CN103764707A - Epoxy compound, epoxy compound mixture, curable composition, and connecting structure - Google Patents
Epoxy compound, epoxy compound mixture, curable composition, and connecting structure Download PDFInfo
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- CN103764707A CN103764707A CN201280040209.XA CN201280040209A CN103764707A CN 103764707 A CN103764707 A CN 103764707A CN 201280040209 A CN201280040209 A CN 201280040209A CN 103764707 A CN103764707 A CN 103764707A
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- ZAVFHLIGXXIPFP-UHFFFAOYSA-N C(C1OC1)Oc1cc(OC2COC2)ccc1 Chemical compound C(C1OC1)Oc1cc(OC2COC2)ccc1 ZAVFHLIGXXIPFP-UHFFFAOYSA-N 0.000 description 1
- FADQRYHGUZKLDD-UHFFFAOYSA-N CC(C)(CC(COC)OCCCCOCC1CC1)Oc1cccc(OCC2OC2)c1 Chemical compound CC(C)(CC(COC)OCCCCOCC1CC1)Oc1cccc(OCC2OC2)c1 FADQRYHGUZKLDD-UHFFFAOYSA-N 0.000 description 1
- CXEJTZYRLVPVAH-VHDKLDBYSA-N CCOc1cccc(OCC(COCC/C=C\C(\C)=C/C)OCCCCOCC2OC2)c1 Chemical compound CCOc1cccc(OCC(COCC/C=C\C(\C)=C/C)OCCCCOCC2OC2)c1 CXEJTZYRLVPVAH-VHDKLDBYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
- H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
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Abstract
An epoxy compound that can be rapidly cured and in which a cured article has excellent adhesiveness and moisture resistance, a curable composition that uses the epoxy compound, and a connecting structure that uses the curable composition are provided. The epoxy compound has an epoxy group at both ends, and has a vinyl group or an epoxy group in a side chain. The weight-average molecular weight of this epoxy compound is 500-150000 inclusive. The curable composition contains the epoxy compound and a thermosetting agent. The connecting structure (1) comprises a first member (2) to be connected, a second member (4) to be connected, and a connector (3) connecting together the first and second members (2, 4) to be connected. The connector (3) is formed using the curable composition.
Description
Technical field
The present invention relates to for example can solidify rapidly and the cementability of cured article and the epoxy compounds of excellent moisture resistance.In addition, the invention still further relates to the epoxy compounds that contains this epoxy compounds mixture, use the solidification compound of this epoxy compounds and use the syndeton body of this solidification compound.
Background technology
The bonding force of the cured article after composition epoxy resin solidifies is high, and the water tolerance of cured article and excellent heat resistance.Therefore, composition epoxy resin has been widely used in the various uses such as electric, electronics, building and vehicle.In addition,, for various connecting object parts are electrically connected to, sometimes in above-mentioned composition epoxy resin, add electroconductive particle.The composition epoxy resin that contains electroconductive particle is called as anisotropic conductive material.
Above-mentioned anisotropic conductive material is specifically used to the connection of IC chip and flexible printed wiring board and IC chip and has the connection etc. of the circuit substrate of ITO electrode.For example, can after configure anisotropic conductive material between the electrode at IC chip and the electrode of circuit substrate, heat and pressurize, thereby these electrodes are connected to each other.
As an example of above-mentioned anisotropic conductive material, a kind of anisotropic conductive adhesive film is disclosed in following patent documentation 1, it contains heat cured insulation caking agent, electroconductive particle, Imidazole Type Latent Curing Agent and amine latent curing agent.Above-mentioned heat cured insulation caking agent preferably contains flexible epoxy resin.According to the record in patent documentation 1, even if make this anisotropic conductive adhesive film solidify at lower temperature, it also has excellent connection reliability.
In addition, in following patent documentation 2, disclose a kind of composition epoxy resin, its diglycidylether that contains dihydroxyphenyl propane-oxyalkylene affixture, bisphenol A diglycidyl ether, do not there is the thinner of epoxy group(ing), the perbutan of carboxy blocking, dodecenylsuccinic anhydride and inorganic filler.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 9-115335 communique
Patent documentation 2: Japanese kokai publication hei 9-235350 communique
Summary of the invention
The problem that invention will solve
In recent years, in order to connect efficiently between the electrode of electronic unit, to require to shorten composition epoxy resin and solidify required heat-up time.And, by shortening heat-up time, can suppress the thermal degradation when of gained electronic unit.
For the anisotropic conductive adhesive film of recording in patent documentation 1, if shorten heat-up time, sometimes can not be fully curing.Therefore,, in order to use anisotropic conductive adhesive film to connect between the electrode of electronic unit, sometimes have to carry out long-time heating.Therefore, sometimes can not make to connect efficiently between electrode.In addition, the composition epoxy resin for recording in patent documentation 2, in order to make it fully curing, also needs long heating.
In addition,, for the composition epoxy resin of recording in the anisotropic conductive adhesive film of recording in patent documentation 1 and patent documentation 2, the cementability of its cured article and wet fastness are sometimes lower.
On the other hand, require to develop the novel curable compound that can shorten heat-up time.The exploitation of novel curable compound makes solidification compound variation.
The object of this invention is to provide a kind of new epoxy compound that can be used in solidification compound.
In addition, limited object of the present invention be to provide a kind of can solidify rapidly and the cementability of cured article and the epoxy compounds of excellent moisture resistance, contain this epoxy compounds epoxy compounds mixture, use the solidification compound of this epoxy compounds and use the syndeton body of this solidification compound.
The method of dealing with problems
According to wider aspect of the present invention, the invention provides a kind of epoxy compounds, it has epoxy group(ing) at two ends, and has vinyl or epoxy group(ing) at side chain, and the weight-average molecular weight of this epoxy compounds is more than 500 and below 150000.
In a certain particular aspects of epoxy compounds of the present invention, this epoxy compounds has altogether more than 2 vinyl or has altogether more than 2 epoxy group(ing) at side chain at side chain.
In other particular aspects of epoxy compounds of the present invention, this epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with following reaction product, above-mentioned reaction product is the reaction product of Bisphenol F or Resorcinol and 1,6-hexanediol diglycidyl ether or resorcinol diglycidyl ether.
In further other the particular aspects of epoxy compounds of the present invention, above-mentioned reaction product is the 1st reaction product, the 2nd reaction product or the 3rd reaction product, above-mentioned the 1st reaction product is Bisphenol F and 1, the reaction product of 6-hexanediol diglycidyl ether, above-mentioned the 2nd reaction product is Resorcinol and 1, the reaction product of 6-hexanediol diglycidyl ether, above-mentioned the 3rd reaction product is the reaction product of Resorcinol and resorcinol diglycidyl ether.
In further other the particular aspects of epoxy compounds of the present invention, when above-mentioned reaction product is above-mentioned the 1st reaction product, in the molecular weight distribution of epoxy compounds, there are 2 peaks, when above-mentioned reaction product is above-mentioned the 2nd reaction product, in the molecular weight distribution of epoxy compounds, have 2 peaks.
Preferred above-mentioned reaction product is above-mentioned the 1st reaction product, is also preferably above-mentioned the 2nd reaction product, is also preferably in addition above-mentioned the 3rd reaction product.In addition, be preferably (methyl) vinylformic acid or 2-(methyl) acryloxy ethyl isocyanate with the compound of above-mentioned reaction, be also preferably 2-(methyl) acryloxy ethyl isocyanate.
The mixture of epoxy compounds of the present invention contains at least 2 kinds of above-mentioned epoxy compoundss.
In a certain particular aspects of the mixture of epoxy compounds of the present invention, it contains the 1st epoxy compounds and the 2nd epoxy compounds, above-mentioned the 1st epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 1st reaction product, above-mentioned the 1st reaction product is the reaction product of Bisphenol F and 1,6-hexanediol diglycidyl ether; Above-mentioned the 2nd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 2nd reaction product, above-mentioned the 2nd reaction product is the reaction product of Resorcinol and 1,6-hexanediol diglycidyl ether.
In other particular aspects of the mixture of epoxy compounds of the present invention, it contains the 2nd epoxy compounds and the 3rd epoxy compounds, above-mentioned the 2nd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 2nd reaction product, above-mentioned the 2nd reaction product is the reaction product of Resorcinol and 1,6-hexanediol diglycidyl ether; Above-mentioned the 3rd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 3rd reaction product, and above-mentioned the 3rd reaction product is the reaction product of Resorcinol and resorcinol diglycidyl ether.
In the other particular aspects of the mixture of epoxy compounds of the present invention, its viscosity at 23 ℃ is more than 50Pas.
Solidification compound of the present invention contains above-mentioned epoxy compounds and thermal curing agents.
In a certain particular aspects of solidification compound of the present invention, it contains at least 2 kinds of above-mentioned epoxy compoundss.
In other particular aspects of solidification compound of the present invention, it further contains photocurable compound and Photoepolymerizationinitiater initiater.
In the other particular aspects of solidification compound of the present invention, it further contains electroconductive particle.
In other particular aspects of solidification compound of the present invention, except above-mentioned epoxy compounds, also contain epoxy (methyl) acrylate, above-mentioned epoxy (methyl) acrylate is to obtain by least one in 2 epoxy group(ing) of (methyl) vinylformic acid and these epoxy compounds two ends reacted.
Syndeton body of the present invention there are the 1st connecting object parts, the 2nd connecting object parts and connect the 1st, the connection section of the 2nd connecting object parts, this connection section is formed by above-mentioned solidification compound.
In a certain particular aspects of syndeton body of the present invention, above-mentioned solidification compound contains electroconductive particle, and above-mentioned the 1st, the 2nd connecting object parts are electrically connected to by above-mentioned electroconductive particle.
The effect of invention
Epoxy compounds of the present invention makes solidification compound variation.In addition, because epoxy compounds of the present invention has epoxy group(ing) and has vinyl or epoxy group(ing) at side chain at two ends, and its weight-average molecular weight is more than 500 and below 150000, therefore can solidifies rapidly, and can improve cementability and the wet fastness of cured article.
Accompanying drawing explanation
Fig. 1 is part intercepting sectional view, and it schematically shows an example of the syndeton body of the solidification compound that has used an embodiment of the present invention.
Nomenclature
1... syndeton body
2... the 1st connecting object parts
2a... upper surface
2b... electrode
3... connection section
4... the 2nd connecting object parts
4a... lower surface
4b... electrode
5... electroconductive particle
Embodiment
Below, the present invention is described in detail.
(epoxy compounds)
Epoxy compounds of the present invention has epoxy group(ing) and has vinyl or epoxy group(ing) at side chain at two ends.The weight-average molecular weight of epoxy compounds of the present invention is more than 500 and below 150000.
Having the epoxy compounds forming as mentioned above can solidify rapidly.For example, can make to have coordinated the solidification compound of above-mentioned epoxy compounds and thermal curing agents to solidify rapidly.For example, can make it under more than 150 ℃ Heating temperatures, in 5 seconds, with interior, solidify.Further, can improve cementability and the wet fastness of the cured article that uses above-mentioned epoxy compounds.Therefore, can improve the reliability of using the syndeton body that the above-mentioned solidification compound contain above-mentioned epoxy compounds is formed by connecting the 1st, the 2nd connecting object parts.
More preferably epoxy compounds of the present invention is the reaction product of using diatomic alcohol compounds to obtain with having the compound of 2 epoxy group(ing).Preferred epoxy compounds of the present invention is the epoxy compounds by compound and the diatomic alcohol compounds that has the compound of vinyl or have epoxy group(ing) and the reaction with the compound of 2 epoxy group(ing) are obtained.
The weight-average molecular weight of epoxy compounds of the present invention is more than 500 and below 150000.The weight-average molecular weight of epoxy compounds of the present invention is preferably more than 1000, is preferably below 50000, more preferably below 15000.
Epoxy compounds of the present invention has more than 1 vinyl or on side chain, has more than 1 epoxy group(ing) on side chain.Epoxy compounds of the present invention can have more than 1 vinyl on side chain, also can on side chain, have more than 1 epoxy group(ing).
Preferred epoxy compounds of the present invention has altogether more than 2 vinyl or on side chain, has altogether more than 2 epoxy group(ing) on side chain.The quantity of vinyl or epoxy group(ing) is more, more can further shorten heat-up time, and can further improve cementability and the wet fastness of cured article.Epoxy compounds of the present invention can have altogether more than 2 vinyl on side chain, also can on side chain, have altogether more than 2 epoxy group(ing).
Preferred epoxy compounds of the present invention is the reaction product that has the compound of 2 above phenol hydroxyls and have the compound of 2 above epoxy group(ing).
As the above-mentioned compound with 2 above phenol hydroxyls, can enumerate bisphenol cpd, Resorcinol and naphthols etc.As above-mentioned bisphenol cpd, can enumerate Bisphenol F, dihydroxyphenyl propane, bisphenol S, bisphenol S A and bis-phenol E etc.
As the above-mentioned compound with 2 above epoxy group(ing), can enumerate aliphatic epoxy compound and aromatic epoxy compound etc.As above-mentioned aliphatic epoxy compound, can enumerate: the compound at two ends of the alkyl chain of carbonatoms 3～12 with glycidyl ether or oxa-cyclobutyl; And there is the polyether skeleton of carbonatoms 2～4 and there is the polyether-type epoxy compounds of the structural unit being formed by 2～10 continuous bondings of this polyether skeleton.
Preferred epoxy compounds of the present invention is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react with following reaction product (being also denoted as below reaction product X) epoxy compounds obtaining, described reaction product is the reaction product of Bisphenol F or Resorcinol and 1,6-hexanediol diglycidyl ether or resorcinol diglycidyl ether.The epoxy compounds that uses such compou nd synthesis to obtain can solidify rapidly, and can improve cementability and the wet fastness of cured article.
Above-mentioned reaction product X is 1 of the Bisphenol F of following formula (1) expression or the Resorcinol of following formula (2) expression and following formula (11) expression, the reaction product of the resorcinol diglycidyl ether that 6-hexanediol diglycidyl ether or following formula (12) represent.
[Chemical formula 1]
[Chemical formula 2]
[chemical formula 3]
[chemical formula 4]
In above-mentioned formula (1), 1 hydroxyl with respect to the bonding position of 1 phenyl ring without particular limitation of.As above-mentioned Bisphenol F, can enumerate 4 of for example following formula (1-1) expression, 2 of 4 '-methylene-bis phenol, following formula (1-2) expression, 2 of 4 '-methylene-bis phenol and following formula (1-3) expression, 2 '-methylene-bis phenol etc.Conventionally these materials are referred to as to Bisphenol F.Above-mentioned Bisphenol F can contain 1 hydroxyl of more than two kinds compound different with respect to the bonding position of 1 phenyl ring.Preferred above-mentioned Bisphenol F is 4,4 '-methylene-bis phenol, 2,4 '-methylene-bis phenol or 2,2 '-methylene-bis phenol.
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
As above-mentioned reaction product X, can enumerate by Bisphenol F and 1, the 1st reaction product that the reaction of 6-hexanediol diglycidyl ether obtains, by Resorcinol and 1, the 2nd reaction product that the reaction of 6-hexanediol diglycidyl ether obtains, the 3rd reaction product being obtained by Resorcinol and resorcinol diglycidyl ether reaction, the 4th reaction product being obtained by Bisphenol F and resorcinol diglycidyl ether reaction.
Above-mentioned the 1st reaction product has by coming from the skeleton of Bisphenol F and coming from the structural unit that the skeleton bonding of 1,6-hexanediol diglycidyl ether forms on main chain, and at two ends, has the epoxy group(ing) that comes from 1,6-hexanediol diglycidyl ether.Above-mentioned the 2nd reaction product has the structural unit that comes from Resorcinol and the structural unit that comes from 1,6-hexanediol diglycidyl ether on main chain, and at two ends, has the epoxy group(ing) that comes from 1,6-hexanediol diglycidyl ether.Above-mentioned the 3rd reaction product has the skeleton that comes from Resorcinol and the skeleton that comes from resorcinol diglycidyl ether on main chain, and at two ends, has the epoxy group(ing) that comes from resorcinol diglycidyl ether.Above-mentioned the 4th reaction product has the skeleton that comes from Bisphenol F and the skeleton that comes from resorcinol diglycidyl ether on main chain, and two ends have the epoxy group(ing) that comes from resorcinol diglycidyl ether.
From easy, synthesize, can make epoxy compounds more promptly to solidify and can further improve the cementability of cured article and the viewpoint of wet fastness, in above-mentioned the 1st, the 2nd, the 3rd, the 4th reaction product, preferred above-mentioned the 1st reaction product, above-mentioned the 2nd reaction product or above-mentioned the 3rd reaction product.Preferred above-mentioned reaction product X is above-mentioned the 1st reaction product, is also preferably above-mentioned the 2nd reaction product, is further also preferably above-mentioned the 3rd reaction product.
Preferably above-mentioned the 1st reaction product has the structure that following formula (51) represents.
[chemical formula 8]
In above-mentioned formula (51), n represents integer.And, n reacts and while obtaining epoxy compounds, the weight-average molecular weight that makes this epoxy compounds is the integer more than 500 and below 150000 at the epoxy compounds that (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (51) are represented.
Preferably above-mentioned the 2nd reaction product has the structure that following formula (52) represents.
[chemical formula 9]
In above-mentioned formula (52), n represents integer.And, n reacts and while obtaining epoxy compounds, the weight-average molecular weight that makes this epoxy compounds is the integer more than 500 and below 150000 at the epoxy compounds that (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (52) are represented.
Preferably above-mentioned the 3rd reaction product has the structure that following formula (53) represents.
[Chemical formula 1 0]
In above-mentioned formula (53), n represents integer.And, n reacts and while obtaining epoxy compounds, the weight-average molecular weight that makes this epoxy compounds is the integer more than 500 and below 150000 at the epoxy compounds that (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (53) are represented.
Preferably above-mentioned the 4th reaction product has the structure that following formula (54) represents.
[Chemical formula 1 1]
In above-mentioned formula (54), n represents integer.And, n reacts and while obtaining epoxy compounds, the weight-average molecular weight that makes this epoxy compounds is the integer more than 500 and below 150000 at the epoxy compounds that (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (54) are represented.
In above-mentioned formula (51), formula (52), formula (53) and formula (54), preferred n is respectively and makes the weight-average molecular weight of above-mentioned epoxy compounds is the integer more than 1000 and below 50000.More preferably to be respectively and to make the weight-average molecular weight of above-mentioned epoxy compounds be the integer more than 1000 and below 15000 to n.
While there is 2 peaks in the molecular weight distribution of epoxy compounds, the peak of high molecular one side is larger than the peak of lower molecular weight one side, is preferably more than 10000, is preferably below 150000, more preferably below 50000, more preferably below 15000.While there is 2 peaks in the molecular weight distribution of epoxy compounds, the peak of lower molecular weight one side is less than the peak of high molecular one side, is preferably more than 1000, more preferably more than 2000, is preferably below 10000, more preferably below 6000.
In above-mentioned formula (51) and formula (54), 1 Sauerstoffatom with respect to the bonding position of 1 phenyl ring without particular limitation of.This bonding position for example, is determined by the kind of Bisphenol F (, above-mentioned formula (1-1)～(1-3)).
As using so that the concrete reaction that Bisphenol F or Resorcinol and 1,6-hexanediol diglycidyl ether or resorcinol diglycidyl ether react can be enumerated polyaddition reaction.
The Bisphenol F that above-mentioned formula (1) is represented is called dikaryon.In addition, Bisphenol F is commercially available prod.This commercially available prod, except comprising the Bisphenol F as dikaryon, sometimes also comprises and has Bisphenol F skeleton and have 3 with the polykaryon of coker.This polykaryon is three nucleomes or has 4 with the polykaryon of coker.Above-mentioned core is also the quantity of phenyl ring.When obtaining above-mentioned reaction product X, can, when using Bisphenol F, also use and there is Bisphenol F skeleton and there are 3 with the polykaryon of coker.
Above-mentioned polykaryon is for example represented by following formula (X).When being used as the Bisphenol F of dikaryon in order to obtain above-mentioned reaction product X and thering is Bisphenol F skeleton and there are 3 coenocytic mixtures with coker, in this mixture of 100 % by weight, as the content of the Bisphenol F of dikaryon preferably more than 70 % by weight, more preferably more than 85 % by weight, preferably below 99.9 % by weight, more preferably below 99 % by weight.If in the said mixture of 100 % by weight, as the content of the Bisphenol F of dikaryon more than above-mentioned lower limit and below the above-mentioned upper limit, use the cementability of the cured article of above-mentioned epoxy compounds further to uprise, and use the reliability of the syndeton body of the above-mentioned solidification compound that contains above-mentioned epoxy compounds further to uprise.
[Chemical formula 1 2]
In above-mentioned formula (X), m represents more than 1 integer.M is preferably below 10, more preferably, below 5, is particularly preferably below 3.For example, in above-mentioned formula (X), the polykaryon that m is 1 is three nucleomes with Bisphenol F skeleton.In above-mentioned formula (X), 1 hydroxyl with respect to the bonding position of 1 phenyl ring without particular limitation of.
In addition, when being used as the Bisphenol F of dikaryon and thering is Bisphenol F skeleton and there are 3 coenocytic mixtures with coker, by Bisphenol F and 1, in the 1st reaction product that the reaction of 6-hexanediol diglycidyl ether obtains, except by coming from as the skeleton of the Bisphenol F of dikaryon and coming from 1, beyond the structural unit that the skeleton bonding of 6-hexanediol diglycidyl ether forms, on its main chain, can also contain by coming from and there is Bisphenol F skeleton and there are 3 coenocytic skeletons with coker and come from 1, the structural unit that the skeleton bonding of 6-hexanediol diglycidyl ether forms.When being used as the Bisphenol F of dikaryon and thering is Bisphenol F skeleton and there are 3 coenocytic mixtures with coker, in above-mentioned the 4th reaction product, except by coming from as the skeleton of the Bisphenol F of dikaryon and coming from the structural unit that the skeleton bonding of resorcinol diglycidyl ether forms, on its main chain, can also contain by coming from and there is Bisphenol F skeleton and there are 3 coenocytic skeletons with coker and come from the structural unit that the skeleton bonding of resorcinol diglycidyl ether forms.
That is, above-mentioned the 1st reaction product can have the structure that following formula (51X) represents.
[Chemical formula 1 3]
In above-mentioned formula (51X), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 with the coenocytic skeleton of coker, and n represents integer.And, n reacts and while obtaining epoxy compounds, the weight-average molecular weight that makes this epoxy compounds is the integer more than 500 and below 150000 at the epoxy compounds that (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (51X) are represented.
Above-mentioned the 4th reaction product can have the structure that following formula (54X) represents.
[Chemical formula 1 4]
In above-mentioned formula (54X), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 with the coenocytic skeleton of coker, and n represents integer.And, n reacts and while obtaining epoxy compounds, the weight-average molecular weight that makes this epoxy compounds is the integer more than 500 and below 150000 at the epoxy compounds that (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (54X) are represented.
X in above-mentioned formula (51X) and above-mentioned formula (54X) is the structural unit that following formula (Xa) represents.
[Chemical formula 1 5]
In above-mentioned formula (Xa), p represents more than 0 integer.P is preferably below 10, more preferably, below 5, is particularly preferably below 3.It should be noted that, in above-mentioned formula (Xa), p is 0 o'clock, represent to come from the skeleton as the Bisphenol F of dikaryon, in above-mentioned formula (Xa), when p is more than 1 integer, represent to come to there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker.In above-mentioned formula (Xa), 1 hydroxyl with respect to the bonding position of 1 phenyl ring without particular limitation of.In above-mentioned formula (Xa), 1 Sauerstoffatom (O-yl) with respect to the bonding position of 1 phenyl ring without particular limitation of.
By (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether are reacted with above-mentioned reaction product X such as above-mentioned the 1st, the 2nd, the 3rd, the 4th reaction product, can on side chain, import vinyl or epoxy group(ing).That is the compound, preferably reacting with above-mentioned reaction product X is (methyl) vinylformic acid, 2-(methyl) the acryloxy ethyl isocyanate of following formula (B) expression or the 4-hydroxyl butylglycidyl ether that following formula (C) represents that following formula (A) represents.The compound reacting with above-mentioned reaction product X can be (methyl) vinylformic acid, can be also 2-(methyl) acryloxy ethyl isocyanate, can also be 4-hydroxyl butylglycidyl ether.It should be noted that, above-mentioned " (methyl) vinylformic acid " represents vinylformic acid and methacrylic acid.Above-mentioned " (methyl) acryl " represents acryl and methacryloyl.
[Chemical formula 1 6]
In above-mentioned formula (A), R represents hydrogen atom or methyl.
[Chemical formula 1 7]
In above-mentioned formula (B), R represents hydrogen atom or methyl.
[Chemical formula 1 8]
In order to import vinyl on the side chain of epoxy compounds of the present invention, the compound preferably reacting with above-mentioned reaction product X is (methyl) vinylformic acid or 2-(methyl) acryloxy ethyl isocyanate.The compound preferably reacting with above-mentioned reaction product X is (methyl) vinylformic acid, is also preferably 2-(methyl) acryloxy ethyl isocyanate.When epoxy compounds of the present invention has vinyl on side chain, can make epoxy compounds photocuring of the present invention and thermofixation.Therefore, for example, can make carrying out illumination the solidification compound that contains epoxy compounds B rank (semicure) occur afterwards, by heating, make it that main solidifying occur.From making epoxy compounds more promptly solidify and further improve the cementability of cured article and the viewpoint of wet fastness, preferred epoxy compounds of the present invention has amino-formate bond.In addition,, by using 2-(methyl) acryloxy ethyl isocyanate, can further improve the mixture of epoxy compounds, epoxy compounds and the package stability of solidification compound.
In order to import epoxy group(ing) on the side chain of epoxy compounds of the present invention, the compound preferably reacting with above-mentioned reaction product X is 4-hydroxyl butylglycidyl ether.By import in this wise epoxy group(ing) on side chain, can improve the cross-linking density of cured article, and further improve the thermotolerance of cured article.
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) acryloxy ethyl isocyanate or the 4-hydroxyl butylglycidyl ether of above-mentioned formula (C) expression and the 1st reaction that above-mentioned formula (51) represents that above-mentioned formula (B) represents, the 1st epoxy compounds that can obtain following formula (61A), (61B) or (61C) represent.
[Chemical formula 1 9]
In above-mentioned formula (61A), R represents hydrogen atom or methyl, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61A) represents be the integer more than 500 and below 150000.
[Chemical formula 2 0]
In above-mentioned formula (61B), R represents hydrogen atom or methyl, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61B) represents be the integer more than 500 and below 150000.
[Chemical formula 2 1]
In above-mentioned formula (61C), n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61C) represents be the integer more than 500 and below 150000.
In above-mentioned formula (61A), formula (61B) and formula (61C), 1 Sauerstoffatom with respect to the bonding position of 1 phenyl ring without particular limitation of.This bonding position for example, is determined by the kind of Bisphenol F (, above-mentioned formula (1-1)～(1-3)).
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) acryloxy ethyl isocyanate or the 4-hydroxyl butylglycidyl ether of above-mentioned formula (C) expression and the 1st reaction that above-mentioned formula (51X) represents that above-mentioned formula (B) represents, the 1st epoxy compounds that can obtain following formula (61XA), (61XB) or (61XC) represent.
[Chemical formula 2 2]
In above-mentioned formula (61XA), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 that R represents hydrogen atom or methyl with the coenocytic skeleton of coker, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61XA) represents be the integer more than 500 and below 150000.
[Chemical formula 2 3]
In above-mentioned formula (61XB), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 that R represents hydrogen atom or methyl with the coenocytic skeleton of coker, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61XB) represents be the integer more than 500 and below 150000.
[Chemical formula 2 4]
In above-mentioned formula (61XC), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 with the coenocytic skeleton of coker, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61XC) represents be the integer more than 500 and below 150000.
X in above-mentioned formula (61XA), above-mentioned formula (61XB) and above-mentioned formula (61XC) is the structural unit that above-mentioned formula (Xa) represents.
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) acryloxy ethyl isocyanate or the 4-hydroxyl butylglycidyl ether of above-mentioned formula (C) expression and the 2nd reaction that above-mentioned formula (52) represents that above-mentioned formula (B) represents, the 2nd epoxy compounds that can obtain following formula (62A), (62B) or (62C) represent.
[Chemical formula 2 5]
In above-mentioned formula (62A), R represents hydrogen atom or methyl, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (62A) represents be the integer more than 500 and below 150000.
[Chemical formula 2 6]
In above-mentioned formula (62B), R represents hydrogen atom or methyl, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (62B) represents be the integer more than 500 and below 150000.
[Chemical formula 2 7]
In above-mentioned formula (62C), n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (62C) represents be the integer more than 500 and below 150000.
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) acryloxy ethyl isocyanate or the 4-hydroxyl butylglycidyl ether of above-mentioned formula (C) expression and the 3rd reaction that above-mentioned formula (53) represents that above-mentioned formula (B) represents, the 3rd epoxy compounds that can obtain following formula (63A), (63B) or (63C) represent.
[Chemical formula 2 8]
In above-mentioned formula (63A), R represents hydrogen atom or methyl, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (63A) represents be the integer more than 500 and below 150000.
[Chemical formula 2 9]
In above-mentioned formula (63B), R represents hydrogen atom or methyl, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (63B) represents be the integer more than 500 and below 150000.
[chemical formula 30]
In above-mentioned formula (63C), n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (63C) represents be the integer more than 500 and below 150000.
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) acryloxy ethyl isocyanate or the 4-hydroxyl butylglycidyl ether of above-mentioned formula (C) expression and the 4th reaction that above-mentioned formula (54) represents that above-mentioned formula (B) represents, the 4th epoxy compounds that can obtain following formula (64A), (64B) or (64C) represent.
[chemical formula 31]
In above-mentioned formula (64A), R represents hydrogen atom or methyl, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64A) represents be the integer more than 500 and below 150000.
[chemical formula 32]
In above-mentioned formula (64B), R represents hydrogen atom or methyl, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64B) represents be the integer more than 500 and below 150000.
[chemical formula 33]
In above-mentioned formula (64C), n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64C) represents be the integer more than 500 and below 150000.
In above-mentioned formula (64A), formula (64B) and formula (64C), 1 Sauerstoffatom with respect to the bonding position of 1 phenyl ring without particular limitation of.This bonding position for example, is determined by the kind of Bisphenol F (, above-mentioned formula (1-1)～(1-3)).
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) acryloxy ethyl isocyanate or the 4-hydroxyl butylglycidyl ether of above-mentioned formula (C) expression and the 4th reaction that above-mentioned formula (54X) represents that above-mentioned formula (B) represents, the 4th epoxy compounds that can obtain following formula (64XA), (64XB) or (64XC) represent.
[chemical formula 34]
In above-mentioned formula (64XA), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 that R represents hydrogen atom or methyl with the coenocytic skeleton of coker, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64XA) represents be the integer more than 500 and below 150000.
[chemical formula 35]
In above-mentioned formula (64XB), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 that R represents hydrogen atom or methyl with the coenocytic skeleton of coker, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64XB) represents be the integer more than 500 and below 150000.
[chemical formula 36]
In above-mentioned formula (64XC), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 with the coenocytic skeleton of coker, and n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64XC) represents be the integer more than 500 and below 150000.
X in above-mentioned formula (64XA), above-mentioned formula (64XB) and above-mentioned formula (64XC) is the structural unit that above-mentioned formula (Xa) represents.
At above-mentioned formula (61A), formula (61B), formula (61C), formula (61XA), formula (61XB), formula (61XC), formula (62A), formula (62B), formula (62C), formula (63A), formula (63B), formula (63C), formula (64A), formula (64B), formula (64C), formula (64XA), in formula (64XB) and formula (64XC), preferred above-mentioned formula (61A), formula (61B), formula (61C), formula (61XA), formula (61XB), formula (61XC), formula (62A), formula (62B), formula (62C), formula (63A), formula (63B) and formula (63C), more preferably above-mentioned formula (61XA), formula (61XB), formula (61XC), formula (62A), formula (62B), formula (62C), formula (63A), formula (63B) and formula (63C).In above-mentioned formula (61A), formula (61B), formula (61C), formula (61XA), formula (61XB), formula (61XC), formula (62A), formula (62B), formula (62C), formula (63A), formula (63B), formula (63C), formula (64A), formula (64B), formula (64C), formula (64XA), formula (64XB) and formula (64XC), preferably n is that to make the weight-average molecular weight of the epoxy compounds of these chemical formulations be the integer more than 1000 and below 50000, and more preferably n is that to make weight-average molecular weight be the integer more than 1000 and below 15000.In addition, n can be for more than 1, also can be for more than 2.The weight-average molecular weight of epoxy compounds is being more than the value of weight-average molecular weight of 1 o'clock more than 500 and at n in preferred above-mentioned formula (61A), formula (61B), formula (61C), formula (61XA), formula (61XB), formula (61XC), formula (62A), formula (62B), formula (62C), formula (63A), formula (63B), formula (63C), formula (64A), formula (64B), formula (64C), formula (64XA), formula (64XB) and formula (64XC), more than 500 and at n, is being more preferably more than the value of weight-average molecular weight of 2 o'clock.
In above-mentioned formula (61A), formula (61B), formula (61C), formula (61XA), formula (61XB), formula (61XC), formula (62A), formula (62B), formula (62C), formula (63A), formula (63B), formula (63C), formula (64A), formula (64B), formula (64C), formula (64XA), formula (64XB) and formula (64XC), show typically the structural formula while making hydroxyl whole (100%) reaction, but also can remaining unreacted hydroxyl.Before reaction in total number 100% of hydroxyl, the number ratio of the hydroxyl (becoming the group (formula hereinafter described (a), (b), (c)) of non-hydroxyl) having reacted can be for more than 0.1%, can be for more than 1%, can, for more than 3%, can, for more than 5%, can be 100%, be preferably below 80%, more preferably below 60%, further more preferably below 40%, be particularly preferably below 30%.The number ratio of above-mentioned hydroxyl can be measured by NMR.
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) the acryloxy ethyl isocyanate of above-mentioned formula (B) expression or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents, react the 1st epoxy compounds that can obtain following formula (71A), (71B) or (71C) represent with the part of hydroxyl of the 1st reaction product of above-mentioned formula (51) expression.
[chemical formula 37]
In above-mentioned formula (71A), Z represents the group that hydroxyl or following formula (a) represent, a plurality of Z comprise the group that following formula (a) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71A) represents be the integer more than 500 and below 150000.
[chemical formula 38]
In above-mentioned formula (a), R represents hydrogen atom or methyl.
[chemical formula 39]
In above-mentioned formula (71B), Z represents the group that hydroxyl or following formula (b) represent, a plurality of Z comprise the group that following formula (b) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71B) represents be the integer more than 500 and below 150000.
[chemical formula 40]
In above-mentioned formula (b), R represents hydrogen atom or methyl.
[chemical formula 41]
In above-mentioned formula (71C), Z represents the group that hydroxyl or following formula (c) represent, a plurality of Z comprise the group that following formula (c) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71C) represents be the integer more than 500 and below 150000.
[chemical formula 42]
In above-mentioned formula (71A), formula (71B) and formula (71C), 1 Sauerstoffatom with respect to the bonding position of 1 phenyl ring without particular limitation of.This bonding position for example, is determined by the kind of Bisphenol F (, above-mentioned formula (1-1)～(1-3)).
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) acryloxy ethyl isocyanate or the 4-hydroxyl butylglycidyl ether of above-mentioned formula (C) expression and the 1st reaction that above-mentioned formula (51X) represents that above-mentioned formula (B) represents, the 1st epoxy compounds that can obtain following formula (71XA), (71XB) or (71XC) represent.
[chemical formula 43]
In above-mentioned formula (71XA), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (a) represent, a plurality of Z comprise the group that above-mentioned formula (a) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71XA) represents be the integer more than 500 and below 150000.
[chemical formula 44]
In above-mentioned formula (71XB), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (b) represent, a plurality of Z comprise the group that above-mentioned formula (b) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71XB) represents be the integer more than 500 and below 150000.
[chemical formula 45]
In above-mentioned formula (71XC), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (c) represent, a plurality of Z comprise the group that above-mentioned formula (c) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71XC) represents be the integer more than 500 and below 150000.
X in above-mentioned formula (71XA), above-mentioned formula (71XB) and above-mentioned formula (71XC) is the structural unit that above-mentioned formula (Xa) represents.
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) acryloxy ethyl isocyanate or the 4-hydroxyl butylglycidyl ether of above-mentioned formula (C) expression and the 2nd reaction that above-mentioned formula (52) represents that above-mentioned formula (B) represents, the 2nd epoxy compounds that can obtain following formula (72A), (72B) or (72C) represent.
[chemical formula 46]
In above-mentioned formula (72A), Z represents the group that hydroxyl or above-mentioned formula (a) represent, a plurality of Z comprise the group that above-mentioned formula (a) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (72A) represents be the integer more than 500 and below 150000.
[chemical formula 47]
In above-mentioned formula (72B), Z represents the group that hydroxyl or above-mentioned formula (b) represent, a plurality of Z comprise the group that above-mentioned formula (b) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (72B) represents be the integer more than 500 and below 150000.
[chemical formula 48]
In above-mentioned formula (72C), Z represents the group that hydroxyl or above-mentioned formula (c) represent, a plurality of Z comprise the group that above-mentioned formula (c) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (72C) represents be the integer more than 500 and below 150000.
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) acryloxy ethyl isocyanate or the 4-hydroxyl butylglycidyl ether of above-mentioned formula (C) expression and the 3rd reaction that above-mentioned formula (53) represents that above-mentioned formula (B) represents, the 3rd epoxy compounds that can obtain following formula (73A), (73B) or (73C) represent.
[chemical formula 49]
In above-mentioned formula (73A), Z represents the group that hydroxyl or above-mentioned formula (a) represent, a plurality of Z comprise the group that above-mentioned formula (a) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (73A) represents be the integer more than 500 and below 150000.
[chemical formula 50]
In above-mentioned formula (73B), Z represents the group that hydroxyl or above-mentioned formula (b) represent, a plurality of Z comprise the group that above-mentioned formula (b) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (73B) represents be the integer more than 500 and below 150000.
[chemical formula 51]
In above-mentioned formula (73C), Z represents the group that hydroxyl or above-mentioned formula (c) represent, a plurality of Z comprise the group that above-mentioned formula (c) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (73C) represents be the integer more than 500 and below 150000.
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) acryloxy ethyl isocyanate or the 4-hydroxyl butylglycidyl ether of above-mentioned formula (C) expression and the 4th reaction that above-mentioned formula (54) represents that above-mentioned formula (B) represents, the 4th epoxy compounds that can obtain following formula (74A), (74B) or (74C) represent.
[chemical formula 52]
In above-mentioned formula (74A), Z represents the group that hydroxyl or above-mentioned formula (a) represent, a plurality of Z comprise the group that above-mentioned formula (a) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74A) represents be the integer more than 500 and below 150000.
[chemical formula 53]
In above-mentioned formula (74B), Z represents the group that hydroxyl or above-mentioned formula (b) represent, a plurality of Z comprise the group that above-mentioned formula (b) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74B) represents be the integer more than 500 and below 150000.
[chemical formula 54]
In above-mentioned formula (74C), Z represents the group that hydroxyl or above-mentioned formula (c) represent, a plurality of Z comprise the group that above-mentioned formula (c) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74C) represents be the integer more than 500 and below 150000.
In above-mentioned formula (74A), formula (74B) and formula (74C), 1 Sauerstoffatom with respect to the bonding position of 1 phenyl ring without particular limitation of.This bonding position for example, is determined by the kind of Bisphenol F (, above-mentioned formula (1-1)～(1-3)).
By (methyl) vinylformic acid that above-mentioned formula (A) is represented, 2-(methyl) acryloxy ethyl isocyanate or the 4-hydroxyl butylglycidyl ether of above-mentioned formula (C) expression and the 4th reaction that above-mentioned formula (54X) represents that above-mentioned formula (B) represents, the 4th epoxy compounds that can obtain following formula (74XA), (74XB) or (74XC) represent.
[chemical formula 55]
In above-mentioned formula (74XA), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (a) represent, a plurality of Z comprise the group that above-mentioned formula (a) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74XA) represents be the integer more than 500 and below 150000.
[chemical formula 56]
In above-mentioned formula (74XB), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (b) represent, a plurality of Z comprise the group that above-mentioned formula (b) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74XB) represents be the integer more than 500 and below 150000.
[chemical formula 57]
In above-mentioned formula (74XC), X represents to come from as the skeleton of the Bisphenol F of dikaryon or comes from and has Bisphenol F skeleton and have 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (c) represent, a plurality of Z comprise the group that above-mentioned formula (c) represents, n represents integer.And n is that to make the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74XC) represents be the integer more than 500 and below 150000.
X in above-mentioned formula (74XA), above-mentioned formula (74XB) and above-mentioned formula (74XC) is the structural unit that above-mentioned formula (Xa) represents.
At above-mentioned formula (71A), formula (71B), formula (71C), formula (71XA), formula (71XB), formula (71XC), formula (72A), formula (72B), formula (72C), formula (73A), formula (73B), formula (73C), formula (74A), formula (74B), formula (74C), formula (74XA), in formula (74XB) and formula (74XC), preferred above-mentioned formula (71A), formula (71B), formula (71C), formula (71XA), formula (71XB), formula (71XC), formula (72A), formula (72B), formula (72C), formula (73A), formula (73B) and formula (73C), more preferably above-mentioned formula (71XA), formula (71XB), formula (71XC), formula (72A), formula (72B), formula (72C), formula (73A), formula (73B) and formula (73C).In above-mentioned formula (71A), formula (71B), formula (71C), formula (71XA), formula (71XB), formula (71XC), formula (72A), formula (72B), formula (72C), formula (73A), formula (73B), formula (73C), formula (74A), formula (74B), formula (74C), formula (74XA), formula (74XB) and formula (74XC), preferably n is that to make the weight-average molecular weight of the epoxy compounds of these chemical formulations be the integer more than 1000 and below 50000, and more preferably n is that to make its weight-average molecular weight be the integer more than 1000 and below 15000.In addition, n can be for more than 1, also can be for more than 2.The weight-average molecular weight of epoxy compounds is being more than the value of weight-average molecular weight of 1 o'clock more than 500 and at n in preferred above-mentioned formula (71A), formula (71B), formula (71C), formula (71XA), formula (71XB), formula (71XC), formula (72A), formula (72B), formula (72C), formula (73A), formula (73B), formula (73C), formula (74A), formula (74B), formula (74C), formula (74XA), formula (74XB) and formula (74XC), more than 500 and at n, is being more preferably more than the value of weight-average molecular weight of 2 o'clock.
From the further viewpoint of improving the cementability of cured article, preferably in the molecular weight distribution of the 1st epoxy compounds, have 2 peaks, described the 1st epoxy compounds is by obtaining (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned the 1st reaction.From the further viewpoint of improving the cementability of cured article, preferably in the molecular weight distribution of the 2nd epoxy compounds, have 2 peaks, described the 2nd epoxy compounds is by obtaining (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned the 2nd reaction.
As the concrete reaction that above-mentioned reaction product X and (methyl) vinylformic acid are reacted, can enumerate condensation reaction.
As the concrete reaction that above-mentioned reaction product X and 2-(methyl) acryloxy ethyl isocyanate is reacted, can enumerate addition reaction.
As the concrete reaction that above-mentioned reaction product X and 4-hydroxyl butylglycidyl ether are reacted, can enumerate condensation reaction.
When using by the Bisphenol F as dikaryon in order to obtain epoxy compounds of the present invention and thering is Bisphenol F skeleton and there is 3 reaction product that obtain with the coenocytic mixture of coker, in the epoxy compounds obtaining, amount in 100 % by weight coming from as the structural unit of the Bisphenol F of dikaryon and come to there is Bisphenol F skeleton and there are 3 coenocytic structural units with coker, come from more than ratio as the structural unit of the Bisphenol F of dikaryon is preferably 70 % by weight, more preferably more than 85 % by weight, be preferably below 99.9 % by weight, more preferably below 99 % by weight.If amounted in 100 % by weight in said structure unit, come from ratio as the structural unit of the Bisphenol F of dikaryon more than above-mentioned lower limit and below the above-mentioned upper limit, the cementability of the cured article that uses above-mentioned epoxy compounds and obtain further uprises, and uses the above-mentioned solidification compound contain above-mentioned epoxy compounds and the reliability of the syndeton body obtaining further uprises.
(mixture of epoxy compounds)
The mixture of epoxy compounds of the present invention contains at least 2 kinds of above-mentioned epoxy compoundss.So, above-mentioned epoxy compounds of more than two kinds can be used in combination.By above-mentioned epoxy compounds of more than two kinds is used in combination, the viscosity of the mixture of regulating ring oxygen compound easily.
From making epoxy compounds more promptly solidify, and can further improve cementability and the wet fastness of cured article, or the viewpoint that produces space in inhibition syndeton body is set out, the mixture of preferred epoxy compounds of the present invention contains the 1st epoxy compounds and the 2nd epoxy compounds, described the 1st epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 1st reaction product, described the 1st reaction product is Bisphenol F and 1, the reaction product of 6-hexanediol diglycidyl ether, described the 2nd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 2nd reaction product, described the 2nd reaction product is Resorcinol and 1, the reaction product of 6-hexanediol diglycidyl ether.
From making epoxy compounds more promptly solidify, and can further improve cementability and the wet fastness of cured article, or the viewpoint that produces space in inhibition syndeton body is set out, the mixture of preferred epoxy compounds of the present invention contains the 2nd epoxy compounds and the 3rd epoxy compounds, described the 2nd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 2nd reaction product, described the 2nd reaction product is Resorcinol and 1, the reaction product of 6-hexanediol diglycidyl ether, described the 3rd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 3rd reaction product, described the 3rd reaction product is the reaction product of Resorcinol and resorcinol diglycidyl ether.
The mixture of preferred epoxy compounds of the present invention contains above-mentioned the 1st epoxy compounds and above-mentioned the 2nd epoxy compounds or contains above-mentioned the 2nd epoxy compounds and above-mentioned the 3rd epoxy compounds.
From improving coating, making to be difficult for producing the viewpoint in space syndeton body, more than the viscosity of the mixture of epoxy compounds at 23 ℃ is preferably 50Pas, more preferably more than 100Pas, be preferably below 1200Pas, more preferably below 600Pas, more preferably below 400Pas.
(solidification compound)
Solidification compound of the present invention contains above-mentioned epoxy compounds and thermal curing agents.That is, solidification compound of the present invention contains following epoxy compounds and thermal curing agents, and two ends of described epoxy compounds have epoxy group(ing) and side chain has vinyl or epoxy group(ing), and weight-average molecular weight is more than 500 and below 150000.Solidification compound of the present invention can solidify rapidly, and can improve cementability and the wet fastness of cured article.
Preferred solidification compound of the present invention contains at least 2 kinds of epoxy compoundss.By above-mentioned epoxy compounds of more than two kinds is used in combination, can easily regulate the viscosity of solidification compound.
From improving coating and making, syndeton body, be difficult for producing the viewpoint in space, more than the viscosity of solidification compound at 23 ℃ is preferably 50Pas, more preferably more than 100Pas, be preferably below 1200Pas, more preferably below 600Pas, more preferably below 400Pas
More preferably solidification compound of the present invention meets the following conditions: (1) above-mentioned epoxy compounds contains the 1st epoxy compounds and contains Bisphenol F diglycidylether or 1,6-hexanediol diglycidyl ether, described the 1st epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 1st reaction product, described the 1st reaction product is the reaction product of Bisphenol F and 1,6-hexanediol diglycidyl ether; Or (2) above-mentioned epoxy compounds contains the 2nd epoxy compounds and contains resorcinol diglycidyl ether or 1,6-hexanediol diglycidyl ether, described the 2nd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 2nd reaction product, described the 2nd reaction product is the reaction product of Resorcinol and 1,6-hexanediol diglycidyl ether; Or (3) above-mentioned epoxy compounds contains the 3rd epoxy compounds and contains resorcinol diglycidyl ether, described the 3rd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 3rd reaction product, and described the 3rd reaction product is the reaction product of Resorcinol and resorcinol diglycidyl ether; Or (4) are contained the 4th epoxy compounds and contain Bisphenol F diglycidylether or resorcinol diglycidyl ether, described the 4th epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 4th reaction product, and described the 4th reaction product is the reaction product of Bisphenol F and resorcinol diglycidyl ether.In this case, the cross-linking density of the cured article of solidification compound uprises, use the cementability of the cured article of above-mentioned epoxy compounds further to uprise, and use the reliability of the syndeton body of the above-mentioned solidification compound that contains above-mentioned epoxy compounds further to uprise.
More preferably solidification compound of the present invention meets the following conditions: (1) above-mentioned epoxy compounds contains above-mentioned the 1st epoxy compounds and contains Bisphenol F diglycidylether or 1,6-hexanediol diglycidyl ether; Or (2) above-mentioned epoxy compounds contains above-mentioned the 2nd epoxy compounds and contains resorcinol diglycidyl ether or 1,6-hexanediol diglycidyl ether; Or (3) above-mentioned epoxy compounds contains above-mentioned the 3rd epoxy compounds and contains resorcinol diglycidyl ether.In this case, the cross-linking density of the cured article of solidification compound uprises, use the cementability of the cured article of above-mentioned epoxy compounds further to uprise, and use the reliability of the syndeton body of the above-mentioned solidification compound that contains above-mentioned epoxy compounds further to uprise.
Solidification compound of the present invention contains above-mentioned the 1st, the 2nd, the 3rd, the 4th epoxy compounds, and contain Bisphenol F diglycidylether, resorcinol diglycidyl ether or 1, in the situation of 6-hexanediol diglycidyl ether, with respect to total amount 100 weight parts above-mentioned the the 1st, the 2nd, the 3rd, the 4th epoxy compounds, Bisphenol F diglycidylether, resorcinol diglycidyl ether and 1, more than the total content of 6-hexanediol diglycidyl ether is preferably 0.1 weight part, more preferably more than 1 weight part, be preferably below 100 weight parts, more preferably below 20 weight parts.If Bisphenol F diglycidylether, resorcinol diglycidyl ether and 1, the total content of 6-hexanediol diglycidyl ether is that above-mentioned lower limit is above with below the above-mentioned upper limit, the cross-linking density of the cured article of solidification compound uprises, use the cementability of the cured article of above-mentioned epoxy compounds further to uprise, and use the reliability of the syndeton body of the above-mentioned solidification compound that contains above-mentioned epoxy compounds further to uprise.
In preferred solidification compound of the present invention except above-mentioned epoxy compounds (epoxy compounds of the present invention), also contain epoxy (methyl) acrylate, described epoxy (methyl) acrylate is to obtain by least one in 2 epoxy group(ing) of (methyl) vinylformic acid and these epoxy compounds two ends reacted.In this case, the cross-linking density of the cured article of solidification compound uprises, use the cementability of the cured article of above-mentioned epoxy compounds further to uprise, and use the reliability of the syndeton body of the above-mentioned solidification compound that contains above-mentioned epoxy compounds further to uprise.
In addition preferred above-mentioned epoxy compounds and there is identical structure by making at least one in 2 epoxy group(ing) of (methyl) vinylformic acid and these epoxy compounds two ends react epoxy (methyl) acrylate obtaining except two terminal portionss (epoxy group(ing) or (methyl) acryl).Preferred above-mentioned epoxy compounds and above-mentioned epoxy (methyl) acrylate all have the skeleton that comes from Bisphenol F, preferably come from Resorcinol.Preferred above-mentioned epoxy compounds and above-mentioned epoxy (methyl) acrylate all have the skeleton that comes from 1,6-hexanediol diglycidyl ether, preferably have the skeleton that comes from resorcinol diglycidyl ether.By using like this epoxy compounds and epoxy (methyl) acrylate, the cross-linking density of the cured article of solidification compound further uprises, use the cementability of the cured article of above-mentioned epoxy compounds further to uprise, and use the reliability of the syndeton body of the above-mentioned solidification compound that contains above-mentioned epoxy compounds further to uprise.
In the situation that solidification compound of the present invention contains above-mentioned epoxy compounds and above-mentioned epoxy (methyl) acrylate, with respect to above-mentioned epoxy compounds 100 weight parts, more than the content of above-mentioned epoxy (methyl) acrylate is preferably 0.1 weight part, more preferably more than 1 weight part, be preferably below 100 weight parts, more preferably below 20 weight parts.If it is above with below the above-mentioned upper limit that the content of above-mentioned epoxy (methyl) acrylate is above-mentioned lower limit, the cross-linking density of the cured article of solidification compound further uprises, use the cementability of the cured article of above-mentioned epoxy compounds further to uprise, and use the reliability of the syndeton body of the above-mentioned solidification compound that contains above-mentioned epoxy compounds further to uprise.
In solidification compound of the present invention contained thermal curing agents without particular limitation of.This thermal curing agents makes the mixture solidified of epoxy compounds of the present invention or epoxy compounds of the present invention.As this thermal curing agents, can use existing known thermal curing agents.This thermal curing agents comprises thermal free radical initiator.This thermal curing agents can only be used a kind, also two or more can be used in combination.
As above-mentioned thermal curing agents, can enumerate cation curing agent, imidazole curing agent, amine hardener, phenol solidifying agent, polythiol solidifying agent, acid anhydrides and thermal free radical initiator etc.Wherein, preferred cationic solidifying agent, imidazole curing agent, polythiol solidifying agent or amine hardener, this is more promptly to solidify because these solidifying agent can make solidification compound.In addition, preferred latent curing agent, this is can improve the storage stability of solidification compound due to such solidifying agent.Preferably latent curing agent is latent imidazole curing agent, latent polythiol solidifying agent or latent amine hardener.It should be noted that, above-mentioned thermal curing agents also can be coated by polymer substances such as urethane resin or vibrin.
As above-mentioned imidazole curing agent, without particular limitation of, can enumerate: 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 and 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine isocyanuric acid affixture etc.
As above-mentioned polythiol solidifying agent, without particular limitation of, can enumerate: trimethylolpropane tris-3-mercaptopropionic acid ester, tetramethylolmethane four-3-mercaptopropionic acid ester and Dipentaerythritol six-3-mercaptopropionic acid ester etc.
As above-mentioned amine hardener, without particular limitation of, can enumerate: hexamethylene-diamine, eight methylene diamine, decamethylene diamine, 3,9-bis-(3-aminopropyl)-2,4,8,10-, tetra-spiral shells [5.5] undecane, two (4-aminocyclohexyl) methane, mphenylenediamine and diaminodiphenylsulfone(DDS) etc.
In above-mentioned thermal curing agents, preferred multi-thioalcohol compound or acid anhydrides etc.Owing to can further accelerating the curing speed of solidification compound, therefore preferred multi-thioalcohol compound.
In above-mentioned multi-thioalcohol compound, more preferably tetramethylolmethane four-3-mercaptopropionic acid ester.By using this multi-thioalcohol compound, can further accelerate the curing speed of solidification compound.
As above-mentioned thermal free radical initiator, without particular limitation of, azo-compound and superoxide etc. can be enumerated.As above-mentioned superoxide, can enumerate diacyl peroxide compound, peroxyester compound, hydroperoxide compound, peroxy dicarbonate, ketal peroxide compound, dialkyl peroxide compound and ketone peroxide compound etc.
As above-mentioned azo-compound, for example can enumerate: 2, 2 '-Diisopropyl azodicarboxylate, 2, 2 '-azo two (2-methylbutyronitrile), 2, 2 '-azo two (2, 4-methyl pentane nitrile), 1, 1 '-azo, two-1-hexanaphthene formonitrile HCN, dimethyl-2, 2 '-azo-bis-iso-butyl, dimethyl-2, 2 '-azo two (2 Methylpropionic acid ester), dimethyl-1, 1 '-azo two (1-cyclohexane carboxylate), 4, 4 '-azo two (4-cyanopentanoic acid), 2, 2 '-azo two (2-amidine propane) dihydrochloride, 2-tertiary butyl azo-2-dicyanopropane, 2, 2 '-azo two (2-methyl propanamide) dihydrate and 2, 2 '-azo two (2, 4, 4-trimethylpentane) etc.
As above-mentioned diacyl peroxide, can enumerate: benzoyl peroxide, diisobutyryl peroxide, two (3,5,5-trimethyl acetyl base) superoxide, dilauroyl peroxide and disuccinic acid peroxide etc.As above-mentioned peroxyester compound, can enumerate: peroxidation neodecanoic acid cumyl ester, peroxidation neodecanoic acid 1, 1, 3, 3-tetramethyl-butyl ester, the tertiary own ester of peroxidation neodecanoic acid, new peroxide tert-butyl caprate, the new enanthic acid tert-butyl ester of peroxidation, the tertiary own ester of peroxidation PIVALIC ACID CRUDE (25), peroxidation-2 ethyl hexanoic acid 1, 1, 3, 3-tetramethyl-butyl ester, 2, 5-dimethyl-2, 5-bis-(peroxidation of 2-ethyl hexyl acyl group) hexane, the tertiary own ester of peroxidation-2 ethyl hexanoic acid, tert-Butyl peroxypivalate, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation tert-butyl isobutyrate, the peroxidation lauric acid tert-butyl ester, the peroxidation m-phthalic acid tert-butyl ester, peroxide acetic acid butyl ester, the peroxidation acid tert-butyl ester and peroxidized t-butyl perbenzoate etc.As above-mentioned hydroperoxide compound, can enumerate: cumene hydroperoxide, p-menthane hydroperoxide etc.As above-mentioned peroxy dicarbonate compound, can enumerate: di-sec-butyl peroxy dicarbonate, two (4-tert-butylcyclohexyl) peroxy dicarbonate, diη-propyl peroxy dicarbonate, di-isopropyl peroxycarbonates and two (2-ethylhexyl) peroxycarbonates etc.In addition, as other examples of above-mentioned superoxide, can enumerate: two (tert-butyl hydroperoxide)-3,3 of methylethyl ketone peroxide, Potassium Persulphate and 1,1-, 5-trimethyl-cyclohexane etc.
Being preferably more than 30 ℃ for obtaining the decomposition temperature of 10 hour transformation period of above-mentioned thermal free radical initiator, more preferably more than 40 ℃, is preferably below 90 ℃, more preferably below 80 ℃, more preferably below 70 ℃.If above-mentioned thermal free radical initiator for the decomposition temperature that obtains 10 hour transformation period lower than 30 ℃, there is the tendency declining in the package stability of solidification compound, if surpass 90 ℃, has the tendency that is difficult to make the abundant thermofixation of solidification compound.
The content of above-mentioned thermal curing agents without particular limitation of.In solidification compound of the present invention, total amount 100 weight parts with respect to above-mentioned epoxy compounds, more than the content of thermal curing agents is preferably 0.01 weight part, more preferably more than 1 weight part, be preferably below 200 weight parts, more preferably below 100 weight parts, more preferably below 75 weight parts.If the content of thermal curing agents is more than above-mentioned lower limit, be easy to make solidification compound fully curing.If the content of thermal curing agents is below the above-mentioned upper limit, after solidifying, be difficult for residually having neither part nor lot in curing unnecessary thermal curing agents, and the thermotolerance of cured article further uprises.
It should be noted that, when above-mentioned thermal curing agents is imidazole curing agent or phenol solidifying agent, with respect to total amount 100 weight parts of above-mentioned epoxy compounds, the content of imidazole curing agent or phenol solidifying agent is preferably below 15 weight parts more than being preferably 1 weight part.In addition,, when above-mentioned thermal curing agents is amine hardener, polythiol solidifying agent or acid anhydrides, with respect to total amount 100 weight parts of above-mentioned epoxy compounds, the content of amine hardener, polythiol solidifying agent or acid anhydrides is preferably below 40 weight parts more than being preferably 15 weight parts.
When above-mentioned thermal curing agents is thermal free radical initiator, the content of above-mentioned thermal free radical initiator without particular limitation of.With respect to total amount 100 weight parts of above-mentioned epoxy compounds, more than the content of above-mentioned thermal free radical initiator is preferably 0.01 weight part, more preferably more than 0.05 weight part, be preferably below 10 weight parts, more preferably below 5 weight parts.If it is above with below the above-mentioned upper limit that the content of above-mentioned thermal free radical initiator is above-mentioned lower limit, can make the abundant thermofixation of solidification compound.
[other compositions]
Preferred solidification compound of the present invention further contains curing catalyst.By using curing catalyst, can further accelerate the curing speed of solidification compound.Curing catalyst can only be used a kind, also two or more can be used in combination.
As the object lesson of above-mentioned curing catalyst, can enumerate imidazoles curing catalyst and amine curing catalyst etc.Preferred imidazoles curing catalyst wherein.In addition, imidazoles curing catalyst or amine curing catalyst also can be used as imidazole curing agent or amine hardener is used.
As above-mentioned imidazoles curing catalyst, can enumerate: 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 and 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine isocyanuric acid affixture etc.
With respect to total amount 100 weight parts of above-mentioned epoxy compounds, more than the content of above-mentioned curing catalyst is preferably 0.5 weight part, more preferably more than 1 weight part, be preferably below 6 weight parts, more preferably below 4 weight parts.If the content of curing catalyst is more than above-mentioned lower limit, be easy to make solidification compound fully curing.If the content of curing catalyst is below the above-mentioned upper limit, after solidifying, be difficult for the residual curing unnecessary curing catalyst that has neither part nor lot in.
For solidification compound of the present invention can be solidified by illumination, solidification compound of the present invention can contain photocurable compound and Photoepolymerizationinitiater initiater.By using above-mentioned photocurable compound and Photoepolymerizationinitiater initiater, can solidification compound be solidified by carrying out illumination.In addition, can make solidification compound carry out semicure and the mobility of solidification compound is reduced.
Above-mentioned photocurable compound without particular limitation of.As this photocurable compound, the resin that preferably uses (methyl) acrylic resin or contain ring-type ether etc., are more preferably used (methyl) acrylic resin.Above-mentioned (methyl) acrylic resin represents methacrylic resin and acrylic resin.Above-mentioned (methyl) acrylic resin has (methyl) acryl.Above-mentioned (methyl) acryl represents methacryloyl and acryl.
As above-mentioned (methyl) acrylic resin, the compound that preferably makes (methyl) vinylformic acid and have a hydroxyl reacts and the ester cpds that obtains, (methyl) vinylformic acid and epoxy compounds is reacted and epoxy (methyl) acrylate that obtains or make has that (methyl) acrylic acid derivative of hydroxyl reacts with isocyanic ester and carbamate (methyl) acrylate that obtains etc.
Above-mentioned making (methyl) vinylformic acid and the compound with hydroxyl react and the ester cpds that obtains without particular limitation of.As this ester cpds, can use any ester cpds in simple function ester cpds, difunctionality ester cpds and ester cpds more than trifunctional.
Preferred above-mentioned photocurable compound comprises the photocurable compound with epoxy group(ing) or thiiranes group and (methyl) acryl.
Preferably the above-mentioned photocurable compound with epoxy group(ing) or thiiranes group and (methyl) acryl is by part epoxy group(ing) or the part thiiranes group with the compound of 2 above epoxy group(ing) or 2 above thiiranes groups are converted into the photocurable compound that (methyl) acryl obtains.Such photocurable compound is part (methyl) acroleic acid esterification epoxy compounds or part (methyl) acroleic acid esterification episulfide compound.
Preferred above-mentioned photocurable compound is the compound and (methyl) acrylic acid reaction product with 2 above epoxy group(ing) or 2 above thiiranes groups.This reaction product can be by making the compound with 2 above epoxy group(ing) or 2 above thiiranes groups react and obtain under the existence of the catalyzer such as basic catalyst according to conventional methods with (methyl) vinylformic acid.Preferably epoxy group(ing) or thiiranes group more than 20% is converted into (methyl) acryl (transformation efficiency).This transformation efficiency more preferably more than 30%, is preferably below 80%, more preferably below 70%.Most preferably more than 40% of epoxy group(ing) or thiiranes group and below 60%, be converted into (methyl) acryl.
As the above-mentioned photocurable compound with epoxy group(ing) or thiiranes group and (methyl) acryl, can enumerate bisphenol type epoxy (methyl) acrylate, cresols phenolic varnish type epoxy (methyl) acrylate, carboxylic acid anhydride modified epoxy (methyl) acrylate and phenol phenolic varnish type epoxy (methyl) acrylate etc.
As above-mentioned photocurable compound, also can use part epoxy group(ing) or the part thiiranes group of the phenoxy resin with 2 above epoxy group(ing) or 2 above thiiranes groups to be converted into the modification phenoxy resin that (methyl) acryl forms.That is, can use the modification phenoxy resin with epoxy group(ing) or thiiranes group or (methyl) acryl.
In the situation that comprises the photocurable compound except above-mentioned photocurable compound, this photocurable compound can be cross-linked compound, can be also non-cross-linked compound.
Object lesson as above-mentioned cross-linked compound, for example can enumerate: 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 methacrylic ester acrylate, tetramethylolmethane three (methyl) acrylate, trimethylolpropane trimethacrylate, (methyl) allyl acrylate, (methyl) vinyl acrylate, Vinylstyrene, polyester (methyl) acrylate and carbamate (methyl) acrylate etc.
Object lesson as above-mentioned non-crosslinked compound, can enumerate: (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate and (methyl) vinylformic acid tetradecyl ester etc.
From making above-mentioned solidification compound that the viewpoint of photocuring occur efficiently, total amount 100 weight parts with respect to above-mentioned epoxy compounds, more than the content of above-mentioned photocurable compound is preferably 0.1 weight part, more preferably more than 1 weight part, more preferably more than 10 weight parts, more than being particularly preferably 50 weight parts, be preferably below 10000 weight parts, more preferably below 1000 weight parts, more preferably below 500 weight parts.
Above-mentioned Photoepolymerizationinitiater initiater without particular limitation of.Above-mentioned Photoepolymerizationinitiater initiater comprises optical free radical initiator.Above-mentioned Photoepolymerizationinitiater initiater can only be used a kind, also two or more can be used in combination.
As the object lesson of above-mentioned Photoepolymerizationinitiater initiater, can enumerate: methyl phenyl ketone Photoepolymerizationinitiater initiater (methyl phenyl ketone optical free radical initiator), benzophenone Photoepolymerizationinitiater initiater (benzophenone optical free radical initiator), thioxanthone, ketal Photoepolymerizationinitiater initiater (ketal optical free radical initiator), halogenated ketone, acylphosphine oxide and acyl phosphonate etc.Also can use Photoepolymerizationinitiater initiater in addition.
Object lesson as above-mentioned methyl phenyl ketone Photoepolymerizationinitiater initiater, can enumerate: 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 and 2-hydroxyl-2-phenylcyclohexane ethyl ketone etc.As the object lesson of above-mentioned ketal Photoepolymerizationinitiater initiater, can enumerate benzoin dimethylether etc.
The content of above-mentioned Photoepolymerizationinitiater initiater without particular limitation of.With respect to above-mentioned Photocurable composition 100 weight parts, more than the content of above-mentioned Photoepolymerizationinitiater initiater is preferably 0.1 weight part, more preferably more than 0.2 weight part, more preferably more than 2 weight parts, be preferably below 10 weight parts, more preferably below 5 weight parts.If the content of Photoepolymerizationinitiater initiater is more than above-mentioned lower limit, be easy to give full play to the effect of having added Photoepolymerizationinitiater initiater.If the content of Photoepolymerizationinitiater initiater is below the above-mentioned upper limit, the bonding force of the cured article of solidification compound is improved fully.
Preferred solidification compound of the present invention further contains phenoloid.This phenoloid has hydroxyl bond and is combined in the phenol hydroxyl on phenyl ring.As above-mentioned phenoloid, can enumerate polyphenol, trivalent alcohol, Resorcinol and tocopherol (vitamin-E) etc.Above-mentioned phenoloid can only be used a kind, also two or more can be used in combination.
Preferred solidification compound of the present invention further contains filler.By using filler, the latent heat that can suppress the cured article of solidification compound expands.As the object lesson of above-mentioned filler, can enumerate silicon-dioxide, aluminium nitride or aluminum oxide etc.Filler can only be used a kind, also two or more can be used in combination.
The content of above-mentioned filler without particular limitation of.With respect to total amount 100 weight parts of solidification compound, more than the content of above-mentioned filler is preferably 5 weight parts, more preferably more than 15 weight parts, be preferably below 200 weight parts, more preferably below 100 weight parts.If it is above with below the above-mentioned upper limit that the content of above-mentioned filler is above-mentioned lower limit, the latent heat that can fully suppress cured article expands, and can make filler be well dispersed in solidification compound.Above-mentioned solidification compound contains above-mentioned epoxy compounds and above-mentioned photocurable compound.
Solidification compound of the present invention can contain solvent.By using this solvent, can easily regulate the viscosity of solidification compound.
As above-mentioned solvent, can enumerate such as ethyl acetate, methyl glycol, toluene, acetone, methylethylketone, hexanaphthene, normal hexane, tetrahydrofuran (THF) and ether etc.
Solidification compound of the present invention can further contain storage stabilizer, ion trap agent or silane coupling agent etc. as required.
[solidification compound that contains electroconductive particle]
Solidification compound of the present invention further contains in the situation of electroconductive particle, can be by solidification compound as electro-conductive material.Preferably this electro-conductive material is anisotropic conductive material.Preferably the mixture of above-mentioned epoxy compounds and above-mentioned epoxy compounds is used as together with electroconductive particle to electro-conductive material, is more preferably used as anisotropic conductive material together with electroconductive particle.
Above-mentioned electroconductive particle is electrically connected to by the 1st, between the electrode of the 2nd connecting object parts.Particularly, above-mentioned electroconductive particle will be electrically connected between the electrode of for example circuit substrate and semi-conductor chip.Above-mentioned electroconductive particle so long as the particle with electroconductibility just without particular limitation of.Above-mentioned electroconductive particle is as long as have conductive part on the surface of electroconductibility.It is coated that the conductive part surface of electroconductive particle can be insulated layer.In this case, when connecting object parts are connected, can get rid of conductive part and interelectrode insulation layer.As above-mentioned electroconductive particle, can enumerate such as organic filler, inorganic particulate except metal, organic inorganic hybridization particle or the electroconductive particle that forms with the surface of conductive layer (metal level) clad metal particle etc., or the metallics in fact only being formed by metal etc.Above-mentioned conductive part without particular limitation of.As the metal that forms above-mentioned conductive part, can enumerate gold and silver, copper, nickel, palladium and tin etc.As above-mentioned conductive layer, the conductive layer that can enumerate gold layer, silver layer, copper layer, nickel dam, palladium layer or contain tin etc.
From increase electrode and electroconductive particle contact area, further improve the viewpoint of interelectrode conducting reliability, preferred above-mentioned electroconductive particle has resin particle and is configured in the lip-deep conductive layer of this resin particle (the 1st conductive layer).From the viewpoint of the interelectrode conducting reliability of further raising, preferred above-mentioned electroconductive particle is the electroconductive particle that at least electroconductibility outside surface is low-melting-point metal layer.More preferably above-mentioned electroconductive particle has resin particle and is configured in the lip-deep conductive layer of this resin particle, and at least outside surface of this conductive layer is low-melting-point metal layer.
Above-mentioned low-melting-point metal layer is the layer that contains low melting point metal.This low melting point metal refers to that fusing point is 450 ℃ of following metals.The fusing point of low melting point metal is preferably below 300 ℃, more preferably below 160 ℃.In addition, preferred above-mentioned low-melting-point metal layer contains tin.In contained metal 100 % by weight of low-melting-point metal layer, more than the content of tin is preferably 30 % by weight, more preferably more than 40 % by weight, more preferably more than 70 % by weight, more than being particularly preferably 90 % by weight.If the content of above-mentioned low-melting-point metal layer is more than above-mentioned lower limit, the connection reliability of low-melting-point metal layer and electrode further uprises.It should be noted that, the content of above-mentioned tin can adopt the mensuration such as high-frequency inductive coupling plasma body emmission spectrometric analysis device (" ICP-AES " that Ku Chang manufacturing company manufactures) or fluorescent x-ray analyzer (" EDX-800HS " that Shimadzu Seisakusho Ltd. manufactures).
The outside surface of conductive part is in the situation of low-melting-point metal layer, low-melting-point metal layer melting and be engaged in electrode, and low-melting-point metal layer makes conducting between electrode.Because low-melting-point metal layer for example and electrode are easy to that generating plane contacts but not some contact, therefore, contact resistance step-down.In addition, by using the electroconductive particle that at least electroconductibility outer surface is low-melting-point metal layer, the bond strength of low-melting-point metal layer and electrode uprises, its result, and the peeling off of low-melting-point metal layer and electrode becomes and is more difficult for occurring, and conducting reliability effectively improves.
The low melting point metal that forms above-mentioned low-melting-point metal layer without particular limitation of.Preferably this low melting point metal is tin or the alloy that contains tin.This alloy can be enumerated tin-silver alloys, tin-copper alloy, tin-silver-copper alloy, tin-bismuth alloy electroplating, tin-zinc alloy, Sn-In alloy etc.Wherein, from the viewpoint of the wettability excellence to electrode, preferred above-mentioned low melting point metal is tin, tin-silver alloys, tin-silver-copper alloy, tin-bismuth alloy electroplating, Sn-In alloy.More preferably tin-bismuth alloy electroplating, Sn-In alloy.
In addition, preferred above-mentioned low-melting-point metal layer is soldering-tin layer.The material that forms above-mentioned soldering-tin layer without particular limitation of, be preferably the Z3001 based on JIS: welding term, liquidus line are at the filler metal below 450 ℃.As the composition of above-mentioned sealing weld, can enumerate such as the metal that contains zinc, gold, lead, copper, tin, bismuth, indium etc. and form.Wherein, preferred low melting point and unleaded tin-indium class (117 ℃ of eutectics) or Sn-Bi class (139 ℃ of eutectics).That is, preferably soldering-tin layer is not leaded, preferably contains the soldering-tin layer of tin and indium or contains tin and the soldering-tin layer of bismuth.
In order further to improve the bond strength of above-mentioned low-melting-point metal layer and electrode, above-mentioned low-melting-point metal layer can contain the metals such as nickel, copper, antimony, aluminium, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese, chromium, molybdenum, palladium.From the viewpoint of the bond strength of further raising low melting point metal and electrode, preferred above-mentioned low melting point metal contains nickel, copper, antimony, aluminium or zinc.From the viewpoint of the bond strength of further raising low-melting-point metal layer and electrode, for improving more than the content of the above-mentioned metal of bond strength is preferably 0.0001 % by weight in low-melting-point metal layer 100 % by weight, be preferably below 1 % by weight.
Preferred above-mentioned electroconductive particle has resin particle and is configured in the lip-deep conductive layer of this resin particle, and the outer surface of this conductive layer is low-melting-point metal layer, between above-mentioned resin particle and above-mentioned low-melting-point metal layer (soldering-tin layer etc.), there is 2nd conductive layer different from above-mentioned low-melting-point metal layer.In this case, above-mentioned low-melting-point metal layer is above-mentioned conductive layer part of the whole, and above-mentioned the 2nd conductive layer is above-mentioned conductive layer part of the whole.
Preferably above-mentioned 2nd conductive layer different from above-mentioned low-melting-point metal layer contains metal.The metal that forms the 2nd conductive layer without particular limitation of.As this metal, can enumerate such as gold and silver, copper, platinum, palladium, zinc, lead, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium and their alloy etc.In addition,, as above-mentioned metal, can use tin-doped indium oxide (ITO).Above-mentioned metal can only be used a kind, also two or more can be used in combination.
Preferably above-mentioned the 2nd conductive layer is nickel dam, palladium layer, copper layer or gold layer, more preferably nickel dam or gold layer, more preferably copper layer.Preferably electroconductive particle has nickel dam, palladium layer, copper layer or gold layer, more preferably has nickel dam or gold layer, further preferably has copper layer.By by the electroconductive particle with these preferred conductive layers for interelectrode connection, interelectrode contact resistance further reduces.In addition, can more easily form low-melting-point metal layer on the surface of these preferred conductive layers.It should be noted that, above-mentioned the 2nd conductive layer can be also the low-melting-point metal layers such as soldering-tin layer.Electroconductive particle can have multilayer low-melting-point metal layer.
More than the thickness of above-mentioned low-melting-point metal layer is preferably 0.1 μ m, more preferably more than 0.5 μ m, more preferably more than 1 μ m, be preferably below 50 μ m, more preferably 10 μ m, more preferably, below 5 μ m, are particularly preferably below 3 μ m.If the thickness of above-mentioned low-melting-point metal layer is that more than above-mentioned lower limit electroconductibility is improved fully.If the thickness of above-mentioned low-melting-point metal layer is below the above-mentioned upper limit, the difference of the thermal expansivity of resin particle and low-melting-point metal layer diminishes, and the peeling off of low-melting-point metal layer becomes and be difficult for occurring.
Conductive layer is in the situation of the conductive layer beyond low-melting-point metal layer, or conductive layer has in the situation of multilayered structure, more than the integral thickness of conductive layer is preferably 0.1 μ m, more preferably more than 0.5 μ m, more preferably more than 1 μ m, be preferably below 50 μ m, more preferably below 10 μ m, more preferably, below 5 μ m, be particularly preferably below 3 μ m.
The median size of electroconductive particle is preferably below 100 μ m, more preferably, below 20 μ m, is further preferably and is less than below 20 μ m, more preferably, below 15 μ m, is particularly preferably below 10 μ m.More than the median size of electroconductive particle is preferably 0.5 μ m, more preferably more than 1 μ m.The viewpoint of the connection reliability of the syndeton body when further raising has stood thermal history, particularly preferably the median size of electroconductive particle is that 1 μ m is above and below 10 μ m, most preferably is 1 μ m above and below 4 μ m.
Particularly preferably the median size of electroconductive particle is in the scope of 1 μ m～100 μ m, this be due to above-mentioned scope be with anisotropic conductive material in the size that adapts of electroconductive particle, and can further dwindle interelectrode interval.
Above-mentioned resin particle can be distinguished use according to the electrode size of the substrate of actual installation or groove bank diameter (ラ Application De footpath).
From making to connect and further suppress more effectively between upper/lower electrode the viewpoint of the short circuit between horizontal adjacent electrode, the median size C of electroconductive particle is greater than 1.0 with the ratio (C/A) of the median size A of resin particle, is preferably below 3.0.In addition, between above-mentioned resin particle and above-mentioned soldering-tin layer, exist in the situation of above-mentioned the 2nd conductive layer, the median size B of the electroconductive particle part except soldering-tin layer is greater than 1.0 with the ratio (B/A) of the median size A of resin particle, is preferably below 2.0.Further, between above-mentioned resin particle and above-mentioned soldering-tin layer, exist in the situation of above-mentioned the 2nd conductive layer, the median size C of the electroconductive particle that contains soldering-tin layer is greater than 1.0 with the ratio (C/B) of the median size B of the part of the electroconductive particle except soldering-tin layer, is preferably below 2.0.Above-mentioned ratio (B/A) in above-mentioned scope or above-mentioned ratio (C/B) in above-mentioned scope time, can make to connect and further suppress more effectively between upper/lower electrode the short circuit between horizontal adjacent electrode.
Be suitable for the electro-conductive material (anisotropic conductive material) of FOB and FOF purposes:
Above-mentioned electro-conductive material is applicable to connection (FOB (Film on Board)) between flexible printing substrate and glass epoxy substrate or the connection (FOF (Film on Film)) between flexible printing substrate and flexible printing substrate.
In FOB and FOF purposes, the size that has the part (line) of electrode and do not have a part (gap) of electrode is that L & S is generally 100～500 μ m.The median size of the resin particle preferably using in FOB and FOF purposes is 10～100 μ m.If the median size of resin particle is more than 10 μ m, the thickness that is configured in interelectrode electro-conductive material and connection section is enough thick, and bonding force further uprises.If the median size of resin particle is below 100 μ m, be more difficult for being short-circuited between adjacent electrode.
Be suitable for the electro-conductive material (anisotropic conductive material) of flip-chip purposes:
Above-mentioned electro-conductive material is applicable to flip-chip purposes.
In flip-chip purposes, groove bank typically has a diameter from 15～80 μ m.The median size of the resin particle preferably using in flip-chip purposes is 1～15 μ m.If the median size of resin particle is more than 1 μ m, the thickness that can make to be configured in the lip-deep soldering-tin layer of this resin particle is enough thick, can between electrode, be electrically connected to more effectively.If the median size of resin particle is below 10 μ m, be more difficult for being short-circuited between adjacent electrode.
Be suitable for the electro-conductive material (anisotropic conductive material) of COF
Above-mentioned electro-conductive material is applicable to the connection (COF (Chip on Film)) between semi-conductor chip and flexible printing substrate.
In COF purposes, the size that has the part (line) of electrode and do not have a part (gap) of electrode is that L & S is generally 10～50 μ m.The median size of the resin particle preferably using in COF purposes is 1～10 μ m.If the median size of resin particle is more than 1 μ m, the thickness that can make to be configured in the lip-deep soldering-tin layer of this resin particle is enough thick, can between electrode, be electrically connected to more effectively.If the median size of resin particle is below 10 μ m, be more difficult for being short-circuited between adjacent electrode.
" median size " of above-mentioned electroconductive particle represents number average bead diameter.The median size of electroconductive particle can be by obtaining with electron microscope or any 50 electroconductive particles of observation by light microscope calculating mean value.
Also can utilize the insulating material such as insulativity particle, solder flux etc. to carry out insulation processing to the surface of electroconductive particle.Preferably under the heat effect when connecting such as insulativity material, solder flux, occur to soften, flow, thereby be excluded from connection section.Can suppress interelectrode short circuit thus.
The content of above-mentioned electroconductive particle without particular limitation of.In solidification compound 100 % by weight, more than the content of above-mentioned electroconductive particle is preferably 0.1 % by weight, more preferably more than 0.5 % by weight, be preferably below 40 % by weight, more preferably below 20 % by weight, more preferably below 15 % by weight.If the content of above-mentioned electroconductive particle is more than above-mentioned lower limit and below the above-mentioned upper limit, can easily electroconductive particle be configured between the upper/lower electrode of wish connection.And, between the adjacent electrode that wish does not connect, be difficult for being electrically connected to by a plurality of electroconductive particles.That is, can prevent the short circuit between adjacent electrode.
(purposes of solidification compound)
Solidification compound of the present invention can be for bonding various connecting object parts.
Solidification compound of the present invention is in the situation of the electro-conductive material that contains electroconductive particle, this electro-conductive material can be used with forms such as electroconductive paste or conducting films.When electro-conductive material is used with conducting film form, can not contain the film of electroconductive particle at this conducting film superimposed layer that contains electroconductive particle.It should be noted that, film comprises sheet material.The electroconductive paste that preferred solidification compound of the present invention is pasty state.Preferred above-mentioned electroconductive paste is that anisotropic conductive is stuck with paste.Preferred above-mentioned conducting film is anisotropic conductive film.
Above-mentioned electro-conductive material is suitable for to obtain by the 1st, the 2nd connecting object parts and is electrically connected to the syndeton body forming.
Fig. 1 is sectional view, schematically shows an example of the syndeton body of the solidification compound that has used an embodiment of the present invention.
The 1st connecting object parts 2 have a plurality of electrode 2b at upper surface 2a (surface).The 2nd connecting object parts 4 have a plurality of electrode 4b at lower surface 4a (surface).Electrode 2b and electrode 4b are electrically connected to by one or more electroconductive particles 5.Therefore, the 1st, the 2nd connecting object parts 2,4 are electrically connected to by electroconductive particle 5.
Preferred solidification compound of the present invention is the electroconductive paste of pasty state, and is that state with pasty state is coated on the electroconductive paste on the 1st connecting object parts.
Above-mentioned the 1st, the 2nd connecting object parts without particular limitation of.As the 1st, the 2nd connecting object parts, specifically can enumerate: the electronic units such as circuit substrate such as the electronic units such as semi-conductor chip, electrical condenser and diode and printed base plate, flexible printing substrate and glass substrate etc.Preferably the 1st, the 2nd connecting object parts are electronic unit.Preferred solidification compound of the present invention is the solidification compound for connecting electronic parts.
The manufacture method of above-mentioned syndeton body without particular limitation of.As an example of the manufacture method of syndeton body, can enumerate above-mentioned solidification compound is configured between the 1st connecting object parts and the 2nd connecting object parts and obtains after multilayer body the method that this multilayer body is heated and pressurizeed.
It should be noted that, above-mentioned solidification compound also can not contain electroconductive particle.In this case, the object of using above-mentioned solidification compound is not for the 1st, the 2nd connecting object parts are electrically connected to, but the 1st, the 2nd connecting object adhering components is connected.
Solidification compound of the present invention is in the situation of electro-conductive material, and this electro-conductive material can be for the connection (COG (Chip on Glass)) of connection (COF (Chip on Film)), semi-conductor chip and glass substrate of the connection such as flexible printing substrate and glass substrate (FOG (Film on Glass)), semi-conductor chip and flexible printing substrate or connection (FOB (Film on Board)) of flexible printing substrate and glass epoxy substrate etc.Wherein, above-mentioned electro-conductive material is suitable for FOG purposes or COG purposes, preferably for COG purposes.Solidification compound of the present invention is preferably the electro-conductive material for the connection of the connection of flexible printing substrate and glass substrate or semi-conductor chip and flexible printing substrate, more preferably for the electro-conductive material of the connection of semi-conductor chip and flexible printing substrate.
In syndeton body of the present invention, as above-mentioned the 2nd connecting object parts and above-mentioned the 1st connecting object parts, preferably use flexible printing substrate and glass substrate or semi-conductor chip and glass substrate, more preferably use semi-conductor chip and glass substrate.
In FOG purposes, because L/S is wider, therefore, the particle diameter of electroconductive particle is large, concentration is also low, therefore, mostly have following problems: pressure during connection is low, can not obtain sufficient impression and resin filling, in interelectrode conducting reliability and cured article layer, producing space (void) etc. becomes problem.To this, the solidification compound of the application of the invention, in FOG purposes, can improve interelectrode conducting reliability effectively, can effectively suppress to produce in cured article layer space (void).
In COG purposes, because the spacing of L/S is narrower, therefore, illiquidity when electric conduction of heating material, electro-conductive material can not fully be filled between electrode wires, therefore, mostly has following problems: in interelectrode conducting reliability and cured article layer, producing space etc. becomes problem.To this, the solidification compound of the application of the invention, in COG purposes, can improve interelectrode conducting reliability effectively, can effectively suppress to produce in cured article layer space (void).
Below, with comparative example, the present invention is specifically described in conjunction with the embodiments.The present invention is not limited to following examples.
It should be noted that, the weight-average molecular weight of the epoxy compounds obtaining in following synthesis example is by gel permeation chromatography (GPC), to be measured and passed through the weight-average molecular weight of polystyrene conversion.
And, the mixture of the epoxy compounds obtaining in following examples and the viscosity of solidification compound be 23 ℃ of using that viscosimeter (manufactures of Dong Ji industry company) measures with 2.5rpm under viscosity.
(synthesis example 1)
(1) synthesizing of the 1st reaction product being obtained by Bisphenol F and 1,6-hexanediol diglycidyl ether:
Bisphenol F (is contained with weight ratio and counts 4 of 31:52:17,4 '-methylene-bis phenol, 2,4 '-methylene-bis phenol and 2,2 '-methylene-bis phenol) 72 weight parts, 1,6-hexanediol diglycidyl ether 100 weight parts and triphenylphosphine 1 weight part join in three-necked flask, and it is dissolved at 150 ℃.Subsequently, by making it carry out the polyaddition reaction of 6 hours at 180 ℃, obtain the 1st reaction product.
Confirm to have carried out polyaddition reaction, and confirmed that the 1st reaction product has by coming from the skeleton of Bisphenol F and coming from 1 on main chain, the structural unit that the skeleton bonding of 6-hexanediol diglycidyl ether forms, and at two ends, there is the epoxy group(ing) that comes from 1,6-hexanediol diglycidyl ether.
(2) above-mentioned the 1st reaction product and vinylformic acid are reacted and the epoxy compounds that obtains synthetic:
The 1st reaction product 100 weight parts that obtain and vinylformic acid 4 weight parts are mixed, and be warming up to 80 ℃.After intensification, add penta fluoro benzene sulfonic acid two sym-trimethylbenzene base ammonium salt 1 weight parts as catalyzer, make it carry out the condensation reaction of 4 hours, obtained thus two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl, described vinyl with respect to reaction before total number 100% of hydroxyl be 20%.
The weight-average molecular weight of the epoxy compounds obtaining is 8000.In the molecular weight distribution of the epoxy compounds obtaining, only there is 1 peak, and do not observe and come from acrylic acid small molecules.In addition, by NMR, confirm that vinylformic acid and hydroxyl have occurred to react, imported vinyl on side chain, described vinyl is 20% with respect to total number 100% of the front hydroxyl of reaction.
(synthesis example 2)
The epoxy compounds that above-mentioned the 1st reaction product that obtains in synthesis example 1 and 2-methacryloxyethyl isocyanic ester is reacted and obtain synthetic:
After above-mentioned the 1st reaction product 100 weight parts that obtain in synthesis example 1,2-methacryloxyethyl isocyanic ester 4 weight parts and dibutyl tin laurate 0.3 weight part are mixed, by making it carry out the addition reaction of 4 hours at 80 ℃, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl, described vinyl with respect to reaction before total number 100% of hydroxyl be 20%.
The weight-average molecular weight of the epoxy compounds obtaining is 12000.In the molecular weight distribution of the epoxy compounds obtaining, only there is 1 peak, and do not observe the micromolecular peak that comes from methacrylic compound.In addition, by NMR, confirm that 2-methacryloxyethyl isocyanic ester has occurred to react with hydroxyl, imported vinyl on side chain, described vinyl is 20% with respect to total number 100% of the front hydroxyl of reaction.
(synthesis example 3)
The epoxy compounds that above-mentioned the 1st reaction product that obtains in synthesis example 1 and 4-hydroxyl butylglycidyl ether is reacted and obtain synthetic:
After above-mentioned the 1st reaction product 100 weight parts that obtain in synthesis example 1,4-hydroxyl butylglycidyl ether 4 weight parts and penta fluoro benzene sulfonic acid two sym-trimethylbenzene base ammonium salt 0.2 weight parts are mixed, by making it carry out the condensation reaction of 4 hours at 80 ℃, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have epoxy group(ing), described epoxy group(ing) with respect to reaction before total number 100% of hydroxyl be 20%.
The weight-average molecular weight of the epoxy compounds obtaining is 12000.In the molecular weight distribution of the epoxy compounds obtaining, only there is 1 peak, and do not observe the micromolecular peak that comes from 4-hydroxyl butylglycidyl ether compound.In addition, confirm to have carried out condensation reaction, and confirm that 4-hydroxyl butylglycidyl ether has occurred to react with hydroxyl, imported epoxy group(ing) on side chain, described epoxy group(ing) is 20% with respect to total number 100% of the front hydroxyl of reaction.
(synthesis example 4)
(1) synthesizing of the 2nd reaction product being obtained by Resorcinol and 1,6-hexanediol diglycidyl ether:
By Resorcinol 48 weight parts, 1,6-hexanediol diglycidyl ether 100 weight parts and triphenylphosphine 1 weight part join in three-necked flask, and it is dissolved at 150 ℃.Subsequently, by making it carry out the polyaddition reaction of 6 hours at 180 ℃, obtain the 2nd reaction product.
Confirm to have carried out polyaddition reaction, and confirmed that the 2nd reaction product has by coming from the skeleton of Resorcinol and coming from 1 on main chain, the structural unit that the skeleton bonding of 6-hexanediol diglycidyl ether forms, and at two ends, there is the epoxy group(ing) that comes from 1,6-hexanediol diglycidyl ether.
(2) above-mentioned the 2nd reaction product and vinylformic acid are reacted and the epoxy compounds that obtains synthetic:
By above-mentioned the 2nd reaction product obtaining, replace above-mentioned the 1st reaction product, identical with synthesis example 1, by condensation reaction, obtain two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl, described vinyl with respect to reaction before total number 100% of hydroxyl be 20%.
The weight-average molecular weight of the epoxy compounds obtaining is 15000, has 1 peak in the molecular weight distribution of epoxy compounds.In addition, by NMR, confirm that vinylformic acid and hydroxyl have occurred to react, imported vinyl on side chain, described vinyl is 20% with respect to total number 100% of the front hydroxyl of reaction.
(synthesis example 5)
The epoxy compounds that above-mentioned the 2nd reaction product that obtains in synthesis example 4 and 4-hydroxyl butylglycidyl ether is reacted and obtain synthetic:
By above-mentioned the 2nd reaction product obtaining in synthesis example 4, replace above-mentioned the 1st reaction product, adopt the method same with synthesis example 3, by carrying out condensation reaction, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have epoxy group(ing), described epoxy group(ing) with respect to reaction before total number 100% of hydroxyl be 20%.
The weight-average molecular weight of the epoxy compounds obtaining is 15000.In the molecular weight distribution of the epoxy compounds obtaining, there is 1 peak.In addition, confirm that 4-hydroxyl butylglycidyl ether has carried out condensation reaction, and on side chain, imported epoxy group(ing) by NMR, described epoxy group(ing) is 20% with respect to total number 100% of the front hydroxyl of reaction.
(synthesis example 6)
The epoxy compounds that above-mentioned the 2nd reaction product that obtains in synthesis example 4 and 2-methacryloxyethyl isocyanic ester is reacted and obtain synthetic:
By above-mentioned the 2nd reaction product obtaining in synthesis example 4, replace above-mentioned the 1st reaction product, adopt the method same with synthesis example 2, by carrying out addition reaction, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl, described vinyl with respect to reaction before total number 100% of hydroxyl be 20%.
The weight-average molecular weight of the epoxy compounds obtaining is 15000.In the molecular weight distribution of the epoxy compounds obtaining, there is 1 peak.In addition, confirmed by addition reaction, having there is reaction in 2-methacryloxyethyl isocyanic ester, has imported vinyl on side chain, and described vinyl is 20% with respect to total number 100% of the front hydroxyl of reaction.
(synthesis example 7)
(1) synthesizing of the 3rd reaction product being obtained by Resorcinol and resorcinol diglycidyl ether:
Resorcinol 33 weight parts, resorcinol diglycidyl ether 100 weight parts and triphenylphosphine 1 weight part are joined in three-necked flask, it is dissolved at 150 ℃.Subsequently, by making it carry out the polyaddition reaction of 6 hours at 180 ℃, obtain the 3rd reaction product.
Confirm to have carried out polyaddition reaction, and confirmed that the 3rd reaction product has by coming from the skeleton of Resorcinol and coming from the structural unit that the skeleton bonding of resorcinol diglycidyl ether forms on main chain, and at two ends, there is the epoxy group(ing) that comes from resorcinol diglycidyl ether.
(2) above-mentioned the 3rd reaction product and vinylformic acid are reacted and the epoxy compounds that obtains synthetic:
By above-mentioned the 3rd reaction product obtaining, replace above-mentioned the 1st reaction product, adopt the method same with synthesis example 1, by carrying out condensation reaction, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl, described vinyl with respect to reaction before total number 100% of hydroxyl be 20%.
The weight-average molecular weight of the epoxy compounds obtaining is 11000.In the molecular weight distribution of the epoxy compounds obtaining, there is 1 peak.In addition, confirmed by condensation reaction, vinylformic acid has occurred to react with hydroxyl, has imported vinyl on side chain, and described vinyl is 20% with respect to total number 100% of the front hydroxyl of reaction.
(synthesis example 8)
The epoxy compounds that above-mentioned the 3rd reaction product that obtains in synthesis example 7 and 2-methacryloxyethyl isocyanic ester is reacted and obtain synthetic:
By above-mentioned the 3rd reaction product obtaining in synthesis example 7, replace above-mentioned the 1st reaction product, adopt the method same with synthesis example 2, by carrying out addition reaction, obtain two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl, described vinyl with respect to reaction before total number 100% of hydroxyl be 20%.
The weight-average molecular weight of the epoxy compounds obtaining is 11000.In the molecular weight distribution of the epoxy compounds obtaining, there is 1 peak.In addition, by NMR, confirmed that 2-methacryloxyethyl isocyanic ester has occurred to react with hydroxyl, imported vinyl on side chain, described vinyl is 20% with respect to total number 100% of the front hydroxyl of reaction.
(synthesis example 9)
The epoxy compounds that above-mentioned the 3rd reaction product that obtains in synthesis example 7 and 4-hydroxyl butylglycidyl ether is reacted and obtain synthetic:
By above-mentioned the 3rd reaction product obtaining in synthesis example 7, replace above-mentioned the 1st reaction product, adopt the method same with synthesis example 3, by carrying out condensation reaction, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have epoxy group(ing), described epoxy group(ing) with respect to reaction before total number 100% of hydroxyl be 20%.
The weight-average molecular weight of the epoxy compounds obtaining is 11000.In the molecular weight distribution of the epoxy compounds obtaining, there is 1 peak.In addition, by NMR, confirm that 4-hydroxyl butylglycidyl ether has occurred to react with hydroxyl, imported epoxy group(ing) on side chain, described epoxy group(ing) is 20% with respect to total number 100% of the front hydroxyl of reaction.
(embodiment 1)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 1 and synthesis example 2 is mixed with weight ratio 5:3, obtain the mixture (1) of epoxy compounds.The viscosity of the mixture of the epoxy compounds obtaining (1) is 320Pas.
Then, in mixture (1) 33 weight part of the epoxy compounds obtaining, add tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight parts as thermal curing agents, 2-ethyl-4-methylimidazole 1 weight part as curing catalyst, epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts as photocurable compound, acylphosphine oxide compounds (" DAROCUR TPO " that CIBA JAPAN company manufactures) 0.1 weight part as Photoepolymerizationinitiater initiater, silicon-dioxide 20 weight parts of median size 0.25 μ m and aluminum oxide 20 weight parts of median size 0.5 μ m as filler, and electroconductive particle 2 weight parts of median size 3 μ m, and under 2000rpm, stir 5 minutes with planetary stirring machine, obtained thus the solidification compound (1) of sticking with paste as anisotropic conductive.It should be noted that, the electroconductive particle of use is the electroconductive particle with metal level, and its surface at divinylbenzene resin particle is formed with nickel layer, and is formed with Gold plated Layer on the surface of this nickel layer.The viscosity of gained solidification compound (1) is 350Pas.
(embodiment 2)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 2 and synthesis example 3 is mixed with weight ratio 5:3, obtain the mixture (2) of epoxy compounds.The viscosity of the mixture of the epoxy compounds obtaining (2) is 300Pas.
Except the mixture of epoxy compounds (1) being changed to the mixture (2) of the epoxy compounds obtaining, implement similarly to Example 1, obtain solidification compound (2).The viscosity of the solidification compound obtaining (2) is 340Pas.
(embodiment 3)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 3 and synthesis example 4 is mixed with weight ratio 5:3, obtain the mixture (3) of epoxy compounds.The viscosity of the mixture of the epoxy compounds obtaining (3) is 280Pas.
Except the mixture of epoxy compounds (1) being changed to the mixture (3) of the epoxy compounds obtaining, implement similarly to Example 1, obtain solidification compound (3).The viscosity of the solidification compound obtaining (3) is 310Pas.
(embodiment 4)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 4 and synthesis example 5 is mixed with weight ratio 5:3, obtain the mixture (4) of epoxy compounds.The viscosity of the mixture of the epoxy compounds obtaining (4) is 330Pas.
Except the mixture of epoxy compounds (1) being changed to the mixture (4) of the epoxy compounds obtaining, implement similarly to Example 1, obtain solidification compound (4).The viscosity of the solidification compound obtaining (4) is 360Pas.
(embodiment 5)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 5 and synthesis example 6 is mixed with weight ratio 5:3, obtain the mixture (5) of epoxy compounds.The viscosity of the mixture of the epoxy compounds obtaining (5) is 260Pas.
Except the mixture of epoxy compounds (1) being changed to the mixture (5) of the epoxy compounds obtaining, implement similarly to Example 1, obtain solidification compound (5).The viscosity of the solidification compound obtaining (5) is 290Pas.
(embodiment 6)
Except tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight parts and 2-ethyl-4-methylimidazole 1 weight part being changed to cation curing agent (San-Aid Si-60 (three new chemistry are manufactured)) 0.6 weight part, implement similarly to Example 1, obtain solidification compound (6).The viscosity of the solidification compound obtaining (6) is 180Pas.
(embodiment 7)
Except tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight parts are changed to as quadrol 20 weight parts of amine hardener, implement similarly to Example 1, obtain solidification compound (7).The viscosity of the solidification compound obtaining (7) is 150Pas.
(embodiment 8)
Except the epoxy acrylate as photocurable compound (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts being changed to urethane acrylate (" EBECRYL8804 " that DAICEL-CYTEC company manufactures) 5 weight parts as photocurable compound, implement similarly to Example 1, obtain solidification compound (8).The viscosity of the solidification compound obtaining (8) is 280Pas.
(embodiment 9)
Except not adding the epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) and the acylphosphine oxide compounds (" DAROCUR TPO " that CIBA JAPAN company manufactures) as Photoepolymerizationinitiater initiater as photocurable compound; implement similarly to Example 1, obtain solidification compound (9).The viscosity of the solidification compound obtaining (9) is 260Pas.
(embodiment 10)
Except not adding the epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) and the acylphosphine oxide compounds (" DAROCUR TPO " that CIBA JAPAN company manufactures) as Photoepolymerizationinitiater initiater as photocurable compound; implement similarly to Example 2, obtain solidification compound (10).The viscosity of the solidification compound obtaining (10) is 310Pas.
(comparative example 1)
Add bisphenol A type epoxy resin 33 weight parts, tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight parts as thermal curing agents, 2-ethyl-4-methylimidazole 1 weight part as curing catalyst, epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts as photocurable compound, acylphosphine oxide compounds (" DAROCUR TPO " that CIBA JAPAN company manufactures) 0.1 weight part as Photoepolymerizationinitiater initiater, silicon-dioxide 20 weight parts of median size 0.25 μ m and aluminum oxide 20 weight parts of median size 0.5 μ m as filler, and electroconductive particle 2 weight parts of median size 3 μ m, and under 2000rpm, stir 5 minutes with planetary stirring machine, obtained thus the solidification compound of sticking with paste as anisotropic conductive.
(comparative example 2)
Except not adding the epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) and the acylphosphine oxide compounds (" DAROCUR TPO " that CIBA JAPAN company manufactures) as Photoepolymerizationinitiater initiater as photocurable compound; similarly implement with comparative example 1, obtain solidification compound.
(evaluation of embodiment 1～10 and comparative example 1～2)
(1) set time 1
Prepare transparent glass substrate, the upper surface of described transparent glass substrate has the ITO electrode pattern that L/S is 10 μ m/10 μ m.In addition, prepare semi-conductor chip, the lower surface of described semi-conductor chip has the gold electrode pattern that L/S is 10 μ m/10 μ m.
The solidification compound that coating obtains on above-mentioned transparent glass substrate, making its thickness is 30 μ m, further by irradiating UV light, (methyl) acrylic resin is solidified, and forms solidification compound layer.Then, the above-mentioned semi-conductor chip of mode lamination also connecting toward each other on solidification compound layer so that between electrode.Subsequently, Yi Bian adjust the temperature that the temperature of heating head makes solidification compound layer, reach 150 ℃, Yi Bian heating head is loaded to the upper surface in semi-conductor chip, solidification compound layer is solidified at 150 ℃, obtain syndeton body A.When obtaining this syndeton body, measure and make solidification compound layer solidify the needed time by heating.
(2) set time 2
Prepare transparent glass substrate, the upper surface of described transparent glass substrate has the ITO electrode pattern that L/S is 10 μ m/10 μ m.In addition, prepare semi-conductor chip, the lower surface of described semi-conductor chip has the gold electrode pattern that L/S is 10 μ m/10 μ m.
The solidification compound that coating obtains on above-mentioned transparent glass substrate, making its thickness is 30 μ m, forms solidification compound layer.Then, the above-mentioned semi-conductor chip of mode lamination also connecting toward each other on solidification compound layer so that between electrode.Subsequently, Yi Bian adjust the temperature that the temperature of heating head makes solidification compound layer, reach 150 ℃, Yi Bian heating head is loaded to the upper surface in semi-conductor chip, solidification compound layer is solidified at 150 ℃, obtain syndeton body B.When obtaining this syndeton body, measure and make solidification compound layer solidify the needed time by heating.
(3) cementability
Syndeton body A, B that use obtains in the evaluation of above-mentioned (1) set time 1 and above-mentioned (2) set time 2, measure stripping strength, evaluated thus cementability.According to following standard, cementability is judged.
[criterion of cementability]
Zero: more than 8N/cm
*: be less than 8N/cm
(4) wet fastness
The syndeton body A, the B that in evaluation in above-mentioned (1) set time 1 and above-mentioned (2) set time 2, obtain (each 15) are placed after 1000 hours under the condition of 85 ℃ and 85%RH, evaluated conduction.By four-end method, evaluated the resistance value at syndeton body A, B upper 20 positions.According to following standard, conducting reliability is judged.
[criterion of wet fastness]
Zero: the resistance value of all sites is below 3 Ω
*: more than there is not 1 place at the position of conducting completely
(5) there is tight
For the syndeton body A, the B that obtain in the evaluation in above-mentioned (1) set time 1 and above-mentioned (2) set time 2, from lower surface one side of transparent glass substrate, whether the cured article layer being formed by solidification compound layer has been produced to space and carried out visual observations.
The results are shown in following table 1.
[table 1]
(synthesis example 10)
(1) synthesizing of the 1st reaction product being obtained by Bisphenol F and 1,6-hexanediol diglycidyl ether:
Except Bisphenol F (is contained with weight ratio and counts 4 of 31:52:17, 4 '-methylene-bis phenol, 2, 4 '-methylene-bis phenol and 2, 2 '-methylene-bis phenol) 72 weight parts change to Bisphenol F and (contain with weight ratio and count 4 of 31:52:17, 4 '-methylene-bis phenol, 2, 4 '-methylene-bis phenol and 2, 2 '-methylene-bis phenol) 64 weight parts and there is Bisphenol F skeleton and have beyond 3 polykaryons with coker (contain with weight ratio and count three nucleomes of 9:2 and there are 4 with the polykaryon of coker) mixture 72 weight parts of 8 weight parts, implement similarly to Example 1, obtained the 1st reaction product.
(2) above-mentioned the 1st reaction product and vinylformic acid are reacted and the epoxy compounds that obtains synthetic:
Except using the 1st reaction product obtain, similarly to Example 1, by adopting the method same with synthesis example 1 to carry out condensation reaction, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl.
The weight-average molecular weight of the epoxy compounds obtaining is 7000.In addition, by NMR, confirmed that vinylformic acid and hydroxyl have occurred to react, and imported vinyl on side chain.
(synthesis example 11)
The epoxy compounds that above-mentioned the 1st reaction product that obtains in synthesis example 10 and 2-methacryloxyethyl isocyanic ester is reacted and obtain synthetic:
After above-mentioned the 1st reaction product 100 weight parts that obtain in synthesis example 10,2-methacryloxyethyl isocyanic ester 4 weight parts and dibutyl tin laurate 0.3 weight part are mixed, by making it carry out the addition reaction of 4 hours at 80 ℃, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl.
The weight-average molecular weight of the epoxy compounds obtaining is 10000.In addition, by NMR, confirm that 2-methacryloxyethyl isocyanic ester has occurred to react with hydroxyl, and imported vinyl on side chain.
(synthesis example 12)
The epoxy compounds that above-mentioned the 1st reaction product that obtains in synthesis example 10 and 4-hydroxyl butylglycidyl ether is reacted and obtain synthetic:
After above-mentioned the 1st reaction product 100 weight parts that obtain in synthesis example 10,4-hydroxyl butylglycidyl ether 4 weight parts and penta fluoro benzene sulfonic acid two sym-trimethylbenzene base ammonium salt 0.2 weight parts are mixed, by making it carry out the condensation reaction of 4 hours at 80 ℃, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have epoxy group(ing).
The weight-average molecular weight of the epoxy compounds obtaining is 10000.In addition, confirm to have carried out condensation reaction, and confirm that 4-hydroxyl butylglycidyl ether has occurred to react with hydroxyl, thereby imported epoxy group(ing) on side chain.
(synthesis example 13)
(1) Bisphenol F (is contained with weight ratio and counts 4 of 31:52:17,4 '-methylene-bis phenol, 2,4 '-methylene-bis phenol and 2,2 '-methylene-bis phenol) 54 weight parts, 1,6-hexanediol diglycidyl ether 75 weight parts and triphenylphosphine 0.75 weight part join in three-necked flask, and it is dissolved at 150 ℃.Subsequently, make it at 180 ℃, carry out the polyaddition reaction of 4 hours, further append Bisphenol F 25 weight parts, 1,6-hexanediol diglycidyl ether 9.5 weight parts and triphenylphosphine 0.25 weight part, and make it at 180 ℃, carry out the polyaddition reaction of 2 hours, obtained thus the 1st reaction product.
Confirm to have carried out polyaddition reaction, and confirmed that the 1st reaction product has by coming from the skeleton of Bisphenol F and coming from 1 on main chain, the structural unit that the skeleton bonding of 6-hexanediol diglycidyl ether forms, and at two ends, there is the epoxy group(ing) that comes from 1,6-hexanediol diglycidyl ether.
(2) above-mentioned the 1st reaction product and vinylformic acid are reacted and the epoxy compounds that obtains synthetic:
The 1st reaction product 100 weight parts that obtain and vinylformic acid 4 weight parts are mixed, and be warming up to 80 ℃.After intensification, add penta fluoro benzene sulfonic acid two sym-trimethylbenzene base ammonium salt 1 weight parts as catalyzer, make its condensation reaction of carrying out 4 hours, obtained thus two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl.
The weight-average molecular weight of the epoxy compounds obtaining is 6000.In the molecular weight distribution of the epoxy compounds obtaining, there are 2 peaks.In addition, by NMR, confirm that vinylformic acid and hydroxyl have occurred to react, and imported vinyl on side chain.
(synthesis example 14)
After above-mentioned the 1st reaction product 100 weight parts that obtain in synthesis example 13,2-methacryloxyethyl isocyanic ester 4 weight parts and dibutyl tin laurate 0.3 weight part are mixed, by making it carry out the addition reaction of 4 hours at 80 ℃, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl.
The weight-average molecular weight of the epoxy compounds obtaining is 7500.In the molecular weight distribution of the epoxy compounds obtaining, there are 2 peaks.In addition, by NMR, confirm that 2-methacryloxyethyl isocyanic ester has occurred to react with hydroxyl, and imported vinyl on side chain.
(embodiment 11)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 10 and synthesis example 11 is mixed with weight ratio 5:3, obtained the mixture (11) of epoxy compounds.
Except the mixture of epoxy compounds (1) being changed to the mixture (11) of the epoxy compounds obtaining, implement similarly to Example 1, obtain solidification compound (11).The viscosity of the solidification compound obtaining (11) is 390Pas.
(embodiment 12)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 11 and synthesis example 12 is mixed with weight ratio 5:3, obtain the mixture (12) of epoxy compounds.
Except the mixture of epoxy compounds (1) being changed to the mixture (12) of the epoxy compounds obtaining, implement similarly to Example 1, obtain solidification compound (12).The viscosity of the solidification compound obtaining (12) is 380Pas.
(embodiment 13)
The mixture (1) of the epoxy compounds obtaining in preparation embodiment 1.The mixture of epoxy compounds (1) contains with weight ratio counts the epoxy compounds obtaining in the epoxy compounds that obtains in the synthesis example 1 of 5:3 and synthesis example 2.
In mixture (1) 33 weight part of above-mentioned epoxy compounds, add Bisphenol F diglycidylether 3 weight parts, tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight parts as thermal curing agents, 2-ethyl-4-methylimidazole 1 weight part as curing catalyst, epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts as photocurable compound, acylphosphine oxide compounds (" DAROCUR TPO " that CIBA JAPAN company manufactures) 0.1 weight part as Photoepolymerizationinitiater initiater, silicon-dioxide 20 weight parts of median size 0.25 μ m and aluminum oxide 20 weight parts of median size 0.5 μ m as filler, and electroconductive particle 2 weight parts that use in embodiment 1, and under 2000rpm, stir 5 minutes with planetary stirring machine, obtained thus the solidification compound (15) of sticking with paste as anisotropic conductive.The viscosity of the solidification compound obtaining (13) is 330Pas.
(embodiment 14)
The mixture (1) of the epoxy compounds obtaining in preparation embodiment 1.The mixture of epoxy compounds (1) contains with weight ratio counts the epoxy compounds obtaining in the epoxy compounds that obtains in the synthesis example 1 of 5:3 and synthesis example 2.
In mixture (1) 33 weight part of above-mentioned epoxy compounds, add resorcinol diglycidyl ether 3 weight parts, tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight parts as thermal curing agents, 2-ethyl-4-methylimidazole 1 weight part as curing catalyst, epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts as photocurable compound, acylphosphine oxide compounds (" DAROCUR TPO " that CIBA JAPAN company manufactures) 0.1 weight part as Photoepolymerizationinitiater initiater, silicon-dioxide 20 weight parts of median size 0.25 μ m and aluminum oxide 20 weight parts of median size 0.5 μ m as filler, and electroconductive particle 2 weight parts that use in embodiment 1, and under 2000rpm, stir 5 minutes with planetary stirring machine, obtained thus the solidification compound (14) of sticking with paste as anisotropic conductive.The viscosity of the solidification compound obtaining (14) is 320Pas.
(embodiment 15)
The mixture (1) of the epoxy compounds obtaining in preparation embodiment 1.The mixture of epoxy compounds (1) contains with weight ratio counts the epoxy compounds obtaining in the epoxy compounds that obtains in the synthesis example 1 of 5:3 and synthesis example 2.
In mixture (1) 33 weight part of above-mentioned epoxy compounds, add Bisphenol F glycidyl ether epoxy acrylate 3 weight parts, tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight parts as thermal curing agents, 2-ethyl-4-methylimidazole 1 weight part as curing catalyst, epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts as photocurable compound, acylphosphine oxide compounds (" DAROCUR TPO " that CIBA JAPAN company manufactures) 0.1 weight part as Photoepolymerizationinitiater initiater, silicon-dioxide 20 weight parts of median size 0.25 μ m and aluminum oxide 20 weight parts of median size 0.5 μ m as filler, and electroconductive particle 2 weight parts that use in embodiment 1, and under 2000rpm, stir 5 minutes with planetary stirring machine, obtained thus the solidification compound (15) of sticking with paste as anisotropic conductive.The viscosity of the solidification compound obtaining (15) is 320Pas.
(embodiment 16)
The mixture (1) of the epoxy compounds obtaining in preparation embodiment 1.The mixture of epoxy compounds (1) contains with weight ratio counts the epoxy compounds obtaining in the epoxy compounds that obtains in the synthesis example 1 of 5:3 and synthesis example 2.
In mixture (1) 33 weight part of above-mentioned epoxy compounds, add Resorcinol glycidyl ether epoxy acrylate 3 weight parts, tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight parts as thermal curing agents, 2-ethyl-4-methylimidazole 1 weight part as curing catalyst, epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts as photocurable compound, acylphosphine oxide compounds (" DAROCUR TPO " that CIBA JAPAN company manufactures) 0.1 weight part as Photoepolymerizationinitiater initiater, silicon-dioxide 20 weight parts of median size 0.25 μ m and aluminum oxide 20 weight parts of median size 0.5 μ m as filler, and electroconductive particle 2 weight parts that use in embodiment 1, and under 2000rpm, stir 5 minutes with planetary stirring machine, obtained thus the solidification compound (16) of sticking with paste as anisotropic conductive.The viscosity of the solidification compound obtaining (16) is 320Pas.
(embodiment 17)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 13 and synthesis example 14 is mixed with weight ratio 5:3, obtain the mixture (17) of epoxy compounds.
Except the mixture of epoxy compounds (1) being changed to the mixture (17) of the epoxy compounds obtaining, implement similarly to Example 1, obtain solidification compound (17).The viscosity of the solidification compound obtaining (17) is 280Pas.
(embodiment 18)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 4 and synthesis example 7 is mixed with weight ratio 5:3, obtain the mixture (18) of epoxy compounds.
Except the mixture of epoxy compounds (1) being changed to the mixture (18) of the epoxy compounds obtaining, implement similarly to Example 1, obtain solidification compound (18).The viscosity of the solidification compound obtaining (18) is 310Pas.
(embodiment 19)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 4 and synthesis example 8 is mixed with weight ratio 5:3, obtain the mixture (19) of epoxy compounds.
Except the mixture of epoxy compounds (1) being changed to the mixture (19) of the epoxy compounds obtaining, implement similarly to Example 1, obtain solidification compound (19).The viscosity of the solidification compound obtaining (19) is 320Pas.
(embodiment 20)
The epoxy compounds that the epoxy compounds obtaining in synthesis example 4 and synthesis example 9 are obtained mixes with weight ratio 5:3, obtains the mixture (20) of epoxy compounds.
Except the mixture of epoxy compounds (1) being changed to the mixture (20) of the epoxy compounds obtaining, implement similarly to Example 1, obtain solidification compound (20).The viscosity of the solidification compound obtaining (20) is 320Pas.
(evaluation of embodiment 11～20)
For the assessment item identical with comparative example 1～2 with embodiment 1～10, evaluate.
The results are shown in following table 2.
[table 2]
It should be noted that, the cementability evaluation result of embodiment 1～20 is " zero ".About the measured value of stripping strength, embodiment 11 is than embodiment 1 height, and embodiment 12 is than embodiment 2 height, and embodiment 13 is than embodiment 1 height, and embodiment 14 is than embodiment 1 height, and embodiment 15 is than embodiment 1 height, and embodiment 16 is than embodiment 1 height.
(synthesis example 15)
(1) synthesizing of the 4th reaction product being obtained by Bisphenol F and resorcinol diglycidyl ether:
Bisphenol F (is contained with weight ratio and counts 4 of 31:52:17,4 '-methylene-bis phenol, 2,4 '-methylene-bis phenol and 2,2 '-methylene-bis phenol) 72 weight parts, resorcinol diglycidyl ether 100 weight parts and triphenylphosphine 1 weight part join in three-necked flask, and it is dissolved at 150 ℃.Subsequently, by making it carry out the polyaddition reaction of 6 hours at 180 ℃, obtain the 4th reaction product.
Confirm to have carried out polyaddition reaction, and confirmed that the 4th reaction product has by coming from the skeleton of Bisphenol F and coming from the structural unit that the skeleton bonding of resorcinol diglycidyl ether forms on main chain, and at two ends, there is the epoxy group(ing) that comes from resorcinol diglycidyl ether.
(2) above-mentioned the 4th reaction product and vinylformic acid are reacted and the epoxy compounds that obtains synthetic:
By above-mentioned the 3rd reaction product obtaining, replace above-mentioned the 1st reaction product, by adopting the method same with synthesis example 1 to carry out condensation reaction, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl.
The weight-average molecular weight of the epoxy compounds obtaining is 132000.In the molecular weight distribution of the epoxy compounds obtaining, only there is 1 peak, and do not observe and come from acrylic acid small molecules.In addition, confirm that vinylformic acid and hydroxyl have occurred to react, and imported vinyl by NMR on side chain, described vinyl is 100% with respect to total number 100% of the front hydroxyl of reaction.
(synthesis example 16)
The epoxy compounds that above-mentioned the 4th reaction product that obtains in synthesis example 15 and 2-(methyl) acryloxy ethyl isocyanate is reacted and obtain synthetic:
By above-mentioned the 4th reaction product obtaining in synthesis example 15, replace above-mentioned the 1st reaction product, by adopting the method same with synthesis example 2 to carry out addition reaction, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have vinyl.
The weight-average molecular weight of the epoxy compounds obtaining is 132000.In the molecular weight distribution of the epoxy compounds obtaining, only there is 1 peak, and do not observe the micromolecular peak that comes from acrylic compound.In addition, confirm that 2-(methyl) acryloxy ethyl isocyanate has occurred to react with hydroxyl, and imported vinyl by NMR on side chain, described vinyl is 100% with respect to total number 100% of the front hydroxyl of reaction.
(synthesis example 17)
The epoxy compounds that above-mentioned the 4th reaction product that obtains in synthesis example 15 and 4-hydroxyl butylglycidyl ether is reacted and obtain synthetic:
By above-mentioned the 4th reaction product obtaining in synthesis example 15, replace above-mentioned the 1st reaction product, by adopting the method same with synthesis example 3 to carry out condensation reaction, obtained two ends and there is the epoxy compounds that epoxy group(ing) and side chain have epoxy group(ing).
The weight-average molecular weight of the epoxy compounds obtaining is 132000.In the molecular weight distribution of the epoxy compounds obtaining, only there is 1 peak, and do not observe the micromolecular peak that comes from 4-hydroxyl butylglycidyl ether compound.In addition, confirm to have carried out condensation reaction, and confirm that 4-hydroxyl butylglycidyl ether has occurred to react with hydroxyl, and imported epoxy group(ing) on side chain, described epoxy group(ing) is 100% with respect to total number 100% of the front hydroxyl of reaction.
(embodiment 21)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 15 and synthesis example 16 is mixed with weight ratio 5:3, obtain the mixture (21) of epoxy compounds.The viscosity of the mixture of the epoxy compounds obtaining (21) is 1000Pas.
Except the mixture of epoxy compounds (1) being changed to the mixture (21) of the epoxy compounds obtaining, implement similarly to Example 1, obtained solidification compound (21).The viscosity of the solidification compound obtaining (21) is 1070Pas.
(embodiment 22)
The epoxy compounds obtaining in the epoxy compounds obtaining in synthesis example 16 and synthesis example 17 is mixed with weight ratio 5:3, obtain the mixture (22) of epoxy compounds.The viscosity of the mixture of the epoxy compounds obtaining (22) is 1130Pas.
Except the mixture of epoxy compounds (1) being changed to the mixture (22) of the epoxy compounds obtaining, implement similarly to Example 1, obtain solidification compound (22).The viscosity of the solidification compound obtaining (22) is 1200Pas.
(embodiment 21 and 22 evaluation)
The assessment item identical with embodiment 1～10 evaluated.
The results are shown in following table 3.
[table 3]
| ? | Embodiment 21 | Embodiment 22 |
| Set time 1 (second) | 2 | 2 |
| Set time 2 (second) | 2 | 2 |
| Cementability (syndeton body A) | ○ | ○ |
| Cementability (syndeton body B) | ○ | ○ |
| Wet fastness (syndeton body A) | ○ | ○ |
| Wet fastness (syndeton body B) | ○ | ○ |
| There is tight (syndeton body A) | ○ | ○ |
| There is tight (syndeton body B) | ○ | ○ |
It should be noted that, in each synthesis example, when making the hydroxyl reaction of (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned the 1st, the 2nd, the 3rd, the 4th reaction product, before reaction in total number 100% of hydroxyl, the number ratio of the hydroxyl (becoming the group (above-mentioned formula (a), (b), (c)) of non-hydroxyl) having reacted changes within 3%～100% (all).The ratio of number is in 3%～100% scope time, with above-described embodiment similarly, confirmed curing speed rapid, cementability and excellent moisture resistance, and be difficult for producing space.
Claims (21)
1. an epoxy compounds, it has epoxy group(ing) at two ends, and on side chain, has vinyl or epoxy group(ing),
The weight-average molecular weight of this epoxy compounds is more than 500 and below 150000.
2. epoxy compounds according to claim 1, it has altogether more than 2 vinyl or on side chain, has altogether more than 2 epoxy group(ing) on side chain.
3. epoxy compounds according to claim 1 and 2, it is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with following reaction product, described reaction product is the reaction product of Bisphenol F or Resorcinol and 1,6-hexanediol diglycidyl ether or resorcinol diglycidyl ether.
4. epoxy compounds according to claim 3, wherein, described reaction product is the 1st reaction product, the 2nd reaction product or the 3rd reaction product,
Described the 1st reaction product is the reaction product of Bisphenol F and 1,6-hexanediol diglycidyl ether,
Described the 2nd reaction product is the reaction product of Resorcinol and 1,6-hexanediol diglycidyl ether,
Described the 3rd reaction product is the reaction product of Resorcinol and resorcinol diglycidyl ether.
5. epoxy compounds according to claim 4, wherein,
When described reaction product is described the 1st reaction product, in the molecular weight distribution of epoxy compounds, there are 2 peaks,
When described reaction product is described the 2nd reaction product, in the molecular weight distribution of epoxy compounds, there are 2 peaks.
6. according to the epoxy compounds described in claim 4 or 5, wherein, described reaction product is described the 1st reaction product.
7. according to the epoxy compounds described in claim 4 or 5, wherein, described reaction product is described the 2nd reaction product.
8. epoxy compounds according to claim 4, wherein, described reaction product is described the 3rd reaction product.
9. according to the epoxy compounds described in any one in claim 1～8, wherein, with the compound of described reaction be (methyl) vinylformic acid or 2-(methyl) acryloxy ethyl isocyanate.
10. epoxy compounds according to claim 9, wherein, with the compound of described reaction be 2-(methyl) acryloxy ethyl isocyanate.
The mixture of 11. 1 kinds of epoxy compoundss, it contains the epoxy compounds described in any one at least 2 kinds of claims 1～10.
The mixture of 12. epoxy compoundss according to claim 11, it contains the 1st epoxy compounds and the 2nd epoxy compounds,
Described the 1st epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 1st reaction product, described the 1st reaction product is Bisphenol F and 1, the reaction product of 6-hexanediol diglycidyl ether
Described the 2nd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 2nd reaction product, described the 2nd reaction product is the reaction product of Resorcinol and 1,6-hexanediol diglycidyl ether.
The mixture of 13. epoxy compoundss according to claim 11, it contains the 2nd epoxy compounds and the 3rd epoxy compounds,
Described the 2nd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 2nd reaction product, described the 2nd reaction product is Resorcinol and 1, the reaction product of 6-hexanediol diglycidyl ether
Described the 3rd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl isocyanate or 4-hydroxyl butylglycidyl ether react and obtain with the 3rd reaction product, and described the 3rd reaction product is the reaction product of Resorcinol and resorcinol diglycidyl ether.
14. according to the mixture of the epoxy compounds described in any one in claim 11～13, and its viscosity at 23 ℃ is more than 50Pas.
15. 1 kinds of solidification compounds, it contains the epoxy compounds described in any one in thermal curing agents and claim 1～10.
16. solidification compounds according to claim 15, it contains at least 2 kinds of described epoxy compoundss.
17. according to the solidification compound described in claim 15 or 16, and it also contains photocurable compound and Photoepolymerizationinitiater initiater.
18. according to the solidification compound described in any one in claim 15～17, and it also contains electroconductive particle.
19. according to the solidification compound described in any one in claim 15～18, wherein, except described epoxy compounds, also contain epoxy (methyl) acrylate, described epoxy (methyl) acrylate is to obtain by least one in 2 epoxy group(ing) of (methyl) vinylformic acid and these epoxy compounds two ends reacted.
20. 1 kinds of syndeton bodies, it possesses:
The 1st connecting object parts,
The 2nd connecting object parts and
Connect the 1st, the connection section of the 2nd connecting object parts,
Described connection section is formed by the solidification compound described in any one in claim 15～19.
21. syndeton bodies according to claim 20, wherein,
Described solidification compound contains electroconductive particle,
Described the 1st, the 2nd connecting object parts are electrically connected to by described electroconductive particle.
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| PCT/JP2012/070637 WO2013024844A1 (en) | 2011-08-18 | 2012-08-13 | Epoxy compound, epoxy compound mixture, curable composition, and connecting structure |
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| JP2015004056A (en) * | 2013-05-22 | 2015-01-08 | 積水化学工業株式会社 | Curable composition for electronic component and connection structure |
| JP6533369B2 (en) * | 2013-05-31 | 2019-06-19 | 積水化学工業株式会社 | Conductive material and connection structure |
| JP6325923B2 (en) * | 2014-07-03 | 2018-05-16 | 積水化学工業株式会社 | Conductive material and connection structure |
| KR102456447B1 (en) * | 2014-12-26 | 2022-10-19 | 세키스이가가쿠 고교가부시키가이샤 | Electrically conductive paste, connection structure, and production method for connection structure |
| US20190031790A1 (en) * | 2016-01-12 | 2019-01-31 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, dry film using same, printed wiring board, and method for manufacturing printed wiring board |
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| JP2008003260A (en) * | 2006-06-21 | 2008-01-10 | Sekisui Chem Co Ltd | Sealant for liquid crystal dripping methods, top-bottom conducting material, and liquid crystal display element |
| CN101512421A (en) * | 2006-09-07 | 2009-08-19 | 三井化学株式会社 | Liquid crystal sealing agent, method for manufacturing liquid crystal display panel using the liquid crystal sealing agent, and liquid crystal display panel |
| CN101617267A (en) * | 2007-02-20 | 2009-12-30 | 三井化学株式会社 | Sealing liquid crystal is with hardening resin composition and use the manufacture method of the display panels of said composition |
| CN102007447A (en) * | 2008-04-18 | 2011-04-06 | 积水化学工业株式会社 | Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element |
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| JP2002284842A (en) | 2001-03-23 | 2002-10-03 | Taiyo Ink Mfg Ltd | Epoxy acrylate compound, curable resin composition containing the same and its cured product |
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| JP3796254B2 (en) * | 2004-07-08 | 2006-07-12 | 積水化学工業株式会社 | Curable resin composition for liquid crystal display element, sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
| JP2006124531A (en) * | 2004-10-29 | 2006-05-18 | Shin Etsu Chem Co Ltd | Anisotropic conductive adhesive |
| JP4240400B2 (en) | 2005-03-15 | 2009-03-18 | Ｄｉｃ株式会社 | Side chain acryloyl group-containing epoxy resin and method for producing the same |
| JP5172321B2 (en) * | 2006-12-26 | 2013-03-27 | 三井化学株式会社 | Liquid crystal sealant |
| JP2009185116A (en) * | 2008-02-04 | 2009-08-20 | Air Water Inc | Carboxy group-containing epoxy acrylate resin, alkali-developable photocurable or heat-curable resin composition containing the same, and cured product of the composition |
| US20120041102A1 (en) | 2009-04-24 | 2012-02-16 | Korea Institute Of Industrial Technology | Novel epoxy resin and epoxy resin composition comprising the same |
| JP5443941B2 (en) * | 2009-10-23 | 2014-03-19 | 積水化学工業株式会社 | Sealant for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
| JP5520265B2 (en) * | 2010-08-31 | 2014-06-11 | 積水化学工業株式会社 | Anisotropic conductive material, B-stage-like cured product, and manufacturing method of connection structure |
| JP5504225B2 (en) * | 2010-08-31 | 2014-05-28 | 積水化学工業株式会社 | Anisotropic conductive material and connection structure |
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2012
- 2012-08-13 JP JP2012539121A patent/JP5899117B2/en not_active Expired - Fee Related
- 2012-08-13 WO PCT/JP2012/070637 patent/WO2013024844A1/en active Application Filing
- 2012-08-13 KR KR1020147002675A patent/KR101774629B1/en active IP Right Grant
- 2012-08-13 CN CN201280040209.XA patent/CN103764707B/en not_active Expired - Fee Related
- 2012-08-16 TW TW101129791A patent/TWI543998B/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008003260A (en) * | 2006-06-21 | 2008-01-10 | Sekisui Chem Co Ltd | Sealant for liquid crystal dripping methods, top-bottom conducting material, and liquid crystal display element |
| CN101512421A (en) * | 2006-09-07 | 2009-08-19 | 三井化学株式会社 | Liquid crystal sealing agent, method for manufacturing liquid crystal display panel using the liquid crystal sealing agent, and liquid crystal display panel |
| CN101617267A (en) * | 2007-02-20 | 2009-12-30 | 三井化学株式会社 | Sealing liquid crystal is with hardening resin composition and use the manufacture method of the display panels of said composition |
| CN102007447A (en) * | 2008-04-18 | 2011-04-06 | 积水化学工业株式会社 | Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105849820A (en) * | 2014-05-14 | 2016-08-10 | 积水化学工业株式会社 | Conductive paste, production method for conductive paste, connection structure, and production method for connection structure |
| CN105849820B (en) * | 2014-05-14 | 2018-10-26 | 积水化学工业株式会社 | The manufacturing method of conductive paste, the manufacturing method of conductive paste, connection structural bodies and connection structural bodies |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5899117B2 (en) | 2016-04-06 |
| TW201309743A (en) | 2013-03-01 |
| WO2013024844A1 (en) | 2013-02-21 |
| TWI543998B (en) | 2016-08-01 |
| KR101774629B1 (en) | 2017-09-04 |
| CN103764707B (en) | 2015-11-25 |
| JPWO2013024844A1 (en) | 2015-03-05 |
| KR20140063584A (en) | 2014-05-27 |
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