JP2007291285A - Optical stabilization group-containing cage-like silsesquioxane and its preparation process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel optical stabilization group-containing cage-like silsesquioxane with a low volatility and an excellent heat-resistance, and its preparation process. <P>SOLUTION: The optical stabilization group-containing cage-like silsesquioxane represented by the following formula (1): [R<SP>1</SP>SiO<SB>3/2</SB>]<SB>m</SB>[R<SP>2</SP>SiO<SB>3/2</SB>]<SB>n</SB>[R<SP>1</SP>SiO<SB>2</SB>R<SP>3</SP>]<SB>p</SB>(1) (wherein R<SP>1</SP>is a mono-valent organic group containing a hindered amino group, R<SP>2</SP>is a substituted or unsubstituted mono-valent hydrocarbon group having 1-30C numbers, R<SP>3</SP>is a hydrogen atom or an alkyl group having 1-6C numbers, each may be the same or different, m is an integer of 0-14, n is an integer of 0-13, p is 0 or 1, however, m and p simultaneously become 0, and m+n+p is an integer of 8-14), and its preparation process are provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a light-stabilizing group-containing cage-shaped silsesquioxane that is suitably used for improving the stability of a polymer material, and a method for producing the same.

  It is well known that many polymers such as vinyl polymers, polyimides, polyamideimides, polyamides, polyurethanes, polyphenylene sulfides, polyether sulfones, polyphenylene ethers, polycarbonates and the like deteriorate with time due to the action of light. This deterioration appears as a deterioration of the physical properties of the polymer material, for example, as a decrease in maximum tensile stress or flexibility with a change in viscosity index.

  In order to combat this type of degradation, stabilizers such as benzotriazole, benzophenone and nickel complexes as ultraviolet absorbers and hindered phenols as antioxidants, particularly 1,6-bis (tert-butyl) -hydroxy A compound containing a hindered amine group, particularly a 2,2,6,6-tetramethylpiperidinyl group or a 1,2,2,6,6-pentamethylpiperidinyl group, together with a toluene stabilizer. Has been studied.

  However, in recent years, the required properties of materials have become increasingly severe, and the stabilizing effect has been sustained by the reduction of added stabilizers such as volatilization during long-term use and volatilization during processing of thermoplastic resins. And surface contamination of the polymer material by the volatilized compound is a problem. In order to solve these problems, a hindered amine compound is directly bonded to a polymer material in a hindered amine compound (Japanese Patent Laid-Open No. 2000-336118 (Patent Document 1)), or a plurality of hindered amine compounds are bonded to increase the molecular weight. Although a method (Japanese Patent Laid-Open No. 2005-112809 (Patent Document 2)) has been reported, further improvement is desired, such as the thermal stability and weather resistance of the high molecular weight hindered amine compound itself are still insufficient. ing.

  Moreover, in order to improve the thermal stability and weather resistance of a hindered amine compound, a method of incorporating a hindered amino group into a silicone polymer is disclosed in Japanese Patent No. 2995141 (Patent Document 3). However, the linear and random structure polymers described in the above patent publications have low stability because alkoxyl groups and silanol groups remain at the ends, and the molecular weight increases due to the crosslinking reaction of residual silanols during storage. However, there is a problem that a solid precipitates due to a decrease in solubility and a problem that a polymer having a hindered amino group whose structure is not controlled exists in the polymer material.

JP 2000-336118 A JP-A-2005-112809 Japanese Patent No. 2954141

  An object of the present invention is to provide a novel light-stabilizing group-containing cage silsesquioxane having low volatility and excellent heat resistance, and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventors have [1] hydrolyzing a hydrolyzable silane having a hindered amino group as a light stabilizing group, and [2] a light stabilizing group. Hydrolyzable silane having a hindered amino group as a coexistence or hydrolytic condensation of a hydrolyzable silane having a monovalent hydrocarbon group, or [3] hydrolyzable having a hindered amino group as a light stabilizing group By reacting silane with trisilanol of cage silsesquioxane, the following general formula (1)
[R ¹ SiO _3/2 ] _m [R ² SiO _3/2 ] _n [R ¹ SiO ₂ R ³ ] _p (1)
Wherein R ¹ is a monovalent organic group containing a hindered amino group, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, R ³ is a hydrogen atom or 1 to 6 carbon atoms. Each may be the same or different, m is an integer of 0 to 14, n is an integer of 0 to 13, and p is 0 or 1, but m and p are not 0 at the same time. And m + n + p is an integer of 8 to 14.)
A new light-stabilizing group-containing cage silsesquioxane represented by the formula (1) and a method for producing the same have been completed.

That is, the present invention provides the following light-stabilizing group-containing cage silsesquioxane and a method for producing the same.
Claim 1:
The following general formula (1)
[R ¹ SiO _3/2 ] _m [R ² SiO _3/2 ] _n [R ¹ SiO ₂ R ³ ] _p (1)
Wherein R ¹ is a monovalent organic group containing a hindered amino group, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, R ³ is a hydrogen atom or 1 to 6 carbon atoms. Each may be the same or different, m is an integer of 0 to 14, n is an integer of 0 to 13, and p is 0 or 1, but m and p are not 0 at the same time. And m + n + p is an integer of 8 to 14.)
A cage-shaped silsesquioxane containing a light-stabilizing group, wherein
Claim 2:
R ¹ in the general formula (1) is characterized in that the hindered amino group is a 2,2,6,6-tetramethyl-piperidinyl group or a 1,2,2,6,6-pentamethyl-piperidinyl group. The cage-shaped silsesquioxane containing the photostabilizing group according to claim 1.
Claim 3:
The general formula (1), wherein R ² is a methyl group, an ethyl group, an isobutyl group, an isooctyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, or a 3-trifluoropropyl group. A cage silsesquioxane containing a light stabilizing group.
Claim 4:
The following general formula (2)
R ¹ SiX ₃ (2)
(In the formula, R ¹ is a monovalent organic group containing a hindered amino group, X is chlorine or an alkoxyl group having 1 to 6 carbon atoms, which may be the same or different.)
The method for producing a light-stabilizing group-containing cage silsesquioxane according to any one of claims 1 to 3, wherein the hydrolyzable silane represented by the formula (1) is hydrolyzed and condensed.
Claim 5:
The following general formula (2)
R ¹ SiX ₃ (2)
(In the formula, R ¹ is a monovalent organic group containing a hindered amino group, X is chlorine or an alkoxyl group having 1 to 6 carbon atoms, which may be the same or different.)
And a hydrolyzable silane represented by the following general formula (3)
R ² SiX ₃ (3)
(Wherein R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, and X is chlorine or an alkoxyl group having 1 to 6 carbon atoms, which may be the same or different.)
The method for producing a light-stabilizing group-containing cage silsesquioxane according to claim 4, wherein the hydrolyzable silane represented by the formula is hydrolyzed and condensed.
Claim 6:
The following general formula (2)
R ¹ SiX ₃ (2)
(In the formula, R ¹ is a monovalent organic group containing a hindered amino group, X is chlorine or an alkoxyl group having 1 to 6 carbon atoms, which may be the same or different.)
And a hydrolyzable silane represented by the following general formula (4)
(R ² SiO _3/2 ) _a (R ² SiO ₂ H) ₃ (4)
(In the formula, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, and each may be the same or different. A is an integer of 4 to 11)
The method for producing a light-stabilizing group-containing cage silsesquioxane according to any one of claims 1 to 3, wherein the trisilanol of cage silsesquioxane represented by the formula is reacted.

  The light-stabilizing group-containing cage silsesquioxane of the present invention has low volatility, excellent stability and heat resistance, and contributes to improvement of physical properties by adding to a polymer material, while providing a light stabilization effect. It is very useful as an additive.

Hereinafter, the present invention will be described in detail.
The light-stabilizing group-containing cage silsesquioxane of the present invention has the following general formula (1):
[R ¹ SiO _3/2 ] _m [R ² SiO _3/2 ] _n [R ¹ SiO ₂ R ³ ] _p (1)
Wherein R ¹ is a monovalent organic group containing a hindered amino group, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, R ³ is a hydrogen atom or 1 to 6 carbon atoms. Each may be the same or different, m is an integer of 0 to 14, n is an integer of 0 to 13, and p is 0 or 1, but m and p are not 0 at the same time. And m + n + p is an integer of 8 to 14.)
It is represented by

R ¹ of the cage-shaped silsesquioxane containing the light stabilizing group represented by the general formula (1) preferably contains a hindered amino group as the light stabilizing group, and is preferably a monovalent organic group having 10 to 20 carbon atoms. R ¹ may be the same or different, and a 2,2,6,6-tetramethyl-piperidinyl group (for example, a 2,2,6,6-tetramethyl-1-piperidinyl group as a hindered amino group) Or 2,2,6,6-tetramethyl-4-piperidinyl group), 1,2,2,6,6-pentamethyl-piperidinyl group (for example, 1,2,2,6,6-pentamethyl-4-piperidinyl group) A group containing a hindered piperidinyl group such as a group) is preferable. Specifically, what is shown in the following general formula (A) is mentioned.

Wherein (A), R _b and R _c are the combination of R _b and Table 2 of R _c in the following Table 1, or combinations Table 3 R _b and Table 4 R _c are preferred, in particular R _b A combination in which H— or CH ₃ —, R _c is —OC ₃ H ₆ — or —NHC ₃ H ₆ —, or a combination in which R _b is —C ₃ H ₆ — and R _c is —H is preferable.

なお、表中ｃ−Ｃ₆Ｈ₁₁−はシクロヘキシル基、Ｐｈはフェニル基を表す。

In the table, c-C ₆ H ₁₁ -represents a cyclohexyl group, and Ph represents a phenyl group.

なお、表中Ｐｈはフェニル基を表す。

In the table, Ph represents a phenyl group.

R ² in the general formula (1) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and R ² may be the same or different. . Specific examples of R ² include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, Neopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group An acyclic or cyclic aliphatic monovalent hydrocarbon group such as a linear or branched alkyl group such as an isodecyl group, an n-undecyl group, an isoundecyl group, an n-dodecyl group or an isododecyl group, a benzyl group, a phenethyl group, 2 -Aralkyl groups such as methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, Examples include an aryl group such as a kenyl group, a phenyl group, a tolyl group, and a xylyl group, and a fluorine-containing alkyl group such as a 3,3,3-trifluoro-n-propyl group. Particularly, an ethyl group, an isobutyl group, an isooctyl group, and the like. Group, cyclopentyl group, cyclohexyl group, phenyl group and 3-trifluoropropyl group are preferable, and methyl group, ethyl group, isobutyl group, isooctyl group, cyclopentyl group, cyclohexyl group, phenyl group and 3-trifluoropropyl group are particularly preferable. .

Moreover, R < ³ > in the said General formula (1) is a hydrogen atom or a C1-C6 alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group etc.), and R < ³ > is the same or different. May be.

  In the general formula (1), m is an integer of 0 to 14, particularly 0 to 12, n is an integer of 0 to 13, particularly 0 to 7, and p is 0 or 1, but m and p are simultaneously It is not 0, and m + n + p is an integer of 8-14.

  The shape of the molecular arrangement of the silsesquioxane represented by the general formula (1) may form a cage-like portion, that is, a three-dimensional network portion formed of siloxane bonds, with 50% by mass or more of the constituent atoms. Preferably, as such a thing, the thing of the structure represented by the following general formula (5)-(10) is mentioned, for example, Silsesquioxane may be single substance or a mixture. Moreover, although the molecular arrangement | sequence may also include a random structure or a ladder structure, Preferably the sum total of the silsesquioxane whose weight average molecular weight (The polystyrene conversion value by GPC (gel permeation chromatography)) is smaller than 5,000 is included. It is preferable that it is 50 mass% or less.

In the general formulas (5) to (10), R ⁴ is R ¹ or R ² in the general formula (1), and includes one or more R ¹ . R ³ is the same as above.

Next, a method for producing the light-stabilizing group-containing cage silsesquioxane of the general formula (1) will be described.
The light-stabilizing group-containing cage silsesquioxane of the general formula (1) is represented by the hydrolyzable silane represented by the following general formula (2) or (3) or the following general formula (4) as a starting material. It can be produced using trisilanol of cage silsesquioxane.
R ¹ SiX ₃ (2)
R ² SiX ₃ (3)
(R ² SiO _3/2 ) _a (R ² SiO ₂ H) ₃ (4)

Formula (2) ~ (4) R ¹ and R ² in are each the same as R ¹ and R ² in the general formula (1), X is an alkoxyl group having 1 to 6 carbon chlorine or C , X may be the same or different, and specific examples include chlorine, methoxy group, ethoxy group, propoxy group, butoxy group and the like. Moreover, a in the said General formula (4) is an integer of 4-11, Preferably a is 4, 6, 8. Specific examples of the general formula (4) are those represented by the following general formulas (11), (12), and (13).

  The trisilanol of the cage silsesquioxane represented by the general formula (4) can be obtained by hydrolyzing a functional silane having a corresponding hydrocarbon group in a solvent using an acid or basic catalyst.

In particular,
[1] The hydrolyzable silane represented by the general formula (2) is reacted with water.
[2] The hydrolyzable silane represented by the general formula (2) is reacted with the hydrolyzable silane represented by the general formula (3) and water, or [3] represented by the general formula (2). By reacting the hydrolyzable silane with the trisilanol of the cage silsesquioxane represented by the general formula (4), the light-stabilizing group-containing cage silyl represented by the general formula (1) of the present invention is obtained. Sesquioxane is obtained.

  In the above reaction, a basic catalyst is preferably used. Examples of basic catalysts include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, etc. And ammonium fluoride salts such as tetrabutylammonium fluoride. Tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferred because of their high catalytic activity. The basic catalyst can be used as an aqueous solution or an alcohol solution.

  The amount of the catalyst used is not particularly limited, but if it is too much, the cost becomes high or difficult to remove, and if it is too little, the reaction becomes slow. 0.001 to 1.0 mol, and more preferably 0.01 to 0.1 mol.

  In the case of hydrolytic condensation (in the case of the above production method [1] or [2]), the amount ratio of hydrolyzable silane to water is 0.1 to 100 mol of water with respect to 1 mol of hydrolyzable silane. In particular, a ratio of 1.5 to 3 mol is preferable. If the amount of water is too small, the reaction may be slowed and the yield of the desired silsesquioxane may be lowered. If the amount of water is too large, the product will have a high molecular weight and the product of the cage structure will decrease. There is a fear. Moreover, when using a basic catalyst as aqueous solution, the water to be used may be substituted with the water, and water may be added separately.

  In the above reaction, the solvent may not be used, but the use of the solvent is preferable because the ratio of the cage structure to be generated increases. As the solvent, polar solvents and nonpolar solvents can be used alone or as a mixture. As the polar solvent, lower alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl isobutyl ketone, and ethers such as tetrahydrofuran are used. In particular, acetone and tetrahydrofuran have a low boiling point and the system becomes uniform. It is preferable because the reactivity is improved.

  As the nonpolar solvent, a hydrocarbon solvent is preferable, a solvent having a boiling point higher than that of water such as toluene and xylene is preferable, and a solvent azeotropic with water such as toluene is particularly preferable because water can be efficiently removed from the system. . In particular, mixing a polar solvent and a nonpolar solvent provides the above-described advantages, so that it is preferably used as a mixed solvent.

  As reaction temperature, it is 0-200 degreeC, Preferably it is 20-200 degreeC, More preferably, it is 20-120 degreeC. This reaction can be carried out regardless of pressure, but is preferably 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa.

  In the hydrolysis reaction, the condensation reaction proceeds together with the hydrolysis, and most of X in the general formulas (2) and / or (3), preferably most, is hydrolyzed to OH groups, and most of the OH groups, It is preferable to condense 95% or more, more preferably almost 100%.

  From the mixed solution after the reaction by the production method of the present invention, the solvent, the alcohol produced by the reaction, and the catalyst are removed by a known method, and the stabilized group-containing cage silsesquioxy of the present invention is obtained as a high-purity target product. You can get sun. The obtained product can be further purified by removing the catalyst by various purification methods such as washing, column separation, solid adsorbent, etc. depending on the target quality, but the catalyst is removed by washing with water. From the viewpoint of efficiency, the solvent and the produced alcohol can be distilled off regardless of the pressure.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

Example 1 Synthesis of Compound I
A 100 ml four-necked flask equipped with a Dimroth type cooling condenser, a Dean Stark, a stirrer, and a thermometer was sufficiently purged with nitrogen. Next, 5.0 g of 3- (2,2,6,6-tetramethyl-piperidinyl-4-oxy) -propyltrimethoxysilane, 22 ml of toluene, and 11 ml of acetone were charged, and 0.5 g of 10% tetraethylammonium hydroxide aqueous solution was added. 0.16 g of water was slowly added. The mixture was aged for 2 hours at room temperature and then aged for 2 hours under reflux. After aging, the solvent was gradually withdrawn at normal pressure, and when the kettle temperature reached 109 ° C., the heating was stopped and the system was cooled. The resulting solution was washed with saturated brine until neutral, and magnesium sulfate was added for dehydration. After removing the solid by filtration, 3.7 g of a colorless and transparent oily product was obtained by concentration, washing with hexane, and drying. The analysis result of the obtained product is shown below. ^{The 1} H-NMR spectrum is as shown in FIG. 1, and the ²⁹ Si-NMR spectrum is as shown in FIG. The measurement results of MALDI-TOFMS [Matrix Assisted Laser Desorption / Ionization-Time of Flight Mass Spectrometry] (Matrix: Co) are as shown in FIG. The measurement result of the FT-IR spectrum is as shown in FIG. From the above results, it was found that the obtained product was a light-stabilizing group-containing cage silsesquioxane represented by the following formula (I).

Example 2 Synthesis of Compound II
A 100 ml four-necked flask equipped with a Dimroth type cooling condenser, a Dean Stark, a stirrer, and a thermometer was sufficiently purged with nitrogen. Next, 5.8 g of 3- (1,2,2,6,6-pentamethyl-piperidinyl-4-oxy) -propyltriethoxysilane, 22 ml of toluene and 11 ml of acetone were charged, and 0.5 g of 10% aqueous tetraethylammonium hydroxide solution was added. And 0.15 g of water were slowly added. The mixture was aged for 2 hours at room temperature and then aged for 2 hours under reflux. After aging, the solvent was gradually withdrawn at normal pressure, and when the pot temperature reached 109 ° C., heating was stopped and cooling was performed. The resulting solution was washed with saturated brine until neutral, and magnesium sulfate was added for dehydration. After removing the solid by filtration, 3.7 g of a colorless and transparent oily product was obtained by concentration, washing with hexane, and drying. The analysis result of the obtained product is shown below. ^{The 1} H-NMR spectrum is as shown in FIG. 5, and the ²⁹ Si-NMR spectrum is as shown in FIG. The measurement result of MALDI-TOFMS is as shown in FIG. The measurement result of the FT-IR spectrum is as shown in FIG. From the above results, it was found that the obtained product was a light-stabilizing group-containing cage silsesquioxane represented by the following formula (II).

Example 3 Synthesis of Compound III
A 100 ml four-necked flask equipped with a Dimroth type cooling condenser, a Dean Stark, a stirrer, and a thermometer was sufficiently purged with nitrogen. Next, 5.0 g of 3- (2,2,6,6-tetramethyl-piperidinyl-4-amino) -propyltrimethoxysilane, 22 ml of toluene and 11 ml of acetone were charged, and 0.5 g of 10% tetraethylammonium hydroxide aqueous solution was added. 0.16 g of water was slowly added. The mixture was aged for 2 hours at room temperature and then aged for 2 hours under reflux. After aging, the solvent was gradually withdrawn at normal pressure, and when the pot temperature reached 109 ° C., heating was stopped and cooling was performed. The resulting solution was washed with saturated brine until neutral, and magnesium sulfate was added for dehydration. After removing the solid by filtration, 3.6 g of a pale yellow transparent oily product was obtained by concentration, washing with hexane, and drying. The analysis result of the obtained product is shown below. ^{The 1} H-NMR spectrum is as shown in FIG. 9, and the ²⁹ Si-NMR spectrum is as shown in FIG. The measurement results of MALDI-TOFMS are as shown in FIG. The measurement result of the FT-IR spectrum is as shown in FIG. From the above results, it was found that the obtained product was a light-stabilizing group-containing cage silsesquioxane represented by the following formula (III).

Example 4 Synthesis of Compound IV
A 100 ml four-necked flask equipped with a Dimroth type cooling condenser, a Dean Stark, a stirrer, and a thermometer was sufficiently purged with nitrogen. _{Then, ((i-C 4 H} 9) SiO 3/2) 4 ((i-C 4 H 9) SiO 2 H) 3 5.0g, 3- (2,2,6,6- tetramethyl - piperidinyl -4-Oxy) -propyltrimethoxysilane (2.1 g) and methanol (100 ml) were charged, and 40% benzyltrimethylammonium hydroxide in methanol (0.14 g) was slowly added. After aging at room temperature for 10 hours, it was left overnight. The precipitated white solid was removed by filtration, purified and dried to obtain 2.6 g of a white solid product. The analysis result of the obtained product is shown below. ^{The 1} H-NMR spectrum is as shown in FIG. 13, and the ²⁹ Si-NMR spectrum is as shown in FIG. The measurement result of MALDI-TOFMS is as shown in FIG. The measurement result of the FT-IR spectrum is as shown in FIG. From the above results, it was found that the obtained product was a light-stabilizing group-containing cage silsesquioxane represented by the following formula (IV).

[Example 5] (Synthesis of Compound V)
A 100 ml four-necked flask equipped with a Dimroth type cooling condenser, a Dean Stark, a stirrer, and a thermometer was sufficiently purged with nitrogen. Then, ((i-C ₄ H ₉ ) SiO _3/2 ) ₄ ((i-C ₄ H ₉ ) SiO ₂ H) ₃ 5.0 g, 3- (1,2,2,6,6-pentamethyl- Piperidinyl-4-oxy) -propyltrimethoxysilane (2.3 g) and methanol (100 ml) were charged, and 40% benzyltrimethylammonium hydroxide in methanol (0.14 g) was slowly added. After aging at room temperature for 10 hours, it was left overnight. The precipitated white solid was removed by filtration, purified and dried to obtain 3.2 g of a white solid product. The analysis result of the obtained product is shown below. ^{The 1} H-NMR spectrum is as shown in FIG. 17, and the ²⁹ Si-NMR spectrum is as shown in FIG. The measurement result of MALDI-TOFMS is as shown in FIG. The measurement result of the FT-IR spectrum is as shown in FIG. From the above results, it was found that the obtained product was a light-stabilizing group-containing cage silsesquioxane represented by the following formula (V).

Heavy chloroform solution (internal standard: tetramethylsilane) of the product of Example 1 shows a ¹ H-NMR spectrum was measured at. The ²⁹ Si-NMR spectrum measured with the deuterated chloroform solution (internal standard: tetramethylsilane) of the product of Example 1 is shown. 2 shows a MALDI-TOFMS spectrum (matrix: Co) of the product of Example 1. 2 shows the FT-IR spectrum of the product of Example 1. Heavy chloroform solution (internal standard: tetramethylsilane) of the product of Example 2 shows a ¹ H-NMR spectrum was measured at. The ²⁹ Si-NMR spectrum measured with the heavy chloroform solution (internal standard: tetramethylsilane) of the product of Example 2 is shown. The MALDI-TOFMS spectrum (matrix: Co) of the product of Example 2 is shown. The FT-IR spectrum of the product of Example 2 is shown. Heavy chloroform solution (internal standard: tetramethylsilane) of the product of Example 3 shows the ¹ H-NMR spectrum was measured at. The ²⁹ Si-NMR spectrum measured with the heavy chloroform solution (internal standard: tetramethylsilane) of the product of Example 3 is shown. 1 shows a MALDI-TOFMS spectrum (matrix: α-cyano-4-hydroxy-cinnamic acid (CHCA)) of the product of Example 3. 2 shows the FT-IR spectrum of the product of Example 3. Heavy chloroform solution (the internal standard: tetramethylsilane) of the product of Example 4 ¹ H-NMR spectrum was measured at. The ²⁹ Si-NMR spectrum measured with the deuterated chloroform solution (internal standard: tetramethylsilane) of the product of Example 4 is shown. The MALDI-TOFMS spectrum (matrix: CHCA) of the product of Example 4 is shown. 2 shows the FT-IR spectrum of the product of Example 4. The ¹ H-NMR spectrum measured with the deuterated chloroform solution (internal standard: tetramethylsilane) of the product of Example 5 is shown. The ²⁹ Si-NMR spectrum measured with the deuterated chloroform solution (internal standard: tetramethylsilane) of the product of Example 5 is shown. The MALDI-TOFMS spectrum (matrix: Co) of the product of Example 5 is shown. 2 shows the FT-IR spectrum of the product of Example 5.

Claims (6)

The following general formula (1)
[R ¹ SiO _3/2 ] _m [R ² SiO _3/2 ] _n [R ¹ SiO ₂ R ³ ] _p (1)
Wherein R ¹ is a monovalent organic group containing a hindered amino group, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, R ³ is a hydrogen atom or 1 to 6 carbon atoms. Each may be the same or different, m is an integer of 0 to 14, n is an integer of 0 to 13, and p is 0 or 1, but m and p are not 0 at the same time. And m + n + p is an integer of 8 to 14.)
A cage-shaped silsesquioxane containing a light-stabilizing group, wherein R ¹ in the general formula (1) is characterized in that the hindered amino group is a 2,2,6,6-tetramethyl-piperidinyl group or a 1,2,2,6,6-pentamethyl-piperidinyl group. The cage-shaped silsesquioxane containing the photostabilizing group according to claim 1. The general formula (1), wherein R ² is a methyl group, an ethyl group, an isobutyl group, an isooctyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, or a 3-trifluoropropyl group. A cage silsesquioxane containing a light stabilizing group. The following general formula (2)
R ¹ SiX ₃ (2)
(In the formula, R ¹ is a monovalent organic group containing a hindered amino group, X is chlorine or an alkoxyl group having 1 to 6 carbon atoms, which may be the same or different.)
The method for producing a light-stabilizing group-containing cage silsesquioxane according to any one of claims 1 to 3, wherein the hydrolyzable silane represented by the formula (1) is hydrolyzed and condensed. The following general formula (2)
R ¹ SiX ₃ (2)
(In the formula, R ¹ is a monovalent organic group containing a hindered amino group, X is chlorine or an alkoxyl group having 1 to 6 carbon atoms, which may be the same or different.)
And a hydrolyzable silane represented by the following general formula (3)
R ² SiX ₃ (3)
(Wherein R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, and X is chlorine or an alkoxyl group having 1 to 6 carbon atoms, which may be the same or different.)
The method for producing a light-stabilizing group-containing cage silsesquioxane according to claim 4, wherein the hydrolyzable silane represented by the formula is hydrolyzed and condensed. The following general formula (2)
R ¹ SiX ₃ (2)
(In the formula, R ¹ is a monovalent organic group containing a hindered amino group, X is chlorine or an alkoxyl group having 1 to 6 carbon atoms, which may be the same or different.)
And a hydrolyzable silane represented by the following general formula (4)
(R ² SiO _3/2 ) _a (R ² SiO ₂ H) ₃ (4)
(In the formula, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, and each may be the same or different. A is an integer of 4 to 11)
The method for producing a light-stabilizing group-containing cage silsesquioxane according to any one of claims 1 to 3, wherein the trisilanol of cage silsesquioxane represented by the formula is reacted.

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