JP4730695B2 - Curable composition and connection structure - Google Patents

Description

  The present invention is an episulfide compound that can be rapidly cured at a low temperature, and can be efficiently connected to the connection target member and can suppress the formation of voids after the connection when used for connection of the connection target member. And an episulfide compound-containing mixture containing the episulfide compound, a method for producing the episulfide compound-containing mixture, a curable composition, and a connection structure.

  Anisotropic conductive materials such as anisotropic conductive pastes, anisotropic conductive inks, anisotropic conductive adhesives, anisotropic conductive films, and anisotropic conductive sheets are widely known.

  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, or 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 a different material containing a thermosetting insulating adhesive, conductive particles, an imidazole-based latent curing agent, and an amine-based latent curing agent. An isotropic conductive adhesive film is disclosed. Patent Document 1 describes that the connection reliability is excellent even when this anisotropic conductive adhesive film is cured at a relatively low temperature.

JP-A-9-115335

  In recent years, in order to efficiently connect electrodes of electronic components, it is required to lower the heating temperature required for the connection and to shorten the pressurization time. Moreover, since electronic components are easily deteriorated by heating, it is strongly required to lower the heating temperature.

  In the anisotropic conductive adhesive film described in Patent Document 1, the heating temperature required to start curing is relatively low. However, in this anisotropic conductive adhesive film, the curing reaction may not proceed sufficiently at low temperatures. For this reason, in order to connect between an electrode of a circuit board and an electronic component using an anisotropic conductive adhesive film, it may be necessary to raise heating temperature or to heat for a long time. Therefore, the electrodes may not be efficiently connected.

  Further, in recent years, miniaturization of electrodes formed on a circuit board or the like has progressed. That is, L / S indicating the dimension (L) in the width direction of the line where the electrode is formed and the dimension (S) in the width direction of the space where the electrode is not formed is further reduced. When circuit boards on which such fine electrodes are formed are connected by the above anisotropic conductive adhesive film, voids may occur in the space between the electrodes because the curing speed of the anisotropic conductive adhesive film is slow. is there.

  The object of the present invention can be cured quickly at a low temperature, and further, when used for connection of a connection target member, the connection target member can be efficiently connected, and generation of voids after connection can be suppressed. An object is to provide an episulfide compound, an episulfide compound-containing mixture containing the episulfide compound, a method for producing the episulfide compound-containing mixture, a curable composition, and a connection structure.

According to a wide aspect of the present invention, an episulfide compound having a structure represented by the following formula (2-1) or (3) (excluding an episulfide compound having a structure represented by the following formula (1-1)) and A curable composition containing a curing agent and conductive particles and being an anisotropic conductive material is provided.

  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 the four groups R3, R4, R5 and R6 represent hydrogen. , R3, R4, R5 and R6 are not hydrogen and represent a group represented by the following formula (4).

  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 hydrogen, and the group that is not hydrogen among R53, R54, R55, R56, R57, and R58 represents a group represented by the following formula (5).

  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 hydrogen, and 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).

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

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

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

In a specific aspect of the curable composition according to the present invention, the episulfide compound having a structure represented by the above formula (2-1) or (3) has a structure represented by the following formula (2) (the following formula (Excluding the structure represented by (1)).

  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 represent hydrogen, and R3 , R4, R5 and R6, which are not hydrogen, represent a group represented by the following formula (4).

  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. The group which is not hydrogen among R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (5).

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

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

In another specific aspect of the curable composition according to the present invention, the structure represented by the formula (2) is a structure represented by the following formula (2A) (a structure represented by the following formula (1A) is: Except).

  In said formula (1A), R1 and R2 represent a C1-C5 alkylene group, respectively.

  In said formula (2A), R51 and R52 represent a C1-C5 alkylene group, respectively.

In a specific aspect of the curable composition according to the present invention, under following formula (12-1) or the epoxy compound represented by (13) (epoxy compound represented by the following formula (11-1) is excluded) but Ru is further contained.

  In said formula (11-1), R11 and R12 represent a C1-C5 alkylene group, respectively, 2-4 groups among four groups of R13, R14, R15, and R16 represent hydrogen. , R13, R14, R15 and R16 are a group which is not hydrogen and represents a group represented by the following formula (14).

  In the formula (12-1), R61 and R62 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R63, R64, R65, R66, R67 and R68. Represents hydrogen, and the non-hydrogen group in R63, R64, R65, R66, R67 and R68 represents a group represented by the following formula (15).

  In the above formula (13), R121 and R122 each represent an alkylene group having 1 to 5 carbon atoms, and 6 to 8 of 8 groups of R123, R124, R125, R126, R127, R128, R129 and R130. The group of represents hydrogen, and 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).

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

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

In said formula (16), R131 represents a C1-C5 alkylene group.
In a specific aspect of the curable composition according to the present invention, the epoxy compound represented by the above formula (12-1) is represented by the epoxy compound represented by the following formula (12) (the following formula (11)). Excluding epoxy compounds).

  In said formula (11), R11 and R12 represent a C1-C5 alkylene group, respectively, 2-4 groups among four groups of R13, R14, R15, and R16 represent hydrogen, R13 , R14, R15 and R16 which are not hydrogen represent a group represented by the following formula (14).

  In the above formula (12), R61 and R62 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R63, R64, R65, R66, R67 and R68 are hydrogen. The group which is not hydrogen among R63, R64, R65, R66, R67 and R68 represents a group represented by the following formula (15).

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

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

In another specific aspect of the curable composition according to the present invention, the structure represented by the formula (12) is a structure represented by the following formula (12A) (a structure represented by the following formula (11A) is: Except).

  In said formula (11A), R11 and R12 represent a C1-C5 alkylene group, respectively.

  In said formula (12A), R61 and R62 represent a C1-C5 alkylene group, respectively.

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

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 with the curable composition of this invention, and the said 1st, 2nd connection object member is electrically connected by the said electroconductive particle .

  Since the episulfide compound according to the present invention has a structure represented by the above formula (1-1), (2-1) or (3), it can be rapidly cured at a low temperature.

  When the episulfide compound according to the present invention has a structure represented by the above formula (1) or (2), it can be cured more rapidly at a low temperature.

  Since the episulfide compound containing mixture which concerns on this invention contains the episulfide compound which has a structure represented by the said Formula (1-1) or (2-1), it can be hardened rapidly at low temperature.

  When the episulfide compound-containing mixture according to the present invention has a structure represented by the above formula (1) or (2), it can be cured more rapidly at a low temperature.

  Moreover, this connection object member can be efficiently connected by using the episulfide compound which concerns on this invention, or the episulfide compound containing mixture which concerns on this invention for the connection of a connection object member. Furthermore, it can suppress that a void arises after a connection. Even if the connection target member having irregularities on the surface is connected, generation of voids can be suppressed.

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.

(Episulfide compounds)
The episulfide compound according to the present invention has 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 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 (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 (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 (4), R7 represents a C1-C5 alkylene group.

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

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

  From the viewpoint of curing more rapidly at a low temperature, the episulfide compound according to the present invention 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 according to the present invention 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).

  Any of the episulfide compounds having the structure represented by the above formula (1-1), (2-1) or (3) and the above formula (1) or (2) has at least two episulfide groups. In addition, a group having an episulfide group is bonded to a benzene ring, a naphthalene ring, or an anthracene ring. Since it has such a structure, the mixture can be rapidly cured at a low temperature by heating a mixture in which, for example, a curing agent is added to the episulfide compound.

  The episulfide compound having the structure represented by the above formula (1-1), (2-1) or (3) has an episulfide group in the above formula (1-1), (2-1) or (3). Reactivity is higher than compounds that are epoxy groups. The episulfide compound having a structure represented by the above formula (1) or (2) has a higher reactivity than a compound in which the episulfide group in the above formula (1) or (2) is an epoxy group. This is because the episulfide group is easier to open and more reactive than the epoxy group. The episulfide compound having the structure represented by the above formula (1-1), (2-1) or (3) and the episulfide compound having the structure represented by the above formula (1) or (2) are reactive. Since it is high, 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 structure represented by (1) is preferably a structure represented by the following formula (1A). An episulfide compound having a structure represented by the following formula (1A) is excellent in curability.

  In said formula (1A), R1 and R2 represent a C1-C5 alkylene group, respectively.

  The structure represented by the above formula (1) is more preferably a structure represented by the following formula (1B). An episulfide compound having a structure represented by the following formula (1B) is more excellent in curability.

  The structure represented by the above (2) is preferably a structure represented by the following formula (2A). An episulfide compound having a structure represented by the following formula (2A) is excellent in curability.

  In said formula (2A), R51 and R52 represent a C1-C5 alkylene group, respectively.

  The structure represented by the above formula (2) is more preferably a structure represented by the following formula (2B). An episulfide compound having a structure represented by the following formula (2B) is more excellent in curability.

  The structure represented by the above (3) is preferably a structure represented by the following formula (3A). An episulfide compound having a structure represented by the following formula (3A) is excellent in curability.

  In said formula (3A), R101 and R102 represent a C1-C5 alkylene group, respectively.

  The structure represented by the above formula (3) is more preferably a structure represented by the following formula (3B). An episulfide compound having a structure represented by the following formula (3B) is more excellent in curability.

(Episulfide compound-containing mixture)
The episulfide compound-containing mixture according to the present invention comprises an episulfide compound represented by the above formula (1-1), (2-1) or (3) and the following formula (11-1), (12-1) or ( And an epoxy compound represented by 13). 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 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 (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 (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.

上記式（１４）中、Ｒ１７は炭素数１〜５のアルキレン基を表す。

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

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

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

  From the viewpoint of curing more rapidly at a low temperature, the episulfide compound-containing mixture according to the present invention comprises a compound represented by the above formula (1), the above formula (2) or the above formula (3), and the following formula (11): ), And an epoxy compound represented by the following formula (12) or the above formula (13). From the viewpoint of curing more rapidly at a low temperature, the episulfide compound-containing mixture according to the present invention is represented by the compound represented by the above formula (1) or (2) and the following formula (11) or (12). It is preferable to contain an epoxy compound.

  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 episulfide compound containing mixture 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.

  The structure represented by (11) is preferably a structure represented by the following formula (11A). An epoxy compound having a structure represented by the following formula (11A) is commercially available and can be easily obtained.

  In said formula (11A), R11 and R12 represent a C1-C5 alkylene group, respectively.

  The structure represented by the above formula (11) is more preferably a structure represented by the following formula (11B). The epoxy compound having a structure represented by the following formula (11B) is resorcinol diglycidyl ether. Resorcinol diglycidyl ether is commercially available and can be easily obtained.

  The structure represented by (12) is preferably a structure represented by the following formula (12A). An epoxy compound having a structure represented by the following formula (12A) can be easily obtained.

  In said formula (12A), R61 and R62 represent a C1-C5 alkylene group, respectively.

  The structure represented by the above formula (12) is more preferably a structure represented by the following formula (12B). An epoxy compound having a structure represented by the following formula (12B) can be easily obtained.

  The structure represented by (13) is preferably a structure represented by the following formula (13A). An epoxy compound having a structure represented by the following formula (13A) can be easily obtained.

  In said formula (13A), R101 and R102 represent a C1-C5 alkylene group, respectively.

  The structure represented by the above formula (13) is more preferably a structure represented by the following formula (13B). An epoxy compound having a structure represented by the following formula (13B) can be easily obtained.

  The episulfide compound-containing mixture according to the present invention contains 10 to 99.9% by weight of an episulfide compound having a structure represented by the above formula (1-1), (2-1) or (3), and the above formula. It is preferable to contain 90 to 0.01% by weight of the epoxy compound represented by (11-1), (12-1) or (13). The episulfide compound-containing mixture according to the present invention contains 80 to 99.9% by weight of an episulfide compound having a structure represented by the above formula (1-1), (2-1) or (3), and the above formula. It is more preferable to contain 0.1 to 20% by weight of the epoxy compound represented by (11-1), (12-1) or (13).

  The episulfide compound-containing mixture according to the present invention contains 10 to 99.9% by weight of an episulfide compound having a structure represented by the above formula (1) or (2), and the above formula (11) or (12) It is preferable to contain 90 to 0.1% by weight of the represented epoxy compound. The episulfide compound-containing mixture according to the present invention contains 80 to 99.9% by weight of an episulfide compound having a structure represented by the above formula (1) or (2), and the above formula (11) or (12) It is more preferable to contain 0.1 to 20% by weight of the represented epoxy compound.

  The content of the episulfide compound having the structure represented by the above formula (1-1), (2-1) or (3) and the episulfide compound having the structure represented by the above formula (1) or (2) If the amount is too small, the curing rate of the episulfide compound-containing mixture may not be sufficiently high. The content of the episulfide compound having the structure represented by the above formula (11-1), (12-1) or (13) and the episulfide compound having the structure represented by the above formula (1) or (2) If the amount is too large, the viscosity of the episulfide compound-containing mixture may become too high, or the episulfide compound-containing mixture may become a solid.

  (Method for producing episulfide compound and method for producing episulfide compound-containing mixture)

  The manufacturing method of the said episulfide compound and the manufacturing method of the said episulfide compound containing mixture are not specifically limited. As this manufacturing method, for example, an epoxy compound represented by the above formula (11-1), (12-1) or (13), or the above formula (11) or (12) is prepared. The manufacturing method which converts all or one part epoxy groups into an episulfide group is mentioned.

  The manufacturing method of the said episulfide compound and the manufacturing method of the said episulfide compound containing mixture are the epoxy represented by the said Formula (11-1) or (12-1) or (13) in the 1st solution containing a thiocyanate. A method in which a compound or a solution containing the epoxy compound is continuously or intermittently added, and then a second solution containing thiocyanate is further added continuously or intermittently is preferable. By the said method, all or one part epoxy groups of the said epoxy compound can be converted into an episulfide group. The epoxy compound or the solution containing the epoxy compound is preferably an epoxy compound represented by the formula (1) or (2) or a solution containing the epoxy compound.

  As a result of all the epoxy groups being converted to episulfide groups, an episulfide compound having a structure represented by the above formula (1-1), (2-1) or (3) can be obtained. Furthermore, an episulfide compound having a structure represented by the above formula (1) or (2) can also be obtained. As a result of conversion of some epoxy groups into episulfide groups, an episulfide compound having a structure represented by the above formula (1-1), (2-1) or (3), and the above formula (11-1), An episulfide compound-containing mixture containing the epoxy compound represented by (12-1) or (13) can be obtained. Furthermore, an episulfide compound-containing mixture containing an episulfide compound having a structure represented by the above formula (1) or (2) and an epoxy compound represented by the above formula (11) or (12) can also be obtained. .

  Specifically, the episulfide compound and the episulfide compound-containing mixture can be produced as follows.

  In a container equipped with a stirrer, a cooler, and a thermometer, a solvent, water, and thiocyanate are added to dissolve the thiocyanate, and a first solution is prepared in the container. Examples of the solvent include methanol or ethanol. Examples of the thiocyanate include ammonium thiocyanate, potassium thiocyanate, and sodium thiocyanate.

  The concentration of thiocyanate in the first solution is preferably in the range of 0.001 to 0.2 g / mL, and more preferably in the range of 0.005 to 0.1 g / mL. If the concentration of thiocyanate is too high, the epoxy compound may be polymerized. If the thiocyanate concentration is too low, epoxy groups may not be converted to episulfide groups.

  Further, separately from the first solution, an epoxy compound having the structure represented by the formula (11-1), (12-1), (13), (11) or (12) or the epoxy compound is used. Prepare a solution containing.

  Next, the first solution contains an epoxy compound having the structure represented by the formula (11-1), (12-1), (13), (11) or (12) or the epoxy compound. The solution is added continuously or intermittently. 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 be polymerized.

  Next, the second solution containing a solvent, water, and thiocyanate is 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. Add more. 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 thiocyanate 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. If the concentration of thiocyanate is too high, the epoxy compound may be polymerized. If the thiocyanate concentration is too low, epoxy groups may not be converted to episulfide groups.

  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. If the addition rate of the second solution is too fast, the epoxy compound may be polymerized. If the addition rate of the second solution is too slow, the production efficiency of the episulfide compound may decrease.

  It is preferable to remove water, a solvent or unreacted thiocyanate after adding the second solution to the mixed solution in which the epoxy compound is added to the first solution. As a method for removing water, solvent or unreacted thiocyanate, a conventionally known method is used.

  The first solution or the second solution may contain a catalyst such as palladium metal particles or titanium oxide. The conversion of episulfide groups can be adjusted by using a solution containing the catalyst. Moreover, since an epoxy group can be converted into an episulfide group in a low temperature environment, the polymerization reaction of the 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 episulfide groups. As a result, an episulfide compound or an episulfide compound-containing mixture can be obtained. Specifically, for example, an episulfide compound containing 100% by weight of an episulfide compound having a structure represented by the above formula (1-1), (2-1), (3), (1) or (2) Obtainable. Further, for example, the episulfide compound having a structure represented by the above formula (1-1), (2-1), (3), (1) or (2) is 10 to 99.9% by weight or 10 to 50%. 90% to 0.1% by weight or 90% to 50% by weight of an epoxy compound containing 1% by weight and represented by the formula (11-1), (12-1), (13), (11) or (12) % Containing an episulfide compound-containing mixture can be obtained.

(Curable composition)
The curable composition concerning this invention contains the episulfide compound of this invention, and a hardening | curing agent. Or the curable composition concerning this invention contains the episulfide compound containing mixture of this invention, and a hardening | curing agent. That is, the curable composition according to the present invention contains the episulfide compound or episulfide compound-containing mixture of the present invention and a curing agent. As for a hardening | curing agent, only 1 type may be used and 2 or more types may be used together.

  The curable composition according to the present invention contains at least one episulfide compound. Or the curable composition concerning this invention contains at least 1 sort (s) of the said episulfide compound containing mixture. Alternatively, the curable composition according to the present invention contains at least one episulfide compound and at least one episulfide compound-containing mixture. Therefore, two or more of the above-mentioned episulfide compounds may be used in combination as the curable resin, or two or more of the above-mentioned episulfide compound-containing mixture may be used together, and the above-mentioned episulfide compound and the above-mentioned episulfide compound-containing mixture are used in combination. May be.

  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, and an acid anhydride. 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 a storage stability can be improved when the said episulfide compound or the said episulfide compound containing mixture and the said hardening | curing agent are mixed, 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. 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 or 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, or 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. More preferably, a polythiol compound is used because the curing rate of the curable composition can be further increased.

  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 curing agent is not particularly limited. 100 parts by weight of the episulfide compound or the episulfide compound-containing mixture ((when the epoxy compound is not included, 100 parts by weight of the episulfide compound is shown, and when the epoxy compound is contained, 100 parts by weight of the episulfide compound-containing mixture) The curing agent is preferably contained in the range of 1 to 40 parts by weight, and the curable composition is sufficiently cured when the content of the curing agent is less than 1 part by weight. When the content of the curing agent exceeds 40 parts by weight, the heat resistance of the cured product of the curable composition may be reduced, based on 100 parts by weight of the episulfide compound or the episulfide compound-containing mixture. The more preferable lower limit of the content of the curing agent is 30 parts by weight, and still more preferable lower limit is 45 parts by weight. A more preferable upper limit is 100 parts by weight, and an even more preferable upper limit is 75 parts by weight.If the content of the curing agent is too small, the curable composition is hard to be cured sufficiently. In some cases, an excessive curing agent that did not participate in curing may remain after curing.

  When the curing agent is an imidazole curing agent or a phenol curing agent, the imidazole curing agent or the phenol curing agent is in the range of 1 to 15 parts by weight with respect to 100 parts by weight of the episulfide compound or the episulfide compound-containing mixture. It is preferable to contain. Moreover, when the said hardening | curing agent is an amine hardening | curing agent, a polythiol hardening | curing agent, or an acid anhydride, an amine hardening | curing agent, a polythiol hardening | curing agent, or an acid anhydride is 15 with respect to 100 weight part of the said episulfide compound or the said episulfide compound containing mixture. It is preferable to contain in the range of -40 weight part.

  The curable composition according to the present invention preferably further contains a storage stabilizer. The curable composition according to the present invention preferably further contains at least one selected from the group consisting of phosphate ester, phosphite ester and borate ester as the storage stabilizer. It is more preferable to contain. By using a phosphite, the storage stability of the episulfide compound or the episulfide compound-containing mixture 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, 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.

  Examples of the boric acid ester include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, and trioctyl. Borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, Tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxaundecyl) (1,4,7,10,13-pentaoxatetradecyl) (1,4,7-tri Xaundecyl) borane, 2- (β-dimethylaminoisopropoxy) -4,5-dimethyl-1,3,2-dioxaborolane, 2- (β-diethylaminoethoxy) -4,4,6-trimethyl-1,3 2-dioxaborinane, 2- (β-dimethylaminoethoxy) -4,4,6-trimethyl-1,3,2-dioxaborinane, 2- (β-diisopropylaminoethoxy) -1,3,2-dioxaborinane, 2- (Β-diisopropylaminoethoxy) -4-methyl-1,3,2-dioxaborinane, 2- (γ-dimethylaminopropoxy) -1,3,6,9-tetrapoxa-2-boracycloundecane, and 2- ( β-dimethylaminoethoxy) -4,4- (4-hydroxybutyl) -1,3,2-dioxaborinane, 2,2-oxybis ( 5,5-dimethyl-1,3,2-dioxabonarine, and epoxy-phenol-boric acid ester blends.

  The content of the storage stabilizer is preferably in the range of 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the episulfide compound or the episulfide compound-containing mixture. The more preferable lower limit of the content of the storage stabilizer is 0.005 parts by weight and the more preferable upper limit is 0.05 parts by weight with respect to 100 parts by weight of the episulfide compound or the episulfide compound-containing mixture. When the content of the storage stabilizer, particularly the phosphite, is within the above range, the storage stability of the episulfide compound or the episulfide compound-containing mixture can be further enhanced.

  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 or 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid addition Thing etc. are mentioned.

  The preferable lower limit of the content of the curing accelerator is 0.5 parts by weight, the more preferable lower limit is 1 part by weight, and the preferable upper limit is 6 parts by weight, more preferably 100 parts by weight of the episulfide compound or the episulfide compound-containing mixture. The upper limit is 4 parts by weight. When there is too little content of a hardening accelerator, it will become difficult to harden a curable composition fully. When there is too much content of a hardening accelerator, the excess hardening accelerator which did not participate in hardening after hardening may remain.

  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 filler content is preferably in the range of 50 to 900 parts by weight with respect to 100 parts by weight of the episulfide compound or the episulfide compound-containing mixture. 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 concerning this invention may further contain a solvent, an ion-trapping agent, or a silane coupling agent as needed.

  The solvent is not particularly limited. Examples of the solvent include ethyl acetate, methyl cellosolve, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran, and diethyl ether. As for a solvent, only 1 type may be used and 2 or more types may be used together.

  The silane coupling agent is not particularly limited. Examples of the silane coupling agent include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 3-gri Doxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methacryloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, dodecyltriethoxysilane, hexyltrimethoxysilane, isobutyldiethoxy Examples thereof include silane, methylphenyldiethoxysilane, methylphenyldimethoxysilane, and imidazolesilane. Of these, imidazolesilane is preferable. As for a silane coupling agent, only 1 type may be used and 2 or more types may be used together.

  The ion scavenger is not particularly limited. Specific examples of the ion scavenger include aluminosilicate, hydrous titanium oxide, hydrous bismuth oxide, zirconium phosphate, titanium phosphate, hydrotalcite, ammonium molybdate, hexacyanozinc or ion exchange resin. Only one type of ion scavenger may be used, or two or more types may be used in combination.

  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. The (meth) acrylic resin indicates a methacrylic resin and an acrylic resin.

  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 contains 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. The (meth) acryloyl refers to acryloyl and methacryloyl.

  From the viewpoint of enhancing the curability of the curable composition, the preferable lower limit of the content of the partially (meth) acrylated epoxy resin is 0.1% by weight and the more preferable lower limit is 0.1% in 100% by weight of the curable compound. 5 wt%, the preferred upper limit is 2 wt%, and the more preferred upper limit is 1.5 wt%.

  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. .

  Examples of the epoxy compound used for obtaining the epoxy (meth) acrylate, and commercial products of the epoxy compound include bisphenol A type epoxy resins such as Epicoat 828EL and Epicoat 1004 (both manufactured by Japan Epoxy Resin Co., Ltd.), and Epicoat. 2, 806 and Epicoat 4004 (both made by Japan Epoxy Resin Co., Ltd.), bisphenol F type epoxy resin, Epicron EXA1514 (DIC Co., etc.) bisphenol S type epoxy resin, RE-810NM (Nihon Kayaku Co., Ltd.) 2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin such as Epicron EXA7015 (manufactured by DIC), propylene oxide-added bisphenol A type epoxy resin such as EP-4000S (manufactured by ADEKA) Resorcinol type epoxy resins such as EX-201 (manufactured by Nagase ChemteX), biphenyl type epoxy resins such as Epicoat YX-4000H (manufactured by Japan Epoxy Resin), and sulfide type epoxies such as YSLV-50TE (manufactured by Toto Kasei) Resin, ether type epoxy resin such as YSLV-80DE (manufactured by Toto Kasei Co., Ltd.), dicyclopentadiene type epoxy resin such as EP-4088S (manufactured by ADEKA), Epicron HP4032 and Epicron EXA-4700 (both manufactured by DIC), etc. Naphthalene type epoxy resin, phenol novolac type epoxy resin such as Epicron N-770 (manufactured by DIC), orthocresol novolak type epoxy resin such as Epicron N-670-EXP-S (manufactured by DIC), Epicron HP7200 (DIC Corporation) Made) Dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.), naphthalene phenol novolac type epoxy resin such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.), Epicoat 630 (Japan epoxy) Resin Co., Ltd.), Epicron 430 (DIC Corporation) and TETRAD-X (Mitsubishi Gas Chemical Co., Ltd.) and other glycidylamine type epoxy resins, ZX-1542 (Toto Kasei Co., Ltd.), Epicron 726 (DIC Corporation), Epolite Alkyl polyol type epoxy resins such as 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) and Denacol EX-611 (manufactured by Nagase ChemteX Corp.), YR-450 and YR-207 (both manufactured by Tohto Kasei Co., Ltd.) and Epolide PB (manufactured by Daicel Chemical Industries, Ltd.) ) Rubber modified epoxy resin, etc. Glycidyl ester compounds such as NACAL EX-147 (manufactured by Nagase ChemteX), bisphenol A type episulfide resins such as Epicoat YL-7000 (manufactured by Japan Epoxy Resin), and YDC-1312, YSLV-80XY and YSLV-90CR Are also manufactured by Toto Kasei Co., Ltd.), XAC4151 (produced by Asahi Kasei Co., Ltd.), Epicoat 1031 and Epicoat 1032 (both from Japan Epoxy Resin Co., Ltd.), EXA-7120 (manufactured by DIC), and TEPIC (manufactured by Nissan Chemical Co., Ltd.). Resin etc. are mentioned.

  Examples of commercially available products of the epoxy (meth) acrylate include Evecryl 3700, Evekril 3600, Evekril 3701, Evekril 3703, Evekrill 3200, Evekrill 3201, Evekril 3600, Evekril 3412, Evekril 860, Evekril RDX63182, EVERCRYL 3800 (all manufactured by Daicel UCB), EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD and EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M- 600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester Tel 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA and Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol acrylate DA-141, Denacol acrylate DA-314 and Denacol acrylate DA -911 (all manufactured by Nagase ChemteX Corporation).

  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, glycerine 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 preferred lower limit of the content of the photocurable compound is 1 part by weight and more preferred lower limit with respect to 100 parts by weight of the episulfide compound or episulfide compound-containing mixture. Is 10 parts by weight, more preferably the lower limit is 50 parts by weight, the preferred upper limit is 10,000 parts by weight, the more preferred upper limit is 1000 parts by weight, and the more preferred upper limit is 500 parts by weight.

  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, or 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 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, and the more preferable lower limit is 2 parts by weight with respect to 100 parts by weight of the photocurable composition. The upper limit is 10 parts by weight, and the more preferable upper limit is 5 parts by weight. When there is too little content of a photoinitiator, the effect which added the photoinitiator may not fully be acquired. When there is too much content of a photoinitiator, the adhesive force of the hardened | cured material of a curable composition may fall.

  The curable resin composition may further contain another epoxy compound other than the epoxy compound represented by the formula (11-1), (12-1), (13), (11) or (12). Good. As this epoxy compound, the epoxy compound used in order to obtain the above-mentioned epoxy (meth) acrylate can be used.

  In a total of 100% by weight of the episulfide compound, the epoxy compound represented by the formula (11-1), (12-1), (13), (11) or (12) and the other epoxy compound, The preferable lower limit of the content of the episulfide compound is 10% by weight, the more preferable lower limit is 25% by weight, the preferable upper limit is 100% by weight, and the more preferable upper limit is 50% by weight.

The curable composition concerning this invention can be used for adhesion | attachment of a liquid crystal panel or a semiconductor chip as a one-pack type adhesive agent. The curable composition may be a paste-like adhesive or a film-like adhesive.
The method for processing the curable composition according to the present invention into a film adhesive is not particularly limited. For example, after applying a curable composition to a substrate such as a release paper and processing it into a film-like adhesive, or adding a solvent to the curable composition and applying to a substrate such as a release paper, Examples thereof include a method of volatilizing the solvent at a temperature lower than the activation temperature of the curing agent and processing it into a film-like adhesive.

  As a method of curing the curable composition according to the present invention, a method of heating the curable composition, a method of heating the curable composition irradiated with light after irradiating the curable composition with light, or The method etc. which heat a curable composition simultaneously with irradiating light to a curable composition are mentioned.

  The heating temperature for curing the curable composition according to the present invention is preferably in the range of 160 to 250 ° C, more preferably in the range of 160 to 200 ° C. Since the curable composition can be quickly cured at a low temperature, the amount of energy required for heating can be reduced.

  When the heating temperature is 200 ° C. or lower, the curable composition containing a conventional epoxy resin has a longer curing time. For example, if the heating temperature is 200 ° C., the curing time exceeds 10 seconds. In contrast, the curable composition according to the present invention can be cured in a short time even when the heating temperature is 200 ° C. or lower.

  When the curable composition according to the present invention is photocured, the light source used for irradiating the curable composition with light is not particularly limited. Examples of the light source include a light source having a sufficient light emission distribution at a wavelength of 420 nm or less. Specific examples of the light source include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, or a metal halide lamp. Of these, a chemical lamp is preferable. The chemical lamp efficiently emits light in the active wavelength region of the photopolymerization initiator and emits less light in the light absorption wavelength region of the composition components other than the photopolymerization initiator. Furthermore, when a chemical lamp is used, light can efficiently reach the photocuring component present in the composition.

For example, when a cleavage type photopolymerization initiator having an acetophenone group is contained, the light irradiation intensity in the wavelength region of 365 nm to 420 nm is preferably in the range of 0.1 to 100 mW / cm ² .

  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 at least the surface has conductivity. 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 content of the conductive particles is not particularly limited. The preferred lower limit of the content of the conductive particles is 0.1 parts by weight, more preferably the lower limit is 0.5 parts by weight, and the preferred upper limit is 10 parts by weight with respect to 100 parts by weight of the episulfide compound or the episulfide compound-containing mixture. A more preferred upper limit is 5 parts by weight. When there is too little content of the said electroconductive particle, electrodes may not be conduct | electrically_connected reliably. When there is too much content of the said electroconductive particle, the short circuit between adjacent electrodes which must not be conducted may arise.

  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 used to obtain 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.

  The connection structure 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. . 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 on which metal foil was laminated, 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 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.

  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.

( Reference Example 1) (Example 1 is a missing number)
(1) Preparation of episulfide compound-containing mixture In a 2 L vessel equipped with a stirrer, a cooler and a thermometer, ethanol 250 mL, pure water 250 mL, and potassium thiocyanate 20 g were added to dissolve potassium thiocyanate, and the vessel A first solution was prepared inside. 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 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 prepared 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 at a rate of 5 mL / min. Stir for 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 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, it was confirmed that the episulfide compound-containing mixture contains 70% by weight of resorcinol diglycidyl ether and 30% by weight of the episulfide compound represented by the above formula (1B). did.

(2) Preparation of curable composition To 33 parts by weight of the resulting episulfide compound-containing mixture, 20 parts by weight of pentaerythritol tetrakis-3-mercaptopropionate as a curing agent and diphenyl mono (tridecyl) as a phosphite ) 0.01 part by weight of phosphite, 1 part by weight of 2-ethyl-4-methylimidazole as a curing accelerator, 20 parts by weight of silica having an average particle diameter of 0.25 μm as filler, and an average particle diameter of 0.5 μm 20 parts by weight of alumina 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 as 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. .

( Reference Example 2) (Example 2 is a missing number)
Anisotropic conduction was performed in the same manner as in Reference Example 1 except that pentaerythritol tetrakis-3-mercaptopropionate and diphenylmono (tridecyl) phosphite were not added during the preparation of the curable composition. A curable composition as a paste was obtained.

(Comparative Example 1)
100 parts by weight of a bisphenol A type epoxy resin and 5 parts by weight of 1,2-dimethylimidazole as a curing agent were added, and the mixture was obtained by stirring for 5 minutes at 2000 rpm using a planetary stirrer.

  By adding 7 parts by weight of silica particles having an average particle diameter of 0.02 μm and 2 parts by weight of conductive particles having an average particle diameter of 3 μm to the obtained mixture and stirring for 8 minutes at 2000 rpm using a planetary stirrer A formulation 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. .

  The obtained composition was filtered through a nylon filter paper (pore diameter: 10 μm) to obtain a curable composition as an anisotropic conductive paste.

(Evaluation of Reference Examples 1 and 2 and Comparative Example 1)
(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.

  The results are shown in Table 1 below.

( Reference Example 3) (Example 3 is a missing number)
In preparing the curable composition, 5 parts by weight of epoxy acrylate (“EBECRYL 3702” manufactured by Daicel-Cytec) and an acylphosphine oxide compound (“DAROCUR TPO” manufactured by Ciba Japan) as a photopolymerization initiator 0 A curable composition as an anisotropic conductive paste was obtained in the same manner as in Reference Example 1 except that 1 part by weight was further added.

( Reference Example 4) (Example 4 is a missing number)
In preparing the curable composition, 5 parts by weight of urethane acrylate (“EBECRYL8804” manufactured by Daicel-Cytec) and an acylphosphine oxide compound (“DAROCUR TPO” manufactured by Ciba Japan) as a photopolymerization initiator 0 A curable composition as an anisotropic conductive paste was obtained in the same manner as in Reference Example 1 except that 1 part by weight was further added.

(Evaluation of Reference Examples 3 and 4)
(1) Curing time
Transparent glass substrates and semiconductor chips used in the evaluation of Reference Examples 1 and 2 and Comparative Example 1 were prepared.

The obtained curable composition was applied on the upper surface of the transparent glass substrate so as to have a thickness of 30 μm, thereby forming a curable composition layer. Furthermore, while applying the anisotropic conductive paste, the ultraviolet ray at 420 nm was applied to the curable composition layer using an ultraviolet irradiation lamp so that the light irradiation intensity was 50 mW / cm ^2, and the curable composition was obtained by photopolymerization. The material layer was B-staged. The time T from coating to when the coated curable composition layer was in contact with the transparent glass substrate until the curable composition layer was irradiated with light was 0.5 seconds. It was.

Next, the semiconductor chip was laminated on the upper surface of the B-staged curable composition layer so that the electrodes faced and connected. Then, while adjusting the temperature of the head so that the temperature of the curable composition layer is 185 ° C., a pressure heating head is placed on the upper surface of the semiconductor chip and a pressure of 10 kg / cm ² is applied to form a B stage. The cured curable composition layer was completely cured at 185 ° C. to obtain a connection structure. 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, the presence / absence of voids was evaluated in the same manner as in Reference Examples 1 and 2 and Comparative Example 1.

  The results are shown in Table 2 below.

( Reference Examples 5 to 14 and Examples 15 to 24) (Examples 5 to 14 are missing numbers)
(1) Preparation of episulfide compound or episulfide compound-containing mixture The episulfide compound represented by the above formula (1), (2) or (3) and the above formula (11), (12) or (13) An episulfide compound or an episulfide compound-containing mixture containing the epoxy compound at the following content was prepared by the same procedure as in Reference Example 1. The episulfide compound or episulfide compound-containing mixture of each reference example and example was obtained by appropriately adjusting the amount of potassium thiocyanate used and adjusting the conversion rate.

(2) Preparation of curable composition In preparing the curable composition, 33 parts by weight of the episulfide compound-containing mixture used in Reference Example 1 was added to the episulfide compound or episulfide compound-containing mixture shown in Tables 3 to 5 below. Except having changed, it carried out similarly to the reference example 1, and obtained the curable composition as anisotropic conductive paste.

( Reference Example 25) (Example 25 and Reference Examples 15 to 24 are missing numbers)
In the preparation of the curable composition, an episulfide compound containing mixture 33 parts by weight used in Reference Example 1, and the episulfide compound-containing mixture 10 parts by weight used in Reference Example 1, episulfide compound containing mixture used in Reference Example 9 A curable composition was obtained in the same manner as in Reference Example 1 except that the content was changed to 20 parts by weight.

( Reference Example 26) (Example 26 is a missing number)
In the preparation of the curable composition, an episulfide compound containing mixture 33 parts by weight used in Reference Example 1, and the episulfide compound-containing mixture 20 parts by weight used in Reference Example 1, was changed to 10 parts by weight resorcinol glycidyl ether Except for this, a curable composition was obtained in the same manner as in Reference Example 1.

( Reference Example 27) (Example 27 is a missing number)
In the preparation of the curable composition, an episulfide compound containing mixture 33 parts by weight used in Reference Example 1, and the episulfide compound-containing mixture 20 parts by weight used in Example 1, the bisphenol A type glycidyl ether 10 parts by weight A curable composition was obtained in the same manner as in Reference Example 1 except that it was changed.

(Evaluation of Reference Examples 5 to 27 and Examples 15 to 24 )
In the same manner as in Reference Examples 1 and 2 and Comparative Example 1, the curing time and the presence or absence of voids were evaluated.

  The results are shown in Tables 3 to 6 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 (13)

Containing an episulfide compound having a structure represented by the following formula (2-1) or (3), a curing agent, and conductive particles;
A curable composition which is an anisotropic conductive material .

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 hydrogen, and the group that is not hydrogen among R53, R54, R55, R56, R57, and R58 represents a group represented by the following formula (5).

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 hydrogen, and 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).

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

In said formula (6), R111 represents a C1-C5 alkylene group. The curable composition of Claim 1 whose content of the said electroconductive particle is 0.1 weight part or more and 10 weight part or less with respect to 100 weight part of said episulfide compounds. The curable composition of Claim 1 or 2 whose said electroconductive particle is the electroconductive particle which coat | covered the surface of the resin particle with the metal layer. The curability according to any one of claims 1 to 3, which is an anisotropic conductive paste, an anisotropic conductive ink, an anisotropic conductive adhesive, an anisotropic conductive film, or an anisotropic conductive sheet. Composition. The curable composition according to any one of claims 1 to 4, which is a liquid or paste-like anisotropic conductive material. The sclerosis | hardenability of any one of Claims 1-5 in which the episulfide compound which has a structure represented by said Formula (2-1) or (3) has a structure represented by following formula (2) . Composition .

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. The group which is not hydrogen among R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (5).

In said formula (5), R59 represents a C1-C5 alkylene group. The curable composition according to claim 6 , wherein the structure represented by the formula (2) is a structure represented by the following formula (2A).

In said formula (2A), R51 and R52 represent a C1-C5 alkylene group, respectively. Containing lower following formula (12-1) or (13) an epoxy compound represented by the further curable composition according to any one of claims 1-7.

In the formula (12-1), R61 and R62 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R63, R64, R65, R66, R67 and R68. Represents hydrogen, and the non-hydrogen group in R63, R64, R65, R66, R67 and R68 represents a group represented by the following formula (15).

In the above formula (13), R121 and R122 each represent an alkylene group having 1 to 5 carbon atoms, and 6 to 8 of 8 groups of R123, R124, R125, R126, R127, R128, R129 and R130. The group of represents hydrogen, and 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).

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

In said formula (16), R131 represents a C1-C5 alkylene group. The curable composition of Claim 8 whose content of the said electroconductive particle is 0.1 weight part or more and 10 weight part or less with respect to a total of 100 weight part of the said episulfide compound and the said epoxy compound. The curable composition according to claim 8 or 9 , wherein the epoxy compound represented by the formula (12-1) is an epoxy compound represented by the following formula (12).

In the above formula (12), R61 and R62 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R63, R64, R65, R66, R67 and R68 are hydrogen. The group which is not hydrogen among R63, R64, R65, R66, R67 and R68 represents a group represented by the following formula (15).

In said formula (15), R69 represents a C1-C5 alkylene group. The curable composition according to claim 10 , wherein the structure represented by the formula (12) is a structure represented by the following formula (12A).

In said formula (12A), R61 and R62 represent a C1-C5 alkylene group, respectively. The curable composition of any one of Claims 1-11 which further contains a photocurable compound and a photoinitiator. A first connection target member, a second connection target member, and a connection part connecting the first and second connection target members;
The connection part is formed of the curable composition according to any one of claims 1 to 12 ,
A connection structure in which the first and second connection target members are electrically connected by the conductive particles .

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