JPH108027A - Production of ultraviolet light absorbing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a readily synthesized ultraviolet light absorbing material without bleeding out an ultraviolet light absorber even at the time of use thereof for a long period without causing unfavorable effects even when including the ultraviolet light absorber at a high concentration therein and realizing the cutoff of long wavelengths. SOLUTION: (a) An aminosilane compound of the formula R<1> is a 1-10C alkylene group or a bivalent group of the formula (CH2 )m -NH [(m) is an integer of 1<=(m)<=4]; R<2> s are each H, OH, a 1-10C alkyl group or a 1-10C alkoxy group, with the proviso that one of the R<2> s is the alkoxy group; (n) is an integer of >=0} or its derivative is at least reacted with (b) an ultraviolet light absorber having carboxyl group in the molecule to form amide bonds derived from the aminosilane compound or its derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an ultraviolet absorbing material.

[0002]

2. Description of the Related Art Heretofore, it has been practiced to share an organic ultraviolet absorber for various resins and the like and to use it as an ultraviolet cut coating. However, when used for a long period of time, there is a problem in that the ultraviolet absorbent bleeds out or volatilizes to deteriorate the performance.

In order to overcome these problems, many attempts have been made to introduce a group capable of reacting with a resin into an ultraviolet absorber and to bond the ultraviolet absorber to the resin itself (JP-A-6-88064). And JP-A-2-243695).

[0004] However, these ultraviolet absorbers need to be synthesized in multiple stages, or if the ultraviolet absorber is contained in a high concentration in order to cut off ultraviolet rays in a long wavelength region, the film becomes brittle, or the film becomes resistant. There was a problem that the solvent properties deteriorated.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, that is, it is easy to synthesize, and the UV absorber does not bleed out even during long-term use, and the UV absorber has a high concentration. Provided is a method for producing a novel ultraviolet-absorbing material which does not cause any harm even when a long-wavelength cut is realized by containing an ultraviolet absorbent.

[0006]

That is, according to the present invention,
(A) an aminosilane compound represented by the general formula (1) or a derivative thereof;

[0007]

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Wherein R ¹ is an alkylene group having 1 to 10 carbon atoms or a divalent group represented by the general formula — (CH ₂ ) m —NH— (m is an integer of 1 ≦ m ≦ 4) In the formula, each R ² is the same or different, and represents a hydrogen atom, a hydroxyl group,
Represents an alkyl group having 10 to 10 or an alkoxy group having 1 to 10 carbon atoms. However, at least one of all R ² represents an alkoxy group. n represents an integer of n ≧ 0. (B) A method for producing an ultraviolet-absorbing material, comprising: causing at least a reaction with an ultraviolet absorber having a carboxyl group in a molecule to generate an amide bond derived from the aminosilane compound or a derivative thereof. .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the production method of the present invention, (a) an aminosilane compound represented by the general formula (1) or a derivative thereof (hereinafter, referred to as “component A”) and (b) an ultraviolet absorber having a carboxyl group in a molecule (Hereinafter, “component B”
) To produce an amide bond derived from the component A.

In the general formula (1), R ¹ is an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or-(CH ₂ ) m -NH- (m is 1 ≦ m ≦ 4 An integer). Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Each R ² is the same or different and represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10, preferably 1 to 3 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. . However, at least one of all R ² is an alkoxy group, preferably having 1 carbon atom.
To 5 alkoxy groups. Examples of the alkyl group for R ² include a methyl group, an ethyl group, a propyl group, and an i-propyl group. Examples of the alkoxy group include a methoxy group,
Examples include an ethoxy group, a propoxy group and an i-propoxy group. n represents an integer of n ≧ 0, preferably 0 ≦ n ≦ 3.

Preferred examples of the aminosilane compound represented by the general formula (1) include 3-aminopropyltriethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropylmethyldiethoxysilane,
3-aminopropyl polydimethylsiloxane, N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane and the like. Further, as the derivative of the aminosilane compound, a hydrolyzate of the above-mentioned suitable compound is preferably exemplified. The component A which is an aminosilane compound or a derivative thereof can be produced by a known method.

In the production method of the present invention, examples of the ultraviolet absorber having a carboxylic acid group in the molecule used as the component B include a compound having one or more carboxyl groups in the side chain of the molecule. Examples thereof include compounds having a triazole skeleton or a benzophenone skeleton.

As the compound having a benzotriazole skeleton, a compound represented by the following general formula (2) is preferably exemplified.

[0014]

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In the formula, R ³ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10, preferably 1 to 6 carbon atoms. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group. The substitution position of R ³ is the 4-position or 5-position of the benzotriazole skeleton,
The halogen atom and the alkyl group are usually located at the 4-position. In the formula, R ⁴ is a hydrogen atom or a carbon atom having 1 to 10, preferably 1
And 6 to 6 alkyl groups. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group.
In the formula, R ⁵ represents an alkylene group or an alkylidene group having 1 to 10, preferably 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Examples of the alkylidene group include an ethylidene group and a propylidene group.

As the compound represented by the general formula (2),
3- (5-chloro-2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -4 -Hydroxy-benzeneethaneanoic acid, 3- (5-methyl-2H-benzotriazole-2
-Yl) -5- (1-methylethyl) -4-hydroxy-benzenepropanoic acid.

Preferred examples of the compound having a benzophenone skeleton include benzophenone-based compounds represented by the following general formulas (3) to (6).

[0018]

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In the formula, R ⁷ and R ⁸ are the same or different groups, and each is a hydroxyl group, having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
Represents an alkyl group or an alkoxy group. n and m are 0 ≦
It represents an integer in the range of m ≦ 3, 0 ≦ n ≦ 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group.Examples of the alkoxy group include a methoxy group, an ethoxy group,
Examples thereof include a propoxy group, an i-propoxy group, and a butoxy group. In the formula, R ⁶ has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
3 represents an alkylene group or an alkylidene group. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Examples of the alkylidene group include an ethylidene group and a propylidene group.

Specific examples of such a compound having a benzophenone skeleton include 2-hydroxy-4-methoxybenzophenone-5-carboxylic acid, 2,2'-dihydroxy-4-methoxybenzophenone-5-carboxylic acid,
Preferable examples include 4- (2-hydroxybenzoyl) -3-hydroxybenzenepropanoic acid.

The ultraviolet absorber having a benzotriazole skeleton or a benzophenone skeleton can be produced by a known method.

In the production method of the present invention, the reaction for causing at least the component A and the component B to react to form an amide bond derived from the component A is usually mainly a dehydration reaction. At this time, the amount of the amide bond generated by the reaction is not particularly limited, but is usually one of the total aminosilanes of the component A.
An amide bond may be formed in an amount of 0 mol% or more, preferably 50 mol% or more.
Although it is mol%, the upper limit may be less than 100 mol%.

In the production method of the present invention, as described above, at least the component A and the component B may be reacted. However, at the time of such a reaction or after the reaction, optional components may be added within a range not to impair the object of the present invention. Further, they may coexist. Next, these optional components will be described.

An example of the optional component is a silicone resin (hereinafter, referred to as "component C"). As the component C, a reactive silicone resin, that is, a silicone resin having a functional group capable of reacting (usually a dehydration reaction and / or a dealcoholization reaction) with an alkoxysilyl group portion of the component A is preferable. As the functional group, an alkoxysilyl group, a silanol group or the like is preferable.

Such a reactive silicone resin can be easily synthesized generally by a partial hydrolysis reaction of alkoxysilane or chlorosilane followed by a condensation reaction. In commercial products, pure silicone varnish (for example,
Product name “XO7931-Clear”: Okitsumo Corporation
), Silicone resin (for example, trade name “SR241
"0": Dow Corning Toray Silicone Co., Ltd.), acrylic-modified silicone resin (for example, trade name "Sylacoat 100": Chisso Co., Ltd.) and the like are preferable. Further, the silicone resin can be used in the form of a solution using various solvents as long as the object of the present invention is not impaired. The solvent is not particularly limited, and examples thereof include various hydrocarbon solvents, ketones, ethers, esters, and ether / esters. Further, various modifications of a silicone resin may be used.

The component C is allowed to coexist at the time of the reaction of the components A and B, or after the reaction, but it is particularly preferable to coexist at the time of the reaction of the components A and B.

Other examples of the optional component include various epoxy silanes (hereinafter, referred to as "component D"), and preferably include epoxy silanes represented by the following general formula.

[0028]

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In the formula, R ⁹ and R ¹¹ are the same or different groups and have an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or a group represented by the formula —R—O—R′— (where R and R ′ each represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms), and each R ¹⁰ is the same or different and is a hydrogen atom, a hydroxyl group, An alkyl group or alkoxy group having 1 to 10, preferably 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. However, at least one of all R ¹⁰ is an alkoxy group, preferably having 1 carbon atom.
To 5 alkoxy groups. n is n ≧ 0, preferably 0
≤n≤3.

The alkylene group includes a methylene group,
Preferable examples include a trimethylene group and a tetramethylene group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group,
Pentyl group, hexyl group, heptyl group, octyl group and the like are preferable, and the alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group and the like. Examples of the aryl group include a phenyl group and a tolyl group.

Component D includes 3-glycidoxypropyltrimethoxysilane, dimethoxy-3-glycidoxypropylmethylsilane, 2- (3,4-epoxycyclohexylethyl) trimethoxysilane, dimethylethoxy-3-glycol Sidoxypropylsilane, 1,3-bis (3-glycidoxypropyl) -1,3-dimethyl-
Suitable examples include 1,3-dimethoxydisiloxane and mixtures thereof.

The component D may be used after being hydrolyzed in advance. Further, the epoxy group can be used by ring-opening polymerization with an appropriate polymerization catalyst in advance. As the polymerization catalyst, a Lewis acid catalyst such as boron trifluoride diethyl ether complex, aluminum chloride, and diethyl zinc is preferable. The polymerization conditions for ring-opening polymerization of the epoxy group are not particularly limited, but are usually -80 ° C to 130 ° C, preferably -20 to 80 ° C.
The reaction temperature is desirably about 0 ° C., and the reaction time can be appropriately selected depending on the reaction conditions, reaction mode, and the like, and is usually about 10 minutes to 10 hours, preferably about 1 hour to 6 hours. The solvent used at this time is not particularly limited, but examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, various ketones and esters.

The component D is allowed to coexist during the reaction of the components A and B or after the reaction, but is preferably added after the reaction of the components A and B. However, in the case of using a component D in which the epoxy group of the component D has been subjected to ring-opening polymerization in advance, it is preferably added during the reaction of the components A and B.

Other optional components include polyether-modified polysiloxanes (hereinafter referred to as “component E”).
Preferably, polyether-modified polysiloxanes represented by the following general formula are exemplified.

[0035]

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Wherein R ¹² , R ¹³ and R ¹⁴ are the same or different and have 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
And R ¹⁵ are the same or different groups, and each represents a hydrogen atom, a hydroxyl group, or a C 1 to C 1 alkylene group.
0, preferably an alkyl group or alkoxy group having 1 to 5 or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. Preferably at least one of all R ¹⁵
One is an alkoxy group having 1 to 10 carbon atoms. m, n, p
Is m ≧ 0, preferably 0 ≦ m ≦ 100, n ≧ 0,
Preferably 0 ≦ n ≦ 10, p ≧ 0, preferably 0 ≦ p ≦
Indicates an integer of 10. Preferable examples of the alkylene group include a methylene group, a trimethylene group, and a tetramethylene group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, i
-Propyl group, butyl group, t-butyl group, pentyl group,
Hexyl, heptyl and octyl groups are preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group, a pentyloxy group, and a hexyloxy group. Examples of the aryl group include a phenyl group and a tolyl group.

Specific examples of the component E represented by the general formula include tetraethylene glycol-bis (triethoxysilylethyl) ether, polyethylene glycol-bis (triethoxysilylethyl) ether,
Examples thereof include polypropylene glycol-bis (triethoxysilylethyl) ether or a mixture thereof.
As the component E, those hydrolyzed in advance may be used.

The component E is allowed to coexist during the reaction of the components A and B or after the reaction, but is preferably added during the reaction of the components A and B.

By using the epoxysilanes of component D and the polyether-modified polysiloxanes of component E as optional components, when an ultraviolet absorbing material is used as a coating material, heat resistance to the substrate can be maintained without impairing the heat resistance. The adhesiveness is improved, and a more excellent effect is exhibited, such as being less likely to be broken even when the film is thick.

As another optional component, an inorganic fine particle dispersion (hereinafter, referred to as “component F”) may be mentioned. The component F is not particularly limited, and examples thereof include a dispersion of fine particles of silica, alumina, titanium oxide, antimony oxide, and the like. The particle diameter of the fine particles is about 1 to 100 nm, and examples of the dispersion medium include water, methanol, xylene, and methyl ethyl ketone. For commercial products, the product name "LUDOX
・ LS ”(manufactured by DuPont) and product name“ XBA-ST ”
(Manufactured by Nissan Chemical Industries, Ltd.) and the like.

The component F is allowed to coexist during the reaction of the components A and B or after the reaction, but is preferably added during the reaction of the components A and B.

Each of the above optional components can be produced by a known method.

In the present invention, an ultraviolet-absorbing material can be easily produced by reacting at least the component A and the component B or, if necessary, reacting in the presence of the optional component. The reaction conditions are as follows: Component A
The conditions are not particularly limited as long as the amide bond derived from is formed, and may be appropriately selected. Usually, after the components A and B, and if desired, any components are mixed in a solvent, To react, room temperature to 35
The reaction can be suitably performed at 0 ° C., preferably 60 to 250 ° C., usually for 5 minutes to 50 hours, preferably 10 minutes to 15 hours. These reaction operations can be performed repeatedly.

The solvent used in this reaction is not particularly limited as long as the object of the present invention is not impaired, and examples thereof include aromatic solvents such as toluene and xylene; ketone solvents such as cyclohexanone and mixtures thereof. .
The solvent may be removed after the reaction, or may be in a solution state without being removed.

In the above reaction, the ratio of the components A and B to be used is not particularly limited, but the amount of the component B is usually 5 to 90% by mass relative to the total amount of the components A and B.
Preferably, it can be arbitrarily selected in the range of 10 to 80% by mass.

When the reaction is carried out using the above-mentioned optional components, or the amount of each of the optional components added after the reaction to coexist is not particularly limited, the amount of the silicone resin (component C) used is 5 to 300 parts by weight, preferably 20 to 15 parts by weight, based on 100 parts by weight of the total of
0 parts by mass is desirable. The amount of the epoxysilanes (component E) to be used is 10 to 500 parts by mass, preferably 100 to 400 parts by mass, based on 100 parts by mass of the total of components A and B. The amount of the polyether-modified polysiloxanes (component E) used is 100% of the total of components A and B.
10 to 500 parts by mass, preferably 10 parts by mass,
0 to 400 parts by mass is desirable. The amount of the inorganic fine particle dispersion (component F) used is 5 to 400 parts by weight, preferably 10 to 200 parts by weight as the inorganic fine particles, based on 100 parts by weight of the total amount of the components A and B.

The ultraviolet absorbing material obtained by the production method of the present invention can be applied to various uses. For example, it is extremely suitable as a coating material.

When the ultraviolet absorbing material obtained by the production method of the present invention is used as a coating material, it may be used as it is, or the ultraviolet absorbing material may be used as a main component and any optional component may be added. Good.

Examples of such optional components include various antioxidants; quencher; radical scavenger; inorganic and organic acids such as hydrochloric acid, sulfuric acid, and acetic acid; boron trifluoride / diethyl ether complex; Lewis acids such as sodium citrate; bases such as potassium hydroxide, sodium hydroxide, triethylamine and aniline; catalysts having a curing promoting action as exemplified by organic metals such as dibutyltin dilaurate and titanium tetraisopropoxide (UV absorption Usually, it is preferable to use 0.1 to 5.0 mass% with respect to the conductive material); toluene, xylene, ethanol,
Isopropanol, thinner, dimethylformamide,
Solvents such as cyclohexanone and 1-methoxy-2-acetoxypropane.

Such a coating material can be used for various applications such as an ultraviolet absorbing paint and an ultraviolet absorbing hard coat material.

By applying and curing such a coating material, an ultraviolet absorbing film having excellent physical properties can be obtained. The application method in this case is not particularly limited, and a known method is appropriately selected.However, usually, a coating material is used as a solution in the form of spin coating, spray coating,
It can be appropriately selected according to the purpose such as cast coat and blade coat. The thickness of the ultraviolet absorbing film is not particularly limited and is appropriately selected, but is preferably in the range of about 0.5 to 50 μm.

The curing reaction of the film can be carried out usually at room temperature to 250 ° C., preferably at about 40 ° C. to 200 ° C. when the catalyst having the above-mentioned curing promoting action is used. In addition, curing can be carried out at room temperature to 350 ° C, preferably at 60 ° C to 250 ° C, without using the above catalyst. The time required for curing can be appropriately selected and is usually about 10 minutes to 5 hours.

The substrate on which the coating material is applied may be any of glass, metal plate, wood plate and plastic substrate.

If necessary, an overcoat layer may be further provided on the ultraviolet absorbing film formed by using the ultraviolet absorbing material of the present invention. Examples of a material for forming the overcoat layer include polyimide, polyamide, polycarbonate, polyacrylate, polyether sulfone, melamine resin, phenol resin, epoxy resin, silicone resin such as silicone varnish; urea resin or a mixture thereof. It is particularly desirable to use a silicone resin such as a silicone varnish. These resins can be shared with glass fillers and inorganic powders. As the inorganic _{powder, ZnO, TiO 2, CeO 2} , fine particles such as silica are used.

As described above, the present invention has been described in detail. Preferred embodiments of the present invention include the following.

1. The reaction between (a) the aminosilane compound represented by the general formula (1) or a derivative thereof (component A) and (b) an ultraviolet absorber having a carboxyl group in the molecule (component B) is performed by a silicone resin (component C). A method for producing an ultraviolet absorbing material in the presence of

2. (A) an amide derived from component A by reacting an aminosilane compound represented by the general formula (1) or a derivative thereof (component A) with (b) an ultraviolet absorber having a carboxyl group in the molecule (component B); A method for producing an ultraviolet-absorbing material, which further comprises adding an epoxysilane (component D) after forming a bond.

3. (A) an amide derived from component A by reacting an aminosilane compound represented by the general formula (1) or a derivative thereof (component A) with (b) an ultraviolet absorber having a carboxyl group in the molecule (component B); A method for producing an ultraviolet absorbing material further comprising adding inorganic fine particles (component F) after forming a bond.

4. (A) an amide derived from component A by reacting an aminosilane compound represented by the general formula (1) or a derivative thereof (component A) with (b) an ultraviolet absorber having a carboxyl group in the molecule (component B); A coating material containing an ultraviolet absorbing material obtained by forming a bond.

5. An ultraviolet absorbing film obtained by applying the coating material.

[0061]

The ultraviolet-absorbing material obtained by the production method of the present invention has a good effect of blocking ultraviolet rays,
It is suitable as a coating material that can easily impart heat resistance. In addition, since the base material and the ultraviolet absorber are bonded by an amide bond, bleed-out does not occur even during long-term use, and good ultraviolet absorption ability can be maintained. By applying the ultraviolet absorbing material obtained by the production method of the present invention, a transparent ultraviolet absorbing film can be obtained, and it can be suitably applied to an ultraviolet absorbing glass, an optical element, and a light control element.

[0062]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.

Example 1 Synthesis of carboxyl group-containing UV absorber 225 g (0.46 mol) of 3- (5-chloro-2H-
Benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid octyl ester (TINUVIN 109, trade name, Ci)
ba-Geigy) was dissolved in 700 ml of acetone, 600 ml of a 2N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 24 hours. After 650 ml of 2N hydrochloric acid was added to make the solution acidic, the insolubilized product was separated by filtration and washed with distilled water until the filtrate became neutral. After vacuum drying the product, recrystallization from toluene gives 3- (5-chloro-2H-benzotriazol-2-yl) -5-.
(1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid (hereinafter referred to as compound A) was obtained.

Preparation of Ultraviolet Absorbing Material 3 g of 3-aminopropyltriethoxysilane was dissolved in 35 g of xylene, and the compound A was heated at 80 ° C.
5 g was added slowly. After the addition was completed, the temperature was raised to 130 ° C., and the mixture was refluxed for 3 hours to obtain a solution-type ultraviolet absorbing material.
When the obtained solution was analyzed by ¹³ C-NMR, the peak of the carbonyl derived from the amide bond (about 173 pp
m) was observed, and it was confirmed that an amide bond derived from aminosilanes as a raw material was present.

Preparation of UV-Absorbing Film To the UV-absorbing material in the form of a solution, 8 g of 3-glycidoxypropyltrimethoxysilane was added, and this was applied as a coating solution on a glass substrate by spray coating. After standing for 20 minutes, the mixture was heated at 200 ° C. for 20 minutes to form an ultraviolet absorbing film having a thickness of about 17 μm on the glass substrate.
FIG. 1 shows an ultraviolet-visible absorption spectrum of this glass substrate. As shown in the spectrum, a glass substrate completely blocking ultraviolet light of 400 nm or less was obtained. In addition, this ultraviolet absorbing film was scraped off from the glass substrate and solid ¹³
C-NMR was measured. As a result, a carbonyl peak (about 173 ppm) derived from the amide bond was observed. This scraped solid is treated with acetone as a solvent for 24 hours.
A time Soxhlet extraction was performed, but nothing derived from the UV absorber was extracted. From this result, it was found that the ultraviolet absorber was bonded to the resin via the aminosilane.

Example 2 Preparation of Ultraviolet Absorbing Material 3 g of 3-aminopropyltriethoxysilane was dissolved in 40 g of xylene, and 5 g of the compound A prepared in Example 1 was gradually added while heating to 60 ° C. . After completion of addition, 1
The temperature was raised to 30 ° C., and the mixture was refluxed for 3 hours to obtain an ultraviolet absorbing material in a solution state. When the obtained solution was analyzed by ¹³ C-NMR, a carbonyl peak (about 173 ppm) derived from an amide bond was observed, and it was confirmed that an amide bond derived from aminosilanes as a raw material was present.

Preparation of Ultraviolet Absorbing Coating The above ultraviolet absorbing material in the form of a solution was applied as a coating liquid on a glass substrate by spraying, left at room temperature for 20 minutes, heated at 130 ° C. for 30 minutes, A 10 μm UV absorbing coating was prepared. The UV-visible absorption spectrum of this glass substrate was measured. As a result, a glass substrate completely blocking ultraviolet rays was obtained as in Example 1.

Example 3 Production of Ultraviolet Absorbing Material 17.7 g of silicone varnish (trade name: XO-7931-Clear, manufactured by Okitsumo Co., Ltd.) and 3 g of 3-aminopropyltriethoxysilane were dissolved in 35 g of xylene. Compound A prepared in Example 1 while heating to 80 ° C.
5 g was added slowly. After the addition was completed, the temperature was raised to 130 ° C., and the mixture was refluxed for 3 hours to obtain a solution-type ultraviolet absorbing material.

Preparation of UV-Absorbing Film The above-mentioned solution-like UV-absorbing material was used as a coating solution and spray-coated on a glass substrate.
After heating for 20 minutes at 200 ° C for about 17μ
A glass substrate provided with a m-ultraviolet absorbing film was prepared.
FIG. 2 shows the result of measuring the ultraviolet-visible absorption spectrum of this glass substrate. As shown in FIG. 2, a glass substrate completely blocking ultraviolet light of 400 nm or less was obtained. JI
The SK 5400 pencil hardness test result was 2H. This UV-absorbing film is scraped off from the glass substrate and solid ^13C
-NMR was measured. As a result, a carbonyl peak (about 173 ppm) derived from the amide bond was observed.
The scraped solid was subjected to Soxhlet extraction using acetone as a solvent for 24 hours, but no substance derived from the ultraviolet absorber was extracted. From this result, it was found that the ultraviolet absorber was bonded to the resin via the aminosilane.

Example 4 Production of Ultraviolet Absorbing Material 17.7 g of silicone varnish (trade name: XO-7931-Clear, manufactured by Okitsumo Co., Ltd.) and 3 g of 3-aminopropyltriethoxysilane were dissolved in 35 g of xylene. Compound A prepared in Example 1 while heating to 80 ° C
5 g was added slowly. After the addition was completed, the temperature was raised to 130 ° C. and refluxed for 3 hours. After cooling, 16 g of 3-glycidoxypropyltrimethoxysilane was added to obtain an ultraviolet absorbing material.

Preparation of UV Absorbing Coating The above UV absorbing material in the form of a solution was applied as a coating liquid on a glass substrate by spray coating, left at room temperature for 20 minutes, and then heated at 200 ° C. for 20 minutes to form a film having a thickness of about 17 μm. A glass substrate provided with an ultraviolet absorbing film was produced. FIG. 3 shows the result of measuring the ultraviolet-visible absorption spectrum of this glass substrate. No peeling was observed in the JIS K 5400 grid test. The prepared ultraviolet-absorbing glass substrate was immersed in acetone, ethanol, toluene, a 1N aqueous hydrochloric acid solution, and a 1N aqueous sodium hydroxide solution for 24 hours, and observed, but no visual abnormality was observed.

Example 5 Production of Ultraviolet Absorbing Material 17.7 g of silicone varnish (trade name: XO-7931-Clear, manufactured by Okitsumo Co., Ltd.) and 3 g of 3-aminopropyltriethoxysilane were dissolved in 35 g of xylene. Compound A prepared in Example 1 while heating to 80 ° C
5 g was added slowly. After the addition was completed, the temperature was raised to 130 ° C. and refluxed for 3 hours. After cooling, 16 g of 3-glycidoxypropyltrimethoxysilane and 8 g of colloidal silica dispersion (manufactured by Nissan Chemical Co., Ltd., trade name: MIBK-ST) were added to obtain an ultraviolet absorbing material.

Preparation of UV Absorbing Coating The above UV absorbing material in the form of a solution was applied as a coating liquid on a glass substrate by spraying, left at room temperature for 20 minutes, heated at 200 ° C. for 20 minutes, and dried to a thickness of about 17 μm. A glass substrate provided with an ultraviolet absorbing film was produced. JIS
The result of the K5400 pencil hardness test was 4H. FIG. 4 shows the result of measuring the ultraviolet-visible absorption spectrum of this glass substrate.

Example 6 Polymerization of Epoxysilane 200 g of 3-glycidoxypropyltrimethoxysilane
Was dissolved in 75 g of xylene, 4 ml of boron trifluoride / diethyl ether complex was gradually added at room temperature, and the mixture was stirred for 4 hours to effect ring-opening polymerization of an epoxy group to obtain an epoxysilane polymer solution. The molecular weight of the obtained polymer was MW =
It was 3300 (in terms of polystyrene).

Production of Ultraviolet Absorbing Material 17.7 g of silicone varnish (trade name: XO-7931-Clear, manufactured by Okitsumo Co., Ltd.) and 3 g of 3-aminopropyltriethoxysilane were dissolved in 29 g of xylene and heated to 80 ° C. Compound A prepared in Example 1 while heating
5 g was added slowly. After the addition was completed, the temperature was raised to 130 ° C. and refluxed for 3 hours. After cooling, 22 g of the epoxysilane polymer solution was added to obtain an ultraviolet absorbing material.

Preparation of UV Absorbing Coating The above UV absorbing material in the form of a solution was applied as a coating liquid on a glass substrate by spray coating, left at room temperature for 20 minutes, and then heated at 150 ° C. for 30 minutes to form a film having a thickness of about 15 μm. A glass substrate provided with an ultraviolet absorbing film was produced. JIS
The result of the K5400 pencil hardness test was 6H. FIG. 5 shows the result of measuring the ultraviolet-visible absorption spectrum of this glass substrate.

Example 7 Preparation of UV-absorbing material Example 6 with 3 g of 3-aminopropyltriethoxysilane
11 g of the epoxysilane polymer solution prepared in 1) was dissolved in 32 g of xylene, and 5 g of the compound A prepared in Example 1 was gradually added while heating to 80 ° C. After completion of addition, 1
The temperature was raised to 30 ° C. and refluxed for 3 hours to obtain an ultraviolet absorbing material.

Production of UV Absorbing Coating The above UV absorbing material in the form of a solution was applied as a coating liquid on a glass substrate by spray coating, left at room temperature for 20 minutes, and then heated at 150 ° C. for 30 minutes to form a film having a thickness of about 15 μm. A glass substrate provided with an ultraviolet absorbing film was produced. JIS
The result of the K5400 pencil hardness test was 5H. FIG. 6 shows the result of measuring the ultraviolet-visible absorption spectrum of this glass substrate.

Comparative Example 1 To 22.2 g of a silicone varnish (trade name: XO-7931-Clear, manufactured by Okitsumo Co., Ltd.) was added 3- (5-chloro-2H-benzotriazol-2-yl) -5-
Octyl (1,1-dimethylethyl) -4-hydroxy-benzenepropanoate (TINUVIN 10
9, trademark, Ciba-Geigy) 10 g
Further, 20 μl of di-n-butyltin dilaurate was added, diluted with 20 ml of dimethylformamide (DMF), and spray-coated on a glass substrate. After drying on a hot plate at 60 ° C for 15 minutes, place in an oven for 2 minutes.
It was cured by heating at 00 ° C. for 1 hour to obtain an ultraviolet absorbing film having a thickness of about 20 μm. However, this ultraviolet absorbing film became cloudy due to precipitation of the absorbent.

Comparative Example 2 To 22.2 g of a silicone varnish (trade name: XO-7931-Clear, manufactured by Okitsumo Co., Ltd.) was added 3- (5-chloro-2H-benzotriazol-2-yl) -5-
Octyl (1,1-dimethylethyl) -4-hydroxy-benzenepropanoate (TINUVIN 10
9, Trademark, Ciba-Geigy) (2.2 g), di-n-butyltin dilaurate (20 μl) was added, diluted with DMF (20 ml), and spray-coated on a glass substrate. After drying on a hot plate at 60 ° C. for 15 minutes, it was placed in an oven and cured by heating at 200 ° C. for 1 hour to obtain an ultraviolet absorbing film having a thickness of about 15 μm. Although this ultraviolet absorbing film did not become cloudy as in Comparative Example 1,
The ultraviolet ray cutting ability was insufficient as shown in the transmittance spectrum of FIG. Further, the formed film was scraped off from the glass substrate, sox-ray extraction was performed in the same manner as in the example, and the dried residual solid was weighed to 15.2%.
Was observed.

[Brief description of the drawings]

FIG. 1 is a graph showing an ultraviolet-visible absorption spectrum of a glass substrate prepared in Example 1.

FIG. 2 is a graph showing an ultraviolet-visible absorption spectrum of a glass substrate prepared in Example 3.

FIG. 3 is a graph showing an ultraviolet-visible absorption spectrum of a glass substrate prepared in Example 4.

FIG. 4 is a graph showing an ultraviolet-visible absorption spectrum of the glass substrate prepared in Example 5.

FIG. 5 is a graph showing an ultraviolet-visible absorption spectrum of the glass substrate prepared in Example 6.

FIG. 6 is a graph showing an ultraviolet-visible absorption spectrum of the glass substrate prepared in Example 7.

FIG. 7 is a graph showing an ultraviolet-visible absorption spectrum of the glass substrate prepared in Comparative Example 2.

Claims (1)

[Claims] (A) an aminosilane compound represented by the general formula (1) or a derivative thereof, and (Wherein, R ¹ represents an alkylene group having 1 to 10 carbon atoms or a divalent group represented by the general formula — (CH ₂ ) m —NH— (m is an integer of 1 ≦ m ≦ 4). R ² is the same or different and represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, provided that at least one of all R ² is an alkoxy group (N represents an integer of n ≧ 0). (B) A amide bond derived from the aminosilane compound or a derivative thereof is formed by reacting at least a UV absorber having a carboxyl group in the molecule. A method for producing an ultraviolet absorbing material.