CN102597044B - Thermopolymerization initiator system and adhesive composition - Google Patents

Thermopolymerization initiator system and adhesive composition Download PDF

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CN102597044B
CN102597044B CN201080050092.4A CN201080050092A CN102597044B CN 102597044 B CN102597044 B CN 102597044B CN 201080050092 A CN201080050092 A CN 201080050092A CN 102597044 B CN102597044 B CN 102597044B
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CN102597044A (en
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川上晋
永井朗
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Lishennoco Co ltd
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Hitachi Chemical Co Ltd
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    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
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    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
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Abstract

A thermopolymerization initiator system which comprises (A) a iodonium salt represented by general formula (I) and (B) a radical polymerization initiator. In general formula (I), R1 and R2 are each independently substituted or unsubstituted aryl; and Y- is an anionic residue.

Description

Thermopolymerization series initiators system and adhesive composite
Technical field
The present invention relates to a kind of thermopolymerization series initiators system and adhesive composite.
Background technology
In recent years, in the field such as semi-conductor, liquid-crystal display, for fixing electronic unit or in order to carry out circuit connection, use various adhesivess.In these purposes, densification, high-precision refinement are more and more developed, so also require high bonding force, reliability for caking agent.
Particularly, as for liquid-crystal display and the connection of connection, FPC and TCP of TCP or the circuit connection material of the connection of FPC and printed-wiring board (PWB), use the anisotropic conductive adhesive that is dispersed with electroconductive particle in caking agent.And recently, while semiconductor silicon chips being installed on substrate, do not adopt wire-bonded in the past, but carry out semiconductor silicon chips to be directly installed on the so-called COG on substrate, wherein at applicable anisotropic conductive adhesive yet.
In addition, in recent years in sophisticated electronics field, the densification of circuit developed, make electrode width and electrode space become very narrow.Therefore,, according to the condition of contact of the circuit connecting adhesive material of use epoxy resin in the past, have the problems such as circuit comes off, peels off, position deviation, and in COG, have the problem that produces warpage because of the thermal expansion difference of chip and substrate.For further cost degradation, must improve turnout, require one within low temperature (100～170 ℃) the lower short period of time (in 10 seconds), to solidify, i.e. the quick-setting caking agent of low temperature.
In the past, as cationic polymerization initiators, the polymerization starter (patent documentation 1) using the represented sulfonium salt of following general formula (II) as the cationically polymerizable material of principal constituent had for example been proposed.
[changing 1]
Figure GDA00002537263400011
[in formula (II), R aany in expression hydrogen, methyl, ethanoyl, methoxycarbonyl, ethoxy carbonyl, benzyloxycarbonyl, benzoyl, phenyloxycarbonyl, 9-fluorenyl methoxy carbonyl, R b, R crepresent independently hydrogen, halogen, C 1～C 4alkyl in any, R drepresent C 1～C 4alkyl, Q represents any in adjacent nitrobenzyl, a nitrobenzyl, dinitrobenzene benzyl, trinitro-benzyl, α-menaphthyl, β-menaphthyl.X is SbF 6, AsF 6, PF 6, BF 4in any.]
In addition,, as making at short notice the polymerization starter of epoxy resin cure by heating, proposed to contain the cationic polymerization initiators (patent documentation 2) of the represented sulfonium salt of following general formula (III) or following general formula (IV).
[changing 2]
Figure GDA00002537263400021
[in formula (III), R erepresent hydrogen atom, alkyl, halogen atom, carboxyl or alkoxy carbonyl, R frepresent alkyl, R grepresenting also can substituted phenyl or also can substituted naphthyl, and X represents SbF 6, AsF 6, PF 6or BF 6.]
[changing 3]
Figure GDA00002537263400022
[in formula (IV), R hrepresent hydrogen atom, alkyl, halogen atom, hydroxyl, alkoxyl group, carboxyl or alkyloyl, R irepresent alkyl, R jrepresent thiazolinyl, alpha-alkyl benzyl, α, α-dialkyl group benzyl, α-phenylbenzyl or fluorenyl, X represents SbF 6, AsF 6, PF 6or BF 4.]
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 3-237107 communique
Patent documentation 2: Japanese kokai publication hei 6-345726 communique
Summary of the invention
The problem that invention will solve
Polymerization starter described in patent documentation 1 or 2, can think to have leavings group (Q ,-CH by selection 2r gor R j) material of the structure that easily departs from is as sulfonium salt, thereby realize solidifying under low temperature, solidifying in the short period of time.Can think in addition, in this sulfonium salt, leavings group is to react or SN2 reaction departs from by cationic SN1.
But as initiator system, known have hot polymerization syzygy and photopolymerization to be.With regard to the initiator system of hot polymerization syzygy, different from the initiator system of photopolymerization system, its requirement have curability at low temperatures and storage stability this be as a rule mutually opposite characteristic.
But, polymerization starter described in patent documentation 1 or 2, owing to having used above-mentioned sulfonium salt, therefore when with the high combination of monomers of the cationically polymerizables such as alicyclic epoxy compound, oxetane compound, vinyl ether compound, have the problem of just having carried out curing reaction in preservation process.In addition, although recorded the content of stability in storage excellence in patent documentation 1, its condition of storage is " under lucifuge, 10 ℃ following ", thereby storage stability may not be abundant.
The present invention In view of the foregoing carries out, its objective is that to provide one to carry out in the short period of time at low temperatures bonding, connection reliability excellence, and the adhesive composite of excellent storage stability, and for manufacturing the useful thermopolymerization series initiators system of this adhesive composite.
The method of dealing with problems
The inventor has carried out active research to achieve these goals, found that by salt compounded of iodine compound represented following general formula (I) and radical polymerization initiator are combined, even if use any situation as polymerizability material in glycidyl ether compound, alicyclic epoxy compound, oxetane compound and vinyl ether compound, also can make the storage stability in solidified nature and actual use the under low temperature and deposit, thereby completing the present invention.
That is to say, the invention provides the described adhesive composite of the described initiator system in following (1)～(6) and following (7)～(17).
(1) contain the represented salt compounded of iodine compound of (A) following general formula (I) and (B) radical polymerization initiator and the thermopolymerization series initiators system that forms.
[changing 4]
R 1-I +-R 2 Y - (I)
[in formula, R 1and R 2represent independently of one another to replace or unsubstituted aryl Y -represent negatively charged ion residue.]
(2) the thermopolymerization series initiators system as described in above-mentioned (1), wherein above-mentioned Y -for SbF 6 -, [P(R 6) a(F) 6-a] -(in formula, R 6represent the alkyl that at least part of hydrogen atom is replaced by fluorine atom, a represents 0～5 integer.In the time that a is more than 2 integers, existing multiple R 6can be same to each other or different to each other.), B(C 6f 5) 4 -or C(CF 3sO 2) 3 -.
(3) the thermopolymerization series initiators system as described in above-mentioned (1) or (2), wherein above-mentioned radical polymerization initiator is organo-peroxide.
(4) the thermopolymerization series initiators system as described in above-mentioned (3), wherein 1 of above-mentioned organo-peroxide minute half life temperature is 80～170 ℃.
(5) the thermopolymerization series initiators system as described in any one in above-mentioned (1)～(4), it solidifies for cationically polymerizable material.
(6) the thermopolymerization series initiators system as described in any one in above-mentioned (1)～(5), it is for solidifying of being undertaken by heating.
(7) contain the represented salt compounded of iodine compound of (A) following general formula (I), (B) radical polymerization initiator and (C) cationically polymerizable material and the adhesive composite that forms.
[changing 5]
R 1-I +-R 2 Y - (I)
[in formula, R 1and R 2represent independently of one another to replace or unsubstituted aryl Y -represent negatively charged ion residue.]
(8) adhesive composite as described in above-mentioned (7), wherein above-mentioned Y -for SbF 6 -, [P(R 6) a(F) 6-a] -(in formula, R 6represent the alkyl that at least part of hydrogen atom is replaced by fluorine atom, a represents 0～5 integer.In the time that a is more than 2 integers, existing multiple R 6can be same to each other or different to each other.), B(C 6f 5) 4 -or C(CF 3sO 2) 3 -.
(9) adhesive composite as described in above-mentioned (7) or (8), wherein above-mentioned radical polymerization initiator is organo-peroxide.
(10) adhesive composite as described in above-mentioned (9), wherein 1 of above-mentioned organo-peroxide minute half life temperature is 80～170 ℃.
(11) adhesive composite as described in any one in above-mentioned (7)～(10), wherein above-mentioned cationically polymerizable material contains at least one in the group of selecting free epoxy compounds, oxetane compound and vinyl ether compound composition.
(12) adhesive composite as described in any one in above-mentioned (7)～(11), it further contains (D) film-forming properties polymkeric substance.
(13) adhesive composite as described in any one in above-mentioned (7)～(12), it further contains (E) electroconductive particle.
(14) adhesive composite as described in above-mentioned (13), it has anisotropic conductive.
(15) adhesive composite as described in any one in above-mentioned (7)～(14), it is as adhesive for circuit connection composition.
(16) adhesive composite as described in any one in above-mentioned (7)～(15), it solidifies by heating.
(17) adhesive composite described in any one in above-mentioned (7)～(16) is made to film-like adhesive composition membranaceous and that form.
In addition, according to the inventor's research, with regard to the represented salt compounded of iodine compound of above-mentioned general formula (I), compared with the sulfonium salt described in patent documentation 1 or 2 for example, be difficult to occur reacted or SN2 reacts the substituent disengaging causing by cationic SN1.Therefore, when the represented salt compounded of iodine compound of above-mentioned general formula (I) not and radical polymerization initiator combination and while using separately, be difficult within low temperature (100～170 ℃) the lower short period of time (in 10 seconds) curing.The inventor finds, by the above-mentioned salt compounded of iodine compound and radical polymerization initiator the use that are difficult to when independent to carry out solidify in low-temperature short-time, can obtain at low temperatures curing initiator system in the short period of time.The reason that can obtain this initiator system is not yet clear and definite, but can think and bring out above-mentioned sulfonium salt compound or above-mentioned salt compounded of iodine compound by the free radical being produced by radical polymerization initiator.
Invention effect
According to the present invention, can provide one to carry out in the short period of time at low temperatures bonding, connection reliability excellence, and the adhesive composite of excellent storage stability, and for manufacturing the useful initiator system of this adhesive composite.
Accompanying drawing explanation
Fig. 1 is the figure that represents the means of differential scanning calorimetry measurement result of embodiment 1,2 and comparative example 1.
Fig. 2 is the figure that represents the means of differential scanning calorimetry measurement result of embodiment 3 and comparative example 2.
Fig. 3 is the figure that represents the means of differential scanning calorimetry measurement result of embodiment 4 and comparative example 3.
Fig. 4 is the figure that represents the means of differential scanning calorimetry measurement result of embodiment 5 and comparative example 4.
Fig. 5 represents the solidification value of film-like adhesive composition gained, embodiment 1～4 and the figure of curing degree relation in curing degree determination test.
Fig. 6 represents the solidification value of film-like adhesive composition gained, comparative example 1～8 and the figure of curing degree relation in curing degree determination test.
Fig. 7 represents the solidification value of film-like adhesive composition gained, comparative example 9～11 and the figure of curing degree relation in curing degree determination test.
Fig. 8 represents the elapsed time of film-like adhesive composition gained, embodiment 1～4 and the figure of curing degree relation in storage stability test.
Fig. 9 represents the elapsed time of film-like adhesive composition gained, comparative example 1～8 and the figure of curing degree relation in storage stability test.
Figure 10 represents the elapsed time of film-like adhesive composition gained, comparative example 9～11 and the figure of curing degree relation in storage stability test.
Embodiment
Below, the preferred embodiment of the present invention is elaborated.But the present invention is not limited to following embodiment.
(initiator system)
Initiator system in present embodiment, contains the represented salt compounded of iodine compound of (A) general formula (I) and (below, is sometimes referred to as " (A) composition ".) and (B) radical polymerization initiator (following, be sometimes referred to as " (B) composition ".）。
[changing 6]
R 1-I +-R 2 Y - (I)
In formula, R 1and R 2represent independently of one another to replace or unsubstituted aryl Y -represent negatively charged ion residue.
As aryl, for example, can enumerate carbon number and be 6～12 aryl.More specifically, can enumerate phenyl, 1-naphthyl, 2-naphthyl.They can have substituting group, and substituent the position of substitution is not particularly limited, and can be optional positions.
The substituting group that can have as above-mentioned each group, for example, can enumerate the alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, hexyl; The aryl such as phenyl, naphthyl; The alkoxyl groups such as methoxyl group, oxyethyl group, propoxy-, butoxy; The alkoxy carbonyls such as acetoxyl group, propionyloxy, decyl ketonic oxygen base, dodecyl ketonic oxygen base; The ester groups such as methoxycarbonyl, ethoxy carbonyl, benzoyloxy; The halogen atoms such as fluorine, chlorine, bromine, iodine; Cyano group, nitro, hydroxyl etc.These substituent the position of substitution are not particularly limited, and can be optional positions.
As negatively charged ion residue, can enumerate the pairing negatively charged ion of monovalence, for example BF 4 -, SbF 6 -, AsF 6 -, [P(R 6) a(F) 6-a] -(in formula, R 6represent the alkyl that at least part of hydrogen atom is replaced by fluorine atom, a represents 0～5 integer.In the time that a is more than 2 integers, multiple R of existence 6, can be same to each other or different to each other.), B(C 6f 5) 4 -, Ga(C 6f 5) 4 -, Ga(C 6f 5) 2f 2 -, Ga(C 6f 5) F 3 -, C(CF 3sO 2) 3 -deng.
In addition, at [P(R 6) a(F) 6-a] -in, R 6be preferably the alkyl more than 80% being replaced by fluorine atom of hydrogen atom, the alkyl more preferably more than 90% of hydrogen atom being replaced by fluorine atom, and the perfluoroalkyl of straight chain or branch more preferably.
About negatively charged ion residue, preferably its nucleophilicity is low.Therefore,, as negatively charged ion residue, be preferably SbF 6 -, [P(R 6) a(F) 6-a] -(in formula, R 6represent the alkyl that at least part of hydrogen atom is replaced by fluorine atom, a represents 0～5 integer.In the time that a is more than 2 integers, multiple R of existence 6, can be same to each other or different to each other.), B(C 6f 5) 4 -, C(CF 3sO 2) 3 -, and SbF more preferably 6 -, B(C 6f 5) 4 -, C(CF 3sO 2) 3 -.If the nucleophilicity of negatively charged ion residue is low, the growth speed of response of cationically polymerizable compound is high, and interior polymerization of short period of time at low temperatures.
As salt compounded of iodine compound, preferably R 1and R 2for the diaryl group iodized salt compound of replacement or unsubstituting aromatic yl.The initiator system that contains this salt compounded of iodine compound, its storage stability and low temperature rapidly-curable are more excellent.
As the object lesson of salt compounded of iodine compound, can enumerate the UVE series of phenylbenzene iodine arsenic hexafluoride, two (4-chloro-phenyl-) iodine arsenic hexafluoride, two (4-bromophenyl) iodine arsenic hexafluoride, phenyl (4-p-methoxy-phenyl) iodine arsenic hexafluoride, General Electric Corporation's system, the FC series of 3M company system, UV-9310C(pairing negatively charged ion: the SbF of organosilicon company of Toshiba system 6 -) and the light trigger 2074(pairing negatively charged ion of Rhone-Poulenc's system: (C 6f 5) 4b -) etc.
In the initiator system of present embodiment, as (A) composition, can use separately the one in salt compounded of iodine compound, also two kinds can be used in combination above.In the initiator system of present embodiment, (A) composition has the function as cationic polymerization initiators.
As (A) composition, consider from the viewpoint of storage stability, preferably at the temperature of 140～250 ℃, express active material, and more preferably in measuring with the means of differential scanning calorimetry of the mixture of glycidyl ether type epoxy compounds, can give the material of 140～250 ℃ of peak temperatures.
As (B) composition, can use known superoxide, azo-compound in the past, and consider preferably organo-peroxide from storage stability and the more excellent viewpoint of low temperature fast setting.
As organo-peroxide, for example, can enumerate diacyl peroxide, peroxy dicarbonate, peroxyester, ketal peroxide, dialkyl peroxide, hydroperoxide, silyl superoxide.Wherein, from the viewpoint of stability, reactive good, preferably peroxyester, diacyl peroxide.Here, have-C(=O of peroxyester) the represented structure of-O-O-, have-C(=O of diacyl peroxide)-O-O-C(=O)-represented structure.Further, as organo-peroxide, more preferably 1 minute half life temperature is 80～170 ℃, and molecular weight be 180～1000 peroxyester or diacyl peroxide.By this organo-peroxide, can provide storage stability and the more excellent initiator system of low temperature rapidly-curable.
As (B) composition, specifically, can enumerate cumyl new decanoate ester peroxide, 1,1,3,3-tetramethyl butyl new decanoate ester peroxide, 1-cyclohexyl-1-methylethyl new decanoate ester peroxide, tertiary hexyl new decanoate ester peroxide, tert-butyl hydroperoxide neodecanoic acid ester, t-butylperoxy pivarate, 1，1，3，3-tetra-methylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis-(peroxidation of 2-ethyl hexyl acyl group) hexane, tertiary hexyl peroxidation-2-ethylhexanoate, tert-butyl hydroperoxide-2-ethylhexanoate, the new heptanoate of tert-butyl hydroperoxide, t-amyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide hexahydro terephthalic acid ester, t-amyl peroxy-3,5,5 Trimethylhexanoic acid ester, 3-hydroxyl-1,1-dimethylbutyl new decanoate ester peroxide, 1，1，3，3-tetra-methylbutyl peroxy-2-ethylhexanoate, t-amyl peroxy neodecanoic acid ester, t-amyl peroxy-2-ethylhexanoate, 2,2 '-azo two-2,4-methyl pentane nitrile, 1,1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane), 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methylbutyronitrile), dimethyl-2,2 '-Diisopropyl azodicarboxylate, 4,4 '-azo two (4-cyanopentanoic acid), 1,1 '-azo two (1-cyclohexane nitrile), tertiary hexyl peroxidation sec.-propyl monocarbonate, tert-butyl hydroperoxide toxilic acid, tert-butyl hydroperoxide-3,5,5 Trimethylhexanoic acid ester, tert-butyl hydroperoxide laurate, 2,5-dimethyl-2,5-bis-(peroxidation of 3-methyl benzoyl) hexane, tert-butyl hydroperoxide-2-ethylhexyl monocarbonate, tertiary hexyl peroxide benzoate, 2,5-dimethyl-2,5-bis-(benzoyl peroxidation) hexane, tert butyl peroxy benzoate, dibutyl peroxidation trimethyladipic acid ester, t-amyl peroxy n-caprylic acid ester, the different pelargonate of t-amyl peroxy, t-amyl peroxy benzoic ether, lauroyl peroxide etc.
Be the peroxyester that 80～170 ℃ and molecular weight are 180～1000 as 1 minute half life temperature, specifically, can enumerate 2,5-dimethyl-2,5-bis-(peroxidation of 2-ethyl hexyl acyl group) hexane etc.
In addition, be the diacyl peroxide that 80～170 ℃ and molecular weight are 180～1000 as 1 minute half life temperature, specifically, can enumerate lauroyl peroxide etc.
With regard to (B) radical polymerization initiator, can use separately a kind, also two or more can be used in combination.
About (B) composition in the initiator system of present embodiment containing proportional, take the total amount of (A) composition as benchmark, more than being preferably 25 quality %, and more preferably more than 50 quality %.By making containing of (B) composition proportional in above-mentioned scope, can obtain storage stability and the more excellent initiator system of low temperature rapidly-curable.During less than above-mentioned scope, have the tendency that cannot fully generate cationoid polymerisation Priming Seeds containing proportional when (B) composition.
In the time that the initiator system of present embodiment contains organo-peroxide as (B) composition, the poor alpha-beta of peak temperature α during 1 minute half life temperature β of this organo-peroxide measures with the means of differential scanning calorimetry of the mixture of, (A) composition and glycidyl ether type epoxy compounds, is preferably 30～200 ℃.
Initiator system of the present invention, also can be to contain in measuring with the means of differential scanning calorimetry of the mixture of glycidyl ether type epoxy compounds to give at least one salt 140～250 ℃ of peak temperatures, that be selected from sulfonium salt compound and salt compounded of iodine compound, and 1 minute half life temperature initiator system that is the organo-peroxide of 80～170 ℃.This initiator system also makes the cationically polymerizable material polymerizations such as epoxy compounds in the short period of time equally at low temperatures with the initiator system of above-mentioned embodiment, and excellent storage stability.Herein, as salt compounded of iodine compound, organo-peroxide, can use separately and above-mentioned same material.
The initiator system of present embodiment, makes the cationically polymerizable material polymerizations such as epoxy compounds in the short period of time at low temperatures, and excellent storage stability.Therefore, according to the initiator system of present embodiment, can manufacture at low temperatures in the short period of time, carry out bonding, connection reliability is excellent and the adhesive composite of excellent storage stability.By by salt compound and radical polymerization initiator not yet clear and definite by the reason that plays this effect, but can think excellent in stability due to salt compound, therefore storage stability is good, and the free radical being produced by radical polymerization initiator can bring out the generation of the positively charged ion kind being caused by the decomposition of salt compound, therefore can realize low temperature fast setting.
(adhesive composite)
The adhesive composite of present embodiment, contain the represented salt compounded of iodine compound of (A) general formula (I), (B) radical polymerization initiator and (C) cationically polymerizable material (following, be sometimes referred to as " (C) composition ".) and form.
Salt compounded of iodine compound, as radical polymerization initiator, can use the material same with (A) composition, (B) composition in above-mentioned initiator system separately.
In the adhesive composite of present embodiment (A) composition containing proportional, take the total amount of (C) composition as benchmark, be preferably 0.05～30 quality %, and 0.1～15 quality % more preferably.When (A) composition during less than above-mentioned scope, have the inadequate situation of solidifying containing proportional, and if exceeded above-mentioned scope, the tendency that has consistency to decline.
(B) composition containing proportional, take the total amount of (A) composition as benchmark, more than being preferably 25 quality %, and more preferably more than 50 quality % in the adhesive composite of present embodiment.In above-mentioned scope time, can obtain storage stability and the more excellent initiator system of low temperature rapidly-curable containing proportional when (B) composition.During less than above-mentioned scope, have the tendency that cannot fully generate cationoid polymerisation Priming Seeds containing proportional when (B) composition.
As (C) composition, can enumerate epoxy compounds, oxetane compound, vinyl ether compound etc., and as epoxy compounds, the glycidyl ether type of can giving an example epoxy compounds, alicyclic epoxy compound.
(C) the cationoid polymerisation substituent equivalent of composition, is preferably 43～1000, and more preferably 50～800, and more preferably 73～600.If cationoid polymerisation substituent equivalent is less than 43 or exceed 1000,, in the time carrying out electrode connection described later, have the tendency that bonding strength declines.Here, cationoid polymerisation substituent equivalent, refer to that the molecular-weight average of a part of contained cationically polymerizable compound, divided by the substituent business of the cationically polymerizable in a part of cationically polymerizable compound, that is to say the substituent molecular-weight average of per unit cationically polymerizable.
As (C) composition, consider from the viewpoint that prevents corrosion, preferably use foreign ion (Na +, Cl -deng), the content of water-disintegrable chlorine etc. is reduced to the high purity goods below 300ppm.
In the adhesive composite of present embodiment (C) composition containing proportional, take the total amount of adhesive composite as benchmark, be preferably 10～90 quality %, and 25～75 quality % more preferably.If (C) composition containing proportional less than 10 quality %, may form the adhesive composite that cured article physical property (second-order transition temperature, Young's modulus etc.) is not enough, and if exceed 90 quality %, have cure shrinkage and become large, the situation that bonding force declines.
As the glycidyl ether type epoxy compounds of (C) composition, as long as thering is the compound of glycidyl ether in molecule, and can solidify by irradiating active ray or heating under solidifying agent exists or not.Wherein, in 1 molecule, there is the material of more than 2 epoxy group(ing), due to solidify time cross-linking density high, therefore preferred.As glycidyl ether type epoxy compounds, as long as thering is the compound of glycidyl ether, be just not particularly limited, can use known material.More specifically, can enumerate by Epicholorohydrin and dihydroxyphenyl propane, the bisphenol-type epoxy resin that Bisphenol F etc. are derivative, polyglycidyl ether, poly glycidyl ester, aromatic epoxy compound, alicyclic epoxy compound, cresols phenolic resin varnish type epoxy resin, the phenolic varnish type epoxy compoundss such as phenol novolak type epoxy resin, glycidyl amine is epoxy compounds, glycidyl ester is epoxy compounds, biphenyldiglycid ether, triglycidyl group isocyanuric acid ester, poly epihydric alcohol ylmethyl acrylate, glycidyl methacrylate and can be with the multipolymer of the vinyl monomer of its copolymerization etc.They may be used singly or in combination of two or more.
As the alicyclic epoxy compound of (C) composition, as long as having in molecule by the compound that forms in the carbon atom of cyclic hydrocarbon skeleton two epoxy group(ing) that form with Sauerstoffatom, and under solidifying agent exists or not by irradiating active ray or heating can be solidified.Wherein, in 1 molecule, there is the material of more than 2 epoxy group(ing), due to solidify time cross-linking density high, therefore preferred.As alicyclic epoxy compound, as long as thering is the compound of ester ring type epoxy group(ing), be just not particularly limited, can use known material.For example, can enumerate the compound that contains cyclohexene oxide, cyclopentene oxide of the compound oxidation gained that contains tetrahydrobenzene, cyclopentenes ring.More specifically, can enumerate 2-(3, 4-epoxy group(ing) cyclohexyl-5, 5-spiral shell-3, 4-epoxy group(ing)) hexanaphthene-trimethylene-formal, 3, 4-epoxy group(ing)-1-methylcyclohexyl-3, 4-epoxy group(ing)-1-methyl hexane carboxylicesters, 3, 4-epoxy group(ing)-3-methyl cyclohexane ylmethyl-3, 4-epoxy group(ing)-3-methylcyclohexanecarboxylic acid ester, 3, 4-epoxy group(ing)-5-methyl cyclohexane ylmethyl-3, 4-epoxy group(ing)-5-methylcyclohexanecarboxylic acid ester, 3, 4-epoxy group(ing)-6-methylcyclohexyl carboxylicesters, 3, 4-epoxy group(ing) cyclohexyl methyl-3, 4-epoxy-cyclohexane carboxylicesters, 6-methyl-3, 4-epoxy group(ing) cyclohexyl methyl-6-methyl-3, 4-epoxy-cyclohexane carboxylicesters, ethylenebis (3, 4-epoxy-cyclohexane carboxylicesters), Dicyclopentadiene (DCPD) diepoxide, two (3, 4-epoxy group(ing) cyclohexyl methyl) adipic acid ester, methylene-bis (3, 4-epoxy-cyclohexane) etc.They may be used singly or in combination of two or more.
As the oxetane compound of (C) composition, as long as thering is the oxetane compound of oxa-cyclobutyl in molecule, and can solidify by irradiation active ray, heating under solidifying agent exists or not.Wherein, there is the compound of more than 2 trimethylene oxide ring, due to solidify time cross-linking density high, therefore preferred.In addition, in molecule, there are 2～6 trimethylene oxide rings, and there is fatty family or the alicyclic series compound of 1～6 hydroxyl, consider it is preferred from the viewpoint of solidified nature excellence.
As oxetane compound, can enumerate the represented compound of following logical formula V.
[changing 7]
Figure GDA00002537263400121
In formula, R 9represent the alkyl of hydrogen atom, fluorine atom or 1 valency, R 10represent hydrogen atom, alkyl or aryl, n represents 1～4 integer.But, work as R 10during for hydrogen atom, n is 1.In the time that n is more than 2 integers, with R 10in conjunction with multiple Sauerstoffatoms, can be each other and R 10same carbon atom combination, also can with R 10different carbon atom combinations.
As oxetane compound, more specifically, can enumerate 1,4-bis-[(3-oxa-cyclobutyl n-butoxy) methyl] benzene, 4,4 '-bis-[(3-oxa-cyclobutyl n-butoxy) methyl] biphenyl, 3-ethyl-3{[(3-Ethyloxetane-3-yl) methoxyl group] methyl } trimethylene oxide, 3-ethyl-3-hydroxymethyl trimethylene oxide, 2-ethylhexyl trimethylene oxide etc.
As the vinyl ether compound of (C) composition, as long as thering is the compound of vinyl ether group in molecule, and can solidify by irradiating active ray or heating under solidifying agent exists or not.Wherein, in 1 molecule, there is the material of more than 2 vinyl ether group, due to solidify time cross-linking density high, therefore preferred.
As vinyl ether compound, can enumerate the represented compound of following general formula (VI).
[changing 8]
Figure GDA00002537263400122
In formula, R 11represent alkyl or aryl, m represents 1～4 integer.In the time that m is more than 2 integers, with R 11in conjunction with multiple Sauerstoffatoms, can be each other and R 11same carbon atom combination, also can with R 11different carbon atom combinations.
As vinyl ether compound, more specifically, can enumerate BDO divinyl ether, cyclohexanedimethanol divinyl ether, Diethylene Glycol divinyl ether, triethylene glycol divinyl ether etc.
In the adhesive composite of present embodiment, (C) composition can use separately a kind, also two or more can be used in combination.
The adhesive composite of present embodiment, can solidify by heating.Heating temperature, is preferably 40～180 ℃, more preferably 50～150 ℃, heat-up time, is preferably 0.1 second～10 hours, more preferably 1 second～1 hour.When Heating temperature is during less than 40 ℃, have the slow situation of curing speed, and if exceed 180 ℃, have and produced undesirable side reaction, the situation that connection reliability declines.In addition, when heat-up time is during less than 0.1 second, have the situation that curing reaction cannot carry out, and if exceed 10 hours, the productivity that has cured article declines, and has produced undesirable side reaction simultaneously, the situation that connection reliability declines.
The adhesive composite of present embodiment, the initiator system that contains above-mentioned present embodiment.That is to say, while making it curing heating the adhesive composite of present embodiment, can think and bring out the salt compound as (A) composition by the free radical producing as the radical polymerization initiator of (B) composition.Therefore, the adhesive composite of present embodiment, does not preferably contain in fact free radical scavenger.In addition, can carry out the content of the vinyl compound of radical polymerization, take the total amount of adhesive composite as benchmark, be preferably 0～10 quality %, more preferably 0～5 quality %, more preferably 0～3 quality %, further be preferably 0～1 quality %, and be particularly preferably 0 quality %.
The adhesive composite of present embodiment, can further contain electroconductive particle.As electroconductive particle, can enumerate metallics or the carbon etc. such as Au, Ag, Ni, Cu, scolding tin.In addition, can also be take dielectric glass, pottery, plastics etc. as core, and on this core, be coated the material of above-mentioned metal, metallics or carbon.When electroconductive particle is take plastics as core, and on this core when material, the hot molten metal particle of coated above-mentioned metal, metallics or carbon, due to the deformability having heating and pressurizing, therefore in the time connecting with the contact area increase of electrode, reliability improves, therefore preferred.In addition, further use the particulate on coated these electroconductive particle surfaces such as macromolecule resin, owing to can suppress to increase electroconductive particle use level time because of the particle short circuit causing that contacts with each other, improve the insulativity between telegraph circuit, therefore independent use that can be suitable, or mix use with electroconductive particle.
The median size of this electroconductive particle, considers from viewpoint dispersed and that electroconductibility is good, is preferably 1～18 μ m.In the adhesive composite of present embodiment electroconductive particle containing proportional, be not particularly limited, but with respect to adhesive composite 100 volume %, be preferably 0.1～30 volume %, and 0.1～10 volume % more preferably.If electroconductive particle containing proportional less than 0.1 volume %, have the tendency of poorly conductive, and if exceed 30 volume %, have the situation that causes short circuit.In addition, " volume % ", is that to solidify the volume of front each composition at 23 ℃ be that basis is determined, but the volume of each composition also can utilize proportion be scaled quality and obtain.In addition, can also in graduated cylinder etc., add and not dissolve or swelling this composition and can fully soak the appropriate solvent (water, alcohol etc.) of this composition, the volume increasing dropping into this composition is obtained as its volume.
In order to prevent the corrosion of bonded object, the adhesive composite of present embodiment can add, mix the sanitas being formed by metal hydroxides or metal oxide.As sanitas, more specifically, be preferably at least one in the group of selecting free aluminium hydroxide, magnesium hydroxide, calcium hydroxide, silicon oxide, aluminum oxide, magnesium oxide, weisspiessglanz, stannic oxide, titanium oxide, manganese oxide and zirconium white composition.In addition, from the dispersion adhesive composite, bondingization of height to bonded object, prevent that the viewpoint such as ability of bonded object corrosion from considering, when sanitas is while being granular, its particle diameter is preferably below 10 μ m.
In the adhesive composite of present embodiment sanitas containing proportional, take the total amount of (A) composition as benchmark, be preferably 0.1～60 quality %, and 1～30 quality % more preferably.When sanitas during less than 0.1 quality %, cannot fully obtain preservative effect containing proportional, and if exceed 60 quality %, have dispersed decline, the situation that the connection reliability of adhesive composite declines.
The adhesive composite of present embodiment, can further contain chain ether compound or cyclic ether compound.Particularly, in the time containing alicyclic epoxy compound as (C) composition, by further containing chain or cyclic ether compound, can be easy to and positively control the curing action of alicyclic epoxy compound.
As chain or cyclic ether compound, as long as there is more than 2 ehter bond in 1 molecule, be not particularly limited, can use known material.For example, as chain ether compound, can enumerate the polyethylene glycols such as Diethylene Glycol, triethylene glycol, TEG; The terminal hydroxyl of polyethylene glycols is carried out to functionalized derivative with ehter bond, ester bond; The polymkeric substance of the monofunctional epoxy compounds such as ethylene oxide, propylene oxide, cyclohexene oxide; Multi-functional epoxy compound's polymkeric substance; The polymkeric substance of simple function or multifunctional oxetane compound; The polymkeric substance of simple function or multifunctional tetrahydrofuran derivatives etc.In addition, as cyclic ether compound, can enumerate cyclisation thing of the polymkeric substance of cyclisation thing, the epoxy compounds of 12-crown-4-ether, 14-hat-4-ether, 15-hat-5-ether, 18-hat-6-ether, 21-hat-7-ether, 24-hat-8-ether, 30-hat-7-ether, phendioxin 8-hat-6-ether, dibenzo-18-hat-6-ether, three benzos-18-hat-6-ether, polyethylene glycols etc.They can use separately, also can be by multiple and use.
In above-mentioned, consider from the viewpoint that regulates response capacity, preferably cyclic ether compound, and more preferably 12-crown-4-ether, 14-hat-4-ether, 15-hat-5-ether, 18-hat-6-ether, 21-hat-7-ether, 24-hat-8-ether, 30-hat-7-ether, phendioxin 8-hat-6-ether, dibenzo-18-hat-6-ether, three benzos-18-hat-6-ether.
The content of chain or cyclic ether compound in the adhesive composite of present embodiment, with respect to (A) composition, is preferably 0.005～10 % by mole, and more preferably 0.01～5 % by mole.When the content of chain or cyclic ether compound is during less than 0.005 % by mole, be difficult to obtain high-adhesive-strength, and if exceed 20 % by mole, may stop curing, thereby cause lower crosslink density.
The adhesive composite of present embodiment, as long as not damaging in the scope of effect of the present invention, just can contain known various additive, for example inorganic filler, strongthener, tinting material, stablizer (thermo-stabilizer, weathering resistance improving agent etc.), extender, viscosity modifier, terpene phenolic multipolymer, terpine resin, rosin derivative, the adhesion imparting agent that alicyclic ring family hydrocarbon resin etc. are representative, fire retardant, UV light absorber, oxidation inhibitor, anti-blushing agent, antiseptic-germicide, mould inhibitor, protective agent, static inhibitor, softening agent, lubricant, whipping agent, releasing agent etc.
As above-mentioned tinting material, can enumerate the mineral dyes such as dyestuff, carbon black, mica such as substantive dyestuff, matching stain, basic dyestuff, metallic complex salt dyestuff and coupling azo system, condensation azo system, anthraquinone system, thioindigo system, two the pigment dyestuffs such as piperazine system, phthalocyanine system etc.In addition,, as aforementioned stable agent, can enumerate the compounds such as hindered phenol system, hydrazine system, phosphorus system, benzophenone series, benzotriazole system, oxanilide system.In addition, as above-mentioned inorganic filler, can enumerate glass fibre, fibrous magnesium silicate, carbon fiber, silica fiber, sapphire whisker, Zirconium oxide fibre, boron nitride fibre, silicon nitride fiber, basic magnesium sulfate fiber, boron fibre, Stainless Steel Fibre, aluminium, titanium, copper, brass, the inanimate matters such as magnesium and steel fiber, copper, iron, nickel, zinc, tin, plumbous, stainless steel, aluminium, the metal-powders such as gold and silver, wood powder, pure aluminium silicate, talcum, clay, carbonate, vitriol, phosphoric acid salt, borate, borosilicate, aluminosilicate, titanate, basic sulfatase, basic carbonate and other basic salt, hollow glass ball, the glass materials such as glass flake, silicon carbide, aluminium nitride, mullite, trichroite etc.
For the object of tackify, one-tenth membranization, the adhesive composite of present embodiment can suitably contain various polymkeric substance.As contained polymkeric substance, only otherwise can, to the larger obstruction of curing generation of (C) composition, just not limit, can use known polymkeric substance.As this polymkeric substance, can use phenoxy resin class, polymethacrylate, polyacrylate(s), polyester, polyvinyl butyral class, SBS(styrene butadiene styrene segmented copolymer) and epoxide modified thing, SEBS(styrene ethylene butylene styrene segmented copolymer) and modifier etc.They can use separately or two or more is mixed and is used.Further, in these polymkeric substance, can also contain siloxane bond, fluoro substituents.As long as they are perhaps to produce microphase-separated completely mutually each other and muddy state with the resin mixing, just can be used as aptly adhesive composite.While particularly turning to object with film forming, preferably contain as YP-50, YP-50S, YP-55U, YP-70, ZX-1356-2, FX-316, FX-293(Dongdu of phenoxy resin and change into (strain) goods name), as DenkaButyral 3000-1,3000-2,3000-4,3000-K, 4000-2,5000-A, 5000-D(electrochemical industry (strain) the goods name of polyvinyl butyral class) etc. film-forming properties polymkeric substance.
If the molecular weight of above-mentioned polymkeric substance is large, easily obtains film-forming properties, and can in relative broad range, set the viscosity that dissolves that affects adhesive composite mobility.The weight-average molecular weight of above-mentioned polymkeric substance, is not particularly limited, but is preferably 5000～150000, and more preferably 10000～80000.When weight-average molecular weight is less than 5000 time, have the poor tendency of film-forming properties, and if exceed 150000, have the tendency with the consistency variation of other composition.
The content of above-mentioned polymkeric substance in the adhesive composite of present embodiment, with respect to (C) composition 100 mass parts, is preferably 20～320 quality %, and 50～150 quality % more preferably.If above-mentioned polymkeric substance containing proportional less than 20 quality % or exceed 320 quality %, have the mobility of adhesive composite and the tendency that cementability declines.
The adhesive composite of present embodiment, while being aqueous at normal temperatures, can use with pasty state.While being at room temperature solid, except heating is used, can also use solvent by its gelatinization.As operable solvent, as long as and adhesive composite and additive there is no reactivity, and demonstrate enough solvabilities, be just not particularly limited, but preferably the boiling point under normal pressure is the solvent of 50～150 ℃.Boiling point, less than the solvent of 50 ℃, while at room temperature placement, may volatilize, and therefore the use in open system is restricted.In addition, boiling point exceedes the solvent of 150 ℃, is difficult to make solvent evaporates, therefore may produce detrimentally affect to the reliability after bonding.
The adhesive composite of present embodiment, can be combined with heating and pressurization is carried out bonding.Heating temperature.Be not particularly limited, but be preferably the temperature of 50～190 ℃.About pressure, as long as not producing to bonded object the scope of damage, be just not particularly limited, but be conventionally preferably 0.1～30MPa.These heating and pressurization are preferably carried out in the scope of 0.5 second～120 seconds.
The adhesive composite of present embodiment, can be as the caking agent of the different not bonded object of the same race of thermal expansivity.Specifically, can be as take anisotropically conducting adhesive, silver pastes, silverskin etc. as the circuit connection material of representative, take elastomerics for CSP, for CSP, underfilling, LOC such as be with at the semiconductor element adhesives as representative.
As by the method that uses the adhesive composite of present embodiment and the anisotropic conductive film of electroconductive particle made to be connected with electrode, for example, can enumerate make anisotropic conductive film be present on substrate relatively to electrode between, and carry out the method for heating and pressurizing.By this method, can obtain bonding between the contact of two electrodes and substrate, and carry out and the connection of electrode.As forming the substrate of electrode, can suitably use their compound various combinations that are formed with base material, the printed-wiring board (PWB) etc. of electrode on the films such as polyimide base material that the inanimate matters such as semi-conductor, glass, pottery, TCP, FPC, COF are representative, polycarbonate, polyester, polyethersulfone.
Above, the preferred embodiment of the present invention is illustrated, but the present invention is not limited to above-mentioned embodiment.
[embodiment]
Below, based on embodiment and comparative example, the present invention is made to more specific description, but the present invention is not limited to following embodiment.In addition, in the following description, " DSC peak temperature " refers to, and the peak temperature of the mixture of glycidyl ether type epoxy compounds in means of differential scanning calorimetry is measured.
(embodiment 1)
Use light trigger 2074(Rhodia goods name; 4-aminomethyl phenyl [4-(1-methylethyl) phenyl] iodine four (pentafluorophenyl group) borate is as (A) composition; use PERHEXA 25O(Japan Oil Co goods name; 2; 5-dimethyl-2; 5-bis-(peroxidation of ethyl hexyl acyl group) hexane; purity is 50%; within 1 minute, half life temperature is 119 ℃) as (B) composition; use glycidyl ether type epoxy compounds YL980(japan epoxy resin Co., Ltd. goods name, bisphenol f type epoxy resin) as (C) composition.As tackiness agent, use phenoxy resin (YP-70, Dongdu changes into (strain) trade(brand)name processed).In addition, make and use on the surface of the particle take polystyrene as core, the nickel dam that thickness is 0.2 μ m is set, and thickness is set on the outside of this nickel dam is that the median size of the metal of 0.02 μ m is the conducting particles that 3 μ m, proportion are 2.5.
Coordinate (A)～(C) composition and tackiness agent with the weight ratio shown in table 1, coordinate again the conducting particles of 8 volume % and disperse, and use apparatus for coating to be coated on the PET resin molding that thickness is 40 μ m, carry out the warm air drying of 70 ℃, 5 minutes, the thickness that obtains bond layer is the film-like adhesive composition of 20 μ m.
(embodiment 2)
Except using PEROYL L(Japan Oil Co goods name, dilauroyl peroxide, purity is that 98%, 1 minute half life temperature is 116 ℃) replace PERHEXA 25O as beyond (B) composition, obtain film-like adhesive composition by the method identical with embodiment 1.In table 1, represent the ratio of mixture of each composition.
(embodiment 3)
Except using alicyclic epoxy compound EPOLEAD GT401(エ Port リ mono-De GT401, Daisel chemical industry Co., Ltd's goods name, epoxidation BTCA four (3-cyclohexenyl methyl) is modified 6-caprolactone) replace YL980 as beyond (C) composition, obtain film-like adhesive composition by the method identical with embodiment 2.In table 1, represent the ratio of mixture of each composition.
(embodiment 4)
Except using oxetane compound OXT-121(Toagosei Co., Ltd goods name, 1,4-bis-[(3-oxa-cyclobutyl n-butoxy) methyl] benzene) replace YL980 as beyond (C) composition, obtain film-like adhesive composition by the method identical with embodiment 2.In table 1, represent the ratio of mixture of each composition.
(embodiment 5)
Except by YL980 and vinyl ether compound CHDVE(Nippon Carbide Kogyo K.K goods name, cyclohexanedimethanol divinyl ether) and with and as beyond (C) composition, obtain film-like adhesive composition by the method identical with embodiment 2.In table 1, represent the ratio of mixture of each composition.
(comparative example 1)
Except not using (B) composition, obtain film-like adhesive composition by the method identical with embodiment 2.In table 2, represent the ratio of mixture of each composition.
(comparative example 2)
Except using alicyclic epoxy compound EPOLEAD GT401(Daisel chemical industry Co., Ltd goods name, epoxidation BTCA four (3-cyclohexenyl methyl) is modified 6-caprolactone) replace YL980 as beyond (C) composition, obtain film-like adhesive composition by the method identical with comparative example 1.In table 2, represent the ratio of mixture of each composition.
(comparative example 3)
Except using oxetane compound OXT-121(Toagosei Co., Ltd goods name, 1,4-bis-[(3-oxa-cyclobutyl n-butoxy) methyl] benzene) replace YL980 as beyond (C) composition, obtain film-like adhesive composition by the method identical with comparative example 1.In table 2, represent the ratio of mixture of each composition.
(comparative example 4)
Except by YL980 and vinyl ether compound CHDVE(Nippon Carbide Kogyo K.K goods name, cyclohexanedimethanol divinyl ether) and with and as beyond (C) composition, obtain film-like adhesive composition by the method identical with comparative example 1.In table 2, represent the ratio of mixture of each composition.
(comparative example 5)
Except not using (A) composition, obtain film-like adhesive composition by the method identical with embodiment 2.In table 2, represent the ratio of mixture of each composition.
(comparative example 6)
Except using alicyclic epoxy compound EPOLEAD GT401(Daisel chemical industry Co., Ltd goods name, epoxidation BTCA four (3-cyclohexenyl methyl) is modified 6-caprolactone) replace YL980 as beyond (C) composition, obtain film-like adhesive composition by the method identical with comparative example 5.In table 2, represent the ratio of mixture of each composition.
(comparative example 7)
Except using oxetane compound OXT-121(Toagosei Co., Ltd goods name, 1,4-bis-[(3-oxa-cyclobutyl n-butoxy) methyl] benzene) replace YL980 as beyond (C) composition, obtain film-like adhesive composition by the method identical with comparative example 5.In table 2, represent the ratio of mixture of each composition.
(comparative example 8)
Except using YL980 and vinyl ether compound CHDVE(Nippon Carbide Kogyo K.K goods name) and with and as (C) composition, obtain film-like adhesive composition by the method identical with comparative example 5.In table 2, represent the ratio of mixture of each composition.
(comparative example 9)
Except using the new chemical industry of San-Aid SI-60(tri-Co., Ltd. goods name, 4-hydroxy phenyl methyl-Alpha-Naphthyl methyl sulfonium hexafluoro antimonate) replace the light trigger 2074 of (A) composition, and do not use beyond (B) composition, obtain film-like adhesive composition by the method identical with embodiment 2.In table 2, represent the ratio of mixture of each composition.
(comparative example 10)
Except using alicyclic epoxy compound EPOLEAD GT401(Daisel chemical industry Co., Ltd goods name, epoxidation BTCA four (3-cyclohexenyl methyl) is modified 6-caprolactone) replace YL980 as beyond (C) composition, obtain film-like adhesive composition by the method identical with comparative example 9.In table 2, represent the ratio of mixture of each composition.
(comparative example 11)
Except using oxetane compound OXT-121(Toagosei Co., Ltd goods name, 1,4-bis-[(3-oxa-cyclobutyl n-butoxy) methyl] benzene) replace YL980 as beyond (C) composition, obtain film-like adhesive composition by the method identical with comparative example 9.In table 2, represent the ratio of mixture of each composition.
In addition, in table 1 and table 2, " PI2074 " represents light trigger 2074.In addition, the ratio of mixture of each composition is expressed as mass parts.
[table 1]
Figure GDA00002537263400201
[table 2]
Figure GDA00002537263400211
[means of differential scanning calorimetry mensuration]
Use the embodiment 1 of glycidyl ether type epoxy compounds YL980 as composition C, 2 and the means of differential scanning calorimetry measurement result of comparative example 1 be shown in Fig. 1, use alicyclic epoxy compound GT401 to be shown in Fig. 2 as the embodiment 3 of composition C and the means of differential scanning calorimetry measurement result of comparative example 2, use trimethylene oxide OXT-121 to be shown in Fig. 3 as the embodiment 4 of composition C and the means of differential scanning calorimetry measurement result of comparative example 3, use glycidyl ether type epoxy compounds YL980 and vinyl ether CHDVE to be shown in Fig. 4 as the embodiment 5 of composition C and the means of differential scanning calorimetry measurement result of comparative example 4.
The embodiment 1～5 that contains salt compound and radical polymerization initiator, is observing exothermal peak near 100 ℃ He under low temperature.The embodiment 2 that uses the PEROYL L that 1 minute half life temperature is lower than embodiment 1, has observed exothermal peak at low temperature side by contrast.On the other hand,, containing the comparative example 1～4 of radical polymerization initiator, exothermal peak is not higher.
[curing degree determination test]
On hot plate, the film-like adhesive composition of embodiment 1～5, comparative example 1～11 is heated to 10 seconds with 110～160 ℃, it is solidified.By infrared absorption spectrum, obtain after area and the heating of strength of signal of epoxy group(ing), oxa-cyclobutyl before heating, vinyl the business of the area of strength of signal separately, and set it as curing degree.Respectively by the Fig. 5 that the results are shown in of embodiment 1～5, comparative example 1～8 the results are shown in Fig. 6, comparative example 9～11 the results are shown in Fig. 7.
The embodiment 1～5 that contains salt compound and radical polymerization initiator, demonstrates the high curing degree under low temperature.On the other hand,, containing the comparative example 1～4 of radical polymerization initiator, be not almost cured at low temperatures.In addition, containing the comparative example 5～8 of salt compound, be not cured.That is to say, although salt compound and radical polymerization initiator, the independent activity for cationically polymerizable material is all low, when both combine, demonstrates the high solidified nature under low temperature.In addition, use the comparative example 9～11 of the salt compound SI-60 that does not belong to the present invention (A) composition, even without radical polymerization initiator, also solidify at low temperatures.
[storage stability test]
The film-like adhesive composition of embodiment 1～5, comparative example 1～11 is placed 1～5 day in the thermostat of 40 ℃.By infrared absorption spectrum, obtain the curing degree after placement.Embodiment 1～5 the results are shown in Fig. 8, comparative example 1～8 the results are shown in Fig. 9, comparative example 9～11 the results are shown in Figure 10.
Embodiment 1～5, is not cured substantially, and storage stability is good.In addition, the comparative example 5～8 not being cured in curing degree determination test, is not cured substantially yet.On the other hand, comparative example 9～11, is cured lentamente, and storage stability is low.
From the above, as the radical polymerization initiator of the salt compound of (A) composition, conduct (B) composition with as the combination of the cationically polymerizable material of (C) composition, be the system of effect excellence of low temperature rapidly-curable and storage stability of getting both.
[making of linker]
By each film-like adhesive composition of embodiment 1～5 and comparative example 1～11, be transferred to glass substrate (healthy and free from worry #1737 from the PET resin molding of 2 × 20mm size, profile is 38mm × 28mm, thickness is 0.5mm, on surface, there is ITO(tin indium oxide) wiring diagram (pattern width is 50 μ m, spacing be 50 μ m)) on.Under the mounting condition shown in table 3 (temperature and time), applying 80MPa(converts with projection area) to load and carry out heating and pressurizing, IC chip is installed, and (profile is 1.7mm × 17.2mm, and thickness is 0.55mm, projection is of a size of 50 μ m × 50 μ m, the spacing of projection be 50 μ m).In addition, the film-like adhesive composition after storage stability test is installed similarly.
[evaluation of contact resistance]
Measure as above make linker in abutting connection with the resistance value between circuit (maximum values in 14 terminals measurement).Acquired results is shown in table 3.
While using the film-like adhesive composition of embodiment 1～5, before and after storage stability test, all demonstrate the good numerical value less than 5 Ω.While using the film-like adhesive composition of comparative example 1～8, cannot connect.In addition, while using the film-like adhesive composition of comparative example 9～11, after storage stability test, cannot connect.
[table 3]

Claims (42)

1. there is an adhesive composite for anisotropic conductive, wherein contain the represented salt compounded of iodine compound of (A) following general formula (I), (B) radical polymerization initiator, (C) cationically polymerizable material and (E) electroconductive particle,
R 1-I +-R 2 Y - (I)
In formula, R 1and R 2represent independently of one another to replace or unsubstituted aryl Y -represent negatively charged ion residue,
Wherein, described radical polymerization initiator is organo-peroxide,
Wherein, take the total amount of this adhesive composite as benchmark, the content of the vinyl compound that can carry out radical polymerization containing in described adhesive composite is 0～10 quality %.
2. adhesive composite as claimed in claim 1, wherein said Y -for BF 4 -, SbF 6 -, AsF 6 -, [P(R 6) a(F) 6-a] -, B(C 6f 5) 4 -, Ga(C 6f 5) 4 -, Ga(C 6f 5) 2f 2 -, Ga(C 6f 5) F 3 -or C(CF 3sO 2) 3 -, in formula, R 6represent the alkyl that at least part of hydrogen atom is replaced by fluorine atom, a represents 0～5 integer, in the time that a is more than 2 integers, and existing multiple R 6be same to each other or different to each other.
3. adhesive composite as claimed in claim 1, wherein said Y -for SbF 6 -, [P(R 6) a(F) 6-a] -, B(C 6f 5) 4 -or C(CF 3sO 2) 3 -, in formula, R 6represent the alkyl that at least part of hydrogen atom is replaced by fluorine atom, a represents 0～5 integer, in the time that a is more than 2 integers, and existing multiple R 6be same to each other or different to each other.
4. adhesive composite as claimed in claim 2 or claim 3, wherein said R 6for the alkyl more than 80% being replaced by fluorine atom of hydrogen atom.
5. adhesive composite as claimed in claim 2 or claim 3, wherein said R 6for the alkyl more than 90% being replaced by fluorine atom of hydrogen atom.
6. adhesive composite as claimed in claim 2 or claim 3, wherein said R 6for the perfluoroalkyl of straight chain or branch.
7. the adhesive composite as described in any one in claim 1～3, wherein said R 1with described R 2be the aryl replacing or unsubstituted carbon number is 6～12 independently of one another.
8. the adhesive composite as described in any one in claim 1～3, wherein said R 1with described R 2be phenyl, 1-naphthyl or 2-naphthyl independently of one another.
9. the adhesive composite as described in any one in claim 1～3, wherein said salt compounded of iodine compound is the material of giving 140～250 ℃ of peak temperatures in measuring with the means of differential scanning calorimetry of the mixture of glycidyl ether type epoxy compounds.
10. the adhesive composite as described in any one in claim 1～3,1 minute half life temperature of wherein said organo-peroxide is 80～170 ℃.
11. adhesive composites as described in any one in claim 1～3, wherein said organo-peroxide is diacyl peroxide, peroxy dicarbonate, peroxyester, ketal peroxide, dialkyl peroxide, hydroperoxide or silyl superoxide.
12. adhesive composites as described in any one in claim 1～3, wherein said organo-peroxide is that 1 minute half life temperature is peroxyester or the diacyl peroxide that 80～170 ℃ and molecular weight are 180～1000.
13. adhesive composites as described in any one in claim 1～3, the poor alpha-beta of the peak temperature α of the means of differential scanning calorimetry of 1 minute half life temperature β of wherein said organo-peroxide and the mixture of described salt compounded of iodine compound and glycidyl ether type epoxy compounds in measuring is 30～200 ℃.
14. adhesive composites as described in any one in claim 1～3, wherein take the total amount of described cationically polymerizable material as benchmark, described salt compounded of iodine compound containing proportional be 0.05～30 quality %.
15. adhesive composites as described in any one in claim 1～3, wherein take the total amount of described cationically polymerizable material as benchmark, described salt compounded of iodine compound containing proportional be 0.1～15 quality %.
16. adhesive composites as described in any one in claim 1～3, wherein take the total amount of described salt compounded of iodine compound as benchmark, described radical polymerization initiator containing proportional be more than 25 quality %.
17. adhesive composites as described in any one in claim 1～3, wherein take the total amount of described salt compounded of iodine compound as benchmark, described radical polymerization initiator containing proportional be more than 50 quality %.
18. adhesive composites as described in any one in claim 1～3, the cationoid polymerisation substituent equivalent of wherein said cationically polymerizable material is 43～1000.
19. adhesive composites as described in any one in claim 1～3, wherein take the total amount of adhesive composite as benchmark, described cationically polymerizable material containing proportional be 10～90 quality %.
20. adhesive composites as described in any one in claim 1～3, wherein said cationically polymerizable material contains at least one in the group of selecting free epoxy compounds, oxetane compound and vinyl ether compound composition.
21. adhesive composites as claimed in claim 20, wherein said epoxy compounds is glycidyl ether type epoxy compounds or alicyclic epoxy compound.
22. adhesive composites as described in any one in claim 1～3, wherein said cationically polymerizable material contains the glycidyl ether type epoxy compounds in 1 molecule with more than 2 epoxy group(ing).
23. the adhesive composite as described in any one in claim 1～3, wherein said cationically polymerizable material contains the alicyclic epoxy compound in 1 molecule with more than 2 epoxy group(ing).
24. adhesive composites as described in any one in claim 1～3, wherein said cationically polymerizable material contains the compound with more than 2 trimethylene oxide ring.
25. adhesive composites as described in any one in claim 1～3, wherein said cationically polymerizable material contains the represented compound of following logical formula V,
Figure FDA0000450807720000031
In formula, R 9represent the alkyl of hydrogen atom, fluorine atom or 1 valency, R 10represent hydrogen atom, alkyl or aryl, n represents 1～4 integer, works as R 10during for hydrogen atom, n is 1, in the time that n is more than 2 integers, with R 10in conjunction with multiple Sauerstoffatoms each other with R 10same carbon atom in conjunction with or and R 10different carbon atom combinations.
26. adhesive composites as described in any one in claim 1～3, wherein said cationically polymerizable material contains the compound in 1 molecule with more than 2 vinyl ether group.
27. adhesive composites as described in any one in claim 1～3, wherein said cationically polymerizable material contains the represented compound of following general formula (VI),
Figure FDA0000450807720000032
In formula, R 11represent alkyl or aryl, m represents 1～4 integer, in the time that m is more than 2 integers, with R 11in conjunction with multiple Sauerstoffatoms each other with R 11same carbon atom in conjunction with or and R 11different carbon atom combinations.
28. adhesive composites as described in any one in claim 1～3, the content of the wherein said vinyl compound that can carry out radical polymerization is 0～5 quality %.
29. adhesive composites as claimed in claim 28, the content of the wherein said vinyl compound that can carry out radical polymerization is 0～3 quality %.
30. adhesive composites as claimed in claim 29, the content of the wherein said vinyl compound that can carry out radical polymerization is 0 quality %.
31. adhesive composites as described in any one in claim 1～3, wherein further contain (D) film-forming properties polymkeric substance.
32. adhesive composites as claimed in claim 31, wherein said (D) film-forming properties polymkeric substance is at least one polymkeric substance of selecting the group from being made up of phenoxy resin class, polymethacrylate, polyacrylate(s), polyester, polyvinyl butyral class, styrene butadiene styrene segmented copolymer and epoxide modified thing thereof and styrene ethylene butylene styrene segmented copolymer and modifier thereof.
The adhesive composite described in any one in claim of right1~32 is solidified the cured article forming by 33..
Adhesive composite in 34. claim of right1~32 described in any one is as the application of adhesive for circuit connection.
Adhesive composite in 35. claim of right1~32 described in any one is as the application of the caking agent curing by heating.
Adhesive composite in 36. claim of right1~32 described in any one is in the application of manufacturing in caking agent.
Adhesive composite in 37. claim of right1~32 described in any one is in the application of manufacturing in adhesive for circuit connection.
Adhesive composite in 38. claim of right1~32 described in any one is in the application of manufacturing in anisotropic conductive film.
The adhesive composite described in any one in claim of right1~32 is made film-like adhesive membranaceous and that form by 39..
40. interelectrode methods of attachment, is characterized in that, make the adhesive composite described in any one in claim of right1~32 be present in relatively to electrode between, and carry out heating and pressurizing.
41. interelectrode methods of attachment, is characterized in that, make film-like adhesive described in claim 39 be present in relatively to electrode between, and carry out heating and pressurizing.
42. 1 kinds of linkers, have the electrode being formed by connecting by the method for attachment described in claim 40 or 41.
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