generator |
-
2013
- 2013-07-17 JP JP2013148174A patent/JP5566510B2/en active Active
- 2013-07-17 CN CN201380038095.XA patent/CN104583276A/en active Pending
- 2013-07-17 KR KR1020157004179A patent/KR20150032746A/en not_active Application Discontinuation
- 2013-07-17 WO PCT/JP2013/069448 patent/WO2014014037A1/en active Application Filing
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503907A (en) * | 2016-01-18 | 2016-04-20 | 北京大学 | Method for enantioselectively synthesizing Vinca alkaloids |
| CN115135697A (en) * | 2020-02-19 | 2022-09-30 | 株式会社大赛璐 | Process for producing polythioether compound |
| CN111234184A (en) * | 2020-03-19 | 2020-06-05 | 南京工业大学 | Preparation method of polyester |
| CN111234184B (en) * | 2020-03-19 | 2022-01-07 | 南京工业大学 | Preparation method of polyester |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014037529A (en) | 2014-02-27 |
| WO2014014037A1 (en) | 2014-01-23 |
| KR20150032746A (en) | 2015-03-27 |
| JP5566510B2 (en) | 2014-08-06 |
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