JP2014131997A - New sulfonium borate complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new sulfonium borate complex which can reduce the amount of fluorine ions formed on thermal cationic polymerization and can achieve the low temperature quick curability of a thermal cationic polymerizable adhesive.SOLUTION: The new sulfonium borate complex is represented by the structure of formula (1), where Ris an aralkyl group; Ris a lower alkyl group; Ris a lower alkoxycarbonyloxy group; X is a halogen atom; and n is an integer of 1-3.

Description

  The present invention relates to a novel sulfonium borate complex useful as a thermal cationic polymerization initiator, a production method thereof, an epoxy resin composition containing the complex, and a connection structure using the composition.

  2. Description of the Related Art Conventionally, a photocationically polymerizable adhesive containing an epoxy resin as a main component has been used as a kind of an adhesive used when an electronic component such as an IC chip is mounted on a wiring board. Such a cationic photopolymerizable adhesive includes a cationic photopolymerization initiator that generates protons by light and initiates cationic polymerization. A sulfonium antimonate complex is known as such a cationic photopolymerization initiator. It has been.

However, since the sulfonium antimonate complex has SbF ₆ ⁻ having a fluorine atom bonded to metal, antimony, as a counter anion, it generates a large amount of fluorine ions during cationic polymerization and corrodes metal wiring and connection pads. There was a problem. Therefore, instead of SbF ₆ ^— , a sulfonium borate complex using a tetrakis (pentafluorophenyl) borate anion [(C ₆ F ₅ ) ₄ B ⁻ ] in which a fluorine atom is bonded to a carbon atom is used as a cationic polymerization initiator. (Patent Document 1), and in fact, a complex of the following formula (1c) [p-hydroxyphenyl-benzyl-methylsulfonium tetrakis (pentafluorophenyl) borate] is commercially available.

  By the way, when electronic components are mounted on a wiring board, there are many cases where light cannot be irradiated to the joint. For this reason, attempts have been made to divert the specific sulfonium borate complexes disclosed in the Examples of Patent Document 1 to thermal cationic polymerization initiators for thermal cationic polymerizable adhesives. In that case, not only the electric corrosion resistance of the thermal cationic polymerizable adhesive is improved by reducing the amount of fluorine ions generated during cationic polymerization, but also the low temperature rapid curability of the thermal cationic polymerizable adhesive is improved to improve productivity. It is demanded to make it.

JP 9-176112 A

  However, when the complex of formula (1c) was used as a thermal cationic polymerization initiator, the amount of fluorine ions generated during thermal cationic polymerization could be reduced to some extent, but an epoxy resin composition as a thermal cationic polymerizable adhesive or the like. The low-temperature fast-curing property was not sufficient.

  The present invention is to solve the above-mentioned problems of the prior art, and can reduce the amount of fluorine ions generated at the time of thermal cation polymerization, improve the electric corrosion resistance, and epoxy as a thermal cation polymerizable adhesive or the like. It is an object of the present invention to provide a novel sulfonium borate complex capable of realizing a low temperature fast curability in a resin composition.

  The present inventor has found that the above object can be achieved by introducing a novel combination of a plurality of specific substituents into the sulfonium residue of the sulfonium borate complex, and has completed the present invention.

  That is, this invention is a sulfonium borate complex represented by Formula (1).

In formula (1), R ₁ is an aralkyl group, R ₂ is a lower alkyl group, and R ₃ is a lower alkoxycarbonyl group. X is a halogen atom, and n is an integer of 1 to 3.

The present invention also provides a method for producing a sulfonium borate complex of the formula (1),
Provided is a production method for obtaining a sulfonium borate complex of formula (1) by reacting a sulfonium antimonate complex of formula (2) with a sodium borate salt of formula (3).

In the formula (1), (2) or (3), R ₁ is an aralkyl group, R ₂ is a lower alkyl group, and R ₃ is a lower alkoxycarbonyl group. X is a halogen atom, and n is an integer of 1 to 3.

  The present invention is also an epoxy resin composition comprising an epoxy resin and a thermal cationic polymerization initiator, wherein the thermal cationic polymerization initiator is a sulfonium borate complex represented by the above formula (1). An epoxy resin composition and a thermosetting product of the epoxy resin composition, and a connection structure characterized in that an electronic component is bonded on a wiring board.

  The several substituent of the sulfonium borate complex of the novel formula (1) of this invention is a novel combination. For this reason, at the time of thermal cationic polymerization of an epoxy resin composition as a thermal cationic adhesive containing this complex as a thermal cationic polymerization initiator, the amount of fluorine ions generated can be reduced, and the electric corrosion resistance can be improved. Low temperature fast curability can be realized.

2 is an IR chart of the sulfonium borate complex of Example 1. 1 is a ¹ H-NMR chart of a sulfonium borate complex of Example 1. ^{1 is} a ¹ H-NMR chart of THF. 2 is a ¹ H-NMR chart of a sulfonium borate complex of Comparative Example 1. 2 is a ¹ H-NMR chart of a sulfonium borate complex of Comparative Example 2.

  The novel compound of the present invention is a sulfonium borate complex represented by the formula (1).

In formula (1), examples of the aralkyl group for R ₁ include a benzyl group, an o-methylbenzyl group, a (1-naphthyl) methyl group, a pyridylmethyl group, and an anthracenylmethyl group. Among these, an o-methylbenzyl group is preferable in terms of good quick curability and availability.

Examples of the lower alkyl group for R ₂ include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a methyl group is preferable from the viewpoint of good quick curability and availability.

  N representing the number of hydroxyl groups of the phenyl group bonded to the sulfonium residue is an integer of 1 to 3. Examples of such a phenyl group include, when n is 1, 4-lower alkoxycarbonyloxyphenyl group, 2-lower alkoxycarbonyloxyphenyl group, 3-lower alkoxycarbonyloxyphenyl group, and the like. 2,4-dilower alkoxycarbonyloxyphenyl group, 2,6-dilower alkoxycarbonyloxyphenyl group, 3,5-dilower alkoxycarbonyloxyphenyl group, 2,3-dilower alkoxycarbonyloxyphenyl group It is done. When n is 3, 2,4,6-tri-lower alkoxycarbonyloxyphenyl group, 2,4,5-tri-lower alkoxycarbonyloxyphenyl group, 2,3,4-tri-lower alkoxycarbonyloxyphenyl group, etc. Can be mentioned. Among these, a 4-lower alkoxycarbonyloxyphenyl group having n of 1, particularly a 4-methoxycarbonyloxyphenyl group is preferable from the viewpoint of good rapid curability and availability.

  The halogen atom for X is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among these, a fluorine atom having high electron withdrawing property is preferable from the viewpoint of improving reactivity.

The novel sulfonium borate complex of the formula (1) of the present invention can be produced according to the following reaction formula. In addition, each substituent in the formula (1), (2) or (3) is as described above, that is, R ₁ is an aralkyl group, R ₂ is a lower alkyl group, and R ₃ Is a lower alkoxycarbonyloxy group. X is a halogen atom, and n is an integer of 1 to 3.

  That is, the sulfonium antimonate complex of formula (2) (refer to Japanese Patent Application Laid-Open No. 2006-96742 for the synthesis method. Specifically, hydroxyphenyl corresponding to a compound obtained by removing the formate residue from the sa complex of formula (2). A sulfonium antimonate complex may be reacted with a lower alkyl ester compound of chloroformate (for example, methyl chloroformate) in acetonitrile in the presence of triethylamine, and dissolved in an organic solvent such as ethyl acetate. An aqueous solution of sodium borate salt (3) (refer to JP-A-10-310587 for the synthesis method) is mixed in an equimolar amount, and the obtained two-layer mixture is heated at a temperature of 20 to 80 ° C. for 1 to 3 hours. Stir and react the sodium borate salt of formula (3) with the sulfonium antimonate complex of formula (2). Can be obtained sulfonium borate complex of 1). Isolation of the sulfonium borate complex of the formula (1) can be carried out by separating the organic solvent layer and drying it, and then evaporating and removing the organic solvent under reduced pressure to obtain the desired product as an evaporation residue.

  The novel sulfonium borate complex of the formula (1) of the present invention can be used as a thermal cationic polymerization initiator for general epoxy resins such as a thermal cationic polymerizable adhesive. Therefore, an epoxy resin composition in which the novel sulfonium borate complex of the formula (1) of the present invention is blended in the epoxy resin as a thermal cationic polymerization initiator is also a part of the present invention.

  As the epoxy resin constituting the epoxy resin composition of the present invention, a thermosetting epoxy resin conventionally used for joining electronic materials can be appropriately used. Such a thermosetting epoxy resin may be liquid or solid, and preferably has an epoxy equivalent of usually about 100 to 4000 and having two or more epoxy groups in the molecule. For example, a bisphenol A type epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, an ester type epoxy compound, an alicyclic epoxy compound, or the like can be preferably used. These compounds include monomers and oligomers.

  In the epoxy resin composition of the present invention, the blending amount of the sulfonium borate complex of the formula (1) with respect to 100 parts by mass of the epoxy resin is insufficient when cured, and when too large, the storage stability decreases. Preferably it is 0.1-10 mass parts, More preferably, it is 0.5-5 mass parts.

  In the epoxy resin composition of the present invention, in addition to the thermosetting epoxy resin as described above, a thermosetting urea resin, a thermosetting melamine resin, a thermosetting phenol resin, etc., as long as the effects of the invention are not impaired. These thermoplastic resins can be used in combination with thermoplastic resins such as polyester resins and polyurethane resins.

  The epoxy resin composition of the present invention may contain a filler such as silica and mica, a pigment, an antistatic agent, a silane coupling agent, and the like as necessary. Moreover, as a form of the epoxy resin composition of this invention, it can use as a solution melt | dissolved in solvents, such as toluene, a paste, and the film formed into a film.

  The epoxy resin composition of the present invention comprises an epoxy resin and a thermal cationic polymerization initiator and other additives such as a silane coupling agent, a thermosetting resin, and a filler that are added as necessary according to a conventional method. It can be produced by uniformly mixing and stirring.

  The epoxy-based fat composition of the present invention thus obtained uses a novel sulfonium borate complex as a thermal cationic polymerization initiator, so that during the thermal cationic polymerization, the amount of fluorine ions produced decreases and the electric corrosion resistance In addition, low temperature rapid curability can be realized.

  Therefore, the epoxy-based fat composition of the present invention can be preferably applied when an electronic component is mounted on a wiring board. In this case, it is possible to obtain a connection structure excellent in electric corrosion resistance, in which an electronic component is bonded onto a wiring board by a thermoset of the epoxy resin composition. This connection structure is also part of the present invention.

  Examples of the wiring board include a flexible printed board, a glass epoxy board, a glass board, and a tape board. Examples of the electronic component include an IC chip, a resistance element, a capacitor element, an antenna element, and a switching element.

  Thermal cationic polymerization of the epoxy-based fat composition of the present invention (paste shape, film shape, etc.) can be performed by heating to 100 to 250 ° C.

Example 1 and Comparative Examples 1-3
A sulfonium antimonate complex of the formulas (2a) to (2d) (see JP-A-10-245378 and JP-A-2006-96742 for a synthesis method) is dissolved in ethyl acetate, and a 10% by mass ethyl acetate solution of the complex Were prepared respectively. Separately from this, a 10% by mass aqueous solution of a sodium borate salt of the formula (3) (refer to JP-A-10-310587 for the synthesis method) was prepared.

  Next, a 10% by mass aqueous solution of the sodium borate salt of the formula (3) was mixed in an equimolar amount at room temperature with a 10% by mass ethyl acetate solution of the complex and stirred as it was for 30 minutes. Thereafter, the ethyl acetate layer was separated from the reaction mixture, dried, and ethyl acetate was removed under reduced pressure. As the evaporation residue, the sulfonium borate complex of the formula (1A) of Example 1 and the sulfonium borate complexes of the formulas (1a) to (1c) of Comparative Examples 1 to 3 were obtained.

Mass spectrometry (measuring instrument: AQUITY UPLC system) for the sulfonium borate complex of the formula (1A) of Example 1 as a novel compound and the sulfonium borate complexes of the formulas (1a) and (1b) of Comparative Example 1 and Comparative Example 2, respectively. , WATERS), elemental analysis (measuring instrument: PHOENIX, EDAX), IR measurement (measuring instrument: 7000e FT-IR, Varian), ¹ H-NMR analysis (measuring instrument: MERCURY PLUS, Varian). . These sulfonium borate complexes were confirmed to be target compounds from the obtained results.

(I) Analysis result of sulfonium borate complex of formula (1A) in Example 1 [p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium tetrakis (pentafluorophenyl) borate]

<MS analysis results>
M ⁺ = 289 (sulfonium residue)
M ⁺ = 679 (borate residue)

<Results of elemental analysis>
The measured value was consistent with the theoretical value.

<IR analysis result (cm < ^-1 >)>
An IR chart of the measurement results is shown in FIG. The IR characteristic absorption of the bond of the sulfonium borate complex of formula (1A) in Example 1 was observed in the IR chart of FIG.

^<1 H-NMR analysis ([delta] value)>
A ¹ H-NMR chart of the measurement results is shown in FIG. 2A, and a ¹ H-NMR chart of THF as a control solvent is shown in FIG. 2B. In the NMR chart of FIG. 2A, the following protons could be assigned.

(Ii) Analysis result of sulfonium borate complex of formula (1a) [4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium tetrakis (pentafluorophenyl) borate]

<MS analysis results>
M ⁺ = 281 (sulfonium residue)
M ⁺ = 679 (borate residue)

<Results of elemental analysis>
Found C; 52.51 H; 1.89
Theoretical value C; 52.52 H; 1.78

<IR analysis result (cm < ^-1 >)>
662 (C-S), 776, 980, 1088, 1276 (Ar-F), 1300, 1374, 1464, 1514, 1583, 1643, 2881 (C-H), 2981 (C-H), 3107 (O--) H)

^<1 H-NMR analysis ([delta] value), see Fig. 3 (THF used)>
2.6 (1H, (d)), 3.3 (3H, (a)), 5.3 (2H, (e)), 6.9 (2H, (c)), 7.6 (2H, (B)), 7.2-8.1 (7H, (f), (g), (h), (i), (j), (k), (l))

(Iii) Analysis result of sulfonium borate complex [4-hydroxyphenyl-methyl- (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate] of formula (1b)

<MS analysis results>
M ⁺ = 245 (sulfonium residue)
M ⁺ = 679 (borate residue)

<Results of elemental analysis>
Found C; 50.39 H; 1.77
Theoretical value C; 50.60 H; 1.80

<IR analysis result (cm < ^-1 >)>
662 (C-S), 773, 980, 1088, 1276 (Ar-F), 1463, 1514, 1583, 1644, 2882 (C-H), 2983 (C-H), 3109 (O-H)

^<1 H-NMR analysis ([delta] value), see FIG. 4 (THF used)>
2.3 (3H, (j)), 2.4 (1H, (d)), 3.3 (3H, (a)), 4.8 (2H, (e)), 7.0 (2H, (C)), 7.6 (2H, (b)), 7.0-7.4 (4H, (f), (g), (h), (i))

<Characteristic evaluation>
Example 1, each sulfonium borate complex (1A), (1a), (1b), (1c) of Comparative Examples 1-3, and sulfonium antimonate complexes (2a)-( For each of 2d), the fluorine ion concentration was measured under temperature conditions during thermal cationic polymerization as described below.

<Evaluation of fluorine ion production of complex>
0.2 g of the complex was added to 10 mL of pure water and heated at 100 ° C. for 10 hours, and then the amount of fluorine ions in the supernatant was measured by ion chromatographic analysis (Dionics). The obtained results are shown in Table 1. Practically, it is desired to be less than 10 ppm.

  From the results of Table 1, it can be seen that the sulfonium borate complex is useful as a thermal cationic polymerization initiator in that respect because it shows a very small amount of fluorine ion generation (less than 10 ppm) compared to the sulfonium antimolybate complex.

Examples 2 and 3, Comparative Examples 4 to 9, Reference Examples 5 to 12
An epoxy resin composition was prepared by uniformly mixing the components having the composition shown in Table 2. Further, for each epoxy resin composition, differential thermal analysis measurement (DSC measurement) was performed as described below, and an electric corrosion resistance test was performed. The liquid epoxy resin used was Epicoat 828 of Japan Epoxy Resin Co., Ltd., the silane coupling agent was γ-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.), and the filler was spherical fused silica. (EB-6D, Denki Kagaku Kogyo Co., Ltd.).

<DSC measurement>
The epoxy resin composition was subjected to differential thermal analysis (heat generation start temperature, peak temperature, heat generation amount) at a temperature rising rate of 10 ° C./min using a thermal analyzer (DSC 5100, Seiko Instruments Inc.). The obtained results are shown in Table 2.

  The exothermic start temperature is a temperature at which protons are generated from the complex and cationic polymerization is started. The lower the heat generation start temperature, the lower the temperature curability, but the tendency to decrease the storage stability arises. If the exothermic peak temperature is too low, the storage stability is lowered, and if it is too high, there is a tendency for curing failure to occur, so it is practically 100 to 110 ° C. The calorific value is the heat of reaction per gram of epoxy resin, and if it is too small, there is a tendency for poor curing, so it varies depending on the epoxy resin used, but generally 200 J / g or more is desirable.

<Electrical corrosion resistance test (migration test)>
An epoxy resin composition to be tested is applied to a glass wiring substrate in which an Al / Cr / ITO electrode or Mo / ITO electrode is provided in a comb-like shape with a 20 μm gap on a glass substrate so as to have a thickness of 20 μm. A test piece was obtained by heating and curing at 200 ° C. for 10 minutes. The obtained test piece was placed in a constant temperature bath at 85 ° C. and 85% RH and left for 12 hours in a state where a voltage of 30 V was applied between the electrodes. Thereafter, whether or not discoloration, defects, disconnection, or the like occurred in the electrodes was observed from the front and back surfaces of the glass wiring board using an optical microscope and evaluated according to the following criteria. The results obtained are shown in Table 2.

Electrical corrosion resistance evaluation criteria G: When discoloration, defect, disconnection, etc. are observed NG: When discoloration, defect, disconnection, etc. are not observed

  In the case of the epoxy resin compositions of Examples 2 and 3 using the novel sulfonium borate complex of the formula (1A) of Examples 1 and 2 having a fluorine ion production amount (see Table 1) of less than 10 ppm, from Table 2, Since the reaction start temperature in the DSC measurement was in the range of 70 to 80 ° C., the exothermic peak temperature was in the range of 100 to 110 ° C., and the calorific value was 200 J / g or more, it was satisfactory in practical use.

  On the other hand, in the case of the epoxy resin compositions of Comparative Examples 4 to 9 using the sulfonium borate complex of Comparative Examples 1 to 3, the fluorine ion generation amount was less than 10 ppm and excellent in electric corrosion resistance. There was a problem with the evaluation item of the exothermic peak temperature.

  Thus, it was found that among the sulfonium borate complexes, the sulfonium borate complex of the formula (1A) of Example 1 of the present invention was superior as a thermal cationic polymerization initiator compared to other complexes.

  In the case of the epoxy resin compositions of Reference Examples 5 to 12 using the sulfonium antimonate complexes of Reference Examples (2a) to (2d), the amount of fluorine ions generated exceeded 10,000 ppm, and there was a problem with resistance to electrolytic corrosion.

  The novel sulfonium borate complex of the present invention reduces the amount of fluorine ions generated during thermal cationic polymerization of an epoxy resin composition such as a thermal cationic adhesive containing this complex as a thermal cationic polymerization initiator, and has resistance to electric corrosion. In addition, low temperature rapid curability can be realized. Therefore, it is useful as a thermal cationic polymerization initiator for the epoxy resin composition.

Electrolytic corrosion resistance Evaluation Criteria G: If discoloration defects, such as disconnection is not recognized NG: If the discoloration defects, such as disconnection is Ru observed

Claims (9)

A sulfonium borate complex represented by the formula (1).

(In formula (1), R ₁ is an aralkyl group, R ₂ is a lower alkyl group, R ₃ is a lower alkoxycarbonyl group, X is a halogen atom, and n is an integer of 1 to 3. is there.) The sulfonium borate complex according to claim 1, wherein R ₁ is an o-methylbenzyl group or a (1-naphthyl) methyl group. The sulfonium borate complex according to claim 1 or 2, wherein R ₂ is a methyl group. The sulfonium borate complex according to claim 1, wherein n is 1 and the R ₃ O group is bonded to the 4-position of the phenyl group. Sulfonium borate complex according to any one of claims 1 to 4 R ₃ is a methoxy group.   X is a fluorine atom, The sulfonium borate complex in any one of Claims 1-4. A process for producing a sulfonium borate complex of formula (1) according to claim 1,
A production method for obtaining a sulfonium borate complex of formula (1) by reacting a sodium borate salt of formula (3) with a sulfonium antimonate complex of formula (2).

(In Formula (1), (2) or (3), R ₁ is an aralkyl group, R ₂ is a lower alkyl group, R ₃ is a lower alkoxycarbonyl group, X is a halogen atom, n is an integer of 1 to 3.)   An epoxy resin composition comprising an epoxy resin and a thermal cationic polymerization initiator, wherein the thermal cationic polymerization initiator is the sulfonium borate complex according to any one of claims 1 to 6. Resin composition.   An electronic component is bonded onto a wiring board by a thermoset of the epoxy resin composition according to claim 8.

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