JP3492724B2 - UV absorber - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ultraviolet absorber containing a specific benzotriazole compound which is liquid at room temperature as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, problems to be solved by the invention
It is well known that an ultraviolet absorber composed of 2- (2'-vidroxyphenyl) benzotriazoles is effective for various organic materials. For example, Japanese Patent Publication 37-
No. 2,476,2- (2′-hydroxy-5′-).
Methylphenyl) -benzotriazole (melting point 129.
5 to 130.5 ° C), 2- (2'-hydroxy-5'-
t-butyl) -benzotriazole (melting point 99 ° C.) and the like are disclosed in U.S. Pat. No. 4,127,586 to 2- (2'-hydroxy-3'-t-butyl-5'-sec-butylphenyl) -benzotriazole. (Melting point 84 ° C.) and the like are disclosed. As a commercial product, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5
-Chlorobenzotriazole (melting point 139-140
° C), 2- (2'-hydroxy-3 ', 5'-di-t-
Amylphenyl) -benzotriazole (melting point 80.5
-81.5 ° C), 2- (2'-hydroxy-3 ', 5'
-Di-t-butylphenyl) -benzotriazole (melting point 153-154.5 ° C), 2- (2'-hydroxy-
5′-t-octylphenyl) -benzotriazole (melting point: 103.5 to 104.5 ° C.) and the like. However, these 2- (2′-hydroxyalkylphenyl) -benzotriazoles are all crystalline substances that have a high melting point and are solid at room temperature. However, recently, with the expansion of application fields such as synthetic polymers and the development of new applications, there is a demand for a more compatible room temperature liquid 2- (2'-hydroxyphenyl) -benzotriazole type UV absorber. It is rising. In the specifications of U.S. Pat. No. 3,983,132 and U.S. Pat. No. 4,129,521, 2- (2 '
A liquid isomer mixture consisting of -hydroxy-5'-dodecylphenyl) -benzotriazole or 2- (2'-hydroxy-5'-nonylphenyl) -benzotriazole is shown, which dodecyl or nonyl group It is a mixture of isomers synthesized from propylene. In JP-A-64-71863, JP-A-1-203371 and JP-A-2-15070, for example, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazoles and olefins are acidified. React under catalyst,
An alkyl group was introduced at the vacant 3'-position to synthesize a liquid isomer mixture, and 2- (2'-hydroxy-5'-t was used.
-Butylphenyl) -benzotriazole and n-dodecene are reacted under an acid catalyst to introduce an alkyl group by a method including elimination and re-reaction of a t-butyl group, and a method for producing a random statistical liquid mixture is shown. There is. However, since the reaction rate changes depending on the reaction temperature and the reaction time, there is a drawback that the composition and physical properties of the resulting mixture are difficult to stabilize.

[0003]

[Purpose] Therefore, an object of the present invention is to provide a benzotriazole-based ultraviolet absorber which is liquid at room temperature and has excellent compatibility with synthetic polymers and the like.

[0004]

[Structure] The present inventor has conducted extensive studies and found that the above-mentioned U.S. Pat. No. 3,983,132 and U.S. Pat. A novel room temperature liquid benzotriazole compound synthesized from butene with different physical and chemical properties, and found an ultraviolet absorber having excellent compatibility with polymer compounds due to the appropriate branching property of its alkyl group. Is. That is, the present invention has the general formula (I)

[Chemical 4] (In the formula, R ¹ is selected from the group consisting of hydrogen, halogen, and a branched or linear alkyl or alkoxy group having 1 to 8 carbon atoms, R ² is a linear alkyl group having 1 to 3 carbon atoms, and R ³ is The invention relates to an ultraviolet absorber containing a benzotriazole compound represented by a branched alkyl group having 6 to 14 carbon atoms) as an active ingredient. In particular, in the above formula,

[Chemical 5] (Wherein, R ² and R ³ are the same as above), the total carbon number is preferably 4 × n (n is an integer of 2 to 5), and R ¹ is hydrogen or chlorine. Certain compounds are preferred. Particularly preferred compounds are those of general formula (II)

[Chemical 6] (In the formula, R is hydrogen or chlorine) and is a benzotriazole-based compound. Examples of R ¹ include hydrogen, chlorine, bromine, methyl,
Ethyl, n-propyl, n-butyl, n-pentyl, n
-Hexyl, n-heptyl, n-octyl, isopropyl, isobutyl, 3-methylbutyl, 4-methylheptyl and the like can be mentioned. R ² is methyl, ethyl or n-propyl. Examples of R ³ are 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3
-Methylhexyl, 4-methylhexyl, 2-ethylpentyl, 2-methylheptyl, 3-methylheptyl,
2,3-dimethylpentyl, 2,4-dimethylpentyl, 4-methylheptyl, 5-methylheptyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl , 2-methyldecyl, 3-methyldecyl, 4-methyldecyl, 5-methyldecyl, 5-methylundecyl, 6-methylundecyl, 5-methyldodecyl, 7-
Methyl tridecyl, etc. can be mentioned.

Next, one example of a method for synthesizing the compound of the present invention will be shown.

[Chemical formula 7] (In the formula, R ¹ is selected from the group consisting of hydrogen, halogen, and a branched or linear alkyl or alkoxy group having 1 to 8 carbon atoms, R ² is a linear alkyl group having 1 to 3 carbon atoms, and R ³ is (A branched alkyl group having 6 to 14 carbon atoms)

First, a phenol is alkylated with butene and / or a butene oligomer (polymerization degree: 2 to 5) in the presence of an acid catalyst and purified to synthesize an alkylphenol. Then, o-nitroanilines are diazotized and coupled to the alkylphenol by a conventional method to synthesize a nitroazo compound. By reducing this, the compound of the present invention is obtained.

As a method for reducing a nitroazo compound, an alkaline method in which zinc is used is often used, but other methods are also known in which hydrazine is used for reduction (Japanese Patent Publication No. Sho 6).
0-9031), a method of catalytic reduction (JP-A-51)
No. 138676 and Japanese Patent Laid-Open No. 51-138677, a method of reducing with alcohol (Japanese Patent Laid-Open No. 4-15)
4771), a method of reducing with hydrogen (Japanese Patent Laid-Open No. Sho 5
2-113974, JP-A-52-113973) and the like. Further, as described below, a method of reducing a nitroazo compound to an N-oxide compound and further reducing it to a triazole (Japanese Patent Application Laid-Open No. 63-72683 of the present applicant,
JP-A-63-72682, JP-A-59-172481
No. 59-170172, etc.), the generation of by-products due to reduction is small.

[0008]

[Chemical formula 8] (In the formula, R ¹ is selected from the group consisting of hydrogen, halogen, and a branched or linear alkyl or alkoxy group having 1 to 8 carbon atoms, R ² is a linear alkyl group having 1 to 3 carbon atoms, and R ³ is (A branched alkyl group having 6 to 14 carbon atoms)

The ultraviolet absorber of the present invention can be added to synthetic resin or synthetic rubber to form a stable composition. Examples of these synthetic resins and synthetic rubbers include polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, ethylene / propylene copolymer, polymethylmethacrylate, polyacrylonitrile, ABS, polyester, polyamide, polyurethane, unsaturated polyester, alkyd resin, and heat. Curable acrylic resin, epoxy resin, urea resin, melamine resin, phenol resin, SB
R, NBR, etc. can be mentioned. Preferably, polypropylene, polyethylene, ethylene / propylene copolymer, ABS and the like can be mentioned. Since the ultraviolet absorbent of the present invention is in a liquid state, it has good miscibility with a coating material, and is preferably used for an organic polymer-containing coating, particularly for an automotive coating material. Further, since the insoluble matter is removed by distillation, it is advantageous that it can be mixed with the photographic material without using a solvent or using a small amount of a solvent. By adding it to synthetic and natural fibers, it is possible to suppress color deterioration of matrix fibers and decolorization of dyes. For example, the triazole of the present invention and a cationic dispersant can be combined to form a stable water-soluble emulsion or organic solvent emulsion having a concentration of 10 to 80%, preferably 30 to 40%. Preferably, it has excellent adsorptivity with polyester fiber, and by adding it at the time of dyeing a disperse dye, it exhibits its characteristic ultraviolet absorptivity.

The UV absorber is added in an amount of 0.05 to 10% by weight based on the substance to be stabilized. It is preferably 0.1 to 5% by weight. Moreover, the thing of this invention can be used individually or in mixture of 2 or more types.
Of course, it is possible to use together with the following conventionally known ultraviolet absorbers, antioxidants, light stabilizers and the like.

The UV absorber of the present invention is synergistic with a composition containing a hindered amine light stabilizer, preferably an N-unsubstituted, N-alkyl substituted 2,2,6,6-tetramethylpiveridine compound. Has a stable effect. As the light stabilizer, bis- (2,2,6,6-tetramethylpiperidyl) sebacate, bis- (1,2,2,6,6-pentamethylpiperidyl) sebacate, 4-benzoyloxy-2,2 , 6,6-Tetramethylpiperidine, 1- [2
-{3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy} -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2 , 4-dione, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate,
Poly [[6- (1,1,3,3-tetramethylbutyl)
Imino-1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalon Acid bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetraxy (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4
A condensate of piperidinol and tridecyl alcohol,
1,2,3,4-butanetetracarboxylic acid and 2,2
6,6-tetramethyl-4-piperidinol and β, β,
β ′, β′-tetramethyl-3,9- (2,4,8,1
Condensate with 0-tetraoxaspiro [5,5] undecane) diethanol, 1,2,2,6,6-pentamethyl-4-piperidyl-methacrylate, 2,2,6,6-
Hindered amines such as tetramethyl-4-piperidyl-methacrylate are included. Further, for example, [2,2-thio-bis- (4-t-octylphenolate)]-n-butylamine-nickel (II), 4,
4'-di-octyloxyoxanilide, dilauryl
Examples thereof include compounds such as thiodipropionate, tris (2,4-di-t-butylphenyl) phosphite, and bis (nonylphenyl) pentaerythritol diphosphite.

Known ultraviolet absorbers that can be used in combination with the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2 Benzophenone-based UV absorbers such as'-dihydroxy-4,4'-dimethoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazo , 2- (2'-hydroxy-3 ',
5'-di-t-amylphenyl) -benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -benzotriazole, 2- (2'-hydroxy-5'- t-butylphenyl) -benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5
-Chlorobenzotriazole, 2- [2'-hydroxy-3 ', 5'-bis- (α, α-dimethylbenzyl) phenyl] -benzotriazole, methyl-3- [3-t
-Butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol a benzotriazole-based UV absorber such as a condensation product with a molecular weight of about 300, p-octylphenyl salicylate, Salicylate type UV absorbers such as phenyl salicylate, t-butyl phenyl salicylate, resorcinol monobenzoate, 3,5-di-t-butyl-4-hydroxybenzoic acid hexadecyl ester, 5-t-butyl -2-Ethoxy-2 ', 2'-
Examples thereof include ultraviolet absorbers such as ethyloxanilide and 5-dihexylamino-2-cyano-2,4-pentadienenitrile.

Known antioxidants that can be used in combination with the ultraviolet absorber of the present invention include, for example, 2,6-di-t-butyl-4-methylphenol and 2-t-butyl-4,6-.
Alkylphenols such as dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-
alkylated hydroquinones such as t-butyl hydroquinone, 2,5-di-t-amyl hydroquinone,
4,4'-thiobis- (3-methyl-6-t-butylphenol), 2,2'-thiobis- (4-methyl-6-
t-butylphenol), 4,4'-thiobis- (2-
Methyl-6-t-butylphenol), thiobisphenols such as 2,2'-thiobis- (4-octylphenol), 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2 , 2'-ethylidene-bis- (4,6-di-t-butylphenol), 4,
4'-methylene-bis- (2,6-di-t-butylphenol), 2,2'-methylene-bis- (4-methyl-)
6-nonylphenol), 1,1,3-tris- (5-
t-butyl-4-hydroxy-2-methylphenyl)-
Alkylidene bisphenols such as butane,
1,3,5-trimethyl-2,4,6-tris- (3,3
5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris- (4-t-butyl-2,6-)
Dimethyl-3-hydroxybenzyl) isocyanurate, 2-t-butyl-6- (3'-t-butyl-5'-
Methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis [2- {3- (3-
t-butyl-5-methyl-4-hydroxyphenyl)
Propionyloxy} -1,1-dimethylethyl]-
2,4,8,10-Tetraoxaspiro [5,5] undecane, Butyric acid 3,3-bis- (3-t-butyl-4)
-Hydroxyphenyl) ethylene ester, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethyleneglycol-bis [3- (3-t-butyl-5) −
Methyl-4-hydroxyphenyl) propionate],
1,6-hexanediol-bis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4
-Hydroxy-3,5-di-t-butylanilino)-
1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di- t-butyl-4-hydroxy-benzylphosphonate-diethyl ester and the like. The ultraviolet absorber of the present invention can be used in combination with, for example, a plasticizer, an emulsifier, a lubricant, a pigment, a fluorescent whitening agent, a flame retardant, an antistatic agent, or the like.

[0014]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 Synthesis of 2- {2'-hydroxy-5 '-(1 ", 4" -dimethylhexyl) phenyl} -benzotriazole 34.6 g of o-nitroaniline and 98.8 g of 62% sulfuric acid.
Was dissolved in water, 65 ml of water was added, and the mixture was suspended. After cooling with ice, a solution of 18.3 g of sodium nitrite and 30 ml of water was added dropwise to obtain a diazonium salt aqueous solution. 5-
(1 ', 4'-dimethylhexyl) phenol 54.2
g, 150 ml of toluene, 100 ml of water and 89.5 g of sodium hydrogencarbonate were added to the above diazonium salt aqueous solution at 0 to 5 ° C over 3 hours. After dropping, the mixture was stirred for 1 hour, adjusted to pH 4, heated to 70 ° C., and the upper toluene layer was washed with 100 ml of hot water. To the upper toluene layer, 125 ml of water and 47.9 g of 48% sodium hydroxide were added, and the temperature was raised to 65 ° C. Hydroquinone 0.8g was added and 60% hydrazine hydrate 12.5 over 2 hours.
g was added dropwise. After dropping, the mixture was stirred for 2 hours, cooled and adjusted to pH 7. Wash the upper toluene layer with 100 ml of hot water,
A toluene solution of 2- {2'-hydroxy-5 '-(1 ", 4" -dimethylhexyl) phenyl} -benzotriazole-N-oxide was obtained. Then, toluene was distilled off, and 241 g of secondary butanol, 60 g of water and 51.5 g of 97% caustic soda were added. 7.5 g of catechol and 7.5 g of 2,3-dichloronaphthoquinone (1,4) were added and the temperature was raised. Reacted under reflux for 7 hours, water 350m
The pH was adjusted to 11.0 with about 75 g of 62% sulfuric acid and extracted with toluene. The toluene layer was distilled with a vacuum distiller equipped with a rectification column to give 2- {2'-hydroxy-5 '-(1 ",
52 g of 4 "-dimethylhexyl) phenyl} -benzotriazole were obtained, which was a yellow transparent viscous liquid b.p.
p. It was 172 to 176 ° C / 0.20 to 0.25 mmHg.

Example 2 In the same manner as in Example 1, except that 35.9 g of o-nitroaniline was replaced by 45.9 g of 2-nitro-4-chloroaniline, the reaction and post-treatment were carried out. 2- {2'-hydroxy-5 '-(1 ",
47 g of 4 ″ -dimethylhexyl) phenyl} -5-chlorobenzotriazole was obtained. Yellow transparent viscous liquid bp1.
75-180 ° C / 0.08-0.12 mmHg.

Example 3 Instead of 54.2 g of 5- (1 ', 4'-dimethylhexyl) phenol in Example 1, it was synthesized from a mixture of phenol and butene (1-butene: 2-butene = 9: 1). Example 1 using 65 g of p-alkylphenol
Reaction and post-treatment were carried out in the same manner as in. 51 g of 2- (2'-hydroxy-5'-branched alkylphenyl) -benzotriazole was obtained by distillation under reduced pressure. Yellow transparent viscous liquid bp 170-185 ° C / 0.18-0.25mmH
g. The results of analysis of the obtained product by a mass spectrometer are shown below.

[Table 1]

Example 4 0.2% by weight of the compound of Example 1 with respect to polypropylene (Sample A), 0.2% by weight of bis- (2,2,6,6-tetramethylpiperidyl) sebacate (Sample B) ), 0.1% by weight of the compound of Example 1 and bis- (2,
2,6,6-tetramethylpiperidyl) sebacate 0.
A test sheet was prepared at 180 ° C. for each of 1 wt% and (C). A weather meter deterioration test was conducted by measuring the bending life.

[Table 2] Apparently the compound of Example 1 stabilized polypropylene compared to the one without addition. Moreover, there was a synergistic effect with bis- (2,2,6,6-tetramethylpiperidyl) sebacate which is a hindered amine.

Comparative Example 1 2- [2'-hydroxy-5 'relative to polypropylene
(1 ″, 1 ″, 3 ″, 3 ″ -tetramethylbutyl) phenyl] -benzotriazole (conventional type) blended at 0.2% by weight (Sample D), and polypropylene with 2- (2′- Hydroxy-5'-nonylphenyl)
The same test as in Example 4 was carried out on a mixture containing 0.2% by weight of benzotriazole (nonyl group was an isomer mixture synthesized from propylene) (Sample E).

[Table 3] Additives Bending life (time) ───────────────────── Sample D 290 Sample E 410 ────────────── It is clear that Samples A and C using the compound of Example 1 more stabilize polypropylene than Samples D and E.

[0019]

By the present invention, a novel benzotriazole-based ultraviolet absorber which is liquid at room temperature and which is industrially advantageous can be provided without introducing a complicated substituent into the molecule. Further, the ultraviolet absorbent of the present invention has clearly superior performance as compared with conventional ultraviolet absorbents which are solid at room temperature. (A) It is possible to uniformly mix even thermosetting resins that cannot be melt-mixed, and (b) it is extremely advantageous as a stabilizer for photographic materials that causes troubles when particles remain. ) Moreover, even if it is used as a stabilizer for a lacquer paint or the like, the problems (a) and (b) do not occur, which is convenient. The benzotriazole-based ultraviolet absorber of the present invention is advantageous because it can be easily purified and adjusted in the alkylation stage of phenol and industrially stable quality can be secured.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09K 3/00 104 C07D 255/04 C08K 5/3475 C08L 101/00-101/16

Claims (4)

(57) [Claims] 1. A compound represented by the general formula (I): (In the formula, R ¹ is selected from the group consisting of hydrogen, halogen, and a branched or linear alkyl or alkoxy group having 1 to 8 carbon atoms, R ² is a linear alkyl group having 1 to 3 carbon atoms, and R ³ is An ultraviolet absorber containing a benzotriazole compound represented by a branched alkyl group having 6 to 14 carbon atoms) as an active ingredient. 2. [Chemical formula 2] The total carbon number of (wherein R ² and R ³ are the same as above) is 4 × n (n is an integer of 2 to 5), and the benzotriazole-based compound is used as an active ingredient. UV absorber contained. 3. An ultraviolet absorber containing the benzotriazole compound according to claim 1 or 2, wherein R ¹ is hydrogen or chlorine. 4. A compound represented by the general formula (II): An ultraviolet absorber containing a benzotriazole compound represented by the formula (wherein R is hydrogen or chlorine) as an active ingredient.