JP7531449B2 - Method for producing silicone resin - Google Patents

Description

The present invention relates to a method for producing a Ti-containing silicone resin.

Traditionally, silicone resins have been used as raw materials for cosmetics, such as makeup cosmetics such as foundations, lipsticks, eye shadows, and mascaras, UV protection cosmetics, and hair cosmetics, due to their film-forming ability and excellent resistance to water, sweat, and sebum.

For example, there are disclosed a skin cosmetic containing an organic silicone resin composed of units of the average formula R _n SiO _4-n/2 and a volatile hydrocarbon oil (Patent Document 1), a skin cosmetic containing a resin composed of R ₃ SiO _1/2 units and SiO _4/2 units and a volatile silicone oil (Patent Document 2), a silicone resin containing two or more types of R ₂ SiO _2/2 units, RSiO _3/2 units and SiO _4/2 units and optionally having terminals blocked with R 3 SiO _1/2 units, a sunscreen cosmetic containing a volatile oil agent and an ultraviolet absorbing agent and/or an ultraviolet scattering agent (Patent Document 3), a cosmetic containing 70 mol % or more of R ₃ SiO 1/2 units and SiO 4/2 units and having R 3 SiO 1/2 units and SiO 4/2 units and a volatile silicone oil (Patent Document 4), and a cosmetic containing 70 mol % or more of R ₃ SiO _1/2 units and SiO _4/2 units and having R ₃ SiO 1/2 units and SiO _4/2 units and a volatile silicone oil (Patent Document 5). Skin cosmetics containing 1 to 70% by mass of an organic silicone resin having a molar ratio of 0.5/1 to 1.5/1 with respect to _4/2 units (Patent Document 4) are known, and it is disclosed that these produce coatings with excellent water resistance.

In recent years, organic silicone resins containing different metals with excellent water and oil repellency have been developed (Patent Document 5). However, this method has the problem that the synthesis is carried out in a humidity-controlled glove box in order to control the hydrolysis rate of titanium isopropoxide, and the dropping and aging times are long, resulting in a low yield.

Special Publication No. 04-59284 Special Publication No. 06-15448 Japanese Unexamined Patent Publication No. 62-234012 Japanese Unexamined Patent Publication No. 62-298511 Patent No. 3799171

The present invention has been made in consideration of the above circumstances, and aims to provide a simple and efficient method for producing Ti-containing silicone resin.

（式中、Ｒは独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基及び炭素数１～８のフッ素置換アルキル基から選ばれる基であり、ａは０．１～０．７、ｂは０～０．５、ｃは０～０．９、ｄは０．２～０．７、ｅは０．０１～０．３であり、ａ＋ｂ＋ｃ＋ｄ＋ｅは１．０である。）
で表されるシリコーン樹脂の製造方法であって、
（ｉ）下記一般式（２）及び下記一般式（３）
Ｒ^１ _３ＳｉＯＳｉＲ^１ _３ （２）
Ｒ^１ _３ＳｉＯＨ （３）
（式中、Ｒ^１は前記Ｒと同じである。）
で表される有機ケイ素化合物から選ばれる１種又は２種以上と、
下記一般式（４）、下記一般式（５）、及び下記一般式（６）
（Ｒ^４Ｏ）_２ＳｉＲ^２ _２ （４）
（Ｒ^４Ｏ）_３ＳｉＲ^３ （５）
（Ｒ^４Ｏ）_４Ｓｉ （６）
（式中、Ｒ^２及びＲ^３は前記Ｒと同じである。Ｒ^４は独立に水素原子又は非置換又は置換一価炭化水素基である。）
で表されるシラン及びその部分加水分解縮合物から選ばれる１種又は２種以上と
を無溶媒又は溶媒中において、加水分解・縮合させる工程と、
（ｉｉ）得られた加水分解・縮合物を加熱して水を除去する工程と、
（ｉｉｉ）下記一般式（７）
Ｔｉ（ＯＲ^４）_４ （７）
（式中、Ｒ^４は前記と同じである。）
で表されるチタンアルコキシド及びその部分加水分解縮合物から選ばれる１種又は２種以上と前記水を除去した加水分解・縮合物とを縮合させる工程と
を含むシリコーン樹脂の製造方法を提供する。 In order to solve the above problems, the present invention provides
The following composition formula (1)

(In the formula, R is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a fluorine-substituted alkyl group having 1 to 8 carbon atoms, a is 0.1 to 0.7, b is 0 to 0.5, c is 0 to 0.9, d is 0.2 to 0.7, e is 0.01 to 0.3, and a+b+c+d+e is 1.0.)
A method for producing a silicone resin represented by the formula:
(i) The following general formula (2) and the following general formula (3):
R ¹ ₃ SiOSiR ¹ ₃ (2)
R ¹ ₃ SiOH (3)
(In the formula, ^R1 is the same as R above.)
and one or more organosilicon compounds represented by the formula:
The following general formula (4), the following general formula (5), and the following general formula (6):
(R ⁴ O) ₂ SiR ² ₂ (4)
(R ⁴ O) ₃ SiR ³ (5)
(R ⁴ O) ₄ Si (6)
(In the formula, ^R2 and ^R3 are the same as R above. ^R4 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group.)
and a partial hydrolysis and condensation product thereof, in the absence of a solvent or in a solvent;
(ii) heating the resulting hydrolysis/condensation product to remove water;
(iii) a compound represented by the following general formula (7):
Ti( ^OR4 ) ₄ (7)
(In the formula, ^R4 is the same as defined above.)
and a partial hydrolysis-condensation product thereof, with the hydrolysis-condensation product from which water has been removed.

This method for producing silicone resin is a method for producing Ti-containing silicone resin with simple steps and improved yield.

In (ii) above, it is preferable to add a solvent to the hydrolysis/condensation product before removing water.

This method of producing silicone resin makes it possible to dissolve solid silicone resin, and to smoothly proceed with the reaction between the hydrolysis/condensation product from which the water has been removed and the titanium alkoxide.

According to the present invention, since there is no need to control the hydrolysis rate of titanium alkoxide using dropwise addition or a solvent, etc., it is possible to provide a method for producing a Ti-containing silicone resin with a simple process and improved yield.

1 is an example of IR spectrum of silicone resins synthesized in Examples and Comparative Examples. 1 is an example of the UV spectrum of the silicone resins synthesized in the examples and comparative examples.

As described above, there was a need for a method for producing Ti-containing silicone resin with simple steps and improved yield.

As a result of investigations conducted by the inventors to achieve the above object, they discovered that Ti-containing silicone resins can be obtained in high yields by hydrolyzing and condensing organosilicon compounds of general formulas (2) and (3) with silanes and their partial hydrolysis condensates of general formulas (4), (5), and (6) in the presence of an acid catalyst, heating to remove excess water, and then reacting titanium alkoxide of general formula (7) with its partial hydrolysis condensate, which led to the present invention.

（式中、Ｒは独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基及び炭素数１～８のフッ素置換アルキル基から選ばれる基であり、ａは０．１～０．７、ｂは０～０．５、ｃは０～０．９、ｄは０．２～０．７、ｅは０．０１～０．３であり、ａ＋ｂ＋ｃ＋ｄ＋ｅは１．０である。）
で表されるシリコーン樹脂の製造方法であって、
（ｉ）下記一般式（２）及び下記一般式（３）
Ｒ^１ _３ＳｉＯＳｉＲ^１ _３ （２）
Ｒ^１ _３ＳｉＯＨ （３）
（式中、Ｒ^１は前記Ｒと同じである。）
で表される有機ケイ素化合物から選ばれる１種又は２種以上と、
下記一般式（４）、下記一般式（５）、及び下記一般式（６）
（Ｒ^４Ｏ）_２ＳｉＲ^２ _２ （４）
（Ｒ^４Ｏ）_３ＳｉＲ^３ （５）
（Ｒ^４Ｏ）_４Ｓｉ （６）
（式中、Ｒ^２及びＲ^３は前記Ｒと同じである。Ｒ^４は独立に水素原子又は非置換又は置換一価炭化水素基である。）
で表されるシラン及びその部分加水分解縮合物から選ばれる１種又は２種以上と
を無溶媒又は溶媒中において、加水分解・縮合させる工程と、
（ｉｉ）得られた加水分解・縮合物を加熱して水を除去する工程と、
（ｉｉｉ）下記一般式（７）
Ｔｉ（ＯＲ^４）_４ （７）
（式中、Ｒ^４は前記と同じである。）
で表されるチタンアルコキシド及びその部分加水分解縮合物から選ばれる１種又は２種以上と前記水を除去した加水分解・縮合物とを縮合させる工程と
を含むシリコーン樹脂の製造方法である。 That is, the present invention provides:
The following composition formula (1)

(In the formula, R is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a fluorine-substituted alkyl group having 1 to 8 carbon atoms, a is 0.1 to 0.7, b is 0 to 0.5, c is 0 to 0.9, d is 0.2 to 0.7, e is 0.01 to 0.3, and a+b+c+d+e is 1.0.)
A method for producing a silicone resin represented by the formula:
(i) The following general formula (2) and the following general formula (3):
R ¹ ₃ SiOSiR ¹ ₃ (2)
R ¹ ₃ SiOH (3)
(In the formula, ^R1 is the same as R above.)
and one or more organosilicon compounds represented by the formula:
The following general formula (4), the following general formula (5), and the following general formula (6):
(R ⁴ O) ₂ SiR ² ₂ (4)
(R ⁴ O) ₃ SiR ³ (5)
(R ⁴ O) ₄ Si (6)
(In the formula, ^R2 and ^R3 are the same as R above. ^R4 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group.)
and a partial hydrolysis and condensation product thereof, in the absence of a solvent or in a solvent;
(ii) heating the resulting hydrolysis/condensation product to remove water;
(iii) a compound represented by the following general formula (7):
Ti( ^OR4 ) ₄ (7)
(In the formula, ^R4 is the same as defined above.)
and a partial hydrolysis-condensation product thereof, and a process for producing a silicone resin, comprising the step of condensing said hydrolysis-condensation product from which water has been removed.

The present invention is described in detail below, but is not limited to these.

（式中、Ｒは独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基及び炭素数１～８のフッ素置換アルキル基から選ばれる基であり、ａは０．１～０．７、ｂは０～０．５、ｃは０～０．９、ｄは０．２～０．７、ｅは０．０１～０．３であり、ａ＋ｂ＋ｃ＋ｄ＋ｅは１．０である。） [Method of manufacturing silicone resin]
The method for producing a silicone resin represented by the following composition formula (1) of the present invention includes the following steps (i) to (iii).

(In the formula, R is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a fluorine-substituted alkyl group having 1 to 8 carbon atoms, a is 0.1 to 0.7, b is 0 to 0.5, c is 0 to 0.9, d is 0.2 to 0.7, e is 0.01 to 0.3, and a+b+c+d+e is 1.0.)

[Step (i)]
The step (i) is a step of reacting a compound represented by the following general formula (2) and the following general formula (3):
R ¹ ₃ SiOSiR ¹ ₃ (2)
R ¹ ₃ SiOH (3)
(In the formula, ^R1 is the same as R above.)
and one or more organosilicon compounds represented by the formula:
The following general formula (4), the following general formula (5), and the following general formula (6):
(R ⁴ O) ₂ SiR ² ₂ (4)
(R ⁴ O) ₃ SiR ³ (5)
(R ⁴ O) ₄ Si (6)
(In the formula, ^R2 and ^R3 are the same as R above. ^R4 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group.)
and partial hydrolysis and condensation products thereof, in the absence of a solvent or in a solvent.

R ¹ , R ² and R ³ are the same as R above, but are preferably a methyl group or an ethyl group, more preferably a methyl group. R ⁴ is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, and is preferably an alkyl group having 1 to 4 carbon atoms. The compounds represented by the above general formulae (2) and (3) and the compounds represented by the above general formulae (4) to (6) can each be used alone or in appropriate combination of two or more kinds.

The hydrolysis and condensation reaction in step (i) is preferably carried out under acidic conditions, and it is preferable to add an acidic substance as a catalyst. Examples of acidic substances include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, acetic acid, and citric acid. These can be used alone or in appropriate combination of two or more. The amount used can be small, and is preferably 0.001 to 10% by mass of the entire hydrolysis and condensation reaction system.

The reaction can be carried out without a solvent or in a solvent, and is preferably carried out in a solvent. Examples of the solvent used in step (i) include hydrocarbon solvents such as toluene, xylene, and isoparaffin, ether solvents such as tetrahydrofuran, and aliphatic alcohol solvents having 1 to 10 carbon atoms such as methanol, ethanol, (iso)propyl alcohol, and butanol. These can be used alone or in appropriate combination of two or more. Among them, aliphatic alcohol solvents having 1 to 10 carbon atoms are preferred, and ethanol and isopropyl alcohol (IPA) are more preferred. The amount of solvent is preferably 5 to 50% by mass of the entire hydrolysis/condensation reaction system.

More specifically, for example, an organosilicon compound, a silane or a partial hydrolysis condensate thereof, and a solvent are charged into a reactor, an acid is added, and water is added dropwise with stirring. The temperature when adding water is preferably 0 to 60°C, particularly 0 to 40°C, and the amount of water added is preferably in the range of 0.6 to 2.5 in terms of molar ratio to the hydrolyzable groups. After adding water, the hydrolysis and condensation reaction is carried out, and it is preferable to heat at 30 to 100°C, particularly 50 to 80°C, for 2 to 8 hours.

After hydrolysis, it is preferable to remove the acid. To remove the acid, a method of neutralizing the acid with an alkali metal carbonate, an alkali metal hydrogen carbonate, an alkali metal hydroxide, etc., or a method of removing the acid in a water washing process can be used.

The solvent in step (i) may be distilled off after completion of the reaction.

[Step (ii)]
The step (ii) is a step of heating the obtained hydrolyzate/condensate to remove water.

In step (ii), a solvent may be added to the hydrolyzate/condensate before removing water. In this case, the solvent is preferably an oil that can be used in cosmetics. Specific examples include organic oily components such as silicone oil and hydrocarbon oil. In particular, volatile siloxane compounds such as octamethyltrisiloxane, decamethyltetrasiloxane, decamethylcyclopentasiloxane, and tristrimethylsiloxymethylsilane, and volatile hydrocarbon compounds such as isododecane are preferred. These can be used alone or in appropriate combination of two or more. The amount of oil is preferably 10 to 80% by mass of the total of the hydrolyzate/condensate obtained in step (i) and the oil.

Such a solvent (oil) can also be added during the hydrolysis and condensation reaction in step (i) above. The solvent (oil) in steps (i) and (ii) can be distilled off after the reaction is completed.

More specifically, step (ii) is, for example, a step in which after removing the acid in step (i) above, a solvent (oil) is preferably added, and the generated alcohol and excess water are removed by heating to 90 to 120°C under normal or reduced pressure.

[Step (iii)]
The step (iii) is a step of reacting a compound represented by the following general formula (7):
Ti( ^OR4 ) ₄ (7)
(In the formula, ^R4 is the same as defined above.)
and partial hydrolysis and condensation products thereof, with the hydrolysis and condensation product from which water has been removed.

^R4 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms.

If titanium alkoxide and its partial hydrolysis condensate are added at the time of the initial charge corresponding to step (i), the titanium alkoxide and its partial hydrolysis condensate will hydrolyze at a high rate, causing cloudiness. In order to avoid this cloudiness, the present invention is characterized in that water is removed in step (ii) and then titanium alkoxide is added in step (iii).

Preferred examples of titanium alkoxides and their partial hydrolysis condensates include tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, diisopropoxybisacetylacetonatotitanium, propanedioxytitaniumbisethylacetoacetate, and oligomers obtained by partial hydrolysis of these. These can be used alone or in appropriate combination of two or more.

Specifically, in step (iii), after cooling, titanium alkoxide or a partial hydrolysis condensate thereof is added to the hydrolysis/condensation product from which the water has been removed, and the mixture is heated at 100 to 150°C for 2 to 5 hours under normal or reduced pressure to carry out a condensation reaction, thereby obtaining a Ti-containing silicone resin solution.

In addition, since the silicone resin obtained by the manufacturing method of the present invention may be a solid, it is preferable to dilute it with a solvent (oil) after the reaction in step (iii) is completed to make a solution. The solvent (oil) used for dilution may be the same as or different from the solvent in step (i) and step (ii), and examples of the solvent (oil) used for dilution include organic oily components such as silicone oil and hydrocarbon oil, and decamethylcyclopentasiloxane, isododecane, and octyl paramethoxycinnamate are preferred. When diluted, it is preferable to make a solvent (oil) solution in which the amount of the silicone resin obtained by the manufacturing method of the present invention is 30 to 70 mass %.

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, unless otherwise specified, "%" in the composition indicates mass %. In addition, ( _CH3 ) _{3SiO1 /2} units are referred to as M units, _{CH3SiO3 /2} units as T units, SiO4 _/2 units as Q units, and TiO4 _/2 units as Ti units.

[Example 1]
26.18 g of hexamethyldisiloxane, 74.68 g of tetraethoxysilane, and 64 g of isopropyl alcohol (hereinafter, IPA) were charged into a reactor, 0.64 g of methanesulfonic acid was added, and the mixture was cooled to 10 to 20° C., and 47.54 g of water was added dropwise with stirring. After the dropwise addition was completed, the mixture was heated at 50 to 80° C. for 5 hours to carry out a hydrolysis and condensation reaction, and a silicone resin solution was obtained.

Next, 1.03 g of 25% sodium hydroxide solution and 0.13 g of calcium carbonate were added to neutralize the acid, and then 100 g of isododecane was added and heated to 90-115°C. The resulting ethanol, IPA, and excess water were removed and the mixture was cooled. Then, 3.96 g of tetraisopropoxytitanium (tetraisopropyl orthotitanate) was added dropwise while stirring, and after stirring for 2 hours, the mixture was heated at 130°C for 3 hours to remove the resulting IPA and water, and then cooled. After further distillation under reduced pressure, the mixture was diluted with decamethylcyclopentasiloxane as an oil agent to a silicone resin concentration of 60%, and then filtered to obtain a 60% silicone resin decamethylcyclopentasiloxane solution with a molar ratio of M units:Q units:Ti units of 0.46:0.52:0.02.

[Example 2]
A reactor was charged with 26.18 g of hexamethyldisiloxane, 74.68 g of tetraethoxysilane, and 64 g of IPA, to which 0.64 g of methanesulfonic acid was added, and the mixture was cooled to 10 to 20° C., and 47.54 g of water was added dropwise with stirring. After completion of the dropwise addition, the mixture was heated at 50 to 80° C. for 5 hours to carry out a hydrolysis and condensation reaction, yielding a silicone resin solution.

Next, 1.03 g of 25% aqueous sodium hydroxide solution and 0.13 g of calcium carbonate were added to neutralize the acid, after which 100 g of isododecane was added and the mixture was heated to 90-115°C. The resulting ethanol, IPA, and excess water were removed and the mixture was cooled. 3.96 g of tetraisopropoxytitanium was then added dropwise while stirring, and after stirring for 2 hours, the mixture was heated at 130°C for 3 hours to remove the resulting IPA and water, and then cooled. After further distillation under reduced pressure, the mixture was diluted with isododecane as an oil agent to a silicone resin concentration of 60%, and then filtered to obtain a 60% silicone resin isododecane solution with a molar ratio of M units:Q units:Ti units of 0.46:0.52:0.02.

[Example 3]
A reactor was charged with 26.18 g of hexamethyldisiloxane, 74.68 g of tetraethoxysilane, and 64 g of IPA, to which 0.64 g of methanesulfonic acid was added, and the mixture was cooled to 10 to 20° C., and 47.54 g of water was added dropwise with stirring. After completion of the dropwise addition, the mixture was heated at 50 to 80° C. for 5 hours to carry out a hydrolysis and condensation reaction, yielding a silicone resin solution.

Next, 1.03 g of 25% aqueous sodium hydroxide solution and 0.13 g of calcium carbonate were added to neutralize the acid, after which 100 g of isododecane was added and heated to 90-115°C. The resulting ethanol, IPA, and excess water were removed and the mixture was cooled. 8.08 g of tetraisopropoxytitanium was added dropwise while stirring, and after stirring for 2 hours, the mixture was heated at 130°C for 3 hours to remove the resulting IPA and water, and then cooled. After further distillation under reduced pressure, the mixture was diluted with decamethylcyclopentasiloxane as an oil agent to a silicone resin concentration of 60%, and then filtered to obtain a 60% silicone resin decamethylcyclopentasiloxane solution with a molar ratio of M units:Q units:Ti units of 0.46:0.50:0.04.

[Example 4]
A reactor was charged with 26.18 g of hexamethyldisiloxane, 74.68 g of tetraethoxysilane, and 64 g of IPA, to which 0.64 g of methanesulfonic acid was added, and the mixture was cooled to 10 to 20° C., and 47.54 g of water was added dropwise with stirring. After completion of the dropwise addition, the mixture was heated at 50 to 80° C. for 5 hours to carry out a hydrolysis and condensation reaction, yielding a silicone resin solution.

Next, 1.03 g of 25% aqueous sodium hydroxide solution and 0.13 g of calcium carbonate were added to neutralize the acid, after which 100 g of isododecane was added and the mixture was heated to 90-115°C. The resulting ethanol, IPA, and excess water were removed and the mixture was cooled. 8.08 g of tetraisopropoxytitanium was then added dropwise while stirring, and after stirring for 2 hours, the mixture was heated at 130°C for 3 hours to remove the resulting IPA and water, and then cooled. After further distillation under reduced pressure, the mixture was diluted with isododecane as an oil agent to a silicone resin concentration of 60%, and then filtered to obtain a 60% silicone resin isododecane solution with a molar ratio of M units:Q units:Ti units of 0.46:0.50:0.04.

[Example 5]
A reactor was charged with 26.18 g of hexamethyldisiloxane, 74.68 g of tetraethoxysilane, and 64 g of IPA, to which 0.64 g of methanesulfonic acid was added, and the mixture was cooled to 10 to 20° C., and 47.54 g of water was added dropwise with stirring. After completion of the dropwise addition, the mixture was heated at 50 to 80° C. for 5 hours to carry out a hydrolysis and condensation reaction, yielding a silicone resin solution.

Next, 1.03 g of 25% aqueous sodium hydroxide solution and 0.13 g of calcium carbonate were added to neutralize the acid, after which 100 g of isododecane was added and heated to 90-115°C. The resulting ethanol, IPA, and excess water were removed and the mixture was cooled. 12.37 g of tetraisopropoxytitanium was then added dropwise while stirring, and after stirring for 2 hours, the mixture was heated at 130°C for 3 hours to remove the resulting IPA and water, and then cooled. After further distillation under reduced pressure, the mixture was diluted with decamethylcyclopentasiloxane as an oil agent to a silicone resin concentration of 60%, and then filtered to obtain a 60% silicone resin decamethylcyclopentasiloxane solution with a molar ratio of M units:Q units:Ti units of 0.45:0.49:0.06.

[Example 6]
A reactor was charged with 26.18 g of hexamethyldisiloxane, 74.68 g of tetraethoxysilane, and 64 g of IPA, to which 0.64 g of methanesulfonic acid was added, and the mixture was cooled to 10 to 20° C., and 47.54 g of water was added dropwise with stirring. After completion of the dropwise addition, the mixture was heated at 50 to 80° C. for 5 hours to carry out a hydrolysis and condensation reaction, yielding a silicone resin solution.

Next, 1.03 g of 25% aqueous sodium hydroxide solution and 0.13 g of calcium carbonate were added to neutralize the acid, after which 100 g of isododecane was added and the mixture was heated to 90-115°C. The resulting ethanol, IPA, and excess water were removed and the mixture was cooled. 12.37 g of tetraisopropoxytitanium was then added dropwise while stirring, and after stirring for 2 hours, the mixture was heated at 130°C for 3 hours to remove the resulting IPA and water, and then cooled. After further distillation under reduced pressure, the mixture was diluted with isododecane as an oil agent to a silicone resin concentration of 60%, and then filtered to obtain a 60% silicone resin isododecane solution with a molar ratio of M units:Q units:Ti units of 0.45:0.49:0.06.

[Example 7]
A reactor was charged with 23.27 g of hexamethyldisiloxane, 74.68 g of tetraethoxysilane, and 64 g of IPA, to which 0.64 g of methanesulfonic acid was added, and the mixture was cooled to 10 to 20° C., and 47.54 g of water was added dropwise with stirring. After completion of the dropwise addition, the mixture was heated at 50 to 80° C. for 5 hours to carry out a hydrolysis and condensation reaction, yielding a silicone resin solution.

Next, 1.03 g of 25% aqueous sodium hydroxide solution and 0.13 g of calcium carbonate were added to neutralize the acid, after which 100 g of isododecane was added and the mixture was heated to 90-115°C. The ethanol, IPA, and excess water produced were removed and the mixture was cooled. 15.97 g of tetraisopropoxytitanium was then added dropwise while stirring, and after stirring for 2 hours, the mixture was heated at 130°C for 3 hours to remove the IPA and water produced, and then cooled. After further distillation under reduced pressure, the mixture was diluted with isododecane as an oil agent to a silicone resin concentration of 60%, and filtered to obtain a 60% silicone resin isododecane solution with a molar ratio of M units:Q units:Ti units of 0.41:0.51:0.08.

[Example 8]
A reactor was charged with 26.18 g of hexamethyldisiloxane, 12.78 g of triethoxymethylsilane, 59.75 g of tetraethoxysilane, and 64 g of IPA, to which 0.64 g of methanesulfonic acid was added, and the mixture was cooled to 10 to 20° C., and 47.54 g of water was added dropwise with stirring. After completion of the dropwise addition, the mixture was heated at 50 to 80° C. for 5 hours to carry out a hydrolysis and condensation reaction, yielding a silicone resin solution.

Next, 1.03 g of 25% aqueous sodium hydroxide solution and 0.13 g of calcium carbonate were added to neutralize the acid, after which 100 g of isododecane was added and the mixture was heated to 90-115°C. The ethanol, IPA, and excess water produced were removed and the mixture was cooled. 21.54 g of tetraisopropoxytitanium was added dropwise while stirring, and after stirring for 2 hours, the mixture was heated at 130°C for 3 hours to remove the IPA and water produced, and then cooled. After further distillation under reduced pressure, the mixture was diluted with isododecane as an oil agent to a silicone resin concentration of 60%, and then filtered to obtain a 60% silicone resin isododecane solution with a molar ratio of M units:T units:Q units:Ti units of 0.43:0.09:0.38:0.10.

[Comparative Example 1]
A reactor was charged with 26.18 g of hexamethyldisiloxane, 74.68 g of tetraethoxysilane, and 64 g of IPA, to which 0.64 g of methanesulfonic acid was added, and the mixture was cooled to 10 to 20° C., and 47.54 g of water was added dropwise with stirring. After completion of the dropwise addition, the mixture was heated at 50 to 80° C. for 5 hours to carry out a hydrolysis and condensation reaction, yielding a silicone resin solution.

Next, 1.03 g of 25% aqueous sodium hydroxide solution and 0.13 g of calcium carbonate were added to neutralize the acid, after which 100 g of isododecane was added and heated at 130°C for 3 hours. The resulting ethanol, IPA, and excess water were removed and then cooled. After further distillation under reduced pressure, the silicone resin was diluted with isododecane as an oil agent to a silicone resin concentration of 60%, and then filtered to obtain a 60% silicone resin isododecane solution with a molar ratio of M units:Q units of 0.47:0.53.

[Comparative Example 2]
A reactor was charged with 26.18 g of hexamethyldisiloxane, 74.68 g of tetraethoxysilane, 7.50 g (0.026 mol) of tetraisopropoxytitanium, and 64 g of IPA, to which 0.64 g of methanesulfonic acid was added and the mixture was cooled to 10 to 20° C., and 47.54 g of water was added dropwise with stirring. The mixture became cloudy and remained cloudy even after heating at 50 to 80° C. for 5 hours.

[Comparative Example 3]
A reactor was charged with 26.18 g of hexamethyldisiloxane, 74.68 g of tetraethoxysilane, and 64 g of IPA, to which 0.64 g of methanesulfonic acid was added, and the mixture was cooled to 10 to 20° C., and 47.54 g of water was added dropwise with stirring. After completion of the dropwise addition, the mixture was heated at 50 to 80° C. for 5 hours to carry out a hydrolysis and condensation reaction, and after cooling, 7.50 g (0.026 mol) of tetraisopropoxytitanium was added dropwise with stirring, causing the mixture to become cloudy.

[Comparative Example 4]
A 500 ml eggplant-shaped flask equipped with a stirrer, tetramethoxysilane, tetraisopropoxytitanium, methoxytrimethylsilane, a thermometer, and silica gel were placed in a sealed glove box, and the inside of the glove box was thoroughly dried over 12 hours to bring the relative humidity to 25%.

In a thoroughly dried eggplant-shaped flask, 25.00g (0.164mol) of tetramethoxysilane, 42.78g (0.410mol) of methoxytrimethylsilane, and 7.50g (0.026mol) of tetraisopropoxytitanium were sequentially added, and immediately a silica gel tube and a reflux condenser with a dropping funnel were attached, and stirring was started using a stirrer. Subsequently, the reaction solution was gradually heated, and after heating and stirring at 60°C for 45 minutes, 128.25g of a 4% by weight isopropanol solution of H ₂ O (ion-exchanged water) separately prepared was dropped into the reaction solution over 7 hours. After the dropwise addition, the reaction solution was heated and refluxed for 15 hours while maintaining it at 60°C. After this, 109.33g (1.048mol) of methoxytrimethylsilane was dropped into the reaction solution over 15 minutes, and the reaction solution temperature was set to 70°C. Next, 122.20 g of a separately prepared isopropanol solution of 20% by weight _H2O (ion-exchanged water) was divided into three equal parts, and 1/3 of the amount was added dropwise over 7 hours. After each drop of 1/3 of the isopropanol solution, the reaction solution was heated to reflux at 70°C for 16 hours. After the dropwise addition of the isopropanol solution was completed, the temperature of the reaction solution was increased to 80°C, and the reaction was completed by heating to reflux for 90 hours.

After the reaction was completed, a rotary evaporator was used to perform vacuum distillation at 80°C to remove the solvent and unreacted materials from the reaction mixture, and the remaining water was removed by azeotropy with 250 ml of cyclohexane. The reaction mixture was then dried under reduced pressure at 75°C in a desiccator containing phosphorus pentoxide, yielding a highly viscous liquid Ti-containing silicone resin.

The yield and process time for each of the silicone resins obtained in the above examples are shown in Table 1 below.

In Examples 1 to 8, Ti-containing silicone resin was obtained with a very high yield and in a short time. In Comparative Example 1, although the yield was 80%, since it did not contain Ti, the problem of obtaining the Ti-containing silicone resin of the present invention was not solved. In Comparative Examples 2 and 3, the resin became cloudy and the desired Ti-containing silicone resin could not be obtained. The reason for the cloudiness in Comparative Examples 2 and 3 is thought to be that the hydrolysis rate of tetraisopropoxytitanium is faster than that of alkoxysilane, and the cloudiness occurs due to hydrolysis and condensation between tetraisopropoxytitanium. In Comparative Example 4, which is a conventional method for producing Ti-containing silicone resin, the yield was poor and it took a long time.

[Infrared absorption characteristics]
The silicone resin solution obtained was applied onto a KBr cell and the IR spectrum was measured using an infrared spectrophotometer Nicolet iS50 (manufactured by Thermo Scientific). The measurement results are shown in Figure 1. A shows the IR spectrum of Comparative Example 1, B shows the IR spectrum of Example 4, and C shows the IR spectrum of Example 8.

In Examples 4 and 8, in which a titanium atom-containing silicone resin was blended, a peak (near 945 cm ⁻¹ ) derived from Ti—O—Si was observed, which was not observed in Comparative Example 1, in which a titanium atom-free silicone resin was blended.

[UV absorption characteristics]
Using an ultraviolet spectrophotometer UV-2200 (manufactured by Shimadzu Corporation), the UV spectrum of an isopropanol solution with a silicone resin concentration of 1 g/L was measured using the silicone resin solution obtained above, with a quartz glass cell having a thickness of 10 mm. The measurement results are shown in Figure 2. A shows the UV spectrum of Comparative Example 1, B shows the UV spectrum of Example 2, C shows the UV spectrum of Example 4, D shows the UV spectrum of Example 6, and E shows the UV spectrum of Example 7.

It was confirmed that the greater the titanium atom content in the resin, the greater the UV absorption ability. This is a desirable property for cosmetics, which is an application of the Ti-containing silicone obtained by the manufacturing method of the present invention.

The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included within the technical scope of the present invention.

Claims (2)

The following composition formula (1)

(In the formula, R is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a fluorine-substituted alkyl group having 1 to 8 carbon atoms, a is 0.1 to 0.7, b is 0 to 0.5, c is 0 to 0.9, d is 0.2 to 0.7, e is 0.01 to 0.3, and a+b+c+d+e is 1.0.)
A method for producing a silicone resin represented by the formula:
(i) The following general formula (2) and the following general formula (3):
R ¹ ₃ SiOSiR ¹ ₃ (2)
R ¹ ₃ SiOH (3)
(In the formula, ^R1 is the same as R above.)
and one or more organosilicon compounds represented by the formula:
The following general formula (4), the following general formula (5), and the following general formula (6):
(R ⁴ O) ₂ SiR ² ₂ (4)
(R ⁴ O) ₃ SiR ³ (5)
(R ⁴ O) ₄ Si (6)
(In the formula, ^R2 and ^R3 are the same as R above. ^R4 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group.)
and one or more silanes represented by the following formula (I) and their partial hydrolysis and condensation products:
in a solvent , and
(ii) a step of heating the obtained hydrolyzate/condensate to remove the solvent used in the step (i), the generated alcohol, and excess water ;
(iii) a compound represented by the following general formula (7):
Ti( ^OR4 ) ₄ (7)
(In the formula, ^R4 is the same as defined above.)
and a partial hydrolysis/condensation product thereof, and condensing the hydrolysis/condensation product from which water has been removed. The method for producing a silicone resin according to claim 1, characterized in that in (ii), a solvent is added to the hydrolysis/condensation product before removing water.