JP4863002B2 - Silanol compound, silanol condensate-containing aqueous solution, and method for producing the same - Google Patents

Description

  The present invention relates to an aqueous solution containing a light-stabilizing group-containing silanol compound and a silanol condensate that are suitably used for improving the stability of a polymer material.

Conventionally, it is well known that many polymers such as vinyl polymers, polyimides, polyamideimides, polyamides, polyurethanes, polyphenylene sulfides, polyether sulfones, polyphenylene ethers, and polycarbonates 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 and benzophenone, which are ultraviolet absorbers, and hindered phenols which are antioxidants, particularly 2,6-bis (tert-butyl) -hydroxy In addition to toluene-based stabilizers, the blending of hindered amine compounds, which are known to exhibit excellent effects in light stabilization, particularly in imparting weather resistance, into polymer materials has been studied. As hindered amine compounds, various compounds mainly containing 2,2,6,6-tetramethylpiperidinyl group and 1,2,2,6,6-pentamethylpiperidinyl group have been proposed and studied. It was.

However, in recent years, the properties required of materials have become more and more stringent, 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. In order to solve these problems, the hindered amine compound is directly bonded to the polymer material in order to solve these problems. 1: JP 2000-336118 A), and a method of combining a plurality of hindered amine compounds to increase the molecular weight has been reported (Patent Document 2: JP 2005-112809 A).
However, even the above high molecular weight hindered amine compound does not completely satisfy the requirements such as low compatibility with the resin and low heat resistance.

As another approach, a method for solving the above problem by using a compound having both a hindered amino group and a hydrolyzable alkoxysilyl group in one molecule has been reported (Patent Document 3: JP-B-6). -80068). This reactive stabilizer compound undergoes a hydrolysis reaction to form a complex resinous structure inside or outside the resin, or chemically binds to the resin or solid support, thereby providing a more excellent phase with the resin. It exhibits solubility and stability in the resin, and can prevent volatilization of the stabilizer and surface contamination.
However, the hindered amine compound having an alkoxysilyl group requires a hydrolysis reaction with water when used. When the alkoxysilyl group is hydrolyzed, it is known that a considerable amount of alcohol is generated, and this generated alcohol is a problem from the viewpoint of user safety and environment.

Usually, for example, alkoxysilanes such as epoxyalkylalkoxysilanes, mercaptoalkylalkoxysilanes, methacryloxyalkylalkoxysilanes, halogenated alkylalkoxysilanes, and polysulfidealkylalkoxysilanes are irreversibly gelled with time. It is known that gelation occurs even when stored at room temperature. Furthermore, if alcohol is removed from these aqueous solutions, gelation easily occurs, making it difficult to synthesize alcohol-free silane aqueous solutions.
Therefore, there has been a strong demand for the development of an aqueous silanol compound solution containing a light stabilizing group that does not generate alcohol during use, is safe for the user, is friendly to the environment, and has good storage stability.

JP 2000-336118 A JP-A-2005-112809 Japanese Patent Publication No. 6-80068

Accordingly, an object of the present invention is to provide an aqueous solution containing a light-stabilizing group-containing silanol compound and a silanol condensate thereof that do not generate alcohol during use and have good storage stability, and a method for producing the same.

  As a result of diligent research to solve the above-mentioned problems, the present inventors added alkoxysilane having a hindered amino group as a light stabilizing group to water, and after hydrolysis, the by-product volatile alcohol was added. It has been found that the removed aqueous solution does not gel and has good storage stability and becomes an aqueous solution containing a light-stabilizing group-containing silanol compound and its silanol condensate.

（式中、Ｒ _b 及びＲ _c は、下記表ｉのＲ _b 及び表ｉｉのＲ _c の組み合わせ、又は表ｉｉｉのＲ _b 及び表ｉｖのＲ _c の組み合わせである。）

（上記表中、ｃ−Ｃ ₆ Ｈ ₁₁ −はシクロヘキシル基、Ｐｈはフェニル基を表す。）
この場合、シラノール縮合体が下記一般式（３）又は（４）で表されるシロキサンオリゴマーの単独又は混合物であることが好ましい。

（式中、Ｒ ⁴ は上記一般式（１）中Ｒ ¹ で表される有機基、炭素数１〜１０の置換又は非置換の１価炭化水素基、又は、ヒドロキシル基で、各々同一又は異なってもよいが、Ｒ ⁴ の少なくとも一つはＲ ¹ である。ｏ、ｐはそれぞれ１〜１，０００の整数である。）
また、ヒンダードアミノ基が、２，２，６，６−テトラメチルピペリジニル基又は１，２，２，６，６−ペンタメチルピペリジニル基であることが好ましい。
更に、ケイ素１モルに対して、水１．５〜５０モルの割合で含有し、かつ、揮発性アルコールの含有量が水溶液中１０質量％未満であるヒンダードアミノ基含有シラノール化合物及びそのシラノール縮合体を含有する水溶液が好ましい。 Accordingly, the present invention provides an aqueous solution as well as a manufacturing method thereof comprising the following hindered group-containing silanol compound and a silanol condensate.
That is, in the present invention, one or more hindered amino group-containing alkoxysilanes represented by the following general formula (1) are contained in water consisting of 5 to 10,000 times moles of water per mole of silicon. An aqueous solution containing a hindered amino group-containing silanol compound represented by the following general formula (2) and its silanol condensate, and an aqueous solution obtained by removing the volatile alcohol produced after addition and hydrolysis Hydrolysis is performed by adding one or more of the hindered amino group-containing alkoxysilanes represented by the general formula (1) to water consisting of 5 to 10,000 times moles of water per mole of silicon. Then, the volatile alcohol produced is removed to obtain an aqueous solution of a hindered amino group-containing silanol compound represented by the following general formula (2) and a condensate thereof. To provide a method of manufacturing an aqueous solution containing a hindered group-containing silanol compound and a silanol condensate that.
R ¹ SiR ² _n (OR ³ ) _3-n (1)
R ¹ SiR ² _n (OH) _3-n (2)
(In the above formula, R ¹ is a monovalent organic group represented by the following (A) containing a hindered amino group, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Each may be the same or different, OR ³ is an alkoxyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 2.)

(Wherein, R _b and R _c is a combination of R _b and Table iv of R _c of R _b and a combination of table ii of R _c, or table iii of Table i.)

(In the above table, c-C ₆ H ₁₁ -represents a cyclohexyl group and Ph represents a phenyl group.)
In this case, the silanol condensate is preferably a single or mixture of siloxane oligomers represented by the following general formula (3) or (4).

(In the formula, R ⁴ is an organic group represented by R ¹ in the general formula (1), a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydroxyl group, which are the same or different. However, at least one of R ⁴ is R ^1. o and p are each an integer of ¹ to 1,000.)
The hindered amino group is preferably a 2,2,6,6-tetramethylpiperidinyl group or a 1,2,2,6,6-pentamethylpiperidinyl group.
Further, a hindered amino group-containing silanol compound containing 1.5 to 50 mol of water with respect to 1 mol of silicon and having a volatile alcohol content of less than 10% by mass in an aqueous solution, and silanol condensation thereof An aqueous solution containing the body is preferred.

  The aqueous solution containing the light-stabilizing group (hindered amino group) -containing silanol compound and the silanol condensate of the present invention does not produce alcohol during use, has a high boiling point, low vapor pressure, and Long-term storage is possible. Moreover, it is very useful as an aqueous solution having a feature that it can be used after being diluted with water at the time of use, such as a silane coupling agent or a surface treatment agent containing a light stabilizing group.

Hereinafter, the present invention will be described in detail.
The aqueous solution containing the silanol compound having a hindered amino group and the silanol condensate of the present invention has the following general formula (1).
R ¹ SiR ² _n (OR ³ ) _3-n (1)
Wherein R ¹ is a monovalent organic group containing a hindered amino group, and R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. OR ³ is an alkoxyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 2.)
It is obtained by adding one or more of the hindered amino group-containing alkoxysilanes represented by the formula (1) to water, hydrolyzing, removing the volatile alcohol produced, and further concentrating or diluting as necessary. be able to.

In the general formula (1), R ¹ is a monovalent organic group containing a hindered amino group, and may be the same or different. The monovalent organic group containing a hindered amino group is preferably a monovalent organic group having 10 to 20 carbon atoms, more preferably a 2,2,6,6-tetramethylpiperidinyl group (for example, 2,2,6,6-tetramethyl-1-piperidinyl group or 2,2,6,6-tetramethyl-4-piperidinyl group) or 1,2,2,6,6-pentamethylpiperidinyl group ( For example, it is a monovalent hydrocarbon group containing a hindered piperidinyl group such as 1,2,2,6,6-pentamethyl-4-piperidinyl group). Specifically, what is shown to the following group ( A ) is mentioned.

（式中、Ｒ_b及びＲ_cは、下記表１のＲ_b及び表２のＲ_cの組み合わせ、又は表３のＲ_b及び表４のＲ_cの組み合わせが好ましいが、特にＲ_bがＨ−、ＣＨ₃−及びＲ_cが−ＯＣ₃Ｈ₆−、−ＮＨＣ₃Ｈ₆−の組み合わせや、Ｒ_bが−Ｃ₃Ｈ₆−及びＲ_cが−Ｈの組み合わせが好ましい。）

(Wherein, 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 H- , CH ₃ — and R _c are preferably —OC ₃ H ₆ —, —NHC ₃ H ₆ —, and R _b is —C ₃ H ₆ — and R _c is —H.

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（以下、同じ）。

In the table, c—C ₆ H ₁₁ — represents a cyclohexyl group, and Ph represents a phenyl group (hereinafter the same).

In the general formula (1), R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. Specific examples 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, isodecyl group , N-undecyl group, isoundecyl group, n-dodecyl group, isododecyl group, etc., acyclic or cyclic aliphatic monovalent hydrocarbon group such as a linear or branched alkyl group, benzyl group, phenethyl group, 2- Aralkyl groups such as methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, araalkeni Group, a phenyl group, a tolyl group, an aryl group such as a xylyl group, a fluorine-containing alkyl group such as 3,3,3-trifluoro -n- propyl group. Preferably, it is a methyl group.
In the general formula (1), OR ³ is an alkoxyl group having 1 to 10 carbon atoms, preferably an alkoxyl group having 1 to 6 carbon atoms, specifically, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Groups and the like. In order to obtain a more stable aqueous solution, it is preferable to have an atom having an unshared electron pair at the γ-position of a silicon atom, particularly a nitrogen atom or an oxygen atom.

Next, a method for producing an aqueous solution containing a light stabilizing group-containing silanol compound and its silanol condensate will be described.
Specifically, it is obtained by adding the alkoxysilane represented by the general formula (1) in water, removing the generated alcohol after hydrolysis, and further concentrating or diluting as necessary.
Water used in the reaction is a 5-10000-fold molar with respect to silicon 1 mol, more preferably 5 to 50 times by mole.
Solvents other than water are not particularly required, but if solubility is poor, polar solvents such as alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, and ketones such as acetone and methyl isobutyl ketone may be used. .

When adding alkoxysilane to water, it is good to add it with good mixing regardless of pressure and temperature, but it is good to carry out at a temperature in the range of 0 to 120 ° C, particularly 20 to 60 ° C at normal pressure. . Then, after the reaction time of 0.5-24 hours in the range of 20-60 degreeC, Preferably after 1-12 hours, it is good to remove the produced | generated alcohol.
The alcohol produced may be removed regardless of pressure and temperature, but may be removed under normal pressure or reduced pressure.
The smaller the remaining amount of the alcohol, the better. However, when 1.5 to 50 mol of water is used, it may be less than 10% by mass, more preferably less than 5% by mass in the aqueous solution.

（式中、Ｒ⁴は上記一般式（１）中Ｒ¹で表される有機基、炭素数１〜１０の置換又は非置換の１価炭化水素基、又は、ヒドロキシル基で、各々同一又は異なってもよいが、Ｒ⁴の少なくとも一つはＲ¹である。ｏは０〜１，０００、好ましくは０〜１００の整数である。）
又は下記一般式（４）

（式中、Ｒ⁴は上記一般式（１）中Ｒ¹で表される有機基、炭素数１〜１０の置換又は非置換の１価炭化水素基、又は、ヒドロキシル基で、各々同一又は異なってもよいが、Ｒ⁴の少なくとも一つはＲ¹である。ｐは１〜１，０００、好ましくは１〜１００の整数である。）
で表されるシロキサンオリゴマーの単独又は混合物であり、その他ラダーやランダムな構造を含むオリゴマー混合物を含んでも良い。 The silanol and silanol condensate aqueous solution of the present invention has the following general formula (2) in the aqueous solution.
R ¹ SiR ² _n (OH) _3-n (2)
Wherein R ¹ is a monovalent organic group containing a hindered amino group, and R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. n is an integer of 0-2.)
And a silanol condensate thereof, for example, the following general formula (3):

(In the formula, R ⁴ is an organic group represented by R ¹ in the general formula (1), a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydroxyl group, which are the same or different. However, at least one of R ⁴ is R ^1. o is an integer of 0 to 1,000, preferably 0 to 100.)
Or the following general formula (4)

(In the formula, R ⁴ is an organic group represented by R ¹ in the general formula (1), a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydroxyl group, which are the same or different. However, at least one of R ⁴ is R ^1. p is an integer of 1 to 1,000, preferably 1 to 100.)
Or a mixture of oligomers containing a ladder or a random structure.

R ^1, R ² in the general formula (2) to (4) are the same as R ^1, R ² in the general formula (1).
In this case, at least one of R ⁴ is a group represented by R ¹ in the above formula (1).
Although there is no particular limitation, the proportion of silicon in the monomer silanol compound is 0.1 mol% to 99.9 mol%, preferably 0.5 mol% to 80.0 mol%, based on the total silicon. Is good.

The silanol compound and the silanol condensate aqueous solution thereof according to the production method of the present invention can be further purified by various purification methods such as filtration, washing, column separation, solid adsorbent and the like depending on the target quality.
In addition, although the aqueous solution obtained in this way can be concentrated or diluted if necessary, the silanol compound and its silanol condensate concentration in this aqueous solution are 0.1-99.9 mass%, especially. It is preferable to set it as 10-99.9 mass%.

  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]
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, 32.1 g of pure water was charged, and 25.4 g of 3- (2,2,6,6-tetramethylpiperidin-4-ylaminopropyl) trimethoxysilane was slowly added dropwise. After aging at 60 ° C. for 2 hours under normal pressure, the produced alcohol was slowly extracted while reducing the pressure to 10 kPa to about 40 ° C. A transparent aqueous solution was obtained by adjusting the concentration by adding pure water to the obtained aqueous solution so that the nonvolatile content was 32 to 33% by mass. ^{The 29} Si-NMR spectrum is as shown in FIG. As a result of analysis by gas chromatography, the residual methanol was 0.2% by mass. Even when stored at room temperature for 3 months or more, no further alcohol was generated, no gel compound was generated, and the aqueous solution remained transparent and could be stored stably at room temperature. ^{The 29} Si-NMR spectrum was as shown in the attached drawing 2 and was the same as before storage. Moreover, even if this aqueous solution is diluted 25 times with pure water, it remains a transparent aqueous solution, and the ²⁹ Si-NMR spectrum after dilution is as shown in FIG. As shown in the accompanying drawings 1 and 3, it is clear that the aqueous solution is in an equilibrium state depending on the concentration of the silicon compound in water. Further, the diluted aqueous solution could be stably stored at room temperature for 3 months or more, and the ²⁹ Si-NMR spectrum after storage did not change as shown in the attached drawing 4.

[Example 2]
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, 32.1 g of pure water was charged, and 28.9 g of 3- (2,2,6,6-tetramethylpiperidin-4-yloxypropyl) triethoxysilane was slowly added dropwise. After aging at 60 ° C. for 18 hours under normal pressure, the produced alcohol was slowly withdrawn while reducing the pressure to 10 kPa to about 40 ° C. A transparent aqueous solution was obtained by adjusting the concentration by adding pure water to the obtained aqueous solution so that the nonvolatile content was 32 to 33% by mass. As a result of analysis by gas chromatography, the residual ethanol was 0.9% by mass. Even when stored at room temperature for 3 months or more, no further alcohol was generated, no gel compound was generated, and the aqueous solution remained transparent and could be stored stably at room temperature.

[Example 3]
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, 32.1 g of pure water was charged, and 25.5 g of 3- (2,2,6,6-tetramethylpiperidin-4-yloxypropyl) trimethoxysilane was slowly added dropwise. After aging at 60 ° C. for 18 hours under normal pressure, the produced alcohol was slowly withdrawn while reducing the pressure to 10 kPa to about 40 ° C. A transparent aqueous solution was obtained by adjusting the concentration by adding pure water to the obtained aqueous solution so that the nonvolatile content was 32 to 33% by mass. As a result of analysis by gas chromatography, the residual methanol was 0.3% by mass. Even when stored at room temperature for 3 months or more, no further alcohol was generated, no gel compound or the like was generated, and the aqueous solution remained transparent and could be stored stably at room temperature.

The ²⁹ Si-NMR spectrum measured with the heavy aqueous solution of the aqueous solution of Example 1 is shown. The ²⁹ Si-NMR spectrum which measured the aqueous solution of Example 1 for 3 months, and measured with the heavy aqueous solution is shown. The ²⁹ Si-NMR spectrum which measured the 25 times dilution aqueous solution of the aqueous solution of Example 1 in the heavy aqueous solution is shown. The ²⁹ Si-NMR spectrum measured by the heavy aqueous solution after storing the 25 times diluted aqueous solution of the aqueous solution of Example 1 for 3 months is shown.

Claims (5)

One or more hindered amino group-containing alkoxysilanes represented by the following general formula (1) were added to water consisting only of 5 to 10,000 times moles of water with respect to 1 mole of silicon and hydrolyzed. Thereafter, an aqueous solution containing a hindered amino group-containing silanol compound represented by the following general formula (2) and its silanol condensate , which is obtained by removing the volatile alcohol produced .
R ¹ SiR ² _n (OR ³ ) _3-n (1)
R ¹ SiR ² _n (OH) _3-n (2)
(In the above formula, R ¹ is a monovalent organic group represented by the following (A) containing a hindered amino group, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Each may be the same or different, OR ³ is an alkoxyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 2.)

(Wherein, R _b and R _c is a combination of R _b and Table iv of R _c of R _b and a combination of table ii of R _c, or table iii of Table i.)

(In the above table, c-C ₆ H ₁₁ -represents a cyclohexyl group and Ph represents a phenyl group.) The aqueous solution according to claim 1, wherein the silanol condensate is a siloxane oligomer represented by the following general formula (3) or (4) alone or in a mixture.

(Wherein R ^Four Is R in the above general formula (1) ¹ An organic group, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydroxyl group, which may be the same or different, ^Four At least one of R ¹ It is. o and p are each an integer of 1 to 1,000. )   The hindered amino group is a 2,2,6,6-tetramethylpiperidinyl group or a 1,2,2,6,6-pentamethylpiperidinyl group. Aqueous solution.   The aqueous solution according to any one of claims 1 to 3, which is contained in a proportion of 1.5 to 50 mol of water with respect to 1 mol of silicon, and the content of volatile alcohol is less than 10% by mass in the aqueous solution. . Hydrolysis is carried out by adding one or more hindered amino group-containing alkoxysilanes represented by the following general formula (1) to water consisting of 5 to 10,000 times moles of water per mole of silicon. The hindered amino group-containing silanol compound is obtained by removing the volatile alcohol produced and then obtaining an aqueous solution of a hindered amino group-containing silanol compound represented by the following general formula (2) and its condensate And a method for producing an aqueous solution containing the silanol condensate thereof.
R ¹ SiR ² _n (OR ^Three ) _3-n (1)
R ¹ SiR ² _n (OH) _3-n (2)
(In the above formula, R ¹ Is a monovalent organic group represented by the following (A) containing a hindered amino group, R ² Are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different. OR ^Three Is an alkoxyl group having 1 to 10 carbon atoms. n is an integer of 0-2. )

(Wherein R _b And R _c Is R in Table i below _b And R in Table ii _c Or R in Table iii _b And R in Table iv _c It is a combination. )

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

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