JP2011225839A - Curable composition and connected structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition excellent in storage stability and a connected structure using the curable composition.SOLUTION: The curable composition contains a compound having at least one of an epoxy group and a thiirane group, at least one ester selected from a phosphoric acid ester and a phosphite ester, and at least one component selected from the group consisting of a phenolic compound, ascorbic acid, a derivative of ascorbic acid, a salt of ascorbic acid, isoascorbic acid, a derivative of isoascorbic acid and a salt of isoascorbic acid. 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 to a curable composition containing a compound having at least one of an epoxy group and a thiirane group, 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.

  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 1 below discloses a curing agent that generates free radicals upon heating, a hydroxyl group-containing resin having a molecular weight of 10,000 or more, a phosphate ester, a radical polymerizable substance, a conductive material. An anisotropic conductive material containing conductive particles is disclosed. Specific examples of the hydroxyl group-containing resin include polymers such as polyvinyl butyral resin, polyvinyl formal, polyamide, polyester, phenol resin, epoxy resin, and phenoxy resin.

JP 2005-314696 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. For this reason, in the conventional anisotropic conductive material as described in Patent Document 1, the curing does not proceed rapidly, and the wiring may fall off, peel off, and be displaced. Furthermore, in the conventional anisotropic conductive material as described in Patent Document 1, when it is stored for a long time, the curing may proceed, and the storage stability may be low.

  An object of the present invention is to provide a curable composition having excellent storage stability and a connection structure using the curable composition.

  A limited object of the present invention is to provide a curable composition that is not only excellent in storage stability but also can be quickly cured, and a connection structure using the curable composition. .

  According to a broad aspect of the present invention, a compound having at least one of an epoxy group and a thiirane group, at least one ester of a phosphate ester and a phosphite ester, a phenolic compound, ascorbic acid, There is provided a curable composition comprising at least one component selected from the group consisting of a derivative of ascorbic acid, a salt of ascorbic acid, isoascorbic acid, a derivative of isoascorbic acid, and a salt of isoascorbic acid.

  In a specific aspect of the curable composition according to the present invention, the ester is a phosphate ester having a pKa of 5 or more and a phosphite ester.

  In another specific aspect of the curable composition according to the present invention, the compound contains a compound having an epoxy group.

  In another specific aspect of the curable composition according to the present invention, the compound contains a compound having a thiirane group.

  In another specific aspect of the curable composition according to the present invention, the compound contains a compound having an epoxy group and a compound having a thiirane group.

  In still another specific aspect of the curable composition according to the present invention, a (meth) acrylic compound is further included.

  The molecular weight of the component is preferably less than 10,000, and more preferably 1500 or less.

  In another specific aspect of the curable composition according to the present invention, the content of the above components is 0.1 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 that connects the first and second connection target members. Is formed by a curable composition constructed 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.

  The curable composition according to the present invention includes a compound having at least one of an epoxy group and a thiirane group, at least one ester of a phosphate ester and a phosphite ester, a phenolic compound, and ascorbic acid. Including at least one component selected from the group consisting of a derivative of ascorbic acid, a salt of ascorbic acid, isoascorbic acid, a derivative of isoascorbic acid, and a salt of isoascorbic acid. .

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 according to the present invention includes at least one of a compound having at least one of an epoxy group and a thiirane group (hereinafter sometimes abbreviated as compound A), a phosphate ester and a phosphite ester. One ester (hereinafter sometimes abbreviated as ester B), phenolic compound, ascorbic acid, ascorbic acid derivative, ascorbic acid salt, isoascorbic acid, isoascorbic acid derivative, and isoascorbic acid salt And at least one component selected from the group consisting of (hereinafter sometimes abbreviated as component C).

  When the ester B and the component C are combined with the compound A in combination, the component C is used without using the component C, or the component C without using the ester B. The storage stability of the curable composition can be improved as compared with the case of using only the curable composition. Furthermore, since the curable composition which concerns on this invention has the said composition, it can raise the hardening rate of a curable composition notably. When the compound A has a thiirane group, the curable composition can be rapidly cured at a lower temperature.

[Compound having at least one of epoxy group and thiirane group]
The 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 a thiirane group-containing compound (episulfide compound). The compound having an epoxy group and a thiirane group is a thiirane group-containing epoxy compound. As for the said compound A, only 1 type may be used and 2 or more types may be used together.

  The curable 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. It may be.

  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.

  The content of the compound having a thiirane group in 100% by weight of the compound A is preferably in the range of 0.1 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 50% 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 curable compound having an epoxy group or thiirane group 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 formula (11-1), (12-1), (13), (17), or (18) described later 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 preferable, and it is more preferable to have a structure represented by the following formula (1-1), (2-1) or (3). 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.

  From the viewpoint of curing more rapidly at a low temperature, the episulfide compound is represented by the following formula (1), the following formula (2), the above formula (3), the above formula (7), or the above formula (8). It preferably has a structure, and more preferably has a structure represented by the following formula (1), the following formula (2), or the above formula (3). From the viewpoint of curing more rapidly at a low temperature, the episulfide compound preferably has a structure represented by the following formula (1) or (2).

  In said formula (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 above formula (4).

  In said formula (2), 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 above formula (5).

  The episulfide compound having the structure represented by the above formula (1-1), (2-1), (3), (7) or (8) and the above formula (1) or (2) is all thiirane. Has at least two groups. In addition, a group having a thiirane group is bonded to a benzene ring, a naphthalene ring, or an anthracene ring. Since it has such a structure, the curable composition containing an episulfide compound can be rapidly cured at a low temperature.

  The episulfide compound having the structure represented by the above formula (1-1), (2-1), (3), (7) or (8) is represented by the above formula (1-1), (2-1), The reactivity is high compared with the compound whose episulfide group in (3), (7) or (8) is an epoxy group. The episulfide compound having a structure represented by the above formula (1) or (2) has higher reactivity than a compound in which the thiirane group in the above formula (1) or (2) is an epoxy group. This is because a thiirane group is easier to open a ring and has higher reactivity than an epoxy group. Episulfide compounds having a structure represented by the above formula (1-1), (2-1), (3), (7) or (8), and a structure represented by the above formula (1) or (2) Since the episulfide compound having a high reactivity, it can be quickly cured at a low temperature.

  R1 and R2 in the above formulas (1-1) and (1), R51 and R52 in the above formulas (2-1) and (2), R101 and R102 in the above formula (3), and the above formula (4) R7 in the formula, R59 in the formula (5) and R111 in the formula (6) are all alkylene groups having 1 to 5 carbon atoms. If the alkylene group has more than 5 carbon atoms, the curing rate of the episulfide compound tends to decrease.

  R1 and R2 in the above formulas (1-1) and (1), R51 and R52 in the above formulas (2-1) and (2), R101 and R102 in the above formula (3), and the above formula (4) R7 in the formula, R59 in the formula (5), and R111 in the formula (6) are each preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group. The alkylene group may be an alkylene group having a straight chain structure or an alkylene group having a branched structure.

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

  In said formula (11), 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 above formula (14).

  In said formula (12), 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 above formula (15).

  R11 and R12 in the above formulas (11-1) and (11), R61 and R62 in the above formulas (12-1) and (12), R121 and R122 in the above formula (13), and the above formula (14). R17 in the formula, R69 in the formula (15), and R131 in the formula (16) are all alkylene groups having 1 to 5 carbon atoms. When carbon number of this alkylene group exceeds 5, the hardening rate of the said compound A will fall easily.

  R11 and R12 in the above formulas (11-1) and (11), R61 and R62 in the above formulas (12-1) and (12), R121 and R122 in the above formula (13), and the above formula (14). R17 in the formula, R69 in the formula (15), and R131 in the formula (16) are each preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group. The alkylene group may be an alkylene group having a straight chain structure or an alkylene group having a branched structure.

  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 (11-1), (12-1), (13), (17) or (18) 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.

[At least one of phosphoric acid ester and phosphorous acid ester]
The ester B is not particularly limited as long as it is at least one of a phosphate ester and a phosphite ester. As for the said ester B, only 1 type may be used and 2 or more types may be used together.

Examples of the phosphate ester include diethyl benzyl phosphate, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, tris (butoxyethyl) phosphate, tris (2-ethylhexyl) phosphate, (RO) ₃ P═O [R = lauryl group Cetyl group, stearyl group or oleyl group], tris (2-chloroethyl) phosphate, tris (2-dichloropropyl) phosphate, triphenyl phosphate, butylpyrophosphate, tricresyl phosphate, trixylenyl phosphate, octyl diphenyl phosphate, Cresyl diphenyl phosphate, xylenyl diphosphate, monobutyl phosphate, dibutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate Feto, ammonium ethyl acid phosphate, and 2-ethylhexyl acid phosphate salt. Of these, diethylbenzyl phosphate is preferably used.

  Examples of the phosphite include trimethyl phosphite, triethyl phosphite, tri n-butyl phosphite, tris (2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, tris (Tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, phenyl diisooctyl phosphite Phyto, phenyl diisodecyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl isooctyl phosphite, diphenyl monodecyl phosphite, diphenyl monoisodecyl phosphite, di Phenyl mono (tridecyl) phosphite, bis (nonylphenyl) dinonylphenyl phosphite, tetraphenyldipropylene glycol diphosphite, poly (dipropylene glycol) phenyl phosphite, diisodecylpentaerythritol diphosphite, bis (tridecyl) pentaerythritol Diphosphite, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4,4′-isopropylidene diphenylphosphite , Trilauryl trithiophosphite, dimethyl hydrogen phosphite, dibutyl hydrogen phosphite, di (2-e Ruhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, and diphenyl mono (tridecyl) phos Fight etc. are mentioned. Among them, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite or diphenyl mono (tridecyl) phosphite is preferable, diphenyl monodecyl phosphite or diphenyl mono (tridecyl) phosphite is more preferable, and diphenyl mono (tridecyl). More preferred are phosphites.

  From the viewpoint of further enhancing the storage stability of the curable composition, the phosphate ester preferably has a pKa of 5 or more. Therefore, it is preferable that the ester B is at least one of a phosphate ester having a pKa of 5 or more and a phosphite ester. From the viewpoint of further improving the storage stability of the curable composition, the pKa of the phosphite is preferably 9 or more. Therefore, the ester B is preferably at least one of a phosphoric acid ester and a phosphite having a pKa of 9 or more. The ester B is preferably at least one of a phosphoric acid ester having a pKa of 5 or more and a phosphite ester having a pKa of 9 or more. From the viewpoint of further improving the storage stability of the curable composition, the phosphate ester preferably has a pKa of 7 or more. From the viewpoint of further improving the storage stability of the curable composition, the ester B is preferably an ester that is not a (meth) acrylate compound, and is preferably not a (meth) acrylic ester.

  In 100% by weight of the curable composition, the content of the ester B is preferably in the range of 0.001 to 5% by weight, preferably in the range of 0.001 to 1% by weight. More preferably, it is in the range of 001 to 0.1% by weight. In 100% by weight of the curable composition, a more preferable lower limit of the content of the ester B is 0.005% by weight, and a more preferable upper limit is 0.05% by weight. When the content of the ester B is within the above range, the storage stability of the curable composition can be further enhanced.

[At least one component selected from the group consisting of phenolic compounds, ascorbic acid, ascorbic acid derivatives, ascorbic acid salts, isoascorbic acid, isoascorbic acid derivatives and isoascorbic acid salts]
The component C is at least one selected from the group consisting of phenolic compounds, ascorbic acid (vitamin C), ascorbic acid derivatives, ascorbic acid salts, isoascorbic acid, isoascorbic acid derivatives, and isoascorbic acid salts. If it is a seed | species, it will not specifically limit. The component C is more preferably at least one selected from the group consisting of phenolic compounds, ascorbic acid and isoascorbic acid. Component C is preferably an antioxidant. As for the said component C, only 1 type may be used and 2 or more types may be used together.

  The reason why the storage stability of the curable composition is enhanced by blending the component C is that the radical generated by the ring opening of the epoxy group or thiirane group of the compound A is effectively captured by the component C. This is probably because of this. Moreover, when a curable composition contains an imidazole hardening | curing agent or an imidazole hardening accelerator, the storage stability of a curable composition is improved. This is considered to be because the component C acts on the nitrogen portion of the heterocyclic ring of the imidazole curing agent or imidazole curing accelerator.

  The phenolic compound has a phenolic hydroxyl group in which a hydroxyl group is bonded to a benzene ring. Examples of the phenolic compound include polyphenol, triol, hydroquinone, and tocopherol (vitamin E). As for the said phenolic compound, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further increasing the curing rate and further enhancing the storage stability, the molecular weight of Component C is preferably less than 10,000, and preferably 1500 or less. In the present specification, the molecular weight means a molecular weight that can be calculated from the structural formula when the component C is not a polymer and when the structural formula of the component C can be specified. Moreover, when the said component C is a polymer, a weight average molecular weight is meant.

  From the viewpoint of further increasing the curing rate and further improving the storage stability, the content of the component C is within the range of 0.001 to 20% by weight in 100% by weight of the curable composition. preferable. In 100% by weight of the curable composition, the more preferable lower limit of the content of the component C is 0.01% by weight, the still more preferable lower limit is 0.1% by weight, the more preferable upper limit is 10% by weight, and the still more preferable upper limit is 5% by weight. %. From the viewpoint of further increasing the curing rate and further enhancing the storage stability, the content of the component C is in the range of 0.1 to 5% by weight in 100% by weight of the curable composition. More preferred.

  Further, from the viewpoint of further increasing the curing rate and further enhancing the storage stability, when the component C is hydroquinone, the content of hydroquinone in 0.1% by weight of the curable composition is 0.1. It is preferable to be within the range of ˜5% by weight. Furthermore, from the viewpoint of further increasing the curing rate and further improving the storage stability, when the component C is hydroquinone, the content of hydroquinone is 0.1% in 100% by weight of the curable composition. When the component C is a component other than hydroquinone, the content of components other than hydroquinone is 0.001 to 20% by weight in 100% by weight of the curable composition. It is preferable to be within the range.

[Other ingredients]
The curable composition according to the present invention preferably contains a curing agent. Moreover, when using the curable composition which concerns on this invention, you may add a hardening | curing agent to this curable composition. Therefore, the curable composition according to the present invention does not necessarily contain a curing agent. The curing agent includes a thermal radical initiator. As for the said hardening | curing agent, only 1 type may be used and 2 or more types may be used together.

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

  The imidazole curing 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- Examples include triazine isocyanuric acid adducts.

  The polythiol curing agent is not particularly limited, and examples thereof include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. .

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

  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 curing agent is not particularly limited. Content of the said hardening | curing agent is suitably adjusted according to the kind of hardening | curing agent. It is preferable that content of the said hardening | curing agent exists in the range of 0.01-200 weight part with respect to 100 weight part of said compound A.

  When the curing agent is a curing agent other than a thermal radical initiator, the preferred lower limit of the content of the curing agent is 0.01 parts by weight, and the more preferred lower limit is 1 part by weight with respect to 100 parts by weight of the compound A. A more preferred lower limit is 30 parts by weight, a preferred upper limit is 200 parts by weight, a more preferred upper limit is 100 parts by weight, a still more preferred upper limit is 75 parts by weight, and a particularly preferred upper limit is 40 parts by weight. When the content of the curing agent satisfies the above lower limit, it is easy to sufficiently cure the curable composition. When the content of the curing agent satisfies the above upper limit, it is difficult for an excessive curing agent that has not been involved in curing after curing to remain, and the heat resistance of the cured product can be further enhanced.

  When the curing agent is an imidazole curing agent or a phenol curing agent, the content of the imidazole curing agent or the phenol curing agent is preferably in the range of 1 to 15 parts by weight with respect to 100 parts by weight of the compound A. . Further, when the curing agent is an amine curing agent, a polythiol curing agent or an acid anhydride, the content of the amine curing agent, the polythiol curing agent or the acid anhydride is 15 to 40 parts by weight with respect to 100 parts by weight of the compound A. It is preferable to be within the range.

  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 5 parts by weight with respect to 100 parts by weight of the compound A. 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 hardening agent or an amine hardening 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 compound A. . 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.

  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. However, when using the curable composition concerning this invention, you may add a photoinitiator to this curable composition. 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.

  In a composition containing the compound A and a (meth) acrylic resin, when the epoxy group or thiirane group of the compound A is ring-opened to generate a radical, polymerization of the (meth) acrylic resin is caused by the action of the radical. Easy to progress. However, by blending the ester B and the component C in combination with the compound A, the epoxy group or thiirane group is difficult to open during storage of the curable composition. As a result, polymerization of the (meth) acrylic resin is difficult to proceed during storage of the curable composition.

  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 compound) 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 (meth) with respect to 100 parts by weight of the compound A, The preferred lower limit of the content of (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, and the more preferred upper limit. Is 1000 parts by weight, and a more preferred upper limit is 500 parts by weight.

  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 preferable lower limit of the content of the photopolymerization initiator is 0.1 parts by weight, the more preferable lower limit is 0.2 parts by weight, the preferable upper limit is 10 parts by weight, and the more preferable upper limit is 100 parts by weight of the photocurable compound. 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 according to the present invention may further contain a storage stabilizer such as boric acid ester, an ion scavenger, or a silane coupling agent, if necessary.

[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.

  When the curable composition is liquid or pasty, the viscosity (25 ° C.) of the curable composition is preferably in the range of 20000 to 100000 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 for adhere | attaching various connection object members.

  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. 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 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 Episulfide Compound-Containing Mixture as Compound A Into a 2 L container equipped with a stirrer, a cooler and a thermometer, ethanol 250 mL, pure water 250 mL, and potassium thiocyanate 20 g were added, and potassium thiocyanate Was dissolved to prepare a first solution. Thereafter, the temperature in the container was kept in the range of 20 to 25 ° C. Next, 160 g of resorcinol diglycidyl ether was dropped into the first solution at a rate of 5 mL / min while stirring the first solution in the container maintained at 20 to 25 ° C. After dropping, the mixture was further stirred for 30 minutes to obtain an epoxy compound-containing solution.

  Next, a second solution in which 20 g of potassium thiocyanate was dissolved in a solution containing 100 mL of pure water and 100 mL of ethanol was prepared. The obtained second solution was added to the obtained epoxy compound-containing solution at a rate of 5 mL / min, and then stirred for 30 minutes. After stirring, a second solution prepared by dissolving 20 g of potassium thiocyanate in a solution containing 100 mL of pure water and 100 mL of ethanol is further prepared, and the second solution is further added to the container at a rate of 5 mL / min. And stirred for 30 minutes. Thereafter, the temperature in the container was cooled to 10 ° C., and stirred for 2 hours to be reacted.

  Next, 100 mL of saturated saline was added to the container and stirred for 10 minutes. After stirring, 300 mL of toluene was further added to the container and stirred for 10 minutes. Thereafter, the solution in the container was transferred to a separating funnel and allowed to stand for 2 hours to separate the solution. The lower solution in the separatory funnel was discharged, and the supernatant was taken out. 100 mL of toluene was added to the removed supernatant, stirred, and allowed to stand for 2 hours. Further, 100 mL of toluene was further added, stirred and allowed to stand for 2 hours.

  Next, 50 g of magnesium sulfate was added to the supernatant liquid to which toluene was added and stirred for 5 minutes. After stirring, magnesium sulfate was removed with a filter paper to separate the solution. The remaining solvent was removed by drying the separated solution under reduced pressure at 80 ° C. using a vacuum dryer. In this way, an episulfide compound-containing mixture was obtained.

¹ H-NMR measurement of the obtained episulfide compound-containing mixture was performed using chloroform as a solvent. As a result, the signal in the region of 6.5 to 7.5 ppm indicating the presence of the epoxy group decreased, and the signal appeared in the region of 2.0 to 3.0 ppm indicating the presence of the episulfide group. This confirmed that some epoxy groups of resorcinol diglycidyl ether were converted into episulfide groups. Moreover, from the integral value of the measurement result of ¹ H-NMR, the episulfide compound-containing mixture contains 70% by weight of resorcinol diglycidyl ether and 30% by weight of the episulfide compound having a structure represented by the following formula (1B). It was confirmed.

(2) Preparation of curable composition 33 parts by weight of the resulting episulfide compound-containing mixture as Component A above, 20 parts by weight of pentaerythritol tetrakis-3-mercaptopropionate as a curing agent, and Component B as above 0.01 part by weight of diphenyl mono (tridecyl) phosphite (pKa = 15.2) which is a phosphite, 0.58 part by weight of hydroquinone (molecular weight: 110) as the component C, and a curing accelerator 1 part by weight of 2-ethyl-4-methylimidazole, 20 parts by weight of silica having an average particle diameter of 0.25 μm and 20 parts by weight of alumina having an average particle diameter of 0.5 μm, and conductive particles 2 having an average particle diameter of 3 μm And adding an anisotropic conductive paste by stirring at 2000 rpm for 5 minutes using a planetary stirrer. The curable compositions of Te 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)
As the component C, a curable composition was obtained in the same manner as in Example 1 except that 0.58 part by weight of ascorbic acid (molecular weight: 176) was used instead of 0.58 part by weight of hydroquinone.

(Example 3)
A curable composition was obtained in the same manner as in Example 1, except that 0.58 parts by weight of isoascorbic acid (molecular weight: 176) was used in place of 0.58 parts by weight of hydroquinone as the component C.

Example 4
A curable composition was obtained in the same manner as in Example 1, except that 0.58 parts by weight of α-tocopherol (molecular weight: 402) was used as Component C instead of 0.58 parts by weight of hydroquinone.

(Example 5)
As the component C, a curable composition was obtained in the same manner as in Example 1 except that 0.58 part by weight of α-methylbenzylphenol was used instead of 0.58 part by weight of hydroquinone.

(Example 6)
A curable composition was obtained in the same manner as in Example 1 except that 0.58 parts by weight of 2,6-ditertiary butylphenol was used as Component C instead of 0.58 parts by weight of hydroquinone.

(Example 7)
A curable composition was obtained in the same manner as in Example 1 except that 0.58 parts by weight of 2,2′-methylenebisbutylphenol was used as Component C instead of 0.58 parts by weight of hydroquinone.

(Example 8)
As the component C, a curable composition was obtained in the same manner as in Example 1 except that 0.58 parts by weight of 2,2′-thiobisphenol was used instead of 0.58 parts by weight of hydroquinone.

Example 9
Example except that 0.01 parts by weight of diethyl hydrogen phosphite (pKa = 12.6), which is a phosphate ester, was used as component B in place of 0.01 parts by weight of diphenylmono (tridecyl) phosphite. In the same manner as in Example 1, a curable composition was obtained.

(Example 10)
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 11)
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 12)
The curable composition was the same as in Example 1 except that 33 parts by weight of the episulfide compound-containing mixture was used as Component A, and 33 parts by weight of bisphenol F glycidyl ether (manufactured by DIC) as an epoxy resin was used. Got.

(Comparative Example 1)
A curable composition was obtained in the same manner as in Example 1 except that neither diphenylmono (tridecyl) phosphite as Component B nor hydroquinone as Component C was added.

(Comparative Example 2)
A curable composition was obtained in the same manner as in Example 1 except that diphenyl mono (tridecyl) phosphite as Component B was not added.

(Comparative Example 3)
A curable composition was obtained in the same manner as in Example 1 except that hydroquinone as Component C was not added.

(Example 13)
As component A, instead of 33 parts by weight of the episulfide compound-containing mixture, 33 parts by weight of bisphenol F glycidyl ether (manufactured by DIC), which is an epoxy resin, was used, and before stirring using a planetary stirrer, 5 parts by weight of epoxy acrylate ("EBECRYL 3702" manufactured by Daicel-Cytec) as a curable compound and an acylphosphine oxide compound ("DAROCUR TPO" manufactured by Ciba Japan) as a photopolymerization initiator ) A curable composition was obtained in the same manner as in Example 1 except that 0.1 part by weight was further added.

(Example 14)
As component A, instead of 33 parts by weight of the episulfide compound-containing mixture, 33 parts by weight of bisphenol F glycidyl ether (manufactured by DIC), which is an epoxy resin, was used, and before stirring using a planetary stirrer, 5 parts by weight of urethane acrylate (“EBECRYL8804” manufactured by Daicel-Cytec) as a curable compound and acylphosphine oxide compound (“DAROCUR TPO” manufactured by Ciba Japan) as a photopolymerization initiator ) A curable composition was obtained in the same manner as in Example 1 except that 0.1 part by weight was further added.

(Example 15)
A curable composition was obtained in the same manner as in Example 1 except that 33 parts by weight of resorcinol diglycidyl ether was used as Component A instead of 33 parts by weight of the episulfide compound-containing mixture.

(Example 16)
As component A, instead of 33 parts by weight of the episulfide compound-containing mixture, 33 parts by weight of resorcinol diglycidyl ether was used, and before stirring with a planetary stirrer, (meth) acrylic as a photocurable compound was used. 5 parts by weight of an epoxy acrylate resin (“EBECRYL 3702” manufactured by Daicel-Cytec) and 0.1 part by weight of an acylphosphine oxide compound (“DAROCUR TPO” manufactured by Ciba Japan) as a photopolymerization initiator are further added. A curable composition was obtained in the same manner as Example 1 except for the addition.

(Example 17)
As component A, instead of 33 parts by weight of the episulfide compound-containing mixture, 33 parts by weight of resorcinol diglycidyl ether was used, and before stirring with a planetary stirrer, (meth) acrylic as a photocurable compound was used. 5 parts by weight of a urethane acrylate resin (“EBECRYL8804” manufactured by Daicel-Cytec) and 0.1 part by weight of an acylphosphine oxide compound (“DAROCUR TPO” manufactured by Ciba Japan) as a photopolymerization initiator A curable composition was obtained in the same manner as Example 1 except for the addition.

(Example 18)
A curable composition was obtained in the same manner as in Example 1 except that the amount of diphenyl mono (tridecyl) phosphite component B was changed from 0.01 parts by weight to 1 part by weight.

(Example 19)
As component B, instead of diphenylmono (tridecyl) phosphite, diethyl hydrogen phosphite (pKa = 12.6) which is a phosphate ester was used, and the amount of diethyl hydrogen phosphite was 0.01. A curable composition was obtained in the same manner as in Example 1 except that the amount was changed from 1 part by weight to 1 part by weight.

(Example 20)
A curable composition was obtained in the same manner as in Example 1 except that the amount of hydroquinone component C was changed from 0.58 parts by weight to 0.2 parts by weight.

(Example 21)
A curable composition was obtained in the same manner as in Example 1 except that the amount of hydroquinone component C was changed from 0.58 parts by weight to 2 parts by weight.

(Example 22)
Example 1 except that ascorbic acid (molecular weight: 176) was used in place of hydroquinone as component C, and that the amount of ascorbic acid was changed from 0.58 parts by weight to 0.1 parts by weight. Similarly, a curable composition was obtained.

(Example 23)
As component C, ascorbic acid (molecular weight: 176) was used instead of hydroquinone, and the amount of the ascorbic acid was changed from 0.58 parts by weight to 10 parts by weight. Thus, a curable composition was obtained.

(Example 24)
Example 1 except that isoascorbic acid (molecular weight: 176) was used in place of hydroquinone as component C, and that the amount of ascorbic acid was changed from 0.58 parts by weight to 0.1 parts by weight. In the same manner as above, a curable composition was obtained.

(Example 25)
As component C, isoascorbic acid (molecular weight: 176) was used instead of hydroquinone, and the amount of the ascorbic acid was changed from 0.58 parts by weight to 10 parts by weight. Thus, a curable composition was obtained.

(Example 26)
As a curing agent, 20 parts by weight of imidazole curing agent (amine adduct type curing agent (“PN-23J” manufactured by Ajinomoto Fine Techno Co.)) 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 27)
A curable composition was obtained in the same manner as in Example 1 except that 20 parts by weight of ethylenediamine as an amine curing agent was used instead of 20 parts by weight of pentaerythritol tetrakis-3-mercaptopropionate as a curing agent. It was.

(Evaluation)
(1) Curing time 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 copper electrode pattern having 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. When obtaining this connection structure, the time until the curable composition layer was cured by heating was measured.

(2) Presence / absence of voids In the connection structure obtained by the evaluation of the curing time, whether or not voids are generated in the cured product layer formed by the curable composition layer is visually observed from the lower surface side of the transparent glass substrate. Was observed.

(3) Storage stability Using an E-type viscometer, the viscosity η1 at 25 ° C. and 2.5 rpm of the curable composition immediately after the preparation was measured. The curable composition was stored at 25 ° C. for 100 hours. The viscosity η2 at 25 ° C. and 2.5 rpm of the curable composition after storage was measured. The rate of change in viscosity after storage was determined by the following formula (I).

  Rate of change (%) = (η2−η1) / η1 × 100 Formula (I)

  The storage stability of the curable composition was determined according to the following criteria.

[Criteria for storage stability]
○: Change rate is less than 130% ○: Change rate is 130% or more and less than 200% Δ: Change rate is 200% or more and less than 300% ×: Change rate is 300% or more

  The results are shown in Tables 1 and 2 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 (14)

A compound having at least one of an epoxy group and a thiirane group;
At least one of a phosphate ester and a phosphite ester;
A curable composition comprising at least one component selected from the group consisting of phenolic compounds, ascorbic acid, derivatives of ascorbic acid, salts of ascorbic acid, isoascorbic acid, derivatives of isoascorbic acid and salts of isoascorbic acid Composition.   The curable composition according to claim 1, wherein the ester is a phosphate ester having a pKa of 5 or more and a phosphite ester.   The curable composition of Claim 1 or 2 in which the said compound contains the compound which has an epoxy group.   The curable composition of any one of Claims 1-3 in which the said compound contains the compound which has a thiirane group.   The curable composition according to any one of claims 1 to 4, wherein the compound contains a compound having an epoxy group and a compound having a thiirane group.   The curable composition according to any one of claims 1 to 5, further comprising a (meth) acrylic compound.   The curable composition of any one of Claims 1-6 whose molecular weight of the said component is less than 10,000.   The curable composition of Claim 7 whose molecular weight of the said component is 1500 or less.   The curable composition of any one of Claims 1-8 whose content of the said component is 0.1 to 5 weight% in 100 weight% of curable compositions. Further comprising conductive particles;
The curable composition according to any one of claims 1 to 9, which is an anisotropic conductive material.   The curable composition of Claim 10 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 1-11. The curable composition is an anisotropic conductive material containing conductive particles,
The connection structure according to claim 12, 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 13, 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.

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