JP2011225831A - Curable composition and connected structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which has high wettability; therefore when used to connect members to be connected, hardly generates voids after connection, and to provide a connected structure using the curable composition.SOLUTION: The curable composition contains a thermosetting compound, a heat curing agent, and a polyether-modified siloxane. The connected structure 1 includes a first member 2 to be connected, a second member 4 to be connected, and a connecting part 3 which connects the first and the second members 2, 4 to be connected. The connecting part 3 is formed from the curable composition.

Description

  The present invention relates to a curable composition, and more particularly relates to a curable composition that has high wettability and therefore is less likely to cause voids after curing, and a connection structure using the curable composition.

  The epoxy resin composition has high adhesive strength of the cured product after curing, and is excellent in water resistance and heat resistance of the cured product. For this reason, epoxy resin compositions are widely used in various applications such as electricity, electronics, architecture, and vehicles.

  As an example of the epoxy resin composition, the following Patent Document 1 discloses an epoxy resin composition containing a naphthalene type epoxy resin, a thermosetting agent for epoxy resin, and a surfactant. Here, the surfactant is used so that the surface tension at 25 ° C. is 30.1 to 39.6 mN / m. In addition, specific examples of the surfactant include polyether-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, perfluoroalkylethylene oxide adduct, and perfluoroalkyl-containing oligomer. In the examples, these preferred surfactants are used.

  Moreover, in order to electrically connect various connection object members, conductive particles may be blended in the epoxy resin composition. The epoxy resin composition containing conductive particles is called an anisotropic conductive material.

  Specifically, the anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, connection between an IC chip and a circuit board having an ITO electrode, and the like. For example, after an anisotropic conductive material is arranged between the electrode of the IC chip and the electrode of the circuit board, these electrodes can be connected by heating and pressurizing.

  As an example of the anisotropic conductive material, Patent Document 2 below includes an epoxy resin, rubber-like polymer particles, a thermally active latent epoxy curing agent, high softening point polymer particles, and conductive particles. An anisotropic conductive paste is disclosed.

Japanese Patent No. 3478225 JP 2000-345010 A

  In recent years, in the field of precision electronic equipment, the density of circuits has been increasing, and the electrode width and electrode interval have become extremely narrow. When the circuit board on which such fine electrodes are formed is connected with the epoxy resin composition described in Patent Document 1, the wettability of the epoxy resin composition is not sufficient. May occur. Even in the anisotropic conductive paste described in Patent Document 2, since the wettability is not sufficient, voids are likely to occur similarly.

  An object of the present invention is to provide a curable composition that has high wettability, and therefore is less likely to cause voids after being connected, and a connection structure using the curable composition. That is.

  According to a broad aspect of the present invention, there is provided a curable composition comprising a thermosetting compound, a thermosetting agent, and a polyether-modified siloxane.

  On the specific situation with the curable composition which concerns on this invention, the said thermosetting compound is a thermosetting compound which has at least 1 sort (s) of an epoxy group and a thiirane group. The thermosetting compound preferably contains a compound having an epoxy group. The thermosetting compound preferably contains a compound having a thiirane group. Moreover, it is preferable that the said thermosetting compound contains the compound which has an epoxy group, and the compound which has a thiirane group.

  In another specific aspect of the curable composition according to the present invention, a (meth) acryl compound and a photopolymerization initiator are further included.

  In another specific aspect of the curable composition according to the present invention, the content of the polyether-modified siloxane is 0.01 to 5% by weight in 100% by weight of the curable composition.

  In another specific aspect of the curable composition according to the present invention, conductive particles are further included, and the curable composition is an anisotropic conductive material.

  In another specific aspect of the curable composition according to the present invention, the curable composition is an anisotropic conductive material used for connection between a flexible printed board and a glass substrate, or between a semiconductor chip and a flexible printed board. Material.

  The connection structure according to the present invention includes a first connection target member, a second connection target member, and a connection portion connecting the first and second connection target members, and the connection The part is formed by a curable composition constituted according to the present invention.

  In a specific aspect of the connection structure according to the present invention, the curable composition is an anisotropic conductive material including conductive particles, and the first and second connection target members are the conductive particles. Are electrically connected.

  In another specific aspect of the connection structure according to the present invention, there is provided a connection structure manufacturing method for connecting a flexible printed circuit board and a glass substrate, or for connecting a semiconductor chip and a glass substrate. As the connection target member and the first connection target member, a flexible printed circuit board and a glass substrate are used, or a semiconductor chip and a glass substrate are used.

  Since the curable composition according to the present invention contains a thermosetting compound, a thermosetting agent, and a polyether-modified siloxane, the wettability is high. Therefore, when the curable composition which concerns on this invention is hardened and various connection object members are connected, it can suppress that a void arises after a connection.

FIG. 1 is a partially cutaway cross-sectional view schematically showing a connection structure using a curable composition according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

(Curable composition)
The curable composition concerning this invention contains a thermosetting compound, a thermosetting agent, and polyether modified siloxane. Since the curable composition concerning this invention has such a composition, wettability is high. Accordingly, when the connection target member is connected with the curable composition, voids are less likely to occur at the interface between the cured product of the curable composition and the connection target member after the connection. Since voids can be reduced, it is difficult for peeling of the cured product to occur, and connection reliability can be improved.

  The curable composition according to the present invention preferably has a surface tension at 25 ° C. of 35 to 45 mN / m. In this case, the wettability of the curable composition is further enhanced, and voids are less likely to occur after connection. When the curable composition has high wettability, the curable composition uniformly spreads on the connection target member such as a circuit board having a concavo-convex surface, and in particular, the fillability of the curable composition into the concave portion is increased. Since the curable composition concerning this invention contains polyether modified siloxane, the said surface tension can be easily controlled in the range of 35-45 mN / m. From the viewpoint of further improving the wettability of the curable composition, a more preferable lower limit of the surface tension at 25 ° C. of the curable composition is 37 mN / m.

  From the viewpoint of making wettability higher and making voids less likely to occur, the curable composition according to the present invention is a curable composition for connecting an electronic device to a circuit board, and is at 25 ° C. The polyether-modified siloxane is preferably included so that the surface tension is 35 to 45 mN / m.

[Thermosetting compound]
The thermosetting compound contained in the curable composition according to the present invention is not particularly limited as long as it is cured by heating. As for a thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  Examples of the thermosetting compound include epoxy compounds, oxetane compounds, episulfide compounds (thiirane group-containing compounds), polyimide compounds, phenol compounds, melamine compounds, unsaturated polyester compounds, and bismaleimide compounds.

  The thermosetting compound is preferably a thermosetting compound having at least one of an epoxy group and a thiirane group (hereinafter sometimes abbreviated as compound A). Compound A is at least one selected from the group consisting of a compound having an epoxy group, a compound having a thiirane group, and a compound having an epoxy group and a thiirane group. The compound having an epoxy group is an epoxy compound. The compound having a thiirane group is an episulfide compound (thiirane group-containing compound). The compound having an epoxy group and a thiirane group is a thiirane group-containing epoxy compound. By using Compound A, the curing rate of the curable composition can be increased. Furthermore, the adhesive force of the hardened | cured material of a curable composition can be made high. As for the said compound A, only 1 type may be used and 2 or more types may be used together.

  The thermosetting composition may contain a compound having an epoxy group, may contain a compound having a thiirane group, and contains both a compound having an epoxy group and a compound having a thiirane group. You may do it.

  From the viewpoint of curing more rapidly at a low temperature, the compound A preferably contains at least one of a compound having a thiirane group and a compound having an epoxy group and a thiirane group, and has a thiirane group. It is more preferable to contain a compound. From the viewpoint of improving the storage stability and handleability of the curable composition, the compound A is an epoxy compound having an epoxy group, a compound having a thiirane group, and at least one of a compound having an epoxy group and a thiirane group. It is preferable to contain an epoxy compound having an epoxy group and a compound having a thiirane group.

  In 100% by weight of the compound A, the content of the compound having a thiirane group is preferably in the range of 0.01 to 100% by weight. The more preferable lower limit of the content of the compound having a thiirane group in 100% by weight of the compound A is 5% by weight, the still more preferable lower limit is 10% by weight, and the particularly preferable lower limit is 20% by weight. Since the compound having a thiirane group has a thiirane group, the reactivity is higher than that of a compound having an epoxy group. Therefore, the higher the content of the compound having a thiirane group, the faster the curable composition can be cured at a low temperature.

  The thermosetting compound preferably has an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, chrysene ring, triphenylene ring, tetraphen ring, pyrene ring, pentacene ring, picene ring, and perylene ring. Especially, it is preferable that the said aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring, and it is more preferable that it is a benzene ring or a naphthalene ring. A naphthalene ring is preferred because it has a planar structure and can be cured more rapidly.

  Examples of the epoxy compound include bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, phenol aralkyl type epoxy resin, and naphthol aralkyl type epoxy resin. , Dicyclopentadiene type epoxy resins, anthracene type epoxy resins, epoxy resins having an adamantane skeleton, epoxy resins having a tricyclodecane skeleton, and epoxy resins having a triazine nucleus in the skeleton.

  Specific examples of the epoxy compound include, for example, epichlorohydrin and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol D type epoxy resin and the like, bisphenol type epoxy resin, and epichlorohydrin and phenol novolac or cresol novolak. And epoxy novolac resins derived from Various epoxy compounds having two or more oxirane groups in one molecule such as glycidylamine, glycidyl ester, and alicyclic or heterocyclic may be used.

  Furthermore, as the epoxy compound, for example, an epoxy compound having a structure represented by the following formula (11-1), (12-1), (13), (17) or (18) may be used.

  Compound A is a monomer of an epoxy compound having a structure represented by the following formula (21), a multimer in which at least two epoxy compounds are bonded, or a mixture of the monomer and the multimer. May be included.

  In said formula (21), R1 represents a C1-C5 alkylene group, R2 represents a C1-C5 alkylene group, R3 is a hydrogen atom, a C1-C5 alkyl group, or following formula ( 22), R4 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a structure represented by the following formula (23).

  In said formula (22), R5 represents a C1-C5 alkylene group.

  In said formula (23), R6 represents a C1-C5 alkylene group.

  The epoxy compound having the structure represented by the above formula (21) has an unsaturated double bond and at least two epoxy groups. By using the epoxy compound having the structure represented by the above formula (21), the curable composition can be rapidly cured at a low temperature.

  The compound A includes a monomer of a compound having a structure represented by the following formula (31), a multimer in which at least two of the compounds are bonded, or a mixture of the monomer and the multimer. May be.

  In the above formula (31), R1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a structure represented by the following formula (32), R2 represents an alkylene group having 1 to 5 carbon atoms, and R3 represents carbon. X 1 represents an oxygen atom or a sulfur atom, and X 2 represents an oxygen atom or a sulfur atom.

  In said formula (32), R4 represents a C1-C5 alkylene group, X3 represents an oxygen atom or a sulfur atom.

  The epoxy compound corresponding to the compound having the structure represented by the above formula (31) can be synthesized, for example, as follows.

  A raw material compound, a fluorene compound having a hydroxyl group, epichlorohydrin, sodium hydroxide, and methanol are mixed, cooled, and reacted. Thereafter, an aqueous sodium hydroxide solution is dropped. After dripping, it is further reacted to obtain a reaction solution. Next, water and toluene are added to the reaction solution, and the toluene layer is taken out. The toluene layer is washed with water and then dried to remove water and the solvent. In this way, an epoxy compound corresponding to the compound having the structure represented by the formula (31) can be easily obtained. In addition, the fluorene compound which has a hydroxyl group which is a raw material compound is marketed, for example from JFE Chemical Company etc., for example.

  Further, the thiirane group-containing compound corresponding to the compound having the structure represented by the above formula (31) has the epoxy group of the epoxy compound corresponding to the compound having the structure represented by the above formula (31) as a thiirane group. It can be synthesized by conversion. For example, after adding an epoxy compound that is a raw material compound or a solution containing the epoxy compound to a solution containing thiocyanate, an epoxy group is easily converted into a thiirane group by further adding a solution containing thiocyanate. it can.

  The compound A may contain an epoxy compound having a heterocyclic ring containing a nitrogen atom. The epoxy compound having a heterocyclic ring containing a nitrogen atom is preferably an epoxy compound represented by the following formula (41) or an epoxy compound represented by the following formula (42). By using such a compound, the curing rate of the curable composition can be further increased, and the heat resistance of the cured product can be further enhanced.

  In said formula (41), R1-R3 represents a C1-C5 alkylene group, respectively, Z represents an epoxy group or a hydroxymethyl group. R1 to R3 may be the same or different.

  In the above formula (42), R1 to R3 each represent an alkylene group having 1 to 5 carbon atoms, p, q and r each represents an integer of 1 to 5, and R4 to R6 each represent an alkylene having 1 to 5 carbon atoms. Represents a group. R1 to R3 may be the same or different. p, q and r may be the same or different. R4 to R6 may be the same or different.

  The epoxy compound having a heterocyclic ring containing a nitrogen atom is preferably triglycidyl isocyanurate or trishydroxyethyl isocyanurate triglycidyl ether. By using these compounds, the curing rate of the curable composition can be further increased.

  The compound A preferably contains an epoxy compound having an aromatic ring. By using an epoxy compound having an aromatic ring, the curing rate of the curable composition can be further increased and the curable composition can be easily applied. From the viewpoint of further improving the applicability of the curable composition, the aromatic ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. Examples of the epoxy compound having an aromatic ring include resorcinol diglycidyl ether or 1,6-naphthalenediglycidyl ether. Of these, resorcinol diglycidyl ether is particularly preferable. By using resorcinol diglycidyl ether, the curing rate of the curable composition can be increased and the curable composition can be easily applied.

  From the viewpoint of curing more rapidly at a low temperature, the episulfide compound has a structure represented by the following formula (1-1), (2-1), (3), (7) or (8). Is preferred. In the following formula (1-1), the bonding sites of the six groups bonded to the benzene ring are not particularly limited. In the following formula (2-1), the bonding sites of the eight groups bonded to the naphthalene ring are not particularly limited. In the following formula (7), the bonding sites of the two groups bonded to the benzene ring are not particularly limited. In the following formula (8), the bonding site of the two groups bonded to the cyclo ring is not particularly limited.

  In said formula (1-1), R1 and R2 represent a C1-C5 alkylene group, respectively. Of the four groups R3, R4, R5 and R6, 2 to 4 groups represent hydrogen. The group which is not hydrogen among R3, R4, R5 and R6 represents a group represented by the following formula (4). All four groups of R3, R4, R5 and R6 may be hydrogen. One or two of the four groups of R3, R4, R5 and R6 is a group represented by the following formula (4), and among the four groups of R3, R4, R5 and R6 The group that is not a group represented by the following formula (4) may be hydrogen.

  In said formula (4), R7 represents a C1-C5 alkylene group.

  In said formula (2-1), R51 and R52 represent a C1-C5 alkylene group, respectively. Of the 6 groups of R53, R54, R55, R56, R57 and R58, 4 to 6 groups represent hydrogen. The group which is not hydrogen among R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (5). All of the six groups of R53, R54, R55, R56, R57 and R58 may be hydrogen. One or two of the six groups of R53, R54, R55, R56, R57 and R58 are groups represented by the following formula (5), and R53, R54, R55, R56, R57 and R58. Of these, a group that is not a group represented by the following formula (5) may be hydrogen.

  In said formula (5), R59 represents a C1-C5 alkylene group.

  In said formula (3), R101 and R102 represent a C1-C5 alkylene group, respectively. Six to eight groups out of the eight groups of R103, R104, R105, R106, R107, R108, R109 and R110 represent hydrogen. The group which is not hydrogen among R103, R104, R105, R106, R107, R108, R109 and R110 represents a group represented by the following formula (6). All of the eight groups of R103, R104, R105, R106, R107, R108, R109 and R110 may be hydrogen. One or two of the eight groups of R103, R104, R105, R106, R107, R108, R109 and R110 are groups represented by the following formula (6), and R103, R104, R105, R106 , R107, R108, R109 and R110, which is not a group represented by the following formula (6), may be hydrogen.

  In said formula (6), R111 represents a C1-C5 alkylene group.

  In said formula (7), R1 and R2 represent a C1-C5 alkylene group, respectively.

  In said formula (8), R3 and R4 represent a C1-C5 alkylene group, respectively.

  The compound A may contain an epoxy compound represented by the following formula (11-1), (12-1), (13), (17) or (18). In the following formula (11-1), the bonding sites of the six groups bonded to the benzene ring are not particularly limited. In the following formula (12-1), the bonding sites of the eight groups bonded to the naphthalene ring are not particularly limited. In the following formula (17), the bonding site of the two groups bonded to the benzene ring is not particularly limited. In the following formula (18), the bonding site of the two groups bonded to the cyclo ring is not particularly limited.

  In said formula (11-1), R11 and R12 represent a C1-C5 alkylene group, respectively. 2 to 4 groups out of the four groups of R13, R14, R15 and R16 represent hydrogen. The group which is not hydrogen among R13, R14, R15 and R16 represents a group represented by the following formula (14). All four groups of R13, R14, R15 and R16 may be hydrogen. One or two of the four groups of R13, R14, R15 and R16 is a group represented by the following formula (14), and among the four groups of R13, R14, R15 and R16 The group that is not a group represented by the following formula (14) may be hydrogen.

  In said formula (14), R17 represents a C1-C5 alkylene group.

  In said formula (12-1), R61 and R62 represent a C1-C5 alkylene group, respectively. 4 to 6 groups out of 6 groups of R63, R64, R65, R66, R67 and R68 represent hydrogen. The group which is not hydrogen among R63, R64, R65, R66, R67 and R68 represents a group represented by the following formula (15). All of the six groups of R63, R64, R65, R66, R67 and R68 may be hydrogen. One or two of the six groups R63, R64, R65, R66, R67 and R68 are groups represented by the following formula (15), and R63, R64, R65, R66, R67 and R68. Of these six groups, the group that is not the group represented by the following formula (15) may be hydrogen.

  In said formula (15), R69 represents a C1-C5 alkylene group.

  In said formula (13), R121 and R122 represent a C1-C5 alkylene group, respectively. Six to eight groups among the eight groups of R123, R124, R125, R126, R127, R128, R129 and R130 represent hydrogen. The group which is not hydrogen among R123, R124, R125, R126, R127, R128, R129 and R130 represents a group represented by the following formula (16). All of the eight groups of R123, R124, R125, R126, R127, R128, R129, and R130 may be hydrogen. One or two of eight groups of R123, R124, R125, R126, R127, R128, R129, and R130 are groups represented by the following formula (16), and R123, R124, R125, R126 Of the eight groups R127 and R128, a group that is not a group represented by the following formula (16) may be hydrogen.

  In said formula (16), R131 represents a C1-C5 alkylene group.

  In said formula (17), R5 and R6 represent a C1-C5 alkylene group, respectively.

  In said formula (18), R7 and R8 represent a C1-C5 alkylene group, respectively.

  From the viewpoint of curing more rapidly at a low temperature, the compound A is represented by the formula (1-1), the formula (2-1), the formula (3), the formula (7), or the formula (8). And the epoxy compound represented by the above formula (11-1), the above formula (12-1), the above formula (13), the above formula (17) or the above formula (18). It is preferable. Further, the compound A is represented by the compound represented by the formula (3), the formula (7) or the formula (8), the formula (13), the formula (17) or the formula (18). It is preferable to contain an epoxy compound.

  A method for producing an episulfide compound having a structure represented by the above formula (1-1), (2-1), (3), (7) or (8), and the above formulas (1-1), (2- An episulfide compound having a structure represented by 1), (3), (7) or (8) and the above formula (11-1), (12-1), (13), (17) or (18) The manufacturing method of the mixture with an epoxy compound represented by (Hereinafter, it may abbreviate as the mixture X) is not specifically limited. As this manufacturing method, for example, an epoxy compound represented by the above formula (1-1), (2-1), (3), (7) or (8) is prepared, and all or part of the epoxy compound is prepared. The manufacturing method which converts the epoxy group of this into a thiirane group is mentioned.

  In the above production method, the epoxy compound represented by the above formula (11-1), (12-1), (13), (17) or (18) or the epoxy is added to the first solution containing thiocyanate. A method of adding a second solution containing thiocyanate continuously or intermittently after adding a solution containing the compound continuously or intermittently is preferable. By this method, all or part of the epoxy groups of the epoxy compound can be converted into thiirane groups. As a result of converting some epoxy groups of the epoxy compound to thiirane groups, the mixture X is obtained.

  The curable composition may include a modified phenoxy resin having a thiirane group in which an epoxy group of the phenoxy resin is converted to a thiirane group as an episulfide compound. Using a sulfurizing agent, the epoxy group of the phenoxy resin can be converted to a thiirane group by a conventionally known method.

  The “phenoxy resin” is generally a resin obtained by reacting, for example, an epihalohydrin and a divalent phenol compound, or a resin obtained by reacting a divalent epoxy compound and a divalent phenol compound.

  In the above reaction for obtaining a phenoxy resin, by using a compound having a thiirane group obtained by converting the epoxy group of the compound having an epoxy group into a thiirane group instead of the compound having an epoxy group as a raw material of the phenoxy resin, The phenoxy resin which has can be obtained. Furthermore, a phenoxy resin having a thiirane group can also be obtained by preparing a phenoxy resin having an epoxy group and converting the epoxy group of the phenoxy resin having an epoxy group into a thiirane group.

  In 100% by weight of the curable composition, the content of the thermosetting compound is preferably 40 to 95% by weight. In 100% by weight of the curable composition, a more preferable lower limit of the content of the thermosetting compound is 50% by weight, and a more preferable upper limit is 70% by weight. When content of the said thermosetting compound satisfy | fills the said minimum and upper limit, a curable composition can fully be thermosetted and the adhesive force of the hardened | cured material of a curable composition can fully be made high.

[Thermosetting agent]
The curable composition according to the present invention preferably contains a thermosetting agent. The curing agent includes a thermal radical initiator. As for a thermosetting agent, only 1 type may be used and 2 or more types may be used together.

  The said thermosetting agent is not specifically limited. Examples of the thermosetting agent include an imidazole thermosetting agent, an amine thermosetting agent, a phenol thermosetting agent, a polythiol thermosetting agent, an acid anhydride, and a thermal radical initiator. Especially, since a curable composition can be hardened more rapidly at low temperature, an imidazole thermosetting agent, a polythiol thermosetting agent, or an amine thermosetting agent is preferable. Moreover, since a storage stability can be improved when the said thermosetting compound and the said thermosetting agent are mixed, a latent thermosetting agent is preferable. The latent thermosetting agent is preferably a latent imidazole thermosetting agent, a latent polythiol thermosetting agent or a latent amine thermosetting agent. As for these thermosetting agents, only 1 type may be used and 2 or more types may be used together. In addition, the said thermosetting agent may be coat | covered with polymeric substances, such as a polyurethane resin or a polyester resin.

  The imidazole thermosetting agent is not particularly limited, but 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2 , 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s -A triazine isocyanuric acid adduct etc. are mentioned.

  Examples of the polythiol thermosetting agent include, but are not limited to, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. It is done.

  Although it does not specifically limit as said amine thermosetting agent, Hexamethylene diamine, octamethylene diamine, decamethylene diamine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraspiro [5.5] Examples include undecane, bis (4-aminocyclohexyl) methane, metaphenylenediamine, and diaminodiphenylsulfone.

  Among the above curing agents, polythiol compounds or acid anhydrides are preferably used. Since the curing rate of the curable composition can be further increased, a polythiol compound is more preferably used.

  Among the polythiol compounds, pentaerythritol tetrakis-3-mercaptopropionate is more preferable. By using this polythiol compound, the curing rate of the curable composition can be further increased.

  The thermal radical initiator is not particularly limited, and examples thereof include azo compounds and peroxides. Examples of the peroxide include diacyl peroxide compounds, peroxyester compounds, hydroperoxide compounds, peroxydicarbonate compounds, peroxyketal compounds, dialkyl peroxide compounds, and ketone peroxide compounds.

  Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), and 2,2′-azobis (2,4-dimethylvaleronitrile). 1,1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, dimethyl-2,2′-azobis (2-methylpropionate), dimethyl-1,1 ′ -Azobis (1-cyclohexanecarboxylate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-amidinopropane) dihydrochloride, 2-tert-butylazo-2-cyanopropane 2,2′-azobis (2-methylpropionamide) dihydrate, 2,2′-azobis (2,4,4-trimethylpentane), and the like.

  Examples of the diacyl peroxide compound include benzoyl peroxide, diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, and disuccinic acid peroxide. Examples of the peroxyester compound include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, tert-hexylperoxyneodecanoate, and tert-butylperoxyneo. Decanoate, tert-butylperoxyneoheptanoate, tert-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2 , 5-di (2-ethylhexanoylperoxy) hexane, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate, tert -Butyl peroxyisobutyrate, tert-butyl per Kishiraureto, tert- butylperoxy isophthalate, tert- butylperoxy acetate, tert- butylperoxy octoate and tert- butyl peroxybenzoate, and the like. Examples of the hydroperoxide compound include cumene hydroperoxide and p-menthane hydroperoxide. Examples of the peroxydicarbonate compound include di-sec-butyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, and di- (2-ethylhexyl) peroxycarbonate and the like. Other examples of the peroxide include methyl ethyl ketone peroxide, potassium persulfate, and 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane.

  The decomposition temperature for obtaining the 10-hour half-life of the thermal radical initiator is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, preferably 80 ° C. or lower, more preferably 70 ° C. or lower. When the decomposition temperature for obtaining the 10-hour half-life of the thermal radical initiator is less than 30 ° C., the storage stability of the curable composition tends to decrease, and when it exceeds 80 ° C., the curable composition There is a tendency that it is difficult to sufficiently heat cure.

  The content of the thermosetting agent is not particularly limited. Content of the said hardening | curing agent is suitably adjusted according to the kind of hardening | curing agent. The content of the thermosetting agent is within the range of 0.01 to 200 parts by weight with respect to 100 parts by weight of the thermosetting compound (or compound A when the thermosetting compound is compound A). preferable.

  When the curing agent is a curing agent other than a thermal radical initiator, the preferred lower limit of the content of the thermosetting agent is 0.01 parts by weight, and the more preferred lower limit is 100 parts by weight of the thermosetting compound. 30 parts by weight, the preferred upper limit is 200 parts by weight, the more preferred upper limit is 100 parts by weight, the still more preferred upper limit is 75 parts by weight, and the particularly preferred upper limit is 40 parts by weight. When content of a thermosetting agent satisfy | fills the said minimum, it is easy to fully harden a curable composition. When content of a thermosetting agent satisfy | fills the said upper limit, the excess thermosetting agent which did not participate in hardening after hardening will not remain easily, and the heat resistance of hardened | cured material can be improved further.

  In addition, when the said thermosetting agent is an imidazole thermosetting agent or a phenol thermosetting agent, content of an imidazole thermosetting agent or a phenol thermosetting agent is 1-15 weight part with respect to 100 weight part of said thermosetting compounds. It is preferable to be within the range. Further, when the thermosetting agent is an amine thermosetting agent, a polythiol thermosetting agent or an acid anhydride, the amine thermosetting agent, the polythiol thermosetting agent or the acid anhydride is used with respect to 100 parts by weight of the thermosetting compound. The content is preferably in the range of 15 to 40 parts by weight.

  When the curing agent is a thermal radical initiator, the content of the thermal radical initiator is not particularly limited. The content of the thermal radical initiator is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, preferably 10 parts by weight or less, more preferably 100 parts by weight of the thermosetting compound. Is 5 parts by weight or less. When the content of the thermal radical curing agent is not less than the above lower limit and not more than the above upper limit, the curable composition can be sufficiently thermoset.

  The curable composition according to the present invention preferably further contains a curing accelerator. By using a curing accelerator, the curing rate of the curable composition can be further increased. As for a hardening accelerator, only 1 type may be used and 2 or more types may be used together.

  Specific examples of the curing accelerator include imidazole curing accelerators and amine curing accelerators. Of these, imidazole curing accelerators are preferred. In addition, an imidazole hardening accelerator or an amine hardening accelerator can be used also as an imidazole thermosetting agent or an amine thermosetting agent.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine and 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid addition Thing etc. are mentioned.

  A preferable lower limit of the content of the curing accelerator is 0.5 parts by weight, a more preferable lower limit is 1 part by weight, a preferable upper limit is 6 parts by weight, and a more preferable upper limit is 4 parts by weight with respect to 100 parts by weight of the thermosetting compound. Part. When the content of the curing accelerator satisfies the above lower limit, it is easy to sufficiently cure the curable composition. When content of a hardening accelerator satisfy | fills the said upper limit, it will become difficult to remain | survive the excessive hardening accelerator which did not participate in hardening after hardening.

[Polyether-modified siloxane]
The polyether-modified siloxane contained in the curable composition according to the present invention acts as a wettability adjusting agent.

  From the viewpoint of further increasing the wettability and making it more difficult to generate voids, the weight average molecular weight of the polyether-modified siloxane is preferably in the range of 400 to 5,000. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC). From the viewpoint of further increasing the wettability and making it more difficult to generate voids, the more preferable lower limit of the weight average molecular weight of the polyether-modified siloxane is 1000, and the more preferable upper limit is 4000.

  In 100% by weight of the curable composition, the content of the polyether-modified siloxane is preferably 0.01 to 5% by weight. In 100% by weight of the curable composition, a more preferable upper limit of the content of the polyether-modified siloxane is 3.0% by weight. When content of the said polyether modified siloxane satisfy | fills the said minimum and upper limit, the wettability of a curable composition will become still higher, and a void will become harder to produce after connection.

(Photocurable composition)
The curable composition concerning this invention may further contain the photocurable compound so that it may harden | cure also by light irradiation. Moreover, when a photocurable compound is contained, the curable composition concerning this invention may further contain the photoinitiator. By using the photocurable compound and the photopolymerization initiator, the curable composition can be cured by light irradiation. Furthermore, the curable composition can be semi-cured to reduce the fluidity of the curable composition.

  The said photocurable compound is not specifically limited. As the photocurable compound, a (meth) acrylic resin or a cyclic ether group-containing resin is preferably used, and a (meth) acrylic resin is more preferably used. The (meth) acrylic resin indicates a methacrylic resin and an acrylic resin. The (meth) acrylic resin has a (meth) acryloyl group. The (meth) acryloyl group represents a methacryloyl group and an acryloyl group.

  As the (meth) acrylic resin, an ester compound obtained by reacting (meth) acrylic acid and a compound having a hydroxyl group, an epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy compound, or Urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with isocyanate is preferably used.

  The ester compound obtained by making the said (meth) acrylic acid and the compound which has a hydroxyl group react is not specifically limited. As the ester compound, any of a monofunctional ester compound, a bifunctional ester compound, and a trifunctional or higher functional ester compound can be used.

  The photocurable compound is a light and thermosetting compound (hereinafter also referred to as a partially (meth) acrylated epoxy resin) having at least one group out of an epoxy group and a thiirane group and a (meth) acryl group. It is preferable to include. The photocurable compound having at least one group out of the epoxy group and thiirane group and having a (meth) acryloyl group is a part of a compound having two or more epoxy groups or two or more thiirane groups. A photocurable compound obtained by converting an epoxy group or a part of thiirane group into a (meth) acryloyl group is preferable. Such a photocurable compound is a partially (meth) acrylated epoxy compound or a partially (meth) acrylated episulfide compound.

  The photocurable compound is preferably a reaction product of a compound having two or more epoxy groups or two or more thiirane groups and (meth) acrylic acid. This reaction product is obtained by reacting a compound having two or more epoxy groups or two or more thiirane groups with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. It is preferable that 20% or more of the epoxy group or thiirane group is converted (converted) to a (meth) acryloyl group. The conversion is more preferably 30% or more, preferably 80% or less, more preferably 70% or less. Most preferably, 40% or more and 60% or less of the epoxy group or thiirane group is converted to a (meth) acryloyl group.

  Examples of the partially (meth) acrylated epoxy compound include bisphenol type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, carboxylic acid anhydride-modified epoxy (meth) acrylate, and phenol novolac type epoxy (meth) acrylate. Is mentioned.

  As the photocurable compound, a modified phenoxy resin obtained by converting a part of epoxy groups or a part of thiirane groups of a phenoxy resin having two or more epoxy groups or two or more thiirane groups into (meth) acryloyl groups is used. Also good. That is, a modified phenoxy resin having an epoxy group or thiirane group and a (meth) acryloyl group may be used.

  When a photocurable compound other than the photocurable compounds described above is included, the photocurable compound may be a crosslinkable compound or a non-crosslinkable compound.

  Specific examples of the crosslinkable compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, (poly ) Ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerol methacrylate acrylate, pentaerythritol tri (meth) acrylate, tri Examples include methylolpropane trimethacrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, polyester (meth) acrylate, and urethane (meth) acrylate.

  Specific examples of the non-crosslinkable compound include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl Examples include (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, and tetradecyl (meth) acrylate.

  From the viewpoint of efficiently photocuring the curable composition, the photocurable compound (when the photocurable compound is a (meth) acrylic resin) with respect to 100 parts by weight of the thermosetting compound. The preferred lower limit of the content of (meth) acrylic resin) is 0.1 parts by weight, the more preferred lower limit is 1 part by weight, the still more preferred lower limit is 10 parts by weight, the particularly preferred lower limit is 50 parts by weight, the preferred upper limit is 10,000 parts by weight, A more preferred upper limit is 1000 parts by weight, and a still more preferred upper limit is 500 parts by weight.

(Photopolymerization initiator)
When a photocurable compound is included, the curable composition according to the present invention may further include a photopolymerization initiator. The photopolymerization initiator is not particularly limited. The photopolymerization initiator includes a photo radical initiator. As for the said photoinitiator, only 1 type may be used and 2 or more types may be used together.

  Specific examples of the photopolymerization initiator include acetophenone photopolymerization initiator (acetophenone photoradical initiator), benzophenone photopolymerization initiator (benzophenone photoradical initiator), thioxanthone, ketal photopolymerization initiator (ketal photoradical initiator). ), Halogenated ketones, acyl phosphinoxides, acyl phosphonates, and the like. You may use photoinitiators other than these.

  Specific examples of the acetophenone photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, methoxy Examples include acetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-cyclohexylacetophenone. Specific examples of the ketal photopolymerization initiator include benzyl dimethyl ketal.

  The content of the photopolymerization initiator is not particularly limited. The preferred lower limit of the content of the photopolymerization initiator is 0.1 parts by weight, more preferred lower limit is 0.2 parts by weight, and still more preferred lower limit is 2 parts by weight, with respect to 100 parts by weight of the photocurable compound. Is 10 parts by weight, and a more preferred upper limit is 5 parts by weight. When the content of the photopolymerization initiator satisfies the above lower limit, it is easy to sufficiently obtain the effect of adding the photopolymerization initiator. When content of a photoinitiator satisfy | fills the said upper limit, the adhesive force of the hardened | cured material of a curable composition will become high enough.

  The curable composition according to the present invention preferably further contains a filler. By using the filler, latent heat expansion of the cured product of the curable composition can be suppressed. As for a filler, only 1 type may be used and 2 or more types may be used together.

  Specific examples of the filler include silica, aluminum nitride, and alumina. The filler is preferably filler particles. The average particle size of the filler particles is preferably in the range of 0.1 to 1.0 μm. When the average particle diameter of the filler particles is within the above range, latent heat expansion of the cured product of the curable composition can be further suppressed. “Average particle diameter” refers to a volume average diameter measured by a dynamic laser scattering method.

  The content of the filler is preferably in the range of 50 to 900 parts by weight with respect to 100 parts by weight of the compound A. When the filler content is within the above range, the latent thermal expansion of the cured product of the curable composition can be further suppressed.

  The curable composition according to the present invention may contain a solvent. By using the solvent, the viscosity of the curable composition can be easily adjusted. Furthermore, for example, when the compound A is solid, the dispersibility of the compound A can be enhanced by adding a solvent to the solid compound A and dissolving it.

  Examples of the solvent include ethyl acetate, methyl cellosolve, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran, and diethyl ether.

  The curable composition concerning this invention may further contain the ion-trapping agent or the silane coupling agent as needed.

[Curable composition containing conductive particles]
When the curable composition according to the present invention further contains conductive particles, the curable composition can be used as an anisotropic conductive material.

  For example, the conductive particles electrically connect the electrodes of the circuit board and the semiconductor chip. The conductive particles are not particularly limited as long as they are conductive particles. Examples of the conductive particles include conductive particles whose surfaces are coated with a metal layer, such as organic particles, inorganic particles, organic-inorganic hybrid particles, or metal particles, or metal particles that are substantially composed of only metal. It is done. The metal layer is not particularly limited. Examples of the metal layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, or a metal layer containing tin.

  From the viewpoint of further enhancing the conduction reliability between the electrodes, the conductive particles preferably include resin particles and a conductive layer provided on the surface of the resin particles.

  The content of the conductive particles is not particularly limited. In 100% by weight of the curable composition, the content of the conductive particles is preferably in the range of 0.1 to 20% by weight. In 100% by weight of the curable composition, the more preferable lower limit of the content of the conductive particles is 0.5% by weight, the more preferable upper limit is 10% by weight, and the still more preferable upper limit is 5% by weight. When the content of the conductive particles is within the above range, the conductive particles can be easily arranged between the upper and lower electrodes to be connected. Furthermore, it becomes difficult to electrically connect adjacent electrodes that should not be connected via a plurality of conductive particles. That is, a short circuit between adjacent electrodes can be prevented.

  Since the curable composition according to the present invention has high wettability, the curable composition is preferably liquid or pasty. When the curable composition is liquid or pasty, the viscosity (25 ° C.) of the curable composition is preferably in the range of 1000 to 300,000 mPa · s. If the viscosity is too low, the conductive particles may settle. If the viscosity is too high, the conductive particles may not be sufficiently dispersed.

(Use of curable composition)
The curable composition concerning this invention can be used in order to adhere | attach various connection object members.

  Since the curable composition concerning this invention has high wettability, it is used suitably as a connection object member material for connecting an electronic component (electronic element) to a circuit board.

  When the curable composition according to the present invention is an anisotropic conductive material containing conductive particles, the anisotropic conductive material includes an anisotropic conductive paste, an anisotropic conductive ink, and an anisotropic conductive adhesive. It can be used as an adhesive, an anisotropic conductive film, or an anisotropic conductive sheet. When the anisotropic conductive material is used as a film-like adhesive such as an anisotropic conductive film or anisotropic conductive sheet, the film-like adhesive containing the conductive particles contains conductive particles. The film-like adhesive which does not carry out may be laminated | stacked. Even when the curable composition according to the present invention is in the form of a film, the curable composition has high wettability. The anisotropic conductive material is preferably a liquid or paste-like anisotropic conductive material.

  The anisotropic conductive material is suitably used for obtaining a connection structure in which the first and second connection target members are electrically connected.

  In FIG. 1, an example of the connection structure using the curable composition which concerns on one Embodiment of this invention is typically shown with sectional drawing.

  A connection structure 1 shown in FIG. 1 includes a first connection target member 2, a second connection target member 4, and a connection part 3 connecting the first and second connection target members 2 and 4. Prepare. The connection part 3 is formed by hardening the curable composition containing the electroconductive particle 5, ie, an anisotropic conductive material.

  A plurality of electrodes 2 b are provided on the upper surface 2 a of the first connection target member 2. A plurality of electrodes 4 b are provided on the lower surface 4 a of the second connection target member 4. The electrode 2b and the electrode 4b are electrically connected by one or a plurality of conductive particles 5. Therefore, the first and second connection target members 2 and 4 are electrically connected by the conductive particles 5.

  The curable composition according to the present invention is a liquid or paste-like anisotropic conductive material, and may be an anisotropic conductive material applied on the first connection target member in a liquid or paste-like state. preferable.

  Specifically, as the connection structure, an electronic component chip such as a semiconductor chip, a capacitor chip or a diode chip is mounted on a circuit board, and the electrode of the electronic component chip is connected to an electrode on the circuit board. Examples include electrically connected structures. As a circuit board, various printed circuit boards, such as various printed circuit boards, such as a flexible printed circuit board, a glass substrate, or a board on which metal foil was laminated, are mentioned. The first and second connection target members are preferably electronic components (electronic elements) or circuit boards. The curable composition according to the present invention is preferably a curable composition for connecting an electronic component or a circuit board.

  The manufacturing method of the connection structure is not particularly limited. As an example of a manufacturing method of a connection structure, the anisotropic conductive material is disposed between a first connection target member such as an electronic component or a circuit board and a second connection target member such as an electronic component or a circuit board. And after obtaining a laminated body, the method etc. which heat and pressurize this laminated body are mentioned.

  In addition, the said curable composition does not need to contain electroconductive particle. In this case, the curable composition is used to bond and connect the first and second connection target members without electrically connecting the first and second connection target members.

  When the curable composition according to the present invention is an anisotropic conductive material, the anisotropic conductive material is, for example, a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), a semiconductor chip, and the like. Connection with flexible printed circuit board (COF (Chip on Film)), connection between semiconductor chip and glass substrate (COG (Chip on Glass)), or connection between flexible printed circuit board and glass epoxy board (FOB (Film on Board)) ) Etc. Especially, the said anisotropic conductive material is suitable for a FOG use or a COG use, and is more suitable for a COG use. The curable composition according to the present invention is preferably an anisotropic conductive material used for connection between a flexible printed circuit board and a glass substrate, or between a semiconductor chip and a flexible printed circuit board. It is more preferable that the conductive material is an anisotropic conductive material used for connection to the.

  In the connection structure according to the present invention, it is preferable to use a flexible printed circuit board and a glass substrate as the second connection target member and the first connection target member, or use a semiconductor chip and a glass substrate, It is more preferable to use a semiconductor chip and a glass substrate.

  In FOG applications, since the L / S is relatively wide, the particle size of the conductive particles is large and the concentration is low, so the pressure at the time of connection is low, sufficient indentation and resin filling properties cannot be obtained, and conduction reliability between electrodes And the occurrence of voids in the cured product layer is often a problem. On the other hand, the use of the curable composition according to the present invention can effectively increase the conduction reliability between the electrodes in the FOG application, and effectively generate voids in the cured product layer. Can be suppressed.

  In COG applications, since the L / S is a relatively narrow pitch, if the fluidity when the anisotropic conductive material is heated is insufficient, the anisotropic conductive material is not sufficiently filled between the electrode lines. The reliability of conduction and the occurrence of voids in the cured product layer often become problems. On the other hand, by using the curable composition according to the present invention, the conduction reliability between the electrodes can be effectively increased in COG applications, and the generation of voids in the cured product layer can be effectively suppressed.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

Example 1
(1) Preparation of curable composition 33 parts by weight of an episulfide compound (YL7007, manufactured by Japan Epoxy Resin Co., Ltd.), 20 parts by weight of pentaerythritol tetrakis-3-mercaptopropionate as a thermosetting agent, and a polyether-modified siloxane ( (Trade name “BYK-349”, manufactured by BYK) 0.05 parts by weight, 1 part by weight of 2-ethyl-4-methylimidazole as a curing accelerator, and 20 parts by weight of silica having an average particle diameter of 0.25 μm as a filler And 20 parts by weight of alumina having an average particle diameter of 0.5 μm and 2 parts by weight of conductive particles having an average particle diameter of 3 μm are added and stirred at 2000 rpm for 5 minutes using a planetary stirrer. A curable composition as a paste was obtained. The conductive particles used are conductive particles having a metal layer in which a nickel plating layer is formed on the surface of divinylbenzene resin particles and a gold plating layer is formed on the surface of the nickel plating layer. .

(Example 2)
A curable composition in the same manner as in Example 1 except that the blending amount of the polyether-modified siloxane (trade name “BYK-349”, manufactured by BYK) was changed from 0.05 parts by weight to 0.01 parts by weight. Got.

(Example 3)
The curable composition was the same as in Example 1 except that the blending amount of the polyether-modified siloxane (trade name “BYK-349”, manufactured by BYK) was changed from polyether-modified siloxane parts by weight to 3.0 parts by weight. I got a thing.

Example 4
Except that the polyether-modified siloxane (trade name “BYK-349”, manufactured by BYK) was changed to the polyether-modified siloxane (trade name “BYK-345”, manufactured by BYK), in the same manner as in Example 1, A curable composition was obtained.

(Example 5)
Except for changing the polyether-modified siloxane (trade name “BYK-349”, manufactured by BYK) to the polyether-modified siloxane (trade name “BYK-348”, manufactured by BYK), in the same manner as in Example 1, A curable composition was obtained.

(Example 6)
Before stirring using a planetary stirrer, 5 parts by weight of an epoxy acrylate (“EBECRYL 3702” manufactured by Daicel-Cytec Co., Ltd.), which is a (meth) acrylic resin as a photocurable compound, and an acylphosphine oxide as a photopolymerization initiator A curable composition was obtained in the same manner as in Example 1 except that 0.1 part by weight of a system compound (“DAROCUR TPO” manufactured by Ciba Japan Co., Ltd.) was further added.

(Example 7)
Before stirring with a planetary stirrer, 5 parts by weight of urethane acrylate ("EBECRYL8804" manufactured by Daicel-Cytec), which is a (meth) acrylic resin as a photocurable compound, and acylphosphine oxide as a photopolymerization initiator A curable composition was obtained in the same manner as in Example 1 except that 0.1 part by weight of a system compound (“DAROCUR TPO” manufactured by Ciba Japan Co., Ltd.) was further added.

(Example 8)
Example 1 except that 33 parts by weight of bisphenol F diglycidyl ether (EXA-830CRP DIC), which is an epoxy compound, was used instead of 33 parts by weight of the episulfide compound (YL7007, manufactured by Japan Epoxy Resin Co., Ltd.). Thus, a curable composition was obtained.

Example 9
Instead of 33 parts by weight of the above-mentioned episulfide compound (YL7007, manufactured by Japan Epoxy Resin), 33 parts by weight of bisphenol F diglycidyl ether (EXA-830CRP DIC), which is an epoxy compound, was used, and a planetary stirrer was used. Before stirring, 5 parts by weight of an epoxy acrylate (“EBECRYL 3702” manufactured by Daicel-Cytec, Inc.) which is a (meth) acrylic resin as a photocurable compound, and an acylphosphine oxide compound (Ciba A curable composition was obtained in the same manner as in Example 1 except that 0.1 part by weight of “DAROCUR TPO” manufactured by Japan Co., Ltd. was further added.

(Example 10)
Instead of 33 parts by weight of the above-mentioned episulfide compound (YL7007, manufactured by Japan Epoxy Resin), 33 parts by weight of bisphenol F diglycidyl ether (EXA-830CRP DIC), which is an epoxy compound, was used, and a planetary stirrer was used. Before stirring, 5 parts by weight of urethane acrylate (“EBECRYL8804” manufactured by Daicel-Cytec Co., Ltd.), which is a (meth) acrylic resin as a photocurable compound, and an acylphosphine oxide compound (Ciba A curable composition was obtained in the same manner as in Example 1 except that 0.1 part by weight of “DAROCUR TPO” manufactured by Japan Co., Ltd. was further added.

(Example 11)
A curable composition was obtained in the same manner as in Example 1 except that 33 parts by weight of resorcinol diglycidyl ether, which is an epoxy compound, was used instead of 33 parts by weight of the episulfide compound (YL7007, manufactured by Japan Epoxy Resin Co., Ltd.). It was.

(Example 12)
In place of 33 parts by weight of the above-described episulfide compound (YL7007, manufactured by Japan Epoxy Resin Co., Ltd.), 33 parts by weight of resorcinol diglycidyl ether, which is an epoxy compound, was used, and before being stirred using a planetary stirrer, photocurable 5 parts by weight of an epoxy acrylate ("EBECRYL 3702" manufactured by Daicel-Cytec) as a compound and an acylphosphine oxide compound ("DAROCUR TPO" manufactured by Ciba Japan) as a photopolymerization initiator 0 A curable composition was obtained in the same manner as in Example 1 except that 1 part by weight was further added.

(Example 13)
In place of 33 parts by weight of the above-described episulfide compound (YL7007, manufactured by Japan Epoxy Resin Co., Ltd.), 33 parts by weight of resorcinol diglycidyl ether, which is an epoxy compound, was used, and before being stirred using a planetary stirrer, photocurable 5 parts by weight of urethane acrylate (“EBECRYL8804” manufactured by Daicel-Cytec) as a (meth) acrylic resin as a compound and acylphosphine oxide compound (“DAROCUR TPO” manufactured by Ciba Japan) as a photopolymerization initiator 0 A curable composition was obtained in the same manner as in Example 1 except that 1 part by weight was further added.

(Example 14)
As a thermosetting agent, 10 parts by weight of an imidazole curing agent (amine adduct type curing agent (“PN-23J” manufactured by Ajinomoto Fine Techno Co., Ltd.)) was used instead of 20 parts by weight of pentaerythritol tetrakis-3-mercaptopropionate. Except for this, a curable composition was obtained in the same manner as in Example 1.

(Example 15)
As in Example 1, except that 20 parts by weight of pentaerythritol tetrakis-3-mercaptopropionate was used as the thermosetting agent, 5 parts by weight of 2-ethyl-4-methylimidazole, which is an amine curing agent, was used. Thus, a curable composition was obtained.

(Comparative Example 1)
A curable composition was obtained in the same manner as in Example 1 except that the polyether-modified siloxane (trade name “BYK-349”, manufactured by BYK) was not added.

(Comparative Example 2)
Example 1 except that the polyether-modified siloxane (trade name “BYK-349”, manufactured by BYK) was changed to polyether-modified polydimethylsiloxane (trade name “BYK-302”, manufactured by BYK). Thus, a curable composition was obtained.

(Comparative Example 3)
Example 1 except that the polyether-modified siloxane (trade name “BYK-349”, manufactured by BYK) was changed to aralkyl-modified polymethylalkylsiloxane (trade name “BYK-322”, manufactured by BYK). Thus, a curable composition was obtained.

(Evaluation)
Presence of voids:
A transparent glass substrate having an ITO electrode pattern with an L / S of 10 μm / 10 μm formed on the upper surface was prepared. Further, a semiconductor chip was prepared in which a gold electrode pattern with L / S of 10 μm / 10 μm was formed on the lower surface.

  On the said transparent glass substrate, the obtained curable composition was applied so that it might become thickness of 30 micrometers, and the curable composition layer was formed. Next, the semiconductor chip was laminated on the curable composition layer so that the electrodes face each other and are connected. Thereafter, while adjusting the temperature of the heating head so that the temperature of the curable composition layer becomes 185 ° C., the heating head is placed on the upper surface of the semiconductor chip, the curable composition layer is cured at 185 ° C., and the connection structure Got.

  In the obtained connection structure, whether or not voids were generated in the cured product layer formed of the curable composition layer was visually observed from the lower surface side of the transparent glass substrate.

  The results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... Connection structure 2 ... 1st connection object member 2a ... Upper surface 2b ... Electrode 3 ... Connection part 4 ... 2nd connection object member 4a ... Lower surface 4b ... Electrode 5 ... Conductive particle

Claims (12)

A thermosetting compound;
A thermosetting agent;
A curable composition comprising a polyether-modified siloxane.   The curable compound according to claim 1, wherein the thermosetting compound is a thermosetting compound having at least one of an epoxy group and a thiirane group.   The curable composition of Claim 1 or 2 in which the said thermosetting compound contains the compound which has an epoxy group.   The curable composition according to any one of claims 1 to 3, wherein the thermosetting compound contains a compound having a thiirane group.   The curable composition according to any one of claims 1 to 4, wherein the thermosetting compound contains a compound having an epoxy group and a compound having a thiirane group. (Meth) acrylic compounds,
The curable composition according to any one of claims 1 to 5, further comprising a photopolymerization initiator.   The curable composition according to any one of claims 1 to 6, wherein a content of the polyether-modified siloxane is 0.01 to 5% by weight in 100% by weight of the curable composition. Further comprising conductive particles;
The curable composition according to any one of claims 1 to 7, which is an anisotropic conductive material.   The curable composition of Claim 8 which is an anisotropic conductive material used for the connection of a flexible printed circuit board and a glass substrate, or the connection of a semiconductor chip and a flexible printed circuit board. A first connection target member, a second connection target member, and a connection part connecting the first and second connection target members;
The connection structure in which the said connection part is formed with the curable composition of any one of Claims 1-9. The curable composition is an anisotropic conductive material containing conductive particles,
The connection structure according to claim 10, wherein the first and second connection target members are electrically connected by the conductive particles. A method for manufacturing a connection structure for connecting a flexible printed circuit board and a glass substrate or connecting a semiconductor chip and a glass substrate,
The connection structure according to claim 11, wherein a flexible printed circuit board and a glass substrate, or a semiconductor chip and a glass substrate are used as the second connection object member and the first connection object member.

Images