JPWO2016111112A1 - Silicone copolymer and method for producing the same - Google Patents

Abstract

The silicone copolymer of the present invention is represented by the general formula: ## STR1 ## wherein a, b, and c represent mol%, Y represents an organic group, and X represents a trimethyl group. a + b) is 40 to 100 mol%, c is 0 to 60 mol%, a + b + c = 100 mol%, a / (a + b) is 0.8 or more and 1 or less, and the number of peaks obtained by gel permeation chromatography measurement is It is a silicone polymer that is 2 or more. Since the silicone copolymer of the present invention has a high deprotection rate of the alkoxy group of the protective group, the alkali dissolution rate is stable, and the pattern can be formed stably. The silicone copolymer of the present invention is a material having good transparency at wavelengths in the visible light region, excellent adhesion and crack resistance, and a stable alkali dissolution rate. The silicone copolymer of this invention is used suitably for electronic components, such as a liquid crystal display element and a semiconductor element.

Description

  The present invention relates to a silicone copolymer and a method for producing the same. The present invention particularly relates to a silicone copolymer useful as a heat-resistant material for electronic components such as liquid crystal display elements and semiconductor elements, and a method for producing the same.

  In recent years, as an electronic material used for an electronic component such as a liquid crystal display element or a semiconductor element, a resin having characteristics such as high transparency, heat resistance, chemical resistance, and crack resistance has been required. Such a resin is required to have transparency with high visible light permeability and heat resistance that can withstand a processing step when manufacturing an element.

  Among them, a silicone polymer having a hydroxy group that dissolves in an alkali solvent, particularly a silicone polymer having a phenol group, has attracted attention. The silicone polymer having a phenol group is dissolved in an alkaline solvent used in fine processing.

  A silicone polymer having a phenol group is produced using a silicone polymer having an alkoxy group in which a phenol group is protected with an alkyl group such as a methyl group or an ethyl group. Silicone polymers having an alkoxy group are generally synthesized by using chlorosilane as a raw material, hydrolyzing with water, and performing a condensation polymerization reaction.

  In the case of producing a silicone polymer containing an alkoxy group, the condensation polymerization reaction, in particular, needs to react under severe conditions such as 200 ° C. for 2 hours, and it was difficult to produce industrially.

  Furthermore, hydrochloric acid generated when chlorosilane is hydrolyzed with water may serve as a catalyst for the condensation polymerization reaction. A silicone polymer synthesized using hydrochloric acid as a catalyst may have a large amount of silanol remaining at the terminal.

  Thus, in order to deprotect a silicone polymer having an alkoxy group to obtain a silicone polymer having a phenol group, it is necessary to first protect the silanol group with some protective group and then deprotect the alkoxy group. There was a problem that the reaction was complicated (Patent Documents 1 to 3).

  Further, in the silicone polymer having a phenol group obtained by the conventional method, about 15% of the protective alkoxy group remains. Further, since the deprotection rate varies depending on the conditions (Patent Document 1), the alkali dissolution rate (Alkali Dissolution Rate, ADR) is not stable, and it may be difficult to form a pattern.

  For the above reasons, there has been a demand for a silicone polymer that can be subjected to polycondensation under mild conditions, has a small residual amount of alkoxy groups as a protective group, and has a high deprotection rate.

Japanese Patent Publication No. 5-58446 Japanese Patent No. 3636242 Japanese Patent No. 4039704

  In the present invention, polycondensation can be performed under mild conditions, the remaining amount of the alkoxy group of the protecting group is small, and the deprotection rate is high, so that the alkali dissolution rate is stable and the pattern can be formed stably. It is in providing a silicone polymer and its manufacturing method.

  The present invention provides a general formula

(Wherein, a, b and c represent mol%, Y represents an organic group, and X represents a trimethylsilyl group.)
(A + b) is 40 to 100 mol%, c is 0 to 60 mol%, a + b + c = 100 mol%, and a / (a + b) is 0.8 or more and 1 or less, and is obtained by gel permeation chromatography. This is a silicone polymer having two or more peaks.

  Furthermore, the present invention provides a general formula

(Wherein, R represents a methyl group, Z ¹ represents a monovalent hydrocarbon group) and a general formula

(Wherein Y represents an organic group and Z ² represents a monovalent hydrocarbon group). A hydrolyzed mixture of silicon compounds represented in the presence of a quaternary ammonium salt is subjected to a polycondensation reaction. Followed by deprotection in aprotic polar solvent, general formula

(Wherein, a, b and c represent mol%, Y represents an organic group, and X represents a trimethylsilyl group.)
(A + b) is 40 to 100 mol%, c is 0 to 60 mol%, a + b + c = 100 mol%, and a / (a + b) is 0.8 or more and 1 or less, and is obtained by gel permeation chromatography measurement. This is a method for producing a silicone polymer, which produces a silicone polymer having 2 or more peaks.

  Since the silicone copolymer of the present invention has a high deprotection rate of the alkoxy group of the protective group, the alkali dissolution rate is stable, and the pattern can be formed stably. Moreover, since the deprotection rate is high and the alkali dissolution rate is stable, the alkali dissolution rate can be precisely controlled by changing the ratio of the component a and the component b. Furthermore, since the silanol group is protected with a trimethylsilyl group, the targeted alkali dissolution rate can be obtained even if other properties such as viscosity and molecular weight are changed.

  Furthermore, since the quaternary ammonium salt is used as a catalyst in the method for producing a silicone polymer of the present invention, the reaction temperature is 0 to 100 ° C., and the polycondensation reaction is carried out under mild conditions compared to the conventional reaction temperature of 200 ° C. It can be carried out. In addition, since the amount of silanol groups is small, silanol group protection and alkoxyl group deprotection can be performed simultaneously, and the reaction can be carried out efficiently. Furthermore, hydrolysis, polycondensation and deprotection can be carried out in one-pot, which is efficient for industrialization.

  The silicone copolymer of the present invention is a material having good transparency at wavelengths in the visible light region, excellent adhesion and crack resistance, and a stable alkali dissolution rate. The silicone copolymer of this invention is used suitably for electronic components, such as a liquid crystal display element and a semiconductor element.

2 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 1. FIG. 2 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 1. FIG. It was divided at the inflection point to show the number of peaks. 7 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 7. 7 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 7. It was divided at the inflection point to show the number of peaks. 7 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 8. 7 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 8. It was divided at the inflection point to show the number of peaks. 7 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 9. 7 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 9. It was divided at the inflection point to show the number of peaks. 2 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 10. FIG. 2 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 10. FIG. It was divided at the inflection point to show the number of peaks. 2 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 11. FIG. 2 is a measurement result of gel permeation chromatography of the silicone copolymer obtained in Example 11. FIG. It was divided at the inflection point to show the number of peaks. 7 is a measurement result of gel permeation chromatography of a silicone polymer obtained in Comparative Example 6.

  The silicone polymer of the present invention has the general formula

(Wherein, a, b and c represent mol%, Y represents an organic group, and X represents a trimethylsilyl group.)
(A + b) is 40 to 100 mol%, c is 0 to 60 mol%, a + b + c = 100 mol%, and a / (a + b) is 0.8 or more and 1 or less, and is obtained by gel permeation chromatography. This is a silicone polymer having two or more peaks.

  The skeleton of the silicone polymer of the present invention is:

A silsesquioxane skeleton is shown, and each silicon atom is bonded to three oxygen atoms, and each oxygen atom is bonded to two silicon atoms. The silsesquioxane skeleton has, for example, a general formula

It can be shown by the structural formula shown in

  In the present invention, a, b and c represent mol%, and a + b + c = 100.

  The components a and b in the present invention are components containing a hydroxybenzyl group, and are components that impart alkali solubility to the silicone polymer. The sum of component a and component b is 40 to 100 mol%. The sum of component a and component b is preferably 50 to 100 mol%, more preferably 60 to 100%. When the sum of the component a and the component b is less than 40 mol%, it may not be dissolved in alkali.

  In the component a and component b in the present invention, a / (a + b) is 0.8 or more and 1 or less. a / (a + b) is preferably 0.85 or more and 1 or less, and more preferably 0.90 or more and 1 or less.

  The component c in the present invention is a component containing an organic group, and is a component that imparts viscosity and heat resistance of the resulting silicone polymer. The component c is preferably 0 to 60 mol%, more preferably 0 to 50 mol%, still more preferably 0 to 40 mol%. When c component exceeds 60 mol%, it may not melt | dissolve in an alkali.

  In the silicone polymer of the present invention, Y is an organic group. Y is preferably a hydrocarbon group. The hydrocarbon group is preferably a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group, a cyclic hydrocarbon group, or an aromatic hydrocarbon group. The linear hydrocarbon group having 1 to 20 carbon atoms is more preferably a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group. The branched hydrocarbon group is preferably an isopropyl group or an isobutyl group. The cyclic hydrocarbon group is preferably a cyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group or a cyclopentyl group, and a bridged hydrocarbon group having a norbornane skeleton is also preferred. The aromatic hydrocarbon group includes a phenyl group, a benzyl group, a phenethyl group, a phenylpropyl group, a diphenylmethyl group, a cinnamyl group, a styryl group, a trityl group, a substituent having a benzene ring and a hydrocarbon group, and a toluyl group. And an aromatic hydrocarbon group having a substituent bonded to a benzene ring, such as a cumenyl group, a mesyl group, or a xylyl group.

  Among these hydrocarbon groups, an alkylene group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group, an aromatic hydrocarbon group such as a phenyl group, and a benzyl group are more preferable because of easy availability of raw materials. More preferred are a methyl group, an ethyl group, and a phenyl group.

  In the silicone polymer of the present invention, X represents a trimethylsilyl group.

  The silicone polymer of the present invention preferably has a weight average molecular weight (polystyrene conversion) in the range of 500 to 20000. More preferably, the weight average molecular weight (polystyrene conversion) is in the range of 1000 to 10,000, and more preferably in the range of 2000 to 5000.

The dispersity of the silicone polymer of the present invention is preferably in the range of 1.0 to 10.0, and most preferably in the range of 1.5 to 5.0. The degree of dispersion is determined by the following calculation formula: weight average molecular weight / number average molecular weight = dispersion degree.

  The silicone polymer of the present invention is a silicone polymer having two or more peaks obtained by gel permeation chromatography measurement.

  In the present invention, the molecular weight distribution region obtained by gel permeation chromatography measurement is separated at the inflection point to determine the number of peaks obtained. However, when the inflection point is not clear, the number of peaks can be determined from a measurement diagram obtained by gel permeation chromatography measurement. When the molecular weight distribution is high, the number of peaks obtained is large, but since the polymer has a high degree of dispersion, characteristics may not be obtained. Therefore, the number of peaks is preferably 2 to 10, and more preferably 2 to 5.

  Since gel permeation chromatography is a peak that appears by distinguishing the size of the molecule, the silicone polymer of the present invention usually has a three-dimensional structure of the molecule because there are two or more peaks as measured by gel permeation chromatography. Suggests that there are multiple.

  In the silicone polymer of the present invention, the following cage structure may be included in the three-dimensional structure of the molecule. A typical vertical structure is a general formula

(In the formula, R represents a general organic group)
A T8 structure having 8 silicon atoms, and a general formula

(In the formula, R represents a general organic group)
A T10 structure having 10 silicon atoms, and a general formula

(In the formula, R represents a general organic group)
The T12 structure which has 12 silicon atoms shown by these is mentioned. Their structure is not a fully condensed form, but a structural formula in which silanol groups remain partially

(In the formula, R represents a general organic group)
Is also included. Furthermore, the silanol group may be protected by a trimethylsilyl group.

  The silicone polymer of the present invention is preferably soluble in an organic solvent. The silicone polymer of the present invention is preferably a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, alcohol solvent such as methanol, ethanol, isopropanol, n-butanol, cyclohexanol, benzene, toluene, Aromatic hydrocarbon solvents such as xylene, ester solvents such as methyl acetate, ethyl acetate, butyl acetate and ethyl lactate, ether solvents such as diethyl ether, dibutyl ether and tetrahydrofuran, nitrile solvents such as acetonitrile and benzonitrile, propylene glycol dimethyl ether It is soluble in glycol solvents such as propylene glycol diethyl ether and propylene glycol monomethyl ether acetate. When the silicone polymer of the present invention is dissolved in an organic solvent such as propylene glycol monomethyl ether acetate, for example, the silicone copolymer dissolved in the organic solvent can be spin-coated on a silicon wafer or a glass substrate, It is particularly preferable to dissolve in a solvent having a high boiling point because the film thickness on the substrate can be adjusted and a flat and dense film can be formed.

  The alkali dissolution rate (Alkali Dissolution Rate, ADR) in the present invention is a rate at which the coating film dissolves when the silicone polymer used as the coating film is immersed in an alkaline solution, for example. As the alkali solution used for measuring the alkali dissolution rate, 1.19%, 2.38%, and 25% tetramethylammonium hydroxide aqueous solutions are generally used for semiconductor / liquid crystal lithography applications. The coating film can be formed by dissolving the silicone polymer of the present invention in a high boiling point solvent and using a technique such as spin coating on a silicon wafer or glass substrate.

  The alkali dissolution rate is determined by measuring the film thickness (A) of the coating film in advance using a light interference type film thickness measuring device or the like. The time (B) until dissolution is measured, and is obtained by the following formula.

A / B = ADR (Å / s)
In semiconductor / liquid crystal lithography, the alkali dissolution rate is preferably 100 Å / s, more preferably 200 Å / s, and still more preferably 300 Å / s. If the alkali dissolution rate is 100 Å / s or more, it can be used for lithography.

  The silicone polymer of the present invention generally has, for example, a general formula

(In the formula, X represents a hydrolyzable group, and n represents 1 to 3.)
Hydrolysis reaction and general formula

(In the formula, X represents a hydrolyzable group, and n represents 1 to 3.)
As described above, it is synthesized from two reactions of hydrolysis and condensation polymerization. When the silicone polymer of the present invention is synthesized from two reactions of a hydrolysis reaction and a condensation polymerization reaction, the polymerization degree can be controlled from the monomers used and reaction conditions, etc., unlike general radical condensation. .

  The method for producing the silicone polymer of the present invention has the general formula

(Wherein R represents a methyl group, Z ¹ represents a monovalent hydrocarbon group) and a general formula

(Wherein Y represents an organic group and Z ² represents a monovalent hydrocarbon group)
A mixture of silicon compounds represented by the following formula is hydrolyzed in the presence of a quaternary ammonium salt, followed by a condensation polymerization reaction, followed by deprotection in an aprotic polar solvent.

(Wherein, a, b and c represent mol%, Y represents an organic group, and X represents a trimethylsilyl group.)
(A + b) is 40 to 100 mol%, c is 0 to 60 mol%, a + b + c = 100 mol%, and a / (a + b) is 0.8 or more and 1 or less, and is obtained by gel permeation chromatography measurement. This is a method for producing a silicone polymer, which produces a silicone polymer having 2 or more peaks.

Here, Z < ¹ > shows a monovalent hydrocarbon group and a C1-C20 linear hydrocarbon group is preferable. Examples of the linear hydrocarbon group having 1 to 20 carbon atoms include hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Among these, Z ¹ is more preferably an alkylene group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, or a propyl group, and a methyl group or an ethyl group is more preferable because of availability of raw materials.

  In the method for producing a silicone polymer of the present invention, Y is an organic group. Y is preferably a hydrocarbon group. The hydrocarbon group is a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group, a cyclic hydrocarbon group, an aromatic hydrocarbon group, or the like. The linear hydrocarbon group having 1 to 20 carbon atoms is more preferably a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group. The branched hydrocarbon group is preferably a hydrocarbon group such as isopropyl group or isobutyl group. The cyclic hydrocarbon group is preferably a cyclopentyl group, a cyclohexyl group or a cyclopentyl group, and a bridged hydrocarbon group having a norbornane skeleton is also preferred. The aromatic hydrocarbon group includes a phenyl group, a benzyl group, a phenethyl group, a phenylpropyl group, a diphenylmethyl group, a cinnamyl group, a styryl group, a trityl group, a substituent having a benzene ring and a hydrocarbon group, a toluyl group, An aromatic hydrocarbon group in which a substituent is bonded to a benzene ring, such as a cumenyl group, a mesyl group, or a xylyl group.

  Among these hydrocarbon groups, an alkylene group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group, and an aromatic hydrocarbon group such as a phenyl group and a benzyl group are more preferable. More preferred are a group, an ethyl group and a phenyl group.

Z ² represents a monovalent hydrocarbon group, preferably a linear hydrocarbon group having 1 to 20 carbon atoms. Examples of the linear hydrocarbon group having 1 to 20 carbon atoms include hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Z ² is more preferably an alkylene group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, or a propyl group, and a methyl group or an ethyl group is more preferable from the viewpoint of availability of raw materials.

  In the method for producing a silicone polymer of the present invention, a quaternary ammonium salt is used as a catalyst. The quaternary ammonium salts include tetrabutylammonium fluoride, benzyltributylammonium chloride, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetra n-butylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, benzyltrin-butylammonium. Bromide, benzyltriethylammonium bromide, benzyltrimethylammonium bromide, n-octyltrimethylammonium bromide, hexyltrimethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium bromide, tetradecyltrimethylammonium bromide, tetramethylammonium Romide, tetra-n-propylammonium bromide, tetrabutylammonium iodide, tetraethylammonium iodide, tetramethylammonium iodide, tetra-n-propylammonium iodide, trimethylphenylammonium iodide, benzyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxy Tetrabutylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydrogen sulfate, tetrabutylammonium tetrafluoroborate, tetramethylammonium thiocyanate, tetramethylammonium p- G Such as Enns Gandolfo sulfonate, and the like. Among them, benzyltributylammonium chloride, benzyltrimethylammonium chloride, tetra n-butylammonium chloride, tetramethylammonium chloride, benzyltrin-butylammonium bromide, benzyltrimethylammonium bromide, hexyltrimethylammonium bromide, tetrabutylammonium bromide, tetradecyltrimethylammonium Bromide, tetramethylammonium bromide, benzyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetra Tylammonium hydrogen sulfate, tetrabutylammonium tetrafluoroborate, tetramethylammonium thiocyanate, tetramethylammonium p-toluenesulfonate are preferred, and tetramethylammonium hydroxide that can control the hydrolysis rate of the monomer with a strong base Is preferred.

  The amount of quaternary ammonium salt used is the general formula

(Wherein, R represents a methyl group, Z ¹ represents a monovalent hydrocarbon group) and a general formula

(Wherein Y represents an organic group and Z ² represents a monovalent hydrocarbon group), 0.001 to 1.0 equivalent is preferable with respect to the total number of moles of the silicon compound. 005 to 0.5 equivalent is more preferable. The quaternary ammonium salt may be neutralized with an appropriate acid after completion of hydrolysis and polycondensation reaction.

  In the method for producing a silicone polymer of the present invention, the reaction temperature of the hydrolysis and condensation polymerization reaction is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and further preferably 20 to 80 ° C. is there. If the reaction temperature is 0 ° C. or higher, hydrolysis and polycondensation reactions are completed in a short time, and if it is 100 ° C. or lower, industrialization is easy.

  Water is used for the hydrolysis and condensation polymerization reactions. The amount of water used is the general formula

(Wherein, R represents a methyl group, Z ¹ represents a monovalent hydrocarbon group) and a general formula

(Wherein Y represents an organic group, and Z ² represents a monovalent hydrocarbon group), it is preferably used in an amount of 0.1 to 20 equivalents relative to the total number of moles of the silicon compound. It is particularly preferable to use 5 to 10 equivalents.

  In the hydrolysis and polycondensation reaction, an organic solvent may be used. Examples of the organic solvent include aprotic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol and 2-propanol, and ether solvents such as diethyl ether and tetrahydrofuran. Can be used. Moreover, you may use high boiling-point solvents, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, and ethyl lactate. When an aprotic solvent is used, it is presumed that the hydrolysis reaction is slowed because it is not mixed with water. In such a case, a hydrolysis reaction may be performed by adding an alcohol solvent soluble in water. Two or more organic solvents may be used.

  In the hydrolysis and polycondensation reaction, the catalyst may be added dropwise to the silicon compound, or the silicon compound may be added dropwise to the catalyst or an organic solvent containing the catalyst.

  The reaction time for the hydrolysis and polycondensation reaction may be a time for obtaining a silicone polymer having a desired molecular weight, preferably 0.5 to 20 hours, and more preferably 1 to 10 hours.

  In the method for producing a silicone polymer of the present invention, the alkoxy group is deprotected to form a hydroxyl group by performing a deprotection reaction in an aprotic polar solvent.

  As the aprotic polar solvent, acetonitrile, chloroform, methylene chloride or the like can be used. Among these, when acetonitrile or chloroform is used, the deprotection rate is high and preferable. Two or more aprotic polar solvents may be used.

  The amount of the aprotic polar solvent is 0.5 to 8.0 times by weight, preferably 1.0 to 7.0 times by weight, and more preferably 1.5 to 8.0 times by weight with respect to the obtained polymer. 6.0 times by weight. If it is 0.5 weight times or more, a deprotection rate will become high, and if it is 8.0 weight times or less, it is preferable from an economical viewpoint.

  In the method for producing a silicone polymer of the present invention, more preferably, the quaternary ammonium salt is tetramethylammonium hydroxide, and the aprotic polar solvent is acetonitrile or chloroform.

  Trimethylsilyl iodide can be used for the deprotection reaction. The trimethylsilyl iodide may be produced by dropping the trimethylsilyl iodide in the solution into the hydrolyzed or condensed polymer of the silane compound, or by adding trimethylsilyl chloride and sodium iodide separately in the reaction system. Trimethylsilyl chloride and sodium iodide are preferred because they are inexpensive.

  The amount of trimethylsilyl iodide is 1.2 to 2.9 equivalents, preferably 1.3 to 2.8 equivalents, more preferably 1.4 to 2.7 equivalents, relative to the number of moles of component a. If it is 1.2 equivalents or more, the deprotection rate is high, and if it is 2.9 equivalents or less, it is economically preferable. Furthermore, when trimethylsilyl chloride and sodium iodide are added separately, it is preferable that trimethylsilyl chloride is excessive with respect to sodium iodide.

  The temperature of the deprotection reaction is 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 65 ° C. or higher. If it is 50 degreeC or more, a deprotection rate becomes high and is preferable.

  The time for the deprotection reaction may be a time for obtaining a desired deprotection rate, and is 6 to 100 hours, preferably 10 to 80 hours, and more preferably 14 to 60 hours. If it is 6 hours or more, the deprotection rate is 80% or more, and if it is 100 hours or less, it is preferable in terms of productivity.

  The amount of water used in the deprotection reaction is 1.0 to 4.0 equivalents, preferably 1.2 to 3.5 equivalents, more preferably 1.5 to 3.0 equivalents relative to the number of moles of trimethylsilyl iodide. Equivalents are preferred.

  In the method for producing a silicone polymer of the present invention, when trimethylsilyl chloride and sodium iodide are used for trimethylsilyl iodide, in order to remove salts generated as by-products and reduce the metal contained in the silicone polymer, You may wash with water. The water used for washing is preferably ion-exchanged water, more preferably ion-exchanged water having an electric conductivity of 5 μS / cm or less. Washing with water may be repeated.

  In the method for producing a silicone polymer of the present invention, preferably, all reactions are carried out in one-pot. Performing the reaction in one pot means performing a multi-stage reaction by sequentially introducing a substrate and a solvent into the reaction vessel. In ordinary synthesis reactions, generally, excess substrates and by-products may inhibit the next step reaction, and isolation and purification are necessary.

  In the method for producing a silicone polymer of the present invention, after the hydrolysis / condensation reaction, the methoxy group can be deprotected at a high deprotection rate while performing the reaction in one pot without performing isolation / purification. it can. Since the reaction can be carried out in one pot, it can be synthesized without using energy and solvent used for isolation and purification, which is economical. Further, since no isolation / purification is performed, no product is lost, no waste liquid is generated, and the burden on the environment is small. In addition, since only one reaction facility is used, the number of facilities is small and efficiency is high.

  Hereinafter, the present invention will be specifically described with reference to examples.

  In the following examples, the following apparatus is used for measurement, and raw materials are purchased from reagent manufacturers (Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., Nacalai Tesque Co., Ltd., Shin-Etsu Chemical Co., Ltd.). The general reagents used were used.

Measuring device NMR measurement
NMR (400 MHz, manufactured by JEOL Ltd.) was used. About 20 to 30 mg of the synthesized compound was dissolved in about 1 g of CDCl ₃ manufactured by Wako Pure Chemical Industries, and the total amount of the solution was transferred to an NMR tube. The internal standard substance was analyzed by adding 0.5% w / w to tetramethylsilane (abbreviated as TMS) CDCl ₃ and setting the peak derived from TMS to 0 ppm. Measurement was performed by auto-locking and the number of integrations was 16 times. The deprotection rate was calculated based on the obtained chart. The deprotection rate is calculated by the following formula using the peak area (A) derived from the proton of phenol in the vicinity of 6 to 7 ppm and the peak area (B) derived from the proton of the methoxy group in the vicinity of 3.6 ppm. (B / 3) / (A / 4) × 100) = Deprotection rate (%)
Asked.

IR measurement
IR Prestige-21 (manufactured by Shimadzu Corporation) was used. A small amount of the synthetic product was applied to the KBr plate and measured by transmitting infrared light.

GC measurement GC-2010 (manufactured by Shimadzu Corporation) was used. The column used was DB-5 manufactured by J & W (length 30 m × film thickness 0.5 mm ID). The measurement conditions were an inlet temperature of 250 ° C and a detector temperature of 300 ° C. In the temperature raising program, the column temperature was raised from 50 ° C. to 300 ° C. at 10 ° C./min and held for 2 minutes.

Gel permeation chromatography (GPC) measurement
An HLC-8220 GPC system (manufactured by Tosoh Corporation) was used. TSKgelSuperHZ3000, TSKgelSuperHZ2000, and TSKgel1000 (all manufactured by Tosoh Corporation) were used for the column. Detection was performed by RI, and TSKgelSuperH-RC was used as a reference column. Tetrahydrofuran was used as the solvent, and the flow rate between the column and the reference column was 0.35 mL / min. The measurement temperature was 40 ° C. for both the plunger pump and the column. For sample preparation, about 0.025 g of a silicone polymer was diluted with 10 ml of tetrahydrofuran and 1 μL was injected. For molecular weight distribution calculation, TSK standard polystyrene (manufactured by Tosoh Corporation, A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F- 20, F-40, F-80) were used as standard substances.

Measurement of Alkali Dissolution Rate (ADR) On a Si single crystal wafer, a spin coater (MS-A100, manufactured by Mikasa) is used to form a silicone polymer with a film thickness of 15,000 to 25,000 mm (A). And baked at 100 ° C. for 90 seconds on a hot plate. The film thickness was measured using an optical interference type film thickness measuring device (Lambda Ace VM-1210, manufactured by Dainippon Screen Mfg. Co., Ltd.). ADR is a time until the coated film disappears by immersing the coated wafer in a 1.19% or 2.38% tetramethylammonium hydroxide aqueous solution (abbreviated as TMAH aqueous solution) (B). Is measured, and A / B = ADR (Å / s) by the following formula
Asked.

Synthesis example 1
Synthesis example of 4-methoxybenzyltrimethoxysilane To a 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 19.0 g (0.784 mol) of magnesium and 300 mL of tetrahydrofuran were added, and iodine pieces were added. added. A small amount of 4-methoxybenzyl chloride was added dropwise thereto to initiate the reaction, and then a total of 116.9 g (0.746 mol) of 4-methoxybenzyl chloride was added dropwise at 5 to 10 ° C. to prepare a Grignard reagent.

  Next, 568 g (3.73 mol) of normal methyl silicate was charged into a 1000 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, and 2 Grignard reagents previously adjusted at a temperature of 70 to 80 ° C. It was added dropwise over time. After cooling and filtering the precipitated magnesium salt, the solvent was distilled off, and 122 g (0.495 mol) of a 128-135 ° C. fraction was recovered at a reduced pressure of 5 mmHg. As a result of GC analysis of the obtained fraction, GC purity was 98.8%, and NMR and IR analysis revealed that it was 4-methoxybenzyltrimethoxysilane.

  The spectrum data of the obtained compound is shown below.

Infrared absorption spectrum 2839, 2941 cm ⁻¹ (—CH ₃ , Ar), 1080 cm ⁻¹ (Si—O)
Nuclear magnetic resonance spectrum _{2.15 (s, 2H, -CH 2} -), 3.52 (s, 9H, -OCH 3), 3.76 (s, 3H, CH 3 -O -), 6.78- 6.80 (d, J = 8.5 Hz, 2H, Ar—H), 7.07-7.09 (d, J = 8.5 Hz, 2H, Ar—H) ppm.

Example 1
Synthesis of 4-hydroxybenzylsilsesquioxane having three peaks obtained by gel permeation chromatography measurement

(1) Hydrolysis, condensation polymerization In a 5 L four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 17.7 g of 25% tetramethylammonium hydroxide aqueous solution, 62.2 g of ion-exchanged water, 2 -390.2 g of propanol and 418.5 g of toluene were charged. After the temperature was raised to 40 ° C., 557.4 g of 4-methoxybenzyltrimethoxysilane obtained in Synthesis Example 1 was added dropwise over 1.5 hours using a dropping funnel. Thereafter, the reaction was carried out at 40 ° C. for 4 hours. After the reaction, 2% citric acid water was added for neutralization. Furthermore, 975.5 g of toluene and 278.7 g of ion-exchanged water were added, followed by liquid separation after stirring. 418.0 g of ion-exchanged water was added to the separated oil layer, and the mixture was stirred and separated. The same operation was performed once more. When the obtained oil layer was concentrated, 510.8 g of a colorless transparent liquid 4-methoxybenzylsilsesquioxane (solid content 77% toluene solution) was obtained.

(2) Deprotection To the obtained polymer, 1570.0 g (4.0 times by weight / polymer) of acetonitrile was added, and while stirring, 509.4 g of sodium iodide and 492.2 g of tetramethoxysilyl chloride (2.0 mol times / Methoxybenzyl unit) was added and the temperature was raised to 65 ° C. Then, after making it react for 16 hours, it cooled and ion-exchange water 163.3g was dripped. After reacting at 30 ° C. for 1.5 hours, 1178.7 g of a 15% aqueous sodium hydrogen sulfite solution was added. 982.1 g of methyl isobutyl ketone was added, followed by liquid separation after stirring. To the oil layer, 392.5 g of ion-exchanged water was added, followed by liquid separation with stirring. This operation was repeated 5 times. Thereafter, the solvent was removed by concentration under reduced pressure, and 950 g of 4-hydroxybenzylsilsesquioxane (solid content 40% PGME solution) was obtained as a yellow transparent liquid by adding propylene glycol monomethyl ether (PGME).

  When the obtained 4-hydroxybenzylsilsesquioxane was analyzed by GPC, molecular weight (Mw) 3530, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 98%. Tables 1 and 2 summarize the composition ratios of component (a) and component (b). The component (a) was 98 mol%, and the component (b) was 2 mol%.

  1 and 2 show the results of gel permeation chromatography measurement of the silicone copolymer obtained in Example 1. In the figure, ◯ indicates a calibration curve measured with polystyrene, and the rightmost ◯ indicates a weight average molecular weight (Mw) 500. The peak in between is the peak of the silicone copolymer. From the GPC analysis results, it was found that there were three peak shapes.

  Table 1 shows the measurement results of alkali dissolution rate (ADR) using a 1.19% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). Table 2 shows the results of measurement of alkali dissolution rate (ADR) using 2.38% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). ADR (1.19% TMAH aqueous solution) was 580 (Å / s). ADR (2.38% TMAH aqueous solution) was 6110 (Å / s).

Example 2
4 in the same manner as in Example 1 except that (2) the amount of acetonitrile in the deprotection step was changed from 1570.0 g (4.0 weight times / polymer) to 981.3 g (2.5 weight times / polymer). 948 g of hydroxybenzylsilsesquioxane (solid content 40% PGME solution) was obtained. When the obtained 4-hydroxybenzylsilsesquioxane was analyzed by GPC, molecular weight (Mw) 3230, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 94%. Table 1 summarizes the composition ratios of the component (a) and the component (b). The component (a) was 94 mol%, and the component (b) was 6 mol%. Table 1 shows the measurement results of alkali dissolution rate (ADR) using a 1.19% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). ADR (1.19% TMAH aqueous solution) was 320 (Å / s).

Example 3
4 in the same manner as in Example 1, except that the amount of acetonitrile in (2) deprotection step was changed from 1570.0 g (4.0 weight times / polymer) to 1962.5 g (5.0 weight times / polymer). -947 g of hydroxybenzylsilsesquioxane (solid content 40% PGME solution) was obtained. When the obtained 4-hydroxybenzylsilsesquioxane was analyzed by GPC, molecular weight (Mw) 3230, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 95%. Table 1 summarizes the composition ratios of the component (a) and the component (b). Component (a) was 95 mol%, and component (b) was 5 mol%. Table 1 shows the measurement results of alkali dissolution rate (ADR) using a 1.19% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). ADR (1.19% TMAH aqueous solution) was 330 (Å / s).

Example 4
In Example 1, 950 g of 4-hydroxybenzylsilsesquioxane (solid content 40% PGME solution) was obtained in the same manner except that the reaction time in the (2) deprotection step was changed from 16 hours to 6 hours. When the obtained 4-hydroxybenzylsilsesquioxane was analyzed by GPC, molecular weight (Mw) 3560, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 85%. Table 1 summarizes the composition ratios of the component (a) and the component (b). The component (a) was 85 mol%, and the component (b) was 15 mol%. Table 1 shows the measurement results of alkali dissolution rate (ADR) using a 1.19% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). ADR (1.19% TMAH aqueous solution) was 140 (Å / s).

Example 5
In Example 1, 946 g of 4-hydroxybenzylsilsesquioxane (solid content 40% PGME solution) was obtained in the same manner except that the reaction time in the (2) deprotection step was changed from 16 hours to 40 hours. When the obtained 4-hydroxybenzylsilsesquioxane was analyzed by GPC, molecular weight (Mw) 3580, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 97%. Table 1 summarizes the composition ratios of the component (a) and the component (b). The component (a) was 97 mol%, and the component (b) was 3 mol%. Table 1 shows the measurement results of alkali dissolution rate (ADR) using a 1.19% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). ADR (1.19% TMAH aqueous solution) was 460 (Å / s).

Example 6
In Example 1, 949 g of 4-hydroxybenzylsilsesquioxane (solid content 40% PGME solution) was obtained in the same manner except that the temperature in the (2) deprotection step was changed from 65 ° C. to 60 ° C. When the obtained 4-hydroxybenzylsilsesquioxane was analyzed by GPC, molecular weight (Mw) 4000, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 86%. Table 1 summarizes the composition ratios of the component (a) and the component (b). The component (a) was 86 mol%, and the component (b) was 14 mol%. Table 1 shows the measurement results of alkali dissolution rate (ADR) using a 1.19% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). ADR (1.19% TMAH aqueous solution) was 160 (Å / s).

Comparative Example 1
In Example 2, the amount of tetramethylsilyl chloride added in the deprotection step (2) was changed from 492.2 g (2.0 mol times / methoxybenzyl unit) to 246.1 g (1.0 mol times / methoxybenzyl unit). 945 g of 4-hydroxybenzylsilsesquioxane (solid content 40% PGME solution) was obtained in the same manner except that When the obtained 4-hydroxybenzylsilsesquioxane was analyzed by GPC, molecular weight (Mw) 3560, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 78%. Table 1 summarizes the composition ratios of the component (a) and the component (b). The component (a) was 78 mol%, and the component (b) was 22 mol%. An attempt was made to measure the alkali dissolution rate (ADR) using a 1.19% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution), but it was not dissolved and could not be measured.

Comparative Example 2
In Example 2, (2) The amount of tetramethylsilyl chloride added in the deprotection step was changed from 492.2 g (2.0 mol times / methoxybenzyl unit) to 738.3 g (3.0 mol times / methoxybenzyl unit). 948 g of 4-hydroxybenzylsilsesquioxane (solid content 40% PGME solution) was obtained in the same manner except that it was changed to. When the obtained 4-hydroxybenzylsilsesquioxane was analyzed by GPC, molecular weight (Mw) 3500, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 77%. Table 1 summarizes the composition ratios of the component (a) and the component (b). The component (a) was 77 mol%, and the component (b) was 23 mol%. An attempt was made to measure the alkali dissolution rate (ADR) using a 1.19% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution), but it was not dissolved and could not be measured.

Comparative Example 3
In Example 2, the addition amount of tetramethylsilyl chloride in (2) deprotection step was changed from 492.2 g (2.0 mol times / methoxybenzyl unit) to 861.4 g (3.5 mol times / methoxybenzyl unit). 946 g of 4-hydroxybenzylsilsesquioxane (solid content 40% PGME solution) was obtained in the same manner except that When the obtained 4-hydroxybenzylsilsesquioxane was analyzed by GPC, molecular weight (Mw) 3490, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 71%. Table 1 summarizes the composition ratios of the component (a) and the component (b). The component (a) was 71 mol%, and the component (b) was 29 mol%. An attempt was made to measure the alkali dissolution rate (ADR) using a 1.19% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution), but it was not dissolved and could not be measured.

Comparative Example 4
In Example 1, the reaction was carried out in the same manner except that acetonitrile in the (2) deprotection step was changed to toluene, but the deprotection rate determined by NMR was 0%. Table 1 summarizes the composition ratios of the component (a) and the component (b). The component (a) was 0 mol%, and the component (b) was 100 mol%. An attempt was made to measure the alkali dissolution rate (ADR) using a 1.19% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution), but it was not dissolved and could not be measured.

Comparative Example 5
In Example 1, the reaction was performed in the same manner except that (2) acetonitrile in the deprotection step was changed to mesitylene, but the deprotection rate determined by NMR was 0%. Table 1 summarizes the composition ratios of the component (a) and the component (b). The component (a) was 0 mol%, and the component (b) was 100 mol%. An attempt was made to measure the alkali dissolution rate (ADR) using a 1.19% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution), but it was not dissolved and could not be measured.

Example 7
Synthesis of 4-hydroxybenzylsilsesquioxane / methylsilsesquioxane copolymer having three peaks obtained by gel permeation chromatography

(70:30 indicates the charged molar composition ratio of raw materials)
(1) Hydrolysis, condensation polymerization In a 5 L four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 14.6 g of 25% tetramethylammonium hydroxide aqueous solution, 54.1 g of ion-exchanged water, 2 -Charged 444.4 g of propanol and 424.4 g of toluene. After raising the temperature to 40 ° C., 324.7 g of 4-methoxybenzyltrimethoxysilane obtained in Synthesis Example 1 and 81.7 g of methyltrimethoxysilane were mixed and added dropwise over 1.5 hours using a dropping funnel. . Thereafter, the reaction was carried out at 40 ° C. for 4 hours. After the reaction, 2% citric acid water was added for neutralization. Furthermore, 848.9 g of toluene and 212.2 g of ion-exchanged water were added, and the mixture was separated after stirring. To the separated oil layer, 331.1 g of ion-exchanged water was added, followed by liquid separation after stirring. The same operation was performed once more. When the obtained oil layer was concentrated, 391.3 g of a colorless transparent liquid 4-methoxybenzylsilsesquioxane / methylsilsesquioxane copolymer (70% solid content toluene solution) was obtained.

(2) Deprotection 1565.2 g (4.0 weight times / polymer) of acetonitrile was added to the obtained polymer, and 314.8 g of sodium iodide and 304.2 g of trimethylsilyl chloride (2.0 mole times / methoxybenzyl) with stirring. Unit) and the temperature was raised to 65 ° C. Then, after making it react for 16 hours, it cooled and ion-exchange water 100.9g was dripped. After reacting at 30 ° C. for 1.5 hours, 1178.7 g of a 15% aqueous sodium hydrogen sulfite solution was added. After adding 707.9 g of methyl isobutyl ketone and stirring, the solution was separated. To the oil layer, 267.5 g of ion-exchanged water was added, followed by liquid separation with stirring. This operation was repeated 5 times. Thereafter, the solvent is removed by concentration under reduced pressure, and 656.5 g of 4-hydroxybenzylsilsesquioxane / methylsilsesquioxane copolymer, which is a yellow transparent liquid, is added by adding propylene glycol monomethyl ether (PGME) ( A 40% solid content PGME solution) was obtained.

  The obtained 4-hydroxybenzylsilsesquioxane / methylsilsesquioxane copolymer was analyzed by GPC. 3 and 4 show the results of gel permeation chromatography measurement of the silicone copolymer obtained in Example 7. FIG. Molecular weight (Mw) 3430, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 91%. Table 2 summarizes the composition ratios of the component (a), the component (b), and the component (c). Component (a) was 64 mol%, component (b) was 6 mol%, and component (c) was 30 mol%.

  Table 2 shows the results of measurement of alkali dissolution rate (ADR) using 2.38% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). ADR (2.38% TMAH aqueous solution) was 730 (Å / s).

Example 8
Synthesis of 4-hydroxybenzylsilsesquioxane / methylsilsesquioxane copolymer having three peaks obtained by gel permeation chromatography

(60:40 indicates the charged molar composition ratio of raw materials)
(1) Hydrolysis, condensation polymerization In a 5 L four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 14.6 g of 25% tetramethylammonium hydroxide aqueous solution, 54.2 g of ion-exchanged water, 2 -402.6 g of propanol and 402.6 g of toluene were charged. After heating up to 40 degreeC, 4-methoxybenzyltrimethoxysilane 293.7 and methyltrimethoxysilane 109.0g which were obtained by the synthesis example 1 were mixed, and it was dripped over 1.5 hours using the dropping funnel. Thereafter, the reaction was carried out at 40 ° C. for 4 hours. After the reaction, 2% citric acid water was added for neutralization. Further, 805.4 g of toluene and 201.4 g of ion-exchanged water were added, followed by liquid separation after stirring. To the separated oil layer, 314.1 g of ion-exchanged water was added and stirred for liquid separation. The same operation was performed once more. When the obtained oil layer was concentrated, 393.6 g of a colorless transparent liquid 4-methoxybenzylsilsesquioxane / methyltrimethoxysilane copolymer (solid content 71% toluene solution) was obtained.

(2) Deprotection 1102.1 g of acetonitrile (4.0 times by weight / polymer) was added to the obtained polymer, and while stirring, 264.4 g of sodium iodide and 263.5 g of trimethylsilyl chloride (2.0 mol times / methoxybenzyl). Unit) and the temperature was raised to 65 ° C. Then, after making it react for 16 hours, it cooled and ion-exchange water 84.8g was dripped. After reacting at 30 ° C. for 1.5 hours, 822.4 g of 15% aqueous sodium bisulfite solution was added. After adding 640.9 g of methyl isobutyl ketone and stirring, the solution was separated. 256.3 g of ion exchange water was added to the oil layer, and the mixture was separated with stirring. This operation was repeated 5 times. Thereafter, the solvent is removed by concentration under reduced pressure, and 604.0 g of 4-hydroxybenzylsilsesquioxane / methylsilsesquioxane copolymer, which is a yellow transparent liquid, is added by adding propylene glycol monomethyl ether (PGME) ( A 40% solid content PGME solution) was obtained. The obtained 4-hydroxybenzylsilsesquioxane / methylsilsesquioxane copolymer was analyzed by GPC. The measurement result of the gel permeation chromatography of the silicone copolymer obtained by Example 8 was shown in FIG. Molecular weight (Mw) 3530, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 94%). Table 2 summarizes the composition ratios of the component (a), the component (b), and the component (c). The component (a) was 56 mol%, the component (b) was 4 mol%, and the component (c) was 40 mol%.

  Table 2 shows the results of measurement of alkali dissolution rate (ADR) using 2.38% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). ADR (2.38% TMAH aqueous solution) was 200 (Å / s).

Example 9
Synthesis of 4-hydroxybenzylsilsesquioxane / methylsilsesquioxane copolymer having three peaks obtained by gel permeation chromatography

(55:45 indicates the charged molar composition ratio of raw materials)
(1) Hydrolysis, condensation polymerization In a 5 L four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 23.0 g of 25% tetramethylammonium hydroxide aqueous solution, 81.1 g of ion-exchanged water, 2 -583.8 g of propanol and 817.3 g of toluene were charged. After raising the temperature to 40 ° C., 399.9 g of 4-methoxybenzyltrimethoxysilane obtained in Synthesis Example 1 and 183.9 g of methyltrimethoxysilane were mixed and added dropwise over 1.5 hours using a dropping funnel. Thereafter, the reaction was carried out at 40 ° C. for 4 hours. After the reaction, 2% citric acid water was added for neutralization. Furthermore, 1167.5 g of toluene and 291.9 g of ion-exchanged water were added, and the mixture was separated after stirring. 437.8 g of ion-exchanged water was added to the separated oil layer, and the mixture was stirred and separated. The same operation was performed once more. When the obtained oil layer was concentrated, 482.3 g of a colorless transparent liquid 4-methoxybenzylsilsesquioxane / methyltrimethoxysilane copolymer (solid content 77% toluene solution) was obtained.

(2) Deprotection 1487.2 g (4.0 times by weight / polymer) of acetonitrile was added to the obtained polymer, and 423.7 g of sodium iodide and 422.1 g of trimethylsilyl chloride (2.0 mol times / methoxybenzyl) with stirring. Unit) and the temperature was raised to 65 ° C. Then, after making it react for 16 hours, it cooled and 140.4g of ion-exchange water was dripped. After reacting at 30 ° C. for 1.5 hours, 1187.3 g of 15% aqueous sodium hydrogen sulfite solution was added. After adding 931.1 g of methyl isobutyl ketone and stirring, the solution was separated. To the oil layer, 371.9 g of ion-exchanged water was added, followed by liquid separation with stirring. This operation was repeated 5 times. Thereafter, the solvent is removed by concentration under reduced pressure, and 883.5 g of 4-hydroxybenzylsilsesquioxane / methylsilsesquioxane copolymer, which is a yellow transparent liquid, is added by adding propylene glycol monomethyl ether (PGME) ( A 40% solid content PGME solution) was obtained. The obtained 4-hydroxybenzylsilsesquioxane / methylsilsesquioxane copolymer was analyzed by GPC. 7 and 8 show the gel permeation chromatography measurement results of the silicone copolymer obtained in Example 9. FIG. Molecular weight (Mw) 4030, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 100%). Table 2 summarizes the composition ratios of the component (a), the component (b), and the component (c). Component (a) was 55 mol%, component (b) was 0 mol%, and component (c) was 45 mol%.

  Table 2 shows the results of measurement of alkali dissolution rate (ADR) using 2.38% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). ADR (2.38% TMAH aqueous solution) was 140 (Å / s).

Example 10
Synthesis of 4-hydroxybenzylsilsesquioxane / phenylsilsesquioxane copolymer having 3 peaks obtained by gel permeation chromatography

(70:30 indicates the charged molar composition ratio of raw materials)
(1) Hydrolysis, condensation polymerization In a 5 L four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 16.0 g of 25% tetramethylammonium hydroxide aqueous solution, 59.5 g of ion-exchanged water, 2 -504.1 g of propanol and 252.0 g of toluene were charged. After raising the temperature to 40 ° C., 373.2 g of 4-methoxybenzyltrimethoxysilane obtained in Synthesis Example 1 and 130.87 g of phenyltrimethoxysilane were added dropwise over 1.5 hours using a dropping funnel. Thereafter, the reaction was carried out at 40 ° C. for 4 hours. After the reaction, 2% citric acid water was added for neutralization. Furthermore, toluene 1008.4g and ion-exchange water 252.0g were added, and it liquid-separated after stirring. 378.1 g of ion-exchanged water was added to the separated oil layer, and the mixture was stirred and separated. The same operation was performed once more. When the obtained oil layer was concentrated, 457.7 g of a colorless transparent liquid 4-methoxybenzylsilsesquioxane / phenylsilsesquioxane copolymer (solid content 70% toluene solution) was obtained.

(2) Deprotection 1408.2 g (4.0 weight times / polymer) of acetonitrile was added to the obtained polymer, and 346.3 g of sodium iodide and 418.3 g of trimethylsilyl chloride (2.5 mole times / methoxybenzyl) with stirring. Unit) and the temperature was raised to 65 ° C. Then, after making it react for 16 hours, it cooled and 138.8g of ion-exchange water was dripped. After reacting at 30 ° C. for 1.5 hours, 921.5 g of a 15% aqueous sodium hydrogen sulfite solution was added. After adding 880.1 g of methyl isobutyl ketone and stirring, the solution was separated. To the oil layer, 352.1 g of ion-exchanged water was added, followed by separation with stirring. This operation was repeated 5 times. Thereafter, the solvent was removed by concentration under reduced pressure, and 587 g (solid content) of 4-hydroxybenzylsilsesquioxane / phenylsilsesquioxane copolymer as a yellow transparent liquid was added by adding propylene glycol monomethyl ether (PGME). 40% PGME solution) was obtained. The obtained 4-hydroxybenzylsilsesquioxane / phenylsilsesquioxane copolymer was analyzed by GPC. 9 and 10 show the results of gel permeation chromatography measurement of the silicone copolymer obtained in Example 10. FIG. Molecular weight (Mw) 4500, two inflection points existed, and the number of peaks was three. The deprotection rate determined by NMR was 100%. Table 2 summarizes the composition ratios of the component (a), the component (b), and the component (c). The component (a) was 70 mol%, the component (b) was 0 mol%, and the component (c) was 30 mol%.

  Table 2 shows the results of measurement of alkali dissolution rate (ADR) using 2.38% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). ADR (2.38% TMAH aqueous solution) was 460 (Å / s).

Example 11
Synthesis of 4-hydroxybenzylsilsesquioxane / phenylsilsesquioxane copolymer having 3 peaks obtained by gel permeation chromatography

(60:40 indicates the charged molar composition ratio of raw materials)
(1) Hydrolysis, condensation polymerization In a 5 L four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 13.8 g of 25% tetramethylammonium hydroxide aqueous solution, 48.7 g of ion-exchanged water, 2 -404.5 g of propanol and 101.1 g of toluene were charged. After the temperature was raised to 40 ° C., 261.7 g of 4-methoxybenzyltrimethoxysilane obtained in Synthesis Example 1 and 142.8 g of phenyltrimethoxysilane were added dropwise over 1.5 hours using a dropping funnel. Thereafter, the reaction was carried out at 40 ° C. for 4 hours. After the reaction, 2% citric acid water was added for neutralization. Furthermore, 1213.5 g of toluene and 202.2 g of ion-exchanged water were added, followed by liquid separation after stirring. To the separated oil layer, 303.4 g of ion-exchanged water was added, followed by liquid separation after stirring. The same operation was performed once more. When the obtained oil layer was concentrated, 366.8 g of a colorless transparent liquid 4-methoxybenzylsilsesquioxane / phenylsilsesquioxane copolymer (solid content 75% toluene solution) was obtained.

(2) Deprotection 1152.0 g of acetonitrile (4.0 times by weight / polymer) was added to the obtained polymer, and while stirring, 404.7 g of sodium iodide and 391.1 g of trimethylsilyl chloride (2.5 mol times / methoxybenzyl). Unit) and the temperature was raised to 65 ° C. Then, after making it react for 16 hours, it cooled and 129.7g of ion-exchange water was dripped. After reacting at 30 ° C. for 1.5 hours, 936.6 g of 15% aqueous sodium bisulfite solution was added. After adding 720.1 g of methyl isobutyl ketone and stirring, the solution was separated. To the oil layer, 288.0 g of ion-exchanged water was added, followed by liquid separation with stirring. This operation was repeated 5 times. Thereafter, the solvent is removed by concentration under reduced pressure, and 632 g of 4-hydroxybenzylsilsesquioxane / phenylsilsesquioxane copolymer (solid content) which is a yellow transparent liquid is added by adding propylene glycol monomethyl ether (PGME). 40% PGME solution) was obtained. The obtained 4-hydroxybenzylsilsesquioxane / phenylsilsesquioxane copolymer was analyzed by GPC. The measurement result of the gel permeation chromatography of Example 11 was shown in FIGS. Molecular weight (Mw) 3470 There were two inflection points, and the number of peaks was three. The deprotection rate determined by NMR was 100%. Table 2 summarizes the composition ratios of the component (a), the component (b), and the component (c). The component (a) was 60 mol%, the component (b) was 0 mol%, and the component (c) was 40 mol%.

  Table 2 shows the results of measurement of alkali dissolution rate (ADR) using 2.38% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). ADR (2.38% TMAH aqueous solution) was 220 (Å / s).

Comparative Example 6
Synthesis of 4-methoxybenzylsilsesquioxane polymer having one peak obtained by gel permeation chromatography measurement

  A 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 3.3 g of 35% aqueous hydrochloric acid and 120 g of water, and stirring was started. Moreover, the toluene 120mL solution of 4-methoxybenzyltrimethoxysilane 78.5g (0.324 mol) was dripped at 15-20 degreeC. Thereafter, the mixture was aged for 2 hours at a temperature of 15 to 20 ° C., extracted by adding toluene, removed the aqueous layer, washed 4 times with an aqueous sodium hydrogen carbonate solution, dilute acetic acid aqueous solution and water, concentrated the oil layer to 4- 57.5 g of a methoxybenzylsilsesquioxane condensation polymer was obtained.

The spectrum data of the obtained copolymer are shown below. Infrared absorption spectrum (IR) data 1026 to 1246 cm ⁻¹ (Si—O), 2951 to 3071 cm ⁻¹ (C—H), 3165 to 3603 cm ⁻¹ (Si— OH)
Nuclear magnetic resonance spectrum (NMR) data ( ¹ H-NMR δ (ppm), solvent: CDCl ₃ )
1.83 (bs, 2H, —CH ₂ —), 3.68 (bs, 3H, CH ₃ —O—), 6.69 (bs, 4H, Ar—H) ppm
GPC analysis data: Mw = 2,530, Mn = 1,610, Mw / Mn = 1.57 (polystyrene conversion).

  In FIG. 13, the measurement result of the gel permeation chromatography of the silicone polymer obtained by the comparative example 6 was shown. In the figure, ◯ indicates a calibration curve measured with polystyrene, and the rightmost ◯ indicates a weight average molecular weight (Mw) 500. The peak in between is the peak of the silicone copolymer. From the GPC analysis results, it was found that there was one peak shape. The substance of Comparative Example 6 tried to measure the alkali dissolution rate (ADR) using a tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution), but did not dissolve and could not be measured.

  The results of Examples and Comparative Examples are shown in Tables 1 and 2.

  The silicone copolymers of Examples 1 to 6 were dissolved in alkali. On the other hand, the substances of Comparative Examples 1 to 5 tried to measure the alkali dissolution rate (ADR) using a tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution), but did not dissolve and could not be measured.

  The silicone copolymers of the examples in Table 1 and Table 2 have tetramethylammonium hydroxide since the component (a) having a phenol group is (a) / ((a) + (b)) = 0.8 or more. Although dissolved in an aqueous solution, the ricone copolymer of the comparative example has tetramethylammonium hydroxide since the component (a) having a phenol group is less than (a) / ((a) + (b)) = 0.8. It did not dissolve in the aqueous solution.

  Since the silicone copolymer of the present invention is a material having good transparency in the visible light wavelength, excellent adhesion, crack resistance, and stable alkali dissolution rate, a liquid crystal display element, a semiconductor element, etc. It is suitably used for electronic components.

  The silicone copolymer of the present invention can be applied to a wide range of fields such as paints and adhesives.

Claims (8)

General formula

(Wherein, a, b and c represent mol%, Y represents an organic group, and X represents a trimethylsilyl group.)
(A + b) is 40 to 100 mol%, c is 0 to 60 mol%, a + b + c = 100 mol%, and a / (a + b) is 0.8 or more and 1 or less, and is obtained by gel permeation chromatography measurement. A silicone polymer having 2 or more peaks. The silicone polymer according to claim 1, having a weight average molecular weight of 500 to 20,000. The silicone polymer according to claim 1 or 2, wherein the alkali dissolution rate is 100 Å / s or more. General formula

(Wherein, R represents a methyl group, Z ¹ represents a monovalent hydrocarbon group) and a general formula

(Wherein Y represents an organic group and Z ² represents a monovalent hydrocarbon group). A hydrolyzed mixture of silicon compounds represented in the presence of a quaternary ammonium salt is subjected to a polycondensation reaction. And then deprotecting in an aprotic polar solvent,

(Wherein, a, b and c represent mol%, Y represents an organic group, and X represents a trimethylsilyl group.)
(A + b) is 40 to 100 mol%, c is 0 to 60 mol%, a + b + c = 100 mol%, and a / (a + b) is 0.8 or more and 1 or less, and is obtained by gel permeation chromatography measurement. A method for producing a silicone polymer, comprising producing a silicone polymer having 2 or more peaks. The method for producing a silicone polymer according to claim 4, wherein all reactions are performed in one-pot. The method for producing a silicone polymer according to claim 4 or 5, wherein the hydrolysis and condensation polymerization reactions are carried out at 0 to 100 ° C. The method for producing a silicone polymer according to claim 4 or 5, wherein the quaternary ammonium salt is tetramethylammonium hydroxide. The method for producing a silicone polymer according to claim 4 or 5, wherein the aprotic polar solvent is acetonitrile or chloroform.

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