JP2012162591A - Mixture of thermosetting compound, curable composition, and connection structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mixture of a thermosetting compound excellent in storage stability.SOLUTION: The mixture of a thermosetting compound includes: a thermosetting compound shown by formula (1-1); and an isomer of the thermosetting compound shown by the formula (1-1), or includes: a thermosetting compound shown by formula (2-1); and an isomer of the thermosetting compound shown by formula (2-1), or includes a thermosetting compound shown by formula (3-1); and an isomer of the thermosetting compound shown by the formula (3-1).

Description

  The present invention relates to a mixture of thermosetting compounds used for connecting various members to be connected, and more specifically, a mixture of thermosetting compounds having excellent storage stability, and a mixture of the thermosetting compounds. The present invention relates to the curable composition and the connection structure used.

  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, the following Patent Document 1 discloses an episulfide compound having a benzene ring, a naphthalene ring or an anthracene ring and having at least two thiirane groups. Here, a curable composition containing the episulfide compound is also disclosed, and the curable composition contains a thermosetting agent, a photocurable compound, a photopolymerization initiator, conductive particles, and the like.

WO2010 / 035459A1

  The properties of the episulfide compound described in Patent Document 1 or the curable composition containing the episulfide compound may vary depending on storage conditions. For example, crystallization of the episulfide compound may proceed.

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

  According to a wide aspect of the present invention, the thermosetting compound represented by the following formula (1-1) and an isomer of the thermosetting compound represented by the formula (1-1) are included. A thermosetting compound represented by the formula (2-1) and an isomer of the thermosetting compound represented by the formula (2-1), or represented by the following formula (3-1): There is provided a mixture of thermosetting compounds comprising the thermosetting compound to be prepared and an isomer of the thermosetting compound represented by the formula (3-1).

  In the above formula (1-1), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, and 2 to 4 groups out of 4 groups of R3, R4, R5 and R6 represent a hydrogen atom. And a group which is not a hydrogen atom among R3, R4, R5 and R6 represents a group represented by the following formula (4), and X1 and X2 each represents an oxygen atom or a sulfur atom.

  In said formula (4), R7 represents a C1-C5 alkylene group, X3 represents an oxygen atom or a sulfur atom.

  In the above formula (2-1), R51 and R52 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R53, R54, R55, R56, R57 and R58. Represents a hydrogen atom, a group that is not a hydrogen atom among R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (5), and X51 and X52 are an oxygen atom or a sulfur atom, respectively. Represents.

  In said formula (5), R59 represents a C1-C5 alkylene group, X53 represents an oxygen atom or a sulfur atom.

  In the above formula (3-1), R101 and R102 each represent an alkylene group having 1 to 5 carbon atoms, and 6 to 8 of 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 Eight groups represent hydrogen atoms, and the groups that are not hydrogen atoms among R103, R104, R105, R106, R107, R108, R109, and R110 represent groups represented by the following formula (6), and X101 and X102 represents an oxygen atom or a sulfur atom, respectively.

  In said formula (6), R111 represents a C1-C5 alkylene group, X103 represents an oxygen atom or a sulfur atom.

  In a specific aspect of the mixture of thermosetting compounds according to the present invention, the isomer of the thermosetting compound represented by the formula (1-1) is bonded to the benzene ring in the formula (1-1). The isomers of the thermosetting compound represented by the above formula (2-1) are bonded to the naphthalene ring in the above formula (2-1). Only the bonding sites of the groups present are different isomers, and the isomer of the thermosetting compound represented by the formula (3-1) is a group bonded to the anthracene ring in the formula (3-1). Only the binding sites are different isomers.

  In another specific aspect of the mixture of thermosetting compounds according to the present invention, the thermosetting compound represented by the formula (1-1) and the thermosetting compound represented by the formula (1-1) In a total of 100% by weight with the isomer, the content of the thermosetting compound represented by the above formula (1-1) is 5.0% by weight or more and 40.0% by weight or less, and the above formula (2- Thermosetting represented by the above formula (2-1) in a total of 100% by weight of the thermosetting compound represented by 1) and the isomer of the thermosetting compound represented by the formula (2-1) The content of the functional compound is 5.0 wt% or more and 40.0 wt% or less, and the thermosetting compound represented by the formula (3-1) and the heat represented by the formula (3-1). In a total of 100% by weight with the isomer of the curable compound, the content of the thermosetting compound represented by the formula (3-1) is 5.0% by weight or more and 40.0% by weight or less. A.

  In another specific aspect of the mixture of thermosetting compounds according to the present invention, the thermosetting compound represented by the above formula (1-1) is a thermosetting compound represented by the following formula (1). The thermosetting compound represented by the above formula (2-1) is a thermosetting compound represented by the following formula (2), and the thermosetting compound represented by the above formula (3-1) is: And a thermosetting compound represented by the following formula (3).

  In the above formula (1), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, 2 to 4 groups out of 4 groups of R3, R4, R5 and R6 each represent a hydrogen atom, The group which is not a hydrogen atom among R3, R4, R5 and R6 represents a group represented by the above formula (4), and X1 and X2 each represent an oxygen atom or a sulfur atom.

  In the above formula (2), R51 and R52 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R53, R54, R55, R56, R57 and R58 are hydrogen. A group which is an atom and is not a hydrogen atom among R53, R54, R55, R56, R57 and R58 represents a group represented by the above formula (5), and X51 and X52 each represents an oxygen atom or a sulfur atom. .

  In the above formula (3), R101 and R102 each represent an alkylene group having 1 to 5 carbon atoms, and 6 to 8 of 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 The group of represents a hydrogen atom, the group which is not a hydrogen atom among R103, R104, R105, R106, R107, R108, R109 and R110 represents a group represented by the above formula (6), and X101 and X102 represent Each represents an oxygen atom or a sulfur atom.

  In still another specific aspect of the mixture of thermosetting compounds according to the present invention, the thermosetting compound represented by the above formula (1) is a thermosetting compound represented by the following formula (1A), The thermosetting compound represented by the above formula (2) is a thermosetting compound represented by the following formula (2A), and the thermosetting compound represented by the above formula (3) is represented by the following formula (3A). It is a thermosetting compound represented by this.

  In said formula (1A), R1 and R2 represent a C1-C5 alkylene group, respectively, and X1 and X2 represent an oxygen atom or a sulfur atom, respectively.

  In said formula (2A), R51 and R52 represent a C1-C5 alkylene group, respectively, and X51 and X52 represent an oxygen atom or a sulfur atom, respectively.

  In said formula (3A), R101 and R102 represent a C1-C5 alkylene group, respectively, and X101 and X102 represent an oxygen atom or a sulfur atom, respectively.

  In another specific aspect of the mixture of thermosetting compounds according to the present invention, the thermosetting compound represented by the formula (2-1) and the thermosetting compound represented by the formula (2-1). Of the isomer.

  In another specific aspect of the mixture of thermosetting compounds according to the present invention, the thermosetting compound represented by the above formula (1-1) has at least one thiirane group, and the above formula (2-1). The thermosetting compound represented by the formula has at least one thiirane group, and the thermosetting compound represented by the formula (3-1) has at least one thiirane group.

  In still another specific aspect of the mixture of thermosetting compounds according to the present invention, in the above formula (1-1), X1 and X2 are each a sulfur atom, and in the above formula (4), X3 is a sulfur atom. In the formula (2-1), X51 and X52 are each a sulfur atom, and in the formula (5), X53 is a sulfur atom, and in the formula (3-1), X101 and X102 are Each is a sulfur atom, and in the above formula (6), X103 is a sulfur atom.

  The mixture of thermosetting compounds according to the present invention is preferably a mixture of thermosetting compounds to which a thermosetting agent is added.

  The curable composition concerning this invention contains the mixture of the said thermosetting compound, and a thermosetting agent.

  In a specific aspect of the curable composition according to the present invention, a photocurable compound and a photopolymerization initiator are further included.

  In another specific aspect of the curable composition according to the present invention, conductive particles are further included.

  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 curing a curable composition constituted according to the present invention.

  On the specific situation with the connection structure which concerns on this invention, the said curable composition contains electroconductive particle, The said 1st, 2nd connection object member is electrically connected by the said electroconductive particle. .

  Does the mixture of thermosetting compounds according to the present invention include a thermosetting compound represented by formula (1-1) and an isomer of the thermosetting compound represented by formula (1-1)? The thermosetting compound represented by formula (2-1) and the isomer of the thermosetting compound represented by formula (2-1), or represented by formula (3-1) The thermosetting compound and the isomer of the thermosetting compound represented by the formula (3-1) are excellent in storage stability.

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

  Hereinafter, the present invention will be described in detail.

(Mixture of thermosetting compounds)
The mixture of thermosetting compounds according to the present invention includes a thermosetting compound represented by the following formula (1-1) and an isomer of the thermosetting compound represented by the formula (1-1). Or a thermosetting compound represented by the following formula (2-1) and an isomer of the thermosetting compound represented by the formula (2-1), or the following formula (3-1) ) And a isomer of the thermosetting compound represented by the formula (3-1). In this way, by mixing at least two thermosetting compounds having a specific skeleton, crystallization can be suppressed and storage stability can be reduced as compared with the case where only one thermosetting compound is used. Can be increased. Storage stability in the state of a mixture of thermosetting compounds can be enhanced.

  The mixture of thermosetting compounds according to the present invention is preferably a mixture of thermosetting compounds to which a thermosetting agent is added. In this invention, the storage stability in the state of the curable composition containing the mixture of a thermosetting compound and a hardening | curing agent can also be improved.

  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 (3-1), the bonding sites of the ten groups bonded to the anthracene ring are not particularly limited.

  In said formula (1-1), R1 and R2 represent a C1-C5 alkylene group, respectively. Of the four groups of R3, R4, R5 and R6, 2 to 4 groups represent hydrogen atoms. A group which is not a hydrogen atom among R3, R4, R5 and R6 represents a group represented by the following formula (4), and X1 and X2 each represents an oxygen atom or a sulfur atom. All four groups of R3, R4, R5 and R6 may be hydrogen atoms. 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 A group that is not a group represented by the following formula (4) may be a hydrogen atom.

  In said formula (4), R7 represents a C1-C5 alkylene group, X3 represents an oxygen atom or a sulfur atom.

  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 atoms. The group which is not a hydrogen atom in R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (5), and X51 and X52 represent an oxygen atom or a sulfur atom. All of the six groups of R53, R54, R55, R56, R57 and R58 may be hydrogen atoms. 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 groups, a group that is not a group represented by the following formula (5) may be a hydrogen atom.

  In said formula (5), R59 represents a C1-C5 alkylene group, X53 represents an oxygen atom or a sulfur atom.

  In said formula (3-1), 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 a hydrogen atom. A group that is not a hydrogen atom among R103, R104, R105, R106, R107, R108, R109, and R110 represents a group represented by the following formula (6), and X101 and X102 each represents an oxygen atom or a sulfur atom. . All of the eight groups of R103, R104, R105, R106, R107, R108, R109 and R110 may be hydrogen atoms. 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 a hydrogen atom.

  In said formula (6), R111 represents a C1-C5 alkylene group, X103 represents an oxygen atom or a sulfur atom.

  The mixture of thermosetting compounds according to the present invention includes the thermosetting compound represented by the above formula (1-1) and the isomer of the thermosetting compound represented by the formula (1-1). The thermosetting compound represented by the above formula (2-1) and the isomer of the thermosetting compound represented by the above formula (2-1) may be included, or the above formula The thermosetting compound represented by (3-1) and the isomer of the thermosetting compound represented by the formula (3-1) may be included.

  As for the isomer of the thermosetting compound represented by the above formula (1-1), only one type may be used, or two or more types may be used in combination. As for the isomer of the thermosetting compound represented by the above formula (2-1), only one type may be used, or two or more types may be used in combination. As for the isomer of the thermosetting compound represented by the above formula (3-1), only one type may be used, or two or more types may be used in combination.

  From the viewpoint of curing more rapidly at a low temperature, the thermosetting compound represented by the above formula (1-1) is preferably a thermosetting compound represented by the following formula (1). The thermosetting compound represented by (2-1) is preferably a thermosetting compound represented by the following formula (2), and the thermosetting compound represented by the above formula (3-1) is It is preferable that it is a thermosetting compound represented by Formula (3). That is, the mixture of thermosetting compounds according to the present invention preferably contains a thermosetting compound represented by the following formula (1), and may contain a thermosetting compound represented by the following formula (2). Preferably, it contains a thermosetting compound represented by the following formula (3). In the mixture of thermosetting compounds according to the present invention, since two or more specific thermosetting compounds are mixed, it is represented by the following formula (1), the following formula (2), or the following formula (3). Even if a thermosetting compound is used, the storage stability of the mixture of thermosetting compounds can be improved.

  In the above formula (1), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, 2 to 4 groups out of 4 groups of R3, R4, R5 and R6 each represent a hydrogen atom, The group which is not a hydrogen atom among R3, R4, R5 and R6 represents a group represented by the above formula (4), and X1 and X2 each represent an oxygen atom or a sulfur atom.

  In the above formula (2), R51 and R52 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R53, R54, R55, R56, R57 and R58 are hydrogen. A group which is an atom and is not a hydrogen atom among R53, R54, R55, R56, R57 and R58 represents a group represented by the above formula (5), and X51 and X52 each represents an oxygen atom or a sulfur atom. .

  In the above formula (3), R101 and R102 each represent an alkylene group having 1 to 5 carbon atoms, and 6 to 8 of 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 The group of represents a hydrogen atom, the group which is not a hydrogen atom among R103, R104, R105, R106, R107, R108, R109 and R110 represents a group represented by the above formula (6), and X101 and X102 represent Each represents an oxygen atom or a sulfur atom.

  From the viewpoint of curing more rapidly at a low temperature, the thermosetting compound represented by the above formula (1-1) preferably has at least one thiirane group, and is represented by the above formula (2-1). The thermosetting compound preferably has at least one thiirane group, and the thermosetting compound represented by the formula (3-1) preferably has at least one thiirane group. In the mixture of thermosetting compounds according to the present invention, since two or more specific thermosetting compounds are mixed, the storage stability of the mixture of thermosetting compounds is good even if a thiirane group is introduced. Can be.

  From the viewpoint of curing more rapidly at a low temperature, in the above formula (1-1), X1 and X2 are each a sulfur atom, and in the above formula (4), X3 is preferably a sulfur atom. In Formula (2-1), X51 and X52 are each a sulfur atom, and in Formula (5), X53 is preferably a sulfur atom. In Formula (3-1), X101 and X102 are each It is preferably a sulfur atom, and in the above formula (6), X103 is preferably a sulfur atom. Even in this case, since two or more specific thermosetting compounds are mixed, the storage stability of the mixture of thermosetting compounds can be improved.

  Any of the thermosetting compounds represented by the above formula (1-1), (2-1) or (3-1) and the above formula (1), (2) or (3) has at least an epoxy group. 2 or at least two thiirane groups, or at least two total epoxy groups and thiirane 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 can be rapidly cured at a low temperature by heating a curable composition containing a mixture of thermosetting compounds and a curing agent. Among these, a naphthalene ring is preferable because it has a planar structure and can be cured more rapidly.

  The thermosetting compound represented by the above formula (1-1), (2-1) or (3-1) and the above formula (1), (2) or (3) is represented by the above formula (1-1). ), (2-1) or (3-1), when X1, X2, X51, X52, X101 and X102 are thiirane groups, X1, X2, X51, X52, which are thiirane groups, Compared with an epoxy compound having a structure in which X101 and X102 are replaced with epoxy groups, the reactivity is high, and the resin 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 formulas (3-1) and (3) R7 in the above formula (4), R59 in the above formula (5), and R111 in the above formula (6) 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 mixture of the thermosetting compound will fall easily.

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

  The thermosetting compound represented by the above (1) is preferably a thermosetting compound represented by the following formula (1A). It is preferable that the mixture of thermosetting compounds according to the present invention includes a thermosetting compound represented by the following formula (1A). The thermosetting compound represented by the following formula (1A) is excellent in curability.

  In said formula (1A), R1 and R2 represent a C1-C5 alkylene group, respectively, and X1 and X2 represent an oxygen atom or a sulfur atom, respectively.

  The thermosetting compound represented by the above (2) preferably has a structure represented by the following formula (2A). The mixture of thermosetting compounds according to the present invention preferably contains a thermosetting compound represented by the following formula (2A). The thermosetting compound represented by the following formula (2A) is excellent in curability.

  In said formula (2A), R51 and R52 represent a C1-C5 alkylene group, respectively, and X51 and X52 represent an oxygen atom or a sulfur atom, respectively.

  The thermosetting compound represented by (3) is preferably a thermosetting compound represented by the following formula (3A). The mixture of thermosetting compounds according to the present invention preferably contains a thermosetting compound represented by the following formula (3A). The thermosetting compound represented by the following formula (3A) is excellent in curability.

  In said formula (3A), R101 and R102 represent a C1-C5 alkylene group, respectively, and X101 and X102 represent an oxygen atom or a sulfur atom, respectively.

  From the viewpoint of further suppressing the crystallization of the thermosetting compound mixture and further improving the storage stability of the thermosetting compound mixture and the curable composition containing the thermosetting compound mixture, the above formula (1- The isomer of the thermosetting compound represented by 1), (1) or (1A) is a bond of a group bonded to the benzene ring in the above formula (1-1), (1) or (1A) It is preferable that only the site | part differs, and the isomer of the thermosetting compound represented by said Formula (2-1), (2) or (2A) is said Formula (2-1), (2 ) Or (2A) is preferably an isomer which is different only in the bonding site of the group bonded to the naphthalene ring, and is represented by the above formula (3-1), (3) or (3A). The isomer of the active compound is bonded to the anthracene ring in the above formula (3-1), (3) or (3A). It is preferred only binding sites are different isomers.

  From the viewpoint of further suppressing the crystallization of the thermosetting compound mixture and further improving the storage stability of the thermosetting compound mixture and the curable composition containing the thermosetting compound mixture, the above formula (1- 1) A total of 100 of the thermosetting compound represented by (1) or (1A) and the isomer of the thermosetting compound represented by the formula (1-1), (1) or (1A) The content of the thermosetting compound represented by the above formula (1-1), (1) or (1A) is preferably 5.0% by weight or more and 40.0% by weight or less in weight%. The isomerism of the thermosetting compound represented by the above formula (2-1), (2) or (2A) and the thermosetting compound represented by the formula (2-1), (2) or (2A) The total content of the thermosetting compound represented by the formula (2-1), (2) or (2A) is 5.0% by weight in 100% by weight with the body The upper limit is preferably 40.0% by weight or less, and the thermosetting compound represented by the above formula (3-1), (3) or (3A) and the formula (3-1), (3) Alternatively, the content of the thermosetting compound represented by the above formula (3-1), (3) or (3A) is 100% by weight in total with the isomer of the thermosetting compound represented by (3A). It is preferably 5.0% by weight or more and 40.0% by weight or less.

  When an example of the specific example of the mixture of the thermosetting compound according to the present invention is given, the thermosetting compound represented by the following formula (2B), the thermosetting compound represented by the following formula (2C), and the following formula The mixture which mixed at least 2 sort (s) among the thermosetting compounds represented by (2D) is mentioned.

  A preferred example of the compounding ratio that can suppress the crystallization of the mixture of the thermosetting compound and can further improve the storage stability of the mixture of the thermosetting compound and the curable composition containing the mixture of the thermosetting compound. For example, the thermosetting compound represented by the following formula (2B) is 10 wt% or more and 30 wt% or less, and the thermosetting compound represented by the following formula (2C) is 0 wt% or more and 30 wt% or less. And a mixture of 40% by weight to 90% by weight of a thermosetting compound represented by the following formula (2D). In this preferable blending ratio, the thermosetting compound represented by the following formula (2C) may not be included.

  When the thermosetting compound described above is an episulfide compound, the episulfide compound can be obtained by converting a part of epoxy groups of the epoxy compound into thiirane groups. Examples of the sulfurizing agent include thiocyanates, thioureas, phosphine sulfide, dimethylthioformamide, N-methylbenzothiazol-2-thione, and the like. Examples of the thiocyanates include sodium thiocyanate, potassium thiocyanate, and sodium thiocyanate.

  Specifically, the episulfide compound can be produced as follows using the epoxy compound and the sulfurizing agent.

  In a container equipped with a stirrer, a cooler, and a thermometer, a solvent and the sulfiding agent are added to dissolve the sulfiding agent to prepare a first solution in the container. Examples of the solvent include methanol or ethanol.

  In addition to the first solution, a solution containing the epoxy compound or the epoxy compound is prepared.

  Next, the epoxy compound or the solution containing the epoxy compound is continuously or intermittently added to the first solution. It is preferable that the temperature of the 1st solution at this time exists in the range of 15-30 degreeC. It is preferable to stir for 0.5 to 12 hours after the addition of the epoxy compound. You may add the said epoxy compound or the solution containing this epoxy compound in several steps. For example, after adding a part of the epoxy compound or the solution containing the epoxy compound, the mixture is stirred for at least 0.5 hour, and then the remaining epoxy compound or the solution containing the epoxy compound is further added. Stir for ~ 12 hours. When using the solution containing the said epoxy compound, the density | concentration of the epoxy compound of this solution is not specifically limited.

  The addition rate of the epoxy compound or the solution containing the epoxy compound in the first solution is preferably in the range of 1 to 10 mL / min, and more preferably in the range of 2 to 8 mL / min. . If the addition rate of the epoxy compound or the solution containing the epoxy compound is too fast, the epoxy compound may be polymerized. If the addition rate of the epoxy compound or the solution containing the epoxy compound is too slow, the production efficiency of the episulfide compound may be reduced.

  In the mixed solution in which the epoxy compound or the solution containing the epoxy compound is added to the first solution, the concentration of the epoxy compound is preferably in the range of 0.05 to 0.8 g / mL. More preferably, it is in the range of 1 to 0.5 g / mL. If the concentration of the epoxy compound is too high, the epoxy compound may polymerize.

  Next, the second solution containing the solvent and the sulfiding agent is further continuously or intermittently added to the mixed solution in which the epoxy compound or the solution containing the epoxy compound is added to the first solution. . It is preferable to stir for 0.5 to 12 hours after the addition of the second solution. Moreover, it is preferable to stir within the range of 15-60 degreeC after addition of the said 2nd solution. The second solution may be added in multiple stages. For example, a part of the second solution may be added and then stirred for at least 0.5 hour, and then the remaining second solution may be further added and stirred for 0.5 to 12 hours.

  The concentration of the sulfiding agent in the second solution is preferably in the range of 0.001 to 0.7 g / mL, and more preferably in the range of 0.005 to 0.5 g / mL. When the concentration of the sulfiding agent is not less than the above lower limit, polymerization of the epoxy compound can be suppressed. When the concentration of the sulfiding agent is not less than the above lower limit, the epoxy group can be more efficiently converted by the thiirane group.

  The rate of addition of the second solution into the mixed solution is preferably in the range of 1 to 10 mL / min, and more preferably in the range of 2 to 8 mL / min. When the addition rate of the second solution is not more than the upper limit, polymerization of the epoxy compound can be suppressed. When the addition rate of the second solution is equal to or higher than the lower limit, the production efficiency of the episulfide compound is further increased.

  It is preferable to remove the solvent or the unreacted sulfiding agent after adding the second solution to the mixed solution in which the epoxy compound is added to the first solution. By removing the sulfurizing agent, the storage stability of the episulfide compound and the curable composition is further enhanced. A conventionally known method is used as a method of removing the solvent or the unreacted sulfurizing agent.

  The first solution or the second solution may contain a catalyst such as palladium metal particles or titanium oxide. By using a solution containing the catalyst, the conversion rate to thiirane groups can be adjusted. Moreover, since an epoxy group can be converted into a thiirane group in a low temperature environment, the polymerization reaction of an epoxy compound can be suppressed. The concentration of the catalyst in the first solution or the concentration of the catalyst in the second solution is preferably in the range of 0.05 to 1.0 g / mL.

  As described above, all or some of the epoxy groups of the epoxy compound can be converted into thiirane groups. As a result, an episulfide compound can be obtained. Moreover, the mixture (episulfide compound containing mixture) of an episulfide compound and an epoxy compound can be obtained by converting all or one part epoxy groups of the said epoxy compound into a thiirane group. The episulfide compound-containing mixture may contain an unreacted epoxy compound and may contain impurities depending on circumstances. The episulfide compound-containing mixture preferably contains 10 to 100% by weight of the episulfide compound and 90 to 0% by weight of the epoxy compound. The episulfide compound-containing mixture may contain only the episulfide compound. The episulfide compound-containing mixture may contain 10 to 99.9% by weight of the episulfide compound and 90 to 0.1% by weight of the epoxy compound, and 10 to 50% by weight of the episulfide compound and 90% of the epoxy compound. Up to 50% by weight.

(Curable composition)
The curable composition which concerns on this invention contains the mixture of the thermosetting compound which concerns on this invention, and a thermosetting agent. In the curable composition according to the present invention, the crystallization of the mixture of thermosetting compounds does not easily proceed, and the storage stability can be improved.

[Thermosetting agent]
The thermosetting agent contained in the curable composition according to the present invention is not particularly limited. The thermosetting agent cures the mixture of the thermosetting compounds. Moreover, when the curable composition concerning this invention contains an epoxy compound, the said thermosetting agent also hardens an epoxy compound. A conventionally known thermosetting agent can be used as the thermosetting agent. As for this thermosetting agent, only 1 type may be used and 2 or more types may be used together.

  Examples of the thermosetting agent include imidazole curing agents, amine curing agents, phenol curing agents, polythiol curing agents, and acid anhydrides. 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 of a curable composition can be improved, a latent hardening | 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. 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 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, Hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5] Examples include undecane, bis (4-aminocyclohexyl) methane, metaphenylenediamine, and diaminodiphenylsulfone.

  Among the thermosetting 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 content of the thermosetting agent is not particularly limited. In the curable composition according to the present invention, the content of the thermosetting agent is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, preferably 100 parts by weight of the mixture of thermosetting compounds. It is 200 parts by weight or less, more preferably 100 parts by weight or less, and still more preferably 75 parts by weight or less. It is easy to fully harden a curable composition as content of a thermosetting agent is more than the said minimum. When the content of the thermosetting agent is not more than the above upper limit, it is difficult for an excess thermosetting agent that did not participate in curing after curing to remain, and the heat resistance of the cured product is further enhanced.

  When the thermosetting 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 1 part by weight or more with respect to 100 parts by weight of the mixture of the thermosetting compound. The amount is preferably 15 parts by weight or less. Moreover, when the said thermosetting agent is an amine hardening agent, a polythiol hardening agent, or an acid anhydride, content of an amine hardening agent, a polythiol hardening agent, or an acid anhydride with respect to 100 weight part of the mixture of the said thermosetting compound. Is preferably 15 parts by weight or more, and preferably 40 parts by weight or less.

[Other curing components]
The curable composition according to the present invention may contain other epoxy compounds and other episulfide compounds different from the thermosetting compounds in the mixture of thermosetting compounds, in addition to the mixture of thermosetting compounds. .

  The epoxy compound is not particularly limited. A conventionally well-known epoxy compound can be used as an epoxy compound. As for the said epoxy compound, only 1 type may be used and 2 or more types may be used together.

  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 ring, epoxy resins having a tricyclodecane ring, and epoxy resins having a triazine nucleus in the ring.

  Furthermore, the curable composition according to the present invention includes, as an epoxy compound, a monomer of an epoxy compound represented by the following formula (21), a multimer in which at least two of the epoxy compounds are bonded, or the monomer And a mixture of the multimers.

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

  The curable composition according to the present invention includes, as an epoxy compound or an episulfide compound, a monomer of a compound represented by the following formula (31), a multimer in which at least two of the compounds are bonded, or the monomer A mixture with the multimer may be contained.

  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. The alkylene group of number 1-5 is represented, X1 and X2 represent an oxygen atom or a sulfur atom, respectively, and X2 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 curable composition concerning this invention may contain the epoxy compound which has a heterocyclic ring containing a nitrogen atom as an epoxy compound. 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. R4-6 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 curable composition according to the present invention preferably contains an epoxy compound having an aromatic ring as the epoxy compound. 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.

[Other ingredients]
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.

  The content of the curing accelerator is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, preferably 6 parts by weight or less, more preferably 100 parts by weight of the mixture of thermosetting compounds. 4 parts by weight or less. It is easy to fully harden a curable composition as content of a hardening accelerator is more than the said minimum. When the content of the curing accelerator is less than or equal to the above upper limit, it is difficult for an excessive curing accelerator that did not participate in curing after curing to remain.

  The curable composition according to the present invention may further contain a photocurable compound and a photopolymerization initiator so as to be cured by light irradiation. 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 the composition containing the episulfide compound and the (meth) acrylic resin, when the thiirane group of the episulfide compound is opened to generate a radical, the polymerization of the (meth) acrylic resin is likely to proceed due to the action of the radical. . By blending the episulfide compound with a phenolic compound and a storage stabilizer described later in combination, it is difficult for the thiirane group 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 preferably includes light having at least one kind of epoxy group and a (meth) acryl group and a thermosetting compound (hereinafter also referred to as a partially (meth) acrylated epoxy resin).

  The partially (meth) acrylated epoxy resin can be obtained, for example, by reacting an epoxy resin and (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 groups are converted to (meth) acryloyl groups (conversion rate) and partially (meth) acrylated. More preferably, 50% of the epoxy groups are converted to (meth) acryloyl groups.

  Examples of the epoxy (meth) acrylate 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. .

  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 content of the photocurable compound is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the thermosetting compound mixture. The amount is preferably 1 part by weight or more, more preferably 10 parts by weight or more, particularly preferably 50 parts by weight or more, preferably 10,000 parts by weight or less, more preferably 1000 parts by weight or less, and still more preferably 500 parts by weight or less.

  The photopolymerization initiator is not particularly limited. 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, benzophenone photopolymerization initiator, thioxanthone, ketal photopolymerization initiator, halogenated ketone, acyl phosphinoxide, and acyl phosphonate.

  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 content of the photopolymerization initiator with respect to 100 parts by weight of the photocurable composition is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, and further preferably 2 parts by weight or more. The amount is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. When the content of the photopolymerization initiator is not less than the above lower limit, it is easy to sufficiently obtain the effect of adding the photopolymerization initiator. When the content of the photopolymerization initiator is not more than the above upper limit, the adhesive strength of the cured product of the curable composition is sufficiently increased.

  The curable composition according to the present invention preferably further contains a phenolic compound. By using the episulfide compound, the thermosetting agent, and the phenolic compound in combination, the thiirane group is more difficult to open during storage of the curable composition. Moreover, when a curable composition containing conductive particles is disposed between the electrodes and the conductive particles are appropriately compressed, an appropriate indentation can be formed on the electrodes. Therefore, the connection resistance between the electrodes can be lowered.

  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.

  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. Specific examples of the filler include silica, aluminum nitride, and alumina. As for a filler, only 1 type may be used and 2 or more types may be used together.

  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 thermosetting compound is solid, the dispersibility of the thermosetting compound can be improved by adding a solvent to the solid thermosetting compound 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 preferably further contains a storage stabilizer. The curable composition according to the present invention preferably contains at least one selected from the group consisting of phosphate ester, phosphite ester and borate ester as the storage stabilizer, and phosphate ester and phosphorous acid. It is more preferable to include at least one of the esters, and it is even more preferable to include a phosphite. By using these storage stabilizers, particularly by using phosphites, the storage stability of the episulfide compound can be further enhanced. As for the said storage stabilizer, only 1 type may be used and 2 or more types may be used together.

  Examples of the phosphate ester include diethyl benzyl phosphate. As the phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite or diphenyl mono (tridecyl) phosphite is preferable, and diphenyl monodecyl phosphite and diphenyl mono (tridecyl) phosphite are listed. It is done.

  The curable composition according to the present invention is at least one component selected from the group consisting of 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 May be included. By blending these components, the storage stability of the curable composition is increased.

  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.

  The conductive particles are preferably conductive particles in which the surface of the resin particles is covered with a conductive layer.

  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 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 20% by weight or less, more preferably 15% by weight or less. More preferably, it is 10% by weight or less. A conductive particle can be easily arrange | positioned between the upper and lower electrodes which should be connected as content of the said electroconductive particle is more than the said minimum and below the said upper limit. 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 in order to adhere | attach 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 can be used as an anisotropic conductive paste, an anisotropic conductive film, or the like. When the anisotropic conductive material is used as a film-like adhesive such as an anisotropic conductive film, the film-like adhesive containing no conductive particles is added to the film-like adhesive containing the conductive particles. May be laminated.

  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.

  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 | substrate with which metal foil was laminated | stacked are mentioned. The first and second connection target members are preferably electronic components or circuit boards.

  The manufacturing method of the connection structure is not particularly limited. As an example of a method for manufacturing a connection structure, the anisotropic conductive material is provided 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. Examples of the method include arranging and obtaining a laminate, and then heating and pressurizing the laminate.

  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.

  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.

(Synthesis Example 1)
Preparation of thermosetting compound represented by formula (2B):
In a 2 L vessel equipped with a stirrer, a cooler and a thermometer, 250 mL of ethanol and 20 g of trimethylthiourea (made by Ouchi Shinsei Chemical Co., Ltd.) as a sulfurizing agent were added, and trimethylthiourea (made by Ouchi Shinsei Chemical Co., Ltd.) was added. ) Was dissolved to prepare a first solution. Thereafter, the temperature in the container was kept in the range of 20 to 25 ° C. Next, while stirring the first solution in the container maintained at 20 to 25 ° C., an epoxy compound represented by the following formula (12B) (represented by the following formula (2B)) is added to the first solution. A solution in which 160 g of an epoxy compound having a structure in which the thiirane group in the structure is replaced with an epoxy group) is dispersed in 200 mL of toluene was dropped at a rate of 5 mL / min. After dropping, the mixture was further stirred for 30 minutes to obtain an epoxy compound-containing solution.

  Next, a second solution was prepared by dissolving 20 g of trimethylthiourea (manufactured by Ouchi Shinsei Chemical Co., Ltd.) in a solution containing 100 mL of ethanol. 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 the stirring, a second solution in which 20 g of trimethylthiourea (manufactured by Ouchi Shinsei Chemical Co., Ltd.) is dissolved in a solution containing 100 mL of ethanol is further prepared. Further added 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, all the epoxy groups of the epoxy compound were converted to thiirane groups to obtain a thermosetting compound represented by the following formula (2B).

¹ H-NMR of the obtained mixture A was measured 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 disappeared, and the signal appeared in the region of 2.0 to 3.0 ppm indicating the presence of the thiirane group. This confirmed that all the epoxy groups of the epoxy compound represented by the said Formula (12B) were converted into the thiirane group.

  Moreover, the thermosetting compound represented by following formula (2C) and the following formula (2D) was synthesize | combined by the procedure similar to the synthesis example 1 of the thermosetting compound represented by Formula (2B).

Example 1
25 parts by weight of the thermosetting compound represented by the above formula (2B) obtained, 75 parts by weight of the thermosetting compound represented by the above formula (2C), and epoxy acrylate which is a photocurable compound ((Meth) acrylic resin, “EBECRYL 3702” manufactured by Daicel-Cytec, Inc.) and 0.1 part by weight of an acylphosphine oxide compound (“DAROCUR TPO” manufactured by Ciba Japan) that is a photopolymerization initiator, 0.58 parts by weight of α-methylbenzylphenol as a phenolic compound, 20 parts by weight of pentaerythritol tetrakis-3-mercaptopropionate as a thermosetting agent, and 2-ethyl-4-methylimidazole as a curing accelerator 1 part by weight, 20 parts by weight of silica having an average particle diameter of 0.25 μm as filler, and Al having an average particle diameter of 0.5 μm 20 parts by weight of Na and 2 parts by weight of conductive particles having an average particle diameter of 3 μm are added and stirred for 5 minutes at 2000 rpm using a planetary stirrer to obtain a curable composition that is an anisotropic conductive paste. It was. 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)
25 parts by weight of the thermosetting compound represented by the above formula (2B) obtained and 75 parts by weight of the thermosetting compound represented by the above formula (2C) thus obtained were obtained by the above formula (2B ) In the same manner as in Example 1 except that it was changed to 30 parts by weight of the thermosetting compound represented by (2) and 70 parts by weight of the thermosetting compound represented by the above formula (2D). A composition was obtained.

(Example 3)
25 parts by weight of the thermosetting compound represented by the above formula (2B) obtained and 75 parts by weight of the thermosetting compound represented by the above formula (2C) thus obtained were obtained by the above formula (2B 25 parts by weight of the thermosetting compound represented by the formula (2), 15 parts by weight of the thermosetting compound represented by the formula (2C) obtained, and the thermosetting represented by the formula (2D) obtained. A curable composition was obtained in the same manner as in Example 1 except that the amount was changed to 60 parts by weight of the compound.

Example 4
Epoxy acrylate ((meth) acrylic resin, “EBECRYL 3702” manufactured by Daicel Cytec Co., Ltd.) that is a photocurable compound, and an acylphosphine oxide compound (“DAROCUR TPO” manufactured by Ciba Japan) that is a photopolymerization initiator. A curable composition was obtained in the same manner as in Example 1 except that it was not blended.

(Example 5)
5 parts by weight of epoxy acrylate ((meth) acrylic resin, “EBECRYL 3702” manufactured by Daicel-Cytec), which is a photocurable compound, and an acylphosphine oxide compound (“DAROCUR TPO”, manufactured by Ciba Japan), which is a photopolymerization initiator ) A curable composition was obtained in the same manner as in Example 2 except that 0.1 part by weight was not added.

(Example 6)
5 parts by weight of epoxy acrylate ((meth) acrylic resin, “EBECRYL 3702” manufactured by Daicel-Cytec), which is a photocurable compound, and an acylphosphine oxide compound (“DAROCUR TPO”, manufactured by Ciba Japan), which is a photopolymerization initiator ) A curable composition was obtained in the same manner as in Example 3 except that 0.1 part by weight was not added.

(Comparative Example 1)
25 parts by weight of the thermosetting compound represented by the above formula (2B) obtained and 75 parts by weight of the thermosetting compound represented by the above formula (2C) thus obtained were obtained by the above formula (2B The curable composition was obtained in the same manner as in Example 1 except that only the thermosetting compound represented by 100) was changed to 100 parts by weight.

(Comparative Example 2)
25 parts by weight of the thermosetting compound represented by the above formula (2B) obtained and 75 parts by weight of the thermosetting compound represented by the above formula (2C) thus obtained were obtained by the above formula (2C The curable composition was obtained in the same manner as in Example 1 except that only the thermosetting compound represented by 100) was changed to 100 parts by weight.

(Comparative Example 3)
25 parts by weight of the obtained thermosetting compound represented by the above formula (2B) and 75 parts by weight of the obtained thermosetting compound represented by the above formula (2C) were used to obtain the above formula (2D The curable composition was obtained in the same manner as in Example 1 except that only the thermosetting compound represented by 100) was changed to 100 parts by weight.

(Evaluation of Examples 1-6 and Comparative Examples 1-3)
(1) Storage stability The curable compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were stored at 20 ° C. and a humidity of 65% for 24 hours. After storage, it was evaluated whether or not there was a crystallized product derived from the thermosetting compound in the curable composition.

  As a result, in Examples 1 to 6, no crystallized product derived from the thermosetting compound was observed after storage. In Comparative Examples 1 to 3, a crystallized product derived from the thermosetting compound was observed after storage.

(2) Preparation of connection structure A 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 transparent glass substrate, the curable compositions obtained in Examples 1 to 3 were applied so as to have a thickness of 30 μm, and the (meth) acrylic resin was cured by irradiating UV light, A 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 A was obtained. In the obtained connection structure A, the electrodes were electrically connected, and the transparent glass substrate and the semiconductor chip were firmly bonded via the cured product layer.

(3) Production of connection structure B 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 curable composition obtained in Examples 4-6 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, and the curable composition layer is cured at 185 ° C. B was obtained. In the obtained connection structure B, the electrodes were electrically connected, and the transparent glass substrate and the semiconductor chip were firmly bonded via the cured product layer.

(Example 7)
25 parts by weight of the thermosetting compound represented by the above formula (2B) and 75 parts by weight of the thermosetting compound represented by the above formula (2C) were mixed, A mixture was obtained.

(Example 8)
30 parts by weight of the thermosetting compound represented by the above formula (2B) and 70 parts by weight of the thermosetting compound represented by the above formula (2D) were mixed, A mixture was obtained.

Example 9
25 parts by weight of the thermosetting compound represented by the above formula (2B) obtained, 15 parts by weight of the thermosetting compound represented by the above formula (2C) obtained, and the above formula (2D) obtained Was mixed with 60 parts by weight of a thermosetting compound represented by the following formula to obtain a mixture of thermosetting compounds.

(Comparative Example 4)
The thermosetting compound represented by the said formula (2B) obtained.

(Comparative Example 5)
The thermosetting compound represented by the above formula (2C).

(Comparative Example 6)
The thermosetting compound represented by the said formula (2D) obtained.

(Evaluation of Examples 7 to 9 and Comparative Examples 4 to 6)
The mixture of the thermosetting compounds obtained in Examples 7 to 9 and the thermosetting compound obtained in Comparative Examples 4 to 6 were stored at 20 ° C. and a humidity of 65% for 24 hours. After storage, it was evaluated whether or not there was a crystallized product derived from the thermosetting compound in the mixture of thermosetting compounds or the thermosetting compound.

  As a result, in Examples 7 to 9, no crystallized product derived from the thermosetting compound was observed after storage. In Comparative Examples 4 to 6, a crystallized product derived from the thermosetting compound was observed after storage.

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)

The thermosetting compound represented by the following formula (1-1) and an isomer of the thermosetting compound represented by the formula (1-1),
A thermosetting compound represented by the following formula (2-1) and an isomer of the thermosetting compound represented by the formula (2-1), or
The mixture of the thermosetting compound containing the thermosetting compound represented by following formula (3-1), and the isomer of the thermosetting compound represented by this formula (3-1).

In the above formula (1-1), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, and 2 to 4 groups out of 4 groups of R3, R4, R5 and R6 represent a hydrogen atom. And a group which is not a hydrogen atom among R3, R4, R5 and R6 represents a group represented by the following formula (4), and X1 and X2 each represents an oxygen atom or a sulfur atom.

In said formula (4), R7 represents a C1-C5 alkylene group, X3 represents an oxygen atom or a sulfur atom.

In the above formula (2-1), R51 and R52 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R53, R54, R55, R56, R57 and R58. Represents a hydrogen atom, a group that is not a hydrogen atom among R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (5), and X51 and X52 are an oxygen atom or a sulfur atom, respectively. Represents.

In said formula (5), R59 represents a C1-C5 alkylene group, X53 represents an oxygen atom or a sulfur atom.

In the above formula (3-1), R101 and R102 each represent an alkylene group having 1 to 5 carbon atoms, and 6 to 8 of 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 Eight groups represent hydrogen atoms, and the groups that are not hydrogen atoms among R103, R104, R105, R106, R107, R108, R109, and R110 represent groups represented by the following formula (6), and X101 and X102 represents an oxygen atom or a sulfur atom, respectively.

In said formula (6), R111 represents a C1-C5 alkylene group, X103 represents an oxygen atom or a sulfur atom. The isomers of the thermosetting compound represented by the formula (1-1) are isomers that differ only in the bonding site of the group bonded to the benzene ring in the formula (1-1).
The isomers of the thermosetting compound represented by the formula (2-1) are isomers that differ only in the bonding site of the group bonded to the naphthalene ring in the formula (2-1),
The isomer of the thermosetting compound represented by the formula (3-1) is an isomer that is different only in the bonding site of the group bonded to the anthracene ring in the formula (3-1). A mixture of thermosetting compounds according to 1. In a total of 100 wt% of the thermosetting compound represented by the formula (1-1) and the isomer of the thermosetting compound represented by the formula (1-1), the formula (1-1) The content of the thermosetting compound represented is 5.0 wt% or more and 40.0 wt% or less,
In a total of 100 wt% of the thermosetting compound represented by the formula (2-1) and the isomer of the thermosetting compound represented by the formula (2-1), the formula (2-1) The content of the thermosetting compound represented is 5.0 wt% or more and 40.0 wt% or less,
In a total of 100 wt% of the thermosetting compound represented by the formula (3-1) and the isomer of the thermosetting compound represented by the formula (3-1), the formula (3-1) The mixture of the thermosetting compound of Claim 1 or 2 whose content of the thermosetting compound represented is 5.0 weight% or more and 40.0 weight% or less. The thermosetting compound represented by the formula (1-1) is a thermosetting compound represented by the following formula (1),
The thermosetting compound represented by the formula (2-1) is a thermosetting compound represented by the following formula (2),
The thermosetting compound according to any one of claims 1 to 3, wherein the thermosetting compound represented by the formula (3-1) is a thermosetting compound represented by the following formula (3). Mixture of.

In the above formula (1), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, 2 to 4 groups out of 4 groups of R3, R4, R5 and R6 each represent a hydrogen atom, The group which is not a hydrogen atom among R3, R4, R5 and R6 represents a group represented by the above formula (4), and X1 and X2 each represent an oxygen atom or a sulfur atom.

In the above formula (2), R51 and R52 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R53, R54, R55, R56, R57 and R58 are hydrogen. A group which is an atom and is not a hydrogen atom among R53, R54, R55, R56, R57 and R58 represents a group represented by the above formula (5), and X51 and X52 each represents an oxygen atom or a sulfur atom. .

In the above formula (3), R101 and R102 each represent an alkylene group having 1 to 5 carbon atoms, and 6 to 8 of 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 The group of represents a hydrogen atom, the group which is not a hydrogen atom among R103, R104, R105, R106, R107, R108, R109 and R110 represents a group represented by the above formula (6), and X101 and X102 represent Each represents an oxygen atom or a sulfur atom. The thermosetting compound represented by the formula (1) is a thermosetting compound represented by the following formula (1A),
The thermosetting compound represented by the formula (2) is a thermosetting compound represented by the following formula (2A),
The mixture of the thermosetting compound of Claim 4 whose thermosetting compound represented by said Formula (3) is a thermosetting compound represented by following formula (3A).

In said formula (1A), R1 and R2 represent a C1-C5 alkylene group, respectively, and X1 and X2 represent an oxygen atom or a sulfur atom, respectively.

In said formula (2A), R51 and R52 represent a C1-C5 alkylene group, respectively, and X51 and X52 represent an oxygen atom or a sulfur atom, respectively.

In said formula (3A), R101 and R102 represent a C1-C5 alkylene group, respectively, and X101 and X102 represent an oxygen atom or a sulfur atom, respectively.   In any one of Claims 1-3 containing the thermosetting compound represented by the said Formula (2-1), and the isomer of the thermosetting compound represented by this Formula (2-1). Mixtures of the thermosetting compounds described. The thermosetting compound represented by the formula (1-1) has at least one thiirane group,
The thermosetting compound represented by the formula (2-1) has at least one thiirane group,
The mixture of thermosetting compounds according to any one of claims 1 to 3, wherein the thermosetting compound represented by the formula (3-1) has at least one thiirane group. In the formula (1-1), X1 and X2 are each a sulfur atom, and in the formula (4), X3 is a sulfur atom,
In the formula (2-1), X51 and X52 are each a sulfur atom, and in the formula (5), X53 is a sulfur atom,
The thermosetting according to any one of claims 1 to 3, wherein in the formula (3-1), X101 and X102 are each a sulfur atom, and in the formula (6), X103 is a sulfur atom. A mixture of compounds.   The mixture of thermosetting compounds according to any one of claims 1 to 8, which is a mixture of thermosetting compounds to which a thermosetting agent is added.   A curable composition comprising the mixture of thermosetting compounds according to claim 1 and a thermosetting agent.   The curable composition of Claim 10 which further contains a photocurable compound and a photoinitiator.   The curable composition according to claim 10 or 11, further comprising conductive particles. A first connection target member, a second connection target member, and a connection part connecting the first and second connection target members;
A connection structure in which the connection portion is formed by curing the curable composition according to claim 10 or 11. The curable composition comprises conductive particles;
The connection structure according to claim 13, wherein the first and second connection target members are electrically connected by the conductive particles.

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