JP7362049B2 - Benzotriazole copolymer and ultraviolet absorber using the same - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Act 2018 Hokuriku Area Polymer Young Research Group (Kureha Heights) Presented on November 16, 2018 67th Society of Polymer Science Hokuriku Branch Research Presentation Abstracts Volume 67, Page 22 Published on November 17, 2018 67th Hokuriku Branch Research Presentation of the Society of Polymer Science (Gofuku Campus, University of Toyama) Published on November 17, 2018

The present invention relates to a novel benzotriazole copolymer, and further relates to an ultraviolet absorbent containing the same. More specifically, it relates to an ultraviolet absorber that absorbs the entire ultraviolet region, exhibits high solubility in hydrophilic cosmetic base materials and organic materials, has a weakly acidic to neutral aqueous solution, and does not cause hydrolysis.

The ultraviolet rays contained in sunlight are divided into UV-A region (320-400 nm), UV-B region (290-320 nm), and UV-C region (290 nm), but UV-A region (320-400 nm) Ultraviolet rays in the UV-B region (290 to 320 nm) have various effects on the skin. The UV-A region is said to cause darkening of the skin and affect blood vessels and skin tissue, while the UV-B region is known to cause erythema and blistering, increased melanin formation, and pigmentation. In order to prevent the harmful effects of light on the skin, various UV absorbers have traditionally been added to cosmetics, such as benzoic acid-based, cinnamic acid-based, benzophenone-based, dibenzoylmethane-based, and salicylic acid-based. Compounds such as are used.

Furthermore, it is well known that organic materials deteriorate due to the action of ultraviolet rays from sunlight, causing phenomena such as decomposition and discoloration. In order to prevent such deterioration due to light, various ultraviolet absorbers have traditionally been added to organic materials, such as benzophenone-based, benzotriazole-based, benzoate-based, salicylate-based, triazine-based compounds, etc. There is.

However, since these ultraviolet absorbers are generally hydrophobic, it has been difficult to use them in hydrophilic cosmetics or organic materials. In addition to the desire to incorporate UV absorbers into hydrophilic cosmetics, it is also desirable to incorporate UV absorbers into water-based inks, water-based paints, deodorants, fragrances, hair care products, body care products, etc. that use hydrophilic organic materials. Use is desired.

Currently used hydrophilic ultraviolet absorbers include 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate (trade name: SEESORB (registered trademark) 101S, which is a benzophenone compound with a sulfo group introduced into it). ”, manufactured by Shipro Kasei Co., Ltd.). By introducing a sulfo group, which is a hydrophilic substituent, a benzophenone compound can be made hydrophilic. However, the pH of the aqueous solution is strongly acidic due to the influence of the sulfo group, and the applications in which it can be used are limited. In Patent Documents 1 and 2, sugar chains are introduced into cinnamic acid compounds to impart hydrophilicity, but since cinnamic acid compounds mainly absorb the UV-B region, they do not absorb the entire ultraviolet region. To absorb UV rays, it is necessary to use them in combination with other UV absorbers. In Patent Document 3, a hydrophilic ultraviolet absorber is realized by introducing a polyethylene glycol derivative compound capable of imparting hydrophilicity to a benzotriazole compound through an ester bond, but the present inventor actually synthesized it. When stored in an aqueous solution, it was found that the ester bonds were gradually hydrolyzed and decomposed products were precipitated.

Japanese Patent Application Publication No. 9-263596 Japanese Patent Application Publication No. 9-268194 JP2014-37352

Under these circumstances, the objective of the present invention is to absorb the entire ultraviolet region and exhibit high solubility in hydrophilic cosmetic base materials and organic materials, while the aqueous solution is not strongly acidic and does not cause hydrolysis. The objective is to provide new compounds.

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］

一般式（２）
［式中、ｎは２以上の整数を表す］ In the present invention, a benzotriazole-based copolymer obtained by copolymerizing a benzotriazole derivative compound represented by the following general formula (1) and a polyethylene glycol derivative compound containing the following general formula (2) as a constituent unit is exposed to ultraviolet light. The main solution to the above problem is to use it as an absorbent.

General formula (1)
[In the formula, 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 having 1 to 7 carbon atoms, a benzoyl group, or a toluoyl group, and 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)
[In the formula, n represents an integer of 2 or more]

The benzotriazole copolymer of the present invention absorbs the entire ultraviolet region, exhibits high solubility in hydrophilic cosmetic base materials and organic materials, has a weakly acidic to neutral aqueous solution, and is resistant to hydrolysis. Since it does not cause UV rays, it is useful as an ultraviolet absorber that can solve the problems of the prior art.

This is an ultraviolet to visible absorption spectrum of copolymer (a). This is an ultraviolet to visible absorption spectrum of copolymer (b). This is an ultraviolet to visible absorption spectrum of copolymer (c). It is an NMR spectrum of copolymer (a). It is an NMR spectrum of copolymer (b). It is an NMR spectrum of copolymer (c).

一般式（１） The present invention will be explained in detail below. The present invention uses a benzotriazole derivative compound represented by the following general formula (1) and a polyethylene glycol derivative compound containing the following general formula (2) as a constituent unit as an ultraviolet absorber. It uses merging. Compounds represented by general formula (1) and polyethylene glycol derivatives containing general formula (2) as constituent units will be explained below.

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 Straight chain or branched alkyl groups having 1 to 8 carbon atoms such as phenyl groups; tolyl groups; formyl groups; alkyl groups such as acetyl groups, propionyl groups, butyryl groups, isobutyryl groups, octanoyl groups, 2-ethylhexanoyl groups, etc. Straight chain or branched alkylcarbonyl group having 1 to 7 carbon atoms; benzoyl group; toluoyl group; _R2 is methylene group, ethylene group, triethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group; Examples include straight chain or branched alkylene groups having 1 to 8 carbon atoms such as groups, and R ₃ is a hydrogen atom; examples include a methyl group.

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

Examples of the benzotriazole derivative compound of 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-yloxy]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-benzotriazole-5 -yloxy]ethyl acrylate, 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-octyloxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate, 2-[2-(4-benzoyl) oxy-2-hydroxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate and the like.

Among the compounds exemplified here, 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-octyloxyphenyl)-2H-benzotriazol-5-yloxy]ethyl acrylate is preferably used.

There is no particular limitation on the method for synthesizing the benzotriazole derivative compound general formula (1), and conventionally known reaction principles can be widely used. be able to. However, X represents a halogen atom.

一般式（２）
［式中、ｎは２以上の整数を表す］

General formula (2)
[In the formula, n represents an integer of 2 or more]

Specific examples of polyethylene glycol derivative compounds having general formula (2) as a constituent unit include polyethylene glycol, monomethoxypolyethylene glycol, methoxypolyethylene glycol methacrylate, octoxypolyethylene glycol methacrylate, lauroxypolyethylene glycol methacrylate, stearoxypolyethylene Glycol methacrylate, phenoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylate, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, 4,4'-azobis(4-cyanopentanoic acid) polyethylene glycol polymer, 4,4'-azobis(4-methyl) (pentanoic acid) polyethylene glycol polymer, etc.

The polymerization method for obtaining a copolymer of general formula (1) and a polyethylene glycol derivative compound containing general formula (2) as a constituent unit is not particularly limited, and various conventionally known polymerization methods may be used, such as , radical polymerization, solution polymerization method using chain polymerization reaction by ionic polymerization, bulk polymerization method, suspension (pearl) polymerization method, living polymerization method, photopolymerization method, etc. can be employed.

Specifically, examples of solvents that can be used when obtaining a copolymer by employing a solution polymerization method include benzene, toluene, xylene, and other high-boiling aromatic solvents; ethyl acetate, butyl acetate. , ester solvents such as cellosolve acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, and 2-propanol, but are not particularly limited. These solvents may be used alone or in an appropriate mixture of two or more. Furthermore, the amount of solvent used is not particularly limited.

Dispersants that can be used when obtaining a copolymer by employing a suspension (pearl) polymerization method include, for example, polyvinyl alcohol, poly(meth)acrylic acid or its salt, styrene and maleic acid. Salts of acid copolymers, salts of α-methylstyrene and acrylic acid copolymers, polyvinylpyrrolidone, poly(meth)acrylamide, methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, carboxymethylcellulose, Polymer surfactants such as gelatin, starch, tragacanth, pectin, glue, alginic acid or its salts; polyoxyalkylene dispersants such as polyethylene oxide and polypropylene oxide; polyoxyethylene-alkyl ether, polyoxyethylene-alkylphenol, Examples include nonionic surfactants such as oxyethylene-polyhydric alcohol esters, esters of polyhydric alcohols and fatty acids, and oxyethylene-oxypropylene block condensates. Further, these dispersants may be used alone or in a suitable mixture of two or more types. Further, the amount of the dispersant used is not particularly limited.

Further, when obtaining a copolymer 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, and 1,1'-azobis(cyclohexane- 1-carbonitrile), benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxy-2-ethylhexanoate, etc.; 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-methylpropionamidine] 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), 4,4-azobis Water-soluble radical polymerization initiators such as (4-cyanopentanoic acid); Polymerization initiators for persulfates and organic peroxides include sodium sulfoxylate formaldehyde, sodium bisulfite, ammonium bisulfite, sodium thiosulfate, thiosulfate, etc. A redox initiator using a polymerization initiator in combination with a reducing agent such as ammonium sulfate, hydrogen peroxide, sodium hydroxymethanesulfinate, L-ascorbic acid, and its salts, cuprous salts, ferrous salts; benzophenone, N , N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio) Aromatic aromas such as phenyl]-2-morpholino-propanone-1,4,4'-bis(dimethylamino)benzophenone (Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. group ketones, quinones such as alkylanthraquinone 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 benzyl dimethyl ketal, 2-(o-chlorophenyl )-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4 -dimethoxyphenyl)-2,4,5-triarylimidazole dimers such as -4,5-diphenylimidazole dimers, N-phenylglycine, N-phenylglycine derivatives, acridine derivatives such as 9-phenylacridine, 1 , 2-octanedione, oxime esters such as 1-[4-(phenylthio)-, 2-(o-benzoyloxime)], coumarin compounds such as 7-diethylamino-4-methylcoumarin, 2,4-diethyl Photo (mainly ultraviolet) cleavage type radical polymerization initiators such as thioxanthone compounds such as thioxanthone, acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; organolithium, sodium compounds, Grignard reagents, Examples include anionic polymerization initiators such as sodium hydroxide, potassium hydroxide, sodium alkoxide, alcohol/tributylphosphine, and amines, but are not particularly limited. Further, these polymerization initiators may be used alone or in an appropriate mixture of two or more types. Moreover, the amount of the polymerization initiator used is not particularly limited.

Further, when a copolymer is obtained by employing a solution polymerization method, a bulk polymerization method, or a suspension polymerization method, a polyethylene glycol derivative compound having a function of a polymerization initiator can be used. Specific examples include 4,4'-azobis(4-cyanopentanoic acid) polyethylene glycol polymer, 4,4'-azobis(4-methylpentanoic acid) polyethylene glycol polymer, etc., but there are no particular limitations. isn't it. Furthermore, these polyethylene glycol derivative compounds having the function of a polymerization initiator may be used alone, or two or more types may be appropriately mixed and used. Moreover, the amount used is not particularly limited.

The reaction temperature is not particularly limited, but is preferably in the range of room temperature to 200°C, more preferably in the range of 50°C to 150°C. The reaction time may be appropriately set depending on the reaction temperature, the type of raw materials used, etc. so that the polymerization reaction is completed.

As the photopolymerization initiator used in obtaining a copolymer by employing a photopolymerization method, any known photopolymerization initiator that exhibits a photopolymerization initiation action upon irradiation with active energy rays can be used. For example, 2,2-dimethoxy-1,2-diphenylethan-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-benzyl)-1-(4-morpholin-4-yl -phenyl)-butan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc., and benzophenone and/or 2-isopropylthioxanthone and the polymerization accelerator 2- Combinations such as 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.

Hydrophilic cosmetic bases to which the benzotriazole copolymer of the present invention can be added are not particularly limited, but examples include glycerin, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, propanediol 1 , 2-hexanediol, 1,2-octanediol, xylitol, xylitol, lanolin, dipentaerythritol fatty acid ester, ethanol, purified water and the like.

Hydrophilic organic materials to which the benzotriazole copolymer of the present invention can be added are not particularly limited, but examples include organic solvents such as tetrahydrofuran, acetone, dimethylformamide, dimethyl sulfoxide, ethanol, and methanol, and polymethacrylic acid. Hydrophilic polymers such as salt, polyacrylate, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, polypropylene glycol, xanthan gum, guar gum, hydroxyethyl cellulose, carboxymethyl cellulose, and the like.

When the benzotriazole copolymer of the present invention is added to a hydrophilic cosmetic base or hydrophilic organic material, the benzotriazole copolymer of the present invention may be used alone as a UV absorber, or in combination with other UV absorbers. Can be used. 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 in the ultraviolet region. For example, benzotriazole derivatives, benzophenone derivatives, salicylate derivatives, cyanoacrylate derivatives, triazine derivatives, cinnamic acid derivatives, etc. are used. These ultraviolet absorbers may be used alone or in an appropriate mixture of two or more.

The benzotriazole copolymer of the present invention can be used by being dissolved in a hydrophilic cosmetic base or a hydrophilic organic material. The dissolution rate in the hydrophilic cosmetic base or hydrophilic organic material is not particularly limited, but it is preferably used in the range of 0.01 to 20% by weight.

The synthesis method and properties of the benzotriazole copolymer carried out in the present invention are shown below. However, the synthesis method for obtaining the copolymer of the present invention is not limited to the embodiments.

(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 beaded condenser, a thermometer, and a stirring device, and 176 ml of 4-(5-methoxy-2H-benzotriazol-2-yl)benzene-1,3-diol synthesized by a conventional method was added. .0 g (0.684 mol), 350 ml of methyl isobutyl ketone, 142.0 g (0.955 mol) of 1-chlorooctane, 62.0 g (0.585 mol) of sodium carbonate, and 5.2 g of potassium iodide. The mixture was dehydrated under reflux at 120 to 130°C for 12 hours. 200 ml of water was added, left to stand, and the lower aqueous layer was separated and removed, and washed with 200 ml of warm water. 350 ml of methyl isobutyl ketone was collected under reduced pressure, 450 ml of isopropyl alcohol was added, and 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 10 L four-necked flask was equipped with a beaded condenser, a thermometer, and a stirring device, and 216.9 g (0.587 mol) of 2-(5-methoxy-2H-benzotriazol-2-yl)-5-octyloxyphenol was added. ), 125.8 g (0.731 mol) of 47% hydrobromic acid, and 1800 ml of sulfolane were added and stirred at 100 to 105° C. for 48 hours. 800 ml of toluene and 3500 ml of water were added, the mixture was allowed to stand, and the lower aqueous layer was separated and removed, washed twice with 1300 ml of warm water, and 800 ml of toluene was recovered 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 isopropyl alcohol aqueous solution (80% V/V), dry, and obtain 2-(5-hydroxy-2H). 126.6 g of -benzotriazol-2-yl)-5-octyloxyphenol was obtained.

A 1000 ml four-necked flask was equipped with a beaded condenser, a thermometer, and a stirring device, and 126.6 g (0.356 mol) of 2-(5-hydroxy-2H-benzotriazol-2-yl)-5-octyloxyphenol was added. ), 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 heated at 113 to 118°C for 10 hours. Reflux dehydration was performed. 250 ml of water was added and left to stand, the lower aqueous layer was separated and removed, and washed 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. The precipitated crystals were filtered, washed with 50 ml of isopropyl alcohol, and dried to obtain 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 was equipped with a beaded condenser, a thermometer, and a stirring device, and 95.3 g of 2-[5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl]-5-octyloxyphenol was added. (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 and dehydrated under reflux at 110 to 115°C for 4 hours. 200 ml of water and 32.8 g (0.309 mol) of sodium carbonate were added, the mixture was allowed to stand, and the lower aqueous layer was separated and removed. 1.8 g of activated carbon was added, and the mixture was decolorized by stirring under reflux. Filter while hot, collect 550 ml of toluene from the filtrate under reduced pressure, add 750 ml of isopropyl alcohol, filter the precipitated crystals, wash with 100 ml of isopropyl alcohol, dry under reduced pressure at 40°C, and collect white crystals at 88° C. .1g 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℃.

Further, the purity of compound (a) was measured by HPLC analysis.
<Measurement conditions>
Equipment: L-2130 (manufactured by Hitachi High-Technologies Corporation)
Column used: SUMIPAX ODS A-212 6 x 150mm 5μm
Column temperature: 40℃
Mobile phase: methanol/water = 99/1
Flow rate: 1.0ml/min
<Measurement results>
HPLC surface purity: 99.9%
Note that 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 compound (a) was measured, the maximum absorption wavelength λmax was 350 nm, and the absorbance ε at this time was 30,900. The spectrum measurement conditions are as follows.
<Measurement conditions>
Equipment: UV-2450 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-450nm
Solvent: Chloroform Concentration: 10ppm
Cell: 1 cm quartz Note that the ultraviolet to visible absorption spectra of the following compounds (b), (c), and (d) were also measured under the same measurement conditions as for compound (a).

Further, as a result of NMR analysis of compound (a), results supporting the above structure were obtained. The measurement conditions are as follows.
<Measurement conditions>
Equipment: JEOL AL-300
Resonance frequency: 300MHz (1H-NMR)
Solvent: chloroform-d
Tetramethylsilane was used as an internal standard substance for 1H-NMR, the chemical shift value was expressed in δ value (ppm), and the coupling constant was expressed in Hertz. Further, s stands for singlet, d stands for double, t stands for triplet, dd stands for double, m stands for multiple, and b stands for broad. 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 = 9.9Hz, benzotriazole-H), 7.78 (dd, 1H, J = 9.92Hz, J = 0.96Hz, J = 0.87Hz, benzotriazole-H), 7.0-7.3 (m, 2H, benzotriazole-H, phenol-H), 6.67 (d, 1H, J = 2.91Hz, phenol-H) , 6.59 (dd, 1H, J=10.2Hz, J=2.94Hz, J=3.06Hz, =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), 1.80 (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 synthesized in the same manner as in Intermediate Synthesis Example 2 except that acrylic acid was used instead of methacrylic acid, with a yield of 43% (2-[5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl] -5-octyloxyphenol). The melting point was 86° C., the HPLC surface purity was 98.7%, and the absorbance ε was 29,700 when the maximum absorption wavelength λmax was 351 nm.

Further, as a result of NMR analysis of compound (b), results supporting the above structure were obtained. The measurement conditions are as follows.
<Measurement conditions>
Equipment: VARIAN Mercury300
Resonance frequency: 300MHz (1H-NMR)
Solvent: chloroform-d
The contents of the obtained NMR spectrum are as follows. Note that the following compounds (c) and (d) were also subjected to NMR measurement under the same measurement conditions as for 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 = 2.3Hz, phenol-H), 7.16 (d, 1H, J = 2.3Hz, 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=10.5Hz, J=0.66Hz, J=0.75Hz, =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-C ₈ H ₁₇ -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 beaded condenser, a thermometer, and a stirring device, and 17.0 g (0.066 g of 4-(5-methoxy-2H-benzotriazol-2-yl)benzene-1,3-diol) 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. Stirred. 35 ml of water was added, the mixture was allowed to stand, and the lower aqueous layer was separated and removed, and washed with 35 ml of warm water. After collecting 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, and dried to give 5-butoxy-2-(5-methoxy-2H-benzotriazole-2). -yl) phenol (15.0 g) was obtained.

A 500 ml four-necked flask was equipped with a beaded condenser, a thermometer, and a stirring device, and 15.0 g (0.048 mol) of 5-butoxy-2-(5-methoxy-2H-benzotriazol-2-yl)phenol was added. , 9.9 g (0.058 mol) of 47% hydrobromic acid, and 145 ml of sulfolane were added and stirred at 100 to 105° C. for 48 hours. 70 ml of toluene and 200 ml of water were added, allowed to stand, and the lower aqueous layer was separated and removed, washed twice with 100 ml of warm water, and 70 ml of toluene was recovered under reduced pressure. Add 30 ml of isopropyl alcohol and 15 ml of water, cool to 5°C, filter the precipitated crystals, wash with 20 ml of isopropyl alcohol aqueous solution (70% V/V), dry, and give 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 beaded condenser, a thermometer, and a stirring device, and 6.2 g (0.021 mol) of 5-butoxy-2-(5-hydroxy-2H-benzotriazol-2-yl)phenol was added. , 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 were added and dehydrated under reflux at 113 to 118°C for 10 hours. did. 50 ml of water was added and left to stand, the lower aqueous layer was separated and removed, and washed with 50 ml of warm water. After recovering 50 ml of methyl isobutyl ketone under reduced pressure, 25 ml of isopropyl alcohol was added and cooled to 5°C. The precipitated crystals were 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 beaded condenser, a thermometer, and a stirrer, and 3.4 g of 5-butoxy-2-(5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl)phenol ( 0.010 mol), 40 ml of toluene, 1.7 g (0.020 mol) of methacrylic acid, and 0.2 g (0.002 mol) of methanesulfonic acid were added and dehydrated under reflux at 110 to 115° C. for 4 hours. 30 ml of water and 0.7 g (0.007 mol) of sodium carbonate were added, left to stand, and the lower aqueous layer was separated and removed. 0.1 g of activated carbon was added and the mixture was stirred under reflux to decolorize it. After filtering while hot, 40 ml of toluene was recovered from the filtrate under reduced pressure, 30 ml of isopropyl alcohol was added, and the precipitated crystals were filtered, washed with 15 ml of isopropyl alcohol, and then dried at 40° C. under reduced pressure to obtain 2. I got 7g. This 2.7g was recrystallized from isopropyl alcohol and dried at 40°C under reduced pressure to obtain 2.2g of compound (c). The yield was 8% (from 4-(5-methoxy-2H-benzotriazol-2-yl)benzene-1,3-diol). The absorbance ε was 29,100 when the melting point was 101° C. and the maximum absorption wavelength λmax was 351 nm.

Further, the purity of compound (c) was measured by HPLC analysis.
<Measurement conditions>
Equipment: L-2130 (manufactured by Hitachi High-Technologies Corporation)
Column used: Inertsil ODS-3 4.6 x 150mm 5μm
Column temperature: 25℃
Mobile phase: Acetonitrile/water = 9/1 (phosphoric acid 3ml/L)
Flow rate: 1.0ml/min
<Measurement results>
HPLC surface purity: 98.7%
Note that the following compound (d) was also subjected to HPLC measurement under the same measurement conditions as compound (c).

Further, as a result of NMR analysis of compound (c), results supporting the above structure were obtained. The contents of the obtained NMR spectrum are as follows.
δ = 11.3 (b, OH), 8.21 (d, 1H, J = 9.24Hz, benzotriazole-H), 7.80 (dd, 1H, J = 9.1Hz, J = 0.66Hz, J = 0.66Hz, benzotriazole-H), 7.18 (d, 1H, J = 2.31Hz, phenol-H), 6.68 (d, 1H, J = 2.64Hz, phenol-H), 6 .60 (dd, 1H, J = 9.2Hz, J = 2.64Hz, J = 2.64Hz, 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-C ₄ H ₉ -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-neck flask was equipped with a beaded condenser, a thermometer, and a stirring device, and 10.0 g (0.039 g of 4-(5-methoxy-2H-benzotriazol-2-yl)benzene-1,3-diol) 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 were added and stirred under reflux 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 was added, and the precipitated crystals were filtered, washed with 25 ml of isopropyl alcohol, and dried to give 5-ethoxy-2-(5-methoxy-2H-benzotriazole-2). 8.2 g of -yl)phenol was obtained.

A 500 ml four-necked flask was equipped with a beaded condenser, 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 added. , 6.2 g (0.036 mol) of 47% hydrobromic acid, and 82 ml of sulfolane were added and stirred at 100 to 105° C. for 33 hours. 50 ml of toluene and 165 ml of water were added, left to stand, and the lower aqueous layer was separated and removed, washed with 80 ml of warm water, and 50 ml of toluene 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 isopropyl alcohol aqueous solution (70% V/V), and dry. 4.6 g of -hydroxy-2H-benzotriazol-2-yl)phenol was obtained.

A 200 ml four-necked flask was equipped with a beaded condenser, a thermometer, and a stirring device, and 4.6 g (0.017 mol) of 5-ethoxy-2-(5-hydroxy-2H-benzotriazol-2-yl)phenol was added. , 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 were added, and the mixture was refluxed at 113 to 118°C for 8 hours. Dehydrated. 30 ml of water was added and left to stand, the lower aqueous layer was separated and removed, and washed with 30 ml of warm water. 35 ml of methyl isobutyl ketone was recovered under reduced pressure to obtain 5.0 g of solid 5-ethoxy-2-[5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl]phenol.

A 300 ml four-necked flask was equipped with a beaded condenser, a thermometer, and a stirrer, and the solid content of 5-ethoxy-2-[5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl]phenol was reduced to 5. .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 under reflux at 110 to 115°C for 4 hours. . 80 ml of water and 1.9 g (0.018 mol) of sodium carbonate were added, allowed to stand, and the lower aqueous layer was separated and removed. 0.1 g of activated carbon was added, and the mixture was decolorized by stirring under reflux. After filtering while hot, 100 ml of toluene was recovered from the filtrate under reduced pressure, 30 ml of isopropyl alcohol was added, and the precipitated crystals were filtered, washed with 20 ml of isopropyl alcohol, and dried at 40°C under reduced pressure to obtain white crystals. I got 2g. This 3.2g was recrystallized from isopropyl alcohol and dried at 40°C under reduced pressure to obtain 1.6g of compound (d). The yield was 11% (from 4-(5-methoxy-2H-benzotriazol-2-yl)benzene-1,3-diol). The melting point was 156° C., the HPLC surface purity was 98.1%, and the absorbance ε was 29,000 when the maximum absorption wavelength λmax was 350 nm.

Further, as a result of NMR analysis of compound (d), results supporting the above structure were 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 = 2.64Hz, 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)

共重合体（ａ） (Example 1)
[Copolymer (a); Copolymerization of compound (a)/4,4'-azobis(4-cyanopentanoic acid) polyethylene glycol polymer]

Copolymer (a)

A 50 ml eggplant flask was equipped with a three-way stopcock and a stirring device, and 0.23 g (0.5 mmol) of compound (a) was added to 4,4'-azobis(4-cyanopentanoic acid) polyethylene glycol polymer (trade name "VPE-"). 0201 (manufactured by Wako Pure Chemicals Industries, Ltd.) was added thereto, and the atmosphere was replaced with nitrogen. 10 ml of toluene was added thereto and stirred at 80°C for 48 hours. It was placed in an ice bath and poured into 100 ml of hexane to precipitate the product. After filtering the precipitate, it was dissolved in 150 ml of methanol, and insoluble matter was removed by filtration. Methanol was removed under reduced pressure, and the remaining solid matter was dried under reduced pressure to obtain 0.81 g of copolymer (a).

Further, as a result of measuring the molecular weight of copolymer (a), the weight average molecular weight (Mw) was 9270, the number average molecular weight (Mn) was 3650, and the polydispersity (Mw/Mn) was 2.54. The measurement conditions are as follows.
<Measurement conditions>
Device: LC-10AD (manufactured by Shimadzu Corporation)
Eluent: Chloroform Column: Shodex K-807L, Shodex K805L, Shodex K-804L (manufactured by Showa Denko K.K.)
The molecular weight of the following copolymer (c) was also measured under the same measurement conditions.

Further, when the ultraviolet to visible absorption spectrum of copolymer (a) was measured, the maximum absorption wavelength λmax was 348.6 nm. The spectrum is shown in Figure 1. The spectrum measurement conditions are as follows.
<Measurement conditions>
Equipment: UV-1850 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-500nm
Solvent: Chloroform Concentration: 4.7 mg/L
Cell: 1cm quartz

Further, as a result of NMR analysis of copolymer (a), results supporting the above structure were obtained. The obtained spectrum is shown in FIG. 4. The measurement conditions are as follows.
<Measurement conditions>
Device: ECX-500 (manufactured by JEOL Ltd.)
Resonance frequency: 500MHz (1H-NMR)
Solvent: chloroform-d
Note that the following copolymers (b) and (c) were also subjected to NMR analysis under the same measurement conditions.

共重合体（ｂ） (Example 2)
[Copolymer (b); Copolymerization of compound (b)/polyethylene glycol]

Copolymer (b)

A 50 ml eggplant flask was equipped with a three-way stopcock and a stirring device, and 1.4 g (3.0 mmol) of compound (b) and 6.0 g (30 mmol) of polyethylene glycol (manufactured by Wako Pure Chemicals Industries, Ltd.) were added. The atmosphere was replaced with nitrogen. 0.30 g (1.5 mmol) of tributylphosphine was added thereto, and the mixture was stirred at 100° C. for 24 hours. 100 ml of dichloromethane was added, and the mixture was transferred to a separating funnel and washed with ion-exchanged water (100 ml x 3). Dichloromethane was removed under reduced pressure, the product was dissolved in 150 ml of methanol, and insoluble materials were removed by filtration. Methanol was removed under reduced pressure, and the remaining solid was dried under reduced pressure to obtain 0.28 g of copolymer (b).

Further, when the ultraviolet to visible absorption spectrum of copolymer (b) was measured, the maximum absorption wavelength λmax was 350.8 nm. The spectrum is shown in Figure 2. The spectrum measurement conditions are as follows.
<Measurement conditions>
Equipment: UV-1850 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-500nm
Solvent: Chloroform Concentration: 4.5 mg/L
Cell: 1cm quartz

Further, as a result of NMR analysis of copolymer (b), results supporting the above structure were obtained. The obtained spectrum is shown in FIG.

共重合体（ｃ） (Example 3)
[Copolymer (c); Copolymerization of compound (a)/polyethylene glycol monomethacrylate]

Copolymer (c)

A 100 ml eggplant flask was equipped with a three-way cock and a stirring device, and 0.32 g (0.68 mmol) of compound (a) and polyethylene glycol monomethacrylate (trade name "Blenmar PE-350" manufactured by NOF Corporation) were added. 4 ml (3.4 mmol) was added, and the atmosphere was replaced with nitrogen. 10 ml of toluene and 28 mg (0.12 mmol) of benzoyl peroxide were added thereto, and nitrogen gas was bubbled through the solution. Thereafter, the mixture was stirred at 80°C for 24 hours. Toluene was removed under reduced pressure, the product was dissolved in 50 ml of methanol, and insoluble materials were removed by filtration. The methanol solution was put into a dialysis membrane (molecular weight cut off: 1000) and stirred in methanol for 48 hours to remove low molecular weight substances. Methanol was removed under reduced pressure, and the remaining solid was dried under reduced pressure to obtain 0.39 g of copolymer (c).

Further, as a result of measuring the molecular weight of copolymer (c), the weight average molecular weight (Mw) was 82,830, the number average molecular weight (Mn) was 16,500, and the polydispersity (Mw/Mn) was 5.02.

Further, when the ultraviolet to visible absorption spectrum of copolymer (c) was measured, the maximum absorption wavelength λmax was 350.4 nm. The spectrum is shown in Figure 3. The spectrum measurement conditions are as follows.
<Measurement conditions>
Equipment: UV-1850 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-500nm
Solvent: Chloroform Concentration: 4.7mg/L
Cell: 1cm quartz

Further, as a result of NMR analysis of copolymer (c), results supporting the above structure were obtained. The obtained spectrum is shown in FIG.

[Measurement of solubility]
Copolymers (a) to (c) obtained in Examples 1 to 3, and compound (e), which is a conventional general ultraviolet absorber as a comparative example; 2-(2-hydroxy-4-octyloxy) Table 1 shows the solubility of phenyl)-2H-benzotriazole at 25°C in ethanol, which is a hydrophilic cosmetic base material and hydrophilic organic material, purified water, which is a hydrophilic cosmetic base material, and methanol, which is a hydrophilic organic material. Shown below.

[Measurement of pH]
Copolymers (a) and (c) obtained in Examples 1 and 3, respectively, and compound (f), which is a conventional general hydrophilic ultraviolet absorber as a comparative example; 2-hydroxy 4-methoxybenzophenone The pH of the aqueous solution of -5-sulfonic acid trihydrate was measured using a pH measuring device. The results are shown in Table 2.

[Confirmation of stability of aqueous solution]
0.1 g of the copolymer (a) obtained in Example 1, and as a comparative example, a compound (g) obtained by introducing a polyethylene glycol derivative compound into a benzotriazole compound through an ester bond to impart hydrophilicity; α- Dissolve 0.1 g of [4-(4-(2H-benzotriazol-2-yl)-3-hydroxyphenoxy)butanoyl]-ω-methoxypoly(oxyethylene) in 50 mL of ion-exchanged water and store at 25°C for 6 months. The mixture was left to stand and the presence or absence of turbidity was checked. When the substituent containing polyethylene glycol is removed by hydrolysis, the remaining benzotriazole skeleton is not water-soluble and precipitates, causing turbidity in the aqueous solution.The presence or absence of turbidity is an indicator of stability in the aqueous solution. . The results are shown in Table 3.

From Table 1, copolymers (a) to (c) have higher solubility in hydrophilic cosmetic base materials and hydrophilic organic materials than compound (e), which is a conventional general UV absorber. It can be seen that it shows gender. Furthermore, from Table 2, compound (f), which is a conventional general hydrophilic ultraviolet absorber, exhibits strong acidity, while copolymers (a) and (c) are weakly acidic to neutral. It has been found that it can be used in applications that cannot be used in strong acids. Additionally, from Table 3, compound (g), which was made by introducing a polyethylene glycol derivative compound into a benzotriazole compound through an ester bond to impart hydrophilicity, decomposed during long-term storage in an aqueous solution, whereas copolymer (g) Since a) is stable without decomposition when stored in an aqueous solution for a long period of time, it is found that it can be used in water for a long period of time, and it is found that it is an unprecedentedly useful hydrophilic ultraviolet absorber. Note that the pH measurement conditions are as follows.
<Measurement conditions>
Device: SevenEasy pH (manufactured by Mettler Toledo)
Temperature: 22℃
Concentration: 2000ppm

The hydrophilic ultraviolet absorber of the present invention absorbs the entire ultraviolet region, exhibits high solubility in hydrophilic cosmetic base materials and hydrophilic organic materials, has a weakly acidic to neutral aqueous solution, and is stable in water. Since it can be used for a long period of time, it can be suitably used for hydrophilic cosmetic base materials and hydrophilic organic materials.

Claims (3)

A benzotriazole-based copolymer characterized by copolymerizing a benzotriazole derivative compound represented by the following general formula (1) and a polyethylene glycol derivative compound containing the following general formula (2) as a constituent unit. .

General formula (1)
[In the formula, 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 having 1 to 7 carbon atoms, a benzoyl group, or a toluoyl group, and 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)
[In the formula, n represents an integer of 2 or more] A benzotriazole derivative compound in which R ₁ in the above general formula (1) is an alkyl group having 2 to 8 carbon atoms and R ₂ is an ethylene group, and a polyethylene glycol derivative containing the above general formula (2) as a constituent unit. The benzotriazole copolymer according to claim 1, which is obtained by polymerizing a compound. An ultraviolet absorber containing the benzotriazole copolymer according to claim 1 or 2.

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