JP5930826B2 - Polysiloxane compound and moisture curable resin composition - Google Patents

Description

  The present invention relates to a polysiloxane compound useful for a moisture curable resin composition excellent in heat resistance and adhesiveness, and a moisture curable resin composition containing the same.

  A composition containing a polymer compound having a hydrolyzable silyl group at the molecular end can be cured at room temperature with moisture in the atmosphere, and particularly those whose main chain is a polyoxyalkylene chain or a polysiloxane chain are acceptable. Because of its excellent flexibility, it is widely used for building sealing materials, coating materials, electrical and electronic component sealing materials, potting materials, automotive, architectural, electrical and electronic adhesives, etc. ( (See Patent Documents 1 and 2).

JP 05-279570 A JP 07-003159 A

However, among the polymer compounds having a hydrolyzable silyl group at the molecular terminal, those having polyoxyalkylene as the main chain are excellent in adhesiveness but have insufficient heat resistance and have polysiloxane as the main chain. Although the thing is excellent in heat resistance, there exists a problem that adhesiveness is inadequate.
In the adhesion and sealing around the heating element, both heat resistance and tackiness are required. However, in a composition containing a polymer compound having a hydrolyzable silyl group at a molecular end known in the past, heat resistance and None of them were excellent in both stickiness.

  Accordingly, an object of the present invention is to provide a polysiloxane compound useful for a curable resin composition capable of obtaining a cured product excellent in heat resistance and adhesiveness, and a moisture curable resin composition containing the same. It is in.

  As a result of investigations to solve the above-mentioned problems, the present inventors have used a polysiloxane compound having a different number of terminal alkoxy groups in the same molecule, thereby providing a moisture curable resin excellent in heat resistance and adhesiveness. The present inventors have found that a composition can be obtained and have completed the present invention.

（式中、Ｒ^１〜Ｒ^４は各々独立して炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表し、Ｒ^５及びＲ^６は各々独立して炭素数１〜４のアルキル基を表し、Ｘ^１は炭素数１〜４のアルキル基、炭素数６〜１０のアリール基又は炭素数１〜４のアルコキシ基を表し、ａは、一般式（１）で表される化合物の質量平均分子量を２０００〜１００万とする数を表し、ｂは０又は１を表し、Ｒ^１及びＲ^２のうち、炭素数６〜１０のアリール基の割合が、１０〜２５モル％である。）

That is, the polysiloxane compound of the present invention is represented by the following general formula (1).

(In the formula, R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ⁵ and R ⁶ each independently represent one having 1 to 4 carbon atoms. Represents an alkyl group, X ¹ represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a is a compound represented by the general formula (1) the mass average molecular weight represents the number of a 2,000 to 1,000,000, b represents 0 or 1, one of ^{R 1} and ^{R 2,} the ratio of the aryl group having 6 to 10 carbon atoms, 10 to 25 mol% .)

  The moisture curable resin composition of the present invention is characterized by containing a siloxane compound represented by the general formula (1) as the component (A) and a curing catalyst as the component (B).

（式中、Ｒ^７〜Ｒ^１０は各々独立して炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表し、Ｒ^１１は炭素数１〜４のアルキル基を表し、Ｘ^２は炭素数１〜４のアルキル基、炭素数６〜１０のアリール基又は炭素数１〜４のアルコキシ基を表し、ｃは、一般式（２）で表される化合物の質量平均分子量を１０００〜１００万とする数を表し、ｄ及びｅは各々独立して０又は１を表す。） The moisture curable resin composition of the present invention preferably further contains a siloxane compound represented by the following general formula (2) as the component (C).

(Wherein R ^{7 to} R ¹⁰ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ¹¹ represents an alkyl group having 1 to 4 carbon atoms, and X ² Represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and c represents a mass average molecular weight of the compound represented by the general formula (2) from 1000 to 1000. (The number is 1 million, and d and e each independently represent 0 or 1.)

（式中、Ｒ^１２〜Ｒ^１７は各々独立して炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表し、Ｒ^１８は炭素数１〜４のアルキル基を表し、ｆは、一般式（３）で表される化合物の質量平均分子量を１０００〜１００万とする数を表し、ｇ及びｈは各々独立に０又は１を表す。） The moisture curable resin composition of the present invention preferably further contains a siloxane compound represented by the following general formula (3) as the component (D).

(Wherein R ^{12 to} R ¹⁷ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ¹⁸ represents an alkyl group having 1 to 4 carbon atoms, and f is And represents a number in which the mass average molecular weight of the compound represented by the general formula (3) is 1,000 to 1,000,000, and g and h each independently represent 0 or 1.)

  According to the present invention, it is possible to provide a polysiloxane compound useful for a moisture curable resin composition excellent in heat resistance and adhesiveness, and a moisture curable resin composition containing the same.

  The polysiloxane compound represented by the general formula (1) of the present invention is characterized in that it has alkoxy groups at both ends of the molecule, and the number of alkoxy groups at the ends is asymmetric. Hereinafter, the polysiloxane compound represented by the general formula (1) will be described.

In the general formula (1), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, and isobutyl, and examples of the aryl group having 6 to 10 carbon atoms include phenyl, 2- Examples include methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 4-t-butylphenyl, naphthyl, and the like. Is a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or an unsubstituted phenyl group. Each of R ¹ and R ² may be the same group or a combination of different groups. R ¹ and R ² are preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint of tackiness, more preferably methyl, and an aryl group having 6 to 10 carbon atoms is preferable from the viewpoint of heat resistance, and phenyl is Further preferred.

When the ratio of the aryl group in R ¹ and R ² is too large, the tackiness of the cured product is lowered, so that R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms and 6 carbon atoms. Is preferably a combination of 10 to 10 aryl groups, and the ratio of 6 to 10 aryl groups in R ¹ and R ² is preferably 1 to 40 mol%, and 3 to 30 mol%. More preferably, it is most preferably 10 to 25 mol%. As R ³ and R ⁴ , methyl is preferable because the raw materials are easily available and the reactivity of the raw materials is good.

R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, and isobutyl. R ³ and R ⁴ are preferably methyl, ethyl, and propyl, and more preferably methyl and ethyl, because a hydrolysis reaction easily occurs.

X ¹ represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ and R ² . Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, second butoxy, third butoxy, isobutoxy and the like. X ¹ is preferably an alkoxy group having 1 to 4 carbon atoms because the tackiness of the cured product is improved, and methoxy and ethoxy are more preferable because hydrolyzability is good.

  In General formula (1), a represents the number which makes the mass mean molecular weight of the compound represented by General formula (1) 2000-1 million. When the mass average molecular weight of the compound represented by the general formula (1) is smaller than 2000, the obtained cured product has insufficient tackiness, and when it is larger than 1 million, the viscosity becomes high and handling properties are increased. descend. The mass average molecular weight of the compound represented by the general formula (1) is preferably 2500 to 50,000, more preferably 3000 to 30,000, and most preferably 3500 to 10,000. In the present invention, the mass average molecular weight means a mass average molecular weight in terms of polystyrene when GPC (Gel Permeation Chromatography, also called gel permeation chromatography) analysis is performed using tetrahydrofuran as a solvent. b represents 0 or 1, and b is preferably 0 because production is easy.

（式中、Ｒ^１、Ｒ^２、Ｒ^５及びａは、一般式（１）と同義である。） Among the compounds represented by the general formula (1), a compound in which b is 0 is represented by the following general formula (1a) by ring-opening polymerization of a cyclic siloxane compound using a catalyst with an alcohol compound as a starting material. An intermediate polymer is synthesized, and the end of the intermediate polymer is reacted with a trialkoxysilane compound or a tetraalkoxysilane compound.

^(Wherein, R ^1, R 2, ^{R 5} and a are as in formula (1) synonymous.)

  Examples of the starting material of the compound represented by the general formula (1a) include alcohol compounds having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, second butanol, third butanol, and isobutanol. .

  Examples of the ring-opening polymerization catalyst include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfated zirconia, and other acid catalysts; lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and other basic catalysts. The base catalyst is preferable because of easy control of the molecular weight, and sodium hydroxide and potassium hydroxide are more preferable from the viewpoint of industrial availability. When a base catalyst is used as the catalyst, the content of by-products can be reduced. Therefore, it is preferable to use the alcohol compound after converting it to an alcoholate of the base catalyst.

  Examples of the cyclic siloxane compound include hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane, and octamethylcyclotetrasiloxane. , Octaethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane, decamethylcyclopentasiloxane, decaethylcyclopentasiloxane, Decaphenylcyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentaphenylcyclopentasiloxane, undecamethylcyclohexasiloxane, etc. are listed and are commercially available. Because it is easy, octamethylcyclotetrasiloxane, octaethyl cyclotetrasiloxane, is octaphenylcyclotetrasiloxane preferred.

  The reaction temperature of the ring-opening polymerization is preferably 80 to 250 ° C, more preferably 100 to 200 ° C, and most preferably 120 to 180 ° C. In the above ring-opening polymerization, dibutyl ether, toluene, xylene or the like may be used as a solvent, if necessary.

  Examples of trialkoxysilane compounds or tetraalkoxysilane compounds to be reacted with the intermediate polymer include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and phenyl. Examples include trimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane.

  In the reaction of the intermediate polymer with the trialkoxysilane compound or the tetraalkoxysilane compound, it is preferable to use a catalyst. Catalysts include organotin compounds such as dibutyltin dimethoxide, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dimethyltin dimethoxide, dimethyltin acetate; tetrapropyl titanate, tetrabutyl titanate, tetra-2-ethylhexyl titanate Organic titanium compounds such as dimethoxytitanium diacetylacetonate and diisopropoxytitanium diacetylacetonate; amine compounds such as hexylamine, 3-aminopropyltrimethoxysilane and tetramethylguanidylpropyltrimethoxysilane or salts thereof; formic acid, Lower aliphatic carboxylic acids such as acetic acid, propionic acid, butanoic acid; oxime compounds such as acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime; Examples include aluminum complexes such as minium methoxide di (ethyl acetoacetonate), aluminum isopropoxide di (ethyl acetoacetonate), aluminum tri (ethyl acetoacetonate), etc. Since there are few side reactions, amine compounds or their salts preferable. The amount of the catalyst used is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 3 parts by mass, and most preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the intermediate polymer. The reaction temperature varies depending on the type of catalyst and the amount used, but is preferably 50 to 150 ° C.

（式中、Ｒ^３及びＲ^４は、一般式（１）と同義である。）

（式中、Ｒ^１〜Ｒ^５及びａは、一般式（１）と同義である。）

（式中、Ｒ^６及びＸ^１は、一般式（１）と同義である。） Among the compounds represented by the general formula (1), the compound in which b is 1 is reacted with the vinyl chlorosilane compound represented by the following general formula (1b) to the intermediate polymer represented by the general formula (1a). Then, the intermediate polymer represented by the following general formula (1c) is used, and the silane compound represented by the following general formula (1d) is hydrosilylated to the vinyl group of the intermediate polymer represented by the following general formula (1c). It can obtain by the method of making it react.

(In the formula, R ³ and R ⁴ have the same meaning as in general formula (1).)

(In formula, R < ¹ > -R < ⁵ > and a are synonymous with General formula (1).)

(In the formula, R ⁶ and X ¹ have the same meaning as in general formula (1).)

  In the reaction of the intermediate polymer represented by the general formula (1a) and the vinylchlorosilane compound represented by the general formula (1b), the above general formula (1) is used in the presence of a basic organic solvent such as pyridine and picoline. The intermediate polymer represented by the general formula (1c) by reacting the chlorosilyl group of the vinylchlorosilane compound represented by the general formula (1b) with the silanol group at the end of the intermediate polymer represented by 1a) Is obtained. Examples of the vinylchlorosilane compound represented by the general formula (1b) include dimethylvinylchlorosilane, ethylmethylvinylchlorosilane, diethylvinylchlorosilane, methylphenylvinylchlorosilane, ethylphenylvinylchlorosilane, diphenylvinylchlorosilane, and the like.

In the hydrosilylation reaction of the intermediate polymer represented by the general formula (1c) and the silane compound represented by the general formula (1d), it is preferable to use a platinum-based catalyst. Examples of the platinum-based catalyst include chloroplatinic acid, complexes of chloroplatinic acid and alcohol, aldehyde, ketone, platinum-olefin complex, platinum-carbonylvinylmethyl complex (Ossko catalyst), platinum-divinyltetramethylsiloxane complex ( KaRstedt catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (eg, Pt [P (C ₆ H ₅ ) ₃ ] ₄ , PtCl [P (C ₆ H ₅ ) ₃ ] ₃ , Pt [P (C ₄ H ₉ ) ₃ ) ₄ ], platinum-phosphite complexes (eg, Pt [P (OC ₆ H ₅ ) ₃ ] ₄ ), Pt [P (OC ₄ H ₉ ) ₃ ] ₄ ) , Dicarbonyldichloroplatinum and the like. From the viewpoint of reactivity, the amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, and most preferably 0.001 to 0.1% by mass of the total amount of each raw material. The reaction temperature is preferably room temperature (25 ° C.) to 130 ° C., and a conventionally known solvent such as toluene, hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used during the reaction.

  Examples of the silane compound represented by the general formula (1d) include methyldimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, ethyldiethoxysilane, propyldimethoxysilane, butyldimethoxysilane, phenyldimethoxysilane, trimethoxysilane, and trimethoxysilane. Examples include ethoxysilane, tripropoxysilane, and tributoxysilane.

  The polysiloxane compound represented by the general formula (1) is useful as a base resin of a moisture curable resin composition, and the siloxane compound represented by the general formula (1) as a component (A) and (B The composition containing a curing catalyst as a component can be suitably used as a moisture curable resin composition. As a curing catalyst of the component (B) of the moisture curable resin composition of the present invention, dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin diacetate, dibutyltin salt and ethyl orthosilicate Organic tin compounds such as reaction products of: tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate, titanium tetrakis (ethylene glycol monomethyl ether), titanium tetrakis (ethylene glycol monoethyl ether), titanium tetrakis (ethylene glycol monobutyl ether) Titanium compounds such as: zirconium (acetylacetone), zirconium tris (acetylacetone), zirconium tetrakis (ethylene glycol monomethyl) Organic) zirconium compounds such as zirconium tetrakis (ethylene glycol monoethyl ether) and zirconium tetrakis (ethylene glycol monobutyl ether); metal carboxylates such as lead octylate, lead naphthenate, nickel naphthenate and cobalt naphthenate; aluminum Examples thereof include metal acetyl acetate complexes such as acetyl acetate complexes; metal acetylacetonate complexes such as vanadium acetylacetonate complexes, etc. Titanium compounds are preferred because of excellent reactivity and low toxicity.

  When the amount of the curing catalyst that is the component (B) of the moisture curable resin composition of the present invention is too small, curing may be insufficient, and when it is too large, an effect of increasing the amount corresponding to the blending amount is obtained. In addition, since the curing catalyst may adversely affect physical properties such as heat resistance, the curing catalyst is preferably 0.005 to 10 parts by mass with respect to 100 parts by mass of the moisture curable resin composition of the present invention. -7 mass parts is still more preferable, and 0.1-5 mass parts is the most preferable.

（式中、Ｒ^７〜Ｒ^１０は各々独立して炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表し、Ｒ^１１は炭素数１〜４のアルキル基を表し、Ｘ^２は炭素数１〜４のアルキル基、炭素数６〜１０のアリール基又は炭素数１〜４のアルコキシ基を表し、ｃは、一般式（２）で表される化合物の質量平均分子量を１０００〜１００万とする数を表し、ｄ及びｅは各々独立して０又は１を表す。） The moisture curable resin composition of the present invention preferably further contains a siloxane compound represented by the following general formula (2) because the curability is improved.

(Wherein R ^{7 to} R ¹⁰ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ¹¹ represents an alkyl group having 1 to 4 carbon atoms, and X ² Represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and c represents a mass average molecular weight of the compound represented by the general formula (2) from 1000 to 1000. (The number is 1 million, and d and e each independently represent 0 or 1.)

In the general formula (2) ^represents the R 7 ^{to R 10} are each independently an alkyl group or an aryl group having 6 to 10 carbon atoms having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and / or the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ and R ² in the general formula (1). Each of R ⁷ and R ⁸ may be the same group or a combination of different groups. From the viewpoint of tackiness, an alkyl group having 1 to 4 carbon atoms is preferable, methyl is more preferable, and from the viewpoint of heat resistance, an aryl group having 6 to 10 carbon atoms is preferable, and phenyl is more preferable. When the ratio of the aryl group in R ⁷ and R ⁸ is too large, the adhesiveness of the cured product is lowered. Therefore, R ⁷ and R ⁸ are an alkyl group having 1 to 4 carbon atoms and 6 carbon atoms. Is preferably a combination of 10 to 10 aryl groups, and the ratio of aryl groups having 6 to 10 carbon atoms in R ⁷ and R ⁸ is preferably 1 to 40 mol%, and 3 to 30 mol%. More preferably, it is most preferably 10 to 25 mol%. R ⁹ and R ¹⁰ are preferably methyl because the raw materials are easily available and the reactivity of the raw materials is good.

R ¹¹ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include groups exemplified for R ⁵ and R ⁶ in the general formula (1). R ¹¹ is preferably methyl, ethyl, or propyl, and more preferably methyl or ethyl, because a hydrolysis reaction easily occurs.

X ² represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the alkoxy group having 1 to 4 carbon atoms include the groups exemplified for X ¹ in the general formula (1). X ² is preferably methyl, ethyl, methoxy, or ethoxy since hydrolyzability is good, and the storage stability of the moisture-curable resin composition of the present invention is good, so that methyl and ethyl are further added. preferable.

  In General formula (2), c represents the number which makes the mass mean molecular weight of the compound represented by General formula (2) 1000-1 million. When the mass average molecular weight of the compound represented by the general formula (2) is smaller than 1000, the obtained cured product has insufficient tackiness, and when it is larger than 1 million, the viscosity becomes high and handling properties are increased. descend. The mass average molecular weight of the compound represented by the general formula (2) is preferably 1500 to 50,000, more preferably 2000 to 30,000, and most preferably 2500 to 10,000. d and e represent 0 or 1, and d and e are preferably 0 because they can be produced by a simple process.

  In the moisture curable resin composition of the present invention, when the content of the component (C) is too small, a sufficient effect cannot be exhibited, and when it is too large, the adhesiveness of the cured product may be lowered. The content of component (C) is preferably 0.05 to 15 parts by mass, more preferably 0.2 to 10 parts by mass, and most preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of component (A). .

（式中、Ｒ^７、Ｒ^８及びｃは、一般式（２）と同義である。） Among the siloxane compounds represented by the general formula (2), a compound in which d and e are 0 is a trialkoxysilane compound or a tetraalkoxy group in the terminal silanol group of the intermediate polymer represented by the following general formula (2a). It can be obtained by reacting a silane compound.

(In formula, R < ⁷ >, R < ⁸ > and c are synonymous with General formula (2).)

  The reaction between the intermediate polymer represented by the general formula (2a) and the trialkoxysilane compound or the tetraalkoxysilane compound is performed by reacting the intermediate polymer represented by the general formula (1a) with the trialkoxysilane compound or the tetraalkoxysilane. The trialkoxysilane compound or tetraalkoxysilane compound or tetraalkoxysilane compound exemplified in the reaction with the intermediate polymer represented by the general formula (1a) may be used in the same manner as the reaction with the compound. Is mentioned.

（式中、Ｒ^１９は炭素数１〜４のアルキル基を表し、Ｒ^７、Ｒ^８及びｃは、一般式（２）と同義である。） The intermediate polymer represented by the general formula (2a) is a hydrolytic condensation of a dichlorosilane compound or a dialkoxysilane compound, or a terminal alkoxy group of the intermediate polymer represented by the following general formula (2b) is hydrolyzed. Can be obtained.

(In the formula, R ¹⁹ represents an alkyl group having 1 to 4 carbon atoms, and R ⁷ , R ⁸ and c have the same meanings as in the general formula (2).)

  Preferred dichlorosilane compounds used for hydrolysis condensation of dichlorosilane compounds or dialkoxysilane compounds include dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, methylethyldichlorosilane, methylphenyldichlorosilane, and ethylphenyldichlorosilane. Diphenyldichlorosilane and the like. Preferred dialkoxysilane compounds include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, ethylphenyldimethoxysilane, diphenyldimethoxysilane, dimethyl Diethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, methylethyldiethoxysilane Methylphenyl diethoxy silane, ethyl phenyl diethoxy silane, and diphenyl diethoxy silane and the like.

  Hydrolytic condensation of a dichlorosilane compound or dialkoxysilane compound is produced by hydrolyzing a halosilane group or alkoxysilane group in water or an organic solvent containing water to produce a silanol group (Si-OH group). It progresses by condensing silanol groups or silanol groups and alkoxysilyl groups. Examples of the organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran and the like. In order to accelerate the reaction, it is preferable to use a catalyst. Specifically, inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p -Organic acids such as toluenesulfonic acid and monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; amine compounds such as trimethylamine, triethylamine, monoethanolamine and diethanolamine (organic base) These may be used, and one of these may be used, or two or more may be used in combination. The temperature of the hydrolysis / condensation reaction varies depending on the type of solvent, the type and amount of the catalyst, etc., but is preferably 0 to 80 ° C, more preferably 5 to 50 ° C, and most preferably 8 to 30 ° C.

  The intermediate polymer represented by the general formula (2b) can be obtained by the same method as the intermediate polymer represented by the general formula (1a). Hydrolysis of the terminal alkoxy group of the intermediate polymer represented by the general formula (2b) may be performed using an inorganic acid such as hydrochloric acid, phosphoric acid, sulfuric acid or the like as a catalyst.

（式中、Ｒ^７〜Ｒ^１０及びｃは、一般式（２）と同義である。）

（式中、Ｒ^１１及びＸ^２は、一般式（２）と同義である。）

（式中、Ｒ^７〜Ｒ^１０及びｃは、一般式（２）と同義である。）

（式中、Ｒ^１１及びＸ^２は、一般式（２）と同義である。） Among the siloxane compounds represented by the general formula (2), a compound in which d and e are 1 is represented by the following general formula (2d) on the vinyl group of the intermediate polymer represented by the following general formula (2c). Can be obtained by a method of reacting a silane compound or a method of reacting a vinyl silane compound represented by the following general formula (2f) with the SiH group of the intermediate polymer represented by the following general formula (2e), The former is preferred because it is easy to obtain industrial raw materials.

(In formula, R < ⁷ > -R < ¹⁰ > and c are synonymous with General formula (2).)

(In the formula, R ¹¹ and X ² have the same meaning as in the general formula (2).)

(In formula, R < ⁷ > -R < ¹⁰ > and c are synonymous with General formula (2).)

(In the formula, R ¹¹ and X ² have the same meaning as in the general formula (2).)

  Reaction of intermediate polymer represented by general formula (2c) with silane compound represented by general formula (2d), and intermediate polymer represented by general formula (2e) and general formula (2f) In the hydrosilylation reaction of the vinylsilane compound represented by general formula (1c), the reaction is carried out under the same conditions as in the hydrosilylation reaction of the intermediate polymer represented by general formula (1c) and the silane compound represented by general formula (1d). You can do it.

  Examples of the silane compound represented by the general formula (2d) include compounds exemplified for the silane compound represented by the general formula (1d).

  Examples of the vinylsilane compound represented by the general formula (2f) include methylvinyldimethoxysilane, methylvinyldiethoxysilane, ethylvinyldimethoxysilane, ethylvinyldiethoxysilane, propylvinyldimethoxysilane, butylvinyldimethoxysilane, phenyl Examples include vinyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, and vinyltributoxysilane.

（式中、Ｒ^９及びＲ^１０は、一般式（２）と同義である。）

（式中、Ｒ^９及びＲ^１０は、一般式（２）と同義である。） The intermediate polymer represented by the general formula (2c) is a method in which the intermediate polymer represented by the general formula (2a) is reacted with a vinylchlorosilane compound represented by the following general formula (2g), or the following general polymer The former is preferred because it can be obtained by a method of inserting and adding a cyclic siloxane compound to the divinylsiloxane compound represented by the formula (2h), and there are few side reactions and the molecular weight can be easily controlled.

(In the formula, R ⁹ and R ¹⁰ have the same meaning as in the general formula (2).)

(In the formula, R ⁹ and R ¹⁰ have the same meaning as in the general formula (2).)

  Examples of the vinylchlorosilane compound represented by the general formula (2g) include dimethylvinylchlorosilane, ethylmethylvinylchlorosilane, diethylvinylchlorosilane, methylphenylvinylchlorosilane, ethylphenylvinylchlorosilane, and diphenylvinylchlorosilane. The reaction between the intermediate polymer represented by the general formula (2a) and the vinylchlorosilane compound represented by the general formula (2g) is carried out in the presence of pyridine, picoline and the like at a reaction temperature of 40 to 120 ° C., preferably 60 to What is necessary is just to perform at 90 degreeC.

  Examples of the divinylsiloxane compound represented by the general formula (2h) include 1,1,3,3-tetramethyl-1,3-divinylsiloxane and 1,1,3,3-tetraethyl-1,3-divinylsiloxane. 1,3-dimethyl-1,3-diphenyl-1,3-divinylsiloxane, 1,1,3,3-tetraphenyl-1,3-divinylsiloxane, and the like. Examples thereof include the cyclic siloxane compounds exemplified in the synthesis of the intermediate polymer represented by the formula (1a).

  An acid catalyst or a base catalyst is used for the insertion addition reaction of the cyclic siloxane compound to the divinylsiloxane compound represented by the general formula (2h). Examples of the acid catalyst include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, activated clay, and sulfated zirconia. Examples of the basic catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide. And the base catalyst. As a catalyst for the insertion addition reaction, a base catalyst is preferable because of good reactivity, and potassium hydroxide is more preferable. The reaction temperature is preferably 80 to 250 ° C, more preferably 100 to 200 ° C, and most preferably 120 to 180 ° C. In the above ring-opening polymerization, dibutyl ether, toluene, xylene or the like may be used as a solvent, if necessary.

（式中、Ｒ^９及びＲ^１０は、一般式（２）と同義である。）

（式中、Ｒ^９及びＲ^１０は、一般式（２）と同義である。） The intermediate polymer represented by the general formula (2e) is a method in which the intermediate polymer represented by the general formula (2a) is reacted with a chlorosilane compound represented by the following general formula (2i), or the following general formula: The former is preferable because it can be obtained by a method of inserting and adding a cyclic siloxane compound to the siloxane compound represented by (2j), has few side reactions, and easily controls the molecular weight.

(In the formula, R ⁹ and R ¹⁰ have the same meaning as in the general formula (2).)

(In the formula, R ⁹ and R ¹⁰ have the same meaning as in the general formula (2).)

  Examples of the chlorosilane compound represented by the general formula (2i) include dimethylchlorosilane, ethylmethylchlorosilane, diethylchlorosilane, methylphenylchlorosilane, ethylphenylchlorosilane, and diphenylchlorosilane. The reaction between the intermediate polymer represented by the general formula (2a) and the chlorosilane compound represented by the general formula (2i) is carried out in the presence of pyridine, picoline and the like, at a reaction temperature of 40 to 120 ° C., preferably 60 to 90. What is necessary is to carry out at a degree C

  Examples of the siloxane compound represented by the general formula (2j) include 1,1,3,3-tetramethylsiloxane, 1,1,3,3-tetraethylsiloxane, and 1,3-dimethyl-1,3-diphenylsiloxane. 1,1,3,3-tetraphenylsiloxane and the like, and examples of the cyclic siloxane compound include the cyclic siloxane compounds exemplified in the synthesis of the intermediate polymer represented by the following general formula (1a).

  An acid catalyst is used for the insertion addition reaction of the cyclic siloxane compound to the siloxane compound represented by the general formula (2h). Examples of the acid catalyst include sulfuric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, activated clay, and sulfated zirconia. As a catalyst for the insertion addition reaction, methanesulfonic acid is preferable because of its good reactivity. The reaction temperature is preferably 80 to 250 ° C, more preferably 100 to 200 ° C, and most preferably 120 to 180 ° C. In the above ring-opening polymerization, dibutyl ether, toluene, xylene or the like may be used as a solvent, if necessary.

（式中、Ｒ^７〜Ｒ^１０及びｃは、一般式（２）と同義である。） Among the siloxane compounds represented by the general formula (2), a compound in which one of d and e is 1 and the other is 0 is cyclic starting from a vinylsilane compound represented by the following general formula (2k) A siloxane compound is subjected to ring-opening polymerization using a catalyst to synthesize an intermediate polymer represented by the following general formula (2m), and a silane compound represented by the above general formula (2d) at the vinyl terminal of the intermediate polymer Can be obtained by reacting a trialkoxysilane compound or a tetraalkoxysilane compound with a silanol terminal.

(In formula, R < ⁷ > -R < ¹⁰ > and c are synonymous with General formula (2).)

（式中、Ｒ^１２〜Ｒ^１７は各々独立して炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表し、Ｒ^１８は炭素数１〜４のアルキル基を表し、ｆは、一般式（３）で表される化合物の質量平均分子量を１０００〜１００万とする数を表し、ｇ及びｈは各々独立に０又は１を表す。） The moisture curable resin composition of the present invention preferably further contains a siloxane compound represented by the following general formula (3) as the component (D) because the adhesiveness is improved.

(Wherein R ^{12 to} R ¹⁷ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ¹⁸ represents an alkyl group having 1 to 4 carbon atoms, and f is And represents a number in which the mass average molecular weight of the compound represented by the general formula (3) is 1,000 to 1,000,000, and g and h each independently represent 0 or 1.)

In the general formula (3), R ^{12 to} R ¹⁷ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ and R ² in the general formula (1). Each of R ¹² and R ¹³ may be the same group or a combination of different groups. From the viewpoint of tackiness, an alkyl group having 1 to 4 carbon atoms is preferable, methyl is more preferable, and from the viewpoint of heat resistance, an aryl group having 6 to 10 carbon atoms is preferable, and phenyl is more preferable. When the ratio of the aryl group in R ¹² and R ¹³ is too large, the adhesiveness of the cured product is lowered, so that R ¹² and R ¹³ are an alkyl group having 1 to 4 carbon atoms and 6 carbon atoms. Is preferably a combination of 10 to 10 aryl groups, and the ratio of aryl groups having 6 to 10 carbon atoms in R ¹² and R ¹³ is preferably 1 to 40 mol%, and 3 to 30 mol%. More preferably, it is most preferably 10 to 25 mol%. As R < ¹⁴ > -R < ¹⁷ >, since acquisition of a raw material is easy and the reactivity of a raw material is also favorable, methyl is preferable.

R ¹⁸ represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms, such as the groups exemplified for by R ⁵ in the general formula (1). R ¹⁸ is preferably methyl, ethyl, or propyl, and more preferably methyl or ethyl because hydrolysis reaction easily occurs.

  In General formula (3), f represents the number which makes the mass mean molecular weight of the compound represented by General formula (3) 1000-100 million. When the mass average molecular weight of the compound represented by the general formula (3) is smaller than 1000, the obtained cured product has insufficient tackiness, and when it is larger than 1,000,000, the viscosity becomes high and handling properties are increased. descend. The mass average molecular weight of the compound represented by the general formula (3) is preferably 2000 to 50,000, more preferably 3000 to 30,000, and most preferably 3500 to 10,000. g and h each independently represent 0 or 1, and g and h are preferably 0 because they can be produced by a simple process.

  In the moisture curable resin composition of the present invention, when the content of the siloxane compound represented by the general formula (3) is too small, sufficient effects cannot be exhibited, and when the content is too large, the curability of the cured product is not achieved. The content of the siloxane compound represented by the general formula (3) is 5 to 200 parts by mass with respect to 100 parts by mass of the siloxane compound represented by the general formula (1). Preferably, 10-150 mass parts is more preferable, and 20-120 mass parts is the most preferable.

（式中、Ｒ^１２、Ｒ^１３、Ｒ^１６〜Ｒ^１８及びｆは、一般式（３）と同義である。）

（式中、Ｒ^１２、Ｒ^１３、Ｒ^１６、Ｒ^１７及びｆは、一般式（３）と同義である。） Among the siloxane compounds represented by the general formula (3), a compound in which g and h are 0 is a silanol group at the terminal of the intermediate polymer (3a) or the intermediate polymer represented by the following general formula (3b). Can be obtained by making an alkoxysilyl group with an ortho ester compound or a tetraalkoxymethane compound.

(In formula, R < ¹² >, R < ¹³ >, R < ¹⁶ > -R < ¹⁸ > and f are synonymous with General formula (3).)

(In formula, R < ¹² >, R <^13> , R <^16> , R < ¹⁷ > and f are synonymous with General formula (3).)

  The intermediate polymer represented by the general formula (3a) can be obtained by the same method as the intermediate polymer represented by the general formula (1a). The intermediate polymer represented by the general formula (3b) is The intermediate polymer represented by the general formula (2a) can be obtained by the same method.

  Examples of orthoester compounds include trimethoxymethane, triethoxymethane, tripropoxymethane, triisopropoxymethane, tributoxymethane, trimethoxyethane, triethoxyethane, tripropoxyethane, triisopropoxyethane, and tributoxyethane. Examples of the tetraalkoxymethane compound include tetramethoxymethane, tetraethoxymethane, and tetraisopropoxymethane. Among these, trimethoxymethane, triethoxymethane, trimethoxyethane, and tetramethoxymethane are preferable because of good reactivity.

  When the silanol group is converted to an alkoxysilyl group by an ortho ester compound or a tetraalkoxymethane compound, an excessive amount of orthoester compound or tetraalkoxymethane compound is used with respect to the silanol group, and the temperature is about 100 to 150 ° C. After the reaction by heating, the unreacted orthoester compound or tetraalkoxymethane compound may be removed.

（式中、Ｒ^１２〜Ｒ^１５、及びｆは、一般式（３）と同義である。）

（式中、Ｒ^１２〜Ｒ^１５、及びｆは一般式（３）と同義である。） Among the siloxane compounds represented by the general formula (3), a compound in which g and h are 1 is represented by the following general formula (3d) on the vinyl group of the intermediate polymer represented by the following general formula (3c). Can be obtained by a method of reacting a silane compound, or an intermediate polymer represented by the following general formula (3e) with a vinyl silane compound represented by the following general formula (3f). The former is preferred because the raw materials are easily available.

(In formula, R < ¹² > -R < ¹⁵ > and f are synonymous with General formula (3).)

(In formula, R < ¹² > -R < ¹⁵ > and f are synonymous with General formula (3).)

  Reaction of intermediate polymer represented by general formula (3c) with silane compound represented by general formula (3d), and intermediate polymer represented by general formula (3e) and general formula (3f) The reaction of the vinyl silane compound represented by the general formula (2c) is represented by the reaction of the intermediate polymer represented by the general formula (2c) and the silane compound represented by the general formula (2d), and the general formula (2e). The reaction may be performed under the same conditions as the reaction between the intermediate polymer and the vinylsilane compound represented by the general formula (2f).

  Examples of the silane compound represented by the general formula (3d) include dimethylmethoxysilane, dimethylethoxysilane, diethylmethoxysilane, diethylethoxysilane, dipropylmethoxysilane, dibutylmethoxysilane, diphenylmethoxysilane, methylethylmethoxysilane, methyl Examples include ethylethoxysilane, methylpropylmethoxysilane, methylbutylmethoxysilane, and methylphenylmethoxysilane.

  Examples of the vinylsilane compound represented by the general formula (3f) include dimethylvinylmethoxysilane, dimethylvinylethoxysilane, diethylvinylmethoxysilane, diethylvinylethoxysilane, dipropylvinylmethoxysilane, dibutylvinylmethoxysilane, and diphenylvinyl. Examples include methoxysilane, methylethylvinylmethoxysilane, methylethylvinylethoxysilane, methylpropylvinylmethoxysilane, methylbutylvinylmethoxysilane, and methylphenylvinylmethoxysilane.

  The intermediate polymer represented by the general formula (3c) can be obtained by the same method as the intermediate polymer represented by the general formula (2c), and the intermediate polymer represented by the general formula (3e). The polymer can be obtained by the same method as the intermediate polymer represented by the general formula (2e).

（式中、Ｒ^１２〜Ｒ^１５、及びｆは、一般式（３）と同義である。） Among the siloxane compounds represented by the general formula (3), a compound in which one of g and h is 1 and the other is 0 is cyclic starting from a vinylsilane compound represented by the following general formula (3g) A siloxane compound is subjected to ring-opening polymerization using a catalyst to synthesize an intermediate polymer represented by the following general formula (3h), and the silane compound represented by the above general formula (3d) at the vinyl terminal of the intermediate polymer Can be obtained by reacting an orthoester compound or a tetraalkoxymethane compound at the silanol terminal.

(In formula, R < ¹² > -R < ¹⁵ > and f are synonymous with General formula (3).)

  The moisture curable resin composition of the present invention further includes a filler because the fluidity and thixotropy are improved and the heat conductivity of the cured product of the present invention can be improved and heat dissipation can be imparted. It is preferable. Examples of the filler include aluminum oxide, magnesium oxide, calcium oxide, silicon oxide, titanium oxide, iron oxide, zinc oxide, beryllium oxide, silicon carbide, calcium carbonate, magnesium carbonate, zinc carbonate, aluminum nitride, boron nitride, and silicon nitride. Inorganic fillers such as aluminum hydroxide, magnesium hydroxide, calcium sulfate and barium sulfate; metal fillers such as silver, copper, aluminum, iron, zinc, nickel and tin; carbon fillers such as carbon and graphite It is done. When high electrical insulation is required, it is preferable to use only an inorganic filler. The said filler may be used individually by 1 type, and may use 2 or more types together.

  In addition to this, the moisture curable resin composition of the present invention may be added with an antioxidant, an antioxidant, a UV absorber, a flame retardant, an antifungal agent, a solvent, a fragrance, a pigment, a dye, and the like as necessary. Also good.

  In the moisture curable resin composition of the present invention, the alkoxysilyl group is hydrolyzed to produce a silanol group and an alcohol, and curing occurs by dehydration condensation between the silanol groups. The curing conditions of the moisture curable resin composition of the present invention vary depending on the type and amount of the curing catalyst, and are not particularly limited. However, when the temperature is 25 ° C. or higher and the humidity is 50%, the curing can be performed in 10 to 30 hours. Thereafter, it is preferable to further heat at 100 to 200 ° C. for 0.5 to 3 hours for the purpose of removing the generated alcohol and promoting dehydration condensation between silanol groups.

  The moisture curable resin composition of the present invention can be applied to automobiles, electrical appliances, civil engineering sealants or sealants, adhesives, paints, coating materials, potting materials, molded articles, and the like. Since the moisture curable resin composition of the present invention is particularly excellent in heat resistance and tackiness, it can be suitably used as a sealing material and adhesive for equipment exposed to high temperatures. In particular, the moisture curable resin composition of the present invention blended with a filler having high thermal conductivity can be suitably used for a heat radiating sheet of electronic equipment.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these Examples. Unless otherwise specified, “parts” and “%” in the examples are based on mass.

[Synthesis Example 1] Synthesis of Intermediate a1 In a glass reaction vessel equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 872 g (1.1 mol) of octaphenyltetrasiloxane and 1305 g (4.4 mol) of octamethyltetrasiloxane. , And 70 g (1 mol) of potassium methoxide were allowed to react under stirring in a nitrogen atmosphere at 150 ° C. for 2 hours. After cooling and washing the reaction solution with ion-exchanged water, water was distilled off under reduced pressure at 100 ° C. to obtain 2033 g of intermediate a1 (yield 92%). The intermediate a1 corresponds to the compound in which R ⁵ is methyl in the general formula (1a) and the compound in which R ¹⁸ is methyl in the general formula (3a), respectively.

Synthesis Example 2 Synthesis of Compound A1 In a glass reaction vessel equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 500 g of intermediate a1, 78 g (0.5 mol) of methyltrimethoxysilane, and acetic acid 0 as a catalyst .6 g (0.1 mmol) was charged and the reaction was allowed to stir at 90 ° C. for 2 hours under a nitrogen atmosphere. The reaction solution was depressurized at 90 ° C. to remove unreacted methyltrimethoxysilane, acetic acid and produced methanol, and after filtration, the low boiling point component was further removed using a thin-film distillation apparatus, and compound A1 was obtained. Obtained. Compound A1 is a compound in which R ⁵ , R ⁶ and X ¹ are methyl, R ¹ and R ² are methyl and phenyl in the general formula (1), and methyl / phenyl = 4/1 molar ratio and b is 0 It is. Moreover, the mass average molecular weight of Compound A1 was 4500.

[Synthesis Example 3] Synthesis of Compound A2 In Synthesis Example 2, the same operation as in Synthesis Example 2 except that 76 g (0.5 mol) of tetramethoxysilane was used instead of 78 g (0.5 mol) of methyltrimethoxysilane. To obtain Compound A2. Compound A2 has the following formula (1): R ⁵ and R ⁶ are methyl, X ¹ is methoxy, R ¹ and R ² are combinations of methyl and phenyl, and methyl / phenyl = 4/1 molar ratio, b is 0 It is a compound of this. Moreover, the mass average molecular weight of Compound A2 was 4500.

[Synthesis Example 4] Synthesis of Intermediate a2 In a glass reaction vessel equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 200 g of intermediate a1, 78 g (0.32 mol) of dimethylvinylchlorosilane, and a solvent 100 g of pyridine was charged and the reaction was allowed to stir at 90 ° C. for 2 hours under a nitrogen atmosphere. The reaction solution was depressurized at 90 ° C. to remove unreacted dimethylvinylchlorosilane and pyridine, then washed with ion-exchanged water, and further depressurized at 100 ° C. to remove the water and remove intermediate a2. Obtained. The intermediate a2 is a compound corresponding to the general formula (1c).

[Synthesis Example 5] Synthesis of Compound A3 In a glass reaction container containing intermediate a2, 36 g (0.3 mol) of methyldimethoxysilane, 20 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) as a catalyst, and as a solvent 100 g of toluene was charged and reacted by stirring at 60 ° C. for 15 hours. Thereafter, unreacted methyldimethoxysilane and toluene were distilled off under reduced pressure at 100 ° C. and filtered, and then the low boiling point component was removed using a thin film distillation apparatus to obtain Compound A3. Compound A3 is a compound in which, in General Formula (1), R ^{3 to} R ⁶ and X ¹ are methyl, R ¹ and R ² are methyl and phenyl, and methyl / phenyl = 4/1 molar ratio and b is 1 It is. Further, the mass average molecular weight of the compound A3 was 4600.

[Synthesis Example 6] Synthesis of Intermediate c1 A glass reaction vessel equipped with a nitrogen gas inlet tube, a thermometer, a reflux device and a stirrer was charged with 500 g of intermediate a1, 250 g of 20% aqueous hydrochloric acid, and 250 g of toluene as a solvent. The mixture was stirred at 100 ° C. for 15 hours. The hydrochloric acid aqueous solution layer was removed from the reaction solution, and the reaction solution was washed with ion-exchanged water and then decompressed at 100 ° C. to remove water and toluene to obtain 480 g of intermediate c1 (yield 96%). The intermediate c1 corresponds to the compound represented by the general formula (2a).

Synthesis Example 7 Synthesis of Compound C1 In a glass reaction vessel equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 200 g of intermediate c1, 44 g (0.32 mol) of methyltrimethoxysilane, and acetic acid 0 as a catalyst .24 g (0.4 mmol) was charged and the reaction was allowed to stir at 90 ° C. for 2 hours under a nitrogen atmosphere. The reaction solution was depressurized at 90 ° C. to remove unreacted methyltrimethoxysilane, acetic acid and generated methanol, and after filtration, the low boiling point component was further removed using a thin-film distillation apparatus to give compound C1. Obtained. Compound C1 is a compound in which, in General Formula (2), R ¹¹ and X ² are methyl, R ⁷ and R ⁸ are a combination of methyl and phenyl, methyl / phenyl = 4/1 molar ratio, and d and e are 0 is there. Further, the mass average molecular weight of the compound C1 was 4200.

[Synthesis Example 8] Synthesis of Compound C2 The same operation as in Synthesis Example 7 except that in Synthesis Example 7, instead of 44 g (0.32 mol) of methyltrimethoxysilane, 49 g (0.32 mol) of tetramethoxysilane was used. And compound C2 was obtained. Compound C2 has the following formula (2): R ¹¹ is methyl, X ² is methoxy, R ⁷ and R ⁸ are combinations of methyl and phenyl, and methyl / phenyl = 4/1 molar ratio, d and e are 0 A compound. Further, the mass average molecular weight of the compound C2 was 4200.

[Synthesis Example 9] Synthesis of Intermediate c2 In a glass reaction vessel equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 200 g of intermediate c1, 78 g (0.32 mol) of dimethylvinylchlorosilane, and as a solvent 100 g of pyridine was charged and the reaction was allowed to stir at 90 ° C. for 2 hours under a nitrogen atmosphere. The reaction solution was depressurized at 90 ° C. to remove unreacted dimethylvinylchlorosilane and pyridine, then washed with ion-exchanged water, and further depressurized at 100 ° C. to remove the water and remove intermediate c2. Obtained. The intermediate c2 is a compound corresponding to the general formula (2c).

Synthesis Example 10 Synthesis of Compound C3 In a glass reaction vessel containing intermediate c2, 36 g (0.3 mol) of methyldimethoxysilane, 20 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) as a catalyst, and as a solvent 100 g of toluene was charged and reacted by stirring at 60 ° C. for 15 hours. Thereafter, unreacted methyldimethoxysilane and toluene were distilled off under reduced pressure at 100 ° C., followed by filtration, and further, low-boiling components were removed using a thin film distillation apparatus to obtain Compound C3. Compound C3 has the following formula (2): R ⁸ and X ³ are methyl, R ⁷ and R ⁸ are a combination of methyl and phenyl, methyl / phenyl = 4/1 molar ratio, R ⁷ and R ⁸ are 1 A compound. Further, the mass average molecular weight of the compound C3 was 4300.

[Synthesis Example 11] Synthesis of Compound D1 Into a glass reaction vessel equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 300 g of intermediate a1 and 53 g (0.5 mmol) of trimethoxymethane were charged, and under a nitrogen atmosphere, The reaction was allowed to stir at 100 ° C. for 6 hours. The reaction solution was depressurized at 100 ° C. to remove unreacted trimethoxymethane and produced methyl formate, and after filtration, the low boiling point component was further removed using a thin film distillation apparatus to obtain Compound D1. It was. Compound D1 has the following formula (3): R ¹⁸ is methyl, R ¹² , R ¹³ , R ¹⁶ and R ¹⁷ are a combination of methyl and phenyl, methyl / phenyl = 4/1 molar ratio, and g and h are 0 It is a compound of this. In addition, the mass average molecular weight of the compound D1 was 4500.

(Preparation of moisture curable resin composition)
Using compounds A1, A2, A3, B1, C1, C2, C3, and D1, the moisture curable resin compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were prepared with the formulations shown in Table 1. In addition, the number in () in a table | surface represents the mass ratio of each component. Compound B1 is diisopropoxytitanium diacetylacetonate.

  About the moisture curable resin composition of Examples 1-15 and Comparative Examples 1-6, the test piece was produced by the following method and the following evaluation was performed. The results are shown in Table 1.

[How to create a test piece]
A moisture curable resin composition was applied to a glass plate having a length of 10 cm and a width of 10 cm so as to have a thickness of 0.1 mm, and stored in a constant temperature and humidity chamber at a temperature of 40 ° C. and a relative humidity of 50% for 24 hours. It heated for 2 hours with the thermostat of ° C, and used for the test piece.

[Bleed test]
The wrapping paper was pressed against the surface of the test piece, and the degree of bleeding due to the wetting of the wrapping paper was determined according to the following criteria.
A: The medicine wrapping paper is not wet and bleeding is not observed.
○: The drug wrapping paper is slightly wet and no bleed is observed.
Δ: Medicine wrapping paper is slightly wet and slightly bleed is observed.
X: The medicine wrapping paper is clearly wet, and there are many bleeds.
Uncured: not cured, no bleed test.

[Adhesion test]
A steel ball having a diameter of 1/4 inch was placed on a horizontally placed test piece, and the tilt angle at which the ball started to move when the tilt angle of the test piece was gradually increased from 0 ° was measured. The larger the tilt angle at which the ball starts to move, the greater the tackiness.

  From the results in Table 1, it can be seen that the cured product obtained from the curable resin composition of the present invention is excellent in heat resistance and adhesiveness.

Claims (4)

A polysiloxane compound represented by the following general formula (1):

(In the formula, R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ⁵ and R ⁶ each independently represent one having 1 to 4 carbon atoms. Represents an alkyl group, X ¹ represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a is a compound represented by the general formula (1) the mass average molecular weight represents the number of a 2,000 to 1,000,000, b will display the 0 or 1, one of ^{R 1} and ^{R 2,} the proportion of the aryl group having 6 to 10 carbon atoms, with 10 to 25 mol% Yes .)   A moisture-curable resin composition comprising a siloxane compound represented by the general formula (1) as a component (A) and a curing catalyst as a component (B). Furthermore, the moisture curable resin composition of Claim 2 containing the siloxane compound represented by following General formula (2) as (C) component.

(Wherein R ^{7 to} R ¹⁰ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ¹¹ represents an alkyl group having 1 to 4 carbon atoms, and X ² Represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and c represents a mass average molecular weight of the compound represented by the general formula (2) from 1000 to 1000. (The number is 1 million, and d and e each independently represent 0 or 1.) Furthermore, the moisture curable resin composition of Claim 2 or 3 containing the siloxane compound represented by following General formula (3) as (D) component.

(Wherein R ^{12 to} R ¹⁷ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ¹⁸ represents an alkyl group having 1 to 4 carbon atoms, and f is And represents a number in which the mass average molecular weight of the compound represented by the general formula (3) is 1,000 to 1,000,000, and g and h each independently represent 0 or 1.)