JP5438447B2 - Method for producing hydrosilyl compound - Google Patents

Description

  The present invention relates to a method for producing a novel hydrosilyl compound. More specifically, the present invention relates to a method for producing a hydrosilyl compound using a Si—H group-containing silicon compound and a carboxylic acid allyl ester as raw materials that can effectively suppress the formation of by-products.

  Silsesquioxane compounds are attracting attention as materials having both the characteristics of inorganic materials having heat resistance, weather resistance, and chemical resistance, and the characteristics of organic materials having flexibility and processability. Patent Document 1 and Patent Document 2 disclose a curable resin composition containing a silsesquioxane compound into which a reactive functional group (oxetanyl group) is introduced. Further, it is described that a cured product formed from the curable resin composition is suitable as a coating agent because the surface hardness is improved.

  Further, Example 14 of Patent Document 3 describes a compound obtained by reacting a methyl silicic acid compound with a caged silsesquioxane compound, but the final product has an isobutyric acid residue and is methacryloyl. Does not have an oxy group.

  By the way, a (meth) acryloyloxy group-containing silsesquioxane is prepared by reacting a cage silsesquioxane containing Si—H group with allyl (meth) acrylate by using a commonly used hydrosilylation reaction. It is known that can be obtained. Since this silsesquioxane has eight (meth) acryloyl groups which are curable functional groups, it has excellent properties such as curability, pattern transferability, and low shrinkage rate, and is a semiconductor resist material. It can be used for various purposes.

However, when the reaction is performed under ordinary conditions, in addition to the target —Si— (CH ₂ ) ₃ OC (O) C (CH ₃ ) ═CH ₂ group, a —Si— (CH ₂ ) ₂ —CH ₃ group is present. There is a problem of being a by-product.

  As a method for suppressing the formation of by-products due to hydrosilylation reaction, Patent Document 4 discloses carboxylic acid 3- (dimethylchlorosilyl) propyl ester in which dimethylchlorosilane and carboxylic acid allyl ester are hydrosilylated using an Ir catalyst. A manufacturing method is disclosed.

JP-A-11-29640 JP-A-11-116682 JP-A-2-67290 JP 2003-96086 A

  However, in the production method disclosed in Patent Document 4, the Si—H group-containing silicon compound is limited to dimethylchlorosilane, and the catalyst is limited to an Ir catalyst. In the hydrosilylation reaction using other substrates and catalysts, the secondary reaction is not possible. There is no suggestion that the production of organisms can be suppressed.

In addition to the manufacturing method disclosed in Patent Document 4, there are the following concerns.
For example, when allyl (meth) acrylate is used as the carboxylic acid allyl ester, the resulting product is high in addition to the silsesquioxane containing the desired curable functional group (methacryloyloxy group). In the concentration, a compound (by-product) having a Si— (CH ₂ ) ₂ —CH ₃ group that is not a curable functional group is included. That is, in the product obtained by the conventional manufacturing method, the number of curable functional groups per unit mass decreases, and the curing characteristics required for the semiconductor resist material application cannot be exhibited. Moreover, in the product obtained by the conventional manufacturing method, the purity of the target silsesquioxane compound varies.

Thus, there has been no report on a production method that can suppress the production of by-products and reduce the variation in purity of the target silsesquioxane compound.
The present invention suppresses the formation of by-products, and can reduce the variation in the purity of the target silsesquioxane compound (stable), and can contain a Si—H group-containing silicon compound (for example, a cage silsesquioxane). It is an object of the present invention to provide a method for producing a hydrosilyl compound using a sun compound) and a carboxylic acid allyl ester (eg, allyl (meth) acrylate) as raw materials.

For example, a caged silsesquioxane that suppresses by-production of —Si— (CH ₂ ) ₂ —CH ₃ group and can provide a high-purity target product with less variation in the purity of the target product (stable). It is an object of the present invention to provide a method for producing a cage silsesquioxane compound having a (meth) acryloyloxy group using a compound and allyl (meth) acrylate as raw materials.

Similarly, -Si- (CH ₂₎ and by-product inhibition of ₂ -CH ₃ group, a highly pure desired product, (stably) less variation in the purity of the target product can be provided, cage Shirusesukioki An object of the present invention is to provide a method for producing a silicon compound having a (meth) acryloyloxy group using a Si-H group-containing silicon compound other than a sun compound and allyl (meth) acrylate as raw materials.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors use a silicon compound having a Si—H group and a carboxylic acid allyl ester compound as raw materials, and carry out a hydrosilylation reaction at a specific raw material quantity ratio. Unlike conventional manufacturing methods, the production of by-products can be suppressed to obtain a product with a high content of the desired silsesquioxane compound (high purity), and the purity of the product It has been found that the variation of the can be reduced. That is, the present invention relates to the following [1] to [7].

[1] A method for producing a hydrosilyl compound in which a Si—H group-containing silicon compound and a carboxylic acid allyl ester compound are hydrosilylated, wherein the Si—H group-containing silicon compound and the Si—H group-containing silicon compound The manufacturing method of the hydrosilyl compound characterized by including the contact process which contacts the said carboxylic acid allyl ester compound equivalent to 2-100 mol in conversion of an allyl group with respect to 1 mol of Si-H groups.
[2] The hydrosilyl group according to [1], wherein the contacting step is performed by adding the Si-H group-containing silicon compound dropwise to a solution containing the carboxylic acid allyl ester compound and a platinum catalyst. Compound production method.
[3] The method for producing a hydrosilyl compound according to [2], wherein the temperature of the solution containing the carboxylic acid allyl ester compound and the platinum catalyst is in the range of room temperature to 80 ° C.
[4] The Si—H group-containing silicon compound is at least one selected from the group consisting of compounds represented by the following formulas (1) to (3): [1] to [3] The manufacturing method of the hydrosilyl compound in any one of.

（式（１）中、Ｒ¹は、それぞれ独立に−ＯＳｉＲ²Ｒ³Ｈ、−ＯＳｉＲ²Ｒ³Ｚ、水素原子またはＺであり、８つのＲ¹のうち、少なくとも１つは、−ＯＳｉＲ²Ｒ³Ｈまたは水素原子であり、Ｚは、それぞれ独立に炭素原子数１〜１０の脂肪族炭化水素基または炭素原子数６〜１４の芳香族炭化水素基であり、Ｒ²およびＲ³はそれぞれ独立に炭素原子数１〜１０の脂肪族炭化水素基または炭素原子数６〜１４の芳香族炭化水素基である。

(In the formula (1), R ¹ are each independently ^{-OSiR 2 R 3 H, -OSiR 2} R 3 Z, a hydrogen atom or Z, among the eight R ^1, at least one, -OSiR ² R ³ H or a hydrogen atom, Z is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and R ² and R ³ are each Independently, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.

R ⁴ and R ⁵ in the formulas (2) and (3) are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. N ¹ is an integer of ¹ to 5, and n ² is an integer of 4 to 10. )
[5] The method for producing a hydrosilyl compound according to any one of [1] to [4], wherein the carboxylic acid allyl ester compound is a compound represented by the following formula (4):

（式（４）中、Ｒ⁶は、炭素原子数１〜１０の脂肪族炭化水素基または下式（ｉ）〜（ｉｉ）で示される基を表す。）

(In the formula (4), R ⁶ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a group represented by the following formulas (i) to (ii)).

（式（ｉ）、（ｉｉ）中Ｒ⁷およびＲ⁸は、それぞれ独立に水素原子または炭素原子数１〜５の脂肪族炭化水素基を示す。）
［６］ 前記ヒドロシリル化合物が、式（５）〜（７）で表される化合物からなる群から選択される少なくとも一種であることを特徴とする［１］〜［５］のいずれかに記載のヒドロシリル化合物の製造方法。

(In formulas (i) and (ii), R ⁷ and R ⁸ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.)
[6] The hydrosilyl compound is at least one selected from the group consisting of compounds represented by formulas (5) to (7), according to any one of [1] to [5] A method for producing a hydrosilyl compound.

（式（５）中、Ｒ⁹は、それぞれ独立に−ＯＳｉＲ²Ｒ³Ｙ、−ＯＳｉＲ²Ｒ³Ｚ、水素原子、ＹまたはＺであり、８つのＲ⁹のうち、少なくとも１つは、−ＯＳｉＲ²Ｒ³ＹまたはＹであり、Ｙはそれぞれ独立に下式（８）で表される基であり、Ｚは、それぞれ独立に炭素原子数１〜１０の脂肪族炭化水素基または炭素原子数６〜１４の芳香族炭化水素基であり、Ｒ²およびＲ³はそれぞれ独立に炭素原子数１〜１０の脂肪族炭化水素基または炭素原子数６〜１４の芳香族炭化水素基である。

(In the formula (5), R ⁹ are each independently ^{-OSiR 2 R 3 Y, -OSiR 2} R 3 Z, a hydrogen atom, Y or Z, of the eight R ^9, at least one, - OSiR ² R ³ Y or Y, each Y is independently a group represented by the following formula (8), and Z is each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or the number of carbon atoms 6 to 14 aromatic hydrocarbon groups, and R ² and R ³ are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.

R ⁴ and R ^{5 in} formulas (6) and (7) are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. N ¹ is an integer of ¹ to 5, n ² is an integer of 4 to 10, and Y is independently a group represented by the following formula (8). )

（式（８）中、Ｒ⁶は、炭素原子数１〜１０の脂肪族炭化水素基または下式（ｉ）〜（ｉｉ）で示される基を表す。）

(In the formula (8), R ⁶ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a group represented by the following formulas (i) to (ii)).

（式（ｉ）、（ｉｉ）中Ｒ⁷およびＲ⁸は、水素原子または炭素原子数１〜５の脂肪族炭化水素基を示す。）

(In formulas (i) and (ii), R ⁷ and R ⁸ represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.)

[7] The Si-H group-containing silicon compound is octakis (dimethylsilyloxy) silsesquioxane, the carboxylic acid allyl ester compound is allyl methacrylate, and the hydrosilyl compound is represented by the following formula (9): The method for producing a hydrosilyl compound according to any one of [1] to [6], wherein the compound is represented by the formula:

（式（９）中のＲ¹⁰は、下式（ｉｖ）で表される。）

(R ¹⁰ in formula (9) is represented by the following formula (iv).)

  According to the method for producing a hydrosilyl compound of the present invention, the content of the silsesquioxane compound, which is the target product, is suppressed by suppressing the formation of by-products from the Si—H group-containing silicon compound and the carboxylic acid allyl ester. A (high purity) product is obtained, and further variations in product purity can be reduced.

  Further, the product obtained by the production method of the present invention has a small amount of by-products, contains a hydrosilyl compound with high purity, and can reduce variations in the purity of the product. When it has a curable functional group such as a (meth) acryloyloxy group, a product capable of exhibiting excellent curing characteristics can be obtained.

  In addition, when a caged silsesquioxane compound is used as the Si-H group-containing silicon compound and allyl (meth) acrylate is used as the carboxylic acid allyl ester, the caged silsesquioxane obtained by the method for producing a hydrosilyl compound of the present invention. Sun compounds are extremely excellent in properties such as curing characteristics and etching selectivity, so resist materials, sealing materials, casting materials, laminated materials, composite materials, adhesives, crack inhibitors, powder coatings, etc. Useful in a wide range of fields and applications.

1A to 1B are diagrams showing ¹ H-NMR spectra of the liquid product produced in Example 1. FIG. 2A to 2B are diagrams showing ¹ H-NMR spectra of the liquid product produced in Example 2. FIG. 3A to 3B are diagrams showing ¹ H-NMR spectra of the liquid product produced in Example 5. FIG. FIG. 4 is a diagram showing the ¹ H-NMR spectrum of the liquid product produced in Comparative Example 2. FIG. 5 is a chart obtained by GPC measurement of the liquid product produced in Example 1. FIG. 6 is a chart obtained by GPC measurement of the liquid product produced in Comparative Example 1.

  The method for producing a hydrosilyl compound of the present invention is a production of a hydrosilyl compound in which a Si—H group-containing silicon compound and a carboxylic acid allyl ester compound are hydrosilylated (addition reaction between a Si—H group and a vinyl group in the allyl group). The carboxylic acid allyl ester compound equivalent to 2 to 100 moles in terms of allyl group per 1 mole of the Si-H group-containing silicon compound and the Si-H group-containing silicon compound. And a contact step of contacting the substrate.

  In the contacting step, the Si—H group-containing silicon compound and the carboxylic acid allyl ester compound corresponding to 3 to 50 mol in terms of allyl group with respect to 1 mol of the Si—H group of the Si—H group-containing silicon compound. Is more preferable, and more preferably 5 to 20 mol. “Allyl group conversion” means that the calculation is based on the number of allyl groups contained in one molecule. That is, when using the carboxylic acid allyl ester compound which has two allyl groups in 1 molecule, 2-100 mol equivalent becomes 1-50 mol in conversion of an allyl group.

When the molar amount of the carboxylic acid allyl ester compound converted to an allyl group with respect to 1 mol of the Si—H group of the Si—H group-containing silicon compound is less than 2 mol, —Si— (CH ₂ ) ₂ —CH ₃ By-product formation cannot be sufficiently suppressed, and if it exceeds 100 moles, it takes more time than necessary to remove the unreacted carboxylic acid allyl ester compound after the reaction.

The excess unreacted carboxylic acid allyl ester compound removed after the reaction can be used again in the production method of the present invention.
_{Further, -Si- (CH 2) 2 -CH} 3 group of the by-product from the viewpoint efficiently inhibit, the Si-H group-containing silicon compound, the solution containing the carboxylic acid allyl ester compound and a platinum catalyst, dropwise It is preferable to perform the said contact process by adding. Here, the temperature of the solution containing the carboxylic acid allyl ester compound and the platinum catalyst is preferably room temperature to 80 ° C.

  Moreover, about the temperature (reaction temperature) with which the silicon compound which has the said Si-H group, and carboxylic acid allyl ester compound are made to react, even if it is about room temperature, reaction progresses enough, but changing temperature depending on the case. Also good. The temperature is preferably room temperature to 80 ° C, more preferably room temperature to 60 ° C. When the reaction temperature is in the above range, the reaction can proceed without decreasing the reaction rate, and the reaction can be completed within a practical process time. Furthermore, even when the target hydrosilyl compound has a curable functional group, the progress of the curing reaction (polymerization reaction) of the hydrosilyl compound can be suppressed.

  In the contact step, preferably, the carboxylic acid allyl ester compound and the platinum catalyst are initially charged at a temperature within the above range, and then the Si-H group-containing silicon compound is added to the mixture of the carboxylic acid allyl ester compound and the platinum catalyst. Etc., for example, by slowly dropping dropwise over about 30 minutes to 1 hour. At this time, the Si-H group-containing silicon compound may be dissolved in a solvent and dropped. The reaction can be carried out by any of batch, continuous and semi-continuous methods.

  As a catalyst used in the reaction between the Si-H group-containing compound and the carboxylic acid allyl ester compound, a transition metal such as platinum, rhodium, palladium, nickel, iridium, ruthenium or a catalyst made of the compound is appropriately selected. can do.

  Specifically, chloroplatinic acid, various platinum complexes (for example, Karsted catalyst which is a kind of platinum and vinylsiloxane complex), various platinum compound solutions (alcohols, ketones, ethers, esters, aromatic hydrocarbons, etc.) Or dispersed), Speier catalyst, catalyst supported on various solids (silica gel, activated carbon, etc.), Rh catalyst such as Wilkinson complex, and various complex catalysts of palladium. In consideration of the amount and cost, a platinum catalyst is preferable, and a Karsted catalyst is more preferable.

For example, when a platinum catalyst is used, the amount used is not particularly limited, but the platinum atom is usually 1.0 × 10 ^{−2 to} 1.0 × 10 ⁻⁸ mol with respect to 1 mol of the Si—H group, The amount is preferably in the range of 1.0 × 10 ^{−3 to} 1.0 × 10 ⁻⁶ mol. When the amount of the platinum catalyst used is in such a range, the reaction rate does not extremely decrease, and further, for example, even when the carboxylic acid allyl ester compound has an epoxy group, ring-opening polymerization of this epoxy group This is economically advantageous.

  The reaction between the Si—H group-containing compound and the carboxylic acid allyl ester compound is preferably performed under atmospheric pressure from the viewpoint of operability and economy, but may be performed under pressure as necessary. Moreover, it is preferable that the atmosphere at the time of reaction is inert gas atmosphere, such as nitrogen gas.

For the purpose of increasing the activity of the catalyst, a known technique of introducing dry air or an oxygen-containing inert gas into the reaction atmosphere can also be applied.
In the reaction of the Si—H group-containing compound and the carboxylic acid allyl ester compound, it is not always necessary to use a solvent, but a solvent for dissolving and dispersing these raw materials may be used, or as necessary. A catalyst solution containing a catalyst to be added may be used as the solvent.

  For example, to dissolve the Si-H group-containing compound or carboxylic acid allyl ester compound or dilute the solution thereof, to control the reaction temperature, to secure a volume necessary for stirring, or to facilitate the addition of a catalyst Therefore, a solvent can be used depending on the necessity. Specific examples of such solvents include saturated hydrocarbons such as pentane, hexane, isooctane, decane, and cyclohexane, aromatic hydrocarbons such as toluene, xylene, mesitylene, ethylbenzene, decalin, and tetralin, diethyl ether, THF, and the like. Ethers, esters such as γ-butyrolactone, various silicones such as polydimethylsiloxanes, and the like, and the amount used can be arbitrarily determined. In addition, these solvents may be used independently and may be used in mixture of 2 or more types.

  The reaction time may vary depending on the temperature, pressure, catalyst concentration, or raw material concentration, but is usually 0.1 to 100 hours, preferably 1 to 10 hours, and is arbitrarily set within this range. be able to.

In purifying the hydrosilyl compound obtained by the production method of the present invention, the purification method is not limited and may be purified by a general method.
Examples include adsorption removal methods such as column chromatography and thin layer chromatography. Specifically, adsorption removal methods using silica gel, hydrous silica gel, alumina, activated carbon, titania, zirconia, or these silica gels, hydrous silica gel, alumina Is a column chromatography using as a filler. Moreover, it can also refine | purify by distillation, such as vacuum distillation and molecular distillation. The product does not necessarily have to be purified.

  There are no particular restrictions on the container for reacting the Si-H group-containing silicon compound with the carboxylic acid allyl ester compound, but it includes devices such as a stirrer, a thermometer, a reflux condenser, and a dropping device. It is preferable.

  When the carboxylic acid allyl ester compound has a curable functional group such as a carbon-carbon double bond in addition to the allyl group, it is curable when the Si-H group-containing silicon compound reacts with the carboxylic acid allyl ester compound. In order to prevent a curing reaction (polymerization reaction) due to the functional group, a polymerization inhibitor can be added. Examples of such a polymerization inhibitor include hydroquinone, methoxyhydroquinone, toluhydroquinone, trimethylhydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, t-butylcatechol, pyrogallol and the like.

  Examples of the Si—H group-containing silicon compound used in this reaction include compounds represented by the following general formulas (1) to (3).

式（１）中、Ｒ¹は、それぞれ独立に−ＯＳｉＲ²Ｒ³Ｈ、−ＯＳｉＲ²Ｒ³Ｚ、水素原子またはＺであり、８つのＲ¹のうち、少なくとも１つは、−ＯＳｉＲ²Ｒ³Ｈまたは水素原子であり、Ｚは、それぞれ独立に炭素原子数１〜１０の脂肪族炭化水素基または炭素原子数６〜１４の芳香族炭化水素基であり、Ｒ²およびＲ³はそれぞれ独立に炭素原子数１〜１０の脂肪族炭化水素基または炭素原子数６〜１４の芳香族炭化水素基である。

In formula (1), each R ¹ is independently —OSiR ² R ³ H, —OSiR ² R ³ Z, a hydrogen atom or Z, and at least one of the eight R ¹ is —OSiR ² R ³ H or a hydrogen atom, Z is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and R ² and R ³ are each independently Or an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.

R ⁴ and R ⁵ in the formulas (2) and (3) are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. N ¹ is an integer of ¹ to 5, and n ² is an integer of 4 to 10.

R ¹ is more preferably —OSiR ² R ³ H, —OSiR ² R ³ Z and Z, and further preferably —OSiR ² R ³ H. Specific examples of Z include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonanyl group, decanyl group, phenyl group, naphthyl group and the like. Is a methyl group or an ethyl group, more preferably a methyl group. Specific examples of R ² and R ³ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonanyl, decanyl, phenyl, naphthyl and the like. However, it is preferably a methyl group or an ethyl group, and more preferably a methyl group.

Specific examples of R ⁴ and R ^{5 in} the above formulas (2) and (3) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group and naphthyl group. A methyl group or an ethyl group is preferable, and a methyl group is more preferable. N ¹ is preferably an integer of 1 to 3, more preferably 1 and 2. N ² is preferably an integer of 4 to 6, more preferably 4 and 5.

  Moreover, as a carboxylic acid allyl ester compound used with the manufacturing method of this invention, the compound represented, for example by the following General formula (4) is mentioned.

式（４）中、Ｒ⁶は、炭素原子数１〜１０の脂肪族炭化水素基または下式（ｉ）〜（ｉｉ）で示される基を表す。

In the formula (4), R ⁶ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a group represented by the following formulas (i) to (ii).

式（ｉ）、（ｉｉ）中Ｒ⁷およびＲ⁸は、それぞれ独立に水素原子または炭素原子数１〜５の脂肪族炭化水素基を示す。

In formulas (i) and (ii), R ⁷ and R ⁸ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.

Specific examples of R ^{6 in} the above formula (4) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonanyl group, decanyl group, formulas (i) to ( and a group represented by formula (i) and (ii), more preferably a methyl group and formula (i), (ii), and the like. It is a group represented by ii). Specific examples of R ⁷ and R ⁸ in formulas (i) and (ii) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, preferably a hydrogen atom or a methyl group. , An ethyl group and a propyl group, more preferably a hydrogen atom and a methyl group.

  Specific examples of the hydrosilyl compound obtained by the production method of the present invention include those represented by the following general formulas (5) to (7).

式（５）中、Ｒ⁹は、それぞれ独立に−ＯＳｉＲ²Ｒ³Ｙ、−ＯＳｉＲ²Ｒ³Ｚ、水素原子、ＹまたはＺであり、８つのＲ⁹のうち、少なくとも１つは、−ＯＳｉＲ²Ｒ³ＹまたはＹであり、Ｙはそれぞれ独立に下式（８）で表される基であり、Ｚは、それぞれ独立に炭素原子数１〜１０の脂肪族炭化水素基または炭素原子数６〜１４の芳香族炭化水素基であり、Ｒ²およびＲ³はそれぞれ独立に炭素原子数１〜１０の脂肪族炭化水素基または炭素原子数６〜１４の芳香族炭化水素基である。

Wherein (5), R ⁹ are each independently ^{-OSiR 2 R 3 Y, -OSiR 2} R 3 Z, a hydrogen atom, Y or Z, of the eight R ^9, at least one, -OSiR ² R ³ Y or Y, each Y is independently a group represented by the following formula (8), and Z is each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or 6 carbon atoms. And R ² and R ³ are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.

R ⁴ and R ⁵ in the formulas (6) and (7) are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. N ¹ is an integer of ¹ to 5, and n ² is an integer of 4 to 10. Y is each independently a group represented by the following formula (8).

式（８）中、Ｒ⁶は、炭素原子数１〜１０の脂肪族炭化水素基または下式（ｉ）〜（ｉｉ）で表わされる。

In the formula (8), R ⁶ is represented by an aliphatic hydrocarbon group having 1 to 10 carbon atoms or the following formulas (i) to (ii).

式（ｉ）、（ｉｉ）中、Ｒ⁷およびＲ⁸は、水素原子または炭素原子数１〜５の脂肪族炭化水素基を示す。

In formulas (i) and (ii), R ⁷ and R ⁸ represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.

Specific examples of R ^{9 in} the above formula (5) include —OSiR ² R ³ Y, —OSiR ² R ³ Z, hydrogen atom, Y and Z, preferably —OSiR ² R ³ Y, —OSiR ^2. R ³ Z and Z, more preferably —OSiR ² R ³ Y. Specific examples of Z include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonanyl group, decanyl group, phenyl group, naphthyl group and the like. Is a methyl group or an ethyl group, more preferably a methyl group. Specific examples of R ² and R ³ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonanyl, decanyl, phenyl, naphthyl and the like. However, it is preferably a methyl group or an ethyl group, and more preferably a methyl group.

Specific examples of R ⁴ and R ^{5 in} the above formulas (6) and (7) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group and naphthyl group. , Preferably a methyl group or an ethyl group, more preferably a methyl group. N ¹ is preferably an integer of 1 to 3, more preferably 1 and 2. N ² is preferably an integer of 4 to 6, more preferably 4 and 5.

Specific examples of R ^{6 in} the above formula (8) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonanyl group, decanyl group, formulas (i) to And a group represented by formula (ii), preferably a methyl group, an ethyl group, a propyl group and a group represented by formulas (i) and (ii), more preferably a methyl group and formula (i), It is a group represented by (ii). Specific examples of R ⁷ and R ⁸ in formulas (i) and (ii) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, preferably a hydrogen atom or a methyl group. , An ethyl group and a propyl group, more preferably a hydrogen atom and a methyl group.

  When the obtained product is used as a resist material, a sealing material or the like, from the viewpoint that the characteristics such as curing characteristics and etching selectivity are very excellent, in the method for producing a hydrosilyl compound of the present invention, Si-H group-containing The silicon compound is octakis (dimethylsilyloxy) silsesquioxane, the carboxylic acid allyl ester compound is allyl methacrylate, and the hydrosilyl compound contained in the resulting product is a methacryloyloxy group represented by the following formula (9) It is preferable that it is a containing cage-like silsesquioxane compound.

式（９）中のＲ¹⁰は、下式（ｉｖ）で表される。

R ¹⁰ in the formula (9) is represented by the following formula (iv).

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to these Examples.

[Example 1]
(1) Production of liquid product containing hydrosilyl compound In a 100 ml three-necked flask equipped with a reflux condenser, a thermometer, a stirrer and a serum cap, 19.83 g (0.16 mol) of allyl methacrylate and 3% divinyltetramethyldi 0.00186 g of a siloxane platinum complex isopropyl alcohol solution (platinum amount: 5.6 × 10 ⁻⁵ g) was added, and the mixture was stirred at a liquid temperature of 60 ° C. (stirring temperature) in a nitrogen atmosphere. Furthermore, 2.0 g (1.96 mmol) of octakisdimethylsilyloxysilsesquioxane (manufactured by Toagosei Co., Ltd .: Q-2) dissolved in 10 ml of toluene was slowly added dropwise using a dropping funnel.
Next, the obtained solution was stirred at a liquid temperature of 60 ° C. (reaction temperature) for 3 hours, and then subjected to reduced pressure to remove the toluene solvent contained in the solution to obtain a liquid product.

(2) Evaluation of liquid product The obtained liquid product was subjected to ¹ H-NMR measurement and GPC measurement under the following measurement conditions.
[GPC measurement conditions]
Solvent: THF
Flow rate: 1.0 ml / min
Column: Shodex LF-804 × 3 RI: JASCO RI-2031
Oven: 40 ° C
The results of ¹ H-NMR measurement (spectrum) and the results of GPC measurement (chart) are shown in FIGS. 1 and 5, respectively.

FIG. 1A is a ¹ H-NMR spectrum obtained by the above evaluation test, and FIG. 1B is an enlarged view of a framed portion in FIG. In the case where an acryloyl group and a methyl group of -OSi- (CH ₂ ) ₂ -CH ₃ group are present, A (chemical shift of 1.960 to 1.915δ) in FIG. A peak is observed at around shift 1.0δ.

Moreover, the numerical value on the peak of A and B has shown the integrated value of each peak.
Since the analysis software is different, each integral value is described above the peak in FIGS. 1 to 3 and below the peak in FIG.

  According to FIG. 1B, a peak is observed at A (chemical shift 1.960 to 1.915δ), but a peak is hardly observed at B (around chemical shift 1.0δ). The peak integration ratio of A and B (A peak integration ratio / B peak integration ratio) was 1.00 / 0.00.

  In the GPC measurement results (chart) shown in FIG. 5, the peaks at C (retention time 29.5-30.5 minutes) and D (retention time 26.5-29 minutes) are respectively silyloxy. The presence of a silsesquioxane compound, its dimer, etc. is indicated. Compared with the peak intensity of C, the peak intensity at D was significantly lower.

From the above, it was confirmed that the target product (hydrosilyl compound represented by the following formula (9)) was produced, and that the —OSi— (CH ₂ ) ₂ —CH ₃ group was not by-produced, and 2 It was confirmed that the quantification reaction was suppressed.

（式（９）中のＲ¹⁰は、式（iv）で表される。）
なお、上述の製造条件や評価結果は、表１にも示す。

(R ¹⁰ in formula (9) is represented by formula (iv).)
The manufacturing conditions and evaluation results described above are also shown in Table 1.

[Example 2]
The agitation and reaction temperatures from 60 ° C. was changed to room temperature (28 ° C.), in the same manner as in Example 1, to produce a liquid product containing a hydrosilyl compound, the resulting liquid product ¹ H- Evaluated by NMR measurement.
As shown in FIG. 2 and Table 1, there was no conspicuous peak in B in the obtained liquid product.

[Example 3]
A liquid product containing a hydrosilyl compound was produced in the same manner as in Example 1 except that the amount of allyl methacrylate used was changed from 19.83 g (0.16 mol) to 9.92 g (78.6 mmol). The obtained liquid product was evaluated by ¹ H-NMR measurement.
As shown in Table 1 and FIG. 3, the integration ratio of A and B was 1.00 / 0.01.

[Example 4]
A liquid product containing a hydrosilyl compound was produced in the same manner as in Example 1 except that the amount of allyl methacrylate used was changed from 19.83 g (0.16 mol) to 3.97 g (31.4 mmol). The obtained liquid product was evaluated by ¹ H-NMR measurement.
As shown in Table 1, the integration ratio of A and B was 1.00 / 0.02.

[Comparative Example 1]
A liquid product containing a hydrosilyl compound was produced in the same manner as in Example 1 except that the amount of allyl methacrylate used was changed from 19.83 g (0.16 mol) to 1.98 g (15.7 mmol). The obtained liquid product was evaluated.

As shown in Table 1, the integration ratio of A and B is 1.00 / 0.06, which is a by-product (—OSi— (CH ₂ ) as compared with the production method in the examples. It was confirmed that the amount of by-produced ( _2- CH ₃ group-containing compound) was large. In addition, as shown in the GPC chart of FIG. 6, in the retention time of 26.5 to 29 minutes (D), there are many peaks on the polymer side (such as a dimer of octakisdimethylsilyloxysilsesquioxane), It was found that the dimerization reaction was not suppressed as compared with Example 1.

[Example 5]
Octakisdimethylsilyloxysilsesquioxane, allyl methacrylate and toluene were simultaneously added to a 100 ml three-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a serum cap, and stirred at room temperature in a nitrogen atmosphere. A liquid product containing a hydrosilyl compound was produced in the same manner as in Example 2 except that a reaction solution was prepared by slowly dropping a% divinyltetramethyldisiloxane platinum complex isopropyl alcohol solution using a syringe. The obtained liquid product was evaluated by ¹ H-NMR measurement.
As shown in Table 1 and FIG. 3, the NMR integral ratio of P ₁ and P ₂ was 1.00 / 0.01.

[Comparative Example 2]
A liquid product containing a hydrosilyl compound was produced in the same manner as in Example 5 except that the amount of allyl methacrylate used was changed from 19.83 g (0.16 mol) to 1.98 g (15.7 mmol). The obtained liquid product was evaluated by ¹ H-NMR measurement.

As shown in Table 1, the NMR integration ratio of A and B is 1.00 / 0.10, which is -OSi- (CH ₂ ) ₂ -CH, as compared with the production method in the examples. It was confirmed that the amount of by-products of the _three units was large.

A: Chemical shift 1.960 to 1.915δ
B: Chemical shift around 1.0δ C: Retention time 29.5-30.5 minutes D: Retention time 26.5-29 minutes

Claims (3)

A method for producing a hydrosilyl compound in which a Si-H group-containing silicon compound and a carboxylic acid allyl ester compound are hydrosilylated, wherein the Si-H group-containing silicon compound and the Si-H group-containing silicon compound are Si-H. A contact step of contacting 2 to 100 moles of the carboxylic acid allyl ester compound in terms of an allyl group with respect to 1 mole of the group;
The Si-H group-containing silicon compound is octakis (dimethylsilyloxy) silsesquioxane, the carboxylic acid allyl ester compound is allyl methacrylate,
The method for producing a hydrosilyl compound , wherein the hydrosilyl compound is a compound represented by the following formula (9) :

(R ¹⁰ in formula (9) is represented by the following formula (iv).)

  2. The production of a hydrosilyl compound according to claim 1, wherein the contacting step is performed by adding the Si—H group-containing silicon compound dropwise to a solution containing the carboxylic acid allyl ester compound and a platinum catalyst. Method.   The method for producing a hydrosilyl compound according to claim 2, wherein the temperature of the solution containing the carboxylic acid allyl ester compound and the platinum catalyst is in the range of room temperature to 80 ° C.

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