JPH09137151A - Ultraviolet absorber and organic material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-mol.-wt. ultraviolet absorber with a high ultraviolet absorption capability in a wide wavelength region by bonding a benzotriazole compd. to a benzophenone compd. dimer through a methylene group. SOLUTION: This ultraviolet absorber is represented by formula I (wherein X is H or a halogen; R<1> is a 1-12C linear or branched alkyl; R<2> and R<3> are each a 1-8C alkyl or an alkoxy; and R<4> is H or a group represented by formula II) and is produced e.g. by bonding a benzophenone compd. dimer [e.g. 5,5'- methylenebis(2-hydroxy-4-methoxybenzophenone)] to a benzotriazole compd. [e.g. 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole] with formaldehyde or by bonding a benzotriazole compd. to a benzophenone compd. with formaldehyde before dimerization.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a UV absorber having a high molecular weight and an excellent UV absorbing ability in a wide wavelength range, and more specifically, a benzotriazole UV absorber having a dimer structure of a benzophenone UV absorber. It relates to an ultraviolet absorbent having a small volatility, which has a structure in which is bonded via a methylene group.

[0002]

2. Description of the Related Art Polymer materials such as polyethylene, polypropylene, styrene resin, polyvinyl chloride and polyester are deteriorated by the action of light and cause discoloration or deterioration of mechanical strength to endure long-term use. Not known to be.

Agricultural films, intraocular lenses, photographic filters and the like are required to selectively block light rays of harmful wavelengths, but resin or gelatin as a base material for film lenses and filters. It was difficult to control the wavelength of transmitted light only by itself.

Further, dyes and pigments used in thermal papers, paints, photographic materials, dyed fiber materials and the like have a problem that they are easily faded or discolored by ultraviolet rays.

Therefore, in order to prevent the deterioration of these organic materials and control the wavelength of transmitted light, various ultraviolet absorbers have been conventionally used. As these ultraviolet absorbers, benzophenone-based, benzotriazole-based, 2,4,6-triaryltriazine-based and cyanoacrylate-based ultraviolet absorbers are known.

However, when these ultraviolet absorbers are kneaded during the processing of the resin, a part of the ultraviolet absorber is volatilized by being exposed to a high temperature during the processing, and the effect is reduced.
The remaining ultraviolet absorber also volatilizes during long-term use and loses its effectiveness. Also, when applied to fibers, satisfactory long-term lightfastness has not been obtained because it is extracted by washing and loses its efficacy. In addition, when used in an intraocular lens or the like, an ultraviolet absorber that is difficult to extract from the viewpoint of safety has been desired. Therefore, as a UV absorber having a high molecular weight and low volatility, a polymerizable UV absorber is disclosed in JP-A-62-81376, and a UV absorber is disclosed in JP-A-50-74579 and JP-A-61-118373. Has proposed a dimerized UV absorber.

Further, the ultraviolet absorber is roughly classified into the limited basic structure as described above, and the maximum absorption wavelength and the molar absorption coefficient largely depend on the basic structure, so that the absorption wavelength region is practically insufficient. The problem of the absorption wavelength region was the same in the above-mentioned dimerized UV absorber.

As an ultraviolet absorber having a wide absorption wavelength range, Japanese Patent Application Laid-Open No. 6-321918 proposes an ultraviolet absorber having both a benzophenone structure and a benzotriazole structure, and an effect is recognized in expanding the absorption wavelength range. However, the volatility was insufficient. for that reason,
A UV absorber having a high molecular weight, low volatility, and high absorption in a wide wavelength range has been desired.

[0009]

Means for Solving the Problems The inventors of the present invention have made earnest studies in view of the above situation, and as a result, the following general formula (I)
The high molecular weight UV absorber represented by
The present invention has been accomplished by finding that it is excellent in extraction resistance and volatility and imparts excellent light resistance for a long period of time.

That is, the present invention provides a high molecular weight ultraviolet absorber represented by the following general formula (I).

[0011]

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[0012]

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Hereinafter, the present invention will be described in detail.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the halogen atom represented by X in the above general formula (I) include fluorine, chlorine, bromine and iodine.

Examples of the alkyl group represented by R ¹ include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl,
Heptyl, octyl, tertiary octyl, nonyl, isononyl, decyl, undecyl and the like can be mentioned.

Examples of the alkyl group represented by R ² and R ³ include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl and tert-octyl. , 2-ethylhexyl and the like, and examples of the alkoxy group include an alkoxy group corresponding to the above alkyl group.

Examples of the ultraviolet absorber represented by the above general formula (I) of the present invention include the following compound No. 1 to N
o. 9 is mentioned.

[0018]

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[0019]

[Chemical 6]

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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The method for synthesizing the compound represented by the general formula (I) of the present invention is not particularly limited, and the benzotriazole compound is dimerized and then the benzotriazole compound is bound with formaldehyde or benzotriazole. The benzophenone compound may be dimerized after being bound with formaldehyde. The method of binding a benzotriazole compound to a dimer of a benzophenone compound is preferable from the viewpoint that the number of bonding moles of the benzotriazole compound can be selected to be 1 or 2 and that the reactivity can be improved.

Next, specific synthesis examples of the compound represented by the general formula (I) used in the present invention will be given.
The present invention is not limited by the synthetic examples below.

(Synthesis Example 1: Synthesis of Compound No. 1) 2-
Paraformaldehyde (3.6 g, 0.12 mol) and diethylamine (8.8 g, 0.12 mol) were added to (2'-hydroxy-5'-tertiary octylphenyl) benzotriazole (32.3 g, 0.1 mol). , Xylene 40 ml
The mixture was heated to 80 ° C. and reacted for 15 hours. After cooling 5,
5′-Methylenebis (2-hydroxy-4-methoxybenzophenone) 56.2 g (0.12 mol) and sodium methoxide 0.54 g (0.01 mol) were added to give 1
The temperature was raised to 50 ° C. and the reaction was performed for 10 hours. After dexylene under reduced pressure, it was recrystallized from isopropanol. The obtained pale yellow crystals were chloroform / hexane = 97 / on a silica column.
Purification with a solvent 3 (weight ratio) gave 43.4 g (yield 54%) of a pale yellow powder having a melting point of 92 ° C. The analysis result of the obtained pale yellow powder was as follows.

UV spectrum: λmax = 345.8 nm, ε _345.8
= 2.78 × 10 ⁴ ; ¹ H-NMR (CHCl ₃ ) shows chemical shift ppm
(Attribution, intensity ratio H), 0.63ppm (CH ₃ , 9H), 1.30ppm
(CH ₃ , 6H), 1.61ppm (CH ₂ , 2H), 3.7-3.8ppm (OCH ₃ , CH ₂ , 8
H), 4.27ppm (CH ₂ , 2H), 6.4-8.2ppm (Ar-H, 19H), 11.56, 1
2.56,12.64ppm (OH, 3H)

(Synthesis Example 2: Synthesis of Compound No. 2) 2-
Paraformaldehyde (7.2 g, 0.24 mol) and diethylamine (17.6 g, 0.24 mol) were added to (2'-hydroxy-5'-tertiary octylphenyl) benzotriazole (64.6 g, 0.2 mol). , Xylene 80m
The mixture was heated to 80 ° C in 1 and reacted for 15 hours. After cooling, 46.8 g (0.10 mol) of 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone) and 1.1 g (0.02 mol) of sodium methoxide were added and the temperature was raised to 150 ° C. And reacted for 10 hours. After dexylene under reduced pressure, it was recrystallized from isopropanol. The pale yellow crystals obtained were filtered through a silica column to chloroform / hexane = 97.
Purification with a / 3 (weight ratio) solvent gave 64.9 g (yield 57%) of a pale yellow powder having a melting point of 97 ° C. The analysis result of the obtained pale yellow powder was as follows.

UV spectrum: λmax = 350.4 nm, ε _350.4
= 5.90 × 10 ⁴ ; ¹ H-NMR (CHCl ₃ ) shows chemical shift ppm
(Association, intensity ratio H), 0.64ppm (CH ₃ , 18H), 1.30pp
m (CH ₃ , 12H), 1.62ppm (CH ₂ , 4H), 3.68ppm (OCH ₃ , 6H), 3.8
_{8ppm (CH 2, 2H),} 4.28ppm (CH 2, 4H), 7.0-8.3ppm (Ar-H, 24
H), 11.55, 12.48ppm (OH, 2H)

(Synthesis Example-3: Synthesis of Compound No. 3) 2
To 22.5 g (0.1 mol) of-(2'-hydroxy-5'-methylphenyl) benzotriazole, 3.6 g (0.12 mol) of paraformaldehyde and 8.8 g (0.12 mol) of diethylamine were added, The mixture was heated to 80 ° C. in 40 ml of xylene and reacted for 15 hours. After cooling 3,
3'-methylenebis (2-hydroxy-4-methoxybenzophenone) 56.2 g (0.12 mol) and sodium methoxide 1.1 g (0.02 mol) were added to give 15
The temperature was raised to 0 ° C. and the reaction was performed for 10 hours. After dexylene under reduced pressure, it was recrystallized from isopropanol. The obtained pale yellow crystals were chloroform / hexane = 97/3 on a silica column.
(Weight ratio) Purification with a solvent gave 36.0 g (yield 51%) of a pale yellow powder having a melting point of 110 ° C. The analysis result of the obtained pale yellow powder was as follows.

UV spectrum: λmax = 346.4 nm,
ε _346.4 : 3.36 × 10 ⁴ ; ¹ H-NMR (CHCl ₃ ) shows 2.26 ppm (CH ₃ ; 3H) as chemical shift ppm (attribution; intensity ratio H), 3.
6-3.8ppm (OCH ₃ , CH ₂ ; 8H), 4.25ppm (CH ₂ ; 2H), 3.68ppm (OC
H ₃ ; 6H), 3.88ppm (CH ₂ ; 2H), 4.28ppm (CH ₂ ; 4H), 6.5-8.2p
pm (Ar-H; 19H), 11.52,12.49,12.63ppm (OH; 3H)

(Synthesis Example-4: Synthesis of Compound No. 4) 2
-(2'-hydroxy-5'-methylphenyl) benzotriazole 45.0 g (0.2 mol) in paraformaldehyde 7.2 g (0.24 mol) and diethylamine 1
7.6 g (0.24 mol) was added, and the mixture was heated to 80 ° C. in 80 ml of xylene and reacted for 15 hours. After cooling 5,
5'-methylenebis (2-hydroxy-4-methoxybenzophenone) 46.8 g (0.10 mol) and sodium methoxide 1.1 g (0.02 mol) were added to give 15
The temperature was raised to 0 ° C. and the reaction was performed for 10 hours. After dexylene under reduced pressure, it was recrystallized from isopropanol. The obtained pale yellow crystals were chloroform / hexane = 97/3 on a silica column.
(Weight ratio) Purification with a solvent gave 50.9 g (yield 54%) of a pale yellow powder having a melting point of 143 ° C. The analysis result of the obtained pale yellow powder was as follows.

UV spectrum: λmax = 348.8 nm,
ε _348.8 : 3.96 × 10 ⁴ ; ¹ H-NMR (CHCl ₃ ) shows 2.24 ppm (CH ₃ , 6H) as chemical shift ppm (attribution, intensity ratio H).
_{3.67ppm (OCH 3, 6H),} 3.88-4.26ppm (CH 2, 6H), 3.68ppm (OC
_{H 3, 6H), 3.88ppm (} CH 2, 2H), 4.28ppm (CH 2, 4H), 6.7-8.1p
pm (Ar-H, 24H), 11.52, 12.52ppm (OH, 2H)

(Synthesis Example-5: Synthesis of Compound No. 6) 2
-(2'-hydroxy-5'-tertiary octylphenyl)
To 64.6 g (0.2 mol) of benzotriazole, 7.2 g (0.24 mol) of paraformaldehyde and 17.6 g (0.24 mol) of diethylamine were added, and xylene 40 was added.
It heated to 80 degreeC in ml, and reacted for 15 hours. After cooling, 56.2 g (0.12 mol) of 3,3′-methylenebis (2-hydroxy-4-methoxybenzophenone) and 1.1 g (0.02 mol) of sodium methoxide were added and the temperature was raised to 150 ° C. And reacted for 10 hours. After dexylene under reduced pressure, it was recrystallized from isopropanol. The pale yellow crystals obtained were filtered through a silica column to chloroform / hexane = 97.
Purification with a / 3 (weight ratio) solvent gave 63.6 g (yield 55%) of a pale yellow powder having a melting point of 69 ° C. The analysis result of the obtained pale yellow powder was as follows.

UV spectrum: λmax = 343.2 nm,
ε _343.2 : 6.49 × 10 ⁴ ; ¹ H-NMR (CHCl ₃ ) shows 0.66 ppm (CH ₃ , 18H) as chemical shift ppm (attribution, intensity ratio H).
1.34ppm (CH ₃ , 12H), 1.63ppm (CH ₂ , 4H), 3.85ppm (OCH ₃ , 6
H), 4.25ppm (CH ₂ , 4H), 6.4-8.2ppm (Ar-H, 24H), 11.44, 1
2.70ppm (OH, 2H)

The organic material to be stabilized by the specific ultraviolet absorber of the present invention is not particularly limited, but is represented by molded articles such as automobile parts, film sheets such as agricultural materials, and PET. In addition to fiber materials such as polyester fibers and nylon fibers, synthetic polymeric materials such as intraocular lenses and tapes, heat-sensitive recording materials, paints, adhesives, putties, binders for lacquers, base materials for photographic materials, and the like. The addition amount of the specific ultraviolet absorber of the present invention depends on the type and application of the organic material to be stabilized, and the organic material 10
It is usually 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight, relative to 0 parts by weight. If it is less than 0.001 part by weight, the stabilizing effect cannot be obtained, and if it is more than 30 parts by weight, the stabilizing effect is not improved, which is economically disadvantageous.

Since the ultraviolet absorbent of the present invention has a small volatility and imparts excellent light resistance for a long period of time, it is used in fields requiring a high degree of light resistance such as agricultural materials and automobile paints, and washing of fibers and the like. It is particularly useful in fields requiring robustness.

Typical materials constituting the organic material stabilized by the ultraviolet absorbent of the present invention are synthetic resins, and usually, the ultraviolet absorbent of the present invention is added to these resins in advance to prepare a resin composition. Molded and processed into various products. Resins that are subject to such stability improvement include
For example, α-olefin polymers such as high density, low density or linear low density polyethylene, polypropylene, polybutene-1, poly-3-methylpentene or ethylene-
Polyolefins such as vinyl acetate copolymers and ethylene-propylene copolymers and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate Copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-
Halogen-containing resins such as maleic acid ester copolymers, vinyl chloride-cyclohexylmaleimide copolymers, vinyl chloride-cyclohexylmaleimide copolymers, petroleum resins, coumarone resins, polystyrene, polyvinyl acetate, acrylic resins, styrene and / or α. -Methylstyrene and other monomers (e.g. maleic anhydride, phenylmaleimide,
Copolymers (eg, AS resin, ABS resin, M) with methyl methacrylate, butadiene, acrylonitrile, etc.
BS resin, heat-resistant ABS resin, etc.), polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal,
Polyvinyl butyral, linear polyester such as polyethylene terephthalate and polytetramethylene terephthalate, polyphenylene oxide, polyamide such as polycaprolactam and polyhexamethylene adipamide, polycarbonate, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, fibrin resin, etc. Thermoplastic synthetic resins and blends thereof or phenolic resins, urea resins, melamine resins,
A thermosetting resin such as an epoxy resin and an unsaturated polycastel resin can be used. Further, it may be an elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber or styrene-butadiene copolymer rubber.

If necessary, the resin composition may be used in combination with other additives such as general-purpose antioxidants and stabilizers.

Particularly preferred as these additives are phenol-based, sulfur-based, phosphite-based antioxidants, hindered amine-based light stabilizers, and ultraviolet absorbers other than the specific ultraviolet absorber of the present invention. Among them, a hindered amine type light stabilizer represented by a 2,2,6,6-tetramethylpiperidine compound is particularly preferable because it exhibits a synergistic effect with the ultraviolet absorber of the present invention.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6
-Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol Bis [(3,5-ditert-butyl-
4-hydroxyphenyl) propionate], 1,6-
Hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butyl) Tributylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid]
Glycol ester, 4,4'-butylidenebis (6-
Tert-butyl-m-cresol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2′-
Ethylidene bis (4-tert-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-
Tert-butyl-4-methyl-6- (2-hydroxy-3-
Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-
Hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-
Hydroxylbenzyl) isocyanurate, 1,3,5-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-
Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tetrakis [methylene-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate] methane, 2
-Tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-{(3-tertiary Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy) -5
Methylphenyl) propionate].

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Examples include β-alkyl mercaptopropionic acid esters.

Examples of the above-mentioned phosphite antioxidants include trisnonylphenyl phosphite, tris (2,4-ditertiary butylphenyl) phosphite,
Tris [2-tert-butyl-4- (3-tert-butyl-4-
[Hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol Diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertbutyl-4-methylphenyl) penta Erythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,
4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
-1,1,3-tris (2-methyl-4-hydroxy-
5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
Examples include tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl) oxy] ethyl) amine. .

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-
Piperidyl benzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide,
1-[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-di-tert-butyl-4- (Hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate, bis (1, 2, 2, 6,
6-pentamethyl-4-piperidyl) -2-butyl-2
-(3,5-di-tert-butyl-4-hydroxybenzyl)
Malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, Tetra (1, 2,
2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,2,2 2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl- 4-piperidyloxycarbonyloxy) butylcarbonyloxydiethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,
1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy)
Butylcarbonyloxydiethyl] -2,4,8,10
-Tetraoxaspiro [5.5] undecane, 1,5
8,12-tetrakis [4,6-bis {N- (2,2,
6,6-tetramethyl-4-piperidyl) butylamino {-1,3,5-triazin-2-yl] -1,5.
8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro -S-triazine / N, N '
-Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / And dibromoethane condensates.

Examples of the ultraviolet absorber other than the specific ultraviolet absorber of the present invention which can be applied to the composition include, for example, 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2-hydroxybenzophenone compounds such as (hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2
-Hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2
-(2-Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-carboctoxyethylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole,
2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tertiaryoctyl-6-benzotriazolylphenol) and the like 2
-Hydroxyphenyl benzotriazole compound; 2,
4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -s-triazine, 2,4-bis (2,4-
Triazine compounds such as dimethylphenyl) -6- (2-hydroxy-4-octoxyphenyl) -s-triazine; phenyl salicylate, resorcin monobenzoate, 2,4-ditert-butylphenyl-3,5-ditertiary Butyl-4-hydroxybenzoate, hexadecyl-
Benzoate compounds such as 3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilide compounds such as 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl-α -Cyano-
Examples of the cyanoacrylate compound include β, β-diphenyl acrylate and methyl-α-cyano-β-methyl-β- (p-methoxyphenyl) acrylate.

In addition, if necessary, the composition contains a nucleating agent such as a metal salt of benzoic acid, sorbitol and a metal salt of an aromatic phosphate ester, a heavy metal deactivator, a metallic soap, hydrotalcites, Organic tin compound, plasticizer,
Epoxy compounds, foaming agents, antistatic agents, flame retardants, lubricants,
Processing aids, dyes, pigments, fillers and the like can be included.

The method of applying the ultraviolet absorber of the present invention to an organic material is not particularly limited, and the form of addition may be a powder, an aqueous dispersion such as an emulsion or suspension, or a solution with an organic solvent. Good. Also,
The processing method of the resin to which the ultraviolet absorbent of the present invention is added is not particularly limited and can be applied to any of the processing methods used for ordinary resins, such as calendar processing, extrusion processing, injection molding, and inflation. Molding,
Blow molding, press processing, etc. are mentioned.

However, since the ultraviolet absorber of the present invention is a high molecular weight substance, it is preferable to knead it into a resin as an addition method. Since the ultraviolet absorbent of the present invention has excellent extraction resistance, it can be added at a high concentration, and in addition to stabilizing the added resin itself, it also has an excellent effect when the resin added at a high concentration is used as an ultraviolet shielding layer. Show. For example, it is particularly useful for a film having a protective layer formed by two-layer extrusion, for controlling the transmittance of ultraviolet rays for agricultural materials, and for application to a top coat paint as a protective layer for the coated surface.

[0052]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

(Example 1) The composition shown in Table 1 below was used to obtain 2
Extrusion processing was performed at 50 ° C. to prepare pellets. Then, injection molding was performed at 250 ° C. to prepare a test piece having a thickness of 2 mm. The test piece was subjected to a weather resistance test using a sunshine weatherometer with a rain cycle of 18 minutes in 120 minutes at a black panel temperature of 83 ° C. The durability of weather resistance was evaluated by the yellowness after 1000 hours and 2000 hours after the start of the test. Further, the time until the occurrence of cracks was measured as the weather resistance time. The results are shown in Table 2 below.

[0054]

[Table 1]

[0055]

[Table 2]

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Example 2 The formulations shown in Table 3 below were dissolved in chloroform to prepare a 1 wt% solution, and then 76 mm × 2
A cast film was prepared on a 6 mm glass plate. The color difference of the obtained film after 48 hours was measured with a xenon weatherometer at a temperature of 63 ° C. and a humidity of 50%. The results are shown in Table 4 below.

[0059]

[Table 3]

[0060]

[Table 4]

Example 3 Using the formulations shown in Table 5 below,
The film was kneaded with a kneading roll to produce a film having a thickness of 0.1 mm. A test piece was cut out from this film, and a weather resistance test was performed using a sunshine weatherometer (without rain). The results are shown in Table-6.

[0062]

[Table 5]

[0063]

[Table 6]

Example 4 30 g of a liquid prepared by finely dispersing 1 part by weight of a nonionic surfactant (addition product of nonylphenol and ethylene oxide) in 64 parts by weight of water and an anthraquinone type red dye (Resolin Red FB: manufactured by Bayer). 10 g, 0.5 parts by weight of an ultraviolet absorber (shown in Table 7) and acetic acid of 0.
3 g was dispersed in 1 liter of water to obtain a dye liquor, with a bath ratio of 1: 1.
100 g of polyester cloth in a closed container at 130
Dyeing was carried out for 30 minutes in a thermostat bath. After cooling, the test piece was washed with water and reduction-washed by a conventional method. 2 of the obtained dyed cloth at sunshine weatherometer 83 ° C (without watering)
A weather resistance test was conducted by the color difference after 40 hours from before the test. The results are shown in Table-7.

[0065]

[Table 7]

(Example 5) Stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 0 was added to 100 parts by weight of bisphenol A polycarbonate powder having an intrinsic viscosity of 0.57 (30 ° C in dioxane). .1
Parts by weight and 10 parts by weight of an ultraviolet absorber (described in Table-8) were added and pelletized at 280 ° C. × 80 rpm to obtain a resin for the surface layer. Also, a pellet obtained by extrusion processing from the above polycarbonate powder containing no ultraviolet absorber at 280 ° C. × 80 rpm as a core layer was coextruded by a two-layer extruder with a core layer of 10 mm and a surface layer of 40 μm to obtain a test piece. . The obtained test piece was irradiated with ultraviolet rays from a high-pressure mercury lamp with the surface layer as the light source side, and the yellowness of the unirradiated test piece and the test piece after 2 weeks of irradiation was measured according to ASTM D1925, and the change (color difference) I asked. Table-
8 shows.

[0067]

[Table 8]

[0068]

From the results of each of the above-mentioned examples, when the specific ultraviolet absorber of the present invention is used, the stabilizing effect is large as compared with the case where the conventionally known ultraviolet absorber is used,
In particular, it is clear that the stability of the stabilizing effect is remarkably superior to that of Example 1 and Comparative Example 1.

Claims (2)

[Claims] 1. An ultraviolet absorber represented by the following general formula (I). Embedded image Embedded image 2. An organic material to which the ultraviolet absorber according to claim 1 is added.