JP2011057577A - Aryloxysilane compound, manufacturing method of the same and application of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel aryloxysilane compound and a manufacturing method of the same, and a curing agent composed of the same for an epoxy resin useful for applications such as a liquid sealing material, an underfill agent, an electroconductive paste and the like, an epoxy resin composition comprising the same and a cured product thereof. <P>SOLUTION: The aryloxysilane compound is represented by formula (1) (wherein Ar is a phenylene group or a naphthalene group). The compound is manufactured from a bifunctional silane compound of formula (4) and an aromatic compound of formula (5). The curing agent for an epoxy resin comprises the compound. The epoxy resin composition comprises the epoxy resin curing agent. The cured product of the same is also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel aryloxysilane compound, a method for producing the same, and uses thereof. Suitable applications relate to epoxy resin curing agents useful in applications such as liquid encapsulants, underfill agents, and conductive pastes, and epoxy resin compositions containing the same, and further cure in the above applications. The present invention relates to an epoxy resin cured product having a low water absorption and a high glass transition temperature, giving an epoxy resin composition capable of controlling the speed and having suitable fluidity and pot life.

  Compounds used so far as epoxy resin curing agents include amines, acid anhydrides, polyamides, imidazoles, mercaptans, phenols, etc. Epoxy resin compositions containing these are semiconductors Widely used in the field of electrical and electronic materials such as sealing materials such as LED and LED, substrate materials such as printed circuit boards and multilayer substrates, and insulating materials such as solder resists and multilayer substrate applications.

  In the semiconductor encapsulation field, in addition to solid phenolic curing agents for transfer molding, in recent years, with the expansion of applications such as liquid sealing materials, underfill agents, and conductive pastes, there is a need for liquid or low-viscosity curing agents. Is growing. Recently, phenolic and amine curing agents have attracted attention from the viewpoint of moisture resistance reliability.

  Generally, when a phenol-based curing agent contains a large amount of hydroxyl groups, the epoxy resin composition has low fluidity. Therefore, as an approach for high fluidity, means for preventing or inhibiting hydrogen bonding due to the hydroxyl group of the phenol-based curing agent is used. For example, a phenol derivative in which a phenolic hydroxyl group is partially or completely protected with an acyl group or a silyl group (see Patent Documents 1 to 5), a means for introducing a substituent into the ortho position of the phenolic hydroxyl group, and the like are used. (See Patent Document 6). By these approaches, while exhibiting desirable characteristics such as high fluidity and low water absorption in the aforementioned applications, it is difficult to obtain a cured product having a slow curing and a high glass transition temperature, and the curing agent is compatible with the epoxy resin composition. There are also difficulties, such as difficult to do.

  In general, amine-based curing agents have a slow curing speed and are difficult to control the curing time, but are usually used to give a cured product having excellent high heat resistance. On the other hand, with regard to the control of the curing rate, there are often no suitable curing accelerators and satisfactory acceleration effects are often not obtained, and there are suitable means such as restrictions on use from the viewpoint of moldability and usable time depending on the application. The current situation is not found.

JP-A-7-53675 JP-A-8-208807 JP-A-10-168283 JP 2001-151783 A JP 2006-96838 A JP 2000-169537 A

This invention creates the hardening | curing agent which implement | achieves coexistence of the solution of the said subject in phenol type and amine type hardening | curing agent, and maintenance of fluidity | liquidity. That is, the present invention provides a curing agent that is rapidly cured and has a low water absorption and a high glass transition temperature, and has excellent fluidity.
Moreover, this invention provides the epoxy resin composition containing this hardening | curing agent useful for uses, such as a liquid sealing material and an underfill agent, and the epoxy resin hardened | cured material formed by hardening | curing this.

  The present invention provides an aryloxysilane compound represented by the following general formula (1).

(In the formula, n is an integer of 0 to 10, R ¹ and R ² are each a hydrocarbon group having 1 to 10 carbon atoms, and Ar is a phenylene group represented by the following general formula (2) or the following general formula (3 ) Naphthalene group represented by

Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ炭素数１〜１０の炭化水素基、ｓ、ｔ、ｕはそれぞれ０〜４の整数）

R ³ , R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 10 carbon atoms, and s, t and u are each an integer of 0 to 4)

  The present invention also provides the following general formula (4):

（式中、ｎ、Ｒ^１、Ｒ^２は前記式１と同じ、Ｘはハロゲン又は炭素数１〜５のアルコキシ基）で表される２官能型シラン化合物と、下記一般式（５）

(Wherein n, R ¹ and R ² are the same as those in formula 1 above, X is a halogen or an alkoxy group having 1 to 5 carbon atoms) and the following general formula (5)

（式中、Ａｒは前記式２または３と同じ）で表される芳香族化合物との混合物を触媒存在下で脱ハロゲン化水素又は脱アルコールにより縮合させる前記アリーロキシシラン化合物の製造方法を提供する。

Provided is a method for producing the aryloxysilane compound, wherein a mixture with an aromatic compound represented by the formula (wherein Ar is the same as in the above formula 2 or 3) is condensed by dehydrohalogenation or dealcoholization in the presence of a catalyst. .

  The above-described method for producing an aryloxysilane compound in which the catalyst is a metal alkoxide, a metal carboxylate, a metal hydroxide, a carboxylic acid, or an amine compound is a preferred embodiment of the present invention.

  Moreover, this invention provides the epoxy resin hardening | curing agent which consists of an aryloxysilane compound, the epoxy resin composition containing it and an epoxy resin, and the epoxy resin hardened | cured material obtained by hardening | curing it.

The present invention provides a novel aryloxysilane compound useful for an epoxy resin curing agent and a method for producing the same. The aryloxysilane compound provided by the present invention is highly compatible with an epoxy resin, and an epoxy resin composition containing this as a curing agent has suitable fluidity and pot life, and the curing rate can be controlled. Yes, it provides a cured product of epoxy resin with low water absorption and high glass transition temperature.
The epoxy resin composition obtained by this application can be used conveniently for uses, such as a liquid sealing material and an underfill agent.

1 is a ¹ H-NMR chart of aryloxysilane 1 obtained in Example 1. 2 is a ¹ H-NMR chart of aryloxysilane 2 obtained in Example 2. FIG.

  The present invention provides an aryloxysilane compound represented by the general formula (1).

  Examples of the hydrocarbon group having 1 to 10 carbon atoms in the above formulas (1) to (3) include an alkyl group and an aryl group which may have a substituent, preferably 1 to 4 carbon atoms. An alkyl group and an aryl group having 6 to 10 carbon atoms are preferred, and a methyl or phenyl group is particularly preferred.

In the formula (1), an aryloxysilane compound in which n is an integer of 0 to 4 and R ¹ and R ² are each selected from a methyl group and a phenyl group is a preferred compound.

Aryloxysilane in which R ³ , R ⁴ and R ^{5 in the} formulas (2) and (3) are each a hydrocarbon group having 1 to 3 carbon atoms, and s, t and u are each an integer of 0 to 1 Compounds are also preferred compounds.

The method for producing the aryloxysilane compound of the present invention is not particularly limited, but the following method can be exemplified as a preferred production method.
That is, a mixture of the bifunctional silane compound represented by the general formula (4) and the aromatic compound represented by the general formula (5) is condensed by dehydrohalogenation or dealcoholization in the presence of a catalyst. An aryloxysilane compound can be obtained.

  Examples of the bifunctional silane compound represented by the formula (4) include dichlorodimethylsilane, dichlorodiethylsilane, dichlorodipropylsilane, dichlorodiisopropylsilane, dichlorodibutylsilane, dichlorodiphenylsilane, dichloromethylphenylsilane, and dichlorodimethyl. Dihalosilane monomers such as silane, dibromomethylethylsilane, diiododiphenylsilane, dimethoxydimethylsilane, dimethoxydiethylsilane, dimethoxydipropylsilane, dimethoxydiisopropylsilane, dimethoxydibutylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, diethoxy Examples of dialkoxysilane monomers such as dimethylsilane, dipropoxymethylethylsilane, diisopropoxydiphenylsilane It can be. In addition, polysiloxane compounds that are these hydrolysis products can also be used as the bifunctional silane compound.

N in the formula (4) is suitable for use from 0 to 10 or more, but considering the balance between high fluidity and heat resistance, a range of 0 to 4 is preferable. Obtaining R ¹ and R ² In view of surface and characteristics, a methyl group or a phenyl group is preferable. For these reasons, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, and polysiloxane type derivatives thereof can be listed.

  Examples of the aromatic compound described in the formula (5) include 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-amino-3-methylphenol, 2-amino-4-methylphenol, 2 -Amino-5-methylphenol, 2-amino-6-methylphenol, 3-amino-1-methylphenol, 3-amino-4-methylphenol, 3-amino-5-methylphenol, 3-amino-6- Methylphenol, 4-amino-2-methylphenol, 4-amino-3-methylphenol, 2-amino-3-methyl-4-methoxyphenol, 3-amino-1-methyl-5-phenylphenol, 4-amino Examples include -3-methyl-5-allylphenol.

Considering the availability and characteristics of the raw materials, R ³ , R ⁴ , and R ^{5 in the} formulas (2) and (3) are each a hydrocarbon group having 1 to 3 carbon atoms, and s, t, and u are each 0. Those represented by an integer of ˜1 are preferred, and preferred specific examples include aminophenols and aminomethylphenols.

  The reaction between the aromatic compound and the bifunctional silane compound can be carried out without solvent, but a solvent can also be used. When using a solvent, the thing which does not react with the raw material to be used but has a boiling point in the range of 50 to 200 ° C. is preferable. Specifically, aliphatic hydrocarbon compounds such as hexane, heptane, octane, nonane, decane, decalin, dodecane, aromatic hydrocarbons such as toluene, xylene, mesitylene, dioxane, cyclopentyl methyl ether, monoethylene glycol dimethyl ether And ethers such as diethylene glycol dimethyl ether and anisole. These may be used alone or in combination of two or more.

  The required time in the reaction between the aromatic compound and the bifunctional silane compound depends on the type of raw material used, but usually requires about 1 to 24 hours. About setting of reaction temperature, what is necessary is just to set reaction temperature of the grade which the raw material to be used does not evaporate. Therefore, specifically, a temperature range of about 50 to 250 ° C. is preferable.

  After completion of the reaction, the desired aryloxysilane compound of the present invention can be isolated by removing the solvent, catalyst, and the like by operations such as distillation under reduced pressure, filtration, and washing as necessary. Since the aryloxysilane compound of the present invention has a high boiling point and is stable to heat, the aryloxysilane compound can be obtained with high purity without being altered even if such a purification operation is introduced.

  The aryloxysilane compound of the present invention is suitably used as an epoxy resin curing agent. The epoxy resin curing agent comprising the aryloxysilane compound is a preferred embodiment of the present invention.

  The epoxy resin composition of this invention contains an epoxy resin and the hardening | curing agent for epoxy resins of this invention. The epoxy resin used in the epoxy resin composition of the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, and is a novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin. Phenol biphenyl aralkyl type epoxy resin, triphenol methane type epoxy resin, dicyclopentadiene type epoxy resin, phenol aralkyl type epoxy resin, triglycidylated product of aminophenol, and the like. For applications in which a liquid epoxy resin composition is used at room temperature, it is preferable to use a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a triglycidylated product of aminophenol.

  In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In curing the epoxy resin, it is desirable to use a curing accelerator in combination. As such a curing accelerator, a known curing accelerator for curing an epoxy resin with a phenol resin curing agent can be used. For example, a tertiary amine, a quaternary ammonium salt, an imidazole, an organic phosphine compound, A quaternary phosphonium salt can be mentioned. More specifically, tertiary amines such as triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7, Imidazoles such as imidazole, 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, triphenylphosphine, tributylphosphine, tri ( Examples thereof include organic phosphine compounds such as p-methylphenyl) phosphine and tri (nonylphenyl) phosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetranaphthoic acid borate and the like.

  The curing accelerator may be either a method of adding to the epoxy resin curing agent of the present invention or a method of adding the epoxy resin curing agent and the epoxy resin to a composition obtained by mixing the epoxy resin curing agent and the epoxy resin. The addition amount of the curing accelerator is preferably 0.001 to 10.0 parts by weight with respect to 100 parts by weight of the epoxy resin curing agent of the present invention.

  The epoxy resin composition of the present invention contains an inorganic filler as necessary. Specific examples of the inorganic filler that can be used include silica, alumina, talc, boron nitride, silicon nitride, and the like. The inorganic filler is used in an amount of 0 to 90% by weight in the epoxy resin composition of the present invention. Furthermore, various compounding agents such as a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, and a pigment can be added to the epoxy resin composition of the present invention.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method.

  It is a preferable aspect that the epoxy resin composition of the present invention is liquefied at room temperature particularly in applications such as liquid sealing.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin, the curing agent, and if necessary, the curing accelerator, the inorganic filler, and the compounding agent are mixed sufficiently until uniform using an extruder, a kneader, a roll, or the like, if necessary. If an epoxy resin composition is obtained and the epoxy resin composition is solid, it is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method or the like, and further at 80 to 200 ° C. for 2 to 10 hours. A cured product can be obtained by heating to. A liquid epoxy resin composition can be made into a cured product at a similar heating temperature by a known sealing method such as a dispensing method, a casting method, or a printing method.

  In particular, the viscosity of the epoxy resin composition of the present invention that is liquid at room temperature depends on the content and use of the composition, but from the viewpoint of use at temperatures around room temperature, the viscosity at 25 ° C. when no inorganic filler is included. 15000 mPa · s or less, preferably 7500 mPa · s or less.

  Moreover, the prepreg obtained by impregnating the epoxy resin composition of the present invention into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating is subjected to hot press molding and cured. You can also get The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.

  The epoxy resin composition of the present invention having the characteristics as described above is suitably used for applications such as liquid sealing materials, underfill materials, solid sealing materials, adhesives, laminated materials, paints, and resists. is there.

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples.

(Reference Example) Synthesis of liquid phenol novolac type curing agent A mixture of phenol 117.6 g (1250 mmol), 2-allylphenol 503.2 g (3750 mmol), 37% -formalin 81.2 g (1000 mmol) was heated to 60 ° C. 2 g of oxalic acid dihydrate was added and the temperature was raised to 95 ° C. over 2 hours. Thereafter, 2 g of oxalic acid dihydrate was further added, and the mixture was kept at 95 ° C. for 3 hours. After completion of the reaction, 232.9 g of a liquid phenol novolac type curing agent was obtained by distillation under reduced pressure (hydroxyl equivalent: 135 g / eq, 50 ° C. viscosity: 430 mPa · s).

Example 1 Synthesis of aryloxysilane 1 [molar ratio (dimethoxymethylphenylsilane / 3-aminophenol / water) = 1/2/0]
In a 200 ml four-necked flask with an outlet at the bottom, 31.8 g (0.175 mol) of dimethoxymethylphenylsilane, 38.2 g (0.350 mol) of 3-aminophenol, and tetraisopropyl orthotitanate were added in a 0.1. 099 g was charged and heated to 150 ° C. Methanol generated in the reaction was volatilized out of the system and kept at 150 ° C. for 8 hours. After confirming by gas chromatography that no unreacted 3-aminophenol remained in the reaction solution, the reaction solution was extracted and turned brown. To 56.9 g of a transparent reaction product (allyloxysilane 1).
The melt viscosity at 50 ° C. of aryloxysilane 1 was measured and found to be 650 mPa · s. The curing agent equivalent was 54.2 g / eq according to the following formula.
Curing agent equivalent [g / eq] = reactant weight [g] / (3-aminophenol eq number [eq] used in reaction)
A ¹ H-NMR chart of the obtained aryloxysilane 1 in dimethyl sulfoxide-d ₆ is shown in FIG. From the chemical shift and area ratio of the signal in FIG. 1, the hydrogen of the amino group derived from 3-aminophenol (δ5.06 ppm), the hydrogen on the benzene ring (δ6.21 to 6.86 ppm), and the methyl group derived from dimethoxymethylphenylsilane Hydrogen (δ0.48 ppm) and phenyl group hydrogen (δ7.41 to 7.67 ppm) are attributed to each other, and the methoxy group of dimethoxymethylphenylsilane is removed as methanol by the reaction with 3-aminophenol, and amino in one molecule It can be seen that a phenoxysilane species having two groups is provided.

(Example 2) Synthesis of aryloxysilane 2 [molar ratio (dimethoxymethylphenylsilane / 3-aminophenol / water) = 2/2/1]
A 200 ml four-necked flask with an outlet at the bottom was charged with 49.1 g (0.270 mol) of dimethoxymethylphenylsilane and 0.068 g of tetraisopropyl orthotitanate, heated to 75 ° C., and then 2.4 g of water. (0.135 mol) and a solution of 21.6 g of methanol were added over 3 hours. The reaction was carried out while volatilizing methanol from the added mixed solution and methanol generated by the reaction out of the system. After holding, 29.4 g (0.270 mol) of 3-aminophenol was added to the reaction solution, and the temperature was raised to 150 ° C. At this time, methanol generated by the reaction was volatilized out of the system as it was and kept at 150 ° C. for 8 hours. After confirming that unreacted 3-aminophenol did not remain in the reaction solution, the reaction solution was It was extracted to obtain 65.2 g (allyloxysilane 2) of a brownish and transparent reaction product.
The obtained aryloxysilane 2 was determined in the same manner as in Example 1 for a melt viscosity of 50 ° C. and a curing agent equivalent. According to this, the melt viscosity at 50 ° C. was 0.24 Pa · s, and the curing agent equivalent was 80.5 g / eq.

A ¹ H-NMR chart of the resulting aryloxysilane 2 in dimethyl sulfoxide-d ₆ is shown in FIG. From the chemical shift and area ratio of the signal in Fig. 2, the amino group hydrogen derived from 3-aminophenol (δ4.98 to 5.06ppm), the hydrogen on the benzene ring (δ6.00 to 6.85ppm) and dimethoxymethylphenylsilane The hydrogen of the methyl group (δ 0.32 to 0.50 ppm) and the hydrogen of the phenyl group (δ 7.41 to 7.67 ppm) are attributed to each other, and the methoxy group of dimethoxymethylphenyl silane is methanol by the reaction of water and 3-aminophenol. It can be seen that an aryloxysilane species having two amino groups in one molecule and also including a siloxane structure is given.

(Comparative Example 1)
Liquid phenol novolak type curing agent obtained in Reference Example, bisphenol F type epoxy resin (Epicoat 806, Japan Epoxy Resin Co., Ltd., epoxy equivalent: 168 g / eq), 1,8-diazabicyclo [5,4,0] undecene -7 was blended in the proportions shown in Table 1, and mixed well to obtain an epoxy resin composition. Using this, the composition viscosity at 25 ° C., the rate of increase in viscosity, and the gelation time were measured. The epoxy composition was heated at 120 ° C. for 1 hour, at 150 ° C. for 1 hour, and further at 180 ° C. for 5 hours to prepare a test piece for measuring the glass transition temperature and the water absorption rate. The results are shown in Table 1.

The physical properties in the present invention were measured by the following methods.
(1) Composition viscosity The viscosity at 25 ° C of the epoxy resin composition was measured.
(2) Viscosity increase rate after 168 hours The viscosity at 25 ° C before and after the epoxy resin composition was allowed to stand at -5 ° C for 168 hours was measured and calculated according to Formula 1.
Rate of increase in viscosity after 168 hours [%] = (viscosity after standing for 168 hours-initial viscosity) x 100 / initial viscosity (formula 1)
(3) Gelation time The time until gelation was observed on a 150 ° C. hot plate was measured.
(4) Glass transition temperature (Tg)
The inflection point of the linear expansion coefficient obtained by TMA was taken as the glass transition temperature.
(5) Water absorption rate after 168 hours The water absorption rate when a disk having a sample shape of 50 mm diameter x 3 mm was absorbed for 168 hours in an atmosphere of 85 ° C and a relative humidity of 85% RH was calculated by Equation 2.
Water absorption [%] after 168 hours = (weight increase after standing for 168 hours / initial weight) × 100 (Formula 2)

(Comparative Example 2)
A liquid aromatic amine type curing agent (EPOX-MKQ544, Printec Co., Ltd., functional group equivalent: 43 g / eq) was used in place of the liquid phenol novolac type curing agent of Comparative Example 1 to obtain the composition shown in Table 1. Except for the above, evaluation was performed in the same manner as in Comparative Example 1. The results are shown in Table 1.

(Comparative Example 3)
A liquid aromatic amine type curing agent (EPOX-MKQ544, Printec Co., Ltd., functional group equivalent: 43 g / eq) was used in place of the liquid phenol novolac type curing agent of Comparative Example 1 to obtain the composition shown in Table 1. Except for the above, evaluation was performed in the same manner as in Comparative Example 1. The results are shown in Table 1.

(Example 3)
Evaluation was performed in the same manner as in Comparative Example 1 except that the arylphenol silane 1 of Example 1 was used instead of the liquid phenol novolac type curing agent of Comparative Example 1 and the composition was as shown in Table 1. The results are shown in Table 1.

Example 4
Evaluation was conducted in the same manner as in Comparative Example 1 except that the arylphenol silane 2 of Example 2 was used instead of the liquid phenol novolak type curing agent of Comparative Example 1 and the composition was as shown in Table 1. The results are shown in Table 1.

(Example 5)
Evaluation was conducted in the same manner as in Comparative Example 1 except that the arylphenol silane 2 of Example 2 was used instead of the liquid phenol novolak type curing agent of Comparative Example 1 and the composition was as shown in Table 1. The results are shown in Table 1.

  The aryloxysilane compound provided by the present invention is highly compatible with the ingredients shown in the above table, and the epoxy resin composition containing the compound is liquid at room temperature. The viscosity is lower than when a liquid phenolic curing agent is used, the viscosity increase rate is lower than when a liquid amine curing agent is used, and the curing rate can be controlled by the amount of catalyst used. A cured product obtained by thermosetting this exhibits a high glass transition temperature and low water absorption. Therefore, it can be seen that the aryloxysilane compound provided by the present invention behaves as a curing agent having characteristics that are incompatible with each other, that is, a phenolic curing agent and an amine curing agent.

  According to the present invention, an epoxy resin composition useful in applications such as a liquid sealing material, an underfill agent, and a conductive paste is provided. The aryloxysilane compound provided by the present invention is useful as a curing agent having the advantages of the phenolic curing agent and the amine curing agent that have been conventionally used in the above applications. That is, it exhibits high compatibility, fast curability, high heat resistance, and low water absorption characteristics with respect to the epoxy resin composition and the cured epoxy resin.

Claims (12)

An aryloxysilane compound represented by the following general formula (1).

(In the formula, n is an integer of 0 to 10, R ¹ and R ² are each a hydrocarbon group having 1 to 10 carbon atoms, and Ar is a phenylene group represented by the following general formula (2) or the following general formula (3 ) Naphthalene group represented by

R ³ , R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 10 carbon atoms, and s, t and u are each an integer of 0 to 4) N is an integer of 0 to 4, R ^1, R ² are each a methyl group, an aryloxy silane compound of claim 1 which is selected from any one of phenyl group of the formula (1). The R ³ , R ⁴ , and R ^{5 in the} formulas (2) and (3) are each a hydrocarbon group having 1 to 3 carbon atoms, and s, t, and u are each represented by an integer of 0 to 1. Or an aryloxysilane compound according to 2; The following general formula (4)

(Wherein n, R ¹ and R ² are the same as those in formula 1 above, X is a halogen or an alkoxy group having 1 to 5 carbon atoms) and the following general formula (5)

(In the formula, Ar is the same as the above formula 2 or 3.)
The method for producing an aryloxysilane compound according to any one of claims 1 to 3, wherein the mixture with the aromatic compound represented by the formula is condensed by dehydrohalogenation or dealcoholization in the presence of a catalyst.   The method for producing an aryloxysilane compound according to claim 4, wherein the catalyst is a metal alkoxide, a metal carboxylate, a metal hydroxide, a carboxylic acid, or an amine compound.   The epoxy resin hardening | curing agent which consists of an aryloxysilane compound in any one of Claims 1-3.   The epoxy resin hardening | curing agent of Claim 6 which exhibits a liquid state at normal temperature.   An epoxy resin composition comprising the epoxy resin curing agent according to claim 6 or 7 and an epoxy resin.   The epoxy resin composition of Claim 8 containing a hardening accelerator.   The epoxy resin composition according to claim 8 or 9, which exhibits a liquid state at normal temperature.   The epoxy resin composition according to claim 10, which is used for a liquid sealing material, an underfill agent, and a conductive paste.   The epoxy resin hardened | cured material obtained by hardening | curing the epoxy resin composition in any one of Claims 8-11.

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