JP5727316B2 - Method for producing sulfonium compound and method for producing sulfonium borate complex - Google Patents

Description

  The present invention relates to a sulfonium compound that can be used for efficiently obtaining a sulfonium borate complex and a method for producing the sulfonium compound. The present invention also relates to a sulfonium borate complex using the sulfonium compound and a method for producing the sulfonium borate complex.

  The curable composition containing a curable compound such as an epoxy compound is, for example, a connection between an IC chip and a flexible printed circuit board, a connection between an IC chip and a circuit board having an ITO electrode, and a circuit board having an ITO electrode and a flexible circuit board. Used for connection to printed circuit boards.

  In the curable composition, various curing agents are used to cure the curable compound. As the curing agent, there is known a photocationic polymerization initiator that generates protons by light to initiate cationic polymerization. Conventionally, sulfonium antimonate complexes have been widely used as the cationic photopolymerization initiator.

However, since the sulfonium antimonate complex has SbF ₆ ⁻ having a fluorine atom bonded to a metal antimony atom as a counter anion, it generates a large amount of fluorine ions during cation polymerization and corrodes metal wiring and connection pads. There is a problem. Therefore, in recent years, SbF ₆ ^- to place, fluorine atom is bonded to a carbon atom, and is sulfonium borate complex having a counter anion having a boron atom, have been used as a cationic polymerization initiator.

  For example, Patent Document 1 below discloses a sulfonium borate complex having a sulfonium cation moiety represented by the following formula (X1) and a borate anion moiety represented by the following formula (X2).

  In the above formula (X1), R1 is benzyl group, substituted benzyl group, phenacyl group, substituted phenacyl group, allyl group, substituted allyl group, alkoxyl group, substituted alkoxyl group, aryloxy group or substituted Represents a substituted aryloxy group. R2 and R3 each represent the same group as that capable of constituting R1, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a monocyclic or 6 to 18 carbon atoms Represents a condensed polycyclic aryl group. R1 and R2, R1 and R3, and R2 and R3 may be a cyclic structure bonded to each other. The linear, branched or cyclic alkyl group having 1 to 18 carbon atoms and the monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms are fluorine, chlorine, bromine, hydroxyl group and carboxyl group. , A mercapto group, a cyano group, a nitro group, or an azide group.

  In the formula (X2), Y represents fluorine or chlorine, and Z represents a phenyl group substituted with an electron-withdrawing group selected from at least two fluorine, cyano group, nitro group and trifluoromethyl group. M represents an integer of 0 to 3, n represents an integer of 1 to 4, and m + n = 4.

  Further, as a sulfonium borate complex having a sulfonium cation moiety represented by the above formula (X1) and a borate anion moiety represented by the above formula (X2), p-hydroxyphenyl-benzyl represented by the following formula (X3) -Methylsulfonium tetrakis (pentafluorophenyl) borate is commercially available.

  Patent Document 1 describes or suggests, for example, a method of reacting in distilled water to obtain a sulfonium borate complex represented by the above formula (X3) by the following reaction formula (Y3).

  In the above formula (Y3), X represents a bromine atom or a chlorine atom.

  Patent Document 2 below discloses a sulfonium borate complex represented by the following formula (X4).

  In the above formula (X4), R1 represents an aralkyl group, R2 represents a lower alkyl group, X represents a halogen atom, and n represents an integer of 1 to 3. However, when R2 is a methyl group, R1 is not a benzyl group.

  Patent Document 2 describes a method in which a sulfonium antimonate complex is used in an organic solvent such as ethyl acetate to obtain a sulfonium borate complex represented by the above formula (X4) by the following reaction formula (Y4). ing.

  In the above formula (Y4), R1, R2, X and n are the same as R1, R2, X and n in the above formula (X4).

  Patent Document 3 below discloses a sulfonium borate complex represented by the following formula (X5).

  In the above formula (X5), R1 represents an aralkyl group, R2 represents a lower alkyl group, R3 represents a lower alkoxycarboxyl group, X represents a halogen atom, and n represents an integer of 1 to 3.

  Patent Document 3 describes a method in which a sulfonium antimonate complex is used in an organic solvent such as ethyl acetate to obtain a sulfonium borate complex represented by the above formula (X5) by the following reaction formula (Y5). ing.

  In the above formula (Y5), R1, R2, R3, X and n are the same as R1, R2, R3, X and n in the above formula (X5).

JP 9-176112 A WO2008 / 152843A1 WO2010 / 064648A1

  In the method of obtaining the sulfonium borate complex described in Patent Documents 1 to 3, the sulfonium borate complex cannot be efficiently obtained, and there is a problem that the yield of the obtained sulfonium borate complex is low. Moreover, in the method for obtaining the sulfonium borate complex described in Patent Documents 2 and 3, since a sulfonium antimonate complex is used, a trace amount of antimony atoms may remain in the obtained sulfonium borate complex. When antimony atoms are contained in the obtained sulfonium borate complex, the curability of the curable composition containing the sulfonium borate complex is reduced, or the metal wiring is corroded by the cured product of the curable composition. There's a problem.

  An object of the present invention is to provide a sulfonium compound that can be used for efficiently obtaining a sulfonium borate complex and a method for producing the sulfonium compound. Another object of the present invention is to provide a sulfonium borate complex in which the sulfonium compound is used and can be used as a curing agent, and a method for producing the sulfonium borate complex.

  The limited object of this invention is to provide the sulfonium borate complex which can suppress corrosion of a metal, and the manufacturing method of this sulfonium borate complex.

  According to a wide aspect of the present invention, there is provided a sulfonium compound obtained by reacting a compound represented by the following formula (1) with a compound represented by the following formula (2).

  In said formula (1), R1 represents an aryl group or a naphthyl group, and X represents a halogen atom.

In the formula (2), R2 represents a hydroxy group or a _CH 3 OCOO group, n represents an integer of 1-3.

  In a specific aspect of the sulfonium compound according to the present invention, the compound represented by the above formula (1) is obtained by reacting a compound represented by the following formula (11) with metallic magnesium.

  In said formula (11), R1 represents an aryl group or a naphthyl group, and X represents a halogen atom.

  Moreover, according to the wide situation of this invention, the sulfonium compound provided with the process of obtaining a sulfonium compound by making the compound represented by the said Formula (1) and the compound represented by the said Formula (2) react. A manufacturing method is provided.

  In a specific aspect of the method for producing a sulfonium compound according to the present invention, a step of obtaining a compound represented by the above formula (1) by reacting a compound represented by the above formula (11) with metallic magnesium. Is further provided.

  The sulfonium borate complex according to the present invention reacts the sulfonium compound according to the present invention or the sulfonium compound obtained by the method for producing the sulfonium compound according to the present invention with a compound having an anion moiety represented by the following formula (21). Is obtained.

  In the above formula (21), X represents a halogen atom.

  The method for producing a sulfonium borate complex according to the present invention comprises a sulfonium compound according to the present invention or a sulfonium compound obtained by the method for producing a sulfonium compound according to the present invention and a compound having an anion moiety represented by the above formula (21) And a step of obtaining a sulfonium borate complex.

  Since the sulfonium compound according to the present invention is obtained by reacting the compound represented by the formula (1) with the compound represented by the formula (2), the sulfonium compound according to the present invention is reacted with a borate compound. Thus, a sulfonium borate complex can be obtained efficiently.

  The method for producing a sulfonium compound according to the present invention includes a step of obtaining a sulfonium compound by reacting a compound represented by the formula (1) with a compound represented by the formula (2). Can be obtained efficiently. For this reason, a sulfonium borate complex can be efficiently obtained by making the sulfonium compound obtained by the manufacturing method of the sulfonium compound which concerns on this invention react with a borate compound.

  Hereinafter, the present invention will be described in detail.

  The sulfonium compound according to the present invention is obtained by reacting a compound represented by the following formula (1) with a compound represented by the following formula (2).

  In said formula (1), R1 represents an aryl group or a naphthyl group, and X represents a halogen atom.

In the formula (2), R2 represents a hydroxy group or a _CH 3 OCOO group, n represents an integer of 1-3.

  The manufacturing method of the sulfonium compound which concerns on this invention comprises the process of obtaining a sulfonium compound by making the compound represented by the said Formula (1), and the compound represented by the said Formula (2) react.

  The sulfonium compound according to the present invention and the method for producing the sulfonium compound according to the present invention utilize a Grignard reaction.

  Conventionally, when a sulfonium borate complex is obtained, the reaction is performed in distilled water without using the Grignard reaction as shown in the above reaction formula (Y3). Moreover, when obtaining a sulfonium borate complex, like the said Reaction Formula (Y4) and the said Reaction Formula (Y5), reaction was performed in organic solvents, such as ethyl acetate, using a sulfonium antimonate complex. Moreover, reaction may be performed in water using a sulfonium antimonate complex. However, the conventional method for producing a sulfonium borate complex has a problem that the sulfonium borate complex cannot be obtained efficiently and the yield is poor. There is also a problem that unreacted sulfonium antimonate complex tends to remain.

  On the other hand, in the present invention, since the Grignard reaction is used, the sulfonium compound can be obtained efficiently and in a high yield. For this reason, a sulfonium borate complex can be obtained efficiently and in good yield using the sulfonium compound.

  In order to obtain the sulfonium compound according to the present invention and in the method for producing a sulfonium compound according to the present invention, it is preferable not to use a compound having an antimony atom. Furthermore, in order to obtain the sulfonium borate complex which concerns on this invention mentioned later, and in the manufacturing method of the sulfonium borate complex which concerns on this invention, it is preferable not to use the compound which has an antimony atom. When a compound having an antimony atom is not used, the curability of the curable composition using the sulfonium borate complex can be increased, and further, corrosion of the metal can be suppressed.

  X in the formula (1) is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. Preferable examples of R1 in the above formula (1) include phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, 1-naphthyl group and 2-naphthyl group. From the viewpoint of obtaining a sulfonium borate complex more efficiently, R1 in the above formula (1) is preferably a phenyl group, an o-methylphenyl group or a 1-naphthyl group. However, R1 may be a group other than these. From the viewpoint of more efficiently obtaining a sulfonium borate complex, the compound represented by the above formula (1) is preferably a compound represented by the following formula (1A) or the following formula (1B).

In the above formula (1A), R 1a represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 or 1. From the viewpoint of obtaining a sulfonium borate complex more efficiently, R 1a is preferably a methyl group. m is preferably 0 so that R1 does not exist. The preferable group of X in the said Formula (1A) is the same as the preferable group of X in the said Formula (1). In addition, the bonding site | part with respect to the benzene ring of R1a is not specifically limited. From the viewpoint of obtaining a sulfonium borate complex more efficiently, R1a is preferably bonded to the ortho position with respect to the CH ₂ MgX group.

  In the above formula (1B), X represents a halogen atom. The preferable group of X in the said Formula (1B) is the same as that of X in the said Formula (1).

In the above formula (2), the binding site of R2 to the benzene ring is not particularly limited. From the viewpoint of obtaining a sulfonium borate complex more efficiently, R 2 is preferably bonded to the para position with respect to the S—CH ₃ group. The CH ₃ OCOO group in the above formula (2) is a methoxycarbonyloxy group. From the viewpoint of obtaining a sulfonium borate complex more efficiently, R2 in the above formula (2) is preferably a hydroxy group. From the viewpoint of obtaining a sulfonium borate complex more efficiently, n in the above formula (2) is preferably 1.

  The sulfonium compound according to the present invention and the sulfonium compound obtained by the method for producing the sulfonium compound according to the present invention are preferably compounds having a cation moiety represented by the following formula (31), and represented by the following formula (32). More preferably, the compound is

In the above formula (31), R1 represents an aryl group or a naphthyl group, R2 represents a hydroxy group or a _CH 3 OCOO group, n represents an integer of 1-3. R1, R2 and n in the formula (31) are derived from R1, R2 and n in the formula (1) and the formula (2). The preferable groups and numbers of R1, R2 and n in the formula (31) are the same as the preferable groups and numbers of R1, R2 and n in the formula (1) and the formula (2).

In the above formula (32), R1 represents an aryl group or a naphthyl group, R2 represents a hydroxy group or a _CH 3 OCOO group, X represents a halogen atom, n is an integer of 1-3. R1, R2, X and n in the formula (32) are derived from R1, R2, X and n in the formula (1) and the formula (2). The preferred groups and numbers of R1, R2, X and n in the above formula (32) are the same as the preferred groups and numbers of R1, R2, X and n in the above formula (1) and the above formula (2). .

  The compound having a cation moiety represented by the above formula (31) is preferably a compound having a cation moiety represented by the following formula (31A) or the following formula (31B). The compound represented by the above formula (32) is preferably a compound represented by the following formula (32A) or the following formula (32B).

In the formula (31A), R1a represents an alkyl group having 1 to 4 carbon atoms, R2 represents a hydroxy group or a _CH 3 OCOO group, m represents 0 or 1, n represents an integer of 1-3. R1a, R2, m and n in the formula (31A) are derived from R1a, R2, m and n in the formula (1A) and the formula (2). The preferred groups and numbers of R1a, R2, m and n in the above formula (31A) are the same as the preferred groups and numbers of R1a, R2, m and n in the above formula (1A) and the above formula (2). .

In the above formula (31B), R2 represents a hydroxy group or a _CH 3 OCOO group, n represents an integer of 1-3. R2 and n in the above formula (31B) are derived from R2 and n in the above formula (2). The preferable group and number of R2 and n in the formula (31B) are the same as the preferable group and number of R2 and n in the formula (2).

In the formula (32A), R1a represents an alkyl group having 1 to 4 carbon atoms, R2 represents a hydroxy group or a _CH 3 OCOO group, X represents a halogen atom, m represents 0 or 1, n is 1 Represents an integer of ~ 3. R1a, R2, X, m and n in the formula (32A) are derived from R1a, R2, X, m and n in the formula (1A) and the formula (2). Preferred groups and numbers of R1a, R2, X, m and n in the above formula (32A) are preferable groups and numbers of R1a, R2, X, m and n in the above formula (1A) and the above formula (2). It is the same.

In the above formula (32B), R2 represents a hydroxy group or a _CH 3 OCOO group, X represents a halogen atom, n is an integer of 1-3. R2, X and n in the formula (32B) are derived from R2, X and n in the formula (1B) and the formula (2). The preferable groups and numbers of R2, X and n in the above formula (32B) are the same as the preferable groups and numbers of R2, X and n in the above formula (1B) and the above formula (2).

  In the sulfonium compound according to the present invention, the compound represented by the above formula (1) is preferably obtained by reacting a compound represented by the following formula (11) with metallic magnesium. In this reaction, the compound represented by the above formula (1) can be easily obtained. Therefore, the sulfonium compound according to the present invention includes a compound represented by the above formula (1) obtained by reacting a compound represented by the following formula (11) with metallic magnesium, and the above formula (2). It is preferably obtained by reacting the compound represented.

  In said formula (11), R1 represents an aryl group or a naphthyl group, and X represents a halogen atom. Preferred groups for R1 and X in the above formula (1) are the same as the preferred groups for R1 and X in the above formula (1).

  The method for producing a sulfonium compound according to the present invention further includes a step of obtaining a compound represented by the above formula (1) by reacting the compound represented by the above formula (11) with metallic magnesium. preferable. In this step, the compound represented by the above formula (1) is easily obtained. Therefore, the method for producing a sulfonium compound according to the present invention comprises a step of obtaining a compound represented by the above formula (1) by reacting a compound represented by the above formula (11) with metallic magnesium, It is preferable to include a step of obtaining a sulfonium compound by reacting the compound represented by the formula (1) with the compound represented by the above formula (2).

  X in the above formula (11) is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. Preferable examples of R1 in the above formula (11) include phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, 1-naphthyl group and 2-naphthyl group. R1 in the formula (11) is preferably a phenyl group, an o-methylphenyl group, or a 1-naphthyl group. However, R1 may be a group other than these. The compound represented by the above formula (11) is preferably a compound represented by the following formula (11A) or the following formula (11B).

In the above formula (11A), R 1a represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 or 1. R1a in the above formula (11A) is preferably a methyl group. M in the formula (11A) is preferably 0 so that R1 does not exist. X in the formula (11A) is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. In addition, the coupling | bonding site | part with respect to the benzene ring of R1a is not specifically limited. R1a is preferably bonded to the ortho position with respect to the CH ₂ X group.

  In the above formula (11B), X represents a halogen atom. X in the formula (11B) is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

  The sulfonium compound according to the present invention and the sulfonium compound obtained by the method for producing a sulfonium compound according to the present invention are preferably sulfonium compounds for obtaining a sulfonium borate complex. The sulfonium compound according to the present invention is preferably a sulfonium compound for reacting with a borate compound to obtain a sulfonium borate complex.

  From the viewpoint of more efficiently obtaining a sulfonium borate complex, the borate compound is a compound having an anion moiety represented by the following formula (21) or tetrakis [3,5-bis (trifluoromethyl) phenyl] borate anion And a compound having a tetrakis (pentafluorophenyl) borate anion or a compound having a tetrakis [3,5-bis (trifluoromethyl) phenyl] borate anion is preferred. More preferred is a compound having a phenyl) borate anion. The cation portion of the borate compound is preferably a lithium cation or a sodium cation, and more preferably a sodium cation.

  In the above formula (21), X represents a halogen atom. X in the above formula (21) is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

  The sulfonium borate complex according to the present invention reacts the sulfonium compound according to the present invention or the sulfonium compound obtained by the method for producing a sulfonium compound according to the present invention with a compound having an anion moiety represented by the above formula (21). It is preferable that it is obtained by making it. The method for producing a sulfonium borate complex according to the present invention comprises a sulfonium compound according to the present invention or a sulfonium compound obtained by the method for producing a sulfonium compound according to the present invention and an anion moiety represented by the above formula (21). It is preferable to provide a step of obtaining a sulfonium borate complex by reacting with a compound having the compound.

  In the method for producing the sulfonium borate complex according to the present invention and the sulfonium borate complex according to the present invention, the sulfonium compound according to the present invention and the sulfonium compound obtained by the method for producing the sulfonium compound according to the present invention are used. The complex can be obtained efficiently and with good yield.

  The sulfonium borate complex according to the present invention and the sulfonium borate complex obtained by the method for producing the sulfonium borate complex according to the present invention are preferably sulfonium borate complexes represented by the following formula (41).

In the above formula (41), R1 represents an aryl group or a naphthyl group, R2 represents a hydroxy group or a _CH 3 OCOO group, X represents a halogen atom, n is an integer of 1-3. R1, R2 and n in the formula (41) are derived from R1, R2 and n in the formula (1) and the formula (2). The preferable group and number of R1, R2 and n in the formula (41) are the same as the preferable group and number of R1, R2 and n in the formula (1) and the formula (2). X in the above formula (41) is derived from X in the above formula (21). The preferable group of X in the said Formula (41) is the same as the preferable group of X in the said Formula (21).

  From the viewpoint of obtaining the sulfonium borate complex more efficiently, the sulfonium borate complex represented by the above formula (41) is a sulfonium borate complex represented by the following formula (41A) or the following formula (41B). preferable.

In the above formula (41A), R 1a represents an alkyl group having 1 to 4 carbon atoms, R 2 represents a hydroxy group or a CH ₃ OCOO group, X represents a halogen atom, m represents 0 or 1, and n represents 1 Represents an integer of ~ 3. R1a, R2, m, and n in the formula (41A) are derived from R1, R2, m, and n in the formula (1A) and the formula (2). Preferred groups and numbers of R1a, R2, m and n in the above formula (41A) are the same as the preferred groups and numbers of R1, R2, m and n in the above formula (1A) and the above formula (2). . X in the above formula (41A) is derived from X in the above formula (21). The preferable group of X in the said Formula (41A) is the same as the preferable group of X in the said Formula (21).

In the above formula (41B), R2 represents a hydroxy group or a _CH 3 OCOO group, X represents a halogen atom, n is an integer of 1-3. R2 and n in the formula (41B) are derived from R2 and n in the formula (1B) and the formula (2). The preferable group and number of R2 and n in the formula (41B) are the same as the preferable group and number of R2 and n in the formula (1B) and the formula (2). X in the above formula (41B) is derived from X in the above formula (21). The preferable group of X in the said Formula (41B) is the same as the preferable group of X in the said Formula (21).

  The sulfonium borate complex is preferably used as a cationic polymerization initiator. The curable composition preferably contains a curable compound and the cationic polymerization initiator. It is preferable that the said curable composition further contains electroconductive particle. The curable composition containing conductive particles is preferably an anisotropic conductive material. The curable composition can be cured by light irradiation or heating. The curable composition may be cured by light irradiation, may be cured by heating, or may be cured by light irradiation and heating.

  The anisotropic conductive material may be a paste-like anisotropic conductive paste or a film-like anisotropic conductive film. The anisotropic conductive material is preferably an anisotropic conductive paste.

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

Example 1
(1) Synthesis of Grignard reagent 10 parts by weight of tetrahydropyran was added to 14 parts by weight of metal magnesium, and 0.6 parts by weight of 1,2-dibromoethane was further added to activate the metal magnesium. Next, 10 parts by weight of 1- (chloromethyl) naphthalene was added dropwise and stirred at 20 ° C. for reaction. Residual magnesium was removed by filtration. In this way, (1-naphthyl) methylmagnesium chloride, which is a Grignard reagent, was synthesized according to the following reaction formula (A-1).

(2) Synthesis of sulfonium compound To 10 parts by weight of the obtained (1-naphthyl) methylmagnesium chloride (molecular weight 201.0), 6.975 parts by weight of 4- (methylthio) phenol (molecular weight 140.2) was added, The mixture was stirred at 20 ° C. for 24 hours to precipitate a crystal. The crystal was taken out and washed. Thus, a sulfonium compound (B1) (sulfonium salt) was synthesized according to the following reaction formula (B-1). The yield of the obtained sulfonium compound (B1) was 97% with respect to the (1-naphthyl) methyl magnesium chloride used.

(3) Synthesis of sulfonium borate complex 100 parts by weight of ethyl acetate was added to 10 parts by weight of the obtained sulfonium compound (B1), and 150 parts by weight of an aqueous solution containing 10% by weight of sodium tetrafluorophenylborate was further added. Stir at 30 ° C. for 30 minutes. The ethyl acetate layer was taken out by a liquid separation operation, washed with water, and then concentrated with an evaporator. Thus, the sulfonium borate complex (C1) was obtained by the following reaction formula (C-1).

(4) Preparation of curable composition 5 parts by weight of EBECRYL 3702 (“epoxy acrylate” manufactured by Daicel Cytec Co., Ltd.) which is a curable compound, 4 parts by weight of the obtained sulfonium borate complex (C1), and alumina (average) (Particle diameter 0.5 μm) and 20 parts by weight, and further, conductive particles having an average particle diameter of 3 μm were added so that the content in 100% by weight of the composition would be 10% by weight. The resulting mixture was stirred at 2000 rpm for 5 minutes to obtain a curable composition (anisotropic conductive paste).

  The conductive particles used are conductive particles having a metal layer in which a nickel plating layer is formed on the surface of divinylbenzene resin particles and a gold plating layer is formed on the surface of the nickel plating layer. is there.

(Example 2)
(1) Synthesis of Grignard reagent 10 parts by weight of tetrahydropyran was added to 14 parts by weight of metal magnesium, and 0.6 parts by weight of 1,2-dibromoethane was further added to activate the metal magnesium. Next, 10 parts by weight of 1- (chloromethyl) benzene was added dropwise and stirred at 15 ° C. for reaction. Residual magnesium was removed by filtration. In this way, benzylmagnesium chloride, which is a Grignard reagent, was synthesized by the following reaction formula (A-2).

(2) Synthesis of sulfonium compound To 10 parts by weight of the obtained benzylmagnesium chloride (molecular weight 150.9), 9.3 parts by weight of 4- (methylthio) phenol (molecular weight 140.2) was added, and the mixture was heated at 15 ° C. for 24 hours. Stirring to precipitate crystals. The crystal was taken out and washed. Thus, a sulfonium compound (B2) (sulfonium salt) was synthesized according to the following reaction formula (B-2). The yield of the obtained sulfonium compound (B2) was 95% with respect to the benzylmagnesium chloride used.

(3) Synthesis of sulfonium borate complex 100 parts by weight of ethyl acetate was added to 10 parts by weight of the obtained sulfonium compound (B2), and 150 parts by weight of an aqueous solution containing 10% by weight of sodium tetrafluorophenylborate was further added. Stir at 30 ° C. for 30 minutes. The ethyl acetate layer was taken out by a liquid separation operation, washed with water, and then concentrated with an evaporator. Thus, the sulfonium borate complex (C2) was obtained by the following reaction formula (C-2).

(4) Preparation of curable composition The curable composition was obtained like Example 1 except having changed the sulfonium borate complex (C1) into the obtained sulfonium borate complex (C2).

(Example 3)
(1) Synthesis of Grignard reagent 10 parts by weight of tetrahydropyran was added to 14 parts by weight of metal magnesium, and 0.6 parts by weight of 1,2-dibromoethane was further added to activate the metal magnesium. Next, 10 parts by weight of 1- (chloromethyl) -2-methylbenzene was added dropwise and stirred at 10 ° C. for reaction. Residual magnesium was removed by filtration. In this way, 2-methylbenzylmagnesium chloride, which is a Grignard reagent, was synthesized according to the following reaction formula (A-3).

(2) Synthesis of sulfonium compound To 10 parts by weight of the obtained 2-methylbenzylmagnesium chloride (molecular weight 164.9), 8.5 parts by weight of 4- (methylthio) phenol (molecular weight 140.2) was added, and 10 ° C. The mixture was stirred for 24 hours to precipitate crystals. The crystal was taken out and washed. Thus, a sulfonium compound (B3) (sulfonium salt) was synthesized according to the following reaction formula (B-3). The yield of the obtained sulfonium compound (B3) was 96% with respect to 2-methylbenzylmagnesium chloride used.

(3) Synthesis of sulfonium borate complex 100 parts by weight of ethyl acetate was added to 10 parts by weight of the obtained sulfonium compound (B3), and 150 parts by weight of an aqueous solution containing 10% by weight of sodium tetrafluorophenylborate was further added. Stir at 30 ° C. for 30 minutes. The ethyl acetate layer was taken out by a liquid separation operation, washed with water, and then concentrated with an evaporator. Thus, a sulfonium borate complex (C3) was obtained by the following reaction formula (C-3).

(4) Preparation of curable composition The curable composition was obtained like Example 1 except having changed the sulfonium borate complex (C1) into the obtained sulfonium borate complex (C3).

Example 4
(1) Synthesis of sulfonium compound To 10 parts by weight of (1-naphthyl) methyl magnesium chloride (molecular weight 201.0) obtained in Example 1, 4- (methoxycarbonyloxy) phenyl methyl sulfide (molecular weight 198.2) 9 .9 parts by weight were added and stirred at 23 ° C. for 24 hours to precipitate a crystal. The crystal was taken out and washed. Thus, a sulfonium compound (B4) (sulfonium salt) was synthesized according to the following reaction formula (B-4). The yield of the obtained sulfonium compound (B4) was 97% with respect to (1-naphthyl) methyl magnesium chloride used.

(2) Synthesis of sulfonium borate complex 100 parts by weight of ethyl acetate was added to 10 parts by weight of the obtained sulfonium compound (B4), and 150 parts by weight of an aqueous solution containing 10% by weight of sodium tetrafluorophenylborate was further added. Stir at 30 ° C. for 30 minutes. The ethyl acetate layer was taken out by a liquid separation operation, washed with water, and then concentrated with an evaporator. Thus, a sulfonium borate complex (C4) was obtained by the following reaction formula (C-4).

(3) Preparation of curable composition The curable composition was obtained like Example 1 except having changed the sulfonium borate complex (C1) into the obtained sulfonium borate complex (C4).

(Comparative Example 1)
In water, 7.95 parts by weight of 4- (methylthio) phenol (molecular weight 140.2) is added to 10 parts by weight of 1- (chloromethyl) naphthalene (molecular weight 176.6), and the mixture is stirred at 23 ° C. for 24 hours. The product was precipitated. The crystal was taken out and washed. In this way, a sulfonium compound (sulfonium salt) was synthesized. The yield of the obtained sulfonium compound with respect to 1- (chloromethyl) naphthalene used was 32%.

(Comparative Example 2)
In water, 11.1 parts by weight of 4- (methylthio) phenol (molecular weight 140.2) is added to 10 parts by weight of 1- (chloromethyl) benzene (molecular weight 126.6), and the mixture is stirred at 23 ° C. for 24 hours. The product was precipitated. The crystal was taken out and washed. In this way, a sulfonium compound (sulfonium salt) was synthesized. The yield of the obtained sulfonium compound was 29% with respect to 1- (chloromethyl) benzene used.

(Comparative Example 3)
10 parts by weight of 4- (methylthio) phenol (molecular weight 140.2) is added to 10 parts by weight of 1- (chloromethyl) -2-methylbenzene (molecular weight 140.6) in water and stirred at 23 ° C. for 24 hours. A crystal was precipitated. The crystal was taken out and washed. In this way, a sulfonium compound (B3) (sulfonium salt) was synthesized. The yield of the obtained sulfonium compound was 28% with respect to 1- (chloromethyl) -2-methylbenzene used.

(Comparative Example 4)
In pure water, 11.23 parts by weight of 4- (methoxycarbonyloxy) phenylmethyl sulfide (molecular weight 198.2) was added to 10 parts by weight of 1- (chloromethyl) naphthalene (molecular weight 176.6), and at 23 ° C. The mixture was stirred for 24 hours to precipitate a crystalline product. The crystal was taken out and washed. In this way, a sulfonium compound (sulfonium salt) was synthesized. The yield of the obtained sulfonium compound with respect to 1- (chloromethyl) naphthalene used was 25%.

(Comparative Example 5)
100 parts by weight of ethyl acetate was added to the sulfonium antimonate complex represented by the following formula (101), 150 parts by weight of an aqueous solution containing 10% by weight of sodium tetrafluorophenylborate was further added, and the mixture was stirred at 23 ° C. for 30 minutes. . The ethyl acetate layer was taken out by a liquid separation operation, washed with water, and then concentrated with an evaporator. Thus, the sulfonium borate complex (Z1) was obtained.

  A curable composition was obtained in the same manner as in Example 1 except that the sulfonium borate complex (C1) was changed to the obtained sulfonium borate complex (Z1).

(Evaluation of Examples 1 to 4 and Comparative Example 5)
Metal corrosivity:
A transparent glass substrate having an ITO electrode pattern with an L / S of 20 μm / 20 μm formed on the upper surface was prepared. Further, a semiconductor chip having a copper electrode pattern with an L / S of 20 μm / 20 μm formed on the lower surface was prepared.

On the transparent glass substrate, the obtained anisotropic conductive paste was applied to a thickness of 20 μm to form an anisotropic conductive paste layer. Next, the semiconductor chip was stacked on the anisotropic conductive paste layer so that the electrodes face each other and are connected. Thereafter, the anisotropic conductive paste layer is irradiated with ultraviolet light of 420 nm so that the light irradiation intensity is 60 mW / cm ^2, and after the anisotropic conductive paste layer is semi-cured, it is heated and cured at 150 ° C., A connection structure was obtained.

  The obtained connection structure was stored at 85 ° C. and a humidity of 85% for 20 days. It was evaluated whether or not corrosion occurred on the surface of the copper electrode after storage. “○” indicates that the copper electrode is not corroded, “△” indicates that the copper electrode is partially corroded to the extent that no poor conduction occurs, and corrodes the copper electrode to the extent that the poor conducting occurs. It was determined as “×”.

  As a result, in the connection structure using the curable compositions of Examples 1 to 4, the evaluation result of the corrosiveness of the metal was “◯”. In the connection structure using the curable composition of Comparative Example 5, the evaluation result of the corrosiveness of the metal was “x”. The reason why the evaluation result of the corrosiveness of the metal was bad in Comparative Example 5 is that the sulfonium antimonate complex remained in the sulfonium borate complex after the sulfonium borate complex was obtained.

Claims (2)

A step of obtaining a compound represented by the following formula (1) by reacting a compound represented by the following formula (11) with metallic magnesium;
And the obtained compound represented by the formula (1), by reacting the Grignard reaction with a compound represented by the following formula (2), and a step of obtaining a sulfonium compound, a manufacturing method of a sulfonium compounds.

In said formula (11), R1 represents an aryl group or a naphthyl group, and X represents a halogen atom.

In said formula (1), R1 represents an aryl group or a naphthyl group, and X represents a halogen atom.

In the formula (2), the R2, represents a hydroxy group or a _CH 3 OCOO group, n represents an integer of 1-3. A step of obtaining a compound represented by the following formula (1) by reacting a compound represented by the following formula (11) with metallic magnesium;
A step of obtaining a sulfonium compound by reacting the obtained compound represented by the formula (1) with a compound represented by the following formula (2) by a Grignard reaction;
And the resulting sulfonium compounds, by reacting a compound having an anion moiety represented by the following formula (21), and a step of obtaining a sulfonium borate complex, method for producing a sulfonium borate complex.

In said formula (11), R1 represents an aryl group or a naphthyl group, and X represents a halogen atom.

In said formula (1), R1 represents an aryl group or a naphthyl group, and X represents a halogen atom.

In the formula (2), the R2, represents a hydroxy group or a _CH 3 OCOO group, n represents an integer of 1-3.

In the formula (21), X represents a halogen atom.