JP2014077076A - Benzotriazole compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel benzotriazole compound with a radical reactive group which exhibits preferable water dispersibility.SOLUTION: The benzotriazole compound is represented by the specified general formula (1). (In the formula, Rand Reach independently represent a hydrogen atom or a C1-C5 alkyl group, Rrepresents a C1-C4 alkylene group, Rrepresents a direct coupling or a residue obtained by removing carboxyl groups from a C3-C10 dibasic acid, Rrepresents a hydrogen atom or a methyl group, a and c represent numbers in the range from 0 to 1000 with a+c equal to 2-1000, and b represents 0 or 1, where b is 0 if c is 0.)

Description

  The present invention relates to a novel 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.

As a result of various investigations on benzotriazole compounds excellent in water dispersibility in order to solve the above problems, the present inventors have completed the present invention.
That is, the present invention provides a benzotriazole compound represented by the following general formula (1).

（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３〜１０の二塩基酸からカルボキシル基を除いた残基を表わし、Ｒ⁵は水素原子又はメチル基を表わし、ａ及びｃはａ＋ｃが２〜１０００となる０〜１０００の数を表わし、ｂは０又は１の数を表わす。但し、ｃが０の数の場合、ｂは０の数を表わす。）

(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. Represents a residue obtained by removing a carboxyl group from 3 to 10 dibasic acids, R ⁵ represents a hydrogen atom or a methyl group, a and c represent a number of 0 to 1000 in which a + c is 2 to 1000, b is Represents a number of 0 or 1. However, when c is a number of 0, b represents a number of 0.)

  The present invention also provides an emulsion polymer obtained by emulsion polymerization of the above benzotriazole compound and another radical polymerizable compound.

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

FIG. 1 is a ¹ H-NMR chart of Compound A1, which is the benzotriazole compound of the present invention produced in Example 1. 2 is a ¹ H-NMR chart of Compound A2, which is the benzotriazole compound of the present invention produced in Example 2. FIG. 3 is a UV chart (measured with a 0.1% ethanol solution) of Compound A1, which is the benzotriazole compound of the present invention produced in Example 1. FIG.

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.

R ⁴ represents a direct bond or a residue obtained by removing a carboxyl group from a dibasic acid having 3 to 10 carbon atoms. Examples of the dibasic acid having 3 to 10 carbon atoms include 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 and the like. Since it is advantageous in production to use an acid anhydride, R ⁴ includes a residue obtained by removing a carboxyl group from succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, and 1,2-cyclohexanedicarboxylic acid. A residue obtained by removing a carboxyl group from succinic acid is more preferable.

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 and c represent the number of 0-1000 from which a + c will be 2-1000, b represents the number of 0 or 1. However, when c is a number of 0, b represents the number of 0. From the viewpoint of water dispersibility, a + c is preferably a large number, but if it is too large, the proportion of the benzotriazole moiety in the molecule decreases and the ultraviolet absorption effect of the benzotriazole compound of the present invention decreases. Therefore, a + c is preferably a number of 3 to 60, more preferably a number of 4 to 30, and most preferably a number of 5 to 15. In addition, since manufacture is easy, it is preferable that a is the number of 0.

  Among the benzotriazole compounds of the present invention, a compound in which b and c are 0 numbers, that is, a compound represented by the following general formula (2) is represented by the general formula (3) as shown in the following reaction formula. It can be obtained by adding ethylene oxide to the hydroxyl group of the compound to obtain a compound represented by the general formula (4) and esterifying with an acid chloride compound represented by the general formula (5).

（式中、ａは２〜１０００の数を表わし、Ｒ¹、Ｒ²、Ｒ³及びＲ⁵は前記一般式（１）と同義である。）

(In the formula, a represents a number of 2 to 1000, and R ¹ , R ² , R ³ and R ⁵ have the same meanings as in the general formula (1).)

（式中、ａは２〜１０００の数を表わし、Ｒ¹、Ｒ²、Ｒ³及びＲ⁵は前記一般式（１）と同義である。）

(In the formula, a represents a number of 2 to 1000, and R ¹ , R ² , R ³ and R ⁵ have the same meanings as in the general formula (1).)

  The compound represented by the general formula (3) can be obtained by the method for producing a benzotriazole compound described in Patent Document 3 (Japanese Patent Laid-Open No. 2-142778). The addition of ethylene oxide to the compound represented by the general formula (3) may be performed by a known method, for example, by reacting at 80 to 150 ° C. using sodium hydroxide, potassium hydroxide or the like as a catalyst. The reaction of the compound represented by the general formula (4) and the acid chloride compound represented by the general formula (5) may be performed in a basic solvent such as pyridine, triethylamine, tributylamine and the like.

  Among the benzotriazole compounds of the present invention, a compound in which a is a number of 0 and b is a number of 1, that is, a compound represented by the following general formula (6) is represented by the following general formula: The compound represented by (3) is reacted with the acid anhydride represented by the general formula (7) to obtain a compound represented by the general formula (8), and the carboxyl group of the compound represented by the general formula (8) is converted into a carboxylic acid. It can be obtained by converting into a chloride group to obtain a compound represented by the general formula (9) and reacting the compound represented by the general formula (9) with the compound represented by the general formula (10).

（式中、ｃは２〜１０００の数を表わし、Ｒ¹〜Ｒ⁵は前記一般式（１）と同義である。）

(In the formula, c represents a number of 2 to 1000, and R ^{1 to} R ⁵ have the same meaning as in the general formula (1).)

（式中、ｃは２〜１０００の数を表わし、Ｒ¹〜Ｒ⁵は前記一般式（１）と同義である。）

(In the formula, c represents a number of 2 to 1000, and R ^{1 to} R ⁵ have the same meaning as in the general formula (1).)

  The reaction between the compound represented by the general formula (3) and the acid anhydride represented by the general formula (7) uses a base catalyst such as triethylamine, and an acid catalyst such as methanesulfonic acid and p-toluenesulfonic acid. Can react. The compound represented by the general formula (8) can convert a carboxyl group into a carboxylic acid chloride group by using thionyl chloride, phosphorus trichloride or the like. The reaction of the compound represented by the general formula (9) and the compound represented by the general formula (10) may be performed in a basic solvent such as pyridine, triethylamine, or tributylamine.

  Among the benzotriazole compounds of the present invention, a compound in which a + c is a number from 1 to 1000 and 2 is a number of 1, that is, a compound represented by the following general formula (12) is represented by the following reaction: As shown by the formula, the compound represented by the general formula (4) is reacted with an acid anhydride of a dibasic acid to obtain a compound represented by the general formula (13), and the carboxyl group of the compound represented by the general formula (13) is The compound represented by the general formula (14) can be converted into a carboxylic acid chloride group, and the compound represented by the general formula (14) can be reacted with the compound represented by the general formula (11).

（式中、ａ及びｃはａ＋ｃは２〜１０００となる１〜１０００の数を表わし、Ｒ¹〜Ｒ⁵は一般式（１）と同義である。）

(In the formula, a and c each represent a number of 1 to 1000 in which a + c is 2 to 1000, and R ^{1 to} R ⁵ are synonymous with the general formula (1).)

（式中、ａ及びｃはａ＋ｃは２〜１０００となる１〜１０００の数を表わし、Ｒ¹〜Ｒ⁵は一般式（１）と同義である。）

(In the formula, a and c each represent a number of 1 to 1000 in which a + c is 2 to 1000, and R ^{1 to} R ⁵ are synonymous with the general formula (1).)

  The reaction between the compound represented by the general formula (4) and the acid anhydride represented by the general formula (7) uses a base catalyst such as triethylamine, and an acid catalyst such as methanesulfonic acid and p-toluenesulfonic acid. Can react. The compound represented by the general formula (13) can convert a carboxyl group into a carboxylic acid chloride group by using thionyl chloride, phosphorus trichloride or the like. The reaction of the compound represented by the general formula (14) and the compound represented by the general formula (11) may be performed in a basic solvent such as pyridine, triethylamine, tributylamine and the like.

  The benzotriazole compound of the present invention has a radical reactive group and can react with other radical reactive 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.

  The emulsion polymer of the present invention is obtained by emulsion polymerization of the benzotriazole compound of the present invention and another radical polymerizable compound other than the benzotriazole compound of the present invention. The reaction conditions for emulsion polymerization are not particularly limited as long as they are known methods.

  The radical polymerizable compound used in the emulsion polymer of the present invention is not particularly limited, and is an acrylate emulsion, styrene emulsion, vinyl acetate emulsion, SBR (styrene / butadiene) emulsion, ABS (acrylonitrile / butadiene / styrene) emulsion, Any of a BR (butadiene) emulsion, an IR (isoprene) emulsion, an NBR (acrylonitrile / butadiene) emulsion, and the like may be used.

  In the emulsion polymer of the present invention, the amount of the benzotriazole compound of the present invention can be arbitrarily used within the range of the usual amount of use, but is preferably 0.1% relative to 100 parts by mass of the radical polymerizable compound. 001-10 mass parts, More preferably, 0.05-7 mass parts, More preferably, 0.01-5 mass parts can be added and used.

  The emulsifier used in the emulsion polymer of the present invention is not particularly limited, and anionic emulsifiers such as alkyl sulfates, alkane sulfonates, alkyl benzene sulfonates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates; Nonionic emulsifiers such as oxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether; polyoxyethylene alkenyl phenyl ether sulfonate, 2-polyoxyethylene (1-allyloxy-3-alkyloxy) propyl ether sulfonate, 2-poly Anionic reactive emulsifiers such as oxyethylene (1-allyloxy-3-alkylphenoxy) propyl ether sulfonate; polyoxyethylene alkenyl phenyl ester Any of nonionic reactive emulsifiers such as tellurium, 2-polyoxyethylene (1-allyloxy-3-alkyloxy) propyl ether, 2-polyoxyethylene {1-allyloxy-3- (4-alkylphenoxy) propyl ether Well, the amount of the emulsifier used is 0.05 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the radical reactive compound. Can be used.

  The resulting emulsion polymer can be used for various plastic products, paints, adhesives, 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 used to 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.

[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. Next, 63 g (250 mmol) of thionyl chloride as a chlorinating agent and 100 mg of N, N-dimethylformamide as a catalyst were added and reacted by heating and stirring at 50 ° C. for 30 minutes, and then excess thionyl chloride was removed under reduced pressure. Thereafter, a mixed solution of 9.6 g (24 mmol) of polyethylene glycol 400 monomethacrylate and 2.53 g (25 mmol) of triethylamine was added dropwise at 40 ° C. over 30 minutes, and stirring was further continued at 40 ° C. for 1 hour. After adding 50 g of toluene and removing by-products by washing with water, the pressure was reduced to remove toluene and water to obtain Compound A1 of the present invention. In addition, 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -5- (2-hydroxyethyl) benzotriazole is a method described in Patent Document 3 (Japanese Patent Laid-Open No. Hei 2-142778). Manufactured by. Compound A1 has the following formula (1): 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, and a is A compound in which 0, b is 1, and c is a number of 10. The compound A1 was identified by ¹ H-NMR and UV spectrum. ^The identification result by ¹ H-NMR is shown in FIG. 1, and the identification result by UV spectrum is shown in FIG.

[Example 2]
In a metal pressure reactor equipped with a stirrer, a thermometer and a nitrogen introduction tube, 38 g of 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5- (2-hydroxyethyl) benzotriazole ( 0.1 mol), 0.2 g of potassium hydroxide as a catalyst, and 50 g of glyme as a solvent were charged. Ethylene oxide (44 g, 1 mol) was fed at 130 ° C., and after completion of the feeding, the mixture was aged at 130 ° C. for 2 hours. The reaction product was transferred to a glass reaction vessel equipped with a stirrer and a thermometer, 3 g of boron trifluoride diethyl ether complex was added, and the mixture was stirred at 80 ° C. for 3 hours to desorb the t-butyl group. 10 g of an acidic material adsorbent (trade name: KYOWARD 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at 80 ° C. for 1 hour, followed by filtration to remove the adsorbent. A glass reaction vessel equipped with a stirrer and a thermometer was charged with 50 g of this filtrate and pyridine, 15.6 g (0.15 mol) of methacrylic acid chloride was added at 30 ° C., and stirring was continued at 30 ° C. for 1 hour. It was. After adding 100 g of toluene and washing with water, the solvent and water were removed under reduced pressure to obtain Compound A2 of the present invention. Compound A2 is a compound in which R ¹ is a t-butyl group, R ² and R ⁵ are methyl groups, R ³ is an ethylene group, a is 10, b and c are 0 in general formula (1). Compound A2 was identified by ¹ H-NMR and UV spectrum. ^The identification result by ¹ H-NMR is shown in FIG. In addition, about the identification result by UV spectrum, since it was substantially the same as that of compound A1, it abbreviate | omitted.

  The following comparative compounds B1, B2 and B3 were prepared as comparative compounds, and the following emulsifier C was prepared as an emulsifier. Comparative compound B2 was prepared according to Example 1 of Patent Document 3 (Japanese Patent Laid-Open No. 2-142778), and Comparative Compound B3 was prepared from Patent Document 4 (Special Table 2002). No. 5,146,62)).

[Examples 3 to 6 and Comparative Examples 1 to 4]
Examples Compound A1 and A2, Comparative Compounds B1 to B3, Emulsifier C, Butyl Acrylate, Methyl Acrylate, or Acrylic Acid as Polymerizable Monomer and Blended in Mass Ratios Shown in Table 1 3-6 and the monomer solution of Comparative Examples 1-4 were prepared, the 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]. In addition, it shows that an ultraviolet absorption effect is excellent and it is maintained for a long time, so that a gloss retention is high.

[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, an accelerated weather resistance test was performed, 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 Equipment used: Precision gloss meter (Murakami Color Research Laboratory, Model: GM26D), Measurement angle: 60 °
Accelerated weather resistance 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 the above [Table 1], the specimens of Examples 3 to 6 have high gloss retention, and the coating film obtained from the emulsion polymer using the benzotriazole compound of the present invention has a severe natural environment. It also shows that an excellent ultraviolet absorption effect can be maintained for a long time. This is because not only the benzotriazole compound of the present invention reacts with other monomers by a radical polymerizable 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. Represents a residue obtained by removing a carboxyl group from 3 to 10 dibasic acids, R ⁵ represents a hydrogen atom or a methyl group, a and c represent a number of 0 to 1000 in which a + c is 2 to 1000, b is Represents a number of 0 or 1. However, when c is a number of 0, b represents a number of 0.)   An emulsion polymer obtained by emulsion polymerization of the benzotriazole compound according to claim 1 and another radical polymerizable compound.

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