JP6031405B2 - Benzotriazole compounds - Google Patents

Description

  The present invention relates to a benzotriazole compound capable of radical reaction and having a hydrophilic group, which can be suitably used particularly for emulsion polymerization.

  The 2- (2-hydroxyphenyl) benzotriazole compound is useful as an ultraviolet absorber that is used to prevent deterioration of a polymer material or the like due to light irradiation. Since many 2- (2-hydroxyphenyl) benzotriazole compounds are low molecular weight compounds, there are drawbacks such as volatilization when heat-treating the polymer material and bleeding from the polymer material after processing. It was. Therefore, a 2- (2-hydroxyphenyl) benzotriazole compound having a radical reactive group for the purpose of bonding a 2- (2-hydroxyphenyl) benzotriazole compound to a polymer material and preventing volatilization and bleeding. (See, for example, Patent Documents 1 to 4).

JP 60-38411 A JP-A 63-185969 JP-A-2-142778 Japanese translation of PCT publication No. 2002-514661

  However, these compounds have a problem in that they are not uniformly bonded to the polymer material due to insufficient dispersibility in water at the time of emulsion polymerization, and the ultraviolet absorption effect cannot be sufficiently exhibited.

（式中、Ｒ¹及びＲ²はそれぞれ独立して水素原子又は炭素数１〜５のアルキル基を表わし、Ｒ³は炭素数１〜４のアルキレン基を表わし、Ｒ⁴は直接結合又は炭素数１〜８の２価炭化水素基を表わし、Ｒ⁵は水素原子又はメチル基を表わし、Ｘは下記一般式（２）〜（５）のいずれかで表される基を表わし、ａは０〜１０００の数を表わす。）

（式中、Ｒ⁶は水素原子又は炭素数１〜５のアルキル基を表わし、ｂは１〜１０００の数を表わす。）

（式中、Ｒ⁷は水素原子又は炭素数１〜５のアルキル基を表わし、ｃは１〜１０００の数を表わす。）

（式中、Ｒ⁸は炭素数１〜５のアルキル基を表わし、ｄは１〜１０００の数を表わす。）

（式中、Ｒ⁹は炭素数１〜５のアルキル基を表わし、ｅは１〜１０００の数を表わす。） In order to solve the above-mentioned problems, the present inventors have made various studies on benzotriazole compounds having excellent dispersibility in water, and as a result, the present invention has been completed. That is, the present invention is a benzotriazole compound represented by the following general formula (1).

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ represents an alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a direct bond or a carbon number. 1 to 8 divalent hydrocarbon groups, R ⁵ represents a hydrogen atom or a methyl group, X represents a group represented by any one of the following general formulas (2) to (5), and a represents 0 to Represents the number 1000)

(In the formula, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and b represents a number of 1 to 1000.)

(In the formula, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and c represents a number of 1 to 1000.)

(In the formula, R ⁸ represents an alkyl group having 1 to 5 carbon atoms, and d represents a number of 1 to 1000.)

(In the formula, R ⁹ represents an alkyl group having 1 to 5 carbon atoms, and e represents a number of 1 to 1000.)

  The effect of the present invention is to provide a benzotriazole compound having a radical reactive group and good water dispersibility.

1 is a ¹ H-NMR chart of Compound A1 of the present invention. ¹ is a ¹ H-NMR chart of Compound A2 of the present invention. ¹ is a ¹ H-NMR chart of Compound A3 of the present invention.

The benzotriazole compound represented by the general formula (1) of the present invention will be described.
In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, pentyl, sec-pentyl, and t-pentyl. Group, isopentyl group and the like. R ¹ is preferably a hydrogen atom, a methyl group, a t-butyl group or a t-pentyl group, more preferably a methyl group or a t-butyl group, since the raw materials are easily available and the ultraviolet absorption effect is great. A t-butyl group is most preferred. R ² is preferably a methyl group, a t-butyl group, or a t-pentyl group, more preferably a methyl group or a t-butyl group, and more preferably a methyl group because the raw material is easily available and has a large ultraviolet absorption effect. Most preferred. R ³ represents an alkylene group having 1 to 4 carbon atoms. Examples of the alkylene group having 1 to 4 carbon atoms include methylene group, ethylene group, methylmethylene group, propylene group, 1-methylethylene group, 2-methylethylene group, ethylmethylene group, butylene group, and 2-methylpropylene group. Can be mentioned. R ³ is preferably an ethylene group because raw materials are easily available and there are few side reactions.

（式中、Ｒ⁴は一般式（１）と同義である。） R ⁴ represents a direct bond or a divalent hydrocarbon group having 1 to 8 carbon atoms. When R ⁴ is combined with two carbonyl groups adjacent to R ⁴ as a group represented by the following general formula (1x), the group represented by the following general formula (1x) is a group having 2 to 10 carbon atoms. A residue obtained by removing two hydroxyl groups from a basic acid, R ⁴ can also be regarded as a residue obtained by removing two carboxyl groups from a dibasic acid having 2 to 10 carbon atoms. In the case of producing the benzotriazole compound of the present invention, it is easy to obtain industrially and the reaction is easy, so that the dibasic acid having 2 to 10 carbon atoms or its acid anhydride, particularly the carbon number, is used as a raw material. Preference is given to using acid anhydrides of 2 to 10 dibasic acids. Examples of the dibasic acid having 2 to 10 carbon atoms include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid , Isophthalic acid, terephthalic acid, tetrahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc., and a dibasic acid having 2 to 10 carbon atoms Examples of the anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, and the like. Therefore, R ⁴ is preferably a residue obtained by removing two carboxyl groups from a dibasic acid having 2 to 10 carbon atoms. Succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, or 1,2-cyclohexanedicarboxylic acid A residue obtained by removing two carboxyl groups from an acid is more preferred, and a residue obtained by removing two carboxyl groups from succinic acid is most preferred.

(In the formula, R ⁴ has the same meaning as in general formula (1).)

R ⁵ represents a hydrogen atom or a methyl group, and R ⁵ is preferably a methyl group since the storage stability of the benzotriazole compound of the present invention is good.

  In the said General formula (1), a represents the number of 0-1000, and since manufacture is easy, it is preferable that a is the number of 0.

（式中、Ｒ⁶は水素原子又は炭素数１〜５のアルキル基を表わし、ｂは１〜１０００の数を表わす。）

（式中、Ｒ⁷は水素原子又は炭素数１〜５のアルキル基を表わし、ｃは１〜１０００の数を表わす。）

（式中、Ｒ⁸は炭素数１〜５のアルキル基を表わし、ｄは１〜１０００の数を表わす。）

（式中、Ｒ⁹は炭素数１〜５のアルキル基を表わし、ｅは１〜１０００の数を表わす。） In the general formula (1), X represents a group represented by any one of the following general formulas (2) to (5), and from the viewpoint of water solubility or water dispersibility of the benzotriazole compound of the present invention, A group represented by the formula (4) or (5) is preferable, and a group represented by the following general formula (5) is more preferable.

(In the formula, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and b represents a number of 1 to 1000.)

(In the formula, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and c represents a number of 1 to 1000.)

(In the formula, R ⁸ represents an alkyl group having 1 to 5 carbon atoms, and d represents a number of 1 to 1000.)

(In the formula, R ⁹ represents an alkyl group having 1 to 5 carbon atoms, and e represents a number of 1 to 1000.)

In the general formula (2), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As a C1-C5 alkyl group, the alkyl group illustrated by R < ¹ > and R < ² > of General formula (1) is mentioned. R ⁶ is preferably a hydrogen atom because the raw material is easily available industrially. b represents the number of 1-1000. From the viewpoint of water solubility or water dispersibility of the benzotriazole compound of the present invention, b is preferably a large number, but if it is too large, the proportion of the benzotriazole moiety in the molecule decreases, Since the ultraviolet absorption effect of the benzotriazole compound of the invention is reduced, a + b is preferably a number of 2 to 60, more preferably a number of 2 to 30, and a number of 2 to 15. Most preferred.

In the general formula (3), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As a C1-C5 alkyl group, the alkyl group illustrated by R < ¹ > and R < ² > of General formula (1) is mentioned. R ⁷ is preferably a hydrogen atom because it is easy to obtain industrial raw materials. c represents a number from 1 to 1000. From the viewpoint of water solubility or water dispersibility of the benzotriazole compound of the present invention, c is preferably a large number, but if it is too large, the proportion of the benzotriazole moiety in the molecule decreases, Since the ultraviolet absorption effect of the benzotriazole compound of the invention is lowered, a + c is preferably a number of 2 to 60, more preferably a number of 2 to 30, and a number of 2 to 15. Most preferred.

In the general formula (4), R ⁸ represents an alkyl group having 1 to 5 carbon atoms. As a C1-C5 alkyl group, the alkyl group illustrated by R < ¹ > and R < ² > of General formula (1) is mentioned. As R ⁸ , an alkyl group having a small number of carbon atoms is preferable from the viewpoint of water solubility or water dispersibility of the benzotriazole compound of the present invention, but an alkyl group having 3 to 4 carbon atoms is preferable because of easy production. More preferred are a butyl group and an isobutyl group. d represents a number from 1 to 1000. From the viewpoint of water solubility or water dispersibility of the benzotriazole compound of the present invention, d is preferably a large number, but if it is too large, the proportion of the benzotriazole moiety in the molecule decreases, Since the ultraviolet absorption effect of the benzotriazole compound of the invention is lowered, a + d is preferably a number of 2 to 60, more preferably a number of 2 to 30, and a number of 2 to 15. Most preferred.

In the general formula (5), R ⁹ represents an alkyl group having 1 to 5 carbon atoms. As a C1-C5 alkyl group, the alkyl group illustrated by R < ¹ > and R < ² > of General formula (1) is mentioned. As R ⁹ , an alkyl group having a small number of carbon atoms is preferable from the viewpoint of water solubility or water dispersibility of the benzotriazole compound of the present invention, but an alkyl group having 3 to 4 carbon atoms is preferable because of easy production. More preferred are a butyl group and an isobutyl group. e represents a number from 1 to 1000. From the viewpoint of water solubility or water dispersibility of the benzotriazole compound of the present invention, e is preferably a large number, but if it is too large, the proportion of the benzotriazole moiety in the molecule decreases, and Since the ultraviolet absorption effect of the benzotriazole compound of the invention is reduced, a + e is preferably a number of 2 to 60, more preferably a number of 2 to 30, and a number of 2 to 15. Most preferred.

（式中、Ｒ¹〜Ｒ⁵及びａは一般式（１）と同義であり、Ｒ⁶及びｂは一般式（２）と同義である。） Next, the manufacturing method of the benzotriazole compound of this invention is demonstrated.
Among the benzotriazole compounds represented by the general formula (1), a compound in which X is a group represented by the general formula (2), that is, a benzotriazole compound represented by the following general formula (1-2), As shown in the following reaction formula, the compound represented by the general formula (1a) is reacted with the acid anhydride represented by the general formula (6) to obtain a compound represented by the general formula (1b). The carboxyl group of the represented compound is converted into a carboxylic acid chloride group to obtain a compound represented by the general formula (1c), and the compound represented by the general formula (1c) and the amine compound represented by the general formula (7) are reacted. It can obtain by making the compound represented by general formula (1-2a) obtained by making it react with the acid chloride compound further represented by general formula (8).

(In formula, R < ¹ > -R < ⁵ > and a are synonymous with General formula (1), and R < ⁶ > and b are synonymous with General formula (2).)

  Among the compounds represented by the general formula (1a), a compound in which a is a number of 1 to 1000 is obtained by addition reaction of ethylene oxide to a compound in which a is a number of 0 in the general formula (1a). Can do. Addition of ethylene oxide to a compound in which a is 0 in general formula (1a) may be carried out by a known method, for example, by reacting at 80 to 150 ° C. using sodium hydroxide, potassium hydroxide or the like as a catalyst. Just do it. In general formula (1a), a compound in which a is 0 can be obtained by the method for producing a benzotriazole compound described in JP-A-2-142778.

The reaction of the compound represented by the general formula (1a) and the acid anhydride represented by the general formula (6) is performed by using a base catalyst such as triethylamine, and an acid catalyst such as methanesulfonic acid or p-toluenesulfonic acid. be able to. Among the amine compounds represented by the general formula (7), a compound in which R ⁶ is a hydrogen atom is a method described in Japanese Patent Application Laid-Open Nos. 7-003009 and 8-020643, in which hydrogen and ammonia are added to polyethylene glycol. It can obtain by making it react. Among the amine compounds represented by the general formula (7), a compound in which R ⁶ is an alkyl group having 1 to 5 carbon atoms is obtained by a known method for the amino group of the compound in which R ⁶ is a hydrogen atom. 5 alkyl groups may be introduced. The carboxyl group of the compound represented by the general formula (1b) can be converted to a carboxylic acid chloride group by using thionyl chloride, phosphorus trichloride or the like.
Reaction of compound represented by general formula (1c) and amine compound represented by general formula (7), and reaction of compound represented by general formula (1-2a) and acid chloride compound represented by general formula (8) May be carried out in a basic solvent such as pyridine, pyrimidine, triethylamine, tributylamine and the like.

（式中、Ｒ¹〜Ｒ⁵及びａは一般式（１）と同義であり、Ｒ⁷及びcは一般式（３）と同義である。） Among the benzotriazole compounds represented by the general formula (1), a compound in which X is a group represented by the general formula (3), that is, a benzotriazole compound represented by the following general formula (1-3), As shown in the following reaction formula, the compound represented by the general formula (1-3a) obtained by reacting the compound represented by the general formula (1c) with the amine compound represented by the general formula (9) is further added. It can be obtained by reacting an epoxy compound represented by the general formula (10).

(In formula, R < ¹ > -R < ⁵ > and a are synonymous with General formula (1), and R < ⁷ > and c are synonymous with General formula (3).)

  The reaction of the compound represented by the general formula (1c) and the amine compound represented by the general formula (9) may be performed in a basic solvent such as pyridine, pyrimidine, triethylamine, tributylamine. The amine compound represented by the general formula (9) is the same compound as the amine compound represented by the general formula (7).

（式中、Ｒ¹〜Ｒ⁵及びａは一般式（１）と同義であり、Ｒ⁸及びｄは一般式（４）と同義である。） Among the benzotriazole compounds represented by the general formula (1), a compound in which X is a group represented by the general formula (4), that is, a benzotriazole compound represented by the following general formula (1-4), As shown in the following reaction formula, the compound represented by the general formula (1-4a) obtained by reacting the compound represented by the general formula (1c) with the amine compound represented by the general formula (11) is further added. It can be obtained by reacting an acid chloride compound represented by the general formula (8).

(In formula, R < ¹ > -R < ⁵ > and a are synonymous with General formula (1), and R < ⁸ > and d are synonymous with General formula (4).)

  Reaction of a compound represented by general formula (1c) with an amine compound represented by general formula (11), and reaction of a compound represented by general formula (1-4a) with an acid chloride compound represented by general formula (8) May be carried out in a basic solvent such as pyridine, pyrimidine, triethylamine, tributylamine and the like.

The amine compound represented by the general formula (11) is obtained by reacting the epoxy compound represented by the general formula (12) with the amine compound represented by the general formula (13) as shown in the following reaction formula. Can do.

（式中、Ｒ¹〜Ｒ⁵及びａは一般式（１）と同義であり、Ｒ⁹及びｅは一般式（５）と同義である。） Among the benzotriazole compounds represented by the general formula (1), a compound in which X is a group represented by the general formula (5), that is, a benzotriazole compound represented by the following general formula (1-5), As shown in the following reaction formula, the compound represented by the general formula (1-5a) obtained by reacting the compound represented by the general formula (1c) with the amine compound represented by the general formula (14) is further added. It can be obtained by reacting an epoxy compound represented by the general formula (10).

(Wherein, R ¹ to R ⁵ and a are as in formula (1) the same meaning, R ⁹ and e in formula (5) interchangeably.)

  The reaction of the compound represented by the general formula (1c) and the amine compound represented by the general formula (14) may be performed in a basic solvent such as pyridine, pyrimidine, triethylamine, tributylamine and the like.

  The amine compound represented by the general formula (14) can be obtained by the same reaction as the amine compound represented by the general formula (11).

  The benzotriazole compound of the present invention has a radical reactive group and can react with other radical polymerizable compounds. There is no limitation on the reaction method, and any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. However, because of its excellent dispersibility in water, the reaction is preferably carried out by emulsion polymerization.

  There is no particular limitation on the radically polymerizable compound used in the emulsion polymerization in which the benzotriazole compound of the present invention is used. For example, styrene, m-methylstyrene, p-methylstyrene, 2,5-dimethylstyrene, p-chlorostyrene , P-bromostyrene, divinylbenzene, vinyl aromatics such as divinylnaphthalene; unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid; methyl (meth) acrylate , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate , Ethile Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (Meth) acrylates such as (meth) acrylate; (meth) acrylaldehyde, (meth) acrylonitrile, Unsaturated carboxylic acid derivatives such as (meth) acrylamide; N-vinyl compounds such as N-vinylpyridine and N-vinylpyrrolidone; vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate; vinyl chloride and vinyl bromide , Vinyl halide compounds such as vinylidene chloride, allyl compounds such as allyl alcohol, allyl methyl ether, allyl ethyl ether, allyl methyl ketone, allyl acetic acid, allyl phenol; N-methylol acrylamide, N-ethylol acrylamide, N- N-substituted unsaturated amides such as propanolacrylamide, N-methylol maleamic acid, N-methylol maleamic acid ester, N-methylol maleimide and N-ethylol maleimide; conjugated dienes such as butadiene and isoprene; divinyl Examples include polyfunctional vinyl compounds such as cyclohexane.

  In the polymer obtained by polymerizing the benzotriazole compound of the present invention and another radical polymerizable compound, the content of the benzotriazole compound of the present invention depends on the use of the polymer, but in general, other radicals It is preferable that the compounding quantity of the benzotriazole compound of this invention with respect to 100 mass parts of polymeric compounds is 0.001-2 mass parts, and it is still more preferable that it is 0.01-1 mass part.

  The obtained polymer can be used for various plastic products, paints, adhesives, pressure-sensitive adhesives, inks, films, coating agents, paper coating agents, sizing agents, sealers, etc., but applied to other substances. It is preferably used for paints, adhesives, pressure-sensitive adhesives, coating agents, paper coating agents, sealers, and the like, which are uses and applications that assist the application of other substances.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these Examples. Unless otherwise specified, “parts” and “%” in the examples are based on mass.

[Production Example 1]
In a glass reaction vessel equipped with a stirrer and a thermometer, 6.5 g (20 mmol) of 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5- (2-hydroxyethyl) benzotriazole, 2.1 g (21 mmol) of succinic anhydride, 40 mg of p-toluenesulfonic acid as a catalyst and 50 g of toluene as a solvent were charged, and the mixture was heated and stirred at 80 ° C. for 2 hours to be reacted. After completion of the reaction, by-products were removed by washing with water, and toluene and water were removed under reduced pressure. Subsequently, 50 g of toluene as a solvent and 100 mg of N, N-dimethylformamide as a catalyst were added. While cooling, 63 g (250 mmol) of thionyl chloride was added dropwise at 15 ° C. over 30 minutes, and the mixture was further stirred at 30 ° C. for 1 hour. Reacted. Toluene was added, and excess thionyl chloride was removed by azeotropy with toluene to obtain a toluene solution of intermediate A. Intermediate A is a general formula (1c) in which R ¹ is a t-butyl group, R ² is a methyl group, R ³ is an ethylene group, R ⁴ is a residue obtained by removing a carboxyl group from succinic acid, and a is 0 It is a compound which is. 2- (2-Hydroxy-3-t-butyl-5-methylphenyl) -5- (2-hydroxyethyl) benzotriazole was produced by the method described in JP-A-2-142778.

[Example 1]
A glass reaction vessel equipped with a stirrer and a thermometer was charged with 4.5 g (9.0 mmol) of polyethylene glycol 400 diglycidyl ether and 6.58 g (90 mmol) of isobutylamine and reacted by heating and stirring at 40 ° C. for 15 hours. Excess isobutylamine was removed by vacuum. Toluene solution containing 2.0 g (4.5 mmol) of Intermediate A was added dropwise at 15 ° C. over 30 minutes while charging 50 g of pyridine as a solvent, and the mixture was further stirred at 30 ° C. for 1 hour for reaction. . Subsequently, 2.82 g (19.84 mmol) of glycidyl methacrylate and 0.45 g (4.5 mmol) of hydroquinone were added and stirred at 100 ° C. for 5 hours for reaction. After completion of the reaction, 50 g of toluene was added and washed with water, and then the solvent and water were removed from the organic layer under reduced pressure. This reaction product was dissolved in toluene and recrystallized from hexane to obtain a product (yield 33%, purity 56%). It was confirmed by ¹ H-NMR that the obtained product was Compound A1, which is a compound of the present invention. The obtained ¹ H-NMR chart is shown in FIG. Compound A1 has the following formula (1-5): R ¹ is a t-butyl group, R ² and R ⁵ are methyl groups, R ³ is an ethylene group, R ⁴ is a residue obtained by removing a carboxyl group from succinic acid, R ^A compound in which ⁹ is an isobutyl group, a is 0, and e is a number of 10.

[Example 2]
In Example 1, instead of 2.82 g (19.84 mmol) of glycidyl methacrylate, the same operation as in Example 1 was carried out except that methacryloyl chloride was changed to 2.10 g (20.09 mmol). %, Purity 63%). It was confirmed by ¹ H-NMR that the obtained product was Compound A2, which is a compound of the present invention. The obtained ¹ H-NMR chart is shown in FIG. Compound A2 has the following formula (1-4): R ¹ is a t-butyl group, R ² and R ⁵ are methyl groups, R ³ is an ethylene group, R ⁴ is a residue obtained by removing a carboxyl group from succinic acid, R ^A compound in which ⁸ is an isobutyl group, a is 0, and d is a number of 10.

Example 3
A glass reaction vessel equipped with a stirrer and a thermometer was charged with 2.67 g (18.0 mmol) of 2,2 ′-(ethylenedioxy) bis (ethylamine) and 50 g of pyridine as a solvent. A toluene solution containing 2.0 g (4.5 mmol) was added dropwise at 15 ° C. over 30 minutes, and the mixture was further stirred at 30 ° C. for 1 hour to be reacted. After completion of the reaction, unreacted 2,2 ′-(ethylenedioxy) bis (ethylamine) was removed by washing with water, and then the solvent and water were removed from the organic layer under reduced pressure. Subsequently, 2.82 g (19.84 mmol) of glycidyl methacrylate, 0.45 g (4.5 mmol) of hydroquinone and 100 g of toluene as a solvent were added, and the mixture was stirred and reacted at 100 ° C. for 5 hours. After completion of the reaction, 50 g of toluene was added and washed with water, and then the solvent and water were removed from the organic layer under reduced pressure. This reaction product was dissolved in toluene and recrystallized from hexane to obtain a product (yield 35%, purity 58%). It was confirmed by ¹ H-NMR that the obtained product was Compound A3, which is a compound of the present invention. The obtained ¹ H-NMR chart is shown in FIG. Compound A3 has a general formula (1-3) in which R ¹ is a t-butyl group, R ² and R ⁵ are methyl groups, R ³ is an ethylene group, R ⁴ is a residue obtained by removing a carboxyl group from succinic acid, R ^A compound in which ⁷ is a hydrogen atom, a is 0, and c is a number 2.

  The compounds A1 to A3 obtained in Examples 1 to 3, the comparative compounds B1 to B3, butyl acrylate, methyl acrylate and acrylic acid as polymerizable monomers, and the emulsifier C are shown in Table 1 below. It mix | blended by mass ratio, the monomer solution of Examples 4-9 and Comparative Examples 1-4 was prepared, emulsion polymerization was performed with the following emulsion polymerization method, and the emulsion polymer was obtained. Each emulsion polymer was measured for gloss retention by the following method. The results are shown in Table 1 below. In addition, it shows that the higher the gloss retention, the better the ultraviolet absorption effect and the longer it can be maintained.

[Emulsion polymerization method]
A glass reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube was charged with 120 g of deionized water, and the system was replaced with nitrogen gas. After adding 10 g of the monomer solution and 0.08 g of ammonium persulfate, the temperature was raised to 60 ° C., 90 g of the monomer solution was added dropwise over 2 hours, and after completion of the dropwise addition, the mixture was further aged by stirring for 2 hours at 60 ° C. Got.

[Gloss retention]
The emulsion polymer was applied to a 50 mm × 70 mm glass plate to a thickness of 1 mm, air-dried for 12 hours, and then dried in a 100 ° C. constant temperature bath for 1 hour to obtain a test piece. After measuring the gloss of each test piece under the following measurement conditions, an accelerated weather resistance test was performed under the following conditions, and the gloss of each test piece after the accelerated weather resistance test was measured. The gloss retention after 100 minutes of the gloss after the accelerated weather resistance test with respect to the gloss before the accelerated weather resistance test was determined.
<Gloss measurement conditions> Equipment used: Precision gloss meter (Murakami Color Research Laboratory, Model: GM26D), Measurement angle: 60 °
<Conditions for accelerated weathering test> Equipment used: Sunshine weatherometer (manufactured by Suga Test Instruments, model: WEL-SUN-HCH-B), test conditions: temperature: 63 ± 3 ° C., cycle: rain for 18 minutes in 120 minutes, Test time: 2,000 hours

  From the results of Table 1, the test pieces of Examples 4 to 9 have a high gloss retention, and the coating film obtained from the emulsion polymer using the benzotriazole compound of the present invention has a long period even under severe natural environment conditions. This indicates that an excellent ultraviolet absorption effect can be maintained. This is because not only the benzotriazole compound of the present invention reacts with other monomers by a radical reactive group to form a coating film, but also in emulsion polymerization, it is uniform in the coating film by being dispersed in the reaction system. It is thought that it exists in.

Claims (2)

A benzotriazole compound represented by the following general formula (1).

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ represents an alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a direct bond or a carbon number. 1 to 8 divalent hydrocarbon groups, R ⁵ represents a hydrogen atom or a methyl group, X represents a group represented by any one of the following general formulas (2) to (5), and a represents 0 to Represents the number 1000)

(In the formula, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and b represents a number of 1 to 1000.)

(In the formula, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and c represents a number of 1 to 1000.)

(In the formula, R ⁸ represents an alkyl group having 1 to 5 carbon atoms, and d represents a number of 1 to 1000.)

(In the formula, R ⁹ represents an alkyl group having 1 to 5 carbon atoms, and e represents a number of 1 to 1000.)   A polymer obtained by polymerizing the benzotriazole compound according to claim 1 and another radical polymerizable compound.

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