CN103764707B - The mixture of epoxy compounds, epoxy compounds, solidification compound and connection structural bodies - Google Patents

The mixture of epoxy compounds, epoxy compounds, solidification compound and connection structural bodies Download PDF

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CN103764707B
CN103764707B CN201280040209.XA CN201280040209A CN103764707B CN 103764707 B CN103764707 B CN 103764707B CN 201280040209 A CN201280040209 A CN 201280040209A CN 103764707 B CN103764707 B CN 103764707B
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epoxy compounds
mentioned
reaction product
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methyl
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CN103764707A (en
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石泽英亮
久保田敬士
结城彰
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Sekisui Chemical Co Ltd
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Emergency Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Conductive Materials (AREA)

Abstract

The invention provides a kind of can rapid solidification and the epoxy compounds of the cementability of cured article and excellent moisture resistance, use the solidification compound of this epoxy compounds and use the connection structural bodies of this solidification compound.Epoxy compounds of the present invention has epoxy group(ing) and side chain has vinyl or epoxy group(ing) at two ends.The weight-average molecular weight of epoxy compounds of the present invention is more than 500 and less than 150000.Solidification compound of the present invention contains above-mentioned epoxy compounds and thermal curing agents.Connection structural bodies of the present invention (1) has the 1st connecting object parts (2), the 2nd connecting object parts (4) and connects the connection section (3) of the 1st, the 2nd connecting object parts (2), (4).Connection section (3) is formed by above-mentioned solidification compound.

Description

The mixture of epoxy compounds, epoxy compounds, solidification compound and connection structural bodies
Technical field
The present invention relates to such as can rapid solidification and the epoxy compounds of the cementability of cured article and excellent moisture resistance.In addition, the invention still further relates to the mixture of the epoxy compounds containing this epoxy compounds, use the solidification compound of this epoxy compounds and use the connection structural bodies of this solidification compound.
Background technology
The bonding force of the cured article after epoxy resin composition is high, and the water tolerance of cured article and excellent heat resistance.Therefore, composition epoxy resin be widely used in electrically, the various uses such as electronics, building and vehicle.In addition, in order to by various connecting object parts electrical connection, sometimes in above-mentioned composition epoxy resin, electroconductive particle is added.Composition epoxy resin containing 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 circuit substrate of ITO electrode.Such as, can carry out heating and pressurizeing by configure anisotropic conductive material between the electrode and the electrode of circuit substrate of IC chip after, thus these electrodes are connected to each other.
As an example of above-mentioned anisotropic conductive material, followingly Patent Document 1 discloses a kind of anisotropic conductive adhesive film, 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 is preferably containing flexible epoxy resin.According to the record in patent documentation 1, even if make this anisotropic conductive adhesive film solidify at a lower temperature, it also has excellent connection reliability.
In addition, followingly Patent Document 2 discloses a kind of composition epoxy resin, it contains the diglycidylether of dihydroxyphenyl propane-alkylen oxide adducts, bisphenol A diglycidyl ether, the thinner without epoxy group(ing), the perbutan of carboxy blocking, dodecenylsuccinic anhydride and inorganic filler.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 9-115335 publication
Patent documentation 2: Japanese Unexamined Patent Publication 9-235350 publication
Summary of the invention
The problem that invention will solve
In recent years, in order to connect between the electrode of electronic unit efficiently, require to shorten the heat-up time needed for epoxy resin composition.Further, by shortening heat-up time, the thermal degradation when of gained electronic unit can be suppressed.
For the anisotropic conductive adhesive film recorded in patent documentation 1, if shorten heat-up time, then sometimes can not fully solidify.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, for the composition epoxy resin recorded in patent documentation 2, in order to make it fully solidify, long heating is also needed.
In addition, for the composition epoxy resin recorded in the anisotropic conductive adhesive film recorded 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 rapid solidification and the epoxy compounds of the cementability of cured article and excellent moisture resistance, epoxy compounds containing this epoxy compounds mixture, use the solidification compound of this epoxy compounds and use the connection structural bodies of this solidification compound.
The method of dealing with problems
According to wider layer face 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 less than 150000.
In a certain particular aspects of epoxy compounds of the present invention, this epoxy compounds has more than 2 vinyl altogether at side chain or has more than 2 epoxy group(ing) altogether at side chain.
In other particular aspects of epoxy compounds of the present invention, this epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and following reaction product and obtains, above-mentioned reaction product is the reaction product of Bisphenol F or Resorcinol and 1,6-hexanediol diglycidyl ether or resorcinol diglycidyl ether.
In other the particular aspects further 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 1st reaction product is Bisphenol F and 1, the reaction product of 6-hexanediol diglycidyl ether, above-mentioned 2nd reaction product is Resorcinol and 1, the reaction product of 6-hexanediol diglycidyl ether, above-mentioned 3rd reaction product is the reaction product of Resorcinol and resorcinol diglycidyl ether.
In other the particular aspects further of epoxy compounds of the present invention, when above-mentioned reaction product is above-mentioned 1st reaction product, there are 2 peaks in the molecular weight distribution of epoxy compounds, when above-mentioned reaction product is above-mentioned 2nd reaction product, in the molecular weight distribution of epoxy compounds, there are 2 peaks.
Preferred above-mentioned reaction product is above-mentioned 1st reaction product, is also preferably above-mentioned 2nd reaction product, is also preferably above-mentioned 3rd reaction product in addition.In addition, be preferably (methyl) vinylformic acid or 2-(methyl) acryloyloxyethyl isocyanate with the compound of above-mentioned reaction, be also preferably 2-(methyl) acryloyloxyethyl 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 1st epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 1st reaction product and obtains, above-mentioned 1st reaction product is the reaction product of Bisphenol F and 1,6-hexanediol diglycidyl ether; Above-mentioned 2nd epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 2nd reaction product and obtains, above-mentioned 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 2nd epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 2nd reaction product and obtains, above-mentioned 2nd reaction product is the reaction product of Resorcinol and 1,6-hexanediol diglycidyl ether; Above-mentioned 3rd epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 3rd reaction product and obtains, and above-mentioned 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 DEG C 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 is further containing photocurable compound and Photoepolymerizationinitiater initiater.
In the other particular aspects of solidification compound of the present invention, it is further containing electroconductive particle.
In other particular aspects of solidification compound of the present invention, except above-mentioned epoxy compounds, also containing epoxy (methyl) acrylate, above-mentioned epoxy (methyl) acrylate is undertaken reacting obtaining by least one making in 2 epoxy group(ing) of (methyl) vinylformic acid and this epoxy compounds two end.
Connection structural bodies of the present invention has the 1st connecting object parts, the 2nd connecting object parts and connects the connection section of the 1st, the 2nd connecting object parts, and this connection section is formed by above-mentioned solidification compound.
In a certain particular aspects of connection structural bodies of the present invention, above-mentioned solidification compound contains electroconductive particle, and above-mentioned 1st, the 2nd connecting object parts are electrically connected by above-mentioned electroconductive particle.
The effect of invention
Epoxy compounds of the present invention makes solidification compound variation.In addition, at two ends, there is epoxy group(ing) due to epoxy compounds of the present invention and at side chain, there is vinyl or epoxy group(ing), and its weight-average molecular weight is more than 500 and less than 150000, therefore, it is possible to rapid solidification, and cementability and the wet fastness of cured article can be improved.
Accompanying drawing explanation
[Fig. 1] Fig. 1 is portion intercepts sectional view, that schematically shows an example of the connection structural bodies of the solidification compound employing an embodiment of the present invention.
Nomenclature
1... connection structural bodies
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) at two ends and has vinyl or epoxy group(ing) at side chain.The weight-average molecular weight of epoxy compounds of the present invention is more than 500 and less than 150000.
Having the epoxy compounds formed as mentioned above can rapid solidification.Such as, the solidification compound rapid solidification having coordinated above-mentioned epoxy compounds and thermal curing agents can be made.Such as, solidify within 5 seconds under its Heating temperature more than 150 DEG C can be made.Further, cementability and the wet fastness of the cured article using above-mentioned epoxy compounds can be improved.Therefore, the reliability of the connection structural bodies using the above-mentioned solidification compound containing above-mentioned epoxy compounds to be formed by connecting by the 1st, the 2nd connecting object parts can be improved.
More preferably epoxy compounds of the present invention uses diatomic alcohol compounds and has the compound of 2 epoxy group(ing) and the reaction product that obtains.Preferred epoxy compounds of the present invention is the reaction of compound by making to have vinyl or the compound with epoxy group(ing) and diatomic alcohol compounds and the compound with 2 epoxy group(ing) and the epoxy compounds that obtains.
The weight-average molecular weight of epoxy compounds of the present invention is more than 500 and less than 150000.The weight-average molecular weight of epoxy compounds of the present invention is preferably more than 1000, is preferably less than 50000, is more preferably less than 15000.
Epoxy compounds of the present invention has the vinyl of more than 1 or on side chain, has the epoxy group(ing) of more than 1 on side chain.Epoxy compounds of the present invention can have the vinyl of more than 1 on side chain, also can have the epoxy group(ing) of more than 1 on side chain.
Preferred epoxy compounds of the present invention has the vinyl of more than 2 altogether or on side chain, has the epoxy group(ing) of more than 2 altogether on side chain.The quantity of vinyl or epoxy group(ing) is more, more can shorten heat-up time further, and can improve cementability and the wet fastness of cured article further.Epoxy compounds of the present invention can have the vinyl of more than 2 altogether on side chain, on side chain, also can have the epoxy group(ing) of more than 2 altogether.
Preferred epoxy compounds of the present invention has the compound of more than 2 phenolic hydroxyl group and has the reaction product of compound of more than 2 epoxy group(ing).
As the above-mentioned compound with more than 2 phenolic hydroxyl group, bisphenol cpd, Resorcinol and naphthols etc. can be enumerated.As above-mentioned bisphenol cpd, Bisphenol F, dihydroxyphenyl propane, bisphenol S, bisphenol S A and bis-phenol E etc. can be enumerated.
As the above-mentioned compound with more than 2 epoxy group(ing), aliphatic epoxy compound and aromatic epoxy compound etc. can be enumerated.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 oxetanylmethoxy; And there is the polyether skeleton of carbonatoms 2 ~ 4 and have by the polyether-type epoxy compounds of the structural unit of 2 ~ 10 continuous bondings of this polyether skeleton.
Preferred epoxy compounds of the present invention is the epoxy compounds by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and following reaction product (being also denoted as reaction product X below) carry out reacting and obtain, 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 using such compou nd synthesis to obtain can rapid solidification, and can improve cementability and the wet fastness of cured article.
Above-mentioned reaction product X is the reaction product of the resorcinol diglycidyl ether that 1, the 6-hexanediol diglycidyl ether that represents of the Resorcinol that represents of the Bisphenol F that represents of following formula (1) or following formula (2) and following formula (11) or following formula (12) represent.
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
[chemical formula 4]
In above-mentioned formula (1), 1 hydroxyl relative to 1 phenyl ring bonding position without particular limitation of.As above-mentioned Bisphenol F, can enumerate that such as following formula (1-1) represents 4,4 '-methylene-bis phenol, following formula (1-2) represent 2,4 '-methylene-bis phenol and following formula (1-3) represent 2,2 '-methylene-bis phenol etc.Usually these materials are referred to as Bisphenol F.Above-mentioned Bisphenol F can contain 1 hydroxyl of more than two kinds compound different relative 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 6-hexanediol diglycidyl ether is obtained by reacting, by Resorcinol and 1, the 2nd reaction product that 6-hexanediol diglycidyl ether is obtained by reacting, the 3rd reaction product be obtained by reacting by Resorcinol and resorcinol diglycidyl ether, the 4th reaction product be obtained by reacting by Bisphenol F and resorcinol diglycidyl ether.
Above-mentioned 1st reaction product has by coming from the skeleton of Bisphenol F and coming from the structural unit of skeleton bonding of 1,6-hexanediol diglycidyl ether on main chain, and has the epoxy group(ing) coming from 1,6-hexanediol diglycidyl ether at two ends.Above-mentioned 2nd reaction product has the structural unit coming from Resorcinol and the structural unit coming from 1,6-hexanediol diglycidyl ether on main chain, and has the epoxy group(ing) coming from 1,6-hexanediol diglycidyl ether at two ends.Above-mentioned 3rd reaction product has the skeleton coming from Resorcinol and the skeleton coming from resorcinol diglycidyl ether on main chain, and has the epoxy group(ing) coming from resorcinol diglycidyl ether at two ends.Above-mentioned 4th reaction product has the skeleton coming from Bisphenol F and the skeleton coming from resorcinol diglycidyl ether on main chain, and two ends have the epoxy group(ing) coming from resorcinol diglycidyl ether.
From the view point of easily synthesis, epoxy compounds can be made more promptly to solidify and can further improve cementability and the wet fastness of cured article, in above-mentioned 1st, the 2nd, the 3rd, the 4th reaction product, preferably above-mentioned 1st reaction product, above-mentioned 2nd reaction product or above-mentioned 3rd reaction product.Preferred above-mentioned reaction product X is above-mentioned 1st reaction product, is also preferably above-mentioned 2nd reaction product, is also preferably above-mentioned 3rd reaction product further.
Preferably above-mentioned 1st reaction product has the structure that following formula (51) represents.
[chemical formula 8]
In above-mentioned formula (51), n represents integer.And, n is when the epoxy compounds making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (51) represent reacts and obtains epoxy compounds, makes the weight-average molecular weight of this epoxy compounds be the integer of more than 500 and less than 150000.
Preferably above-mentioned 2nd reaction product has the structure that following formula (52) represents.
[chemical formula 9]
In above-mentioned formula (52), n represents integer.And, n is when the epoxy compounds making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (52) represent reacts and obtains epoxy compounds, makes the weight-average molecular weight of this epoxy compounds be the integer of more than 500 and less than 150000.
Preferably above-mentioned 3rd reaction product has the structure that following formula (53) represents.
[chemical formula 10]
In above-mentioned formula (53), n represents integer.And, n is when the epoxy compounds making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (53) represent reacts and obtains epoxy compounds, makes the weight-average molecular weight of this epoxy compounds be the integer of more than 500 and less than 150000.
Preferably above-mentioned 4th reaction product has the structure that following formula (54) represents.
[chemical formula 11]
In above-mentioned formula (54), n represents integer.And, n is when the epoxy compounds making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (54) represent reacts and obtains epoxy compounds, makes the weight-average molecular weight of this epoxy compounds be the integer of more than 500 and less than 150000.
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 be the integer of more than 1000 and less than 50000.More preferably n is respectively and makes the weight-average molecular weight of above-mentioned epoxy compounds be the integer of more than 1000 and less than 15000.
When there is 2 peaks in the molecular weight distribution of epoxy compounds, the peak of high molecular side is larger than the peak of lower molecular weight side, is preferably more than 10000, is preferably less than 150000, is more preferably less than 50000, and more preferably less than 15000.When there is 2 peaks in the molecular weight distribution of epoxy compounds, the peak of lower molecular weight side is less than the peak of high molecular side, is preferably more than 1000, is more preferably more than 2000, is preferably less than 10000, is more preferably less than 6000.
In above-mentioned formula (51) and formula (54), 1 Sauerstoffatom relative to 1 phenyl ring bonding position without particular limitation of.This bonding position is determined by the kind (such as, above-mentioned formula (1-1) ~ (1-3)) of Bisphenol F.
As in order to make Bisphenol F or Resorcinol and 1,6-hexanediol diglycidyl ether or resorcinol diglycidyl ether carry out the concrete reaction of reacting, polyaddition reaction can be enumerated.
The Bisphenol F that above-mentioned formula (1) represents 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, while use Bisphenol F, also can use and there is Bisphenol F skeleton and there are 3 with the polykaryon of coker.
Above-mentioned polykaryon is such as represented by following formula (X).In order to obtain above-mentioned reaction product X be used as the Bisphenol F of dikaryon and there is Bisphenol F skeleton and there are 3 coenocytic mixtures with coker time, in this mixture of 100 % by weight, as the content preferably more than 70 % by weight of the Bisphenol F of dikaryon, more preferably more than 85 % by weight, preferably less than 99.9 % by weight, more preferably less than 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, then use the cementability of the cured article of above-mentioned epoxy compounds to uprise further, and use the reliability of the connection structural bodies of the above-mentioned solidification compound containing above-mentioned epoxy compounds to uprise further.
[chemical formula 12]
In above-mentioned formula (X), m represents the integer of more than 1.M is preferably less than 10, is more preferably less than 5, is particularly preferably less than 3.Such as, in above-mentioned formula (X), m be 1 polykaryon be three nucleomes with Bisphenol F skeleton.In above-mentioned formula (X), 1 hydroxyl relative to 1 phenyl ring bonding position without particular limitation of.
In addition, when being used as the Bisphenol F of dikaryon and there is Bisphenol F skeleton and there are 3 coenocytic mixtures with coker, by Bisphenol F and 1, in the 1st reaction product that 6-hexanediol diglycidyl ether is obtained by reacting, except by come from as the Bisphenol F of dikaryon skeleton and come from 1, beyond the structural unit of the skeleton bonding of 6-hexanediol diglycidyl ether, its main chain can also have Bisphenol F skeleton containing by coming from and have 3 with the coenocytic skeleton of coker and come from 1, the structural unit of the skeleton bonding of 6-hexanediol diglycidyl ether.When being used as the Bisphenol F of dikaryon and there is Bisphenol F skeleton and there are 3 coenocytic mixtures with coker, in above-mentioned 4th reaction product, except by come from as the Bisphenol F of dikaryon skeleton and come from resorcinol diglycidyl ether the structural unit of skeleton bonding except, its main chain can also have Bisphenol F skeleton containing by coming from and have 3 with the coenocytic skeleton of coker and the structural unit of skeleton bonding coming from resorcinol diglycidyl ether.
That is, above-mentioned 1st reaction product can have the structure that following formula (51X) represents.
[chemical formula 13]
In above-mentioned formula (51X), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, n represents integer.And, n is when the epoxy compounds making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (51X) represent reacts and obtains epoxy compounds, makes the weight-average molecular weight of this epoxy compounds be the integer of more than 500 and less than 150000.
Above-mentioned 4th reaction product can have the structure that following formula (54X) represents.
[chemical formula 14]
In above-mentioned formula (54X), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, n represents integer.And, n is when the epoxy compounds making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned formula (54X) represent reacts and obtains epoxy compounds, makes the weight-average molecular weight of this epoxy compounds be the integer of more than 500 and less than 150000.
X in above-mentioned formula (51X) and above-mentioned formula (54X) is the structural unit that following formula (Xa) represents.
[chemical formula 15]
In above-mentioned formula (Xa), p represents the integer of more than 0.P is preferably less than 10, is more preferably less than 5, is particularly preferably less than 3.It should be noted that, in above-mentioned formula (Xa), when p is 0, represent the skeleton of the Bisphenol F come from as dikaryon, in above-mentioned formula (Xa), when p is the integer of more than 1, represent to come from there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker.In above-mentioned formula (Xa), 1 hydroxyl relative to 1 phenyl ring bonding position without particular limitation of.In above-mentioned formula (Xa), 1 Sauerstoffatom (-O-base) relative to 1 phenyl ring bonding position without particular limitation of.
By making the above-mentioned reaction product X such as (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned 1st, the 2nd, the 3rd, the 4th reaction product react, vinyl or epoxy group(ing) can be imported on side chain.That is, the compound preferably reacted with above-mentioned reaction product X is the 4-hydroxyl butylglycidyl ether that 2-(methyl) acryloyloxyethyl isocyanate that represents of (methyl) vinylformic acid, following formula (B) that following formula (A) represents or following formula (C) represent.The compound reacted with above-mentioned reaction product X can be (methyl) vinylformic acid, also can be 2-(methyl) acryloyloxyethyl 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 16]
In above-mentioned formula (A), R represents hydrogen atom or methyl.
[chemical formula 17]
In above-mentioned formula (B), R represents hydrogen atom or methyl.
[chemical formula 18]
In order to import vinyl on the side chain of epoxy compounds of the present invention, the compound preferably reacted with above-mentioned reaction product X is (methyl) vinylformic acid or 2-(methyl) acryloyloxyethyl isocyanate.The compound preferably reacted with above-mentioned reaction product X is (methyl) vinylformic acid, is also preferably 2-(methyl) acryloyloxyethyl isocyanate.When epoxy compounds of the present invention has vinyl on side chain, epoxy compounds photocuring of the present invention can be made and thermofixation.Therefore, such as, can make solidification compound generation B rank (semicure) containing epoxy compounds carrying out illumination after, make it that main solidification occur by carrying out heating.More promptly solidify from the view point of making epoxy compounds and further cementability and the wet fastness improving cured article, preferred epoxy compounds of the present invention has amino-formate bond.In addition, by using 2-(methyl) acryloyloxyethyl isocyanate, epoxy compounds, the mixture of epoxy compounds and the package stability of solidification compound can be improved further.
In order to import epoxy group(ing) on the side chain of epoxy compounds of the present invention, the compound preferably reacted with above-mentioned reaction product X is 4-hydroxyl butylglycidyl ether.By importing epoxy group(ing) in this wise on side chain, the cross-linking density of cured article can be improved, and improve the thermotolerance of cured article further.
2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 1st reaction that above-mentioned formula (51) represents, can obtain following formula (61A), the 1st epoxy compounds that (61B) or (61C) represents.
[chemical formula 19]
In above-mentioned formula (61A), R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61A) is represented be more than 500 and less than 150000.
[chemical formula 20]
In above-mentioned formula (61B), R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61B) is represented be more than 500 and less than 150000.
[chemical formula 21]
In above-mentioned formula (61C), n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61C) is represented be more than 500 and less than 150000.
In above-mentioned formula (61A), formula (61B) and formula (61C), 1 Sauerstoffatom relative to 1 phenyl ring bonding position without particular limitation of.This bonding position is determined by the kind (such as, above-mentioned formula (1-1) ~ (1-3)) of Bisphenol F.
2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 1st reaction that above-mentioned formula (51X) represents, can obtain following formula (61XA), the 1st epoxy compounds that (61XB) or (61XC) represents.
[chemical formula 22]
In above-mentioned formula (61XA), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61XA) is represented be more than 500 and less than 150000.
[chemical formula 23]
In above-mentioned formula (61XB), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61XB) is represented be more than 500 and less than 150000.
[chemical formula 24]
In above-mentioned formula (61XC), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (61XC) is represented be more than 500 and less than 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.
2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 2nd reaction that above-mentioned formula (52) represents, can obtain following formula (62A), the 2nd epoxy compounds that (62B) or (62C) represents.
[chemical formula 25]
In above-mentioned formula (62A), R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (62A) is represented be more than 500 and less than 150000.
[chemical formula 26]
In above-mentioned formula (62B), R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (62B) is represented be more than 500 and less than 150000.
[chemical formula 27]
In above-mentioned formula (62C), n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (62C) is represented be more than 500 and less than 150000.
2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 3rd reaction that above-mentioned formula (53) represents, can obtain following formula (63A), the 3rd epoxy compounds that (63B) or (63C) represents.
[chemical formula 28]
In above-mentioned formula (63A), R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (63A) is represented be more than 500 and less than 150000.
[chemical formula 29]
In above-mentioned formula (63B), R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (63B) is represented be more than 500 and less than 150000.
[chemical formula 30]
In above-mentioned formula (63C), n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (63C) is represented be more than 500 and less than 150000.
2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 4th reaction that above-mentioned formula (54) represents, can obtain following formula (64A), the 4th epoxy compounds that (64B) or (64C) represents.
[chemical formula 31]
In above-mentioned formula (64A), R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64A) is represented be more than 500 and less than 150000.
[chemical formula 32]
In above-mentioned formula (64B), R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64B) is represented be more than 500 and less than 150000.
[chemical formula 33]
In above-mentioned formula (64C), n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64C) is represented be more than 500 and less than 150000.
In above-mentioned formula (64A), formula (64B) and formula (64C), 1 Sauerstoffatom relative to 1 phenyl ring bonding position without particular limitation of.This bonding position is determined by the kind (such as, above-mentioned formula (1-1) ~ (1-3)) of Bisphenol F.
2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 4th reaction that above-mentioned formula (54X) represents, can obtain following formula (64XA), the 4th epoxy compounds that (64XB) or (64XC) represents.
[chemical formula 34]
In above-mentioned formula (64XA), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64XA) is represented be more than 500 and less than 150000.
[chemical formula 35]
In above-mentioned formula (64XB), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, R represents hydrogen atom or methyl, and n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64XB) is represented be more than 500 and less than 150000.
[chemical formula 36]
In above-mentioned formula (64XC), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (64XC) is represented be more than 500 and less than 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).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), the integer of preferred n to be the weight-average molecular weight of the epoxy compounds making these chemical formulations be more than 1000 and less than 50000, more preferably n makes weight-average molecular weight be the integer of more than 1000 and less than 15000.In addition, n can be more than 1, also can be more than 2.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), more than the value of the weight-average molecular weight of weight-average molecular weight more than 500 and when n is 1 of formula (64XB) and the middle epoxy compounds of formula (64XC), more than the value of the weight-average molecular weight more preferably more than 500 and when n is 2.
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), representatively illustrate structural formula when making hydroxyl whole (100%) reaction, but also can remaining unreacted hydroxyl.In total number 100% of hydroxyl before the reaction, the number ratio of the hydroxyl (becoming the group (formula (a) hereinafter described, (b), (c)) of non-hydroxyl) reacted can be more than 0.1%, can be more than 1%, can be more than 3%, can be more than 5%, can be 100%, be preferably less than 80%, be more preferably less than 60%, be more preferably less than 40% further, be particularly preferably less than 30%.The number ratio of above-mentioned hydroxyl can be measured by NMR.
The part of hydroxyl of 2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 1st reaction product that above-mentioned formula (51) represents is reacted, and can obtain following formula (71A), the 1st epoxy compounds that (71B) or (71C) represents.
[chemical formula 37]
In above-mentioned formula (71A), Z represents the group that hydroxyl or following formula (a) represent, multiple Z comprises the group that following formula (a) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71A) is represented be more than 500 and less than 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, multiple Z comprises the group that following formula (b) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71B) is represented be more than 500 and less than 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, multiple Z comprises the group that following formula (c) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71C) is represented be more than 500 and less than 150000.
[chemical formula 42]
In above-mentioned formula (71A), formula (71B) and formula (71C), 1 Sauerstoffatom relative to 1 phenyl ring bonding position without particular limitation of.This bonding position is determined by the kind (such as, above-mentioned formula (1-1) ~ (1-3)) of Bisphenol F.
2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 1st reaction that above-mentioned formula (51X) represents, can obtain following formula (71XA), the 1st epoxy compounds that (71XB) or (71XC) represents.
[chemical formula 43]
In above-mentioned formula (71XA), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (a) represent, multiple Z comprises the group that above-mentioned formula (a) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71XA) is represented be more than 500 and less than 150000.
[chemical formula 44]
In above-mentioned formula (71XB), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (b) represent, multiple Z comprises the group that above-mentioned formula (b) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71XB) is represented be more than 500 and less than 150000.
[chemical formula 45]
In above-mentioned formula (71XC), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (c) represent, multiple Z comprises the group that above-mentioned formula (c) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (71XC) is represented be more than 500 and less than 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.
2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 2nd reaction that above-mentioned formula (52) represents, can obtain following formula (72A), the 2nd epoxy compounds that (72B) or (72C) represents.
[chemical formula 46]
In above-mentioned formula (72A), Z represents the group that hydroxyl or above-mentioned formula (a) represent, multiple Z comprises the group that above-mentioned formula (a) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (72A) is represented be more than 500 and less than 150000.
[chemical formula 47]
In above-mentioned formula (72B), Z represents the group that hydroxyl or above-mentioned formula (b) represent, multiple Z comprises the group that above-mentioned formula (b) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (72B) is represented be more than 500 and less than 150000.
[chemical formula 48]
In above-mentioned formula (72C), Z represents the group that hydroxyl or above-mentioned formula (c) represent, multiple Z comprises the group that above-mentioned formula (c) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (72C) is represented be more than 500 and less than 150000.
2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 3rd reaction that above-mentioned formula (53) represents, can obtain following formula (73A), the 3rd epoxy compounds that (73B) or (73C) represents.
[chemical formula 49]
In above-mentioned formula (73A), Z represents the group that hydroxyl or above-mentioned formula (a) represent, multiple Z comprises the group that above-mentioned formula (a) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (73A) is represented be more than 500 and less than 150000.
[chemical formula 50]
In above-mentioned formula (73B), Z represents the group that hydroxyl or above-mentioned formula (b) represent, multiple Z comprises the group that above-mentioned formula (b) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (73B) is represented be more than 500 and less than 150000.
[chemical formula 51]
In above-mentioned formula (73C), Z represents the group that hydroxyl or above-mentioned formula (c) represent, multiple Z comprises the group that above-mentioned formula (c) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (73C) is represented be more than 500 and less than 150000.
2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 4th reaction that above-mentioned formula (54) represents, can obtain following formula (74A), the 4th epoxy compounds that (74B) or (74C) represents.
[chemical formula 52]
In above-mentioned formula (74A), Z represents the group that hydroxyl or above-mentioned formula (a) represent, multiple Z comprises the group that above-mentioned formula (a) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74A) is represented be more than 500 and less than 150000.
[chemical formula 53]
In above-mentioned formula (74B), Z represents the group that hydroxyl or above-mentioned formula (b) represent, multiple Z comprises the group that above-mentioned formula (b) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74B) is represented be more than 500 and less than 150000.
[chemical formula 54]
In above-mentioned formula (74C), Z represents the group that hydroxyl or above-mentioned formula (c) represent, multiple Z comprises the group that above-mentioned formula (c) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74C) is represented be more than 500 and less than 150000.
In above-mentioned formula (74A), formula (74B) and formula (74C), 1 Sauerstoffatom relative to 1 phenyl ring bonding position without particular limitation of.This bonding position is determined by the kind (such as, above-mentioned formula (1-1) ~ (1-3)) of Bisphenol F.
2-(methyl) acryloyloxyethyl isocyanate that (methyl) vinylformic acid represented by making above-mentioned formula (A), above-mentioned formula (B) represent or the 4-hydroxyl butylglycidyl ether that above-mentioned formula (C) represents and the 4th reaction that above-mentioned formula (54X) represents, can obtain following formula (74XA), the 4th epoxy compounds that (74XB) or (74XC) represents.
[chemical formula 55]
In above-mentioned formula (74XA), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (a) represent, multiple Z comprises the group that above-mentioned formula (a) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74XA) is represented be more than 500 and less than 150000.
[chemical formula 56]
In above-mentioned formula (74XB), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (b) represent, multiple Z comprises the group that above-mentioned formula (b) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74XB) is represented be more than 500 and less than 150000.
[chemical formula 57]
In above-mentioned formula (74XC), X represent come from as the Bisphenol F of dikaryon skeleton or come from and there is Bisphenol F skeleton and there are 3 with the coenocytic skeleton of coker, Z represents the group that hydroxyl or above-mentioned formula (c) represent, multiple Z comprises the group that above-mentioned formula (c) represents, n represents integer.Further, the integer of n to be the weight-average molecular weight of the epoxy compounds that above-mentioned formula (74XC) is represented be more than 500 and less than 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).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), the integer of preferred n to be the weight-average molecular weight of the epoxy compounds making these chemical formulations be more than 1000 and less than 50000, more preferably n makes its weight-average molecular weight be the integer of more than 1000 and less than 15000.In addition, n can be more than 1, also can be more than 2.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), more than the value of the weight-average molecular weight of weight-average molecular weight more than 500 and when n is 1 of formula (74XB) and the middle epoxy compounds of formula (74XC), more than the value of the weight-average molecular weight more preferably more than 500 and when n is 2.
From the view point of the cementability improving cured article further, preferably in the molecular weight distribution of the 1st epoxy compounds, there are 2 peaks, described 1st epoxy compounds obtains by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned 1st reaction.From the view point of the cementability improving cured article further, there are 2 peaks in the molecular weight distribution of preferred the 2nd epoxy compounds, described 2nd epoxy compounds obtains by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned 2nd reaction.
As making above-mentioned reaction product X and (methyl) vinylformic acid carry out the concrete reaction of reacting, condensation reaction can be enumerated.
As making above-mentioned reaction product X and 2-(methyl) acryloyloxyethyl isocyanate carry out the concrete reaction of reacting, addition reaction can be enumerated.
As making above-mentioned reaction product X and 4-hydroxyl butylglycidyl ether carry out the concrete reaction of reacting, condensation reaction can be enumerated.
In order to obtain epoxy compounds of the present invention use by as dikaryon Bisphenol F and there is Bisphenol F skeleton and have 3 obtain with the coenocytic mixture of coker reaction product time, in the epoxy compounds obtained, come from as the Bisphenol F of dikaryon structural unit and come to there is Bisphenol F skeleton and there are 3 and amount in 100 % by weight with the coenocytic structural unit of coker, the ratio coming from the structural unit of the Bisphenol F as dikaryon is preferably more than 70 % by weight, be more preferably more than 85 % by weight, be preferably less than 99.9 % by weight, be more preferably less than 99 % by weight.If amount in 100 % by weight at said structure unit, come from the ratio of the structural unit of the Bisphenol F as dikaryon more than above-mentioned lower limit and below the above-mentioned upper limit, then use above-mentioned epoxy compounds and the cementability of cured article that obtains uprises further, and the reliability of the connection structural bodies using the above-mentioned solidification compound containing above-mentioned epoxy compounds and obtain uprises further.
(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 combinationally used.By above-mentioned epoxy compounds of more than two kinds is combinationally used, can the viscosity of the easily mixture of regulating ring oxygen compound.
More promptly solidify from epoxy compounds can be made, and can further improve cementability and the wet fastness of cured article, or the viewpoint producing space in suppression connection structural bodies is set out, the mixture of preferred epoxy compounds of the present invention contains the 1st epoxy compounds and the 2nd epoxy compounds, described 1st epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 1st reaction product carry out reacting obtaining, described 1st reaction product is Bisphenol F and 1, the reaction product of 6-hexanediol diglycidyl ether, described 2nd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 2nd reaction product carry out reacting obtaining, described 2nd reaction product is Resorcinol and 1, the reaction product of 6-hexanediol diglycidyl ether.
More promptly solidify from epoxy compounds can be made, and can further improve cementability and the wet fastness of cured article, or the viewpoint producing space in suppression connection structural bodies is set out, the mixture of preferred epoxy compounds of the present invention contains the 2nd epoxy compounds and the 3rd epoxy compounds, described 2nd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 2nd reaction product carry out reacting obtaining, described 2nd reaction product is Resorcinol and 1, the reaction product of 6-hexanediol diglycidyl ether, described 3rd epoxy compounds is by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 3rd reaction product carry out reacting obtaining, described 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 1st epoxy compounds and above-mentioned 2nd epoxy compounds or contains above-mentioned 2nd epoxy compounds and above-mentioned 3rd epoxy compounds.
From the view point of raising coating, make not easily to produce space in connection structural bodies, the viscosity of mixture at 23 DEG C of epoxy compounds is preferably more than 50Pas, is more preferably more than 100Pas, is preferably below 1200Pas, be 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 less than 150000.Solidification compound of the present invention can rapid solidification, 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 being combinationally used by above-mentioned epoxy compounds of more than two kinds, the viscosity of solidification compound easily can be regulated.
From the view point of improving coating and making not easily to produce space in connection structural bodies, the viscosity of solidification compound at 23 DEG C is preferably more than 50Pas, is more preferably more than 100Pas, is preferably below 1200Pas, be 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 1st epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 1st reaction product and obtains, described 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 2nd epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 2nd reaction product and obtains, described 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 3rd epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 3rd reaction product and obtains, and described 3rd reaction product is the reaction product of Resorcinol and resorcinol diglycidyl ether; Or (4) are containing the 4th epoxy compounds and containing Bisphenol F diglycidylether or resorcinol diglycidyl ether, described 4th epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 4th reaction product and obtains, and described 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 to uprise further, and use the reliability of the connection structural bodies of the above-mentioned solidification compound containing above-mentioned epoxy compounds to uprise further.
More preferably solidification compound of the present invention meets the following conditions: (1) above-mentioned epoxy compounds contains above-mentioned 1st epoxy compounds and contains Bisphenol F diglycidylether or 1,6-hexanediol diglycidyl ether; Or (2) above-mentioned epoxy compounds contains above-mentioned 2nd epoxy compounds and contains resorcinol diglycidyl ether or 1,6-hexanediol diglycidyl ether; Or (3) above-mentioned epoxy compounds contains above-mentioned 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 to uprise further, and use the reliability of the connection structural bodies of the above-mentioned solidification compound containing above-mentioned epoxy compounds to uprise further.
Solidification compound of the present invention contains above-mentioned 1st, the 2nd, the 3rd, the 4th epoxy compounds, and containing Bisphenol F diglycidylether, resorcinol diglycidyl ether or 1, when 6-hexanediol diglycidyl ether, relative to total amount 100 weight part of above-mentioned 1st, the 2nd, the 3rd, the 4th epoxy compounds, Bisphenol F diglycidylether, resorcinol diglycidyl ether and 1, the total content of 6-hexanediol diglycidyl ether is preferably more than 0.1 weight part, be more preferably more than 1 weight part, be preferably below 100 weight parts, be more preferably below 20 weight parts.If Bisphenol F diglycidylether, resorcinol diglycidyl ether and 1, the total content of 6-hexanediol diglycidyl ether is below more than above-mentioned lower limit and the above-mentioned upper limit, then the cross-linking density of the cured article of solidification compound uprises, use the cementability of the cured article of above-mentioned epoxy compounds to uprise further, and use the reliability of the connection structural bodies of the above-mentioned solidification compound containing above-mentioned epoxy compounds to uprise further.
In preferred solidification compound of the present invention except above-mentioned epoxy compounds (epoxy compounds of the present invention), also containing epoxy (methyl) acrylate, described epoxy (methyl) acrylate is undertaken reacting obtaining by least one making in 2 epoxy group(ing) of (methyl) vinylformic acid and this epoxy compounds two end.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 to uprise further, and use the reliability of the connection structural bodies of the above-mentioned solidification compound containing above-mentioned epoxy compounds to uprise further.
In addition, preferred above-mentioned epoxy compounds and epoxy (methyl) acrylate that obtains by making (methyl) vinylformic acid carry out reacting with at least one in 2 epoxy group(ing) of this epoxy compounds two end have identical structure 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 coming from Bisphenol F, preferably come from Resorcinol.Preferred above-mentioned epoxy compounds and above-mentioned epoxy (methyl) acrylate all have the skeleton coming from 1,6-hexanediol diglycidyl ether, preferably have the skeleton coming from resorcinol diglycidyl ether.By using epoxy compounds and epoxy (methyl) acrylate like this, the cross-linking density of the cured article of solidification compound uprises further, use the cementability of the cured article of above-mentioned epoxy compounds to uprise further, and use the reliability of the connection structural bodies of the above-mentioned solidification compound containing above-mentioned epoxy compounds to uprise further.
When solidification compound of the present invention contains above-mentioned epoxy compounds and above-mentioned epoxy (methyl) acrylate, relative to above-mentioned epoxy compounds 100 weight part, the content of above-mentioned epoxy (methyl) acrylate is preferably more than 0.1 weight part, be more preferably more than 1 weight part, be preferably below 100 weight parts, be more preferably below 20 weight parts.If the content of above-mentioned epoxy (methyl) acrylate is below more than above-mentioned lower limit and the above-mentioned upper limit, then the cross-linking density of the cured article of solidification compound uprises further, use the cementability of the cured article of above-mentioned epoxy compounds to uprise further, and use the reliability of the connection structural bodies of the above-mentioned solidification compound containing above-mentioned epoxy compounds to uprise further.
Thermal curing agents contained in solidification compound of the present invention 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, existing known thermal curing agents can be used.This thermal curing agents comprises thermal free radical initiator.This thermal curing agents can only use a kind, also two or more can be combinationally used.
As above-mentioned thermal curing agents, cation curing agent, imidazole curing agent, amine hardener, phenol solidifying agent, polythiol solidifying agent, acid anhydrides and thermal free radical initiator etc. can be enumerated.Wherein, preferred cationic solidifying agent, imidazole curing agent, polythiol solidifying agent or amine hardener, this is because these solidifying agent can make solidification compound more promptly solidify.In addition, preferred latent curing agent, this is because such solidifying agent can improve the storage stability of solidification compound.Preferred 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 the polymer substance 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 adduct 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 shell [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.Due to the curing speed of solidification compound can be accelerated further, 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, the curing speed of solidification compound can be accelerated further.
As above-mentioned thermal free radical initiator, without particular limitation of, can azo-compound and superoxide etc. be enumerated.As above-mentioned superoxide, diacyl peroxide compound, peroxyester compound, hydroperoxide compound, peroxy dicarbonate, ketal peroxide compound, dialkyl peroxide compound and ketone peroxide compound etc. can be enumerated.
As above-mentioned azo-compound, can enumerate such as: 2, 2 '-Diisopropyl azodicarboxylate, 2, 2 '-azo two (2-methylbutyronitrile), 2, 2 '-azo two (2, 4-methyl pentane nitrile), 1, 1 '-azo two-1-cyclohexane carbonitrile, 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 heptanoic 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-(2-ethylhexanoyl-peroxy) 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 peroxylauric 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: methylethyl ketone peroxide, Potassium Persulphate and 1,1-two (tert-butyl hydroperoxide)-3,3,5-trimethyl-cyclohexane etc.
Above-mentioned thermal free radical initiator be preferably more than 30 DEG C for the decomposition temperature obtaining 10 hr half-life, be more preferably more than 40 DEG C, be preferably less than 90 DEG C, be more preferably less than 80 DEG C, more preferably less than 70 DEG C.If above-mentioned thermal free radical initiator for obtaining the decomposition temperature of 10 hr half-life lower than 30 DEG C, then solidification compound package stability exist decline tendency, if more than 90 DEG C, then exist be difficult to the tendency making 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, relative to total amount 100 weight part of above-mentioned epoxy compounds, the content of thermal curing agents is preferably more than 0.01 weight part, be more preferably more than 1 weight part, be preferably below 200 weight parts, be 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 then easy to solidification compound is fully solidified.If the content of thermal curing agents is below the above-mentioned upper limit, then not easily remain the unnecessary thermal curing agents having neither part nor lot in solidification after hardening, and the thermotolerance of cured article uprises further.
It should be noted that, above-mentioned thermal curing agents be imidazole curing agent or phenol solidifying agent time, relative to total amount 100 weight part of above-mentioned epoxy compounds, the content of imidazole curing agent or phenol solidifying agent is preferably more than 1 weight part, is preferably below 15 weight parts.In addition, when above-mentioned thermal curing agents is amine hardener, polythiol solidifying agent or acid anhydrides, relative to total amount 100 weight part of above-mentioned epoxy compounds, the content of amine hardener, polythiol solidifying agent or acid anhydrides is preferably more than 15 weight parts, is preferably below 40 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.Relative to total amount 100 weight part of above-mentioned epoxy compounds, the content of above-mentioned thermal free radical initiator is preferably more than 0.01 weight part, is more preferably more than 0.05 weight part, is preferably below 10 weight parts, is more preferably below 5 weight parts.If the content of above-mentioned thermal free radical initiator is below more than above-mentioned lower limit and the above-mentioned upper limit, then can make the abundant thermofixation of solidification compound.
[other compositions]
Preferred solidification compound of the present invention is further containing curing catalyst.By using curing catalyst, the curing speed of solidification compound can be accelerated further.Curing catalyst can only use a kind, also two or more can be combinationally used.
As the object lesson of above-mentioned curing catalyst, imidazoles curing catalyst and amine curing catalyst etc. can be enumerated.Wherein preferred imidazoles curing catalyst.In addition, imidazoles curing catalyst or amine curing catalyst also can use as imidazole curing agent or amine hardener.
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 adduct etc.
Relative to total amount 100 weight part of above-mentioned epoxy compounds, the content of above-mentioned curing catalyst is preferably more than 0.5 weight part, is more preferably more than 1 weight part, is preferably below 6 weight parts, is more preferably below 4 weight parts.If the content of curing catalyst is more than above-mentioned lower limit, be then easy to solidification compound is fully solidified.If the content of curing catalyst is below the above-mentioned upper limit, then not easily remain the unnecessary curing catalyst having neither part nor lot in solidification after hardening.
In order to make 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, solidification compound can be solidified by carrying out illumination.In addition, solidification compound can be made to carry out semicure and the mobility of solidification compound is reduced.
Above-mentioned photocurable compound without particular limitation of.As this photocurable compound, preferably use (methyl) acrylic resin or the resin etc. containing cyclic ether group, more preferably use (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, preferably make (methyl) vinylformic acid and the compound with hydroxyl carry out reacting and obtain ester cpds, make (methyl) vinylformic acid and epoxy compounds carry out reacting and carbamate (methyl) acrylate etc. that epoxy (methyl) acrylate that obtains or (methyl) acrylic acid derivative making to have hydroxyl and isocyanic ester carry out reacting and obtain.
Above-mentioned make (methyl) vinylformic acid and the compound with hydroxyl carry out reacting and the ester cpds that obtains without particular limitation of.As this ester cpds, any ester cpds in the ester cpds of more than simple function ester cpds, difunctional esterified compound and trifunctional can be used.
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 the photocurable compound being converted into (methyl) acryl by PART EPOXY base or the part thiiranes group of the compound by having more than 2 epoxy group(ing) or more than 2 thiiranes groups and being obtained.Such photocurable compound is part (methyl) Acrylated Epoxy compound or part (methyl) acroleic acid esterification episulfide compound.
Preferred above-mentioned photocurable compound is have the compound of more than 2 epoxy group(ing) or more than 2 thiiranes groups and (methyl) acrylic acid reaction product.This reaction product can obtain by making the compound with more than 2 epoxy group(ing) or more than 2 thiiranes groups carry out according to conventional methods reacting under the existence of the catalyzer such as basic catalyst with (methyl) vinylformic acid.More than 20% of preferred epoxy group(ing) or thiiranes group is converted into (methyl) acryl (transformation efficiency).This transformation efficiency is more preferably more than 30%, is preferably less than 80%, is more preferably less than 70%.Most preferably epoxy group(ing) or thiiranes group more than 40% and less than 60% be converted into (methyl) acryl.
As the above-mentioned photocurable compound with epoxy group(ing) or thiiranes group and (methyl) acryl, biphenol type epoxy (methyl) acrylate, cresol novolak type epoxy (methyl) acrylate, carboxylic acid anhydride modified epoxy (methyl) acrylate and phenol novolak-type epoxy (methyl) acrylate etc. can be enumerated.
As above-mentioned photocurable compound, the PART EPOXY base of the phenoxy resin with more than 2 epoxy group(ing) or more than 2 thiiranes groups or part thiiranes group also can be used to be converted into the modification phenoxy resin of (methyl) acryl.That is, the modification phenoxy resin with epoxy group(ing) or thiiranes group or (methyl) acryl can be used.
When comprising the photocurable compound except above-mentioned photocurable compound, this photocurable compound can be cross-linked compound, also can be non-cross-linked compound.
As the object lesson of above-mentioned cross-linked compound, can enumerate such as: 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, 1, 9-nonanediol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, glycerol methacrylate acrylate, tetramethylolmethane three (methyl) acrylate, trimethylolpropane trimethacrylate, (methyl) allyl acrylate, (methyl) vinyl acrylate, Vinylstyrene, polyester (methyl) acrylate and carbamate (methyl) acrylate etc.
As the object lesson of above-mentioned non-crosslinked compound, can enumerate: (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) 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.
Photocuring is there is efficiently from the view point of making above-mentioned solidification compound, relative to total amount 100 weight part of above-mentioned epoxy compounds, the content of above-mentioned photocurable compound is preferably more than 0.1 weight part, be more preferably more than 1 weight part, more preferably more than 10 weight parts, be particularly preferably more than 50 weight parts, be preferably below 10000 weight parts, be 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 use a kind, also two or more can be combinationally used.
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 Photoepolymerizationinitiater initiater in addition can be used.
As the object lesson of 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, benzoin dimethylether etc. can be enumerated.
The content of above-mentioned Photoepolymerizationinitiater initiater without particular limitation of.Relative to above-mentioned Photocurable composition 100 weight part, the content of above-mentioned Photoepolymerizationinitiater initiater is preferably more than 0.1 weight part, is more preferably more than 0.2 weight part, more preferably more than 2 weight parts, be preferably below 10 weight parts, be more preferably below 5 weight parts.If the content of Photoepolymerizationinitiater initiater is more than above-mentioned lower limit, be then easy to give full play to the effect that with the addition of Photoepolymerizationinitiater initiater.If the content of Photoepolymerizationinitiater initiater is below the above-mentioned upper limit, then the bonding force of the cured article of solidification compound is improved fully.
Preferred solidification compound of the present invention is further containing phenoloid.This phenoloid has hydroxyl bond and is combined in phenolic hydroxyl group on phenyl ring.As above-mentioned phenoloid, polyphenol, trivalent alcohol, Resorcinol and tocopherol (vitamin-E) etc. can be enumerated.Above-mentioned phenoloid can only use a kind, also two or more can be combinationally used.
Preferred solidification compound of the present invention is further containing filler.By using filler, the latent heat of the cured article of solidification compound can be suppressed to expand.As the object lesson of above-mentioned filler, silicon-dioxide, aluminium nitride or aluminum oxide etc. can be enumerated.Filler can only use a kind, also two or more can be combinationally used.
The content of above-mentioned filler without particular limitation of.Relative to total amount 100 weight part of solidification compound, the content of above-mentioned filler is preferably more than 5 weight parts, is more preferably more than 15 weight parts, is preferably below 200 weight parts, is more preferably below 100 weight parts.If the content of above-mentioned filler is below more than above-mentioned lower limit and the above-mentioned upper limit, then the latent heat of cured article fully can be suppressed to expand, and filler can be made to 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, the viscosity of solidification compound easily can be regulated.
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 contain storage stabilizer, ion trap agent or silane coupling agent etc. as required further.
[solidification compound containing electroconductive particle]
When solidification compound of the present invention is further containing electroconductive particle, solidification compound can be used as electro-conductive material.Preferably this electro-conductive material is anisotropic conductive material.Preferably above-mentioned epoxy compounds is used as electro-conductive material with the mixture of above-mentioned epoxy compounds together with electroconductive particle, is more preferably used as anisotropic conductive material together with electroconductive particle.
Above-mentioned electroconductive particle is electrically connected between the electrode of the 1st, the 2nd connecting object parts.Specifically, above-mentioned electroconductive particle is electrically connected between the electrode of such as circuit substrate and semi-conductor chip.As long as the particle that above-mentioned electroconductive particle has electroconductibility just without particular limitation of.As long as above-mentioned electroconductive particle has conductive part on the surface of electroconductibility.The conductive part surface of electroconductive particle can be coated by insulation layer.In this case, when being connected by connecting object parts, conductive part and interelectrode insulation layer can be got rid of.As above-mentioned electroconductive particle, the electroconductive particle on such as organic filler, inorganic particulate except metal, organic inorganic hybridization particle or the surface with conductive layer (metal level) clad metal particle etc. can be enumerated, or the metallics etc. be in fact only made up of metal.Above-mentioned conductive part without particular limitation of.As the metal forming above-mentioned conductive part, gold and silver, copper, nickel, palladium and tin etc. can be enumerated.As above-mentioned conductive layer, layer gold, silver layer, layers of copper, nickel dam, palladium layers or the conductive layer etc. containing tin can be enumerated.
From the view point of the contact area, the further interelectrode conducting reliability of raising that increase electrode and electroconductive particle, preferred above-mentioned electroconductive particle has resin particle and is configured in the conductive layer (the 1st conductive layer) on this resin particle surface.From the view point of improving interelectrode conducting reliability further, preferred above-mentioned electroconductive particle is that at least electroconductibility outside surface is the electroconductive particle of low-melting-point metal layer.More preferably above-mentioned electroconductive particle has resin particle and is configured in the conductive layer on this resin particle surface, 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 containing low melting point metal.This low melting point metal refers to that fusing point is the metal of less than 450 DEG C.The fusing point of low melting point metal is preferably less than 300 DEG C, is more preferably less than 160 DEG C.In addition, preferred above-mentioned low-melting-point metal layer contains tin.In metal 100 % by weight contained by low-melting-point metal layer, the content of tin is preferably more than 30 % by weight, is more preferably more than 40 % by weight, and more preferably more than 70 % by weight, be particularly preferably more than 90 % by weight.If the content of above-mentioned low-melting-point metal layer is more than above-mentioned lower limit, then the connection reliability of low-melting-point metal layer and electrode uprises further.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).
When the outside surface of conductive part is low-melting-point metal layer, low-melting-point metal layer melting and be engaged in electrode, low-melting-point metal layer makes conducting between electrode.Contact but not point cantact because such as low-melting-point metal layer and electrode are easy to generating plane, 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 stripping of low-melting-point metal layer and electrode becomes and more not easily occurs, and conducting reliability effectively improves.
The low melting point metal forming above-mentioned low-melting-point metal layer without particular limitation of.Preferably this low melting point metal is tin or the alloy containing tin.This alloy can enumerate tin-silver alloys, tin-copper alloy, tin-silver-copper alloy, tin-bismuth alloy electroplating, tin-zinc alloy, Sn-In alloy etc.Wherein, from the view point 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.Be 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 forming above-mentioned soldering-tin layer without particular limitation of, be preferably based on JISZ3001: welding term, the filler metal of liquidus line below 450 DEG C.As the composition of above-mentioned sealing weld, the metal can enumerated such as containing zinc, gold, lead, copper, tin, bismuth, indium etc. forms.Wherein, preferred low melting point and unleaded tin-indium class (117 DEG C of eutectics) or Sn-Bi class (139 DEG C of eutectics).That is, preferred soldering-tin layer is not leaded, preferably contains the soldering-tin layer of tin and indium or contains the soldering-tin layer of tin and bismuth.
In order to improve the bond strength of above-mentioned low-melting-point metal layer and electrode further, 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 view point of the bond strength improving low melting point metal and electrode further, preferred above-mentioned low melting point metal contains nickel, copper, antimony, aluminium or zinc.From the view point of the bond strength improving low-melting-point metal layer and electrode further, for the content improving the above-mentioned metal of bond strength is preferably more than 0.0001 % by weight in low-melting-point metal layer 100 % by weight, be preferably less than 1 % by weight.
Preferred above-mentioned electroconductive particle has resin particle and is configured in the conductive layer on this resin particle surface, and the outer surface of this conductive layer is low-melting-point metal layer, there is between above-mentioned resin particle and above-mentioned low-melting-point metal layer (soldering-tin layer etc.) 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 2nd conductive layer is above-mentioned conductive layer part of the whole.
Preferably different from above-mentioned low-melting-point metal layer above-mentioned 2nd conductive layers contains metal.The metal forming 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, tin-doped indium oxide (ITO) can be used.Above-mentioned metal can only use a kind, also two or more can be combinationally used.
Preferably above-mentioned 2nd conductive layer is nickel dam, palladium layers, layers of copper or layer gold, is more preferably nickel dam or layer gold, more preferably layers of copper.Preferred electroconductive particle has nickel dam, palladium layers, layers of copper or layer gold, more preferably has nickel dam or layer gold, preferably has layers of copper further.By the electroconductive particle with these preferred conductive layers is used for interelectrode connection, interelectrode contact resistance reduces further.In addition, more easily low-melting-point metal layer can be formed on the surface of these preferred conductive layers.It should be noted that, above-mentioned 2nd conductive layer also can be the low-melting-point metal layers such as soldering-tin layer.Electroconductive particle can have multilayer low-melting-point metal layer.
The thickness of above-mentioned low-melting-point metal layer is preferably more than 0.1 μm, is more preferably more than 0.5 μm, more preferably more than 1 μm, is preferably less than 50 μm, is more preferably 10 μm, more preferably less than 5 μm, is particularly preferably less than 3 μm.If the thickness of above-mentioned low-melting-point metal layer is more than above-mentioned lower limit, then electroconductibility is improved fully.If the thickness of above-mentioned low-melting-point metal layer is below the above-mentioned upper limit, then the difference of the thermal expansivity of resin particle and low-melting-point metal layer diminishes, and the stripping of low-melting-point metal layer becomes and not easily occurs.
When conductive layer is the conductive layer beyond low-melting-point metal layer, or conductive layer is when having multilayered structure, the integral thickness of conductive layer is preferably more than 0.1 μm, be more preferably more than 0.5 μm, more preferably more than 1 μm, be preferably less than 50 μm, be more preferably less than 10 μm, more preferably less than 5 μm, be particularly preferably less than 3 μm.
The median size of electroconductive particle is preferably less than 100 μm, is more preferably less than 20 μm, is further preferably less than less than 20 μm, more preferably less than 15 μm, is particularly preferably less than 10 μm.The median size of electroconductive particle is preferably more than 0.5 μm, is more preferably more than 1 μm.From the view point of the connection reliability improving connection structural bodies when subjected to thermal history further, particularly preferably the median size of electroconductive particle is more than 1 μm and less than 10 μm, most preferably is more than 1 μm and less than 4 μm.
Particularly preferably the median size of electroconductive particle is in the scope of 1 μm ~ 100 μm, and this is because above-mentioned scope is the size adapted with the electroconductive particle in anisotropic conductive material, and can reduce interelectrode interval further.
Above-mentioned resin particle can be distinguished according to the electrode size of the substrate of actual installation or groove bank diameter (ラ Application De footpath) and use.
From the view point of making connect more effectively between upper/lower electrode and suppress the short circuit between horizontal adjacent electrode further, 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 less than 3.0.In addition, when there is above-mentioned 2nd conductive layer between above-mentioned resin particle and above-mentioned soldering-tin layer, the median size B of 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 less than 2.0.Further, when there is above-mentioned 2nd conductive layer between above-mentioned resin particle and above-mentioned soldering-tin layer, the median size C of the electroconductive particle containing soldering-tin layer is greater than 1.0 with the ratio (C/B) of the median size B of the electroconductive particle part except soldering-tin layer, is preferably less than 2.0.Above-mentioned ratio (B/A) in above-mentioned scope or above-mentioned ratio (C/B) in above-mentioned scope time, can to make between upper/lower electrode to connect more effectively and the short circuit suppressed further 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 (FilmonBoard)) between flexible printing substrate and glass epoxy substrate or the connection between flexible printing substrate and flexible printing substrate (FOF (FilmonFilm)).
In FOB and FOF purposes, size and the L & S of the part (line) with electrode and the part (gap) without electrode are generally 100 ~ 500 μm.The median size of the resin particle preferably used in FOB and FOF purposes is 10 ~ 100 μm.If the median size of resin particle is more than 10 μm, then the thickness being configured in interelectrode electro-conductive material and connection section is enough thick, and bonding force uprises further.If the median size of resin particle is less than 100 μm, be then more not easily 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 μm.The median size of the resin particle preferably used in flip-chip purposes is 1 ~ 15 μm.If the median size of resin particle is more than 1 μm, then the thickness of the soldering-tin layer be configured on this resin particle surface can be made enough thick, can be electrically connected between electrode more effectively.If the median size of resin particle is less than 10 μm, be then more not easily 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 (ChiponFilm)) between semi-conductor chip and flexible printing substrate.
In COF purposes, size and the L & S of the part (line) with electrode and the part (gap) without electrode are generally 10 ~ 50 μm.The median size of the resin particle preferably used in COF purposes is 1 ~ 10 μm.If the median size of resin particle is more than 1 μm, then the thickness of the soldering-tin layer be configured on this resin particle surface can be made enough thick, can be electrically connected between electrode more effectively.If the median size of resin particle is less than 10 μm, be then more not easily short-circuited between adjacent electrode.
" median size " of above-mentioned electroconductive particle represents number average bead diameter.The median size of electroconductive particle can by with electron microscope or any 50 electroconductive particles of observation by light microscope and calculating mean value and obtaining.
Also insulating material, the solder flux etc. such as insulativity particle can be utilized to carry out insulation processing to the surface of electroconductive particle.There is softening, flowing under the heat effect when connecting such as preferred Ins. ulative material, solder flux, thus be excluded from connection section.Interelectrode short circuit can be suppressed thus.
The content of above-mentioned electroconductive particle without particular limitation of.In solidification compound 100 % by weight, the content of above-mentioned electroconductive particle is preferably more than 0.1 % by weight, is more preferably more than 0.5 % by weight, is preferably less than 40 % by weight, is more preferably less than 20 % by weight, more preferably less than 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, then can be easily configured in by electroconductive particle between the upper/lower electrode for connecting.And, not easily pass through multiple electroconductive particle between the adjacent electrode not for connection and be electrically connected.That is, the short circuit between adjacent electrode can be prevented.
(purposes of solidification compound)
Solidification compound of the present invention may be used for bonding various connecting object parts.
When solidification compound of the present invention is the electro-conductive material containing electroconductive particle, this electro-conductive material can be used with the form such as electroconductive paste or conducting film.When electro-conductive material uses with conducting film form, can at this conducting film superimposed layer containing electroconductive particle not containing the film of electroconductive particle.It should be noted that, film comprises sheet material.Preferred solidification compound of the present invention is the electroconductive paste of 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 the connection structural bodies obtaining and be electrically connected by the 1st, the 2nd connecting object parts.
Fig. 1 is sectional view, schematically shows an example of the connection structural bodies of the solidification compound employing an embodiment of the present invention.
Connection structural bodies 1 shown in Fig. 1 has the 1st connecting object parts 2, the 2nd connecting object parts 4 and connects the connection section 3 of the 1st, the 2nd connecting object parts 2,4.Connection section 3 is solidified to form by making the solidification compound containing electroconductive particle 5 and electro-conductive material.
1st connecting object parts 2 have multiple electrode 2b at upper surface 2a (surface).2nd connecting object parts 4 have multiple electrode 4b at lower surface 4a (surface).Electrode 2b and electrode 4b is electrically connected by one or more electroconductive particles 5.Therefore, the 1st, the 2nd connecting object parts 2,4 are electrically connected by electroconductive particle 5.
Preferred solidification compound of the present invention is the electroconductive paste of pasty state, and is the electroconductive paste be coated on the state of pasty state on the 1st connecting object parts.
Above-mentioned 1st, the 2nd connecting object parts without particular limitation of.As the 1st, the 2nd connecting object parts, specifically can enumerate: the electronic units etc. 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.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 unit.
The manufacture method of above-mentioned connection structural bodies without particular limitation of.As an example of the manufacture method of connection structural bodies, can enumerate to be configured in by above-mentioned solidification compound between the 1st connecting object parts and the 2nd connecting object parts and after obtaining multilayer body, to the method that this multilayer body heats and pressurizes.
It should be noted that, above-mentioned solidification compound also can not contain electroconductive particle.In this case, use the object of above-mentioned solidification compound not to be to be electrically connected by the 1st, the 2nd connecting object parts, but the 1st, the 2nd connecting object adhering components is connected.
When solidification compound of the present invention is electro-conductive material, this electro-conductive material may be used for the connection (FOG (FilmonGlass)) of such as flexible printing substrate and glass substrate, the connection (COF (ChiponFilm)) of semi-conductor chip and flexible printing substrate, semi-conductor chip and the connection (COG (ChiponGlass)) of glass substrate or the connection (FOB (FilmonBoard)) etc. of flexible printing substrate and glass epoxy substrate.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 flexible printing substrate and the connection of glass substrate or the connection of semi-conductor chip and flexible printing substrate, is more preferably the electro-conductive material of the connection for semi-conductor chip and flexible printing substrate.
In connection structural bodies of the present invention, as above-mentioned 2nd connecting object parts and above-mentioned 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 there is following problems: pressure during connection is low, sufficient impression and resin filling can not be obtained, produce space (void) etc. and become problem in interelectrode conducting reliability and solidification nitride layer.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 space (void) in solidification nitride layer.
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 there is following problems: produce space etc. and become problem in interelectrode conducting reliability and solidification nitride layer.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 space (void) in solidification nitride layer.
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 obtained in following synthesis example is undertaken measuring by gel permeation chromatography (GPC) and through the weight-average molecular weight of polystyrene conversion.
Further, the mixture of the epoxy compounds obtained in following examples and the viscosity of solidification compound are the viscosity under 23 DEG C and 2.5rpm using viscosimeter (manufacture of Dong Ji industry companies) to measure.
(synthesis example 1)
(1) synthesis of the 1st reaction product obtained by Bisphenol F and 1,6-hexanediol diglycidyl ether:
By Bisphenol F, (containing with mass ratio range is 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 part and triphenylphosphine 1 weight part join in three-necked flask, make it dissolve at 150 DEG C.Subsequently, by the polyaddition reaction making it carry out at 180 DEG C 6 hours, obtain the 1st reaction product.
Confirm to have carried out polyaddition reaction, and confirm the 1st reaction product have on main chain by come from Bisphenol F skeleton and come from 1, the structural unit of the skeleton bonding of 6-hexanediol diglycidyl ether, and there is at two ends the epoxy group(ing) coming from 1,6-hexanediol diglycidyl ether.
(2) synthesis of the epoxy compounds making above-mentioned 1st reaction product and vinylformic acid carry out reacting and obtain:
The 1st reaction product 100 weight part obtained and vinylformic acid 4 weight part are mixed, and is warming up to 80 DEG C.After intensification, add penta fluoro benzene sulfonic acid two sym-trimethylbenzene base ammonium salt 1 weight part as catalyzer, it is made to carry out the condensation reaction of 4 hours, resulting in two ends and have epoxy group(ing) and side chain has the epoxy compounds of vinyl, described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
The weight-average molecular weight of the epoxy compounds obtained is 8000.Only there is 1 peak in the molecular weight distribution of the epoxy compounds obtained, and do not observe and come from acrylic acid small molecules.In addition, confirm that vinylformic acid and hydroxyl there occurs reaction, side chain has imported vinyl by NMR, described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
(synthesis example 2)
The synthesis of the epoxy compounds making above-mentioned 1st reaction product that obtains in synthesis example 1 and 2-methacryloxyethyl isocyanic ester carry out reacting and obtain:
After above-mentioned 1st reaction product 100 weight part, 2-methacryloxyethyl isocyanic ester 4 weight part and dibutyl tin laurate 0.3 weight part that obtain in synthesis example 1 are mixed, by the addition reaction making it carry out at 80 DEG C 4 hours, obtain two ends and have epoxy group(ing) and side chain has the epoxy compounds of vinyl, described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
The weight-average molecular weight of the epoxy compounds obtained is 12000.Only there is 1 peak in the molecular weight distribution of the epoxy compounds obtained, and do not observe the micromolecular peak coming from methacrylic compound.In addition, confirm that 2-methacryloxyethyl isocyanic ester and hydroxyl there occurs reaction, side chain has imported vinyl by NMR, described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
(synthesis example 3)
The synthesis of the epoxy compounds making above-mentioned 1st reaction product that obtains in synthesis example 1 and 4-hydroxyl butylglycidyl ether carry out reacting and obtain:
After above-mentioned 1st reaction product 100 weight part, 4-hydroxyl butylglycidyl ether 4 weight part and penta fluoro benzene sulfonic acid two sym-trimethylbenzene base ammonium salt 0.2 weight part that obtain in synthesis example 1 are mixed, by the condensation reaction making it carry out at 80 DEG C 4 hours, obtain two ends and have epoxy group(ing) and side chain has the epoxy compounds of epoxy group(ing), described epoxy group(ing) is 20% relative to total number 100% of hydroxyl before reaction.
The weight-average molecular weight of the epoxy compounds obtained is 12000.Only there is 1 peak in the molecular weight distribution of the epoxy compounds obtained, and do not observe the micromolecular peak coming from 4-hydroxyl butylglycidyl ether compound.In addition, confirm to have carried out condensation reaction, and confirm that 4-hydroxyl butylglycidyl ether and hydroxyl there occurs reaction, side chain has imported epoxy group(ing), described epoxy group(ing) is 20% relative to total number 100% of hydroxyl before reaction.
(synthesis example 4)
(1) synthesis of the 2nd reaction product obtained by Resorcinol and 1,6-hexanediol diglycidyl ether:
Resorcinol 48 weight part, 1,6-hexanediol diglycidyl ether 100 weight part and triphenylphosphine 1 weight part are joined in three-necked flask, makes it dissolve at 150 DEG C.Subsequently, by the polyaddition reaction making it carry out at 180 DEG C 6 hours, obtain the 2nd reaction product.
Confirm to have carried out polyaddition reaction, and confirm the 2nd reaction product have on main chain by come from Resorcinol skeleton and come from 1, the structural unit of the skeleton bonding of 6-hexanediol diglycidyl ether, and there is at two ends the epoxy group(ing) coming from 1,6-hexanediol diglycidyl ether.
(2) synthesis of the epoxy compounds making above-mentioned 2nd reaction product and vinylformic acid carry out reacting and obtain:
Above-mentioned 1st reaction product is replaced by above-mentioned 2nd reaction product obtained, identical with synthesis example 1, obtain two ends by condensation reaction and have epoxy group(ing) and side chain has the epoxy compounds of vinyl, described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
The weight-average molecular weight of the epoxy compounds obtained is 15000, there is 1 peak in the molecular weight distribution of epoxy compounds.In addition, confirm that vinylformic acid and hydroxyl there occurs reaction, side chain has imported vinyl by NMR, described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
(synthesis example 5)
The synthesis of the epoxy compounds making above-mentioned 2nd reaction product that obtains in synthesis example 4 and 4-hydroxyl butylglycidyl ether carry out reacting and obtain:
Above-mentioned 1st reaction product is replaced by above-mentioned 2nd reaction product obtained in synthesis example 4, adopt the method same with synthesis example 3, by carrying out condensation reaction, obtain two ends and have epoxy group(ing) and side chain has the epoxy compounds of epoxy group(ing), described epoxy group(ing) is 20% relative to total number 100% of hydroxyl before reaction.
The weight-average molecular weight of the epoxy compounds obtained is 15000.1 peak is there is in the molecular weight distribution of the epoxy compounds obtained.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% relative to total number 100% of hydroxyl before reaction.
(synthesis example 6)
The synthesis of the epoxy compounds making above-mentioned 2nd reaction product that obtains in synthesis example 4 and 2-methacryloxyethyl isocyanic ester carry out reacting and obtain:
Above-mentioned 1st reaction product is replaced by above-mentioned 2nd reaction product obtained in synthesis example 4, adopt the method same with synthesis example 2, by carrying out addition reaction, obtain two ends and have epoxy group(ing) and side chain has the epoxy compounds of vinyl, described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
The weight-average molecular weight of the epoxy compounds obtained is 15000.1 peak is there is in the molecular weight distribution of the epoxy compounds obtained.In addition, confirm by addition reaction, 2-methacryloxyethyl isocyanic ester there occurs reaction, and side chain has imported vinyl, and described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
(synthesis example 7)
(1) synthesis of the 3rd reaction product obtained by Resorcinol and resorcinol diglycidyl ether:
Resorcinol 33 weight part, resorcinol diglycidyl ether 100 weight part and triphenylphosphine 1 weight part are joined in three-necked flask, makes it dissolve at 150 DEG C.Subsequently, by the polyaddition reaction making it carry out at 180 DEG C 6 hours, obtain the 3rd reaction product.
Confirm to have carried out polyaddition reaction, and confirm the 3rd reaction product and have on main chain by coming from the skeleton of Resorcinol and coming from the structural unit of skeleton bonding of resorcinol diglycidyl ether, and there is at two ends the epoxy group(ing) coming from resorcinol diglycidyl ether.
(2) synthesis of the epoxy compounds making above-mentioned 3rd reaction product and vinylformic acid carry out reacting and obtain:
Above-mentioned 1st reaction product is replaced by above-mentioned 3rd reaction product obtained, adopt the method same with synthesis example 1, by carrying out condensation reaction, obtain two ends and have epoxy group(ing) and side chain has the epoxy compounds of vinyl, described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
The weight-average molecular weight of the epoxy compounds obtained is 11000.1 peak is there is in the molecular weight distribution of the epoxy compounds obtained.In addition, confirm by condensation reaction, vinylformic acid and hydroxyl there occurs reaction, and side chain has imported vinyl, and described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
(synthesis example 8)
The synthesis of the epoxy compounds making above-mentioned 3rd reaction product that obtains in synthesis example 7 and 2-methacryloxyethyl isocyanic ester carry out reacting and obtain:
Above-mentioned 1st reaction product is replaced by above-mentioned 3rd reaction product obtained in synthesis example 7, adopt the method same with synthesis example 2, by carrying out addition reaction, obtain two ends and have epoxy group(ing) and side chain has the epoxy compounds of vinyl, described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
The weight-average molecular weight of the epoxy compounds obtained is 11000.1 peak is there is in the molecular weight distribution of the epoxy compounds obtained.In addition, confirm 2-methacryloxyethyl isocyanic ester and hydroxyl there occurs reaction by NMR, side chain has imported vinyl, described vinyl is 20% relative to total number 100% of hydroxyl before reaction.
(synthesis example 9)
The synthesis of the epoxy compounds making above-mentioned 3rd reaction product that obtains in synthesis example 7 and 4-hydroxyl butylglycidyl ether carry out reacting and obtain:
Above-mentioned 1st reaction product is replaced by above-mentioned 3rd reaction product obtained in synthesis example 7, adopt the method same with synthesis example 3, by carrying out condensation reaction, obtain two ends and have epoxy group(ing) and side chain has the epoxy compounds of epoxy group(ing), described epoxy group(ing) is 20% relative to total number 100% of hydroxyl before reaction.
The weight-average molecular weight of the epoxy compounds obtained is 11000.1 peak is there is in the molecular weight distribution of the epoxy compounds obtained.In addition, confirm that 4-hydroxyl butylglycidyl ether and hydroxyl there occurs reaction, side chain has imported epoxy group(ing) by NMR, described epoxy group(ing) is 20% relative to total number 100% of hydroxyl before reaction.
(embodiment 1)
The epoxy compounds obtained in the epoxy compounds obtained in synthesis example 1 and synthesis example 2 is mixed with weight ratio 5:3, obtains the mixture (1) of epoxy compounds.The viscosity of the mixture (1) of the epoxy compounds obtained is 320Pas.
Then, tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight part as thermal curing agents is added in mixture (1) 33 weight part of the epoxy compounds obtained, as 2-ethyl-4-methylimidazole 1 weight part of curing catalyst, as epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts of photocurable compound, as acylphosphine oxide compounds (" DAROCURTPO " that CIBAJAPAN company manufactures) 0.1 weight part of Photoepolymerizationinitiater initiater, as silicon-dioxide 20 weight part of the median size 0.25 μm of filler and aluminum oxide 20 weight part of median size 0.5 μm, and electroconductive particle 2 weight part of median size 3 μm, and stir 5 minutes under 2000rpm with planetary stirring machine, resulting in the solidification compound (1) stuck with paste as anisotropic conductive.It should be noted that, the electroconductive particle of use is the electroconductive particle with metal level, and it is formed with nickel layer on the surface of divinylbenzene resin particle, 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 obtained in the epoxy compounds obtained in synthesis example 2 and synthesis example 3 is mixed with weight ratio 5:3, obtains the mixture (2) of epoxy compounds.The viscosity of the mixture (2) of the epoxy compounds obtained is 300Pas.
Except the mixture (1) of epoxy compounds being changed to the mixture (2) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (2).The viscosity of the solidification compound (2) obtained is 340Pas.
(embodiment 3)
The epoxy compounds obtained in the epoxy compounds obtained in synthesis example 3 and synthesis example 4 is mixed with weight ratio 5:3, obtains the mixture (3) of epoxy compounds.The viscosity of the mixture (3) of the epoxy compounds obtained is 280Pas.
Except the mixture (1) of epoxy compounds being changed to the mixture (3) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (3).The viscosity of the solidification compound (3) obtained is 310Pas.
(embodiment 4)
The epoxy compounds obtained in the epoxy compounds obtained in synthesis example 4 and synthesis example 5 is mixed with weight ratio 5:3, obtains the mixture (4) of epoxy compounds.The viscosity of the mixture (4) of the epoxy compounds obtained is 330Pas.
Except the mixture (1) of epoxy compounds being changed to the mixture (4) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (4).The viscosity of the solidification compound (4) obtained is 360Pas.
(embodiment 5)
The epoxy compounds obtained in the epoxy compounds obtained in synthesis example 5 and synthesis example 6 is mixed with weight ratio 5:3, obtains the mixture (5) of epoxy compounds.The viscosity of the mixture (5) of the epoxy compounds obtained is 260Pas.
Except the mixture (1) of epoxy compounds being changed to the mixture (5) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (5).The viscosity of the solidification compound (5) obtained is 290Pas.
(embodiment 6)
Except tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight part and 2-ethyl-4-methylimidazole 1 weight part being changed to cation curing agent (San-AidSi-60 (three new chemistry manufacture)) 0.6 weight part, implement similarly to Example 1, obtain solidification compound (6).The viscosity of the solidification compound (6) obtained is 180Pas.
(embodiment 7)
Except tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight part is changed to except quadrol 20 weight part of amine hardener, implement similarly to Example 1, obtain solidification compound (7).The viscosity of the solidification compound (7) obtained is 150Pas.
(embodiment 8)
Except epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts as photocurable compound are changed to except urethane acrylate (" EBECRYL8804 " that DAICEL-CYTEC company manufactures) 5 weight parts of photocurable compound, implement similarly to Example 1, obtain solidification compound (8).The viscosity of the solidification compound (8) obtained is 280Pas.
(embodiment 9)
Except not adding the epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) as photocurable compound and the acylphosphine oxide compounds (" DAROCURTPO " that CIBAJAPAN company manufactures) as Photoepolymerizationinitiater initiater; implement similarly to Example 1, obtain solidification compound (9).The viscosity of the solidification compound (9) obtained is 260Pas.
(embodiment 10)
Except not adding the epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) as photocurable compound and the acylphosphine oxide compounds (" DAROCURTPO " that CIBAJAPAN company manufactures) as Photoepolymerizationinitiater initiater; implement similarly to Example 2, obtain solidification compound (10).The viscosity of the solidification compound (10) obtained is 310Pas.
(comparative example 1)
Add bisphenol A type epoxy resin 33 weight part, as tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight part of thermal curing agents, as 2-ethyl-4-methylimidazole 1 weight part of curing catalyst, as epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts of photocurable compound, as acylphosphine oxide compounds (" DAROCURTPO " that CIBAJAPAN company manufactures) 0.1 weight part of Photoepolymerizationinitiater initiater, as silicon-dioxide 20 weight part of the median size 0.25 μm of filler and aluminum oxide 20 weight part of median size 0.5 μm, and electroconductive particle 2 weight part of median size 3 μm, and stir 5 minutes under 2000rpm with planetary stirring machine, resulting in the solidification compound stuck with paste as anisotropic conductive.
(comparative example 2)
Except not adding the epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) as photocurable compound and the acylphosphine oxide compounds (" DAROCURTPO " that CIBAJAPAN company manufactures) as Photoepolymerizationinitiater initiater; implement in the same manner as 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 μm/10 μm.In addition, prepare semi-conductor chip, the lower surface of described semi-conductor chip has the gold electrode pattern that L/S is 10 μm/10 μm.
Above-mentioned transparent glass substrate is coated with the solidification compound obtained, makes its thickness be 30 μm, further by irradiation UV light, (methyl) acrylic resin is solidified, form solidification compound layer.Then, on solidification compound layer to make between electrode toward each other and the above-mentioned semi-conductor chip of mode lamination connected.Subsequently, the temperature of adjustment heating head makes the temperature of solidification compound layer reach 150 DEG C, while heating head is placed in the upper surface of semi-conductor chip, solidification compound layer is solidified at 150 DEG C, obtains connection structural bodies A.When obtaining this connection structural bodies, measure by heating the time made required for the solidification of solidification compound layer.
(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 μm/10 μm.In addition, prepare semi-conductor chip, the lower surface of described semi-conductor chip has the gold electrode pattern that L/S is 10 μm/10 μm.
Above-mentioned transparent glass substrate is coated with the solidification compound obtained, makes its thickness be 30 μm, form solidification compound layer.Then, on solidification compound layer to make between electrode toward each other and the above-mentioned semi-conductor chip of mode lamination connected.Subsequently, the temperature of adjustment heating head makes the temperature of solidification compound layer reach 150 DEG C, while heating head is placed in the upper surface of semi-conductor chip, solidification compound layer is solidified at 150 DEG C, obtains connection structural bodies B.When obtaining this connection structural bodies, measure by heating the time made required for the solidification of solidification compound layer.
(3) cementability
Be used in the connection structural bodies A, the B that obtain in the evaluation of above-mentioned (1) set time 1 and above-mentioned (2) set time 2, measure stripping strength, have rated cementability thus.According to following standard, cementability is judged.
[criterion of cementability]
Zero: more than 8N/cm
×: be less than 8N/cm
(4) wet fastness
After connection structural bodies A, the B (each 15) that obtain in the evaluation of above-mentioned (1) set time 1 and above-mentioned (2) set time 2 are placed 1000 hours under 85 DEG C of conditions with 85%RH, have rated conduction.The resistance value at upper 20 positions of connection structural bodies A, B is have rated by four-end method.According to following standard, conducting reliability is judged.
[criterion of wet fastness]
Zero: the resistance value of all sites is 3 below Ω
×: there is more than 1 place at the position of completely non-conducting
(5) tight is had
For the connection structural bodies A, the B that obtain in the evaluation of above-mentioned (1) set time 1 and above-mentioned (2) set time 2, from the lower surface side of transparent glass substrate, whether space is created to the solidification nitride layer formed by solidification compound layer and carried out visual observations.
Result is shown in following table 1.
[table 1]
(synthesis example 10)
(1) synthesis of the 1st reaction product obtained by Bisphenol F and 1,6-hexanediol diglycidyl ether:
Except by Bisphenol F, (containing with mass ratio range is 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 (containing being 4 of 31:52:17 with mass ratio range, 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 there are 3 with beyond mixture 72 weight part of the polykaryon of coker (containing taking mass ratio range as three nucleomes of 9:2 and there are 4 with the polykaryon of coker) 8 weight parts, implement similarly to Example 1, obtain the 1st reaction product.
(2) synthesis of the epoxy compounds making above-mentioned 1st reaction product and vinylformic acid carry out reacting and obtain:
Except using the 1st reaction product that obtains, similarly to Example 1, by adopting the method same with synthesis example 1 to carry out condensation reaction, obtaining two ends and there is epoxy group(ing) and side chain has the epoxy compounds of vinyl.
The weight-average molecular weight of the epoxy compounds obtained is 7000.In addition, confirm vinylformic acid by NMR and hydroxyl there occurs reaction, and on side chain, import vinyl.
(synthesis example 11)
The synthesis of the epoxy compounds making above-mentioned 1st reaction product that obtains in synthesis example 10 and 2-methacryloxyethyl isocyanic ester carry out reacting and obtain:
After above-mentioned 1st reaction product 100 weight part, 2-methacryloxyethyl isocyanic ester 4 weight part and dibutyl tin laurate 0.3 weight part that obtain in synthesis example 10 are mixed, by the addition reaction making it carry out at 80 DEG C 4 hours, obtain two ends and there is epoxy group(ing) and side chain has the epoxy compounds of vinyl.
The weight-average molecular weight of the epoxy compounds obtained is 10000.In addition, confirm that 2-methacryloxyethyl isocyanic ester and hydroxyl there occurs reaction by NMR, and on side chain, imported vinyl.
(synthesis example 12)
The synthesis of the epoxy compounds making above-mentioned 1st reaction product that obtains in synthesis example 10 and 4-hydroxyl butylglycidyl ether carry out reacting and obtain:
After above-mentioned 1st reaction product 100 weight part, 4-hydroxyl butylglycidyl ether 4 weight part and penta fluoro benzene sulfonic acid two sym-trimethylbenzene base ammonium salt 0.2 weight part that obtain in synthesis example 10 are mixed, by the condensation reaction making it carry out at 80 DEG C 4 hours, obtain two ends and there is epoxy group(ing) and side chain has the epoxy compounds of epoxy group(ing).
The weight-average molecular weight of the epoxy compounds obtained is 10000.In addition, confirm to have carried out condensation reaction, and confirm that 4-hydroxyl butylglycidyl ether and hydroxyl there occurs reaction, thus on side chain, imported epoxy group(ing).
(synthesis example 13)
(1) by Bisphenol F, (containing with mass ratio range is 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 part and triphenylphosphine 0.75 weight part join in three-necked flask, make it dissolve at 150 DEG C.Subsequently, make the polyaddition reaction that it carries out 4 hours at 180 DEG C, add Bisphenol F 25 weight part, 1 further, 6-hexanediol diglycidyl ether 9.5 weight part and triphenylphosphine 0.25 weight part, and the polyaddition reaction making it carry out at 180 DEG C 2 hours, resulting in the 1st reaction product.
Confirm to have carried out polyaddition reaction, and confirm the 1st reaction product have on main chain by come from Bisphenol F skeleton and come from 1, the structural unit of the skeleton bonding of 6-hexanediol diglycidyl ether, and there is at two ends the epoxy group(ing) coming from 1,6-hexanediol diglycidyl ether.
(2) synthesis of the epoxy compounds making above-mentioned 1st reaction product and vinylformic acid carry out reacting and obtain:
The 1st reaction product 100 weight part obtained and vinylformic acid 4 weight part are mixed, and is warming up to 80 DEG C.After intensification, add penta fluoro benzene sulfonic acid two sym-trimethylbenzene base ammonium salt 1 weight part as catalyzer, make it carry out the condensation reaction of 4 hours, resulting in two ends and there is epoxy group(ing) and side chain has the epoxy compounds of vinyl.
The weight-average molecular weight of the epoxy compounds obtained is 6000.There are 2 peaks in the molecular weight distribution of the epoxy compounds obtained.In addition, confirm that vinylformic acid and hydroxyl there occurs reaction by NMR, and on side chain, imported vinyl.
(synthesis example 14)
After above-mentioned 1st reaction product 100 weight part, 2-methacryloxyethyl isocyanic ester 4 weight part and dibutyl tin laurate 0.3 weight part that obtain in synthesis example 13 are mixed, by the addition reaction making it carry out at 80 DEG C 4 hours, obtain two ends and there is epoxy group(ing) and side chain has the epoxy compounds of vinyl.
The weight-average molecular weight of the epoxy compounds obtained is 7500.There are 2 peaks in the molecular weight distribution of the epoxy compounds obtained.In addition, confirm that 2-methacryloxyethyl isocyanic ester and hydroxyl there occurs reaction by NMR, and on side chain, imported vinyl.
(embodiment 11)
The epoxy compounds obtained in the epoxy compounds obtained in synthesis example 10 and synthesis example 11 is mixed with weight ratio 5:3, obtains the mixture (11) of epoxy compounds.
Except the mixture (1) of epoxy compounds being changed to the mixture (11) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (11).The viscosity of the solidification compound (11) obtained is 390Pas.
(embodiment 12)
The epoxy compounds obtained in the epoxy compounds obtained in synthesis example 11 and synthesis example 12 is mixed with weight ratio 5:3, obtains the mixture (12) of epoxy compounds.
Except the mixture (1) of epoxy compounds being changed to the mixture (12) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (12).The viscosity of the solidification compound (12) obtained is 380Pas.
(embodiment 13)
Prepare the mixture (1) of the epoxy compounds obtained in embodiment 1.The mixture (1) of epoxy compounds is containing taking mass ratio range as the epoxy compounds obtained in the epoxy compounds and synthesis example 2 that obtain in the synthesis example 1 of 5:3.
Bisphenol F diglycidylether 3 weight part is added in mixture (1) 33 weight part of above-mentioned epoxy compounds, as tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight part of thermal curing agents, as 2-ethyl-4-methylimidazole 1 weight part of curing catalyst, as epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts of photocurable compound, as acylphosphine oxide compounds (" DAROCURTPO " that CIBAJAPAN company manufactures) 0.1 weight part of Photoepolymerizationinitiater initiater, as silicon-dioxide 20 weight part of the median size 0.25 μm of filler and aluminum oxide 20 weight part of median size 0.5 μm, and electroconductive particle 2 weight part used in embodiment 1, and stir 5 minutes under 2000rpm with planetary stirring machine, resulting in the solidification compound (15) stuck with paste as anisotropic conductive.The viscosity of the solidification compound (13) obtained is 330Pas.
(embodiment 14)
Prepare the mixture (1) of the epoxy compounds obtained in embodiment 1.The mixture (1) of epoxy compounds is containing taking mass ratio range as the epoxy compounds obtained in the epoxy compounds and synthesis example 2 that obtain in the synthesis example 1 of 5:3.
Resorcinol diglycidyl ether 3 weight part is added in mixture (1) 33 weight part of above-mentioned epoxy compounds, as tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight part of thermal curing agents, as 2-ethyl-4-methylimidazole 1 weight part of curing catalyst, as epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts of photocurable compound, as acylphosphine oxide compounds (" DAROCURTPO " that CIBAJAPAN company manufactures) 0.1 weight part of Photoepolymerizationinitiater initiater, as silicon-dioxide 20 weight part of the median size 0.25 μm of filler and aluminum oxide 20 weight part of median size 0.5 μm, and electroconductive particle 2 weight part used in embodiment 1, and stir 5 minutes under 2000rpm with planetary stirring machine, resulting in the solidification compound (14) stuck with paste as anisotropic conductive.The viscosity of the solidification compound (14) obtained is 320Pas.
(embodiment 15)
Prepare the mixture (1) of the epoxy compounds obtained in embodiment 1.The mixture (1) of epoxy compounds is containing taking mass ratio range as the epoxy compounds obtained in the epoxy compounds and synthesis example 2 that obtain in the synthesis example 1 of 5:3.
Bisphenol F diglycidyl ether epoxy acrylate 3 weight part is added in mixture (1) 33 weight part of above-mentioned epoxy compounds, as tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight part of thermal curing agents, as 2-ethyl-4-methylimidazole 1 weight part of curing catalyst, as epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts of photocurable compound, as acylphosphine oxide compounds (" DAROCURTPO " that CIBAJAPAN company manufactures) 0.1 weight part of Photoepolymerizationinitiater initiater, as silicon-dioxide 20 weight part of the median size 0.25 μm of filler and aluminum oxide 20 weight part of median size 0.5 μm, and electroconductive particle 2 weight part used in embodiment 1, and stir 5 minutes under 2000rpm with planetary stirring machine, resulting in the solidification compound (15) stuck with paste as anisotropic conductive.The viscosity of the solidification compound (15) obtained is 320Pas.
(embodiment 16)
Prepare the mixture (1) of the epoxy compounds obtained in embodiment 1.The mixture (1) of epoxy compounds is containing taking mass ratio range as the epoxy compounds obtained in the epoxy compounds and synthesis example 2 that obtain in the synthesis example 1 of 5:3.
Resorcinol diglycidyl ether epoxy acrylate 3 weight part is added in mixture (1) 33 weight part of above-mentioned epoxy compounds, as tetramethylolmethane four-3-mercaptopropionic acid ester 20 weight part of thermal curing agents, as 2-ethyl-4-methylimidazole 1 weight part of curing catalyst, as epoxy acrylate (" EBECRYL3702 " that DAICEL-CYTEC company manufactures) 5 weight parts of photocurable compound, as acylphosphine oxide compounds (" DAROCURTPO " that CIBAJAPAN company manufactures) 0.1 weight part of Photoepolymerizationinitiater initiater, as silicon-dioxide 20 weight part of the median size 0.25 μm of filler and aluminum oxide 20 weight part of median size 0.5 μm, and electroconductive particle 2 weight part used in embodiment 1, and stir 5 minutes under 2000rpm with planetary stirring machine, resulting in the solidification compound (16) stuck with paste as anisotropic conductive.The viscosity of the solidification compound (16) obtained is 320Pas.
(embodiment 17)
The epoxy compounds obtained in the epoxy compounds obtained in synthesis example 13 and synthesis example 14 is mixed with weight ratio 5:3, obtains the mixture (17) of epoxy compounds.
Except the mixture (1) of epoxy compounds being changed to the mixture (17) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (17).The viscosity of the solidification compound (17) obtained is 280Pas.
(embodiment 18)
The epoxy compounds obtained in the epoxy compounds obtained in synthesis example 4 and synthesis example 7 is mixed with weight ratio 5:3, obtains the mixture (18) of epoxy compounds.
Except the mixture (1) of epoxy compounds being changed to the mixture (18) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (18).The viscosity of the solidification compound (18) obtained is 310Pas.
(embodiment 19)
The epoxy compounds obtained in the epoxy compounds obtained in synthesis example 4 and synthesis example 8 is mixed with weight ratio 5:3, obtains the mixture (19) of epoxy compounds.
Except the mixture (1) of epoxy compounds being changed to the mixture (19) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (19).The viscosity of the solidification compound (19) obtained is 320Pas.
(embodiment 20)
The epoxy compounds epoxy compounds obtained in synthesis example 4 and synthesis example 9 obtained, with weight ratio 5:3 mixing, obtains the mixture (20) of epoxy compounds.
Except the mixture (1) of epoxy compounds being changed to the mixture (20) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (20).The viscosity of the solidification compound (20) obtained is 320Pas.
(evaluation of embodiment 11 ~ 20)
Evaluate for the assessment item identical with comparative example 1 ~ 2 with embodiment 1 ~ 10.
Result is shown in following table 2.
[table 2]
It should be noted that, the cementability evaluation result of embodiment 1 ~ 20 is "○".About the measured value of stripping strength, embodiment 11 is higher than embodiment 1, and embodiment 12 is higher than embodiment 2, and embodiment 13 is higher than embodiment 1, and embodiment 14 is higher than embodiment 1, and embodiment 15 is higher than embodiment 1, and embodiment 16 is higher than embodiment 1.
(synthesis example 15)
(1) synthesis of the 4th reaction product obtained by Bisphenol F and resorcinol diglycidyl ether:
By Bisphenol F, (containing with mass ratio range is 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 part and triphenylphosphine 1 weight part join in three-necked flask, makes it dissolve at 150 DEG C.Subsequently, by the polyaddition reaction making it carry out at 180 DEG C 6 hours, obtain the 4th reaction product.
Confirm to have carried out polyaddition reaction, and confirm the 4th reaction product and have on main chain by coming from the skeleton of Bisphenol F and coming from the structural unit of skeleton bonding of resorcinol diglycidyl ether, and there is at two ends the epoxy group(ing) coming from resorcinol diglycidyl ether.
(2) synthesis of the epoxy compounds making above-mentioned 4th reaction product and vinylformic acid carry out reacting and obtain:
Replace above-mentioned 1st reaction product by above-mentioned 3rd reaction product obtained, by adopting the method same with synthesis example 1 to carry out condensation reaction, obtaining two ends and there is epoxy group(ing) and side chain has the epoxy compounds of vinyl.
The weight-average molecular weight of the epoxy compounds obtained is 132000.Only there is 1 peak in the molecular weight distribution of the epoxy compounds obtained, and do not observe and come from acrylic acid small molecules.In addition, confirm that vinylformic acid and hydroxyl there occurs reaction, and on side chain, imported vinyl by NMR, described vinyl is 100% relative to total number 100% of hydroxyl before reaction.
(synthesis example 16)
The synthesis of the epoxy compounds making above-mentioned 4th reaction product that obtains in synthesis example 15 and 2-(methyl) acryloyloxyethyl isocyanate carry out reacting and obtain:
Replace above-mentioned 1st reaction product by above-mentioned 4th reaction product obtained in synthesis example 15, by adopting the method same with synthesis example 2 to carry out addition reaction, obtaining two ends and there is epoxy group(ing) and side chain has the epoxy compounds of vinyl.
The weight-average molecular weight of the epoxy compounds obtained is 132000.Only there is 1 peak in the molecular weight distribution of the epoxy compounds obtained, and do not observe the micromolecular peak coming from acrylic compound.In addition, confirm that 2-(methyl) acryloyloxyethyl isocyanate and hydroxyl there occurs reaction, and on side chain, imported vinyl by NMR, described vinyl is 100% relative to total number 100% of hydroxyl before reaction.
(synthesis example 17)
The synthesis of the epoxy compounds making above-mentioned 4th reaction product that obtains in synthesis example 15 and 4-hydroxyl butylglycidyl ether carry out reacting and obtain:
Replace above-mentioned 1st reaction product by above-mentioned 4th reaction product obtained in synthesis example 15, by adopting the method same with synthesis example 3 to carry out condensation reaction, obtaining two ends and there is epoxy group(ing) and side chain has the epoxy compounds of epoxy group(ing).
The weight-average molecular weight of the epoxy compounds obtained is 132000.Only there is 1 peak in the molecular weight distribution of the epoxy compounds obtained, and do not observe the micromolecular peak coming from 4-hydroxyl butylglycidyl ether compound.In addition, confirm to have carried out condensation reaction, and confirm that 4-hydroxyl butylglycidyl ether and hydroxyl there occurs reaction, and on side chain, imported epoxy group(ing), described epoxy group(ing) is 100% relative to total number 100% of hydroxyl before reaction.
(embodiment 21)
The epoxy compounds obtained in the epoxy compounds obtained in synthesis example 15 and synthesis example 16 is mixed with weight ratio 5:3, obtains the mixture (21) of epoxy compounds.The viscosity of the mixture (21) of the epoxy compounds obtained is 1000Pas.
Except the mixture (1) of epoxy compounds being changed to the mixture (21) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (21).The viscosity of the solidification compound (21) obtained is 1070Pas.
(embodiment 22)
The epoxy compounds obtained in the epoxy compounds obtained in synthesis example 16 and synthesis example 17 is mixed with weight ratio 5:3, obtains the mixture (22) of epoxy compounds.The viscosity of the mixture (22) of the epoxy compounds obtained is 1130Pas.
Except the mixture (1) of epoxy compounds being changed to the mixture (22) of the epoxy compounds obtained, implement similarly to Example 1, obtain solidification compound (22).The viscosity of the solidification compound (22) obtained is 1200Pas.
(evaluation of embodiment 21 and 22)
The assessment item identical with embodiment 1 ~ 10 is evaluated.
Result is shown in following table 3.
[table 3]
Embodiment 21 Embodiment 22
Set time 1 (second) 2 2
Set time 2 (second) 2 2
Cementability (connection structural bodies A) ○ ○
Cementability (connection structural bodies B) ○ ○
Wet fastness (connection structural bodies A) ○ ○
Wet fastness (connection structural bodies B) ○ ○
There is tight (connection structural bodies A) ○ ○
There is tight (connection structural bodies B) ○ ○
It should be noted that, in each synthesis example, when making the hydroxyl reaction of (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and above-mentioned 1st, the 2nd, the 3rd, the 4th reaction product, in total number 100% of hydroxyl before the reaction, the number ratio of the hydroxyl (becoming the group (above-mentioned formula (a), (b), (c)) of non-hydroxyl) reacted changes within 3% ~ 100% (all).When the ratio of number is in the scope of 3% ~ 100%, in the same manner as above-described embodiment, confirm curing speed rapid, cementability and excellent moisture resistance, and not easily produced space.

Claims (20)

1. an epoxy compounds, it has epoxy group(ing) at two ends, and on side chain, have vinyl or epoxy group(ing),
The weight-average molecular weight of this epoxy compounds is more than 500 and less than 150000,
This epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and following reaction product and obtains, described reaction product is the reaction product of Bisphenol F or Resorcinol and 1,6-hexanediol diglycidyl ether or resorcinol diglycidyl ether.
2. epoxy compounds according to claim 1, it has more than 2 vinyl altogether or on side chain, has more than 2 epoxy group(ing) altogether on side chain.
3. epoxy compounds according to claim 1, wherein, described reaction product is the 1st reaction product, the 2nd reaction product or the 3rd reaction product,
Described 1st reaction product is the reaction product of Bisphenol F and 1,6-hexanediol diglycidyl ether,
Described 2nd reaction product is the reaction product of Resorcinol and 1,6-hexanediol diglycidyl ether,
Described 3rd reaction product is the reaction product of Resorcinol and resorcinol diglycidyl ether.
4. epoxy compounds according to claim 3, wherein,
When described reaction product is described 1st reaction product, in the molecular weight distribution of epoxy compounds, there are 2 peaks,
When described reaction product is described 2nd reaction product, in the molecular weight distribution of epoxy compounds, there are 2 peaks.
5. the epoxy compounds according to claim 3 or 4, wherein, described reaction product is described 1st reaction product.
6. the epoxy compounds according to claim 3 or 4, wherein, described reaction product is described 2nd reaction product.
7. epoxy compounds according to claim 3, wherein, described reaction product is described 3rd reaction product.
8. the epoxy compounds according to any one of Claims 1 to 4 wherein, is (methyl) vinylformic acid or 2-(methyl) acryloyloxyethyl isocyanate with the compound of described reaction.
9. epoxy compounds according to claim 8 wherein, is 2-(methyl) acryloyloxyethyl isocyanate with the compound of described reaction.
10. a mixture for epoxy compounds, it contains the epoxy compounds according to any one of at least 2 kinds of claims 1 ~ 9.
The mixture of 11. epoxy compoundss according to claim 10, it contains the 1st epoxy compounds and the 2nd epoxy compounds,
Described 1st epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 1st reaction product and obtains, described 1st reaction product is Bisphenol F and 1, the reaction product of 6-hexanediol diglycidyl ether
Described 2nd epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 2nd reaction product and obtains, described 2nd reaction product is the reaction product of Resorcinol and 1,6-hexanediol diglycidyl ether.
The mixture of 12. epoxy compoundss according to claim 10, it contains the 2nd epoxy compounds and the 3rd epoxy compounds,
Described 2nd epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 2nd reaction product and obtains, described 2nd reaction product is Resorcinol and 1, the reaction product of 6-hexanediol diglycidyl ether
Described 3rd epoxy compounds is undertaken reacting by making (methyl) vinylformic acid, 2-(methyl) acryloyloxyethyl isocyanate or 4-hydroxyl butylglycidyl ether and the 3rd reaction product and obtains, and described 3rd reaction product is the reaction product of Resorcinol and resorcinol diglycidyl ether.
The mixture of 13. epoxy compoundss according to any one of claim 10 ~ 12, its viscosity at 23 DEG C is more than 50Pas.
14. 1 kinds of solidification compounds, it contains the epoxy compounds according to any one of thermal curing agents and claim 1 ~ 9.
15. solidification compounds according to claim 14, it contains at least 2 kinds of described epoxy compoundss.
16. solidification compounds according to claims 14 or 15, it is also containing photocurable compound and Photoepolymerizationinitiater initiater.
17. solidification compounds according to any one of claims 14 or 15, it is also containing electroconductive particle.
18. solidification compounds according to any one of claims 14 or 15, wherein, except described epoxy compounds, also containing epoxy (methyl) acrylate, described epoxy (methyl) acrylate is undertaken reacting obtaining by least one making in 2 epoxy group(ing) of (methyl) vinylformic acid and this epoxy compounds two end.
19. 1 kinds of connection structural bodies, it possesses:
1st connecting object parts,
2nd connecting object parts and
Connect the connection section of the 1st, the 2nd connecting object parts,
The solidification compound of described connection section according to any one of claim 14 ~ 18 is formed.
20. connection structural bodies according to claim 19, wherein,
Described solidification compound contains electroconductive particle,
Described 1st, the 2nd connecting object parts are electrically connected by described electroconductive particle.
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