JP2018188589A - Benzotriazole-based copolymer and ultraviolet absorber using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer ultraviolet absorber that does not cause volatilization or decomposition of ultraviolet-absorbing components during resin processing and has high compatibility with other resins.SOLUTION: There is provided a polymer ultraviolet absorber employing a novel benzotriazole-based copolymer formed by polymerizing a polybutadiene comprising a 1,2-vinyl structure as an essential constitutional unit and a benzotriazole derivative compound represented by the general formula (1) in the figure. [Preferably, Ris a C2-8 alkyl group, and Ris an ethylene group.]SELECTED DRAWING: Figure 1

Description

  The present invention relates to a novel benzotriazole copolymer. More specifically, the present invention relates to an ultraviolet absorber using the same, and more particularly, to an ultraviolet absorber that exhibits high heat resistance that hardly causes volatilization or decomposition even at high temperatures and exhibits high compatibility with a resin.

  It is well known that a resin is deteriorated by the action of natural ultraviolet light, and its mechanical strength is remarkably lowered with a phenomenon such as softening, embrittlement or discoloration. In order to prevent such deterioration due to light, various ultraviolet absorbers have been conventionally used by being added during the resin processing step. As such ultraviolet absorbers, for example, benzophenone, benzotriazole, benzoate, salicylate, or triazine compounds are known.

  However, conventional UV absorbers volatilize and decompose themselves at high temperatures during resin processing. Therefore, contamination of resin molds and UV absorption due to volatilization of UV absorbers during resin processing. There were problems such as coloring of the resin due to thermal decomposition of the agent.

  In order to solve these problems, volatilization as a highly heat-resistant UV absorber with improved molecular weight by dimerizing the above UV-absorbing compound or adding a bulky substituent to the UV-absorbing compound Proposals have been made to prevent decomposition, but such compounds are generally poorly compatible with the resin, and after processing the resin, the UV absorber bleeds out to the resin surface. There was a problem.

  Patent Documents 1 and 2 propose a polymer ultraviolet absorber obtained by copolymerizing a benzotriazole derivative containing a (meth) acryloyl group and a (meth) acrylic acid ester. By incorporating it as a body component, there has been a proposal that prevents the ultraviolet absorbing component from being volatilized or decomposed at a high temperature during processing, and further prevents bleeding out of the ultraviolet absorbing component after processing.

JP 2012-25811 A JP 60-38411 A

  Although the polymer ultraviolet absorbers described in these applications have been shown to be used for contact lenses, films, paints, etc., all of these polymer ultraviolet absorbers are molded or formed alone, The compatibility with the resin is expected to be inadequate, and there is a problem that the use method such as adding these polymer ultraviolet absorbers to the resin cannot be performed, and there is no versatility. Therefore, an object of the present invention is to provide a high molecular weight UV absorber excellent in compatibility with other resins, and to provide a novel copolymer therefor.

  In the present invention, the skeleton is constituted by the benzotriazole derivative compound represented by the following general formula (1) and the structural unit represented by the following general formula (2) or the following general formula (3), and the above structure. The use of a novel benzotriazole-based copolymer obtained by polymerizing polybutadiene containing at least one of the general formula (2) as a unit as a polymer ultraviolet absorber is a main means for solving the above-mentioned problems.

一般式（１）
［式中、Ｒ_１は水素原子、炭素数１〜８のアルキル基、フェニル基、トリル基、ホルミル基、アルキル炭素数１〜７のアルキルカルボニル基、ベンゾイル基、またはトルオイル基を表し、Ｒ_２は炭素数１〜８のアルキレン基を表し、Ｒ_３は水素原子、またはメチル基を表す］

General formula (1)
[Wherein, R ₁ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a tolyl group, a formyl group, an alkylcarbonyl group of an alkyl having 1 to 7 carbon atoms, a benzoyl group or a toluoyl group,, R ₂ Represents an alkylene group having 1 to 8 carbon atoms, and R ₃ represents a hydrogen atom or a methyl group]

一般式（２）

General formula (2)

一般式（３）
［一般式（３）中の炭素−炭素二重結合はシス構造、トランス構造のいずれであってもよい。］

General formula (3)
[The carbon-carbon double bond in the general formula (3) may be either a cis structure or a trans structure. ]

Preferably, in the benzotriazole derivative compound represented by the general formula (1), R ₁ is an alkyl group having 2 to 8 carbon atoms, and R ₂ is an ethylene group.

  The benzotriazole-based copolymer of the present invention has a UV-absorbing structure incorporated as a polymer component, so there is no volatilization or decomposition of the UV-absorbing component during resin processing, and with other resins. Therefore, it is useful as an ultraviolet absorber that can solve the problems of the prior art without causing bleed-out even when added to other resins.

  The present invention will be described in detail below. In the present invention, a benzotriazole copolymer obtained by copolymerizing a benzotriazole derivative compound represented by the following general formula (1) and polybutadiene is used as an ultraviolet absorber or a resin composition.

一般式（１）

General formula (1)

In general formula (1), R ₁ is a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, octyl group, 2-ethylhexyl. A linear or branched alkyl group having 1 to 8 carbon atoms such as a group; phenyl group; tolyl group; formyl group; alkyl such as acetyl group, propionyl group, butyryl group, isobutyryl group, octanoyl group, 2-ethylhexanoyl group A straight or branched alkylcarbonyl group having 1 to 7 carbon atoms; a benzoyl group; a toluoyl group, and R ₂ represents a methylene group, an ethylene group, a triethylene group, a propylene group, a tetramethylene group, a hexamethylene group, and an octamethylene group. include linear or branched alkylene group having 1 to 8 carbon atoms such as groups, R ₃ is a hydrogen atom; et al mentioned methyl That.

The benzotriazole derivative compound represented by the general formula (1) is preferably a compound represented by R ₁ being an alkyl group having 2 to 8 carbon atoms and R ₂ being an ethylene group.

  Benzotriazole derivative compound Examples of the general formula (1) include the following. 2- [2- (2,4-Dihydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl methacrylate, 2- [2- (4-ethoxy-2-hydroxyphenyl) -2H-benzotriazol-5-yloxy ] Ethyl methacrylate, 2- [2- (4-butoxy-2-hydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl methacrylate, 2- [2- (2-hydroxy-4-octyloxyphenyl) -2H -Benzotriazol-5-yloxy] ethyl methacrylate, 2- [2- (4-benzoyloxy-2-hydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl methacrylate, 4- [2- (2,4- Dihydroxyphenyl) -2H-benzotriazol-5-ylo Si] butyl methacrylate, 4- [2- (4-ethoxy-2-hydroxyphenyl) -2H-benzotriazol-5-yloxy] butyl methacrylate, 4- [2- (4-butoxy-2-hydroxyphenyl) -2H -Benzotriazol-5-yloxy] butyl methacrylate, 4- [2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazol-5-yloxy] butyl methacrylate, 4- [2- (4-benzoyloxy) -2-hydroxyphenyl) -2H-benzotriazol-5-yloxy] butyl methacrylate, 2- [2- (2,4-dihydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl acrylate, 2- [2- (4-Ethoxy-2-hydroxyphenyl) -2 -Benzotriazol-5-yloxy] ethyl acrylate, 2- [2- (4-butoxy-2-hydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl acrylate, 2- [2- (2-hydroxy-4) -Octyloxyphenyl) -2H-benzotriazol-5-yloxy] ethyl acrylate, 2- [2- (4-benzoyloxy-2-hydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl acrylate, and the like.

  Among the compounds exemplified herein, 2- [2- (4-ethoxy-2-hydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl methacrylate, 2- [2- (4-butoxy-2- Hydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl methacrylate, 2- [2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazol-5-yloxy] ethyl methacrylate, 2- [2- (4-Ethoxy-2-hydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl acrylate, 2- [2- (4-butoxy-2-hydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl acrylate , 2- [2- (2-hydroxy-4-octyloxypheny) ) -2H- benzotriazole-5-yloxy] ethyl acrylate is preferably used.

There is no particular limitation on the method for synthesizing the general formula (1) of the benzotriazole derivative compound, and a conventionally known reaction principle can be widely used. For example, the synthesis is performed via the reaction formulas shown below (Chemical Formula 4 to Chemical Formula 7). be able to. However, X represents a halogen atom.

  Polybutadiene (monopolymer) is generally obtained by cleaving and polymerizing butadiene. Therefore, the structural unit constituting the skeleton is a 1,2-vinyl structure represented by the following general formula (2) or a cis-form represented by the following general formula (3) by the cleavage of the molecular bond during polymerization. It can be either a 1,4 structure or a transformer-1,4 structure.

一般式（２）

General formula (2)

一般式（３）

General formula (3)

  However, the polybutadiene used as a raw material for the benzotriazole-based copolymer of the present invention contains the 1,2-vinyl structure represented by the general formula (2) as an essential constituent unit. That is, it may be a polybutadiene composed only of the general formula (2) as a structural unit, or may be a polybutadiene composed of a mixture of the general formula (2) and the general formula (3) as a structural unit. In addition, when general formula (3) is included as a structural unit, the structure may be only a cis-1,4 structure or only a trans-1,4 structure, and both are mixed and comprised. Also good.

  Therefore, specific examples of the polybutadiene used in the present invention include 1,2-polybutadiene; mixed polybutadiene of 1,2-vinyl structure and cis-1,4 structure; mixed of 1,2-vinyl structure and trans-1,4 structure Polybutadiene; mixed polybutadiene having a 1,2-vinyl structure, a cis-1,4 structure, and a trans-1,4 structure may be mentioned.

  The polymerization method of the benzotriazole derivative compound and polybutadiene used for the polymerization of the benzotriazole copolymer of the present invention is not particularly limited, and various conventionally known polymerization methods such as radical polymerization and ionic polymerization are used. A solution polymerization method using a chain polymerization reaction, a bulk (bulk) polymerization method, a suspension (pearl) polymerization method, a photopolymerization method, or the like can be employed.

  Specific examples of solvents that can be used when a copolymer is obtained by employing the solution polymerization method include, for example, benzene, toluene, xylene, and other high-boiling aromatic solvents; ethyl acetate, butyl acetate. And ester solvents such as cellosolve acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, 2-propanol, and the like, but are not particularly limited. Only one kind of these solvents may be used, or two or more kinds may be appropriately mixed and used. Moreover, the usage-amount of a solvent is not specifically limited.

  Specific examples of the dispersant that can be used in the case of obtaining a copolymer by employing the suspension (pearl) polymerization method include, for example, polyvinyl alcohol, poly (meth) acrylic acid or a salt thereof, styrene and malee. Salt of acid copolymer, salt of α-methylstyrene and acrylic acid copolymer, polyvinylpyrrolidone, poly (meth) acrylamide, methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, carboxymethylcellulose, Polymer surfactants such as gelatin, starch, tragacanth, pectin, glue, alginic acid or salts thereof; polyoxyalkylene dispersants such as polyethylene oxide and polypropylene oxide; poly Kishiechiren - alkyl ether, polyoxyethylene - alkyl phenols, polyoxyethylene - polyol esters, esters of polyhydric alcohols and fatty acids, a nonionic surfactant such as oxyethylene-oxypropylene block condensates thereof. Moreover, these dispersing agents may use only one type, and may mix and use two or more types suitably. Moreover, the usage-amount of a dispersing agent is not specifically limited.

  In addition, when a copolymer is obtained by employing a solution polymerization method, a bulk polymerization method, or a suspension polymerization method, a polymerization initiator can be used. Specific examples of the polymerization initiator include 2,2′-azobis- (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane- 1-carbonitrile), benzoyl peroxide, di-t-butyl peroxide, oil-soluble radical polymerization initiators such as t-butylperoxy-2-ethylhexanoate; ammonium persulfate, potassium persulfate, sodium persulfate , T-butyl peroxide, 2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2-azobis [2- (2-imidazolin-2-yl) propane] Disulfuric acid dihydrate, 2,2-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis [N- (2-carboxyethyl) -2-methylpropion Midine] hydrate, 2,2-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2-azobis [2- (2- Imidazolin-2-yl) propane], 2,2-azobis (1-imino-1-pyrrolidino-2-ethylpropane) dihydrochloride, 2,2-azobis {2-methyl-N- [1,1- Bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2-azobis (N-hydroxyethylisobutyramide) Water-soluble radical polymerization initiators such as 4,4-azobis (4-cyanopentanoic acid); polymerization initiators of persulfates and organic peroxides, sodium sulfooxylate formaldehyde, sodium hydrogensulfite As a polymerization initiator, a reducing agent such as sodium, ammonium bisulfite, sodium thiosulfate, ammonium thiosulfate, hydrogen peroxide, sodium hydroxymethanesulfinate, L-ascorbic acid, and salts thereof, cuprous salts, ferrous salts, etc. Redox initiators used in combination; benzophenone, N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1,4,4'-bis (dimethylamino) benzophenone (Michler ketone), 4,4'-bis (diethylamino) benzophenone, 4-methoxy Aromatic ketones such as -4'-dimethylaminobenzophenone, alkyl Quinones such as anthraquinone and phenanthrenequinone, benzoin compounds such as benzoin and alkylbenzoin, benzoin ether compounds such as benzoin alkyl ether and benzoin phenyl ether, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5 -Diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl)- 2,4, such as 4,5-diphenylimidazole dimer 5-triarylimidazole dimer, N-phenylglycine, N-phenylglycine derivative, acridine derivative such as 9-phenylacridine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o -Benzoyloxime)], coumarin compounds such as 7-diethylamino-4-methylcoumarin, thioxanthone compounds such as 2,4-diethylthioxanthone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide Examples thereof include, but are not particularly limited to, light (mainly ultraviolet) cleavage type radical polymerization initiators such as acylphosphine oxide compounds. Moreover, these polymerization initiators may use only 1 type, and may mix and use 2 or more types suitably. Moreover, the usage-amount of a polymerization initiator is not specifically limited.

  Although reaction temperature is not specifically limited, The range of room temperature-200 degreeC is preferable, and the range of 50 degreeC-150 degreeC is more preferable. In addition, what is necessary is just to set reaction time suitably so that a polymerization reaction may be completed according to reaction temperature or the kind of raw material to be used.

  As the photopolymerization initiator used in the case of obtaining a copolymer by employing the photopolymerization method, any of known photopolymerization initiators that exhibit photopolymerization initiating action upon irradiation with active energy rays can be used. For example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [ 4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) ) -Benzyl] -phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzene) And (zyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. A combination of 2-isopropylthioxanthone and the polymerization accelerators 2-ethylhexyl-4-dimethylaminobenzoate and / or ethyl-4-dimethylaminobenzoate can also be used. In the present invention, these photopolymerization initiators may be used alone or in combination of two or more.

  The resin to which the benzotriazole copolymer of the present invention can be added is not particularly limited. For example, α-olefin heavy polymers such as polyethylene, polypropylene, polybutene, polypentene, poly-3-methylbutylene, and polymethylpentene can be used. Polyolefins such as coalesced or ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, rubber chloride, 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-vinyl acetate ternary copolymer Halogen-containing synthesis such as polymers, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internal plastic polyvinyl chloride Resin, petroleum resin, coumarone resin, polystyrene, copolymer of styrene and other monomers (maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene resin, acrylate-butadiene-styrene resin, methacryl Acid ester-butadiene Styrene resin such as styrene resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic resin, methacrylate resin, polyacrylonitrile, polyphenylene oxide, polycarbonate, modified polyphenylene oxide, polyacetal, phenol resin, urea resin, melamine resin, Epoxy resin, silicone resin, polyethylene terephthalate, reinforced polyethylene terephthalate, polybutylene terephthalate, polysulfone resin, polyethersulfone, polyphenylene sulfide, polyetherketone, polyetherimide, polyoxybenzoyl, polyimide, polymaleimide, polyamideimide, alkyd resin , Amino resin, vinyl resin, water-soluble resin, resin for powder coating, polyamide Examples thereof include a resin, a polyurethane resin, a polythiourethane resin, and an unsaturated polyester resin.

  When the benzotriazole copolymer of the present invention is added to a resin, only the benzotriazole copolymer of the present invention can be used as a UV absorber, or a combination with other UV absorbers. The ultraviolet absorber other than the benzotriazole copolymer of the present invention is not particularly limited as long as it is generally available on the market and can absorb the ultraviolet region. For example, benzotriazole derivatives, benzophenone derivatives, salicylate derivatives, cyanoacrylate derivatives, triazine derivatives and the like are used. These ultraviolet absorbers may be used alone or in a suitable mixture of two or more.

  The benzotriazole copolymer of the present invention is used in an amount of 0.01 to 20% by weight, preferably 0.1 to 2% by weight, based on the resin.

  The synthesis method and characteristics of the benzotriazole copolymer carried out in the present invention are shown below. However, the synthesis method is not limited to this.

(Intermediate Synthesis Example 1)
[Precursor; Synthesis of 2- [5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl] -5-octyloxyphenol]

  A 1000 ml four-necked flask was equipped with a condenser with a ball, a thermometer, and a stirring device, and 176 of 4- (5-methoxy-2H-benzotriazol-2-yl) benzene-1,3-diol synthesized by a conventional method was obtained. 0.0 g (0.684 mol), methyl isobutyl ketone 350 ml, 1-chlorooctane 142.0 g (0.955 mol), sodium carbonate 62.0 g (0.585 mol), potassium iodide 5.2 g, The mixture was refluxed and dehydrated at 120 to 130 ° C. for 12 hours. 200 ml of water was added, the mixture was allowed to stand, and the lower aqueous layer was separated and removed, followed by washing with 200 ml of warm water. 350 ml of methyl isobutyl ketone was recovered under reduced pressure, 450 ml of isopropyl alcohol was added, the precipitated crystals were filtered, washed with 200 ml of isopropyl alcohol and dried to give 2- (5-methoxy-2H-benzotriazol-2-yl) 216.9 g of -5-octyloxyphenol was obtained.

  A condenser with a ball, a thermometer, and a stirrer were attached to a 10 L four-necked flask, and 216.9 g (0.587 mol) of 2- (5-methoxy-2H-benzotriazol-2-yl) -5-octyloxyphenol was attached. ), 475.8 g of hydrobromic acid (0.731 mol) and 1800 ml of sulfolane were added and stirred at 100 to 105 ° C. for 48 hours. Toluene (800 ml) and water (3500 ml) were added, and the mixture was allowed to stand. The lower aqueous layer was separated and removed, washed with warm water (1300 ml) twice, and toluene (800 ml) was collected under reduced pressure. Add 800 ml of isopropyl alcohol and 200 ml of water, cool to 5 ° C., filter the precipitated crystals, wash with 200 ml of an aqueous isopropyl alcohol solution (80% V / V), dry and 2- (5-hydroxy-2H -126.6g of -benzotriazol-2-yl) -5-octyloxyphenol was obtained.

  A 1000 ml four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirring device, and 126.6 g (0.356 mol) of 2- (5-hydroxy-2H-benzotriazol-2-yl) -5-octyloxyphenol is attached. ), 450 ml of methyl isobutyl ketone, 35.8 g (0.445 mol) of 2-chloroethanol, 23.5 g (0.222 mol) of sodium carbonate, and 17.8 g of potassium iodide, and at 113 to 118 ° C. for 10 hours. Reflux dehydration. 250 ml of water was added, the mixture was allowed to stand, and the lower aqueous layer was separated and removed, followed by washing with 150 ml of warm water. After recovering 450 ml of methyl isobutyl ketone under reduced pressure, 500 ml of isopropyl alcohol was added and cooled to 10 ° C., and the precipitated crystals were filtered, washed with 50 ml of isopropyl alcohol and dried to give 2- [5- (2-hydroxyethoxy). 95.3 g of -2H-benzotriazol-2-yl] -5-octyloxyphenol was obtained. The yield was 35% (from 4- (5-methoxy-2H-benzotriazol-2-yl) benzene-1,3-diol).

化合物（ａ） (Intermediate Synthesis Example 2)
[Compound (a); Synthesis of 2- [2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazol-5-yloxy] ethyl methacrylate]

Compound (a)

  A 1000 ml four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirring device, and 95.3 g of 2- [5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl] -5-octyloxyphenol is attached. (0.239 mol), 550 ml of toluene, 50.6 g (0.588 mol) of methacrylic acid, and 29.8 g (0.310 mol) of methanesulfonic acid were added, followed by reflux dehydration at 110 to 115 ° C. for 4 hours. 200 ml of water and 32.8 g (0.309 mol) of sodium carbonate were added, and the mixture was allowed to stand to separate and remove the lower aqueous layer. 1.8 g of activated carbon was added, and the mixture was refluxed and decolorized. Filtration was performed while hot, and 550 ml of toluene was recovered from the filtrate under reduced pressure. Then, 750 ml of isopropyl alcohol was added. The precipitated crystals were filtered, washed with 100 ml of isopropyl alcohol, and then dried at 40 ° C. under reduced pressure. 0.1 g was obtained. The entire amount was recrystallized from isopropyl alcohol and dried at 40 ° C. under reduced pressure to obtain 77.8 g of compound (a). The yield was 70% (from 2- [5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl] -5-octyloxyphenol). Melting point is 92 ° C.

Moreover, the purity of the compound (a) was measured by HPLC analysis.
<Measurement conditions>
Device: L-2130 (manufactured by Hitachi High-Technologies Corporation)
Column used: SUMPAX ODS A-212 6 × 150 mm 5 μm
Column temperature: 40 ° C
Mobile phase: Methanol / water = 99/1
Flow rate: 1.0 ml / min
<Measurement results>
HPLC area purity: 99.9%
The following compound (b) was also subjected to HPLC analysis under the same measurement conditions as for compound (a).

Further, when the ultraviolet to visible absorption spectrum of the compound (a) was measured, the maximum absorption wavelength λmax was 350 nm, and the absorbance ε at this time was 30900. The spectrum measurement conditions are as follows.
<Measurement conditions>
Apparatus: UV-2450 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-450 nm
Solvent: Chloroform Concentration: 10 ppm
Cell: 1 cm quartz In addition, the following compounds (b), (c), and (d) were also measured for ultraviolet to visible absorption spectra under the same measurement conditions as for the compound (a).

Further, as a result of conducting NMR analysis of the compound (a), a result supporting the above structure was obtained. The measurement conditions are as follows.
<Measurement conditions>
Device: JEOL AL-300
Resonant frequency: 300 MHz (1H-NMR)
Solvent: chloroform-d
Tetramethylsilane was used as an internal standard of 1H-NMR, the chemical shift value was represented by δ value (ppm), and the coupling constant was represented by Hertz. S is a singlet, d is a doublet, t is a triplet, dd is a double doublet, m is a multiplet, and b is abbreviated. The same applies to the following compounds (b), (c), and (d). The contents of the obtained NMR spectrum are as follows.
δ = 11.3 (s, OH), 8.19 (d, 1H, J = 9.9 Hz, benzotriazole-H), 7.78 (dd, 1H, J = 9.92 Hz, J = 0.96 Hz, J = 0.87 Hz, benzotriazole-H), 7.0-7.3 (m, 2H, benzotriazole-H, phenol-H), 6.67 (d, 1H, J = 2.91 Hz, phenol-H) 6.59 (dd, 1H, J = 10.2 Hz, J = 2.94 Hz, J = 3.06 Hz, = CH ₂ -H), 6.17 (s, 1H, phenol-H), 5.61. (T, 1H, ═CH ₂ —H), 4.57 (t, 2H, O—CH ₂ —CH ₂ —O—H), 4.32 (t, 2H, O—CH ₂ —CH ₂ —O) -H), 4.00 (t, 2H , pH-O-CH 2 -H), 1.8 _{(M, 2H, CH 2 -H} ), 1.2-1.6 (m, 10H, (CH 2) 5-H), 0.89 (s, 3H, CH 3 -H)

化合物（ｂ） (Intermediate Synthesis Example 3)
[Compound (b); Synthesis of 2- [2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazol-5-yloxy] ethyl acrylate]

Compound (b)

  Compound (b) was obtained in the same manner as in Intermediate Synthesis Example 2 except that methacrylic acid was acrylic acid, and the yield of compound (b) was 43% (2- [5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl]. -5-octyloxyphenol). The absorbance ε was 29,700 when the melting point was 86 ° C., the HPLC surface purity was 98.7%, and the maximum absorption wavelength λmax was 351 nm.

Further, as a result of conducting NMR analysis of the compound (b), a result supporting the above structure was obtained. The measurement conditions are as follows.
<Measurement conditions>
Equipment: VARIAN Mercury300
Resonant frequency: 300 MHz (1H-NMR)
Solvent: chloroform-d
The contents of the obtained NMR spectrum are as follows. The following compounds (c) and (d) were subjected to NMR measurement under the same measurement conditions as for the compound (b).
δ = 11.3 (b, OH), 8.21 (d, 1H, J = 9.07 Hz, benzotriazole-H), 7.79 (d, 1H, J = 9.07 Hz, benzotriazole-H), 7 .18 (d, 1H, J = 2.3 Hz, phenol-H), 7.16 (d, 1H, J = 2.3 Hz, phenol-H), 7.15 (d, 1H, J = 1.81) , benzotriazole-H,), 6.67 (s, 1H, phenol-H), 6.60 (m, 1H, = CH 2 -H), 6.20 (q, 1H, CH = -H), 5 .89 (dd, 1H, J = 10.5 Hz, J = 0.66 Hz, J = 0.75 Hz, = CH ₂ —H), 4.32 (t, 2H, O—CH ₂ —CH ₂ —O—) _{H), 4.00 (t, 2H} , O-CH 2 -CH 2 -O-H), 0.8 2 (m, 17H, n-C8H17-H)

化合物（ｃ） (Intermediate Synthesis Example 4)
[Compound (c); Synthesis of 2- [2- (4-butoxy-2-hydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl methacrylate]

Compound (c)

  A 200 ml four-necked flask was equipped with a condenser with a ball, a thermometer, and a stirring device, and 17.0 g (0.066) of 4- (5-methoxy-2H-benzotriazol-2-yl) benzene-1,3-diol was added. Mol), 35 ml of methyl isobutyl ketone, 9.2 g (0.067 mol) of 1-bromobutane, 5.6 g (0.053 mol) of sodium carbonate, and 4.9 g of potassium iodide, and refluxed at 105 to 115 ° C. for 4 hours. Stir. 35 ml of water was added, and the mixture was allowed to stand to separate and remove the lower aqueous layer, followed by washing with 35 ml of warm water. After recovering 35 ml of methyl isobutyl ketone under reduced pressure, 100 ml of isopropyl alcohol was added, and the precipitated crystals were filtered, washed with 20 ml of isopropyl alcohol, dried, and 5-butoxy-2- (5-methoxy-2H-benzotriazole-2 -Yl) 15.0 g of phenol was obtained.

  A 500 ml four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirring device, and 15.0 g (0.048 mol) of 5-butoxy-2- (5-methoxy-2H-benzotriazol-2-yl) phenol 47% hydrobromic acid (9.9 g, 0.058 mol) and sulfolane (145 ml) were added, and the mixture was stirred at 100 to 105 ° C. for 48 hours. 70 ml of toluene and 200 ml of water were added and left standing to separate and remove the lower aqueous layer, washed twice with 100 ml of warm water, and 70 ml of toluene was recovered under reduced pressure. 30 ml of isopropyl alcohol and 15 ml of water were added and cooled to 5 ° C., and the precipitated crystals were filtered, washed with 20 ml of aqueous isopropyl alcohol (70% V / V), dried, and 5-butoxy-2- (5 6.2 g of -hydroxy-2H-benzotriazol-2-yl) phenol was obtained.

  A 200 ml four-necked flask was equipped with a ball condenser, thermometer, and stirring device, and 6.2 g (0.021 mol) of 5-butoxy-2- (5-hydroxy-2H-benzotriazol-2-yl) phenol was attached. , 50 ml of methyl isobutyl ketone, 7.4 g (0.092 mol) of 2-chloroethanol, 4.9 g (0.046 mol) of sodium carbonate, and 0.2 g of potassium iodide, and refluxed at 113 to 118 ° C. for 10 hours. did. 50 ml of water was added, the mixture was allowed to stand, and the lower aqueous layer was separated and removed, followed by washing with 50 ml of warm water. After recovering 50 ml of methyl isobutyl ketone under reduced pressure, 25 ml of isopropyl alcohol is added and cooled to 5 ° C., and the precipitated crystals are filtered, washed with 15 ml of isopropyl alcohol and dried to give 5-butoxy-2- (5- (2 3.4 g of -hydroxyethoxy) -2H-benzotriazol-2-yl) phenol was obtained.

  A 200 ml four-necked flask was equipped with a ball condenser, a thermometer, and a stirring device, and 3.4 g of 5-butoxy-2- (5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl) phenol ( 0.010 mol), toluene 40 ml, methacrylic acid 1.7 g (0.020 mol), and methanesulfonic acid 0.2 g (0.002 mol) were added and reflux dehydrated at 110-115 ° C. for 4 hours. 30 ml of water and 0.7 g (0.007 mol) of sodium carbonate were added and left standing to separate and remove the lower aqueous layer, 0.1 g of activated carbon was added, and the mixture was stirred under reflux to decolorize. Filtration was performed while hot, and 40 ml of toluene was collected from the filtrate under reduced pressure, 30 ml of isopropyl alcohol was added, the precipitated crystals were filtered, washed with 15 ml of isopropyl alcohol, and then dried at 40 ° C. under reduced pressure to give 2. 7 g was obtained. 2.7 g of this was recrystallized from isopropyl alcohol and dried at 40 ° C. under reduced pressure to obtain 2.2 g of compound (c). The yield was 8% (from 4- (5-methoxy-2H-benzotriazol-2-yl) benzene-1,3-diol). When the melting point was 101 ° C. and the maximum absorption wavelength λmax was 351 nm, the absorbance ε was 29100.

Moreover, the purity of the compound (c) was measured by HPLC analysis.
<Measurement conditions>
Device: L-2130 (manufactured by Hitachi High-Technologies Corporation)
Column used: Inertsil ODS-3 4.6 × 150 mm 5 μm
Column temperature: 25 ° C
Mobile phase: acetonitrile / water = 9/1 (phosphoric acid 3 ml / L)
Flow rate: 1.0 ml / min
<Measurement results>
HPLC area purity: 98.7%
The following compound (d) was also subjected to HPLC measurement under the same measurement conditions as for compound (c).

Further, as a result of conducting NMR analysis of the compound (c), a result supporting the above structure was obtained. The contents of the obtained NMR spectrum are as follows.
δ = 11.3 (b, OH), 8.21 (d, 1H, J = 9.24 Hz, benzotriazole-H), 7.80 (dd, 1H, J = 9.1 Hz, J = 0.66 Hz, J = 0.66 Hz, benzotriazole-H), 7.18 (d, 1H, J = 2.31 Hz, phenol-H), 6.68 (d, 1H, J = 2.64 Hz, phenol-H), 6 .60 (dd, 1H, J = 9.2 Hz, J = 2.64 Hz, J = 2.64 Hz, benzotriazole-H,), 6.18 (s, 1H, ═CH ₂ —H), 5.62 ( _{m, 1H, = CH 2 -H} ), 0.9-2.1 (m, 3H, 9H, CH 3, n-C4H9-H)

化合物（ｄ） (Intermediate Synthesis Example 5)
[Compound (d); Synthesis of 2- [2- (4-Ethoxy-2-hydroxyphenyl) -2H-benzotriazol-5-yloxy] ethyl methacrylate]

Compound (d)

  A 200 ml four-necked flask was equipped with a condenser with a ball, a thermometer, and a stirring device, and 10.0 g (0.039) of 4- (5-methoxy-2H-benzotriazol-2-yl) benzene-1,3-diol was attached. Mol), 40 ml of methyl isobutyl ketone, 6.4 g (0.059 mol) of bromoethane, 3.3 g (0.031 mol) of sodium carbonate, and 3.0 g of potassium iodide, and the mixture was refluxed and stirred at 95 to 110 ° C. for 6 hours. . 20 ml of water was added, the mixture was allowed to stand, and the lower aqueous layer was separated and removed, and washed with 20 ml of warm water. After recovering 40 ml of methyl isobutyl ketone under reduced pressure, 100 ml of isopropyl alcohol is added, and the precipitated crystals are filtered, washed with 25 ml of isopropyl alcohol, dried, and 5-ethoxy-2- (5-methoxy-2H-benzotriazole-2 -Yl) 8.2 g of phenol was obtained.

  A 500 ml four-necked flask was equipped with a condenser with a ball, a thermometer, and a stirring device, and 8.2 g (0.029 mol) of 5-ethoxy-2- (5-methoxy-2H-benzotriazol-2-yl) phenol was attached. 47% hydrobromic acid (6.2 g, 0.036 mol) and sulfolane (82 ml) were added and stirred at 100 to 105 ° C. for 33 hours. Toluene (50 ml) and water (165 ml) were added and allowed to stand to separate and remove the lower aqueous layer, washed with warm water (80 ml), and toluene (50 ml) was recovered under reduced pressure. Add 35 ml of isopropyl alcohol and 15 ml of water, cool to 5 ° C., filter the precipitated crystals, wash with 20 ml of an aqueous isopropyl alcohol solution (70% V / V), dry and dry 5-ethoxy-2- (5 4.6 g of -hydroxy-2H-benzotriazol-2-yl) phenol was obtained.

  A 200 ml four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirring device, and 4.6 g (0.017 mol) of 5-ethoxy-2- (5-hydroxy-2H-benzotriazol-2-yl) phenol is attached. , 35 ml of methyl isobutyl ketone, 1.7 g (0.021 mol) of 2-chloroethanol, 1.1 g (0.010 mol) of sodium carbonate and 0.9 g of potassium iodide, and refluxed at 113 to 118 ° C. for 8 hours. Dehydrated. 30 ml of water was added, the mixture was allowed to stand, and the lower aqueous layer was separated and removed, followed by washing with 30 ml of warm water. 35 ml of methyl isobutyl ketone was recovered under reduced pressure to obtain 5.0 g of a solid content of 5-ethoxy-2- [5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl] phenol.

  A 300 ml four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirrer, and the solid content of 5-ethoxy-2- [5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl] phenol is 5 0.0 g (0.016 mol), 100 ml of toluene, 2.7 g (0.031 mol) of methacrylic acid, and 2.0 g (0.021 mol) of methanesulfonic acid were added and dehydrated at 110 to 115 ° C. for 4 hours. . 80 ml of water and 1.9 g (0.018 mol) of sodium carbonate were added and left standing to separate and remove the lower aqueous layer, 0.1 g of activated carbon was added, and the mixture was stirred and refluxed to decolorize. After hot filtration, 100 ml of toluene was recovered from the filtrate under reduced pressure, 30 ml of isopropyl alcohol was added, the precipitated crystals were filtered, washed with 20 ml of isopropyl alcohol, and then dried at 40 ° C. under reduced pressure to obtain white crystals. 2 g was obtained. 3.2 g of this was recrystallized from isopropyl alcohol and dried at 40 ° C. under reduced pressure to obtain 1.6 g of compound (d). The yield was 11% (from 4- (5-methoxy-2H-benzotriazol-2-yl) benzene-1,3-diol). The absorbance ε was 29000 when the melting point was 156 ° C., the HPLC area purity was 98.1%, and the maximum absorption wavelength λmax was 350 nm.

Further, as a result of conducting NMR analysis of the compound (d), a result supporting the above structure was obtained. The contents of the obtained NMR spectrum are as follows.
δ = 11.3 (b, OH), 8.21 (d, 1H, J = 9.07 Hz, benzotriazole-H), 7.79 (d, 1H, J = 9.72, benzotriazole-H), 7 .16 (m, 1H, phenol-H), 6.68 (d, 1H, J = 2.64 Hz, phenol-H), 6.59 (dd, 1H, J = 9.2, J = 2.8) _{, J = 2.64, phenol-H} ,), 6.17 (s, 1H, C = CH 2 -H), 5.61 (t, 1H, = CH 2 -H), 4.58 (m, 2H, O—CH ₂ —CH ₂ —O—H), 4.32 (t, 2H, O—CH ₂ —CH ₂ —O—H), 4.08 (q, 2H, —CH ₂ —CH _{3). -H), 1.67 (s, 3H} , C = CH 2 -CH 3 -H), 1.57 (t, 3H, CH 2 -CH 3 -H)

(Example 1)
[Copolymer (a); Copolymerization of Compound (a) / 1,2-Polybutadiene]
In a 100-ml glass tube, 1.87 g (0.004 mol) of compound (a); 2- [2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazol-5-yloxy] ethyl methacrylate, After 20 ml of benzene, 1.30 g (0.024 mol) of 1,2-polybutadiene (“Product No. 466867-250 ML” manufactured by Aldrich) and 0.097 g (0.0004 mol) of benzoyl peroxide were freeze-dried. Sealed. The glass tube was placed in a 90 ° C. oil bath and polymerized for 24 hours. The polymerization solution was transferred to a 100 ml flask, and benzene was distilled off with an evaporator. Thereto was added 10 ml of chloroform to dissolve the product, and the solution was dropped into 200 ml of acetone. The precipitated polymer was filtered, washed with 100 ml of acetone, and then dried at room temperature under reduced pressure to obtain 1.90 g of a pale yellow solid copolymer (a).

As a result of measuring the molecular weight of the copolymer (a), the weight average molecular weight (Mw) was 28800, the number average molecular weight (Mn) was 14600, and the polydispersity (Mw / Mn) was 1.97. The measurement conditions are as follows.
<Measurement conditions>
Apparatus: LC-10AD (manufactured by Shimadzu Corporation)
Eluent: Chloroform Column: Shodex K-807L, Shodex K805L, Shodex K-804L (manufactured by Showa Denko KK)

Further, when the ultraviolet to visible absorption spectrum of the copolymer (a) was measured, the maximum absorption wavelength λmax was 348.4 nm. The spectrum is shown in FIG. The spectrum measurement conditions are as follows.
<Measurement conditions>
Apparatus: UV-1850 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-450 nm
Solvent: Chloroform Concentration: 10 ppm
Cell: 1cm quartz

Moreover, as a result of measuring the infrared absorption spectrum of the copolymer (a), absorption peaks peculiar to the compound (a) and the vinyl group were observed, which supported that the target product was obtained. The obtained infrared absorption spectrum is shown in FIG. The measurement conditions are as follows. In addition, Example 2 below also performed infrared absorption spectrum measurement under the same measurement conditions as in this example.
<Measurement conditions>
Equipment: Nicolet iS5, Thermo Fisher
Sample: Polymer thin film (ATR method)

(Example 2)
[Copolymer (b); Copolymerization of Compound (a) / 1,2-Vinyl Structure, Cis-1,4 Structure and Trans-1,4 Structure Mixed Polybutadiene]
In a 100 ml glass tube, 2.81 g (0.006 mol) of compound (a); 2- [2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazol-5-yloxy] ethyl methacrylate, 2.17 g (0.040 mol) of mixed polybutadiene having 20 ml of benzene, 9% of 1,2-vinyl structure, 36% of cis-1,4 structure and 55% of trans-1,4 structure (product number 181382, manufactured by Aldrich) −100G ”), 0.097 g (0.0004 mol) of benzoyl peroxide was added, freeze-dried, and sealed. The glass tube was placed in a 90 ° C. oil bath and polymerized for 24 hours. The polymerization solution was transferred to a 100 ml flask, and benzene was distilled off with an evaporator. Thereto was added 10 ml of chloroform to dissolve the product, and the solution was dropped into 200 ml of acetone. The precipitated polymer was filtered, washed with 100 ml of acetone, and then dried at room temperature under reduced pressure to obtain 2.80 g of a light yellow solid copolymer (b). As a result of measuring the infrared absorption spectrum of the copolymer (b), absorption peaks peculiar to the compound (a) and the vinyl group were observed, which supported that the desired product was obtained. The obtained infrared absorption spectrum is shown in FIG.

[Measurement of heat resistance]
The copolymer (a) obtained in Example 1 and a compound (e) which is a conventional general ultraviolet absorber as a comparative example; 2- (2H-benzotriazol-2-yl] -4-methylphenol Table 1 shows the results of measuring the heat resistance of the samples using a differential thermothermal gravimetric simultaneous measurement apparatus.

[Preparation of UV absorbing film]
The copolymer (a) obtained in Example 1 or the compound (e) of Comparative Example, polystyrene, polycarbonate, or polymethyl methacrylate and dichloromethane were mixed in the ratio shown in Table 2, and an ultraviolet absorber was added. A resin composition solution was obtained. Transfer 20 ml of the obtained resin composition solution containing an ultraviolet absorber to a petri dish having a diameter of 12 cm, remove the solvent by drying at 25 ° C. for 48 hours, and drying at 25 ° C. for 3 hours. Then, an ultraviolet absorbing film containing 1% of an ultraviolet absorber having a film thickness of 20 μm was obtained.

[Glossiness measurement]
Table 3 shows the glossiness of the surface of the ultraviolet absorbing film obtained above. When the compatibility between the resin material and the ultraviolet absorber is insufficient, the ultraviolet absorber bleeds out to the film surface, and thus the surface of the film becomes rough and the glossiness is lowered. Therefore, it becomes a compatibility index between the resin material and the ultraviolet absorber.

  From Table 1, the copolymer (a) which is the benzotriazole copolymer of the present invention has a 5% weight loss temperature higher than that of the compound (e) which is a conventional general ultraviolet absorber, It can be seen that there is a high heat resistance that prevents volatilization and decomposition. Further, from Table 3, the ultraviolet absorbing film to which the copolymer (a) which is the benzotriazole copolymer of the present invention is added is an ultraviolet absorbing material to which the compound (e) which is a conventional general ultraviolet absorber is added. The film shows the same or superior glossiness with various resin materials, which indicates that various resins have a property that bleed-out hardly occurs, and that it is a useful ultraviolet absorber. In addition, the measurement conditions of heat resistance and glossiness are as follows.

<Heat resistance measurement conditions>
Apparatus: TG / DTA6300 (manufactured by Seiko Instruments Inc.)
Measurement temperature: 60-500 ° C
Temperature increase rate: 10 ° C / min Measurement atmosphere: Nitrogen

<Glossiness measurement conditions>
Equipment: UNI GLOSS 60 (Konica Minolta Sensing Co., Ltd.)
Measurement angle: 60 ° C

  The benzotriazole-based copolymer of the present invention has a UV-absorbing structure incorporated as a polymer component, so there is no volatilization or decomposition of the UV-absorbing component during resin processing, and with other resins. Because of its high compatibility, bleeding out does not occur even when added to other resins, and it can be suitably used as an ultraviolet absorber for resins. In particular, it can be suitably used for resins having a high processing temperature.

It is an ultraviolet-visible absorption spectrum of a copolymer (a). It is an infrared absorption spectrum of a copolymer (a). It is an infrared absorption spectrum of a copolymer (b).

Claims (4)

A benzotriazole derivative compound represented by the following general formula (1);
The skeleton is constituted by the structural unit represented by the following general formula (2) or the following general formula (3) and polymerized with polybutadiene containing at least one of the above general formula (2) as the structural unit. A benzotriazole copolymer characterized by

General formula (1)
[Wherein, R ₁ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a tolyl group, a formyl group, an alkylcarbonyl group of an alkyl having 1 to 7 carbon atoms, a benzoyl group or a toluoyl group,, R ₂ Represents an alkylene group having 1 to 8 carbon atoms, and R ₃ represents a hydrogen atom or a methyl group]

General formula (2)

General formula (3)
[The carbon-carbon double bond in the general formula (3) may be either a cis structure or a trans structure. ] The benzotriazole derivative compound of the general formula (1), wherein R ₁ is an alkyl group having 2 to 8 carbon atoms and R ₂ is an ethylene group in the general formula (1). Copolymer.   The ultraviolet absorber containing the benzotriazole type copolymer of Claim 1 or Claim 2.   An ultraviolet-absorbing resin composition in which the benzotriazole copolymer according to claim 1 or 2 is blended with a resin.

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