CN105175727A - Episulfide compound, episulfide compound-containing mixture, method for producing episulfide compound-containing mixture, curable composition and connection structure - Google Patents

Episulfide compound, episulfide compound-containing mixture, method for producing episulfide compound-containing mixture, curable composition and connection structure Download PDF

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CN105175727A
CN105175727A CN201510628123.4A CN201510628123A CN105175727A CN 105175727 A CN105175727 A CN 105175727A CN 201510628123 A CN201510628123 A CN 201510628123A CN 105175727 A CN105175727 A CN 105175727A
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久保田敬士
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Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D331/00—Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
    • C07D331/02—Three-membered rings
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • C08G75/08—Polythioethers from cyclic thioethers from thiiranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

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Abstract

An episulfide compound which can be quickly cured at a low temperature and is capable of efficiently connecting an object member to be connected when used for the purpose of connecting the object member to be connected. The episulfide compound is also capable of suppressing occurrence of voids after connection. Specifically disclosed is an episulfide compound having a structure represented by formula (1-1), (2-1) or (3). In formulae (1-1), (2-1) and (3), R1, R2, R51, R52, R101 and R102 each represents an alkylene group having 1-5 carbon atoms; 2-4 groups among the four groups of R3-R6 each represents a hydrogen, and the other groups each represents a group containing an episulfide group; 4-6 groups among the six groups of R53-R58 each represents a hydrogen and the other groups each represents a group containing an episulfide group; and 6-8 groups among the eight groups of R103-R110 each represents a hydrogen and the other groups each represents a group containing an episulfide group.

Description

The manufacture method of episulfide compounds, the mixture containing episulfide compounds, the mixture containing episulfide compounds, solidification compound and connection structural bodies
The application is Chinese application number is 200980137603.3, denomination of invention is " manufacture method of episulfide compounds, the mixture containing episulfide compounds, the mixture containing episulfide compounds, solidification compound and connection structural bodies " and the applying date is the divisional application of the patent application of on 09 24th, 2009.
Technical field
The present invention relates to episulfide compounds, containing this episulfide compounds containing the mixture of episulfide compounds, the manufacture method of the mixture containing episulfide compounds, solidification compound and connection structural bodies, described episulfide compounds can rapid solidification at low temperatures, and when the connection for connecting object parts, effectively these connecting object parts can be connected, and produce gap after can suppressing to connect.
Background technology
The anisotropic conductive material such as known anisotropic conductive paste, anisotropic conductive ink, anisotropic-electroconductive adhesive, anisotropic conductive film or anisotropic conductive sheet.
Anisotropic conductive material is used for the connection of IC chip and pliable and tough tellite, or IC chip and have the connection etc. of circuit substrate of ITO electrode.Such as, after assembling anisotropic conductive material between IC chip electrode and circuit substrate electrode, can to connect between above-mentioned electrode by heating and pressurizeing.
As an example of above-mentioned anisotropic conductive material, the following anisotropic conductive adhesive film that Patent Document 1 discloses containing heat cured insulation tackiness agent, electroconductive particle, Imidazole Type Latent Curing Agent and amine latent curing agent.Record in patent documentation 1, even if anisotropic conductive adhesive film solidifies at a lower temperature, also there is excellent connection reliability.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 9-115335 publication
Summary of the invention
The problem that invention will solve
In recent years, in order to effectively connect between the electrode to electronic unit, require that the Heating temperature needed for connecting is low, and clamping time is short.In addition, because electronic unit is easily deteriorated when heating, therefore an urgent demand Heating temperature is low.
Anisotropic conductive adhesive film described in patent documentation 1, the Heating temperature making it start needed for solidification is lower.But described anisotropic conductive adhesive film fully can not be cured reaction at low temperatures.Therefore, use anisotropic conductive adhesive film to when connecting between circuit substrate and the electrode of electronic unit, Heating temperature must be improved or carry out long-time heating.Therefore, sometimes can not connection electrode effectively.
Further, in recent years, the electrode be formed on circuit substrate etc. is tending towards miniaturization.That is, the size (S) of the cross direction size (L) being formed with the circuit of electrode and the spacing not forming electrode become less than value L/S.By above-mentioned anisotropic conductive adhesive film, when connecting the above-mentioned circuit substrate being formed with trickle electrode, the curing speed of anisotropic conductive adhesive film is comparatively slow, meeting generation gap, spacing place in-between the electrodes.
The object of the present invention is to provide episulfide compounds, containing this episulfide compounds containing the mixture of episulfide compounds, the manufacture method of the mixture containing this episulfide compounds, solidification compound and connection structural bodies, described episulfide compounds can rapid solidification at low temperatures, and when the connection for connecting object parts, effectively these connecting object parts can be connected, and produce gap after can suppressing to connect.
The method of dealing with problems
According to the present invention aspect widely, the episulfide compounds with following formula (1-1), (2-1) or the structure represented by (3) can be provided.
[chemical formula 1]
In above formula (1-1), R1 and R2 represents C respectively 1 ~ 5alkylidene group,
2 ~ 4 groups in these 4 groups of R3, R4, R5 and R6 are hydrogen,
Group not for hydrogen in R3, R4, R5 and R6 is the group that following formula (4) represents.
[chemical formula 2]
In above formula (2-1), R51 and R52 represents C respectively 1 ~ 5alkylidene group,
4 ~ 6 groups in these 6 groups of R53, R54, R55, R56, R57 and R58 are hydrogen,
Group not for hydrogen in R53, R54, R55, R56, R57 and R58 is the group that following formula (5) represents.
[chemical formula 3]
In above formula (3), R101 and R102 represents C respectively 1 ~ 5alkylidene group,
6 ~ 8 groups in 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 are hydrogen,
Group not for hydrogen in R103, R104, R105, R106, R107, R108, R109 and R110 is the group that following formula (6) represents.
[chemical formula 4]
In above formula (4), R7 represents C 1 ~ 5alkylidene group.
[chemical formula 5]
In above formula (5), R59 represents C 1 ~ 5alkylidene group.
[chemical formula 6]
In above formula (6), R111 represents C 1 ~ 5alkylidene group.
Under the particular case of the episulfide compounds that the present invention relates to, this episulfide compounds has the structure that following formula (1) or (2) represent.
[chemical formula 7]
In above formula (1), R1 and R2 represents C respectively 1 ~ 5alkylidene group,
2 ~ 4 groups in these 4 groups of R3, R4, R5 and R6 are hydrogen,
Group not for hydrogen in R3, R4, R5 and R6 is the group that following formula (4) represents.
[chemical formula 8]
In above formula (2), R51 and R52 represents C respectively 1 ~ 5alkylidene group,
4 ~ 6 groups in these 6 groups of R53, R54, R55, R56, R57 and R58 are hydrogen,
Group not for hydrogen in R53, R54, R55, R56, R57 and R58 is the group that following formula (5) represents.
[chemical formula 9]
In above formula (4), R7 represents C 1 ~ 5alkylidene group.
[chemical formula 10]
In above formula (5), R59 represents C 1 ~ 5alkylidene group.
Under other particular cases of the episulfide compounds that the present invention relates to, the structure that above formula (1) or (2) represent is the structure that following formula (1A) or (2A) represent.
[chemical formula 11]
In above formula (1A), R1 and R2 represents C respectively 1 ~ 5alkylidene group.
[chemical formula 12]
In above formula (2A), R51 and R52 represents C respectively 1 ~ 5alkylidene group.
The present invention relates to containing the mixture of episulfide compounds, it contains the epoxy compounds that episulfide compounds of the present invention and following formula (11-1), (12-1) or (13) represent.
[chemical formula 13]
In above formula (11-1), R11 and R12 represents C respectively 1 ~ 5alkylidene group,
2 ~ 4 groups in these 4 groups of R13, R14, R15 and R16 are hydrogen,
Group not for hydrogen in R13, R14, R15 and R16 is the group that following formula (14) represents.
[chemical formula 14]
In above formula (12-1), R61 and R62 represents C1 ~ 5 alkylidene group respectively,
4 ~ 6 groups in these 6 groups of R63, R64, R65, R66, R67 and R68 are hydrogen,
Group not for hydrogen in R63, R64, R65, R66, R67 and R68 is the group that following formula (15) represents.
[chemical formula 15]
In above formula (13), R121 and R122 represents C respectively 1 ~ 5alkylidene group,
6 ~ 8 groups in these 8 groups of R123, R124, R125, R126, R127, R128, R129 and R130 are hydrogen,
Group not for hydrogen in R123, R124, R125, R126, R127, R128, R129 and R130 is the group that following formula (16) represents.
[chemical formula 16]
In above formula (14), R17 represents C 1 ~ 5alkylidene group.
[chemical formula 17]
In above formula (15), R69 represents C 1 ~ 5alkylidene group.
[chemical formula 18]
In above formula (16), R131 represents C 1 ~ 5alkylidene group.
Under the particular case of the mixture containing episulfide compounds that the present invention relates to, above-mentioned epoxy compounds is the epoxy compounds that following formula (11) or (12) represent.
[chemical formula 19]
In above formula (11), R11 and R12 represents C respectively 1 ~ 5alkylidene group,
2 ~ 4 groups in these 4 groups of R13, R14, R15 and R16 are hydrogen,
Group not for hydrogen in R13, R14, R15 and R16 is the group that following formula (14) represents.
[chemical formula 20]
In above formula (12), R61 and R62 represents C respectively 1 ~ 5alkylidene group,
4 ~ 6 groups in these 6 groups of R63, R64, R65, R66, R67 and R68 are hydrogen,
Group not for hydrogen in R63, R64, R65, R66, R67 and R68 is the group that following formula (15) represents.
[chemical formula 21]
In above formula (14), R17 represents C 1 ~ 5alkylidene group.
[chemical formula 22]
In above formula (15), R69 represents C 1 ~ 5alkylidene group.
Under other particular cases of the mixture containing episulfide compounds that the present invention relates to, the structure of the structure that above formula (11) or (12) represent represented by following formula (11A) or (12A).
[chemical formula 23]
In above formula (11A), R11 and R12 represents C respectively 1 ~ 5alkylidene group,
[chemical formula 24]
In above formula (12A), R61 and R62 represents C respectively 1 ~ 5alkylidene group,
In the manufacture method of the mixture containing episulfide compounds that the present invention relates to, to containing in the 1st solution of thiocyanate-, add above formula (11-1), (12-1) or the epoxy compounds represented by (13) or the solution containing this epoxy compounds continuously or discontinuously, then, add the 2nd solution containing thiocyanate-more continuously or discontinuously, thus, a part of epoxy group(ing) of above-mentioned epoxy compounds changes epithio base into.
Under a certain particular case of the manufacture method of the mixture containing episulfide compounds that the present invention relates to, as above-mentioned epoxy compounds or the solution containing this epoxy compounds, the epoxy compounds using above formula (11) or (12) to represent or the solution containing this epoxy compounds.
The solidification compound that the present invention relates to, containing episulfide compounds of the present invention and solidifying agent.
In addition, the solidification compound that the present invention relates to contains the mixture and the solidifying agent that contain episulfide compounds of the present invention.Above-mentioned containing in the mixture of episulfide compounds in described solidification compound contains above-mentioned episulfide compounds.
Under a certain particular case of the solidification compound that the present invention relates to, also containing photocurable compound and Photoepolymerizationinitiater initiater.
Under other particular cases of the solidification compound that the present invention relates to, also containing electroconductive particle.
The connection structural bodies that the present invention relates to, possess the 1st connecting object parts, the 2nd connecting object parts and connect the connection section of the 1st, the 2nd connecting object parts, this connection section is formed by solidification compound of the present invention.
Under a certain particular case of the connection structural bodies that the present invention relates to, above-mentioned solidification compound contains electroconductive particle, and above-mentioned 1st, the 2nd connecting object parts carry out conduction by above-mentioned electroconductive particle and connect.
Invention effect
The structure that the episulfide compounds that the present invention relates to has above formula (1-1), (2-1) or (3) represents, can rapid solidification at low temperatures.
The episulfide compounds that the present invention relates to, when having the structure that above formula (1) or (2) represent, can more promptly solidify at low temperatures.
What the present invention relates to contains containing the mixture of episulfide compounds the episulfide compounds possessing the structure that above formula (1-1) or (2-1) represent, therefore can rapid solidification at low temperatures.
The mixture containing episulfide compounds that the present invention relates to, when having the structure that above formula (1) or (2) represent, can more promptly solidify at low temperatures.
In addition, by by the episulfide compounds that the present invention relates to or the connection being used for connecting object parts containing the mixture of episulfide compounds that the present invention relates to, these connecting object parts can effectively be connected.And produce gap after can suppressing to connect.Even if the irregular connecting object parts of connecting surface, also can suppress to produce gap.
Brief Description Of Drawings
[Fig. 1] Fig. 1 is that part blocks sectional view, and it schematically shows an example of the connection structural bodies of the solidification compound used involved by one embodiment of the present invention.
the embodiment of invention
Hereafter present invention will be described in more detail.
(episulfide compounds)
The structure that the episulfide compounds that the present invention relates to has following formula (1-1), (2-1) or (3) represents.In following formula (1-1), be not particularly limited with the bonding position of 6 groups of phenyl ring bonding.In following formula (2-1), the bonding position of 8 groups be combined with naphthalene nucleus is not particularly limited.
[chemical formula 25]
In above formula (1-1), R1 and R2 represents C respectively 1 ~ 5alkylidene group.
2 ~ 4 groups in these 4 groups of R3, R4, R5 and R6 are hydrogen.
Group not for hydrogen in R3, R4, R5 and R6 is the group that following formula (4) represents.
These 4 groups of R3, R4, R5 and R6 can be all hydrogen.
1 in these 4 groups of R3, R4, R5 and R6 or 2 groups are the group that following formula (4) represents, and be not the group that following formula (4) represents in these 4 groups of R3, R4, R5 and R6 can be hydrogen.
[chemical formula 26]
In above formula (2-1), R51 and R52 represents C respectively 1 ~ 5alkylidene group.
4 ~ 6 groups in these 6 groups of R53, R54, R55, R56, R57 and R58 are hydrogen,
Group not for hydrogen in R53, R54, R55, R56, R57 and R58 is the group that following formula (5) represents.
These 6 groups of R53, R54, R55, R56, R57 and R58 can be all hydrogen.
1 in these 6 groups of R53, R54, R55, R56, R57 and R58 or 2 groups are the group that following formula (5) represents, and be not the group that following formula (5) represents in R53, R54, R55, R56, R57 and R58 can be hydrogen.
[chemical formula 27]
In above formula (3), R101 and R102 represents C respectively 1 ~ 5alkylidene group.
6 ~ 8 groups in these 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 are hydrogen.
Group not for hydrogen in R103, R104, R105, R106, R107, R108, R109 and R110 is the group that following formula (6) represents.
These 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 can be all hydrogen.
1 in these 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 or 2 groups are the group that following formula (6) represents, and the group that in these 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110, non-following formula (6) represents can be hydrogen.
[chemical formula 28]
In above formula (4), R7 represents C 1 ~ 5alkylidene group.
[chemical formula 29]
In above formula (5), R59 represents C 1 ~ 5alkylidene group.
[chemical formula 30]
In above formula (6), R111 represents C 1 ~ 5alkylidene group.
From can the viewpoint of rapid solidification more at low temperatures, the episulfide compounds that the present invention relates to preferably has the structure that following formula (1), following formula (2) or above formula (3) represent.From can the viewpoint of rapid solidification more further at low temperatures, the episulfide compounds that the present invention relates to preferably has the structure that following formula (1) or following formula (2) represent.
[chemical formula 31]
In above formula (1), R1 and R2 represents C respectively 1 ~ 5alkylidene group.
2 ~ 4 groups in these 4 groups of R3, R4, R5 and R6 are hydrogen.
Group not for hydrogen in R3, R4, R5 and R6 is the group that following formula (4) represents.
[chemical formula 32]
In above formula (2), R51 and R52 represents C respectively 1 ~ 5alkylidene group,
4 ~ 6 groups in these 6 groups of R53, R54, R55, R56, R57 and R58 are hydrogen,
Group not for hydrogen in R53, R54, R55, R56, R57 and R58 is the group that above formula (5) represents.
There is the episulfide compounds of the structure that above formula (1-1), (2-1) or (3) and above formula (1) or (2) represent, all at least containing 2 epithio bases.In addition, there is the group bonding of epithio base on phenyl ring, naphthalene nucleus or anthracene nucleus.Owing to having said structure, by the mixture heating of such as solidifying agent will be with the addition of in episulfide compounds, mixture rapid solidification can be made at low temperatures.
There is above formula (1-1), the episulfide compounds of structure that (2-1) or (3) represents, with the Compound Phase ratio that the epithio base in above formula (1-1), (2-1) or (3) is epoxy group(ing), reactive behavior is high.With the Compound Phase ratio that the epithio base in above formula (1) or (2) is epoxy group(ing), the episulfide compounds reactive behavior with the structure that above formula (1) or (2) represent is high.This is because the open loop easier than epoxy group(ing) of epithio base, therefore reactive behavior is high.There is above formula (1-1), the episulfide compounds of structure that (2-1) or (3) represents and to have the episulfide compounds reactive behavior of the structure that above formula (1) or (2) represent high, therefore can rapid solidification at low temperatures.
R59 in R51 and R52, R101 and R102 in above formula (3) in R1 and R2 in above formula (1-1) and (1), above formula (2-1) and (2), the R7 in above formula (4), above formula (5) and the R111 in above formula (6) is C 1 ~ 5alkylidene group.When the carbonatoms of this alkylidene group is more than 5, the curing speed of above-mentioned episulfide compounds easily reduces.
R59 in R51 and R52, R101 and R102 in above formula (3) in R1 and R2 in above formula (1-1) and (1), above formula (2-1) and (2), the R7 in above formula (4), above formula (5) and the R111 preferred C respectively in above formula (6) 1 ~ 3alkylidene group, more preferably methylene radical.Above-mentioned alkylidene group can be the alkylidene group with linear chain structure, also can be the alkylidene group with branched structure.
The structure that the structure optimization following formula (1A) that above-mentioned (1) represents represents.The episulfide compounds solidified nature with the structure that following formula (1A) represents is excellent.
[chemical formula 33]
In above formula (1A), R1 and R2 represents C respectively 1 ~ 5alkylidene group.
The structure that above formula (1) represents is the structure that represents of following formula (1B) more preferably.Have the episulfide compounds of the structure that following formula (1B) represents, solidified nature is more excellent.
[chemical formula 34]
The structure that the structure optimization following formula (2A) that above-mentioned (2) represent represents.Have the episulfide compounds of the structure that following formula (2A) represents, solidified nature is excellent.
[chemical formula 35]
In above formula (2A), R51 and R52 represents C respectively 1 ~ 5alkylidene group.
The structure that above formula (2) represents is the structure that represents of following formula (2B) more preferably.Have the episulfide compounds of the structure that following formula (2B) represents, solidified nature is more excellent.
[chemical formula 36]
The structure that the structure optimization following formula (3A) that above-mentioned (3) represent represents.Have the episulfide compounds of the structure that following formula (3A) represents, solidified nature is excellent.
[chemical formula 37]
In above formula (3A), R101 and R102 represents C respectively 1 ~ 5alkylidene group.
The structure that above formula (3) represents is the structure that represents of following formula (3B) more preferably.Have the episulfide compounds of the structure that following formula (3B) represents, solidified nature is more excellent.
[chemical formula 38]
(mixture containing episulfide compounds)
The epoxy compounds represented containing the episulfide compounds that mixture contains above formula (1-1), (2-1) or (3) represents of episulfide compounds and following formula (11-1), (12-1) or (13) that the present invention relates to.In following formula (11-1), be not particularly limited with the bonding position of these 6 groups of phenyl ring bonding.In following formula (12-1), be not particularly limited with the bonding position of 8 groups of naphthalene nucleus bonding.
[chemical formula 39]
In above formula (11-1), R11 and R12 represents C respectively 1 ~ 5alkylidene group.
2 ~ 4 groups in these 4 groups of R13, R14, R15 and R16 are hydrogen.
Group not for hydrogen in R13, R14, R15 and R16 is the group that following formula (14) represents.
These 4 groups of R13, R14, R15 and R16 can be all hydrogen.
1 in these 4 groups of R13, R14, R15 and R16 or 2 groups are the group that following formula (14) represents, and the group that in these 4 groups of R13, R14, R15 and R16, non-following formula (14) represents can be hydrogen.
[chemical formula 40]
In above formula (12-1), R61 and R62 represents C respectively 1 ~ 5alkylidene group.
4 ~ 6 groups in these 6 groups of R63, R64, R65, R66, R67 and R68 are hydrogen.
Group not for hydrogen in R63, R64, R65, R66, R67 and R68 is the group that following formula (15) represents.
These 6 groups of R63, R64, R65, R66, R67 and R68 can be all hydrogen.
1 in these 6 groups of R63, R64, R65, R66, R67 and R68 or 2 groups are the group that following formula (15) represents, further, the group that the non-following formula (15) in these 6 groups of R63, R64, R65, R66, R67 and R68 represents can be hydrogen.
[chemical formula 41]
In above formula (13), R121 and R122 represents C respectively 1 ~ 5alkylidene group,
6 ~ 8 groups in these 8 groups of R123, R124, R125, R126, R127, R128, R129 and R130 are hydrogen,
Group not for hydrogen in R123, R124, R125, R126, R127, R128, R129 and R130 is the group that following formula (16) represents,
These 8 groups of R123, R124, R125, R126, R127, R128, R129 and R130 can be all hydrogen,
1 in these 8 groups of R123, R124, R125, R126, R127, R128, R129 and R130 or 2 groups are the group that following formula (16) represents, further, the group that the non-following formula (16) in these 8 groups of R123, R124, R125, R126, R127, R128, R129 and R130 represents can be hydrogen.
[chemical formula 42]
In above formula (14), R17 represents C 1 ~ 5alkylidene group.
[chemical formula 43]
In above formula (15), R69 represents C 1 ~ 5alkylidene group.
[chemical formula 44]
In above formula (16), R131 represents C 1 ~ 5alkylidene group.
The viewpoint of more promptly solidifying from low temperature, the compound that the mixture containing episulfide compounds that the present invention relates to preferably represents containing above formula (1), above formula (2) or above formula (3) and the epoxy compounds that following formula (11), following formula (12) or above formula (13) represent.The viewpoint of more promptly solidifying further from low temperature, the epoxy compounds that the compound that the mixture containing episulfide compounds that the present invention relates to preferably represents containing above formula (1) or (2) and following formula (11) or (12) represent.
[chemical formula 45]
In above formula (11), R11 and R12 represents C respectively 1 ~ 5alkylidene group.
2 ~ 4 groups in these 4 groups of R13, R14, R15 and R16 are hydrogen,
Group not for hydrogen in R13, R14, R15 and R16 is the group that above formula (14) represents.
[chemical formula 46]
In above formula (12), R61 and R62 represents C respectively 1 ~ 5alkylidene group,
4 ~ 6 groups in these 6 groups of R63, R64, R65, R66, R67 and R68 are hydrogen,
Group not for hydrogen in R63, R64, R65, R66, R67 and R68 is the group that above formula (15) represents,
R69 in R61 and R62, R121 and R122 in above formula (13) in R11 and R12 in above formula (11-1) and (11), above formula (12-1) and (12), the R17 in above formula (14), above formula (15) and the R131 in above formula (16) is C 1 ~ 5alkylidene group.When the carbonatoms of this alkylidene group is more than 5, the curing speed of the above-mentioned mixture containing episulfide compounds easily reduces.
R69 in R61 and R62, R121 and R122 in above formula (13) in R11 and R12 in above formula (11-1) and (11), above formula (12-1) and (12), the R17 in above formula (14), above formula (15) and the preferred C of R131 in above formula (16) 1 ~ 3alkylidene group, more preferably methylene radical.Above-mentioned alkylidene group can be the alkylidene group with linear chain structure, also can be the alkylidene group with branched structure.
The structure that the structure optimization following formula (11A) that above-mentioned (11) represent represents.The epoxy compounds of the structure represented containing following formula (11A) has commercially available product, easily obtains.
[chemical formula 47]
In above formula (11A), R11 and R12 represents C respectively 1 ~ 5alkylidene group.
The structure that above formula (11) represents is the structure that represents of following formula (11B) more preferably.The epoxy compounds with the structure that following formula (11B) represents is resorcinol diglycidyl ether.Resorcinol diglycidyl ether has commercially available product, easily obtains.
[chemical formula 48]
The structure that the structure optimization following formula (12A) that above-mentioned (12) represent represents.The epoxy compounds with the structure that following formula (12A) represents easily obtains.
[chemical formula 49]
In above formula (12A), R61 and R62 represents C respectively 1 ~ 5alkylidene group.
The structure that above formula (12) represents is the structure that represents of following formula (12B) more preferably.The epoxy compounds with the structure that following formula (12B) represents easily obtains.
[chemical formula 50]
The structure that the structure optimization following formula (13A) that above-mentioned (13) represent represents.The epoxy compounds with the structure that following formula (13A) represents easily obtains.
[chemical formula 51]
In above formula (13A), R101 and R102 represents C respectively 1 ~ 5alkylidene group.
The structure that above formula (13) represents is the structure that represents of following formula (13B) more preferably.The epoxy compounds of the structure represented containing following formula (13B) easily obtains.
[chemical formula 52]
The mixture containing episulfide compounds that the present invention relates to, preferably containing 10 ~ 99.9 % by weight there is above formula (1-1), the episulfide compounds of structure that (2-1) or (3) represents, and containing 90 ~ 0.01 % by weight the epoxy compounds that represents of above formula (11-1), (12-1) or (13).The mixture containing episulfide compounds that the present invention relates to, more preferably containing 80 ~ 99.9 % by weight there is above formula (1-1), the episulfide compounds of structure that (2-1) or (3) represents, and containing 0.1 ~ 20 % by weight the epoxy compounds that represents of above formula (11-1), (12-1) or (13).
The mixture containing episulfide compounds that the present invention relates to preferably containing 10 ~ 99.9 % by weight the episulfide compounds with the structure that above formula (1) or (2) represent, and containing 90 ~ 0.1 % by weight above formula (11) or (12) epoxy compounds of representing.The mixture containing episulfide compounds that the present invention relates to more preferably containing 80 ~ 99.9 % by weight the episulfide compounds with the structure that above formula (1) or (2) represent, and containing the epoxy compounds that 0.1 ~ 20 % by weight above formula (11) or (12) represent.
If there is above formula (1-1), the episulfide compounds of structure that (2-1) or (3) represents and have the content of episulfide compounds of the structure that above formula (1) or (2) represent very few time, then the curing speed of the mixture containing episulfide compounds can not reach rapid enough sometimes.If there is above formula (11-1), the content of the episulfide compounds of structure that (12-1) or (13) represents and the episulfide compounds with the structure that above formula (1) or (2) represent be too much, the viscosity of the mixture then containing episulfide compounds becomes too high sometimes, and the mixture containing episulfide compounds becomes solid sometimes.
(manufacture method of the manufacture method of episulfide compounds and the mixture containing episulfide compounds)
The manufacture method of above-mentioned episulfide compounds and the manufacture method of the above-mentioned mixture containing episulfide compounds, be not particularly limited.As described manufacture method, can be listed below: prepare above formula (11-1), (12-1), (13), or the epoxy compounds that above formula (11), (12) represent, all or part of epoxy group(ing) of this epoxy compounds is changed into the manufacture method of epithio base.
The preferred following method of manufacture method of the manufacture method of above-mentioned episulfide compounds and the above-mentioned mixture containing episulfide compounds: to containing in the 1st solution of thiocyanate-, add above-mentioned formula (11-1), (12-1) or the epoxy compounds represented by (13) continuously or discontinuously or contain this epoxy compounds solution, then, more continuously or discontinuously add the 2nd solution containing thiocyanate-.According to the method described above, all or part of epoxy group(ing) of above-mentioned epoxy compounds can change epithio base into.Solution containing above-mentioned epoxy compounds or this epoxy compounds, the epoxy compounds that preferred above formula (1) or (2) represent or the solution containing this epoxy compounds.
After changing whole epoxy group(ing) into epithio base, the episulfide compounds of the structure that result can obtain having above formula (1-1), (2-1) or (3) represents.Further, the episulfide compounds of the structure that above formula (1) or (2) represent can be obtained having.A part is after epoxy group(ing) changes epithio base into, the mixture containing episulfide compounds of the epoxy compounds that the episulfide compounds of the structure that result can obtain containing possessing above formula (1-1), (2-1) or (3) represents and above formula (11-1), (12-1) or (13) represent.Further, can obtain the mixture containing episulfide compounds, this mixture contains the epoxy compounds that the episulfide compounds of the structure that above formula (1) or (2) represent and above formula (11) or (12) represent.
Specifically, above-mentioned episulfide compounds and the above-mentioned mixture containing episulfide compounds can according to following manufactures.
To in the container being equipped with stirrer, cooler and thermometer, add solvent, water and thiocyanate-, thiocyanate-is dissolved, in container, prepare the 1st solution.As solvent, methyl alcohol or ethanol etc. can be enumerated.As thiocyanate-, ammonium thiocyanate, potassium sulfocyanate or Sodium Thiocyanate 99 etc. can be enumerated.
The concentration of thiocyanate-in 1st solution, preferably in the scope of 0.001 ~ 0.2g/mL, more preferably in the scope of 0.005 ~ 0.1g/mL.The excessive concentration of thiocyanate-, then epoxy compounds is polymerized sometimes.The concentration of thiocyanate-is too low, then epoxy group(ing) can not change epithio base into sometimes.
Further, so-called above-mentioned 1st solution, prepares to have above formula (11-1), the epoxy compounds of structure that (12-1), (13), (11) or (12) represent or the solution containing this epoxy compounds in addition.
Then, add continuously or discontinuously in the 1st solution there is above formula (11-1), the epoxy compounds of structure that (12-1), (13), (11) or (12) represent or the solution containing this epoxy compounds.In this case, the temperature of the 1st solution is preferably in the scope of 15 ~ 30 DEG C.After adding above-mentioned epoxy compounds, preferably stir 0.5 ~ 12 hour.Also can multistep be divided to add above-mentioned epoxy compounds or the solution containing this epoxy compounds.Such as, add a part of above-mentioned epoxy compounds or containing after the solution of this epoxy compounds, at least stir 0.5 hour, then, then adding remaining above-mentioned epoxy compounds or the solution containing this epoxy compounds, stir 0.5 ~ 12 hour.When using the solution containing above-mentioned epoxy compounds, the concentration of this solution in ethylene compound is not particularly limited.
The interpolation speed of above-mentioned epoxy compounds or the solution containing this epoxy compounds is added preferably in the scope that 1 ~ 10mL/ divides, more preferably in the scope that 2 ~ 8mL/ divides in the 1st solution.The interpolation excessive velocities of above-mentioned epoxy compounds or the solution containing this epoxy compounds, then epoxy compounds is polymerized sometimes.The interpolation speed of above-mentioned epoxy compounds or the solution containing this epoxy compounds is excessively slow, then the formation efficiency of episulfide compounds reduces sometimes.
In above-mentioned 1st solution, add above-mentioned epoxy compounds or containing the solution of this epoxy compounds, in the mixed solution obtained, the concentration of above-mentioned epoxy compounds preferably in the scope of 0.05 ~ 0.8g/mL, more preferably in the scope of 0.1 ~ 0.5g/mL.The excessive concentration of epoxy compounds, then epoxy compounds is polymerized sometimes.
Then, with the addition of in the mixed solution of above-mentioned epoxy compounds or the solution containing this epoxy compounds in above-mentioned 1st solution, continuous or interruption adds the 2nd solution containing solvent, water and thiocyanate-further.After adding above-mentioned 2nd solution, preferably stir 0.5 ~ 12 hour.In addition, after adding above-mentioned 2nd solution, preferably stir in the scope of 15 ~ 60 DEG C.Can multistep be divided to add above-mentioned 2nd solution.Such as, after adding above-mentioned 2nd solution of a part, at least stir 0.5 hour, then, then add remaining above-mentioned 2nd solution, 0.5 ~ 12 hour can be stirred.
In above-mentioned 2nd solution, the concentration of thiocyanate-is preferably in the scope of 0.001 ~ 0.7g/mL, more preferably in the scope of 0.005 ~ 0.5g/mL.The excessive concentration of thiocyanate-, then epoxy compounds is polymerized sometimes.The concentration of thiocyanate-is too low, then epoxy group(ing) can not change epithio base into sometimes.
The speed of above-mentioned 2nd solution is added preferably in the scope that 1 ~ 10mL/ divides, more preferably in the scope that 2 ~ 8mL/ divides in above-mentioned mixed solution.The interpolation excessive velocities of above-mentioned 2nd solution, then epoxy compounds is polymerized sometimes.The interpolation speed of above-mentioned 2nd solution is excessively slow, then the formation efficiency of episulfide compounds reduces sometimes.
Preferably, in the 1st solution, add above-mentioned epoxy compounds, then in the mixed solution obtained, add above-mentioned 2nd solution, then except anhydrating, solvent or unreacted thiocyanate-.As except anhydrating, the method for solvent or unreacted thiocyanate-, use existing known method.
1st solution or the 2nd solution, can containing catalyzer such as metallic palladium particle, titanium oxide.By using containing the solution of above-mentioned catalyzer, can the transformation efficiency of adjustment ring sulfenyl.In addition, epoxy group(ing) can be changed into epithio base at low ambient temperatures, therefore can suppress the polyreaction of epoxy compounds.The concentration of catalyzer in above-mentioned 1st solution, or in above-mentioned 2nd solution the concentration of catalyzer preferably in the scope of 0.05 ~ 1.0g/mL.
According to above-mentioned, can all or part of epoxy group(ing) of above-mentioned epoxy compounds be changed into epithio base.Result can obtain episulfide compounds or the mixture containing episulfide compounds.Specifically, such as, can obtain containing 100 % by weight there is above formula (1-1), the episulfide compounds of the episulfide compounds of structure that (2-1), (3), (1) or (2) represent.Further, such as, the mixture containing episulfide compounds can be obtained, this mixture contain 10 ~ 99.9 % by weight or 10 ~ 50 % by weight there is above formula (1-1), the episulfide compounds of structure that (2-1), (3), (1) or (2) represent and containing 90 ~ 0.1 % by weight or 90 ~ 50 % by weight there is above formula (11-1), epoxy compounds that (12-1), (13), (11) or (12) represent.
(solidification compound)
The solidification compound that the present invention relates to, containing episulfide compounds of the present invention and solidifying agent.In addition, the solidification compound that the present invention relates to contains the mixture and the solidifying agent that contain episulfide compounds of the present invention.That is, the solidification compound that the present invention relates to contains episulfide compounds of the present invention or contains mixture and the solidifying agent of episulfide compounds.Solidifying agent can only use a kind, also can two or more combinationally use.
The solidification compound that the present invention relates to is at least containing a kind of above-mentioned episulfide compounds.Or the solidification compound that the present invention relates to is at least containing a kind of above-mentioned mixture containing episulfide compounds.Or the solidification compound that the present invention relates to is at least containing a kind of above-mentioned episulfide compounds and the above-mentioned mixture containing episulfide compounds of at least one.Therefore, as curable resin, above-mentioned episulfide compounds of more than two kinds can be combinationally used, also can combinationally use the above-mentioned mixture containing episulfide compounds of more than two kinds, also can combinationally use above-mentioned episulfide compounds and the above-mentioned mixture containing episulfide compounds.
Above-mentioned solidifying agent is not particularly limited.As above-mentioned solidifying agent, imidazole curing agent, amine hardener, phenol cured agent, Polymercaptan curing agent or acid anhydrides etc. can be enumerated.Wherein, because solidification compound can more promptly solidify at low temperatures, therefore preferred imidazole curing agent, Polymercaptan curing agent or amine hardener.In addition, when above-mentioned episulfide compounds or the above-mentioned mixture containing episulfide compounds being mixed with above-mentioned solidifying agent, storage stability can be improved, therefore preferred latent curing agent.The preferred latent imidazole curing agent of latent curing agent, latent Polymercaptan curing agent or latent amine hardener.Above-mentioned solidifying agent can only use a kind, also can two or more combinationally use.It should be noted that, above-mentioned solidifying agent, can be coated by the polymer substance such as urethane resin or vibrin.
As above-mentioned imidazole curing agent, be not particularly limited, can enumerate, such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine or 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine cyamelide affixture etc.
As above-mentioned polythiol solidifying agent, be not particularly limited, can enumerate, such as trimethylolpropane tris-3-mercaptopropionic acid ester, tetramethylolmethane four-3-mercaptopropionic acid ester or dipentaerythritol six-3-mercaptopropionic acid ester etc.
As above-mentioned amine hardener, be not particularly limited, can enumerate, such as 1,6-hexanediamine, 1,8-octamethylenediamine, 1,10-decamethylene diamine, 3,9-bis-(3-aminopropyls) 2,4,8,10-tetra-oxaspiro [5.5] undecane, two (4-aminocyclohexyl) methane, mphenylenediamine or diamino diphenyl sulfone etc.
In above-mentioned solidifying agent, preferably use multi-thioalcohol compound or acid anhydrides etc.Due to the curing speed of solidification compound can be improved further, therefore more preferably use multi-thioalcohol compound.
In above-mentioned multi-thioalcohol compound, more preferably tetramethylolmethane four-3-mercaptopropionic acid ester.By using this multi-thioalcohol compound, the curing speed of solidification compound can be improved further.
The content of above-mentioned solidifying agent, is not particularly limited.Relative to the above-mentioned episulfide compounds of 100 weight parts or the above-mentioned mixture containing episulfide compounds ((when containing above-mentioned epoxy compounds, represent the above-mentioned episulfide compounds of 100 weight parts, when containing above-mentioned epoxy compounds, represent the above-mentioned mixture containing episulfide compounds of 100 weight parts), the content of above-mentioned solidifying agent is preferably in the scope of 1 ~ 40 weight part.If above-mentioned solidifying agent containing quantity not sufficient 1 weight part, then solidification compound can not fully solidify.If the content of above-mentioned solidifying agent is more than 40 weight parts, then in solidification compound, the thermotolerance of cured article reduces.Relative to above-mentioned episulfide compounds or the above-mentioned mixture containing episulfide compounds of 100 weight parts, the preferred lower limit of content of above-mentioned solidifying agent is 30 weight parts, preferred lower limit is 45 weight parts further, and the preferred upper limit is 100 weight parts, and the preferred upper limit is 75 weight parts further.If the content of solidifying agent is very few, then solidification compound becomes and is difficult to abundant solidification.If the content of solidifying agent is too much, then after solidification, the remaining residue solidifying agent having neither part nor lot in solidification sometimes.
It should be noted that, above-mentioned solidifying agent be imidazole curing agent or phenol cured agent when, relative to above-mentioned episulfide compounds or the above-mentioned mixture containing episulfide compounds of 100 weight parts, the content of imidazole curing agent or phenol cured agent is preferably in the scope of 1 ~ 15 weight part.In addition, when above-mentioned solidifying agent is amine hardener, polythiol solidifying agent or acid anhydrides, relative to above-mentioned episulfide compounds or the above-mentioned mixture containing episulfide compounds of 100 weight parts, the content of amine hardener, polythiol solidifying agent or acid anhydrides is preferably in the scope of 15 ~ 40 weight parts.
The solidification compound that the present invention relates to is preferably further containing storage-stable agent.The solidification compound that the present invention relates to, preferably further containing at least one be selected from phosphoric acid ester, phosphorous acid ester and boric acid ester as above-mentioned storage-stable agent, more preferably containing phosphorous acid ester.By using phosphorous acid ester, the storage-stable agent of above-mentioned episulfide compounds or the mixture containing episulfide compounds can be improved further.Above-mentioned storage-stable agent can only use a kind, also can two or more combinationally use.
As above-mentioned phosphoric acid ester, can be listed below, such as phosphoric acid benzyl diethyl ester, trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate n-butyl, tricresyl phosphate (butoxyethyl group) ester, tri-2-ethylhexyl phosphate, (RO) 3p=O [R=dodecyl, hexadecyl, hard ester group or oleyl], tricresyl phosphate (2-chloroethyl) ester, tricresyl phosphate (2-bis-chloropropyl) ester, triphenylphosphate, tetra-sodium butyl ester, tritolyl phosphate, tricresyl phosphate (xylyl) ester, octyl diphenyl phosphate, diphenyl phosphate cresols ester, xylyl bisphosphate, monobutyl phosphate, dibutyl phosphate, di(2-ethylhexyl)phosphate (2-ethylhexyl) ester, mono phosphoric acid ester isodecyl ester, ammonium acid phosphate ethyl ester and acid phosphatase 2-(ethylhexyl) ester salt etc.Wherein preferably use di(2-ethylhexyl)phosphate ethyl benzyl ester.
As above-mentioned phosphorous acid ester, can be listed below, such as trimethyl phosphite, triethyl-phosphite, tri-n-butylphosphite, tricresyl phosphite (2-ethylhexyl) ester, the different monooctyl ester of tricresyl phosphite, tridecyl phosphite, triisodecyl phosphite ester, tricresyl phosphite (tridecyl) ester, tricresyl phosphite oleyl ester (Trioleylphosphite), tricresyl phosphite (octadecyl) ester, triphenyl phosphite, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, Phosphorous acid diisooctyl phenyl ester, phenyl two isodecyl ester, phosphorous acid list (2-ethylhexyl) diphenyl ester, the different monooctyl ester of phosphorous acid phenylbenzene, phosphorous acid phenylbenzene list ester in the last of the ten Heavenly stems, phosphorous acid phenylbenzene list isodecyl ester, phosphorous acid phenylbenzene list (tridecyl) ester, two (nonyl phenyl) dinonylphenyl phosphorous acid ester, tetraphenyl dipropyleneglycol, poly-(dipropylene glycol) phenyl phosphites, diiso decyl pentaerythritol diphosphites, two (tridecyl) pentaerythritol diphosphites, two hard ester acyl pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, tetraphenyl four (tridecyl) tetramethylolmethane four phosphorous acid ester, four (tridecyl)-4,4 '-isopropylidene diphenylphosphite, three (dodecyl) trithiophosphite, hydrogen phosphite dimethyl ester, hydrogen phosphite dibutylester, hydrogen phosphite two (2-ethylhexyl) ester, hydrogen phosphite two (dodecyl) ester, hydrogen phosphite two oleyl ester, hydrogen phosphite diphenyl ester, phenylbenzene list (2-ethylhexyl) phosphorous acid ester, phenylbenzene list decyl phosphorous acid ester and phenylbenzene list (three decyls) phosphorous acid ester etc.Wherein, preferred phenylbenzene list (2-ethylhexyl) phosphorous acid ester, phenylbenzene list decyl phosphorous acid ester or phenylbenzene list (tridecyl) phosphorous acid ester, more preferably phenylbenzene list decyl phosphorous acid ester or phenylbenzene list (tridecyl) phosphorous acid ester, further preferred phenylbenzene list (tridecyl) phosphorous acid ester.
As above-mentioned boric acid ester, can be listed below, such as trimethyl borate, triethyl borate, boric acid three n-propyl, triisopropyl borate ester, tri-n-butyl borate, triamyl borate, boric acid triallyl, the own ester of boric acid three, tricyclohexyl borate, boric acid trioctylphosphine ester, boric acid three nonyl ester, boric acid three decyl ester, boric acid three (dodecyl) ester, boric acid three (hexadecyl) ester, boric acid three (octadecyl) ester, boric acid tribenzyl ester, boric acid triphenyl ester, boric acid tri-o-tolyl ester, boric acid three tolyl esters, triethanolamine borate, three (2-ethyl hexyl oxy) borine, two (Isosorbide-5-Nitrae, 7,10-tetra-oxaundecyl) (Isosorbide-5-Nitrae, 7,10,13-five oxa-tetradecyl) (Isosorbide-5-Nitrae, 7-trioxaundecane base) borine, 2-(the amino isopropoxy of beta-dimethyl-)-4,5-dimethyl-1,3,2-dioxa hexamethylene borines, 2-(β-diethyl amino base oxethyl)-4,4,6-trimethylammonium-1,3,2-dioxa hexamethylene borine, 2-(beta-dimethyl-amino ethoxy)-4,4,6-trimethylammonium-1,3,2-dioxa hexamethylene borine, 2-(β-diisopropylaminoethyl oxyethyl group)-1,3,2-dioxa hexamethylene borine, 2-(β-diisopropylaminoethyl oxyethyl group)-4-methyl isophthalic acid, 3,2-dioxa hexamethylene borine, 2-(γ-dimethylamino propoxy)-1,3,6,9-tetra-oxa--2-boron heterocycle undecane, 2-(beta-dimethyl-amino ethoxy)-4,4-(4-hydroxybutyl)-1,3,2-dioxa hexamethylene borine, 2,2-oxo two (5,5-dimethyl-1,3,2-dioxa hexamethylene borine) and epoxy-phenol-boric acid ester title complex etc.
Relative to above-mentioned episulfide compounds or the above-mentioned mixture containing episulfide compounds of 100 weight parts, the content of above-mentioned storage-stable agent is preferably in the scope of 0.001 ~ 0.1 weight part.Relative to above-mentioned episulfide compounds or the above-mentioned mixture containing episulfide compounds of 100 weight parts, the preferred lower limit of content of above-mentioned storage-stable agent is 0.005 weight part, and the preferred upper limit is 0.05 weight part.The content of storage-stable agent, particularly phosphorous acid ester, in above-mentioned scope, can improve the storage stability of above-mentioned episulfide compounds or the above-mentioned mixture containing episulfide compounds further.
The solidification compound that the present invention relates to is preferably further containing curing catalyst.By using curing catalyst, the curing speed of solidification compound can be accelerated further.Curing catalyst, can only use a kind, also can two or more combinationally use.
As the object lesson of above-mentioned curing catalyst, imidazoles curing catalyst or amine curing catalyst etc. can be enumerated.Wherein, preferred imidazoles curing catalyst.It should be noted that, imidazoles curing catalyst or amine curing catalyst also can be used as imidazole curing agent or amine hardener.
As above-mentioned imidazoles curing catalyst, can be listed below, such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine or 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine cyamelide affixture etc.
Above-mentioned episulfide compounds relative to 100 weight parts or the mixture containing above-mentioned episulfide compounds, the preferred lower limit of content of above-mentioned curing catalyst is 0.5 weight part, preferred lower limit is 1 weight part, and the preferred upper limit is 6 weight parts, and the preferred upper limit is 4 weight parts.The content of curing catalyst is very few, then solidification compound becomes and is difficult to abundant solidification.If the content of solidifying agent is too much, then after solidification, can the remaining residue curing catalyst having neither part nor lot in reaction.
The solidification compound that the present invention relates to, preferably further containing filler.By using filler, the latent heat of cured article in solidification compound can be suppressed to expand.Filler can only use a kind, also can two or more combinationally use.
As the object lesson of above-mentioned filler, silicon-dioxide, aluminium nitride or aluminum oxide etc. can be enumerated.Above-mentioned filler preferred filler particle.The median size of filler grain, preferably in the scope of 0.1 ~ 1.0 μm.If the median size of filler grain is in above-mentioned scope, the latent heat of cured article in solidification compound can be suppressed further to expand.Described " median size ", refers to the volume average particle size by Dynamic Laser Scattering Method.
Above-mentioned episulfide compounds relative to 100 weight parts or the mixture containing above-mentioned episulfide compounds, the content of above-mentioned filler is preferably in the scope of 50 ~ 900 weight parts.If the content of filler is in above-mentioned scope, the latent heat of cured article in solidification compound can be suppressed further to expand.
As required, the solidification compound that the present invention relates to can also contain solvent, ion trap agent or silane coupling agent further.
Above-mentioned solvent, is not particularly limited.As above-mentioned solvent, can be listed below, such as ethyl acetate, methylcyclohexane, toluene, acetone, methylethylketone, hexanaphthene, normal hexane, tetrahydrofuran (THF) or ether etc.Solvent can only use a kind, also can two or more combinationally use.
Above-mentioned silane coupling agent, is not particularly limited.As above-mentioned silane coupling agent, can be listed below, such as N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-APTES, 3-dimethyl Ethoxysilane, 3-amino propyl methyl diethoxy silane, 3-TSL 8330, APTES, vinyltriethoxysilane, vinyltrimethoxy silane, vinyltriacetoxy silane, vinyl trichloro silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl group triethoxyl silane, 3-mercaptopropyi Trimethoxy silane, 3-mercaptopropyi methyl dimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, ethyl trimethoxy silane, propyl trimethoxy silicane, propyl-triethoxysilicane, dodecyl triethoxysilane, hexyl Trimethoxy silane, isobutyl-diethoxy silane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxysilane or imidizole silane etc.Wherein, preferred imidizole silane.Silane coupling agent can only use a kind, also can two or more combinationally use.
Above-mentioned ion trap agent is not particularly limited.As the object lesson of above-mentioned ion trap agent, aluminosilicate, hydrous titanium oxide, aqua oxidation bismuth, zirconium phosphate, titanium phosphate, hydrotalcite, ammonium phosphomolybdate, six cyanogen conjunction zinc or ion exchange resin etc. can be enumerated.Ion trap agent can only use a kind, also can two or more combinationally use.
The solidification compound that the present invention relates to, in order to be solidified by rayed, can contain photocurable compound and Photoepolymerizationinitiater initiater further.By using above-mentioned photocurable compound and above-mentioned Photoepolymerizationinitiater initiater, can rayed be passed through, solidification compound is solidified.In addition, make solidification compound semicure, the mobility of solidification compound can be reduced.
Above-mentioned photocurable compound is not particularly limited.As this photocurable compound, preferably use (methyl) acrylic resin or the resin etc. containing cyclic ethers base.Above-mentioned (methyl) acrylic resin, refers to methacrylic resin and acrylic resin.
As above-mentioned (methyl) acrylic resin, urethane (methyl) acrylate etc. that epoxy (methyl) acrylate that the ester compound, (methyl) vinylformic acid and the epoxy compounds that preferably use (methyl) vinylformic acid and the compound with hydroxyl to be obtained by reacting are obtained by reacting or isocyanic ester and (methyl) acrylic acid derivative with hydroxyl are obtained by reacting.
The ester compound that above-mentioned (methyl) vinylformic acid and the compound with hydroxyl are obtained by reacting, is not particularly limited.As this ester compound, can use the ester compound of simple function, 2 officials can ester compound and 3 officials can any one in ester compound above.
Above-mentioned photocurable compound, preferably containing photocurable compound and the Thermocurable compound (hereinafter also referred to as part (methyl) acrylated epoxy resins) with at least one epoxy group(ing) and (methyl) acrylic.
Above-mentioned part (methyl) acrylated epoxy resins such as can conventionally, under basic catalyst exists, make epoxy resin and (methyl) vinylformic acid be obtained by reacting.Preferably the epoxy group(ing) of more than 20% is converted into (methyl) acryl (transformation efficiency), generating portion (methyl) acrylated.More preferably the epoxy group(ing) of 50% is converted into (methyl) acryl.Above-mentioned (methyl) acryl, refers to acryl and methacryloyl.
From the viewpoint of the solidified nature of raising solidification compound, in the above-mentioned solidified nature compound of 100 % by weight, the preferred lower limit of content of above-mentioned part (methyl) acrylated epoxy resins is 0.1 % by weight, preferred lower limit is 0.5 % by weight, and the preferred upper limit is 2 % by weight, the preferred upper limit is 1.5 weight.
As above-mentioned epoxy (methyl) acrylate, can be listed below, such as biphenol type epoxy (methyl) acrylate, cresol novolak type epoxy (methyl) acrylate, carboxylic acid anhydride modified epoxy (methyl) acrylate and phenol novolak-type epoxy (methyl) acrylate etc.
In order to the epoxy compounds that obtained above-mentioned epoxy (methyl) acrylate uses, and as the commercially available product of this epoxy compounds, can be listed below, such as: the bisphenol A type epoxy resins such as Epikote828EL and Epikote1004 (being JapanEpoxyResins company to manufacture), the bisphenol f type epoxy resins such as Epikote806 and Epikote4004 (being JapanEpoxyResins company to manufacture), the bisphenol-s epoxy resins such as EpiclonEXA1514 (manufacture of DIC company), RE-810NM (Japanese chemical drug Inc. makes) etc. 2, 2 '-diallyl bisphenol type epoxy resin, the A Hydrogenated Bisphenol A type epoxy resin such as EpiclonEXA7015 (manufacture of DIC company), the propylene oxide addition bisphenol A type epoxy resins such as EP-4000S (manufacture of ADEKA company), the Resorcinol type epoxy resin such as EX-201 (manufacture of NagaseChemteX company), the biphenyl type epoxy resins such as EpikoteYX-4000H (manufacture of JapanEpoxyResins company), the thioether-type epoxy resin such as YSLV-50TE (Dongdu changes into company and manufactures), the ether type epoxies such as YSLV-80DE (Dongdu changes into company and manufactures), the dicyclopentadiene-type epoxy resin such as EP-4088S (manufacture of ADEKA company), the naphthalene type epoxy resin such as EpiclonHP4032 and EpiclonEXA-4700 (being DIC company to manufacture), the phenol novolak type epoxy resin such as EpiclonN-770 (manufacture of DIC company), the o-cresol phenolic epoxy varnish such as EpiclonN-670-EXP-S (manufacture of DIC company), the Dicyclopentadiene (DCPD) type epoxy resins such as EpiclonHP7200 (manufacture of DIC company), the xenyl phenolic resin varnish type epoxy resins such as NC-3000P (Japanese chemical drug Inc. makes), the naphthalene phenol novolak type epoxy resin such as ESN-165S (Dongdu changes into company and manufactures), Epikote630 (manufacture of JapanEpoxyResins company), the glycidyl amine type epoxy resins such as Epiclon430 (manufacture of DIC company) and TETRAD-X (manufacture of MitsubishiGasChemical company), ZX-1542 (Dongdu changes into company and manufactures), Epiclon726 (manufacture of DIC company), alkyl many alcohol type epoxy resin such as Epolite80MFA (manufacture of chemical company of common prosperity society) and DenacolEX-611 (manufacture of NagaseChemteX company), YR-450, the modified rubber type epoxy resin such as YR-207 (be Dongdu and change into company's manufacture) and EpoleadPB (manufacture of DaicelChemical company), the Racemic glycidol ester compounds such as DenacolEX-147 (manufacture of NagaseChemteX company), the bisphenol A-type episulfide resins such as EpikoteYL-7000 (manufacture of JapanEpoxyResins company), YDC-1312, YSLV-80XY, YSLV-90CR (be Dongdu and change into company's manufacture), XAC4151 (Asahi Kasei Corporation's manufacture), Epikote1031, Epikote1032 (being JapanEpoxyResins company to manufacture), other epoxy resin etc. such as EXA-7120 (manufacture of DIC company) and TEPIC (manufacture of Nissan Chemical company).
As the commercially available product of above-mentioned epoxy (methyl) acrylate, can be listed below, such as, EBECRYL3700, EBECRYL3600, EBECRYL3701, EBECRYL3703, EBECRYL3200, EBECRYL3201, EBECRYL3600, EBECRYL3702, EBECRYL3412, EBECRYL860, EBECRYLRDX63182, EBECRYL6040 and EBECRYL3800 (being Daicel-UCB company to manufacture), EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD and EMA-1020 (being chemical industrial company of Xin Zhong village to manufacture), EpoxyEsterM-600A, EpoxyEster40EM, EpoxyEster70PA, EpoxyEster200PA, EpoxyEster80MFA, EpoxyEster3002M, EpoxyEster3002A, EpoxyEster1600A, EpoxyEster3000M, EpoxyEster3000A, EpoxyEster200EA and EpoxyEster400EA (being chemical company of common prosperity society to manufacture), DenacolAcrylateDA-141, DenacolAcrylateDA-314 and DenacolAcrylateDA-911 (being NagaseChemteX company to manufacture) etc.
When containing photocurable compound beyond above-mentioned photocurable compound, this photocurable compound can be cross-linked compound, also can be non-cross-linked compound.
As the object lesson of above-mentioned cross-linked compound, can be listed below, such as 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, 1, 9-nonanediol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, glycerol methacrylate acrylate, tetramethylolmethane three (methyl) acrylate, trimethylolpropane trimethacrylate, (methyl) allyl acrylate, (methyl) vinyl acrylate, Vinylstyrene, polyester (methyl) acrylate and urethane (methyl) acrylate etc.
As the object lesson of above-mentioned non-crosslinked compound, can be listed below: ethyl (methyl) acrylate, n-propyl (methyl) acrylate, sec.-propyl (methyl) acrylate, normal-butyl (methyl) acrylate, isobutyl-(methyl) acrylate, the tertiary butyl (methyl) acrylate, amyl group (methyl) acrylate, hexyl (methyl) acrylate, heptyl (methyl) acrylate, 2-ethylhexyl (methyl) acrylate, n-octyl (methyl) acrylate, iso-octyl (methyl) acrylate, nonyl (methyl) acrylate, decyl (methyl) acrylate, undecyl (methyl) acrylate, dodecyl (methyl) acrylate, tridecyl (methyl) acrylate, with tetradecyl (methyl) acrylate etc.
From the viewpoint making above-mentioned solidification compound photocuring effectively, above-mentioned episulfide compounds relative to 100 weight parts or the mixture containing episulfide compounds, the preferred lower limit of content of above-mentioned photocurable compound is 1 weight part, preferred lower limit is 10 weight parts, preferred lower limit is 50 weight parts further, the preferred upper limit is 10000 weight parts, and the preferred upper limit is 1000 weight parts, and the preferred upper limit is 500 weight parts further.
Above-mentioned Photoepolymerizationinitiater initiater, is not particularly limited.Above-mentioned Photoepolymerizationinitiater initiater can only use a kind, also can two or more combinationally use.
As the object lesson of above-mentioned Photoepolymerizationinitiater initiater, methyl phenyl ketone Photoepolymerizationinitiater initiater, benzophenone Photoepolymerizationinitiater initiater, thioxanthone, ketal Photoepolymerizationinitiater initiater, halogenation ketone, acylphosphine oxide or acylphosphate (acylphosphonate) etc. can be enumerated.
As the object lesson of above-mentioned methyl phenyl ketone Photoepolymerizationinitiater initiater, can be listed below: 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, methoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone or 2-hydroxyl-2-phenylcyclohexane ethyl ketone etc.The object lesson of above-mentioned ketal Photoepolymerizationinitiater initiater, can enumerate benzyl dimethyl ketal etc.
The content of above-mentioned Photoepolymerizationinitiater initiater is not particularly limited.Relative to the above-mentioned Photocurable composition of 100 weight parts, the preferred lower limit of content of above-mentioned Photoepolymerizationinitiater initiater is 0.1 weight part, and preferred lower limit is 0.2 weight part, and preferred lower limit is 2 weight parts further, the preferred upper limit is 10 weight parts, and the preferred upper limit is 5 weight parts.The content of Photoepolymerizationinitiater initiater is very few, then sometimes fully can not obtain the effect of adding Photoepolymerizationinitiater initiater.The content of Photoepolymerizationinitiater initiater is too much, then in solidification compound, the cohesive force of cured article reduces sometimes.
Curable resin composition, can contain above formula (11-1), other epoxy compoundss beyond epoxy compounds that (12-1), (13), (11) or (12) represent further.As this epoxy compounds, the epoxy compounds for the preparation of above-mentioned epoxy (methyl) acrylate can be used.
In the total amount 100 % by weight of episulfide compounds, above formula (11-1), (12-1), (13), epoxy compounds that (11) or (12) represent and other epoxy compoundss above-mentioned, the preferred lower limit of content of episulfide compounds is 10 % by weight, preferred lower limit is 25 % by weight, the preferred upper limit is 100 % by weight, and the preferred upper limit is 50 % by weight.
The solidification compound that the present invention relates to, as one-package adhesive, may be used for the bonding of liquid crystal board or semi-conductor chip etc.Solidification compound can be paste adhesive, also can be film adhesive.
The method that the solidification compound that the present invention relates to is processed as film adhesive is not particularly limited.Such as, solidification compound is coated on the body materials such as release paper, be processed as the method for film adhesive, or in solidification compound, add solvent, and be coated on after on the body materials such as release paper, at the temperature of the activation temperature lower than above-mentioned solidifying agent, make solvent evaporates, be processed as the method etc. of film adhesive.
As the method for the solidification compound solidification making the present invention relates to, can be listed below: the method for being heating and curing property composition, by carrying out illumination to solidification compound, the method heated the solidification compound after rayed again or by while carrying out illumination to solidification compound, to the method etc. that solidification compound heats.
Make the Heating temperature during solidification compound solidification that the present invention relates to preferably in the scope of 160 ~ 250 DEG C, more preferably in the scope of 160 ~ 200 DEG C.Due to solidification compound fast setting at low temperatures can be made, the energy needed when therefore can reduce heating.
If the above-mentioned Heating temperatures such as the solidification compound containing epoxy resin are in the past below 200 DEG C, set time is elongated, and such as, if Heating temperature is 200 DEG C, set time was more than 10 seconds.In contrast to this, the solidification compound that the present invention relates to, even if above-mentioned Heating temperature is below 200 DEG C, also can solidify at short notice.
The solidification compound that the present invention relates to is when photocuring, and the light source that solidification compound is used when rayed, is not particularly limited.As this light source, the light source etc. such as at below wavelength 420nm with sufficient luminescence distribution can be enumerated.As the object lesson of this light source, can be listed below: such as Cooper-Hewitt lamp, middle medium pressure mercury lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, chemical lamp, black lamp, microwave-excitation mercuryvapour lamp or metal halide lamp etc.Wherein preferred chemical lamp.Chemical lamp not only can the light of the activating wavelengths scope of utilizing emitted light polymerization starter efficiently, and within the scope of the light absorption wavelength of composition components beyond Photoepolymerizationinitiater initiater, luminous quantity is few.Further, when using chemical lamp, light can arrive the photocuring composition being present in composition inside effectively.
Such as, when containing when having the cracking type Photoepolymerizationinitiater initiater of phenacyl, the photo-irradiation intensity of 365nm ~ 420nm wavelength region is preferably at 0.1 ~ 100mW/cm 2scope in.
When the solidification compound that the present invention relates to is further containing electroconductive particle, solidification compound can be used as anisotropic conductive material.
Above-mentioned electroconductive particle is used for such as connecting carrying out conduction between circuit substrate and the electrode of semi-conductor chip.As long as above-mentioned electroconductive particle at least surface has the particle of electroconductibility, be not particularly limited.As above-mentioned electroconductive particle, can be listed below: such as organic filler, inorganic particulate, organic-inorganic stuff and other stuff or at the electroconductive particle of the Surface coating metal level of metallics etc. or the metallics etc. to be in fact only made up of metal.Above-mentioned metal level, is not particularly limited.As above-mentioned metal level, layer gold, silver layer, layers of copper, nickel dam, palladium layers or the metal level etc. containing tin can be enumerated.
The content of above-mentioned electroconductive particle is not particularly limited.Relative to the above-mentioned episulfide compounds of 100 weight part or the mixture containing above-mentioned episulfide compounds, the preferred lower limit of content of above-mentioned electroconductive particle is 0.1 weight part, preferred lower limit is 0.5 weight part, and the preferred upper limit is 10 weight parts, and the preferred upper limit is 5 weight parts.If the content of above-mentioned electroconductive particle is very few, then sometimes cannot realize being communicated with substantially between electrode etc.If the content of above-mentioned electroconductive particle is too much, then can be short-circuited between the adjacent electrode that should not be communicated with.
When solidification compound be liquid or pasty state when, the viscosity (25 DEG C) of solidification compound is preferably in the scope of 20000 ~ 100000mPas.If above-mentioned viscosity is too low, then electroconductive particle precipitates sometimes.If above-mentioned viscosity is too high, then electroconductive particle cannot fully disperse sometimes.
(purposes of solidification compound)
The solidification compound that the present invention relates to may be used for the bonding of various connecting object parts.
When the solidification compound that the present invention relates to is the anisotropic conductive material containing electroconductive particle, this anisotropic conductive material, can make anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive tacky adhesive, anisotropic conductive film or anisotropic conductive sheet etc.When anisotropic conductive material makes the use of the film adhesive such as anisotropic conductive film, anisotropic conductive sheet, containing in the film adhesive of this electroconductive particle, can the film adhesive of lamination containing electroconductive particle.
Above-mentioned anisotropic conductive material is preferred for the 1st, the 2nd connecting object parts being carried out conduction and connects, thus obtains connection structural bodies.
Fig. 1 is schematic cross sectional view, and it illustrates the connection structural bodies using solidification compound in one embodiment of the present invention.
Connection structural bodies shown in Fig. 1 has the 1st connecting object parts 2, the 2nd connecting object parts 4 and is connected the connection section 3 of the 1st, the 2nd connecting object parts 2 and 4.Connection section 3 is the solidification compounds containing electroconductive particle 5, that is, by making anisotropic conductive material solidify to form.
The upper surface 2a of the 1st connecting object parts 2 has multiple electrode 2b.The lower surface 4a of the 2nd connecting object parts 4 has multiple electrode 4b.Electrode 2b carries out conduction with electrode 4b by one or more electroconductive particle 5 and is connected.Therefore, the 1st, the 2nd connecting object parts 2 and 4 carry out conduction by electroconductive particle 5 and are connected.
As above-mentioned connection structural bodies, specifically, the connection structural bodies that can be listed below: load the electronic unit chips such as semi-conductor chip, capacitor chip or diode chip for backlight unit on circuit substrate, the electrode of this electronic unit chip is connected with the electrodes conduct on circuit substrate.As circuit substrate, can be listed below: the various printed circuit board (PCB) such as flexible print wiring board, glass substrate or lamination have the various circuit substrates such as the substrate of tinsel.1st, the 2nd connecting object parts preferred electron parts or circuit substrate.
The manufacture method of above-mentioned connection structural bodies is not particularly limited.As an example of the manufacture method of connection structural bodies, following methods can be enumerated: at the 1st connecting object parts and electronic unit or the circuit substrate etc. the 2nd between connecting object parts such as electronic unit or circuit substrate, configure above-mentioned anisotropic conductive material, obtain multilayer body, then by the heating of this multilayer body and pressurization.
It should be noted that, above-mentioned solidification compound can not contain electroconductive particle.In this case, the 1st, the 2nd connecting object parts do not conduct electricity connection, but in order to be connected by the 1st, the 2nd connecting object parts bonding, use above-mentioned solidification compound.
Hereafter by embodiment and comparative example, specifically will set forth the present invention.The present invention is not limited to following examples.
(embodiment 1)
(1) mixture of preparation containing episulfide compounds
To in the container of 2L being equipped with stirrer, water cooler and thermometer, add ethanol 250mL, pure water 250mL and potassium sulfocyanate 20g, potassium sulfocyanate is dissolved, in container, prepare the 1st solution.Then, the temperature in maintenance container is in the scope of 20 ~ 25 DEG C.
Then, stir the 1st solution being held in 20 ~ 25 DEG C, while the speed of dividing with 5mL/, in the 1st solution, drip resorcinol diglycidyl ether 160g.After dropwising, continue stirring 30 minutes, obtain the solution containing epoxy compounds.
Then, potassium sulfocyanate 20g is dissolved in the solution containing pure water 100mL, ethanol 100mL, prepares the 2nd solution.With the speed that 5mL/ divides, to obtain containing epoxy compounds solution in add ready 2nd solution after, stir 30 minutes.After stirring, again potassium sulfocyanate 20g is dissolved in the solution containing pure water 100mL, ethanol 100mL, again prepares the 2nd solution, and add the 2nd solution with the speed that 5mL/ divides, stir 30 minutes.Then, temperature in container is cooled to 10 DEG C, stirs 2 hours, make it react.
Then, in container, add saturated aqueous common salt 100mL, stir 10 minutes.After stirring, in container, add toluene 300mL, stir 10 minutes.Then the solution in container is transferred to separating funnel, leaves standstill 2 hours, make solution separating.Discharge the solution of below in separating funnel, take out supernatant liquor.In the supernatant liquor taken out, add toluene 100mL, stir, leave standstill 2 hours.Add toluene 100mL again, stir, leave standstill 2 hours.
Then, in the supernatant liquor adding toluene, add magnesium sulfate 50g, stir 5 minutes.After stirring, remove magnesium sulfate by filter paper, separation solution.The solution drying under reduced pressure at 80 DEG C using Vacuumdrier to be separated, removes remaining solvent.According to the method described above, the mixture containing episulfide compounds is obtained.
Take chloroform as solvent, measure gained and contain the mixture of episulfide compounds 1h-NMR.Result shows, and represents the signal weakening in 6.5 ~ 7.5ppm region that epoxy group(ing) exists, occurs the signal in 2.0 ~ 3.0ppm region that representative ring sulfenyl exists.Can confirm thus, a part of epoxy group(ing) of resorcinol diglycidyl ether changes epithio base into.In addition, according to 1the integrated value of H-NMR measurement result, confirms in the mixture containing episulfide compounds, the episulfide compounds that the resorcinol diglycidyl ether containing 70 % by weight, above formula (1B) containing 30 % by weight represent.
(2) solidification compound is prepared
Contain in mixture 33 weight part of episulfide compounds to obtained, add tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight part as solidifying agent respectively, as phenylbenzene list (tridecyl) phosphorous acid ester 0.01 weight part of phosphorous acid ester, as 2-ethyl-4-methylimidazole 1 weight part of curing catalyst, as silicon-dioxide 20 weight part and aluminum oxide 20 weight part of median size 0.5 μm, electroconductive particle 2 weight part of median size 3 μm of the median size 0.25 μm of filler.Use planetary stirring machine, stir 5 minutes with 2000rpm, obtain the solidification compound stuck with paste as anisotropic conductive thus.It should be noted that, electroconductive particle used is the electroconductive particle with metal level, and it forms nickel layer on the surface of divinylbenzene resin particle, and form Gold plated Layer on the surface of this nickel layer.
(embodiment 2)
When preparing solidification compound, except not adding tetramethylolmethane four-3-mercaptopropionic acid ester and phenylbenzene list (tridecyl) phosphorous acid ester, identical with embodiment 1, obtain the solidification compound stuck with paste as anisotropic conductive.
(comparative example 1)
Add bisphenol A type epoxy resin 100 weight part, as 1,2 dimethylimidazole 5 weight part of solidifying agent, use planetary stirring machine, stir 5 minutes with 2000rpm, obtain mixture A.
In gained mixture A, add silicon dioxide granule 7 weight part of median size 0.02 μm, electroconductive particle 2 weight part that median size is 3 μm, use planetary stirring machine, stir 8 minutes with 2000rpm, obtain mixture B.It should be noted that, electroconductive particle used is the electroconductive particle with metal level, and it forms nickel layer on the surface of divinylbenzene resin particle, and form Gold plated Layer on the surface of this nickel layer.
Use nylon filter paper (10 μm, aperture), gained mixture B is filtered, obtain the solidification compound stuck with paste as anisotropic conductive.
(evaluation of embodiment 1,2 and comparative example 1)
(1) set time
Prepare transparent glass substrate, its upper surface is formed with the ITO electrode pattern that L/S is 10 μm/10 μm.In addition, prepare semi-conductor chip, its lower surface is formed with the copper electrode pattern that L/S is 10 μm/10 μm.
The solidification compound obtained is coated on above-mentioned transparent glass substrate, makes its thickness be 30 μm, form solidification compound layer.Then between the above-mentioned semi-conductor chip of solidification compound layer superimposed layer is with electrode, mutually opposing formation connects.Then adjust the temperature of heating head, make the temperature of solidification compound layer be 185 DEG C, load heating head at the upper surface of chip simultaneously, solidification compound layer is solidified at 185 DEG C, obtains connection structural bodies.When obtaining described connection structural bodies, measuring and making solidification compound layer reach time needed for solidification by heating.
(2) have seamless
In the evaluation of above-mentioned set time, carry out visual observation from the lower surface side of transparent glass substrate to whether producing gap in the solidification nitride layer formed by solidification compound layer the connection structural bodies of gained.
Result as described in Table 1.
[table 1]
Set time Have seamless
Embodiment 1 1 second Nothing
Embodiment 2 6 seconds Nothing
Comparative example 1 2 minutes Have
(embodiment 3)
When preparing solidification compound; except adding epoxy acrylate (" EBECRYL3702 " that DAICELCYTEC company manufactures) 5 weight parts further, as except acylphosphine oxide compounds (" DAROCURTPO " that CibaJapan company manufactures) 0.1 weight part of Photoepolymerizationinitiater initiater; identical with embodiment 1, obtain the solidification compound stuck with paste as anisotropic conductive.
(embodiment 4)
When preparing solidification compound; except adding urethane acrylate (AICELCYTEC Inc. " EBECRYL8804 ") 5 weight parts, acylphosphine oxide compounds (Ciba as Photoepolymerizationinitiater initiater further; Japan Inc. " DAROCURTPO ") beyond 0.1 weight part; identical with embodiment 1, obtain the solidification compound stuck with paste as anisotropic conductive.
(evaluation of embodiment 3,4)
(1) set time
Prepare transparent glass substrate and the semi-conductor chip of the evaluation being used for embodiment 1,2 and comparative example 1.
Gained solidification compound is coated on the upper surface of above-mentioned transparent glass substrate, makes its thickness be 30 μm, form solidification compound layer.Further, coating anisotropic conductive is stuck with paste, while use ultraviolet radiator to irradiate 50mW/cm to solidification compound layer 2the 420nm ultraviolet of photo-irradiation intensity, by photopolymerization, make solidification compound layer B rank.After coating, the solidification compound layer be namely coated with and above-mentioned transparent glass substrate time of contact, until the time T of rayed solidification compound layer is 0.5 second.
Then at the above-mentioned semi-conductor chip of solidification compound layer upper surface lamination on B rank, and make mutually opposing between electrode and connect.Then while the temperature of adjustment heating head, make the temperature of solidification compound layer reach 185 DEG C, pressurized, heated head is loaded into the upper surface of semi-conductor chip, apply 10kg/cm 2pressure, the solidification compound layer on B rank is solidified completely at 185 DEG C, obtains connection structural bodies.When obtaining described connection structural bodies, measuring and making solidification compound layer reach the time of solidification by heating.
(2) have seamless
Identical with comparative example 1 with embodiment 1,2, have seamless to the connection structural bodies evaluation of gained in the evaluation of above-mentioned set time.
Result as described in Table 2.
[table 2]
Set time Have seamless
Embodiment 3 1 second Nothing
Embodiment 4 1 second Nothing
(embodiment 5 ~ 24)
(1) episulfide compounds or the mixture containing episulfide compounds is prepared
According to the order identical with embodiment 1, the episulfide compounds that preparation represents containing the above formula (1) of following content, (2) or (3) and the episulfide compounds of epoxy compounds that above formula (11), (12) or (13) represent or the mixture containing episulfide compounds.The episulfide compounds of each embodiment or the mixture containing episulfide compounds by suitably adjusting the consumption of potassium sulfocyanate, thus can adjust transformation efficiency and obtain.
(2) solidification compound is prepared
When preparing solidification compound, except by mixture 33 weight part containing episulfide compounds used in embodiment 1, change into the episulfide compounds shown in following table 3 ~ 5 or containing episulfide compounds mixture beyond, other are identical with embodiment 1, obtain the solidification compound stuck with paste as anisotropic conductive.
(embodiment 25)
When preparing solidification compound, except by mixture 33 weight part containing episulfide compounds used in embodiment 1, change into embodiment 1 used containing mixture 10 weight part of episulfide compounds and embodiment 9 used containing beyond mixture 20 weight part of episulfide compounds, other are identical with embodiment 1, obtain solidification compound.
(embodiment 26)
When preparing solidification compound, except by mixture 33 weight part containing episulfide compounds used in embodiment 1, change into beyond mixture 20 weight part containing episulfide compounds used in embodiment 1 and Resorcinol glycidyl ether 10 weight part, other are identical with embodiment 1, obtain solidification compound.
(embodiment 27)
When preparing solidification compound, except by mixture 33 weight part containing episulfide compounds used in embodiment 1, change into beyond mixture 20 weight part containing episulfide compounds used in embodiment 1 and bisphenol A-type glycidyl ether 10 weight part, other are identical with embodiment 1, obtain solidification compound.
(evaluation of embodiment 5 ~ 27)
Evaluate cure time and have seamless in the same manner as the evaluation of embodiment 1,2 and comparative example 1.
Result is as shown in following table 3 ~ 6.
[table 6]
Set time Have seamless
Embodiment 25 0.8 second Nothing
Embodiment 26 1.2 second Nothing
Embodiment 27 1.4 second Nothing
Nomenclature
1 ... connection structural bodies
2 ... 1st connecting object parts
2a ... upper surface
2b ... electrode
3 ... connection section
4 ... 2nd connecting object parts
4a ... lower surface
4b ... electrode
5 ... electroconductive particle

Claims (17)

1. a solidification compound, it contains:
Episulfide compounds,
Be selected from least one in phosphoric acid ester, phosphorous acid ester and boric acid ester,
Solidifying agent and electroconductive particle,
Above-mentioned episulfide compounds has the structure that following formula (1-1), formula (2-1) or formula (3) represent,
In above formula (1-1), R1 and R2 represents C respectively 1 ~ 5alkylidene group,
2 ~ 4 groups in these 4 groups of R3, R4, R5 and R6 represent hydrogen,
Group not for hydrogen in R3, R4, R5 and R6 represents the group that following formula (4) represents,
In above formula (2-1), R51 and R52 represents C respectively 1 ~ 5alkylidene group,
4 ~ 6 groups in these 6 groups of R53, R54, R55, R56, R57 and R58 represent hydrogen, and the group not for hydrogen in R53, R54, R55, R56, R57 and R58 represents the group that following formula (5) represents,
In above formula (3), R101 and R102 represents C respectively 1 ~ 5alkylidene group,
6 ~ 8 groups in these 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 represent hydrogen,
Group not for hydrogen in R103, R104, R105, R106, R107, R108, R109 and R110 represents the group that following formula (6) represents,
In above formula (4), R7 represents C 1 ~ 5alkylidene group,
In above formula (5), R59 represents C 1 ~ 5alkylidene group,
In above formula (6), R111 represents C 1 ~ 5alkylidene group.
2., according to the solidification compound described in claim 1, it contains the imidazoles curing catalyst different from above-mentioned solidifying agent.
3. according to the solidification compound described in claim 1 or 2, wherein, above-mentioned solidifying agent is poly-thiol compound.
4., according to the solidification compound described in claim 1 or 2, it is aqueous or the anisotropic conductive material of pasty state.
5. according to the solidification compound described in claim 1 or 2, wherein, above-mentioned episulfide compounds has following formula (1) or the structure represented by (2),
In above formula (1), R1 and R2 represents C respectively 1 ~ 5alkylidene group,
2 ~ 4 groups in these 4 groups of R3, R4, R5 and R6 represent hydrogen,
Group not for hydrogen in R3, R4, R5 and R6 represents the group that following formula (4) represents,
In above formula (2), R51 and R52 represents C respectively 1 ~ 5alkylidene group,
4 ~ 6 groups in these 6 groups of R53, R54, R55, R56, R57 and R58 are hydrogen,
Group not for hydrogen in R53, R54, R55, R56, R57 and R58 represents the group that following formula (5) represents,
In above formula (4), R7 represents C 1 ~ 5alkylidene group,
In above formula (5), R59 represents C 1 ~ 5alkylidene group.
6. according to the solidification compound described in claim 5, wherein, above-mentioned formula (1) or the structure of the structure represented by (2) represented by following formula (1A) or (2A),
In above formula (1A), R1 and R2 represents C respectively 1 ~ 5alkylidene group,
In above formula (2A), R51 and R52 represents C respectively 1 ~ 5alkylidene group.
7., according to the solidification compound described in claim 1 or 2, it contains following formula (11-1), (12-1) or the epoxy compounds represented by (13),
In above formula (11-1), R11 and R12 represents C respectively 1 ~ 5alkylidene group,
2 ~ 4 groups in these 4 groups of R13, R14, R15 and R16 represent hydrogen,
Group not for hydrogen in R13, R14, R15 and R16 represents the group that following formula (14) represents,
In above formula (12-1), R61 and R62 represents C respectively 1 ~ 5alkylidene group,
4 ~ 6 groups in these 6 groups of R63, R64, R65, R66, R67 and R68 represent hydrogen,
Group not for hydrogen in R63, R64, R65, R66, R67 and R68 represents the group that following formula (15) represents,
In above formula (13), R121 and R122 represents C respectively 1 ~ 5alkylidene group,
6 ~ 8 groups in these 8 groups of R123, R124, R125, R126, R127, R128, R129 and R130 represent hydrogen,
Group not for hydrogen in R123, R124, R125, R126, R127, R128, R129 and R130 represents the group that following formula (16) represents,
In above formula (14), R17 represents C 1 ~ 5alkylidene group,
In above formula (15), R69 represents C 1 ~ 5alkylidene group,
In above formula (16), R131 represents C 1 ~ 5alkylidene group.
8. according to the solidification compound described in claim 7, wherein, the epoxy compounds of above-mentioned epoxy compounds represented by following formula (11) or (12),
In above formula (11), R11 and R12 represents C respectively 1 ~ 5alkylidene group,
2 ~ 4 groups in these 4 groups of R13, R14, R15 and R16 represent hydrogen,
Group not for hydrogen in R13, R14, R15 and R16 represents the group that following formula (14) represents,
In above formula (12), R61 and R62 represents C respectively 1 ~ 5alkylidene group,
4 ~ 6 groups in these 6 groups of R63, R64, R65, R66, R67 and R68 represent hydrogen,
Group not for hydrogen in R63, R64, R65, R66, R67 and R68 represents the group that following formula (15) represents,
In above formula (14), R17 represents C 1 ~ 5alkylidene group,
In above formula (15), R69 represents C 1 ~ 5alkylidene group.
9. according to Claim 8 described in solidification compound, wherein, the structure that above-mentioned formula (11) or (12) represent is the structure that following formula (11A) or (12A) represent,
In above formula (11A), R11 and R12 represents C respectively 1 ~ 5alkylidene group,
In above formula (12A), R61 and R62 represents C respectively 1 ~ 5alkylidene group.
10., according to the solidification compound described in claim 1 or 2, it is also containing photocurable compound and Photoepolymerizationinitiater initiater.
11. according to the solidification compound described in claim 1 or 2, and wherein, the viscosity at 25 DEG C is in the scope of 20000 ~ 100000mPas.
12. according to the solidification compound described in claim 1 or 2, and it contains filler.
13. according to the solidification compound described in claim 12, and wherein, the median size of above-mentioned filler is 0.1 ~ 1.0 μm.
14. according to the solidification compound described in claim 12, and wherein, above-mentioned filler is silicon-dioxide, aluminium nitride or aluminum oxide.
15. according to the solidification compound described in claim 1 or 2, and it is provided with for directly utilizing the anisotropic conductive material of aqueous or pasty state the purposes connecting object parts of electrode carrying out apply at upper surface.
16. according to the solidification compound described in claim 1 or 2, and wherein, above-mentioned electroconductive particle is that the surface metal level of resin particle has carried out coated electroconductive particle.
17. 1 kinds of connection structural bodies, its connection section that there are the 1st connecting object parts, the 2nd connecting object parts and be connected above-mentioned 1st connecting object parts and the 2nd connecting object parts, wherein, above-mentioned connection section is formed by the solidification compound in claim 1 ~ 16 described in any one
Above-mentioned 1st connecting object parts and the 2nd connecting object parts realize electrical connection by above-mentioned electroconductive particle.
CN201510628123.4A 2008-09-25 2009-09-24 Episulfide compound, episulfide compound-containing mixture, method for producing episulfide compound-containing mixture, curable composition and connection structure Pending CN105175727A (en)

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