TW201020243A - Episulfide, mixture containing episulfide, method for producing mixture containing episulfide, curable composition and connection structure - Google Patents

Abstract

This invention provides an episulfide that can be rapidly hardened at a low temperature and that effectively connects the object component when it is used for connecting the object component and that inhibits generated voids after connection. The episulfide of this invention has the structure represented by the following formulas (1-1), (2-1) or (3). In the foregoing formulas (1-1), (2-1) or (3), R1 and R2, R51 and R52, and R101 and R102 respectively represent alkylene group of 1 to 5 carbon atoms; 2 to 4 groups in the four groups of R3 to R6 represent hydrogen, others represent groups containing episulfide groups; 4 to 6 groups in the six groups of R53 to R58 represent hydrogen, others represent groups containing episulfide groups; and 6 to 8 groups in the eight groups of R103 to R110 represent hydrogen, others represent groups containing episulfide groups.

Description

201020243 6. Technical Field of the Invention The present invention relates to an episulfide compound, a mixture containing an episulfide compound containing the episulfide compound, a method for producing the mixture containing the episulfide compound, and a hardenable combination. In the object and the connection structure, the above-mentioned episulfide-based system can be rapidly hardened at a low temperature, and when it is used to connect the member to be connected, the member to be connected can be effectively connected, and the void can be suppressed after the connection. . [Prior Art] An anisotropic conductive material such as an anisotropic conductive paste, an anisotropic conductive ink, an anisotropic conductive adhesive, an anisotropic conductive film, or an anisotropic conductive sheet is widely known. The anisotropic conductive material is used to connect an IC (integrated circuh) wafer to a flexible printed circuit board, or to connect 1 (: a wafer and a circuit board having an ITO (indium tin oxide) electrode, etc. For example, after the anisotropic conductive material is disposed between the electrode of the 1C wafer and the electrode of the circuit board, the heating and pressurization are performed, whereby the isoelectric 35 can be connected to each other. As an example of the anisotropic conductive material, Patent Document i discloses an anisotropic conductive adhesive film comprising a thermosetting insulating adhesive, conductive particles, an imidazole latent curing agent, and an amine-based or latent curing agent. [Patent Document 丨 (4) In the case where the anisotropic conductive adhesive film is hardened at a relatively low temperature, the connection reliability is also excellent. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9/1 15335 [Abstract] 143470.doc 201020243 [Problems to be Solved by the Invention] In recent years, in order to effectively connect the electrodes of an electronic component, it is required to lower the heating temperature required for the connection and to shorten the pressurization time. In the anisotropic conductive adhesive film described in Patent Document 1, the heating temperature required to start hardening is relatively low. However, the anisotropic conductive adhesive film is low in temperature. The lower hardening reaction does not proceed sufficiently. Therefore, in order to connect the electrodes of the circuit board and the electronic component by using a different conductive outer film, it is necessary to increase the heating temperature or heat for a long time. In the case where the electrodes are effectively connected to each other. Further, in recent years, the electrode formed on the circuit board or the like is miniaturized. That is, the stepwise reduction indicates the dimension in the width direction of the line in which the electrode is formed (L). 'L/S of the dimension in the width direction of the gap in which the electrode is formed. When the above-mentioned anisotropic conductive adhesive film is connected to the circuit substrate on which the fine electrode is formed, the hardening speed of the anisotropic conductive adhesive film is higher. φ 杈, therefore, there is a case where a space is created in the space between the electrodes. It is an object of the present invention to provide an anthracene sulfide and to contain the ring sulfide The mixture of the episulfide-containing mixture, the method for producing the mixture containing the episulfide, the curable composition, and the joint structure, wherein the episulfide compound can be rapidly cured at a low temperature and used for joining the members to be joined. When the connection target member is operatively connected, it is possible to suppress the generation of voids after the connection. [Technical means for solving the problem] According to a broader aspect of the present invention, there is provided a formula having the following formula: 143470.doc 201020243 ( Cyclosulfide of the structure represented by 2-1) or (3): [Chemical 1]

In the above formula (1-1), R1 and R2 each represent an alkylene group having a carbon number of 1 to 5, and 2 to 4 of the four groups of R3, R4, R5 and R6 represent hydrogen, and R3, R4, The non-hydrogen group in R5 and R6 represents a group represented by the following formula (4): [Chemical 4]

In the above formula (4), R7 represents an alkylene group having a carbon number of 1 to 5; [Chemical 2]

R56 Formula (2-1) In the above formula (2-1), R51 and R52 each represent an alkylene group having a carbon number of 1 to 5, and R5 3, R5 4, R5 5, R5 6 , R 5 7 and R 5 8 4 to 6 of the 6 groups represent hydrogen, and the non-hydrogen group of R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (5): 143470.doc -6- 201020243 [Chemical 5]

In the above formula (5), R59 represents an alkylene group having a carbon number of 1 to 5; [Chemical 3]

R101 R103 X0 R110

R109 R108 ...(3)

In the above formula (3), R101 and R102 each represent an alkylene group having a carbon number of 1 to 5, and 6 to 8 of the 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 represent Hydrogen, a non-hydrogen group of R103, R104, R105, R106, R107, R108, R109 and R110 represents a group represented by the following formula (6): [Chemical Formula 6] /0, ... Formula (6) 〆R111 In the above formula (6), R111 represents an alkylene group having a carbon number of 1 to 5. In a specific aspect of the episulfide of the present invention, the episulfide has a structure represented by the following formula (1) or (2) of 143470.doc 201020243 · [Chem. 7]

In the above formula (1), R1 and R2 each represent an alkylene group having a carbon number of 1 to 5, and 2 to 4 of the four groups of R3, R4, R5 and R6 represent hydrogen, and R3, R4, and R5 are The non-hydrogen group in R6 represents a group represented by the following formula (4): [Chemical 9]

In the above formula (4), R7 represents an alkylene group having a carbon number of 1 to 5; [Chemical 8]

In the above formula (2), R51 and R52 each represent an alkylene group having a carbon number of 1 to 5, and 4 to 6 of the 6 groups of R53, R54, R5 5, R56, R5 7 and R5 8 represent argon. The non-hydrogen group of R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (5): 143470.doc 201020243 [Chemical]

In the above formula (5), R59 represents an alkylene group having a carbon number of 1 to 5. In other specific aspects of the episulfide of the present invention, the structure represented by the above formula (1) or (2) is represented by the following formula (1A) or (2A): [Chem. 11]

...(1A)

In the above formula (1A), R1 and R2 each represent an alkylene group having a carbon number of 1 to 5;

(2A) In the above formula (2A), R51 and R52 each represent an alkylene group having 1 to 5 carbon atoms. The episulfide-containing mixture of the present invention contains the episulfide compound of the present invention, and an epoxy compound represented by the following formula (11-1), (12-1) or (13): 143470.doc -9- 201020243 [化13]

In the above formula (11-1), R11&R12 respectively represent an alkyl group having a carbon number, and 2 to 4 of the four groups of R13, R14, R15 and R16 represent hydrogen, R13, R14, Rl5 and R16. The non-hydrogen group in the middle represents a group represented by the following formula (14): [Chemical 16] 4r

In the above formula (14), R17 represents an alkylene group having a carbon number of 1 to 5;

Ο

R67 〇/

Formula (12-1) In the above formula (12-1), R61 and R62 each represent a stretching group having a carbon number of 1 to 5, and 4 of 6 groups of R63, R64, R65, R66, R67 and R68. ～6 groups represent hydrogen, and the non-hydrogen group of R63, R64, R65, R66, R67 and R68 represents a group represented by the following formula (15): I43470.doc -10- , 0 201020243 [Chem. 17] Formula (15) /〇, R69 In the above formula (15), R69 represents an alkylene group having a carbon number of 1 to 5; [Chem. 15] R121 R123 \〇R130

R129 R128 'Formula (13) In the above formula (13), R121 and R122 each represent an alkylene group having a carbon number of 1 to 5, and 8 of R123, R124, R125, R126, R127, R128, R129 and R130. 6 to 8 groups represent hydrogen, and the non-hydrogen group of R123, R124, R125, R126, R127, R128, R129 and R130 represents a group represented by the following formula (16): [Formula 18], 0 formula (16) */〇R131 In the above formula (16), R131 represents an alkylene group having a carbon number of 1 to 5. In a specific aspect of the episulfide-containing mixture of the present invention, the above-mentioned 143470.doc -11 - 201020243 epoxy compound is an epoxy compound represented by the following formula (11) or (12): [Chem. 19]

R16 Formula (11) In the above formula (11), R11 and R12 each represent an alkylene group having a carbon number of 1 to 5, and 2 to 4 of the four groups of R13, R14, R15 and R16 represent hydrogen. The non-hydrogen group in R13, R14, R15 and R16 represents a group represented by the following formula (14): [Chem. 21] *

In the above formula (14), R17 represents an alkylene group having a carbon number of 1 to 5; [Chem. 20]

In the above formula (12), R61 and R62 each represent an alkylene group having a carbon number of 1 to 5, and 4 to 6 of the 6 groups of R63, R64, R65, R66, R67 and R68. 143470.doc -12- 201020243, which represents hydrogen, and non-hydrogen of R63, R64, R65, R66, R67 and R68, represents a group represented by the following formula (15): [Chem. 22]

In the above formula (15), R69 represents an alkylene group having a carbon number of 1 to 5. In other specific aspects of the episulfide-containing mixture of the present invention, the structure represented by the above formula (11) or (12) is represented by the following formula (11A) or (12A): ]

In the above formula (11A), Rii&R12 represents an alkylene group having a carbon number of 1 to 5, respectively.

In the above formula (12A), R61 and R62 each represent an alkylene group having a carbon number of 1 to 5. In the method for producing an episulfide-containing mixture of the present invention, the first solution containing thiocyanate is continuously or intermittently added by the above formula (11-1), (12-1) or (13). After the epoxy compound or the solution containing the epoxy compound 143470.doc -13· 201020243 is added, the second solution containing thiocyanate is continuously or intermittently added, thereby partially epoxyizing the above epoxy compound. The base is converted to an aryl group. In a specific sample of the method for producing an episulfide-containing mixture of the present invention, as the epoxy compound or a solution containing the epoxy compound, an epoxy represented by the above formula (u) 4 (12) is used. a compound or a solution comprising the epoxy compound. The curable composition of the present invention contains the episulfide compound of the present invention and a curing agent. Alternatively, the curable composition of the present invention contains the mixture containing the episulfide of the present invention and a curing agent. The curable composition also contains the above episulfide in the above mixture containing the episulfide. In a specific aspect of the curable composition of the present invention, a photohardenable compound and a photopolymerization initiator are further contained. In another specific aspect of the curable composition of the present invention, conductive particles are further contained. The connection structure of the present invention includes a second connection target member, a second connection target member, and a connection ′ connecting the second and second connection target members, and the connection portion is formed of the curable composition of the present invention. In a specific aspect of the connection structure of the present invention, the curable composition contains conductive particles. The first and second connection members are electrically connected by the upper conductive particles. [Effects of the Invention] The episulfide compound of the present invention can be rapidly cured at a low temperature because it has a structure represented by the above formula 〇_1}, (2_1} or 143470.doc •14-201020243. When the episulfide compound has a structure represented by the above formula (1) or (2), it can be hardened more rapidly at a low temperature. The episulfide-containing mixture of the present invention has a composition (1) 1) or an epicyclic sulfide of the structure represented by (2-1), and thus can be rapidly hardened at a low temperature. The episulfide-containing mixture of the present invention has a composition represented by the above formula (1) or (2) In the case of the structure, it can be hardened more rapidly at a low temperature. The connecting object can also be obtained by connecting the episulfide compound of the present invention or the mixture containing the episulfide of the present invention to connect the connecting member. Further, it is possible to suppress the occurrence of voids after the connection, and it is possible to suppress the occurrence of voids even when the connection member having the uneven surface is connected. [Embodiment] Hereinafter, the present invention will be described in detail. (Cyclosulfide) hair The cyclic sulfide has a structure represented by the following formula (4), (5)) or (3); in the following formula (4), a bond bonded to the 6-base of the benzene ring is not particularly limited; In the formula (4), the bonding site of the 8 groups bonded to the naphthalene ring is not particularly limited: 143470.doc -15- 201020243 [Chem. 25]

Formula (l-1) In the above formula (1-1), R1 and R2 each represent an alkylene group having a carbon number of 1 to 5. Two to four of the four groups of R3, R4, R5 and R6 represent hydrogen; and the non-hydrogen group of R3, R4, R5 and R6 represents a group represented by the following formula (4). The four groups of R3, R4, R5 and R6 may all be hydrogen; one or two of the four groups of R3, R4, R5 and R6 are represented by the following formula (4), and R3, The group of the four groups of R4, R5 and R6 which are not represented by the following formula (4) may be hydrogen; [Chem. 26]

In the above formula (2-1), R51 and R52 each represent an alkylene group having a carbon number of 1 to 5; and 4 to 6 of the 6 groups of R53, R54, R55, R56, R57 and R58 represent hydrogen; The non-hydrogen group in R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (5); all of the groups of R53, R54, R55, R56, R57 and R5 8 may be hydrogen. One or two of the six groups of R53, R54, R55, R56, R57 and R58 are represented by the following formula (5): 143470.doc -16 - 201020243, and R53, R54, R55, The group of R56, R57 and R58 which is not represented by the following formula (5) may be hydrogen; [Chem. 27]

R101 R103,. R110

R109 R108 ...(3)

In the above formula (3), R101 and R102 represent an alkylene group having a carbon number of 1 to 5, respectively; R103, R104, R105, R106, R107, R108, R109 and

6 to 8 of the 8 groups of R110 represent hydrogen; the non-hydrogen group of R103, R104, R105, R106, R107, R108, R109 and R110 represents a group represented by the following formula (6); R103 And all of the eight groups of R104, R105, R109, 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 a group represented by the following formula (6), and a group other than the group represented by the following formula (6) of R103, R104, R105, R106, R107, R108, R109 and R110 may be hydrogen; 143470. Doc 17- 201020243 [化28] ic

• " (4) In the above formula (4), R7 represents an alkylene group having a carbon number of 丨5; [Chem. 29]

In the above formula (5), R59 represents an alkylene group having a carbon number of 丨~5; [Chemical 30] ★ 0, R11

In the above formula (6), R111 represents an alkylene group having a carbon number of 丨5. The cyclosulfide of the present invention preferably has a structure represented by the following formula (1) and the following formula ((10), the above formula (3), from the viewpoint of hardening at a lower temperature; From the viewpoint of further hardening and further hardening, the episulfide of the present invention preferably has a structure represented by the following formula (1) or (7):

(1) In the above formula (1), R1 and (10) represent a stretching group having a carbon number of 5. 2 to 4 of the 4 groups of R3, R4, R5 and 6 represent hydrogen; 非, 143470.doc 18 201020243 R5 and R6 represent a group represented by the above formula (4) ; [化32]

In the above formula (2), R51 and R52 each represent an alkylene group having a carbon number of 1 to 5; and 4 to 6 of the 6 groups of R53, R54, R5 5, R5 6 , R57 and R5 8 represent hydrogen. The non-hydrogen group of R53, R54, R55, R56, R57 and R58 represents a group represented by the above formula (5). ...(2)

The episulfide compound 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 cyclic thio groups. Further, a group having an epoxide group is bonded to a benzene ring, a naphthalene ring or an anthracene ring. Due to such a structure, the mixture can be rapidly hardened at a low temperature by heating a mixture of, for example, a hardener added to the cyclic sulfide.

An episulfide compound having a structure represented by the above formula (1-1), (2-1) or (3) and an episulfide group in the above formula (1-1), (2-1) or (3) The reactivity is higher than that of the epoxy group compound. The episulfide compound having the structure represented by the above formula (1) or (2) is more reactive than the compound having an epoxy group in the above formula (1) or (2). The reason for this is that the cyclothio group is easier to open than the epoxy group, and the reactivity is high. An episulfide compound having a structure represented by the above formula (1-1), (2-1) or (3), and an episulfide compound having a structure represented by the above formula (1) or (2), It has high reactivity and can be rapidly hardened at 143470.doc -19- 201020243 at low temperatures. RaR2 in the above formulas (1-1) and (1), R51 & R52 in the above formulas (21) and (7), R101 and R102 in the above formula (3), and R7 in the above formula (4) in the above formula (5) R59, and the ruler (1) in the above formula (6) are each an alkylene group having a carbon number of 1 to 5. If the carbon number of the alkylene group exceeds 5, the curing rate of the above-mentioned cyclic sulfide is liable to lower. In the above formulas (1-1) and (1), the old and the rule 2, the above formulas (21) and (7), R51 and R52, and the above formula (3), R1〇1 & Rl〇2, the above formula (in the sentence) R7 in the above formula (5) and Rin in the above formula (6) are each preferably an alkylene group having a carbon number of 1 to 3, more preferably a methylene group. The alkylene group having a direct bond structure may also be an alkylene group having a branched structure. The structure represented by the above formula (1) is preferably a structure represented by the following formula (1A). The epoxy sulfide of the structure represented by the above formula (1A) is excellent in hardenability: [Chem. 33]

...(1A)

In the above formula (1A), R1 & R2 each represents an alkylene group having a carbon number of 1 to 5. The structure represented by the above formula (1) is more preferably a structure represented by the following formula (1B); and the episulfide compound having a structure represented by the following formula (1B) is more excellent in hardenability: 143470. Doc •20· 201020243 [化34]

(1) The structure represented by the above (2) is preferably a structure represented by the following formula (2A); and the hardening of an episulfide compound having a structure represented by the following formula (2A); Excellent sex: [Chem. 35]

In the above formula (2A), R51 and R52 each represent an alkylene group having a carbon number of 1 to 5.

The structure represented by the above formula (2) is more preferably a structure represented by the following formula (2B); and the epoxy sulfide having a structure represented by the following formula (2B) is more excellent in hardenability: 36]

The structure represented by the above (3) is preferably a structure represented by the following formula (3A); the hardening of the episulfide compound having the structure represented by the following formula (3 A) 143470 .doc -21 - 201020243 Excellent: [Chem. 37] <1, 0 R101

Formula (3A)

In the above formula (3A), R101 and R102 each represent an alkylene group having a carbon number of 1 to 5. The structure represented by the above formula (3) is more preferably a structure represented by the following formula (3B); and the epoxy sulfide having a structure represented by the following formula (3B) is more excellent in curability: 38] <!

Formula (3B) 143470.doc • 22-201020243 (mixture containing episulfide) The episulfide-containing mixture of the present invention contains the formula (1 - 1), (2-1) or (3) An episulfide compound, and an epoxy compound represented by the following formula (111), (121) or (13); in the following formula (111), bonded to a bonding site of a 6-base of a benzene ring It is not particularly limited; in the following formula (m), the bonding site of the 8 groups bonded to the naphthalene ring is not particularly limited: [Chem. 39]

In the above formula (11-1), 'R11& R12 represents a stretching group having a carbon number of i to 5; and 2 to 4 of the four groups of R13, R14, R15 and R16 represent hydrogen; R13, R14, The non-hydrogen group in R15 and R16 represents a group represented by the following formula (14); the four groups of R13, R14, R15 and R16 may all be hydrogen; in the four groups of R13, R14, R15 and R16 One or two of the groups represented by the following formula (14), and the group of the four groups of 1113, 1114, 1115 and 1116 which are not represented by the following formula (14) may be hydrogen. ; [化40]

_ ••式(12-1) 143470.doc -23- 201020243 In the above formula (12-1), R61$R62 represents an alkylene group having a carbon number of 1 to 5; R63, R64, R65, R> And 4 to 6 of the 6 groups of R67 and R68 represent hydrogen; the non-hydrogen group of R63, R64, R65, R66, R67 and R68 represents a group represented by the following formula (15); R63 6 of R64, R65, R66, R67 and R68 may be all hydrogen; one or two of the six groups of R63, R64, R65, R66, R67 and R68 are represented by the following formula (15) The group represented, and the group of the six groups of R63, R64, R65, R66, R67 and R68 which are not represented by the following formula (15) may be hydrogen; [Chem. 41]

R121 R123 \〇 R130

R129 R128 ... (13)

In the above formula (13), R121 and R122 each represent an alkylene group having a carbon number of 1 to 5; and 6 to 8 of the 8 groups of R123, R124, R125, R126, R127, R128, R129 and R130 represent Hydrogen; a non-hydrogen group of R123, R124, R125, R126, R127, R128, R129 and R130 represents a group represented by the following formula (16); R123, R124, R125, R126, R127, R128, R129 and The eight groups of R130 may all be hydrogen; R123, 143470.doc -24- 201020243 One or two of the eight groups of R124, R125, R126, R127, R128, R129 and R130 are represented by the following formula (16) And the base of the group represented by the following formula (16) which may be hydrogen; and the base of the R123, R124, R125, R126, R127 and the ruler 128 may be hydrogen;

Formula (14)

In the above formula (14), R17 represents an alkylene group having a carbon number of 丨~5; [Chem. 43] */C), R6〆^ (15) In the above formula U5), R69 represents a carbon number of 5 (1) In the above formula (16), R131 represents a stretching group having a carbon number of 丨5. The cyclosulfide-containing compound of the present invention preferably contains a compound represented by the above formula (1), the above formula (7) or the above formula (3) from the viewpoint of hardening more rapidly at a low temperature, and The epoxy compound represented by the following formula (1)), the following formula (12) or the above formula (13); the cyclosulfide-containing full compound of the present invention is more preferably at a lower temperature and more rapidly The oxime 3 has a compound represented by the above formula (1) or (2), and an epoxy compound represented by the following formula (11) or (12): 143470.doc • 25· 201020243 [Chem. 45]

In the above formula (11), 'R11 and R12 respectively represent a stretching group having a carbon number of 1 to 5; and 2 to 4 of the 4 groups of R13, R14, R15 and R16 represent a nitrogen. R13, R14, R15 and The non-hydrogen group in R16 represents a group represented by the above formula (14); [Chem. 46]

In the above formula (12), R61 and R62 each represent a stretching group having a carbon number of i to 5, and 4 to 6 of the 6 groups of R63, R64, R65, R66, R67 and R68.虱; a non-hydrogen group of 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), the above R61 and R62 in the formulas (12-1) and (12), R121 and R122 in the above formula (13), R17 in the above formula (14), R69 in the above formula (15), and the above formula (16) R131 is an alkylene group having a carbon number of 1 to 5; if the carbon number of the alkylene group exceeds 5, the curing rate of the above-mentioned mixture containing the episulfide is likely to be lowered. 143470.doc -26· 201020243 R11 and R12 in the above formulas (11-1) and (11), R61 and R62 in the above formula, R121 and R122 in the above formula (13), and the above formula (14) R69 in the above formula (15) and R131 in the above formula (16) are each preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group. The above-mentioned stretching group may be an alkylene group having a linear structure or an alkylene group having a branched structure. The structure represented by the above (11) is preferably represented by the following formula (11A)

The structure; an epoxy compound having a structure represented by the following formula (11 A) is commercially available and is easily available: [Chem. 47]

In the above formula (11A), R11 & R12 represent a group having a carbon number of 5, respectively.

A structure represented by '------; an epoxidized phenylene oxide having a structure represented by the following formula (1) B). The meta-phenylene diglyceride bond is commercially available and is readily available: [Chem. 48]

(11B) The structure represented by the above (12) is preferably a structure represented by the following formula (12A): 143470.doc • 27- 201020243; and has a formula represented by the following formula (12A) The structure of the epoxy compound is easily available: [Chem. 49]

In the above formula (12A), R61 and R62 each represent an alkylene group having a carbon number of 1 to 5. The structure represented by the above formula (12) is more preferably a structure represented by the following formula (12B); an epoxide having a structure represented by the following formula (12B) can be easily obtained:

The structure represented by the above (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: 143470.doc -28 - 0 201020243 Formula (13Α) In the above formula (13Α), R101 and R102 each represent an alkylene group having a carbon number of 1 to 5. The structure represented by the above formula (13) is more preferably a structure represented by the following formula (13Β); an epoxide having a structure represented by the following formula (13Β) can be easily obtained:

0^ [化52] .0 Ό

Formula (13Β) 143470.doc -29- 201020243 The mixture of the episulfide of 3 in this month preferably contains 1 〇 to 99.9 wt% of having the above formula (1_1), (2_1) or (3) The ring-forming compound of the structure shown and containing 9% by weight of the epoxy compound represented by the above formula, (121) or (13). The episulfide-containing mixture of the present invention more preferably contains 80 to 99% by weight of an episulfide compound having a structure represented by the above formula (1, (2-1) or (3), and contains ruthenium. The epoxy compound represented by the above formula (11-1), (12_ι) or (13) is ι 2 〇 〇 〇. The cyclosulfide-containing mixture of the present invention preferably contains from 〇 to 99 9 wt. The episulfide compound having the structure represented by the above formula (!) or (2), and containing 90 to 0.1% by weight of the epoxy compound represented by the above formula (11) or (12). The episulfide-containing mixture of the present invention is more preferably an anthracene having a structure represented by the above formula (丨) or (2) in an amount of 80 99.9% by weight, and containing 1 2% by weight of the above An epoxy compound represented by the formula (11) or (12). If the content of the episulfide compound having the structure represented by the above formula (1-1), (2-1) or (3) is too small, and the content of the episulfide compound having the structure represented by the above formula (1) or Then, the hardening speed of the mixture containing the episulfide does not become sufficiently fast. If the content of the episulfide compound having the structure represented by the above formula (11_1}, (121) or (13), and the episulfide compound having the structure represented by the above formula (1) or (2) is excessive, The case where the viscosity of the autoclay containing the episulfide becomes too high, or the mixture containing the episulfide becomes a solid. (Manufacturing method of the episulfide and manufacturing method of the mixture containing the episulfide) 143470.d〇 c. 30-201020243 The method for producing the above-mentioned episulfide compound and the method for producing the above-described mixture containing the episulfide compound are not particularly limited. Examples of the production method include the following production method: preparation of the above formula (11·1), (12-1) or (13), or an epoxy compound represented by the above formula (11) or (12), which converts all or a part of the epoxy group of the epoxy compound into an episulfide group. The production method and the method for producing the above-described mixture containing the episulfide are preferably a method of continuously or intermittently adding the above formula (η_1) or (12-1) or in the first solution containing thiocyanate. (13) represented by epoxidation After the compound or the solution containing the epoxy compound, the second solution containing the thiocyanate is continuously or intermittently added. By the above method, all or a part of the epoxy group of the epoxy compound can be converted into a ring. The above epoxy compound or a solution containing the epoxy compound is preferably an epoxy compound represented by the above formula (1) or (2) or a solution containing the epoxy compound. As a result of the episulfide group, an episulfide compound having a structure represented by the above formula (1-1), (2-1) or (3) can be obtained. Further, it can also be obtained by the above formula (1) or 2) an episulfide compound of the structure represented by a structure in which a part of the epoxy group is converted into an episulfide group, and a structure having a structure represented by the above formula (1-1), (2-1) or (3) can be obtained. An episulfide compound and an episulfide-containing mixture of the epoxy compound represented by the above formula (11-1), (12-1) or (13). Further, it may be obtained to have a formula (1) Or (2) the represented cyclic sulfide ' and the epoxidation represented by the above formula (11) or (12) The mixture of the above-mentioned episulfide and the above-mentioned episulfide-containing compound can be produced by the following method: 143470.doc -31· 201020243. It is added to a container equipped with a mixer, a cooler and a thermometer. Solvent, water, and thiocyanate' dissolve thiocyanate and prepare a second liquid in a container. Examples of the solvent include methanol or ethanol. Examples of the thiocyanate include ammonium thiocyanate and thiocyanate. Potassium acid or sodium thiocyanate, etc. The concentration of the cyanate salt of the first solution is preferably in the range of 〇〇〇1 to 〇2, more preferably 0.005 〜(M g/mL). If the concentration of the thiocyanate is too high, there is a case where the epoxy compound is polymerized. If the concentration of the thiocyanate is too low, there is a case where the epoxy group cannot be converted into an episulfide group. Further, unlike the above-mentioned second liquid, an epoxy compound having a structure represented by the above formula (1)_〇, (12·υ, (13), (1)) or (12) or a solution containing the epoxy compound is prepared. . Then, an epoxide having a structure represented by the above formula () (12^(13), (1)) or 〇2) or a solution containing the epoxy compound is continuously or intermittently added to the i-th solution. At this time! The temperature of the solution is in the range of 15 to 较. Preferably, the above epoxy compound is added, and the mixture is stirred for 5 to 12 hours. The above epoxidized solution containing the epoxy compound may be added in plural stages. For example, after adding - part of the above ring or a solution containing the compound of the county, stirring at least 0.5 small person Υ Μ adding the remaining epoxy compound or a solution containing the epoxy compound, and milking for 12 hours . The use of a solution containing the above epoxidized mouth is particularly limited. The concentration of the epoxy compound of the @^ liquid is not in the range of 丨(10)mL/min, and the addition of the above epoxy compound or the solution containing the epoxy compound to the 143470.doc-32-201020243 solution is preferably in the range of 丨(10)mL/min. More preferably, it is in the range of 2 to 8 mL/min. If the rate of addition of the above epoxy compound or the solution containing the oxygen-releasing compound is too fast, polymerization of the epoxy compound may occur. When the rate of addition of the epoxy compound or the solution containing the epoxy compound is too slow, the production efficiency of the episulfide is lowered.

The epoxy compound or a solution containing the epoxy compound is added to the mixed solution of the first solution, and the concentration of the epoxy compound is preferably within the range of 〇·05~G·8 §/, and Good is in the range of ~0.5 g/mL. If the concentration of the epoxy compound is too high, it causes polymerization of the epoxy compound. Then, the epoxy compound or a solution containing the epoxy compound is added to the mixture of the i-th solution, and a second solution containing a solvent, water, and thiocyanate is continuously or intermittently added. It is preferred to add the above second solution and stir it for 5 to 12 hours. Preferably, it is preferred to add the above second solution at 15 to 6 Torr. Stir in the range of 〇. The above second solution can be added in plural stages. For example, after adding a part of the above-mentioned spherical liquid, 'at least 5 hours of stirring is carried out, and thereafter, the remaining second solution is further added' and stirred for 0.5 to 12 hours.

The concentration of the thiocyanate of the second solution is preferably in the range of 〇〇〇ι to 〇7 g/mL, more preferably in the range of 0.005 to 0.5 g/mL. High, there are cases where the epoxy compound is polymerized. If the concentration of sulphuric acid salt is too low, there is a case where the epoxy group cannot be converted into an epoxide group. 〇 143470.doc • 33 - 201020243 The addition rate of the above second solution to the above mixture is better. In the range of 10 mL/min, more preferably in the range of 2 to 8 mL/min, if the addition rate of the above second solution is too fast, polymerization of the epoxy compound may occur. When the rate of addition of the second solution is too slow, the production efficiency of the sulfide may be lowered. It is preferred to add the above second solution to the mixture obtained by adding the above epoxy compound to the first solution, and then remove water, a solvent or an unreacted thiocyanate. As a method of removing water, a solvent or unreacted thiocyanate, a previously known method can be used. The first solution or the second solution may contain a catalyst such as palladium metal particles or titanium oxide. The conversion ratio of the cyclic thio group can be adjusted by using a solution containing the above catalyst. Further, since the 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 of the second enthalpy solution or the concentration of the catalyst of the second solution is preferably in the range of 〇.MM 〇 g/mL. All or a part of the epoxy groups of the above epoxy compounds can be converted into an episulfide group as described above. As a result, an episulfide or a mixture containing an episulfide can be obtained. Specifically, for example, an episulfide compound having a structure represented by the above formula (1-1), (2-1), (3), (1) or (2) may be obtained in an amount of 1% by weight. Cyclic sulfide. Further, for example, an episulfide compound having a structure represented by the above formula (丨^, (21), (1) or (2)) containing 1 〇 to 99 9 wt% or 10 to 50 wt% may be obtained, and The ring-containing vulcanization of an epoxy compound represented by the above formula (11-1), 024), (13), (11) or (12) containing 9% by weight to 〇丨% by weight or 9% by weight to 5% by weight a mixture of things. 143470.doc -34- 201020243 (curable composition) The curable composition of the present invention contains the episulfide compound of the present invention and a hardener. Or the curable composition of the present invention contains the mixture containing the episulfide of the present invention and a hardener. Namely, the curable composition of the present invention contains the episulfide or the mixture containing the episulfide of the present invention, and a curing agent. The hardening agent may be used alone or in combination of two or more. The curable composition of the present invention contains at least the above-mentioned episulfide. Or φ The curable composition of the present invention contains at least a mixture of the above-mentioned episulfide-containing compounds. Or the curable composition of the present invention contains at least the above-mentioned episulfide compound and at least the above-mentioned mixture containing the above episulfide. Therefore, as the curable resin, two or more kinds of the above-mentioned episulfide compounds may be used in combination, or a mixture of two or more kinds of the above-mentioned episulfide-containing compounds may be used in combination, or a mixture of the above-mentioned episulfide compound and the above-mentioned episulfide-containing compound may be used in combination. The above hardener is (4) job ^. Examples of the above hard (four) include a flavoring agent, an amine curing agent, a hardening agent, a polythiol curing agent, or a sour liver. Among them, since the curable composition can be hardened more rapidly at a low temperature, it is preferable to (4) a hardener, a polythiol hardener or an amine hardener. Further, since the storage stability can be improved when the above-mentioned episulfide or the above-mentioned episulfide-containing mixture is mixed with the above-mentioned curing agent, a latent curing agent is preferred. The latent hardener is preferably a latent taste sclerosing hardener, a latent polythiol hardener or a latent amine hardener. These hardeners may be used alone or in combination of two or more. Further, the curing agent may be coated with a polymer material such as a polyurethane resin or a polyolefin resin. The hydrazine curing agent is not particularly limited, and examples thereof include 2 methyl 143470.doc • 35- 201020243 imidazole, 2-ethyl-4-mercaptoimidazole, ι_cyanoethyl-2-phenylimidazole, Cyanoethyl-2-phenylimidine β rust trimellitate, 2,4-diamino] 6-[2,-mercaptoimidazolyl-(indenyl)-ethyl 2,4-Diaminomercaptoimidazolyl-(1,)]-ethyl-homogeneous isocyanuric acid addition product and the like. The polythiol curing agent is not particularly limited, and examples thereof include trishydroxypropyl propane tri-3-mercaptopropionate, pentaerythritol tetra- 3 -mercaptopropionate or dipentaerythritol hexa-3-indenyl group. Propionate and the like. The amine curing agent is not particularly limited, and examples thereof include: 1>6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, and 3 9-bis(3-aminopropyl) 2,4,8,10-tetraspiro[5.5]undecane, bis(4-aminocyclohexyl)decane, m-phenylenediamine or diaminodiphenyl hard. A polythiol compound, an acid anhydride or the like can also be preferably used in the above curing agent. More preferably, a polythiol compound is used because the hardening speed of the hardenable composition can be further accelerated. More preferably, the above polythiol compound is pentaerythritol tetra- 3 - mercaptopropionic acid vinegar. By using the polythiol compound, the hardening rate of the curable composition can be further accelerated. The content of the above hardener is not particularly limited. 1 part by weight with respect to the above episulfide or the above-mentioned mixture containing the episulfide (in the case where the above epoxy compound is not contained, it represents 1 part by weight of the above episulfide, in the case of containing the above epoxy compound) In the case of the above-mentioned mixture containing the episulfide compound, it is preferred that the content of the above-mentioned hardener is within the range of the weight fraction. If the content of the above curing agent is less than i part by weight, the hardening composition may not be sufficiently cured. When the content of the above-mentioned curing agent exceeds 40 parts by weight of 143470.doc -36 to 201020243, the heat resistance of the cured product of the curable composition may be lowered. The lower limit of the content of the above-mentioned hardener is preferably 邛 by weight based on 100 parts by weight of the above episulfide or the above-mentioned mixture containing the episulfide, and the lower limit is preferably 45 parts by weight, more preferably 1 〇〇. The weight and the weight are preferably 75 parts by weight. If the content of the curing agent is too small, the curable composition becomes difficult to be sufficiently cured. If the content of the hardener is too large, there is a case where the remaining hardener remaining after hardening remains. Further, when the curing agent is an imidazole curing agent or a phenol curing agent, it is preferably an imidazole curing agent or a phenol curing agent with respect to the above-mentioned episulfide or the above-mentioned episulfide-containing mixture. The content is in the range of 丨 15 parts by weight. Further, in the case of the above-mentioned hardened (tetra)amine hardener, polythiol hardener or acid anhydride, it is preferably an amine hardener or a polythiol hardened with respect to 100 parts by weight of the above episulfide or the above-mentioned mixture containing the episulfide. The content of the agent or acid anhydride is in the range of 15 to 40 parts by weight. The curable composition of the present invention preferably further contains a storage stabilizer. The curable composition of the present invention preferably further contains at least one selected from the group consisting of phosphates, phosphites, and boric acid esters, and more as the above-mentioned storage stabilizer. The storage stability of the above episulfide or a mixture containing the episulfide can be further improved by using phosphorous acid:. The above storage stabilizers may be used alone or in combination of two or more. Examples of the above-mentioned fillings include H ethyl hydrazine, trimethyl phosphate 3, triethyl citrate, tri-n-butyl succinate, tris(butoxyethyl) vinegar, and tris(2-ethylhexyl) citrate. ) vinegar, (r〇) 3P = 〇 [r = laurel base 143470.doc • 37- 201020243 base, stearyl or oleyl], tris(2-e-ethyl) phosphate, squaric acid three (2 - Di-propyl propyl) S, Dish vinegar, butyl arsenate, tricate trimethyl vinegar, tris (dimethyl benzoate), octyl diphenyl phosphate, bismuth phosphate Ester, diphenyl phenyl dicarbonate, monobutyl silicate, dibutyl phosphate, di-2-ethylhexyl phthalate, monoisodecyl phosphate, ammonium acid ammonium phosphate, and acid phosphate 2_ Ethylhexyl ester salt and the like. Among them, diethyl benzyl phosphate can be preferably used. Examples of the phosphite include trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tris(2-ethylhexyl) phosphite, diisooctyl phosphite, and phosphoric acid triphosphate. Oxime ester, triisodecyl phosphite, tris(dodecyl) phosphite, trioleyl phosphite, tristearyl phosphite, diphenyl phosphite, tris(nonylphenyl) phosphite Ester, tris(2,4-di-tert-butylphenyl) S, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, diphenyl monophosphate (2_B Ethyl hexyl ester, diphenylisooctyl phosphite, bisphosphonium phosphite, diphenyl monoisodecyl phosphite, monophenyl tridecyl phosphite, phosphorous acid Bis(nonylphenyl)dimercaptobenzene s 曰 本 一 一 propylene glycol di arsenate, sulfonate poly(dipropylene glycol) phenyl ester, diisodecyl pentaerythritol diphosphite, bis (tridecane) Base) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis(indenyl) pentaerythritol diphosphite, tetraphenyltetrakis(tridecyl) Pentaerythritol: phosphite, tetrakis(tridecyl)-4, isopropylidene diphenyl diphosphite s曰-lauryl trithiophosphite, dimethyl hydrogen phosphite, dibutyl hydrogen Phosphate vinegar, bis(2-ethylhexyl)hydrogen sulfonic acid vinegar, dilauryl hydrogen arsenate _ bis oleyl hydrogen phosphite vinegar, diphenyl phthalic acid cool, phosphite phenyl single (2- Ethylhexyl) vinegar, diphenyl monohydrazine vinegar, and 143470.doc -38· 201020243 diphenyl mono(tridecyl) phosphate and the like. Among them, preferred is diphenyl mono(2·ethylhexyl) ruthenate, diphenylmonodecanoate or diphenyl mono(tridecyl) vinegar. It is an acid-filled diphenyl-based monoterpene vinegar or a sub-acid-phenyl mono(didecyl) group, and further preferably a diphenyl mono(tridecyl) vinegar. Examples of the above-mentioned boric acid ester include trimethyl borate, triethyl sulfonium borate, n-propyl hydrazine, triisopropyl borate, tri-n-butyl borate, dipentane borate, and diallyl borate. , trihexyl borate, tricyclohexyl borate, trioctyl borate, tridecyl borate, tridecyl borate, tris(dodecyl) bo borate, dihexadecyl borate, boric acid tri Octadecyl)ester, tribenzyl borate, diphenyl borate, tri-o-methyl ester of boric acid, tri-n-phenylphenyl borate, triethanolamine borate, tris(2-ethylhexyloxy)borane, double (1,4,7,1〇_tetraoxadecyl) (1,4,7,1〇,13-pentaoxatetradecyl) (1,47-trioxadecane) Borane, 2-(β-dimethylaminoisopropoxy)-4,5-dimethyl-1,3,2-dioxaborane, 2-(β-diethylamino Ethoxy)_4,4,6-trimethyl-1,3,2-dioxaboronium, 2-(β-dimethylaminoethoxy)_4,4,6-trimethyl 1,3,2-dioxaboronium, 2-(β·diisopropylaminoethoxy)4,3,2-dioxaboronium, 2-(β-diisopropylamino Ethoxy)_4•methyl 4, 3,2-dioxaboron, mountain 2-(γ-dimethylaminopropyloxy)_ι, 3,6,9-tetraoxa-2-indane undecane, and 2-(0 -didecylaminoethoxy)-4,4-(4-hydroxybutyl)-1,3,2-dioxane ρ,2,2-oxybis(5,5·didecyl) -1,3,2_dioxaboron, and an epoxy-phenol-boron ester formulation, etc. 1 part by weight relative to the above episulfide or the above mixture containing the episulfide The content of the above storage stabilizer is in the range of 0.001 to 〇.1 by weight 143470.doc -39 to 201020243 parts, and the content of the above storage stabilizer is 100 parts by weight relative to the above episulfide or the above mixture containing the episulfide. A more preferable lower limit is 0 side by weight, and a more preferable upper limit is G G5 parts by weight. When the content of the storage stabilizer, particularly the phosphite, is within the above range, the above-mentioned episulfide or the above-mentioned ring-containing vulcanization can be further improved. Storage stability of the mixture of the materials. The curable composition of the present invention preferably further contains a curing accelerator. The curing rate of the curable composition can be further accelerated by using a curing accelerator. The hardening accelerator may be used alone or in combination of two or more. Specific examples of the hardening accelerator include an imidazole hardening accelerator and an amine hardening accelerator. Among them, cerium hardening promotion is preferred. Further, an imidazole hardening accelerator or an amine hardening-promoting sword can also be used as an amino β-stable hardener or an amine hardener. As the above-mentioned imidazole hardening accelerator, 2-methylimidazole and 2-ethyl-4 can be mentioned. -methylimidazole, r-cyanoethyl-2-phenylimidazole, i-cyanoethyl-2-phenylimidazole rust trimellitate, 2,4-diaminos-6-[2,-methylcarbazole The group -(1,)]_ethyl_allicin or 2,4-diaminoindenyl imidazolyl-yl,]]ethyl-averaged isocyanuric acid adduct and the like. The lower limit of the content of the hardening accelerator is preferably 〇5 parts by weight, more preferably 1 part by weight, more preferably the upper limit, with respect to the above-mentioned episulfide or the above-mentioned mixture containing the episulfide. For 6 parts by weight, a better upper limit is 4 weight injuries. If the content of the hardening accelerator is too small, the curable composition becomes difficult to be sufficiently cured. When the content of the hardening accelerator is too large, there is a case where the remaining hardening accelerator that does not participate in hardening remains after curing. The curable composition of the present invention preferably further contains a filler. By substituting 143470.doc • 40· 201020243 ::, the latent thermal expansion of the cured product of the curable composition can be suppressed. The filler may be used alone or in combination of two or more. Specific examples of the above fillers include dioxane, nitriding or oxidizing. The above filler is preferably a filler particle. The average particle size of the filler particles is preferably in the range of Ο.ΚΟ μηι. If the average particle diameter of the filler particles is in the above range, the material is further inhibited from hardening of the hard pure composition.

The latent heat expansion. The "average particle diameter" means the volume average diameter measured by the dynamic laser scattering method. It is preferred that the content of the above filler is in the range of 5 () to _ part by weight based on the above-mentioned episulfide or the above-mentioned episulfide-containing mixture (10) by weight. If the content of the filler is the above-mentioned range, the latent thermal expansion of the cured product of the curable composition is further suppressed. The curable composition of the present invention may further contain a solvent, an ion trapping agent or a decane coupling agent as needed. The solvent is not particularly limited. The solvent may, for example, be ethyl acetate, thiol cellosolve, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran or diethyl ether. The solvent may be used alone or in combination of two or more. The broth coupling agent is not particularly limited. As the above-mentioned oxime coupling agent, for example, Ν-(2-aminoethyl)-3-aminopropyltrimethoxy zeoxime, Ν-(2-aminoethyl)·3·aminopropyl Methyl dimethyl decyl decane, Ν (2-aminoethyl)-3-aminopropyltrimethoxy oxalate, Ν-(2-aminoethyl)·3_aminopropyldiethyl Oxycene, * 3-aminopropyl monomethyl ethoxylate, 3-aminopropylmethyldiethoxydecane, 3-aminopropyltrimethoxy sylvestre, 3_H3470. Doc • 41 · 201020243 Aminopropyl triethoxy decane, vinyl triethoxy decane vinyl trimethoxy decane, vinyl triethoxy decane, vinyl trioxane, 3-glycidoxy Propyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxyxanthine, 3-glycidoxypropyltriethoxysulfate, 3-disylpropyldimethoxyxide Burning, 3-benzylpropylmethylmethicone, 3-apropylpropyltrimethoxydecane, 3·gaspropyltriethoxydecane,%methacryloxypropyltrimethoxy Baseline, 3-methacryloxypropyltriethoxy Decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysulfonium, ethyldimethoxycalcene, propyltrimethoxycarbazide, propyltriethoxydecane,dodecane A triethoxy decane, a hexyl trimethoxy decane, an isobutyl diethoxy decane, a methyl phenyl diethoxy oxime, a methyl phenyl dimethoxy sulphide or a scented saliva. Among them, the best one is the sulphur stone. The only one type of the coupling agent may be used alone or two or more types may be used in combination. The ion trapping agent is not particularly limited. Specific examples of the ion trapping agent include aluminosilicate, hydrous titanium oxide, hydrated oxidized neonate, strontium phosphate, titanium phosphate, hydrotalcite, ammonium phosphomolybdate, hexacyano zinc or an ion exchange resin. The ion trapping agent may be used alone or in combination of two or more. The curable composition of the present invention may further contain a photocurable compound and a photopolymerization initiator in order to be cured by light irradiation. The curable composition can be cured by irradiation of light by using the photocurable compound and the photopolymerization initiator. Further, the curable composition can be semi-cured, and the fluidity of the curable composition can be lowered. The photocurable compound is not particularly limited. As the photocurable 143470.doc -42·201020243, a (meth)acrylic resin or a cyclic ether group-containing resin can be preferably used. The above (meth)acrylic resin means a mercaptoacrylic resin and an acrylic resin. As the (meth)acrylic resin, an ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group, and a ring obtained by reacting (mercapto)acrylic acid with an epoxy compound can be preferably used. Oxy (meth)acrylic acid vinegar, or (mercapto)acrylic acid amide phthalate obtained by reacting a trans (meth)propanoid derivative with an isocyanate. The ester compound obtained by reacting the above (meth)acrylic acid with a compound having a hydroxyl group is not particularly limited. As the ester compound, any of a monofunctional vinegar compound, a bifunctional ester compound, and a trifunctional or higher ester compound can be used. The photocurable compound is preferably a light and a thermosetting compound containing at least one group having an epoxy group and a (meth) acrylonitrile group (hereinafter, also referred to as a partially (meth) acrylated epoxy resin). ). Q The above-mentioned partial (meth)acrylated epoxy resin is obtained, for example, by reacting an epoxy resin with (meth)acrylic acid in the presence of a basic catalyst in accordance with a conventional method. It is preferred that at least 2% by weight of the epoxy group is converted into a (meth) propyl fluorenyl group (conversion ratio), and partial (meth) propylene oximation is achieved. More preferably, 50% of the epoxy group is converted to a (meth) acrylonitrile group. The above (meth) acrylonitrile group means an acryl fluorenyl group and a decyl acryl fluorenyl group. From the viewpoint of improving the hardenability of the curable composition, the lower limit of the content of the partial (meth)acrylated epoxy resin in the above-mentioned hardenable β-content is 100% by weight. A preferred lower limit is 05 weight 143470.doc -43· 201020243%, a preferred upper limit is 2% by weight, and a more preferred upper limit is i 5% by weight. Examples of the epoxy (meth)acrylic acid vinegar include a double-presence epoxy (meth)acrylic acid vinegar, a acetal-type epoxy (meth)acrylic acid vinegar, and a carboxylic acid needle modification. Epoxy (mercapto) acrylic vinegar, and phenol novolac type epoxy (meth) acrylate. As an epoxy compound for obtaining the above epoxy (meth) acrylate, and a commercial product of the epoxy compound, for example,

4 ^ · Epikote 828EL and Epikote 1004 (both manufactured by Japan Epoxy Resins & Division) bisphenol a type epoxy resin, Epikote 806 and Epikote 4〇〇4"a & ^ sentence for Japan Epoxy

2,2'-diallyl, etc., which are made of Resins, etc., double-aged F-type epoxy resin, Epielmi exa1514 (manufactured by DIC), etc., S-type epoxy resin, RE_8l〇NM (manufactured by Sakamoto Chemical Co., Ltd.) Double-anti-type epoxy resin, Epiclon EXA7015 (manufactured by DIC), hydrogenated double-anti-epoxy resin, ερ· 4000 S (made by ADEKA), epoxy propylene alloy addition double-type epoxy resin, EX- 201 (manufactured by Nagase chemteX), etc.; biphenyl type epoxy resin such as epoxide resin ' Epikote YX-4000H (manufactured by Japan Epoxy Resins Co., Ltd.), YSLV-50TE (manufactured by Dongdu Chemical Co., Ltd.) ) Sulfide type epoxy resin, ether type epoxy resin such as YSLV-80DE (made by Tohto Kasei Co., Ltd.), dicyclopentadiene type epoxy resin such as EP-4088S (made by ADEKA), Epiclon HP4032 and Epiclon EXA- Naphthalene type epoxy resin such as 4700 (made by DIC), phenol novolak type epoxy resin such as Epiclon N-770 (made by DIC), ortho-cresol such as Epiclon N-670-EXP-S (made by DIC) Novolac type epoxy resin, dicyclopentadiene such as Epiclon HP7200 (manufactured by DIC) Aldehyde lacquer 143470.doc 201020243 type epoxy resin, NC-3000P (manufactured by Sakamoto Chemical Co., Ltd.) and other bi-phenol novolac type epoxy resin, ESN-165S (made by Tohto Chemical Co., Ltd.) and other naphthalene phenol phenol varnish type epoxy Resin, glycidylamine type epoxy resin such as Epikote 630 (made by Japan Epoxy Resins Co., Ltd.), Epiclon 430 (made by DIC Corporation), and TETRAD-X (made by Mitsubishi Gas Chemical Co., Ltd.), ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), Epiclon Alkyl polyol type epoxy resin such as 726 (made by DIC), Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX-611 (manufactured by Changchun Chemical Co., Ltd.), YR-450 and YR-207 (both are Dongdu) Rubber-modified epoxy resin such as Chemicals Co., Ltd. and Epolead PB (manufactured by Daicel Chemical Industries), glycidyl ester compound such as Denacol EX-147 (manufactured by Nagase Chemical Co., Ltd.), Epikote YL-7000 ( Japan Epoxy Resins Co., Ltd.), such as A-type A-ring sulfur resin, YDC-1312, YSLV-80XY and YSLV-90CR (both manufactured by Tohto Kasei Co., Ltd.), XAC4151 (made by Asahi Kasei Co., Ltd.), Epikote 103 1 Other epoxy resins such as Epikote 1032 (both manufactured by Japan Epoxy Resins Co., Ltd.), EXA-7120 (manufactured by DIC Corporation), and TEPIC (manufactured by Nissan Chemical Co., Ltd.). As the commercial product of the above epoxy (meth) acrylate, for example, Ebecryl 3700, Ebecryl 3600, Ebecryl 3701, Ebecryl 3703, Ebecryl 3200, Ebecryl 3201, Ebecryl 3600, Ebecryl 3702, Ebecryl 3412, Ebecryl 860, Ebecryl RDX63182, Ebecryl 6040 and Ebecryl 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 Industry Co., Ltd.), 143470.doc -45- 201020243

Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, and Epoxy Ester 400EA ( It is manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol Acrylate DA-141, Denacol Acrylate DA-314, and Denacol Acrylate DA-9 11 (all manufactured by Nagase Chemical Co., Ltd.). When the photocurable compound other than the photocurable compound is contained, the photocurable compound may be a crosslinkable compound or a non-crosslinkable compound. Specific examples of the crosslinkable compound include 1,4-butanediol di(indenyl)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-fluorene. Alcohol bis(mercapto) acrylate, (poly)ethylene glycol bis(indenyl)propionate, (poly)propylene glycol bis(indenyl) acrylate, neopentyl glycol bis(indenyl) acrylate, pentaerythritol Di(meth)acrylate, glycerol methacrylate acrylate, pentaerythritol tri(meth) acrylate, trimethylolpropane tridecyl acrylate, allyl (mercapto) acrylate, fluorenyl ) Vinyl acrylate, divinyl benzene, polyester (fluorenyl) acrylate, and (mercapto) urethane acrylate. Specific examples of the non-crosslinkable compound include ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. Isobutyl methacrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (mercapto)acrylic acid-2- Ethylhexyl ester, (meth)acrylic acid 143470.doc -46- 201020243 Octyl ester, (decyl) isooctyl acrylate, methacrylate (meth) acrylate, (F) Undecyl acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, and tetradecyl (meth) acrylate. From the viewpoint of effectively photohardening the curable composition, a preferred lower limit of the content of the photocurable compound is i weight with respect to 1 part by weight of the above episulfide or episulfide-containing mixture. A preferred lower limit is ίο parts by weight, and a preferred lower limit is 50 parts by weight, a preferred upper limit is 10,000 parts by weight, a more preferred upper limit is 1 part by weight, and a good upper limit is 500 parts by weight. The photopolymerization initiator is not particularly limited. The photopolymerization initiator may be used alone or in combination of two or more. Specific examples of the photopolymerization initiator include phenethyl hydrazine photopolymerization initiator, benzophenone photopolymerization initiator, 9 oxysulfuron, ketal photopolymerization initiator, and halogenated ketone. , fluorenylphosphine oxide or thiophosphoric acid ester. Specific examples of the above-mentioned acetophenone photopolymerization initiator include 4-(2-phenyloxy)phenyl(2-carbo-2-propyl)anthracene and 2-butyryl-2-methyl. _ι_Phenylpropan-1-one, methoxyphenylethyl, 2,2-dimethoxy·ι,2-diphenylethane-1-one, or 2-hydroxy-2-cyclo Hexyl acetophenone and the like. Specific examples of the ketal photopolymerization initiator include benzoin dimethyl ketal and the like. The content of the above photopolymerization initiator is not particularly limited. The lower limit of the content of the above photopolymerization initiator is preferably 0.1 part by weight based on 100 parts by weight of the photocurable composition. The lower limit is preferably 〇·2 parts by weight, and further preferably the lower limit is 2 parts by weight. A preferred upper limit is 1 part by weight, and a higher upper limit is 143470.doc • 47· 201020243 is 5 parts by weight. If the content of the photopolymerization initiator is too small, the effect of adding a photopolymerization initiator may not be sufficiently obtained. If the content of the photopolymerization initiator is too large, the adhesion of the cured product of the curable composition is lowered. The curable resin composition may further contain an epoxide other than the epoxy compound represented by the above formula (丨_丨), (丨2_丨), (13), (11) or (12). As the epoxy compound, an epoxy compound used to obtain the above epoxy (meth) acrylate can be used. In the episulfide compound, and the epoxy compound represented by the above formula (11_υ, (η"), (13), (11) or 〇 (12), and 100% by weight of the total juice of the above other epoxy compound, A preferred lower limit of the content of the episulfide is 丨〇 weight/〇, a more preferred lower limit is 25 ❶/., a preferred upper limit is j 〇〇% by weight, and a more preferred upper limit is 50% by weight. The curable composition may be used in the form of a one-component adhesive for a liquid crystal panel or a semiconductor wafer, etc. The curable composition may be a paste-like adhesive or a film-like adhesive. The curable composition of the present invention The method of processing the film-form adhesive agent is specifically limited, for example, a method of applying a curable composition to a substrate such as release paper, and processing it into a film-like adhesive; or a curable composition When the mixture is applied to a substrate such as release paper, the solvent is volatilized at a temperature lower than the activation temperature of the curing agent, and the film is processed into a film-like adhesive. The method of hardening the composition can be enumerated: a method for heating a composition; a method of heating a curable composition of 143470.doc -48* 201020243 after irradiation of light to a curable composition; or irradiating light to a curable composition while combining a hardenability The method of heating the material, etc. The heating temperature at the time of hardening the curable composition of the present invention is preferably in the range of 160 to 250 ° C, more preferably in the range of 160 to 200 ° C. It can be rapidly hardened at low temperatures, thus reducing the amount of energy required for heating.

In the conventional hardening composition containing an epoxy resin or the like, if the heating temperature is 200 ° C or lower, the curing time becomes long. For example, if the heating temperature is 200 ° C, the curing time exceeds 1 〇 second. On the other hand, the curable composition of the present invention can be cured in a short time even when the heating temperature is 20 (rc or less). When the curable composition of the present invention is photocured, the curable composition is irradiated with light. The light source used in the present invention is not particularly limited, and 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, and a high pressure mercury lamp. , ultra-high pressure mercury lamp, chemical lamp, black light, microwave excited mercury lamp or metal lamp, etc. Among them, a chemical lamp is preferred. The chemical lamp can effectively emit light in the active wavelength region of the photopolymerization initiator. The composition of the composition other than the polymerization initiator has a smaller amount of luminescence in the light absorption wavelength region. Further, when a chemical lamp is used, the light can be efficiently brought to the photocured component existing inside the composition. In the case of the acetophenone-based cleavage type photopolymerization initiator, the light irradiation intensity in the wavelength region of 365 nm to 420 nm is preferably 0. In the range of 1-100 mW/cm 2 143470.doc 49· 201020243 When the curable composition B# m of the present invention further contains conductive particles, a curable composition can be used as the anisotropic conductive material. For example, the particles are electrically connected between the electrodes of the circuit Φ Shuangxing Qian. The conductive particles are not particularly limited as long as the surface of the conductive particles is electrically conductive, and the particles are not particularly limited as the above-mentioned guide 2 2 ^ ^ ^ particles For example, there may be mentioned conductive particles in which a surface is covered with a metal layer, such as a sub-particle, an inorganic particle, an organic-inorganic hybrid particle or a metal particle, or a metal particle composed of only a metal on a pneumatic shell. There is no special parameter ^ X,, ^ . , a ^ 疋 as the above metal layer, 歹〗, gold layer, silver layer, copper layer, gold layer, etc. Spicy layer palladium layer or metal containing tin refers to the above conductivity The content of the particles is not particularly limited. The lower limit of the content of the conductive: raw: is preferably 〇" by weight, based on 1 part by weight of the above episulfide or the above-mentioned mixture containing the episulfide. The lower limit is •5 The upper limit of the amount of the component is preferably 1 G by weight, and the upper limit is more preferably 5 parts by weight. If the content of the conductive particles is too small, the electrodes may not be reliably electrically connected to each other. However, there is a case where the short circuit is not formed between the adjacent electrodes. When the curable composition is in the form of a liquid or a paste, the viscosity of the curable composition (25. 〇 is preferably 2000 〇 1 〇〇〇) In the range of 〇〇mpa·8, if the upper (four) degree is too low, the conductive particles may settle. If the viscosity is too high, the conductive particles may not be sufficiently dispersed. Uses The curable composition of the present invention can be used to carry out various connecting member members. 143470.doc -50- 201020243 When the curable composition of the present invention is an anisotropic conductive material containing conductive particles, the anisotropic conductive material may be an anisotropic conductive paste, an anisotropic conductive ink, an anisotropic A conductive conductive adhesive, an anisotropic conductive film, or an anisotropic conductive sheet or the like is used. When the anisotropic conductive material is used as a film-like adhesive such as an anisotropic conductive anisotropic conductive sheet, the conductive layer may be laminated on the film-like adhesive containing the conductive particles. Film-like adhesive. ❹ The anisotropic conductive material can be preferably used for obtaining a connection structure in which the first and second connection members are electrically connected. Fig. 1 is a cross-sectional view schematically showing an example of a connection structure using a curable composition according to an embodiment of the present invention. The connection structure shown in Fig. 1 includes an i-th connection object member 2, a second connection object member 4, and a connection portion 3 that connects the second and second connection object members 2, 4. The connecting portion 3 is formed by curing an anisotropic conductive material which is a curable composition containing the conductive particles 5. • A plurality of electrodes 2b are provided on the upper surface 2a of the first connection object member 2. A plurality of electrodes are disposed on the lower surface of the second connection 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, 4 are electrically connected by the conductive particles 5. Specifically, as the connection structure, an electronic component wafer such as a semiconductor wafer, a capacitor wafer, or a diode wafer is mounted on a circuit board, and an electrode of the electronic component wafer is electrically connected to an electrode on the circuit board. Structure, etc. Examples of the circuit board include various types of circuit boards such as a flexible printed substrate 143470.doc • 51·201020243 glass substrate or a substrate in which gold is laminated. The second connection target member is preferably an electronic device or a circuit substrate. The manufacturing method of the above-mentioned connection structure is not limited thereto. As an example of the manufacturing method of the connection structure, the following may be mentioned: r Wan 沄. The electronic component circuit board or the like is connected to the (four) pieces, and the electronic parts or The anisotropic conductive material is disposed between the second connection member such as the circuit board, and the laminate is heated and pressurized. The curable composition may contain conductive particles. In this case, it is not necessary to electrically connect the first and second connection target members, and the first and second connection target members can be connected by using the curable composition. Hereinafter, the present invention will be described by way of examples and comparative examples. The present invention is not limited to the following examples. (Example 1) (1) Preparation of a mixture containing an episulfide is provided with a stirrer, a cooler, and a thermometer 2 L container is added with 250 mL of ethanol, 250 mL of pure water, and 20 g of thiocyanate clock to dissolve the thiocyanate, and the first solution is prepared in the vessel. Thereafter, the temperature in the vessel is maintained at In the range of 20 to 25 ° C. Then, the first solution was kept at 20 to 25 ° C while stirring, and 16 μg of the stupid phenol condensate was added dropwise to the first solution at a rate of 5 mL / minute. Glycerol ether. After adding dropwise, stirring for further 30 minutes to obtain a solution containing an epoxy compound. Then, preparing a solution containing 100 mL of pure water and 100 mL of ethanol, 143470.doc -52· 201020243 dissolved 20 g of thiocyanate The second solution of potassium acid is added to the obtained epoxy compound-containing solution, and the prepared second solution is added at a rate of 5 mL/min, and then stirred for 30 minutes. After stirring, it is further prepared to contain 100 mL of pure water. The second solution of 20 g of potassium thiocyanate was dissolved in a solution of 100 mL of ethanol, and the second solution was further added at a rate of 5 mL/min and stirred for 30 minutes. Thereafter, the temperature in the vessel was cooled to l. 〇°C, stir for 2 hours, carry out the reaction. Then, add 100 mL of saturation to the vessel. The brine was stirred for 10 minutes. After stirring, 300 mL of toluene was added to the vessel and stirred for 10 minutes. Thereafter, the solution in the vessel was transferred to a separatory funnel and allowed to stand for 2 hours to separate the solution. The solution in the lower part of the funnel was taken out, and the supernatant was taken out. 100 mL of toluene was added to the supernatant, and the mixture was stirred and allowed to stand for 2 hours. Further, 100 mL of toluene was further added, and the mixture was stirred and allowed to stand for 2 hours. Then, 50 g of magnesium sulfate was added to the supernatant containing toluene, and the mixture was stirred for 5 minutes. After stirring, magnesium sulfate was taken out using a filter paper, and the solution was separated. The residual solution was removed by vacuum drying at 80 ° C using a vacuum dryer. In this way, a mixture containing an episulfide compound is obtained. The obtained episulfide-containing mixture was subjected to W-NMR measurement using a gas-like solvent. As a result, a signal indicating a region of 6.5 to 7.5 ppm in which an epoxy group exists is reduced, and a signal indicating a region of 2.0 to 3.0 ppm in which an epoxy group is present appears. Thereby, it was confirmed that a part of the resorcinol diglycidyl ether was converted into an epoxy group by an epoxy group. Further, according to the measurement result of W-NMR, the integral value of 143470.doc -53-201020243 was confirmed: the mixture containing the episulfide contained 7% by weight of the benzenediol diglycidyl ether, and 30% by weight of the above formula (1B) The episulfide compound represented. (2) Preparation of curable composition Into 33 parts by weight of the obtained episulfide-containing mixture, 2 parts by weight of pentaerythritol tetra- 3 - mercaptopropionate as a hardener, and 1 part by weight of phosphoric acid were added as a hardening agent. Diphenyl mono(tridecyl) phosphite, bismuth 2-ethyl-4-methylimidazole as a hardening accelerator, 2 〇 by weight as a filler, the average particle size is 0.25 μηι Cerium oxide and 2 parts by weight of alumina having an average particle diameter of 〇5 _μηι, and 2 parts by weight of conductive particles having an average particle diameter of 3 μηη, obtained by stirring at 2000 rpm for 5 minutes using a planetary mixer A curable composition of an anisotropic conductive paste. Further, the conductive particles to be used are conductive particles having a metal layer in which a nickel plating layer is formed on the surface of the diethylbenzene resin particles, and a gold layer is formed on the surface of the nickel plating layer. (Example 2) In the preparation of the curable composition, the addition of the quaternary tetral of the quaternary phosphonium vinegar and the diphenyl monotridecyl phosphite was used in addition to Example 1 In the same manner, a curable composition as an anisotropic conductive paste was obtained. (Comparative Example 1) * 100 parts by weight of a bisphenolphthalein type epoxy resin was added, and 5 parts by weight of dimethyl dimethyl hydrazine as a curing agent was stirred at 2000 rpm for 5 minutes using a planetary mixer to obtain a mixture. I43470.doc -54· 201020243 7 parts by weight of cerium oxide particles having an average particle diameter of 〇〇2 ^ melon and 2 parts by weight of conductive particles having an average particle diameter of 3 μηι were added to the obtained mixture, using a planetary type The mixture was stirred at 2 rpm for 8 minutes to thereby obtain a formulation. Further, the conductive particles to be used are conductive particles having a metal layer formed on the surface of the divinylbenzene resin particles to form a nickel plating layer, and a gold plating layer is formed on the surface of the nickel plating layer. . The curable composition as an anisotropic conductive paste was obtained by filtering the obtained preparation by using a nylon paper; a paper having a pore size of 1 〇 μηη. (Evaluation of Examples 1, 2 and Comparative Example 1) (1) Curing time A moon-glass substrate in which L/S was a 1 〇 μηι/10 μηΐ2ΙΤ〇 electrode pattern formed on the upper surface was prepared. Further, a semiconductor wafer in which a copper electrode pattern having an L/s of 1 Å was formed on the lower surface was prepared. The curable composition obtained was applied onto the above transparent glass substrate so as to have a thickness of 30 μm to form a curable composition layer. Then, the semiconductor wafer is laminated on the hardened φ-group 0 layer so that the electrodes face each other and are connected to each other. Thereafter, the temperature of the heating head was adjusted so that the temperature of the curable composition layer was 185 C, and the heating head was placed on the upper surface of the semiconductor wafer, and the curable composition layer was hardened at 185 Å: to obtain a connection. Construct. When the joined structure was obtained, the time until the curable composition layer was cured by heating was measured. (2) With or without voids The bonded structure obtained in the evaluation of the hardening time described above was visually observed from the lower surface side of the transparent glass substrate to the hardened layer formed of the curable composition layer shape 143470.doc -55 - 201020243 Whether there is a gap in the middle. The results are shown in Table 1 below. [Table 1] Hardening time with or without voids Example 1 1 second No Example 2 6 seconds No Comparative Example 1 2 minutes (Example 3) In the preparation of the curable composition, in addition to further adding 5 parts by weight of epoxy acrylate ( "EBECRYL3702" manufactured by Daicel-Cytec Co., Ltd. was obtained in the same manner as in Example 1 except that 0.1 part by weight of a fluorenylphosphine oxide-based compound ("DAROCUR TPO" manufactured by Ciba Japan Co., Ltd.) as a photopolymerization initiator was obtained. As a curable composition of an anisotropic conductive paste. (Example 4) In the preparation of the curable composition, in addition to 5 parts by weight of urethane acrylate ("EBECRYL8804" manufactured by Daicel-Cytec Co., Ltd.), and 0.1 part by weight of thiol oxidation as a photopolymerization initiator A curable composition as an anisotropic conductive paste was obtained in the same manner as in Example 1 except that a phosphine-based compound ("DAROCUR TPO" manufactured by Ciba Japan Co., Ltd.) was used. (Evaluation of Examples 3 and 4) (1) Curing time The transparent glass substrate and the semiconductor wafer used in the evaluation of Examples 1 and 2 and Comparative Example 1 were prepared. The curable composition layer 143470.doc - 56 - 201020243 was applied to the upper surface of the above transparent glass substrate to have a thickness of 30 (four)' to form a curable composition layer. Further, an anisotropic conductive paste was applied, and an ultraviolet irradiation lamp was used, and the curable composition layer was irradiated with ultraviolet light of 420 coffee so that the curable composition layer was light-emitting, and the curable composition layer was photopolymerized. Perform B-stage. After the application, the time from the contact of the coated hard pure composition layer to the transparent glass substrate until the light of the curable composition layer is irradiated is 0.5 seconds. Then, the semiconductor wafer is laminated on the surface of the B-staged curable composition layer so that the electrodes face each other and are connected to each other. Thereafter, the temperature of the head was adjusted so that the temperature of the curable composition layer was 185 t, and a pressure heating head was placed on the upper surface of the semiconductor wafer, and a pressure of 10 kg/cm 2 was applied to harden the B-stage. The composition layer was completely cured under i85 (>c to obtain a bonded structure. When the joined structure was obtained, the time until the hardenable composition layer was cured by heating was measured. (2) Whether or not there was void The connection structure obtained in the evaluation of the hardening time was evaluated for the presence or absence of voids in the same manner as in Examples 1 and 2 and Comparative Example 1. The results are shown in Table 2 below. [Table 2] Examples of the hardening time 3 m Example 4 1 benefit (Examples 5 to 24) (1) Preparation of an episulfide or a mixture containing an episulfide 143470.doc • 57- 201020243 Prepared in the same manner as in Example 1 with the following The content includes an episulfide compound represented by the above formula (1), (2) or (3), and an episulfide compound or an epoxy compound represented by the above formula (11), (12) or (13). a mixture of episulfides. The episulfide of each example or The mixture containing the episulfide is obtained by appropriately adjusting the amount of potassium thiocyanate used and adjusting the conversion ratio. (2) Preparation of the curable composition In the preparation of the curable composition, except that it is used in the examples An anisotropic conductive paste was obtained in the same manner as in Example 33, except that 33 parts by weight of the mixture containing the episulfide compound was changed to the episulfide compound or the mixture containing the episulfide compound shown in the following Tables 3 to 5. (Example 25) In the preparation of the curable composition, 33 parts by weight of the mixture containing the episulfide compound used in the Example was changed to the 3 ring sulfide used in the Example. A curable composition was obtained in the same manner as in Example 以外, except that 20 parts by weight of the mixture and 20 parts by weight of the mixture containing the episulfide compound used in Example 9 were obtained. (Example 26) Preparation of a hardenable combination In the case of the present invention, in addition to the trisulfide-containing mixture used in the Example, 33 parts by weight was changed to 20 parts by weight of the mixture containing the episulfide used in the Example, and resorcin. A curable composition was obtained in the same manner as in Example 以外 except for 10 parts by weight of the glycidyl ether. (Example 27) In the preparation of the curable composition, the 143470.doc-58 was used in addition to the Example 丨. - 201020243 Cyclosulfide "The mixture Μ part by weight is changed to 20 parts by weight of the mixture containing the episulfide used in Example i and bisphenol A type glycidyl ether! 〇 by weight, in the same manner as in Example 1. The curable composition was obtained. (Evaluation of Examples 5 to 27) The curing time and the presence or absence of voids were evaluated in the same manner as in the evaluations of Examples 1 and 2 and Comparative Example 1. The results are shown in Tables 3 to 6 below. 143470.doc -59- 201020243 [ε<] 1 embodiment η 1 1 positive thiol group 1 1 argon atom 1 1 hydrogen atom | 1 hydrogen atom | 1 argon atom 1 * ' • 1 n-pentyl group I 1 hydrogen atom | 1 Argon atom 1 1 Argon atom | 1 Hydrogen atom 1 • ' 1 1 Example 丨〇 1 1 Forward pentyl 1 1 Scorpion 1 1 Hydrogen atom 1 1 Argon atom 1 1 Hydrogen atom 1 • - * 1 pentyl group | 1 Argon atom | 1 Argon atom 1 1 Hydrogen atom | 1 Hydrogen atom 1 * 〇VJ·1 Example 9 1 1 Forward propyl 1 1 Helium atom 1 1 Argon atom 1 1 Hydrogen atom 1 1 Argon atom 1 ' • ' • 1 * 1 1 〇〇σ\ 〇1 Example 8 | 1 n-propyl propyl | 1 氲 atom 1 1 hydrogen atom | 1 hydrogen atom 1 1 argon atom 1 • • 1 n-propyl group | 1 hydrogen atom | 1 argon atom 1 1 hydrogen atom 1 1 argon atom 1 1 1 1 - 1 Example 7 | 1 n-propyl group | 1 氲 atom 1 1 hydrogen atom 1 1 argon atom 1 1 argon atom 1 • | n-propyl group | 1 hydrogen atom 1 1 argon Atom 1 1 Argon atom 1 1 Argon atom i 1 1 1 〇 <N 1 Example 6 1 | Methylene | | Hydrogen atom j 1 Argon atom | | Argon atom 1 1 Argon atom 1 1 • • • • 1 1 〇 〇r» ο 墀1 Example 5 | 1 methylene | 1 argon atom I 1 hydrogen atom 1 1 argon atom 1 1 argon atom 1 i '1 methylene group 1 argon atom | 1 argon atom 1 1 argon atom | 1 argon atom 1 • • 00 ο disc | R1 and R2 IS | R51 and R52 1 [R53_1 [R54__1 [R55__1 1 in 6-__ 1 [R57_I [R58_I [R5?_I | R101 and R102 1 | H103 ~ R110 | |R11 and R12 1 |Ri3....." 丨R14 -_ 1 [R15__1 iR!6___J ίΜΖ_1 |R61 and R62 1 [R63_I [R64_1 |R65 | |R66 I \ml___J |R68 I \m___1 |R121 and R122 IR123-R130 | i ? m Μ If s If Δ3 Cylon < -Φ | Content of compound with structure represented by formula (% by weight) ※〗 | 1 Hardening time 1 Whether there is empty Chen 1 (1) The type of the episulfide compound having the structure represented by the formula (2) The type of the episulfide compound having the structure represented by the formula (2) has the structure of the episulfide compound represented by the formula (3) The type of the epoxy compound having the structure represented by the formula (12) has the type of the epoxy compound having the structure represented by the formula (13). w as v3⁄4/. w*0Ql is <°3⁄4<w--3⁄4ί祙♦'fe3⁄4/3⁄4辋Q0l3⁄4πrl/. w 003⁄4l-l3⁄43⁄4ffllfeκ%1^8t [※ -60- 143470.doc 201020243 | Example 18 1 • 1 n-propyl | 1 hydrogen atom 1 1 hydrogen atom 1 1 argon atom 1 1 hydrogen atom 1 1 argon atom 1 1 Argon atom 1 • • • I is a propyl group | 1 Argon atom 1 1 Hydrogen atom 1 1 Argon atom 1 1 Hydrogen atom | 1 Argon atom 1 1 Argon atom 1 • 1 〇»n 1 Example 17 1 Methylene group 1 Hydrogen Atom 1 Hydrogen atom 1 Hydrogen atom, 1 Hydrogen atom 丨1 Argon atom 1 1 Hydrogen atom | 1 ' * ' • ' • • ' 1 〇〇〇〇|Example 16 | • 1 methylene 1 1 argon atom | 1 Argon atom 1 1 argon atom | 1 hydrogen atom | 1 argon atom 1 I argon atom | 1 * 1 methylene group | 1 hydrogen atom 1 1 hydrogen atom 1 1 hydrogen atom | 1 hydrogen atom | I argon atom | 1 hydrogen atom 1 1 1 卜d disc|Example 15 - 1 methylene 1 argon atom 1 argon atom 1 hydrogen atom 1 argon atom i 1 argon atom 1 1 hydrogen atom | * 1 methylene group 1 1 argon atom 1 1 argon atom 1 ! Hydrogen atom 1 Argon atom 1 i Argon atom | 1 Hydrogen atom 1 1 〇00 〇1 Example 14 Methylene group 1 Formula (4) 1 Formula (4) 1 Hydrogen atom 1 Hydrogen atom 1 1 Methylene group! 1 '1 methylene group 1 1 formula (4) 1 1 formula (4) 丨 1 argon atom | 1 argon atom 1 1 methylene group 1 ' ' 〇 - 碡 | Example 13 1 methylene group 1 Formula (4) 1 Argon atom 1 Hydrogen atom 1 Hydrogen atom 1 methylene! 1 ' 1 methylene group | 1 Formula (4) 1 1 Hydrogen atom 1 1 Argon atom | 1 Argon atom 1 1 Methylene group 1 • • 〇- | Example 12: 1 sec-pentyl group 1 hydrogen atom 1 hydrogen atom 1 Hydrogen atom 1 Argon atom 1 1 * • • 1 1 • • 〇〇 (N 碡|R1 and R2 2 V» οά S £ |R51 and R52 |R53 |R54 |R55 [R56_ί ^57_Ί \m_1 ^59_ R101 and R102 R103-R110 |R11 and R12 I [R13_1 [R14_1 1^5_1 \m_I ίΜΖ_1 |R61 and R62 I [R63_ [R64_1 :R65 1 R66 | \Ml_1 IR68 | R69 | R121 and R122 R123-R130 |With Formula (1H3 The content of the compound represented by the structure (weight %) ※! | | The content of the compound having the structure represented by the formula (11) to (13) (% by weight of the 1 | | hardening time | 1 with or without (1) The type of the episulfide compound having the structure represented by the formula (1), the type of the episulfide compound having the structure represented by the formula (2), and the type of the episulfide compound having the structure represented by the formula (3) The type of the epoxy compound having the structure represented by the formula (1) has an epoxy group having a structure represented by the formula (2) and has an epoxidation of the structure represented by the formula (13) The type of the object -^^^^./.^ The vehicle is a 荽^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ %:!.^^}2!※ 143470.doc -61- 201020243 [5崦] 丨Example 24 | ' • 1 methylene 1 1 argon atom | • • • 〇〇00 〇m I Example 23 I 1 methylene | 1 argon 1 • • 1 methylene 1 1 hydrogen atom 1 〇 - Example 22 | ' 1 methylene 1 1 Formula (5) 1 1 Argon atom 1 1 Hydrogen atom | 1 Hydrogen atom | 1 Argon atom 1 1 Hydrogen atom | 1 Methylene group I • • 1 methylene group | 1 Formula (5) I 1 Argon atom | 1 Hydrogen atom 1 1 Hydrogen atom 1 1 Argon atom 1 1 Argon atom 1 1 Methylene group | * 〇〇墀 Example 21 | '1 sec-pentyl group 1 1 gas atom 1 1 argon atom 1 1 argon atom 1 1 hydrogen atom 1 1 argon atom 1 1 argon atom 1 • • 1 positive pentyl group 1 1 argon atom 1 1 argon atom 1 1 argon atom 1 1 argon atom | 1 argon atom | 1 hydrogen atom 1 • ' 〇 «ΛΙ 〇墀 1 Example 20 | ' 1 methylene group 1 1 argon atom 1 1 argon atom 1 1 argon atom 1 1 Argon atom 1 1 Argon atom 1 1 Argon atom | . • • ' - ' • ' 1 〇〇fO 〇墀 Example 19 | 1 Methylene 1 1 Argon atom 1 1 Hydrogen atom 1 1 Hydrogen atom 1 1 Argon atom 1 1 Hydrogen atom 1 1 Hydrogen atom 1 • '1 Methylene group 1 1 Argon atom 1 1 Helium atom 1 1 Hydrogen atom 1 1 Hydrogen atom 1 1 Argon atom | 1 Argon Atom 1 • ' 〇磲|R1 and R2 | ΓΛ Oi 2 «Λ 0< |R51 and R52 I ίΜ3____1 loyalty 54- __1 1R55 _____J [R56_____I ^57_ _| as 8 — _1 [R59 ____1 | RKH and R102 I IR103-R110 | |R11 and R12 | ___1 [R14_1 \m_1 [R16___J 1ri7 ____1 |R61 and R62 | [R63_____1 \m_____J [R65. —_I |R66 | [R67___I [R68 J IR69 __ _____I 1^121 and R122 1 | R123〜R130 | i 翱Μ者安寒龙< m X § •9 spider im if Φ 班龙< in' X § -9 1 hardening time 1 1 with or without empty team 1 has represented by formula (1) The type of the ring-forming compound having the structure represented by the formula (2) has the structure of the episulfide compound having the structure represented by the formula (3), and the type of the episulfide compound having the structure represented by the formula (3) has the structure represented by the formula (11). The type of the cyclic ruthenium compound has an epoxy compound having a structure represented by the formula (12) and an epoxy compound having a structure represented by the formula (13) Class. An umbrella Νψβ/οί^οοι If the umbrella 畦:^娄-^蛘杯如啦^%!.·©2^^* %1-¥81If-饽 shirt length <%1^0011来-62- 143470 .doc 201020243 [Table 6] Hardening time with or without voids Example 25 0.8 seconds without Example 26 1.2 seconds without Example 27 1.4 seconds without [schematic description] Fig. 1 is a schematic representation of hardening using an embodiment of the present invention A partially cutaway cross-sectional view of an example of a joined structure of a composition. [Description of main component symbols] 1 Connection structure 2 First connection target member 2a Upper surface 2b Electrode 3 Connection part 4 Second connection member 4a Lower surface 4b Electrode 5 Conductive particle 143470.doc -63-

Claims (1)

201020243 VII. Patent application scope: An episulfide compound having the structure: [Chemical Formula 1] having the formula (U), (2-1) or (3) Formula (1-1) In the above formula (1-1), and "respectively, the carbon number is the alkyl group of the group 5, and the "group" of the group and the group of the group represent chlorine, and R3, R4, R5 and R6 The non-hydrogen group represents a group represented by the following formula (4): [Chemical 4] Formula (4) In the above formula (4), 'R7 represents a stretching base having a carbon number of 1 to 5; [Chemical 2] 4 to 6 of the 6 bases of R', R54, R55, R56, R57 and R58 143470.doc 201020243 The group represents hydrogen, and the non-hydrogen group of R53, R54, R55, R56, R57 and R58 is represented by The base represented by the following formula (5): [Chemical 5] •k "Formula (5) In the above formula (5), R59 represents an alkylene group having a carbon number of 1 to 5; [Chemical 3] R101 R103 N0 R110 R109 R108 ...(3) In the above formula (3), R101 and R102 each represent an alkylene group having a carbon number of 1 to 5, and 6 to 8 of the 8 groups of R103, R104, R105, R106, R107, R108, R109 and R110 represent Hydrogen, a non-hydrogen group of R103, R104, R105, R106, R107, R108, R109 and R110 represents a group represented by the following formula (6): [Chem. 6] •k "•Formula (6) 143470.doc 201020243 In the above formula (6), Rill represents an alkylene group having a carbon number of 1 to 5. 2. The episulfide compound of claim 1, which has a structure represented by the following formula (1) or (2): [Chem. 7] In the above formula (1), R1 and R2 each represent an alkylene group having a carbon number of 1 to 5, and 2 to 4 of the four groups of R3, R4, R5 and R6 represent hydrogen, and R3, R4, and R5 are The non-hydrogen group in R6 represents a group represented by the following formula (4): [Chemical 9] ...(4) In the above formula (4), R7 represents an alkylene group having a carbon number of 1 to 5; In the above formula (2), R51 and R52 each represent an alkylene group having a carbon number of 1 to 5, and 4 to 6 143470 of 6 groups of R53, R54, R55, R56, R57 and R58. Doc 201020243 The group represents hydrogen, and the non-hydrogen group of R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (5): [Chemical 10] /0, ... Formula (5) 〆R59 \ In the above formula (5), R59 represents an alkylene group having a carbon number of 1 to 5. 3. The episulfide compound of claim 2, wherein the structure represented by the above formula (1) or (2) is a structure represented by the following formula (1A) or (2A): [Chem. 11] • (1A) In the above formula (1A), R1 and R2 each represent an alkylene group having a carbon number of 1 to 5; In the above formula (2A), R51 and R52 each represent an alkylene group having a carbon number of 1 to 5. A mixture containing an episulfide compound containing the episulfide compound according to any one of claims 1 to 3, and 143470 represented by the following formula (11-1), (12-1) or (13) .doc -4- 201020243 Epoxy compound shown: [Chem. 13] R13 R15 In the above formula (11-1), 'R11& R12 represents an alkylene group having a carbon number of 1 to 5, respectively, and 2 to 4 of the four groups of R13, R14, R15 and R16 represent hydrogen, R13, R14, The non-hydrogen group in R15 and R16 represents a group represented by the following formula (14): [Chem. 16] Formula (14) In the above formula (14), Ri7 represents an alkylene group having a carbon number of 1 to 5; Formula (12-1) In the above formula (12-1), R61 and R62 each represent an alkylene group having a carbon number of i to 5, and 4 of the 6 groups of R63, R64, R65, R66, R67 and R68. ～6 groups represent hydrogen, and the non-hydrogen group of R63, R64, R65, R66, R67 and R68 represents a group represented by the following formula (15): 143470.doc 201020243 [Chem. 17] * In the above formula (15), R69 represents an alkylene group having a carbon number of 1 to 5; R121 R123 X0 R130 R129 R128 ... (13) In the above formula (13), R121 and R122 each represent an alkylene group having a carbon number of 1 to 5, and 6 to 8 of the 8 groups of R123, R124, R125, R126, R127, R128, R129 and R130 represent Hydrogen, a non-hydrogen group of R123, R124, R125, R126, R127, R128, R129 and R130 represents a group represented by the following formula (16): [Chem. 18] * (16) In the above formula (16), R131 represents an alkylene group having a carbon number of 1 to 5. 5. The episulfide-containing mixture according to claim 4, wherein the epoxidized 143470.doc -6-201020243 is an epoxy compound represented by the following formula (11) or (12): [Chem. 19] In the above formula (11), R11 and R12 each represent an alkylene group having a carbon number of 1 to 5, and 2 to 4 of the four groups of R13, R14, R15 and R16 represent hydrogen, and R13, R14 and R15 and The non-hydrogen group in R16 represents a group represented by the following formula (14): [Chem. 21] In the above formula (14), R17 represents an alkylene group having a carbon number of 1 to 5; [Chem. 20] (12) In the above formula (12), R61 and R62 each represent an alkylene group having a carbon number of 1 to 5, and 4 to 6 of 6 groups of R63, R64, R65, R66, R67 and R68. The group represents hydrogen, and the non-hydrogen group of R63, R64, R65, R66, R67 and R68 represents a group represented by the following formula (15): 143470.doc 201020243 [Chem. 22] In the above formula (15), R69 represents an alkylene group having a carbon number of u. 6. The mixture containing an episulfide compound according to claim 5, wherein the structure represented by the above formula (i i) or (12) is represented by the following formula (11A) or (12A): [Chem. 23] Formula (11A) In the above formula (11A), R11 and R12 respectively represent a stretching base having a carbon number of 1 to 5; In the above formula (12A), 'R61 and R62' respectively represent a stretching group having a carbon number of 2. a method for producing a mixture containing an episulfide, which is a mixture of an episulfide-containing mixture according to any one of claims 4 to 6; and a continuity or discontinuity in the first solution containing thiocyanate Addition of an epoxy compound represented by the above formula (11-1), (12-1) or (13) or a solution containing the epoxy compound of 143470.doc 201020243, followed by continuous or intermittent addition of thiocyanate The second solution of the acid salt thereby converts the octacyclic oxy group of the above epoxy compound into an epoxide group. 8. The method for producing a mixture containing an episulfide compound according to claim 7, wherein the epoxy compound or the solution containing the epoxy compound is the epoxy compound represented by the above formula (1)) or (10) or comprises the epoxy compound a solution of the compound. 9. A hardenable composition comprising the cyclic sulfide of any one of claims 3 to 3, and a hardener. 10. A curable composition comprising the mixture comprising an episulfide compound according to any one of claims 4 to 6, and a hardener. 3: The curable composition according to claim 9 or 10, which initially contains a photocurable compound and a photopolymerization initiator. 12. The sclerosing composition of claim 9 or 10, which in turn contains conductive particles. A connection structure comprising: a first connection target member, a second connection target member, and a connection portion connecting the second connection target member; wherein the connection portion is entered by the request item 9 $ η & The curable composition of any one of ninth to eleventh. 14. The connection structure according to claim 13, wherein the pot and the upper-stage curable composition contain conductive particles; and the first and second connection-object-constructing members 1 are electrically connected by the conductive particles. 143470.doc