JP2001106677A - Benzotriazole-based compound and light stabilizer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new benzotriazole-based compound useful as a light stabilizer capable of improving both the weatherability and discoloration resistance of organic materials. SOLUTION: This new benzotriazole-based compound as a light stabilizer is shown by the formula (1) (X is H or Cl; R is a 1-18C alkyl, aryl or alkylaryl; and the methylene group is bound to ortho- or para-position with respect to the OH group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel benzotriazole compound, and more particularly to a novel benzotriazole compound and a light stabilizer useful as a light stabilizer.

[0002]

2. Description of the Related Art Conventionally, organic materials such as natural polymers, synthetic polymers, fats and oils are often degraded by the action of light, and their mechanical strength is remarkably reduced with phenomena such as softening, embrittlement or discoloration. Are known. In order to prevent such deterioration due to light, various light stabilizers have conventionally been added and used during the production and processing steps of organic materials. Such light stabilizers include, for example, benzophenone-based, benzotriazole-based, benzoate-based, salicylate-based, triazine-based, and hindered amine-based light stabilizers, and are known to have a stabilizing effect when used alone or in combination of two or more. ing.

[0003]

The light stabilizers conventionally used include coloring, volatilization, bleeding,
Furthermore, the added organic materials are not yet satisfactory in terms of weather resistance, discoloration resistance, and the like. In particular, as the processing temperature increases, the low molecular weight type light stabilizer volatilizes intensely,
Problems such as deterioration of the working environment due to volatilization and clogging of devices occur. For this reason, Japanese Patent Application Laid-Open Nos. 61-118373 and 61-118374 propose a specific bisbenzotriazolylphenol compound, and Japanese Patent Application Laid-Open No. 10-175963 discloses a benzotriazolyl compound. -Alkylenebisphenols have been proposed. In the compound, the molecular weight is increased by dimerization of benzotriazole or addition of alkylphenol to suppress volatilization to improve the compound.

[0004] Japanese Patent Application Laid-Open No. 9-136060 proposes a specific bisbenzotriazolylphenol. This bisbenzotriazolylphenol is
It is reported that, since it can be copolymerized with a polycondensable monomer, it can be introduced into a main chain or a side chain of polycarbonate, polyester, polyurethane, polyurethane urea, etc., and can impart weatherability to a product for a long period of time.

[0005] However, these light stabilizers are still unsatisfactory in terms of their own coloration, and the weather resistance and discoloration resistance of the added organic material.

Accordingly, an object of the present invention is to provide a light stabilizer which is non-colorable and can improve weather resistance and discoloration resistance. Another object of the present invention is to provide a light stabilizer in which volatilization and bleeding are suppressed or prevented in addition to the above characteristics. Still another object of the present invention is to provide a novel benzotriazole-based compound.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventor has obtained a novel benzotriazole-based compound as a novel compound. That is, the present invention is a benzotriazole-based compound represented by the following formula (1).

Embedded image (In the formula, X represents a hydrogen atom or a chlorine atom. R represents an alkyl group, an aryl group, or an alkylaryl group having 1 to 18 carbon atoms. In addition, the methylene group is located ortho or para to the hydroxyl group. Are joined.)

The present inventors have made intensive studies to overcome the problems of the conventional light stabilizers. As a result, when a specific high molecular weight benzotriazole compound is added to an organic material, the weather resistance can be improved. Further, the present inventors have found that the degree of coloring before and after light irradiation can be improved, and that the weather resistance and the discoloration resistance of the organic material are compatible at a high level, thereby completing the present invention. That is, the present invention is a light stabilizer containing the benzotriazole-based compound represented by the formula (1).

When the benzotriazole-based compound represented by the formula (1) is used as a light stabilizer, both weather resistance and discoloration resistance can be improved. Also, coloring by the light stabilizer itself hardly occurs. In addition, the light stabilizer of the present invention exhibiting these excellent properties is easy to prepare and purify, easy to handle, and can be used in the same manner as a conventional light stabilizer. Furthermore, volatilization is suppressed or prevented because of the high molecular weight, and bleeding hardly occurs.

The present invention also includes an organic material containing the benzotriazole compound of the formula (1) as a light stabilizer.

When the benzotriazole-based compound of the above formula (1) is contained in an organic material as a light stabilizer, the weather resistance of the organic material can be improved, and the discoloration of the organic material can be suppressed over a long period of time. Can be prevented.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The benzotriazole compound of the present invention is represented by the above formula (1). That is, it is a benzotriazole-based compound having a high molecular weight.

In the above formula (1), R has 1 to 1 carbon atoms.
Examples of the alkyl group 8 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like. The alkyl group may be linear or branched.

As the aryl group for R, for example,
Examples include a phenyl group and the like, and examples of the alkylaryl group include various alkylaryl groups such as a tolyl group.

In the above formula (1), a methylene group (—C
H ₂ —) is attached ortho or para to the hydroxyl group in the benzene ring to which the hydroxyl group is attached. Therefore, the benzotriazole-based compound represented by the formula (1) has three types of isomers.
In addition, since there are two reaction positions at the ortho position and the para position with respect to the hydroxyl group, multimers such as trimers and tetramers are also formed.

As the three isomers, a methylene group is located ortho to the hydroxyl group on a benzene ring to which one hydroxyl group is bonded, and a hydroxyl group is located on the benzene ring to which the other hydroxyl group is bonded. A dimer or methylene group bonded to the ortho-position to the benzene group, a benzene ring bonded to the ortho-position to the hydroxyl group and the other hydroxyl group on the benzene ring to which one hydroxyl group is bonded. In the ring, a dimer bonded to the hydroxyl group at the para position, a methylene group,
On the benzene ring to which one hydroxyl group is bonded, there is a dimer bonded to the hydroxyl group in the para position, and in the benzene ring to which the other hydroxyl group is bonded, the dimer is bonded to the hydroxyl group in the para position. .

[0017] Among these three isomers, the ratio of each isomer is not particularly limited. In addition, multimers such as trimers and tetramers may be present.

The benzotriazole compound represented by the above formula (1) can be prepared by various known methods. For example, a benzotriazole-based compound represented by the following formula (2) and an amine compound (NHR ¹ R ² )
And formaldehyde (HCHO) to prepare a Mannich base compound represented by the following formula (3), and then to a benzotriazole-based compound represented by the following formula (2) by the following formula (3) It can be prepared by reacting the represented Mannich base compound.

[0019]

Embedded image (In the formula, X represents a hydrogen atom or a chlorine atom. R represents an alkyl group having 1 to 18 carbon atoms, an aryl group, or an alkylaryl group.)

[0020]

Embedded image (In the formula, X represents a hydrogen atom or a chlorine atom. R represents an alkyl group having 1 to 18 carbon atoms, an aryl group, or an alkylaryl group. R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. , R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Further, an amino methyl group which may have a substituent group is attached at the ortho or para position to the hydroxyl group.)

This reaction can be carried out using an alkali under an alkaline condition. As such an alkali, a hydroxide of an alkali metal element such as sodium hydroxide or a hydroxide of an alkaline earth metal element is suitably used. This reaction can be carried out under normal pressure or reduced pressure, or under heating.

In the reaction between the benzotriazole compound represented by the formula (2) and the Mannich base compound represented by the formula (3), the dimer of the dimer is controlled by controlling the ratio between the two. It is possible to control the proportion.

When a light stabilizer based on the benzotriazole compound represented by the formula (1) is blended with an organic material, the weather resistance of the organic material is improved, and the organic material is hardly colored for a long period of time. The discoloration is improved. Also,
This benzotriazole-based compound is a compound that is easy to prepare, easy to purify, and easy to handle. Therefore, the benzotriazole-based compound of the present invention is useful as a stabilizer (light stabilizer) for suppressing or preventing photodeterioration of an organic material, particularly as an ultraviolet absorber.

In the organic material of the present invention, the benzotriazole-based compound represented by the formula (1) is used as a light stabilizer. Such an organic material is not particularly limited. Examples of such an organic material include an organic material containing an organic polymer such as a plastic or a resin or a rubber. As the organic polymer, various resins such as a thermoplastic resin, a thermosetting resin, and an ultraviolet curable resin can be used. The organic materials can be used alone or in combination of two or more.

More specifically, examples of the organic material include α-olefin-based polymers such as polyethylene, polypropylene, polybutene, polypentene, and poly-3-methylbutylene; ethylene-vinyl acetate copolymer; Polyolefins such as propylene copolymer, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer,
Vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride Terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-acetic acid Vinyl terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer,
Halogen-containing synthetic resins such as vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, petroleum resin, coumarone resin, polystyrene, styrene and other copolymerizable monomers (for example, , Maleic anhydride, butadiene, acrylonitrile, etc.) and acrylonitrile-butadiene-
Styrene resin, styrene resin such as acrylate-butadiene-styrene resin, methacrylate-butadiene-styrene resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic resin, methacrylate resin, polyacrylonitrile, straight chain Polyester, polyphenylene oxide, polyamide, polycarbonate, modified polyphenylene oxide, polyacetal, polyurethane, fibrous resin, unsaturated polyester resin, phenol resin,
Urea resin, melamine resin, epoxy resin, silicone resin, polyethylene terephthalate, reinforced polyethylene terephthalate, polybutylene terephthalate, polysulfone resin, polyether sulfone, polyphenylene sulfide, polyether ketone, polyether imide,
Polyoxybenzoyl, polyimide, polymaleimide,
Polyamide imide and the like can be mentioned. Further, rubbers can also be used as the organic material, and examples of the rubbers include synthetic rubbers such as natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene copolymer rubber, and acrylonitrile-butadiene copolymer rubber. Is mentioned. Also, a blend of these resins and rubber may be used, and various cosmetics and various photographic drugs may be used.

When this compound is used as a light stabilizer for organic materials, for example, 0.01 to 1 with respect to the total amount of the organic materials.
It is desirable to mix at 0% by weight, preferably 0.05 to 5% by weight.

When the benzotriazole compound represented by the formula (1) of the present compound is used as a light stabilizer, other light stabilizers (for example, other ultraviolet absorbers, hindered amine light stabilizers, etc.), When combined with an antioxidant (eg, a phenolic antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, etc.), the weather resistance, discoloration resistance, light resistance, and thermal stability can be further improved. .

Other ultraviolet absorbers which can be used in combination with the benzotriazole-based compound represented by the formula (1) are not particularly limited, and include, for example, benzophenone-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers. And other ultraviolet absorbers.

As the benzophenone type ultraviolet absorber,
For example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, -Dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'
-Dimethoxybenzophenone and the like.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole and 5-chloro-2-
(3,5-di-tert-butyl-2-hydroxyphenyl)
Chloro-2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5
Chloro-2H-benzotriazole, 2- (3,5-di-tert-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-tert-butyl-2)
-Hydroxyphenyl) -2H-benzotriazole,
2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2H-benzotriazol-2-yl) -4 Tertiary octyl-6- (3,
4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H -Benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and the like.

Other ultraviolet absorbers include, for example,
Phenyl salicylate, 4-tertiary butyl phenyl salicylate, ethyl 2-cyano-3,3-diphenyl acrylate, 2'-ethylhexyl 2-cyano-3,
3-diphenyl acrylate, 2 ', 4'-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2- {4-[(2-hydroxy-3-
Alkyl) -oxy] -2-hydroxyphenyl}-
4,6-bis (2,4-dimethylphenyl) -1,3
5-triazine, 2- (4,6-diphenyl-1,3,
5-triazin-2-yl) -5- (hexyl) oxy-phenol.

Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl). -2- (3,5-ditert-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) -bis ( 3,5-ditert-butyl-4-hydroxybenzyl) malonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly [6- (1,1,3,3-tetramethylbutyl) imino-s-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, poly {(6-morpholino-s-triazine-2,4-diyl) [(2
2,6,6-tetramethyl-4-piperidyl) imino]
Hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]｝, 1-hydroxyethyl-
2,2,6,6-tetramethyl-4-piperidinol /
Succinic acid condensate, cyanuric chloride / tertiary octylamine / 1,6-bis (2,2,6,6-tetramethyl-4-
Piperidylamino) hexane condensate.

In the antioxidants, phenolic antioxidants include, for example, 2,6-ditert-butyl-4-methylphenol, 4-hydroxymethyl-2,
6-di-tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, butylated hydroxyanisole, n-octadecyl 3- (4-hydroxy-3,
5-di-tert-butylphenyl) propionate, distearyl (4-hydroxy-3-methyl-5-tert-butyl) benzylmalonate, tocopherol, 2,2 '
-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-ditert-butylphenol) ), 4,4'-butylidenebis (6-tert-butyl-m-cresol),
4,4'-thiobis (6-tert-butyl-m-cresol), styrenated phenol, N, N'-hexamethylenebis (3,5-ditert-butyl-4-hydroxyhydrocinnamide, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl ester) calcium, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxymethyl] methane, 1,6-hexanediol-bis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate], 2,2
'-Methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 1,3,5-
Tris (4-tert-butyl-3-hydroxy-2,6-
Dimethylbenzyl) isocyanuric acid, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanuric acid, triethyleneglycol-bis [3- (3-tert-butyl-4-) Hydroxy-5-methylphenyl) propionate], 2,2'-oxamidobis [ethyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate], 6- (4-hydroxy-3,5- Di-tert-butylanilino) -2,4-dioctylthio-1,3,5-triazine, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-
Tertiary butyl-5-methylbenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1- Dimethylethyl｝ -2,4,8,
10-tetraoxaspiro [5.5] undecane, 3,
9-bis {2- [3- (3,5-ditert-butyl-4-)
[Hydroxyphenyl) propionyloxy] -1,1-
Dimethylethyl {-2,4,8,10-tetraoxaspiro [5.5] undecane and the like.

Examples of the sulfur-based antioxidants include pentaerythritol tetrakis- (3-dodecylthiopropionate), didodecyl thiodipropionate, ditetradecyl thiodipropionate, dioctadecyl thiodipropionate and the like.

Examples of the phosphorus-based antioxidant include tris (2,4-ditert-butylphenyl) phosphite,
Tetrakis (2,4-ditert-butylphenyl) -4,
4'-biphenylenediphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphonite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite , 2,
2'-methylenebis (4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite, tetrakis (2,4-di-tert-butyl-5-methylphenyl)-
4,4'-biphenylenediphosphonite and the like can be mentioned.

The present compound can be used in combination with metal soap, heavy metal deactivator, nucleating agent, plasticizer, foaming agent, antistatic agent, flame retardant, lubricant, processing aid and the like.

[0037]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 A 1000 cc four-necked flask was charged with 6- (benzotriazol-2-yl) -3-n
-Octyloxyphenol: 115.6 g, dibutylamine: 50.0 g, and paraformaldehyde (purity: 92%): 6.1 g, and the mixture was added at 95 to 98 ° C for about 6 g.
After refluxing for an hour, the temperature was raised to 120 ° C. under a reduced pressure of 15 mmHg, and dibutylamine and water were recovered in 1.5 hours. At this time, when checked by thin-layer chromatography, formation of two kinds of Mannich-based compounds was confirmed.

Next, 5.0 g of an aqueous sodium hydroxide solution (concentration of sodium hydroxide: 48% by weight) was added, and the reaction was completed under reduced pressure (15 mmHg) at about 160 ° C. for about 4 hours. After cooling to 120-130 ° C., xylene:
200 g was charged and extracted, and acetic acid: 20.0 g was added for neutralization. Thereafter, 200 ml of warm water was added to precipitate crystals. After cooling to 5 ° C., the crystals were separated by filtration and washed with warm water and isopropyl alcohol. As a result, 86.5 g (yield: 73.5%) of off-white crystals were obtained. Obtained.

The crystals: 50.0 g, toluene: 50
ml, isopropyl alcohol: 150 ml, and activated carbon: 1 g, and the mixture was refluxed, filtered, and then cooled to 5 ° C., and the precipitated crystals were separated by filtration to obtain 48.6 g of slightly yellow-white granular crystals. . The melting point of this crystal is 14
4.0 to 159.0 ° C. The crystal was analyzed by elemental analysis, mass spectrum, nuclear magnetic resonance spectrum, and the like, and was confirmed to be a benzotriazole-based compound represented by the following formula (1a). The results of these analyzes are shown below.

[0041]

Embedded image (In the formula, X ^1a represents a hydrogen atom. R ^1a represents an n-octyl group. Further, the methylene group is bonded to the hydroxyl group at the ortho or para position.)

(Elemental analysis) C (carbon atom) Actual value: 71.3% (calculated value: 71.3%) H (hydrogen atom) Actual value: 7.3% (calculated value: 7.3%・ N (nitrogen atom) Actual value: 12.3% (calculated value: 12.2%) (Nuclear magnetic resonance spectrum) ¹ H-NMR (in CDCl ₃ , based on TMS) ・ δ = 0.7536 to 1.536. 9220 (multiplet,
_{- (CH 2) 6 CH 3} ), 3.1858~4.4095 ( _{multiplet, -CH 2 -, Ph-O} -CH 2 -), 6.5195~
8.3087 (multiplet, hydrogen atom of benzene ring), 11.3023-11.7012 (multiplet, -OH) (where Ph represents a phenyl group)

When the crystals were analyzed by liquid chromatography using a mobile phase (acetonitrile: dichloromethane = 1: 1) at a detection wavelength of 254 nm, a mixture having three peaks was confirmed as a main product. This is because in the benzotriazole-based compound represented by the formula (1a), a dimer in which a methylene group is bonded to an ortho-position and an ortho-position to a hydroxyl group, and an ortho-position to a hydroxyl group This is because there are three types of isomers: a dimer bonded to the para-position and a dimer bonded to the para-position and the para-position to the hydroxyl group.

Example 2 6- (Benzotriazole-
Instead of 2-yl) -3-n-octyloxyphenol, 6- (benzotriazol-2-yl) -3-n
When -butyloxyphenol was used and the reaction was carried out in the same manner as in Example 1, yield was 84.2%, and pale yellowish white powder crystals having a melting point of 163.8 to 168.4 ° C were obtained. Was. The crystal was analyzed by elemental analysis, mass spectrum, and the like, and it was confirmed that the crystal was a benzotriazole-based compound represented by the following formula (1b). The results of these analyzes are shown below.

[0045]

Embedded image (In the formula, X ^1b represents a hydrogen atom, R ^1b represents an n-butyl group, and the methylene group is bonded to the hydroxyl group at the ortho or para position.)

(Elemental analysis) • C (carbon atom) Actual value: 68.6% (calculated value: 68.5%) • H (hydrogen atom) Actual value: 6.0% (calculated value: 5.9%) ) N (nitrogen atom) Observed value: 14.4% (calculated value: 14.5%)

Example 3 6- (Benzotriazole-
Instead of 2-yl) -3-n-octyloxyphenol, using 6- (5-chlorobenzotriazol-2-yl) -3-n-octyloxyphenol,
When the reaction was carried out in the same manner as in Example 1, the yield: 6
A slightly greenish white powder crystal having a melting point of 130.0 to 150.0 ° C. at 2.9% was obtained. When the crystal was analyzed by elemental analysis, mass spectrum, and the like, it was confirmed that the crystal was a benzotriazole-based compound represented by the following formula (1c). The results of these analyzes are shown below.

[0048]

Embedded image (In the formula, X ^1c represents a chlorine atom, R ^1c represents an n-octyl group, and the methylene group is bonded to the hydroxyl group at the ortho or para position.)

(Elemental analysis) C (carbon atom) Actual value: 64.9% (calculated value: 64.8%) H (hydrogen atom) Actual value: 6.4% (calculated value: 6.4%・ N (nitrogen atom) actual value: 11.0% (calculated value: 11.1%) ・ Cl (chlorine atom) actual measured value: 9.3% (calculated value: 9.3%)

(Evaluation) (Weather resistance test) After mixing the test compounds shown in Table 1, unstabilized polypropylene, and calcium stearate with the following composition or ratio using a mixer for 5 minutes,
The mixture was melt-kneaded at 180 ° C with a mixing roll, and the obtained compound was pressed with a hot press at 210 ° C,
A film having a thickness of 0.1 mm was produced. This film was treated with a carbon arc sunshine weather meter (63
C., 18 minutes / 120 minutes with rain), and the infrared absorption spectrum was measured every 60 hours. From the infrared absorption spectrum, the absorbance of a methylene group at 2740 cm ^-1 (ABS1) and the absorbance of a carbonyl group at 1705 to 1720 m ^-1 (ABS2) were determined, and ABS2 / AB
The time (induction period) until the value of S1 became 1 or more was measured, and weather resistance or light resistance was evaluated. The results are shown in the column of “Induction period (time)” in Table 1. Of course, the longer the induction period, the better the weather resistance. (Blending composition or ratio) Unstabilized polypropylene: 100 parts by weight Calcium stearate: 0.1 parts by weight Test compound: 0.2 parts by weight

[0051]

[Table 1]

(Light fastness and thermal discoloration test) The test compounds shown in Table 2, unstabilized polypropylene, calcium stearate, and tetrakis [3- (3,5-ditert-butyl-4-) Hydroxyphenyl) propionyloxymethyl] methane, with the following composition or ratio:
After extrusion granulation using a 40 mmφ extrusion granulator, a test piece was prepared using a 5.5 oz injection molding machine (manufactured by Toshiba, Model IS100E). A test piece of 40 × 60 × 1 mm was placed on a carbon arc sunshine weather meter (63 ° C., 18 minutes /
Light irradiation was performed during 120 minutes of rain), and the surface condition of the test piece was observed every 60 hours. Then, the time until the surface crack was generated in the test piece was measured, and the light resistance was evaluated based on the surface crack time. The evaluation results are shown in the column of "Weather resistance" in Table 2. On the other hand, a test piece of 40 × 40 × 1 mm was placed in a gear oven at 160 ° C. and heated. Then, the color difference ΔYI between the test piece before deterioration and the test piece three days after the start of the test was measured to evaluate the degree of thermal discoloration. The evaluation results are shown in the column of "thermochromicity" in Table 2. (Blending composition or ratio) Unstabilized polypropylene: 100 parts by weight Calcium stearate: 0.1 parts by weight Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane: 0.1 parts by weight Test compound: 0.2 parts by weight

[0053]

[Table 2]

(Discoloration resistance test) The test compounds listed in Table 3, polyvinyl chloride, dioctyl phthalate, epoxidized soybean oil, calcium stearate, and zinc stearate were mixed at 180 ° C. in the following composition or ratio. The mixture was kneaded with a roll to produce a film having a thickness of 0.2 mm. This film is carbon-arc sunshine weather meter (63 ° C, 18 minutes / 120 minutes with rain)
The light was irradiated for 360 hours in the inside, and the degree of discoloration was observed.
The observation results are shown in the column of "degree of discoloration" in Table 3. (Blending composition or ratio) Polyvinyl chloride: 100 parts by weight Dioctyl phthalate: 48 parts by weight Epoxidized soybean oil: 2 parts by weight Calcium stearate: 1 part by weight Zinc stearate: 0.1 parts by weight Test compound: 0.2 parts by weight Department

[0055]

[Table 3]

In Tables 1 to 3, the compound obtained in Example 1 is a benzotriazole compound represented by the formula (1a), and the compound obtained in Example 2 is the same as the compound obtained in the formula (1a). A benzotriazole compound represented by the formula (1c)
It is a benzotriazole type compound represented by these. Also,
UVA-1 represents 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole; UVA-2 represents 2-hydroxy-4-
Represents octyloxybenzophenone, and UVA-3 represents 2,2'-methylenebis-[(6-benzotriazol-2-yl) -4-tertiary octyl] phenol. In addition, no addition indicates that the test compound was not used.

According to Table 1, when the compounds obtained in Examples 1 to 3 (that is, the benzotriazole compound having a high molecular weight) were used, the conventional ultraviolet absorbers (that is, UVA-1, UVA-) were used. 2. The induction period is longer and the weather resistance is better than when UVA-3) is used.

From Table 2, it can be seen that when the compounds obtained in Examples 1 to 3 (that is, the benzotriazole compound having a high molecular weight) were used, the conventional ultraviolet absorbers (that is, UVA-1, UVA-) were used. 2, the surface cracking time is longer than in the case of using UVA-3), and the light resistance is excellent. In addition, the degree of thermal discoloration is extremely small, almost the same as in the case of no addition, and the thermal discoloration of the ultraviolet absorbers of the examples (the compounds obtained in Examples 1 to 3) is extremely excellent.

From Table 3, it can be seen that when the compounds obtained in Examples 1 to 3 (that is, the benzotriazole compound having a high molecular weight) are used, the conventional ultraviolet absorbers (that is, UVA-1, UVA- 2, the degree of discoloration is smaller than when UVA-3) is used, and the discoloration resistance is excellent.

Thus, the compounds according to the invention, ie
When the benzotriazole-based compound represented by the formula (1) is used, both the weather resistance and the discoloration resistance of the organic material can be improved.

[0061]

The compound of the present invention can improve the weather resistance and discoloration resistance of an organic material, and can suppress or prevent discoloration of the organic material for a long period of time.

Continuation of the front page F term (reference) 4J002 AA001 AB011 AC011 AC031 AC061 AC071 AC081 AC121 BA011 BB031 BB061 BB121 BB151 BB171 BB241 BC031 BC041 BC061 BC071 BD041 BD051 BD061 BD071 BD081 BD111 CC131 BF1001 BF 001 BF 001 BF 001 CF211 CG001 CH071 CH091 CK011 CK021 CL001 CM041 CN011 CN031 CP001 EU176 FD046

Claims (3)

[Claims] 1. A benzotriazole compound represented by the following formula (1). Embedded image (In the formula, X represents a hydrogen atom or a chlorine atom. R represents an alkyl group, an aryl group, or an alkylaryl group having 1 to 18 carbon atoms. In addition, the methylene group is located ortho or para to the hydroxyl group. Are joined.) 2. A light stabilizer containing the benzotriazole compound according to claim 1. 3. An organic material containing the benzotriazole compound according to claim 1 as a light stabilizer.