Benzotriazole derivative compound

Abstract

To provide a new benzotriazole derivative compound well dispersible in a polyvinyl alcohol and suitably utilizable as an ultraviolet absorber strongly absorbing the whole ultraviolet region including a long wavelength ultraviolet region.SOLUTION: The benzotriazole derivative compound is represented by general formula (1). Where R1 represents an alkylene group or an alkylenecarbonyl group, and R2 represents an alkylene group, an alkyleneoxy group, an alkylenecarbonyl group, an alkylenecarbonyloxy group, or an alkyleneoxycarbonyl group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel benzotriazole derivative compound and to an ultraviolet absorber which disperses well in polyvinyl alcohol and exhibits strong absorption throughout the entire ultraviolet region, including the long-wavelength ultraviolet region. [Background technology]

[0002] Polyvinyl alcohol resin is a water-soluble polymeric material that is used in a variety of fields, including films and adhesives. When producing films, the resin is generally dissolved in water and then formed into a film using the solution method. It is widely used in applications such as display films, agricultural films, and packaging films.

[0003] These polyvinyl alcohol films are required to have the ability to prevent deterioration of products and materials inside the film due to the ultraviolet rays contained in sunlight, and a method of producing a film is used in which an ultraviolet absorber such as benzotriazoles or benzophenones is added to an aqueous polyvinyl alcohol solution.

[0004] However, since most conventional ultraviolet absorbers are not water-soluble or hydrophilic, they are not sufficiently dispersed in aqueous polyvinyl alcohol solutions, making it difficult to impart ultraviolet absorption ability to polyvinyl alcohol films. Furthermore, since light in the long-wavelength ultraviolet region of 380 to 390 nm deteriorates display materials and the like, there is a demand for polyvinyl alcohol films that absorb the entire ultraviolet region, including the long-wavelength ultraviolet region, but no ultraviolet absorbers that can absorb in the long-wavelength ultraviolet region and are applicable to polyvinyl alcohol films have been known.

[0005] Patent Document 1 discloses that the use of inorganic ultraviolet absorbers such as fine particles of titanium oxide or zinc oxide in a polyvinyl alcohol film provides ultraviolet absorption that can block ultraviolet rays at 340 nm, but does not disclose ultraviolet absorption in the long-wavelength ultraviolet region. Furthermore, it is believed that the ultraviolet absorber is not sufficiently dispersed in the polyvinyl alcohol film, causing the film to become cloudy and resulting in a low visible light transmittance at 550 nm, limiting its applications.

[0006] Patent Documents 2 and 3 disclose that the use of 2,4-dihydroxybenzophenone or the like as a water-soluble ultraviolet absorber in a polyvinyl alcohol film provides ultraviolet absorption capable of blocking 340 nm ultraviolet light, but do not disclose ultraviolet light absorption in the long wavelength ultraviolet region. The present inventors actually produced a polyvinyl alcohol film using 2,4-dihydroxybenzophenone and measured the absorbance, but found that the ultraviolet light absorption in the long wavelength ultraviolet region of 380 to 390 nm was insufficient. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 11-29680 [Patent Document 2] Japanese Patent Publication No. 11-189660 [Patent Document 3] JP 2007-231299 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide an ultraviolet absorber that disperses well in polyvinyl alcohol and that strongly absorbs the entire ultraviolet region, including the long-wavelength ultraviolet region. [Means for solving the problem]

[0009] In the present invention, the main means for solving the above problems is to use a benzotriazole derivative compound represented by the following general formula (1). [ka] General formula (1) [In the formula, R1 represents an alkylene group having 1 to 8 carbon atoms or an alkylenecarbonyl group having 1 to 8 carbon atoms, and R2 represents an alkylene group having 1 to 8 carbon atoms, an alkyleneoxy group having 1 to 8 carbon atoms, an alkylenecarbonyl group having 1 to 8 carbon atoms, an alkylenecarbonyloxy group having 1 to 8 carbon atoms, or an alkyleneoxycarbonyl group having 1 to 8 carbon atoms]

[0010] Preferably, R1 in the above general formula (1) is an alkylene group having 1 to 2 carbon atoms or an alkylenecarbonyl group having 1 to 2 carbon atoms, and R2 is an alkylene group having 1 to 2 carbon atoms, an alkyleneoxy group having 1 to 2 carbon atoms, an alkylenecarbonyl group having 1 to 2 carbon atoms, an alkylenecarbonyloxy group having 1 to 2 carbon atoms, or an alkyleneoxycarbonyl group having 1 to 2 carbon atoms.

[0011] More preferably, R1 in the above general formula (1) is an alkylene group having 1 to 2 carbon atoms, and R2 is an alkylene group having 1 to 2 carbon atoms, an alkyleneoxy group having 1 to 2 carbon atoms, or an alkyleneoxycarbonyl group having 1 to 2 carbon atoms. [Effects of the Invention]

[0012] The benzotriazole derivative compound of the present invention is well dispersed in a polyvinyl alcohol film, and therefore has high absorbance at the maximum absorption wavelength and absorbs the entire ultraviolet region, including the long-wavelength ultraviolet region of 380 to 390 nm. Therefore, the ultraviolet absorbent and resin composition of the present invention are useful as ultraviolet absorbents and resin compositions that can solve the problems of the prior art. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is an ultraviolet-visible absorption spectrum of compound (a). [Figure 2] 1 is an ultraviolet-visible absorption spectrum of compound (b). [Figure 3] 1 is an ultraviolet-visible absorption spectrum of compound (c). BEST MODE FOR CARRYING OUT THE INVENTION

[0014] The present invention is described in detail below. The present invention uses a benzotriazole derivative compound represented by the following general formula (1) as an ultraviolet absorber or resin composition. The compound represented by the following general formula (1) is described below.

[0015] [ka] General formula (1)

[0016] In the general formula (1), R1 is a linear or branched alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a methylmethylene group, a propylene group, a methylethylene group, a butylene group, a pentylene group, a hexylene group, a 1-methylpentylene group, a heptylene group, or an octylene group; a methylenecarbonyl group, an ethylenecarbonyl group, a methylmethylenecarbonyl group, a propylenecarbonyl group, a methylethylenecarbonyl group, a butylenecarbonyl group, a pentylenecarbonyl group, a hexylenecarbonyl group, a 1-methylpentylenecarbonyl group, or a 1-methylpentylenecarbonyl group; R2 is a linear or branched alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a methylmethylene group, a propylene group, a methylethylene group, a butylene group, a pentylene group, a hexylene group, a 1-methylpentylene group, a heptylene group, or an octylene group; R3 is a linear or branched alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a methylmethylene group, a propylene group, a methylethylene group, a butylene group, a pentylene group, a hexylene group, a 1-methylpentylene group, a heptylene group, or an octylene group; linear or branched alkyleneoxy groups having 1 to 8 carbon atoms, such as a methylenecarbonyl group, an ethylenecarbonyl group, a methylmethylenecarbonyl group, a propylenecarbonyl group, a methylethylenecarbonyl group, a butylenecarbonyl group, a pentylenecarbonyl group, a hexylenecarbonyl group, a 1-methylpentylenecarbonyl group, a heptylenecarbonyl group, and an octylenecarbonyl group; a linear or branched alkylenecarbonyl group having 1 to 8 prime atoms; a linear or branched alkylenecarbonyloxy group having 1 to 8 carbon atoms, such as a methylenecarbonyloxy group, an ethylenecarbonyloxy group, a methylmethylenecarbonyloxy group, a propylenecarbonyloxy group, a methylethylenecarbonyloxy group, a butylenecarbonyloxy group, a pentylenecarbonyloxy group, a hexylenecarbonyloxy group, a 1-methylpentylenecarbonyloxy group, a heptylenecarbonyloxy group, or an octylenecarbonyloxy group;Examples of such alkyleneoxycarbonyl groups include linear or branched alkyleneoxycarbonyl groups having 1 to 8 carbon atoms, such as methyleneoxycarbonyl, ethyleneoxycarbonyl, methylmethyleneoxycarbonyl, propyleneoxycarbonyl, methylethyleneoxycarbonyl, butyleneoxycarbonyl, pentyleneoxycarbonyl, hexyleneoxycarbonyl, 1-methylpentyleneoxycarbonyl, heptyleneoxycarbonyl, and octyleneoxycarbonyl groups;

[0017] Preferably, the compound is one in which R1 in the above general formula (1) is an alkylene group having 1 to 2 carbon atoms or an alkylenecarbonyl group having 1 to 2 carbon atoms, and R2 is an alkylene group having 1 to 2 carbon atoms, an alkyleneoxy group having 1 to 2 carbon atoms, an alkylenecarbonyl group having 1 to 2 carbon atoms, an alkylenecarbonyloxy group having 1 to 2 carbon atoms, or an alkyleneoxycarbonyl group having 1 to 2 carbon atoms.

[0018] More preferably, it is a compound in which R1 in the above general formula (1) is an alkylene group having 1 to 2 carbon atoms, and R2 is an alkylene group having 1 to 2 carbon atoms, an alkyleneoxy group having 1 to 2 carbon atoms, or an alkyleneoxycarbonyl group having 1 to 2 carbon atoms.

[0019] Specific examples of the benzotriazole derivative compound represented by the above general formula (1) include the following: 2-[5-(3-hydroxypropoxy)-2H-benzotriazol-2-yl]-5-(3-hydroxypropoxy)phenol, 2-[5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl]-5-(3-hydroxypropoxy)phenol, 5-(2-hydroxyethoxy)-2-[5-(3-hydroxypropoxy)-2H-benzotriazol-2-yl]phenol, 3-hydroxypropyl 2-[2-hydroxy-4-(3-hydroxypropoxy)phenyl]-2H-benzotriazole-5-carboxylate, hydroxymethyl 2-[2-hydroxy-4-(3-hydroxypropoxy)phenyl]-2H-benzotriazole-5-carboxylate, 3-hydroxypropyl 2-[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-2H-benzotriazole-5-carboxylate, 2-[5-(4-hydroxybutyl)-2H-benzotriazol-2-yl]-5-(3-hydroxypropoxy)phenol, 5-(3-hydroxypropoxy)-2-[5-(3-hydroxypropyl)-2H-benzotriazol-2-yl]phenol, 5-(2-hydroxyethoxy)-2-[5-(4-hydroxybutyl)-2H-benzotriazol-2-yl]phenol, 3-hydroxy-4-[5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl]phenyl 2-hydroxyacetate, 2-hydroxyethyl 2-[2-hydroxy-4-(2-hydroxyacetoxy)phenyl]-2H-benzotriazole-5-carboxylate, 3-hydroxy-4-[5-(2-hydroxyethyl)-2H-benzotriazol-2-yl]phenyl 2-Hydroxyacetate, 5-(2-hydroxyethoxy)-2-[5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl]phenol, 5-(2-hydroxyethoxy)-2-[5-(hydroxymethoxy)-2H-benzotriazol-2-yl]phenol, 2-hydroxyethyl 2-[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-2H-benzotriazole-5-carboxylate, hydroxymethyl2-[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-2H-benzotriazole-5-carboxylate, 5-(2-hydroxyethoxy)-2-[5-(3-hydroxypropyl)-2H-benzotriazol-2-yl]phenol, 5-(2-hydroxyethoxy)-2-[5-(2-hydroxyethyl)-2H-benzotriazol-2-yl]phenol and the like.

[0020] Among the compounds exemplified above, preferred are 3-hydroxy-4-[5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl]phenyl 2-hydroxyacetate, 2-hydroxyethyl 2-[2-hydroxy-4-(2-hydroxyacetoxy)phenyl]-2H-benzotriazole-5-carboxylate, 3-hydroxy-4-[5-(2-hydroxyethyl)-2H-benzotriazol-2-yl]phenyl 2-hydroxyacetate, 5-(2-hydroxyethoxy)-2-[5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl]phenol, 5-(2-hydroxyethoxy)-2-[5-(hydroxymethoxy)-2H-benzotriazol-2-yl]phenol, 2-hydroxyethyl 2-[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-2H-benzotriazole-5-carboxylate, hydroxymethyl 2-[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-2H-benzotriazole-5-carboxylate, 5-(2-hydroxyethoxy)-2-[5-(2-hydroxyethyl)-2H-benzotriazol-2-yl]phenol.

[0021] More preferred are 5-(2-hydroxyethoxy)-2-[5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl]phenol, 5-(2-hydroxyethoxy)-2-[5-(hydroxymethoxy)-2H-benzotriazol-2-yl]phenol, 2-hydroxyethyl 2-[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-2H-benzotriazole-5-carboxylate, hydroxymethyl 2-[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-2H-benzotriazole-5-carboxylate, and 5-(2-hydroxyethoxy)-2-[5-(2-hydroxyethyl)-2H-benzotriazol-2-yl]phenol.

[0022] There is no particular limitation on the method for synthesizing the benzotriazole derivative compound of the general formula (1) of the present invention, and a synthetic route can be constructed using multiple conventionally known reaction principles. For example, the compound can be synthesized according to the reaction formulas shown in the following (Chemical Formulas 2 to 7). [ka] [ka] [ka] [ka] [ka] [ka]

[0023] The polyvinyl alcohol used in the present invention is usually obtained by saponifying a polyvinyl ester polymer obtained by radical polymerization of a vinyl ester monomer such as vinyl acetate. Examples of polymerization methods for polyvinyl ester monomers include solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.

[0024] Examples of polyvinyl ester polymers include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, and vinyl benzoate.

[0025] Furthermore, as long as the effects of the present invention are not impaired, the vinyl ester monomer may be a copolymer obtained by copolymerizing a copolymerizable monomer with the vinyl ester monomer. Examples of the copolymerizable monomer include olefins such as ethylene, propylene, 1-butene, and isobutene; (meth)acrylic acid and its salts; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; acrylamide, n-methylacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide; ) (meth)acrylamide derivatives such as acrylamidopropanesulfonic acid and salts thereof, N-vinylamides such as N-vinylpyrrolidone, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, and n-butyl vinyl ether, nitriles such as acrylonitrile and methacrylonitrile, vinyl halides such as vinyl chloride and vinylidene chloride, allyl compounds such as allyl acetate and allyl chloride, maleic acid and salts thereof or esters thereof, itaconic acid and salts thereof or esters thereof, vinylsilyl compounds such as vinyltrimethoxysilane, and isopropynyl acetate.

[0026] The saponification degree of polyvinyl alcohol is preferably from 60 to 99.9 mol %, more preferably from 70 to 99.5 mol %, and particularly preferably from 80 to 99 mol %.

[0027] The average degree of polymerization of polyvinyl alcohol is preferably from 300 to 30,000, more preferably from 500 to 20,000, and particularly preferably from 1,000 to 10,000.

[0028] When the benzotriazole derivative compound of the present invention is added to a polyvinyl alcohol resin, the benzotriazole derivative compound of the present invention can be used alone as an ultraviolet absorber, or in combination with other ultraviolet absorbers. The ultraviolet absorber other than the benzotriazole derivative compound of the present invention is not particularly limited as long as it is a commercially available ultraviolet absorber that can absorb ultraviolet light. For example, benzotriazole derivatives, benzophenone derivatives, salicylate derivatives, cyanoacrylate derivatives, triazine derivatives, etc. can be used. These ultraviolet absorbers may be used alone or in a suitable mixture of two or more.

[0029] The benzotriazole derivative compound of the present invention is contained in the polyvinyl alcohol resin composition in an amount of preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight.

[0030] The polyvinyl alcohol resin composition containing the benzotriazole derivative compound of the present invention may contain resin additives other than the ultraviolet absorber, such as antioxidants, light stabilizers, plasticizers, antistatic agents, flame retardants, colorants, lubricants, and foaming agents.

[0031] The polyvinyl alcohol resin composition containing the benzotriazole derivative compound of the present invention can be molded by a general resin molding method such as injection molding, blow molding, extrusion molding, etc. When molding a film or sheet, in addition to the above, a solution casting method or a casting method can be used. [Example]

[0032] The synthesis methods of the benzotriazole derivative compounds used in the present invention and the properties of the compounds are shown below, but the present invention is not limited to these embodiments.

[0033] Example 1 [Compound (a): 5-(2-hydroxyethoxy)-2-[5-(2-hydroxyethoxy)-2H-benzotriazol-2-yl]phenol] [ka] compound (a)

[0034] A 500 ml four-neck flask equipped with a ball condenser, thermometer, and stirrer was charged with 10.0 g (0.0411 mol) of 5-hydroxy-2-(2,4-dihydroxyphenyl)-2H-benzotriazole (synthesized by conventional methods), 80 ml of methyl isobutyl ketone, 11.8 g (0.147 mol) of 2-chloroethanol, 9.0 g (0.0849 mol) of sodium carbonate, 1.0 g of potassium iodide, and 1.5 g of PEG-400. The mixture was refluxed at 110-120 °C for 24 hours. Then, 80 ml of water was added, the mixture was left to stand, and the lower aqueous layer was separated and removed. The mixture was then washed with 80 ml of warm water. After recovering the methyl isobutyl ketone under reduced pressure, 80 ml of isopropyl alcohol was added and the mixture was cooled to 10 °C. The precipitated crystals were filtered, washed with 40 ml of isopropyl alcohol, and dried to obtain 2.1 g of crude crystals. The crude crystals were recrystallized from isopropyl alcohol to obtain 1.4 g of compound (a). The yield was 10% (based on 5-hydroxy-2-(2,4-dihydroxyphenyl)-2H-benzotriazole). The melting point was 168°C.

[0035] The purity of compound (a) was measured by HPLC analysis. <Measurement conditions> Equipment: LC-20A (Shimadzu Corporation) Column used: SUMIPAX ODS A-212 6.0 x 150 mm 5 μm Column temperature: 40℃ Mobile phase: acetonitrile / water = 4 / 6 (phosphoric acid 3ml / L) Flow rate: 1.0ml / min Detection: UV 250 nm <Measurement results> HPLC surface purity: 97.8%

[0036] Furthermore, when the ultraviolet-visible absorption spectrum of compound (a) was measured, the maximum absorption wavelength λmax was 349.5 nm, and the molar absorption coefficient ε at that wavelength was 30900. The spectrum is shown in Figure 1. The conditions for measuring the spectrum are as follows. In the following Examples 2 and 3, the ultraviolet-visible absorption spectrum was measured under the same measurement conditions as in this Example. <Measurement conditions> Equipment: UV-1850 (Shimadzu Corporation) Measurement wavelength: 250~500nm Solvent: Chloroform Concentration: 10ppm

[0037] Furthermore, NMR analysis of compound (a) provided results supporting the above structure. The measurement conditions were as follows: NMR measurements were also carried out in the following Examples 2 and 3 under the same measurement conditions as in this Example. <Measurement conditions> Device: ECX-500II (manufactured by JEOL Ltd.) Resonance frequency: 500MHz (1H-NMR) Solvent: dimethyl sulfoxide-d6 Tetramethylsilane was used as the internal standard for 1H-NMR, and chemical shift values ​​were expressed in δ (ppm), and coupling constants in Hertz. s stands for singlet, d for doublet, t for triplet, dd for double doublet, and m for multiplet. This also applies to compounds (b) and (c) below. The contents of the obtained 1H-NMR spectrum are as follows: δ=10.62(s,1H,phenolic OH),7.89(d, J=9.2Hz,1H,phenol-H),7.71(d,J=9.2Hz, 1H,benzotriazole-H),7.32(d,J=1.5 Hz,1H,benzotriazole-H),7.16(dd,J=9.2,2.3Hz,1H,benzotriazole-H),6.67(d,J=2.3Hz,1H,phenol-H),6.61(dd,J=8.4,2.3Hz,1H,phenol-H),4.95-4.91(m,2H ,methylene-OH),4.09(t,J=4.6Hz,2H,methylene-H),4.02(t,J=5.0Hz,2H,methylene-H),3.78(q,J=4.6Hz,2H,methylene-H),3.73(q,J=4.8Hz,2H,methylene-H)

[0038] (Example 2) [Compound (b);2-ヒドロキシエチル2-[2-ヒドロキシ-4-(2-ヒドロ[キシエトキシ]フェニル]-2H-ベンゾトリアゾール-5-カルボキシレート]

change

[0039] A 1000 ml four-neck flask equipped with a ball condenser, thermometer, and stirrer was charged with 100.0 g (0.369 mol) of 5-carboxy-2-(2,4-dihydroxyphenyl)-2H-benzotriazole (synthesized by conventional methods), 100 ml of N,N-dimethylformamide, 67.5 g (0.454 mol) of octyl chloride, 100.0 g (0.774 mol) of N,N-diisopropylethylamine, and 5.0 g of potassium iodide, and the mixture was stirred at 150-160 ° C for 8 hours. After recovering the N,N-dimethylformamide and N,N-diisopropylethylamine under reduced pressure, 250 ml of isopropyl alcohol was added and the mixture was cooled to 10 ° C. The precipitated crystals were filtered, washed with 50 ml of isopropyl alcohol, and dried to obtain 85.2 g of octyl 2-(2,4-dihydroxyphenyl)-2H-benzotriazole-5-carboxylate.

[0040] A 500 ml four-neck flask equipped with a ball condenser, a thermometer, and a stirrer was charged with 85.2 g (0.222 mol) of octyl 2-(2,4-dihydroxyphenyl)-2H-benzotriazole-5-carboxylate, 200 ml of methyl isobutyl ketone, 50.0 g (0.147 mol) of 2-chloroethanol, 50.0 g (0.0849 mol) of sodium carbonate, and 1.0 g of potassium iodide, and the mixture was refluxed and dehydrated for 24 hours at 110-120° C. 100 ml of water was then added, and the mixture was allowed to stand, after which the lower aqueous layer was separated and removed, and the mixture was washed with 100 ml of warm water. After recovering methyl isobutyl ketone under reduced pressure, 200 ml of isopropyl alcohol was added and the mixture was cooled to 10°C. The precipitated crystals were filtered, washed with 40 ml of isopropyl alcohol, and dried to obtain 58.0 g of octyl 2-(2-hydroxy)-4-(2-hydroxyethoxy)phenyl-2H-benzotriazole-5-carboxylate.

[0041] A 500 ml four-neck flask was equipped with a ball condenser, a thermometer, and a stirrer, and 58.0 g (0.136 mol) of octyl 2-(2-hydroxy)-4-(2-hydroxyethoxy)phenyl-2H-benzotriazole-5-carboxylate, 100 ml of isopropyl alcohol, 100 ml of water, and 50.0 g (0.400 mol) of 32% aqueous sodium hydroxide solution were added and stirred for 3 hours at 70 ° C. After that, the mixture was left to stand, the lower aqueous layer was separated and removed, and the mixture was cooled to 10 ° C. The precipitated crystals were filtered, washed with 40 ml of isopropyl alcohol, and dried to obtain 47.1 g of 5-carboxy-2-(2-hydroxy)-4-(2-hydroxyethoxy)phenyl-2H-benzotriazole.

[0042] A 500 ml four-neck flask was equipped with a ball condenser, thermometer, and stirrer. 20.0 g (0.0634 mol) of 5-carboxy-2-(2-hydroxy)-4-(2-hydroxyethoxy)phenyl-2H-benzotriazole, 20 ml of N,N-dimethylformamide, 10.0 g (0.124 mol) of 2-chloroethanol, 20.0 g (0.155 mol) of N,N-diisopropylethylamine, and 1.0 g of potassium iodide were added and stirred at 150-160 °C for 8 hours. After that, N,N-dimethylformamide and N,N-diisopropylethylamine were recovered under reduced pressure, and then 80 ml of isopropyl alcohol was added and the mixture was cooled to 10 °C. The precipitated crystals were filtered, washed with 20 ml of isopropyl alcohol, and dried to obtain 19.9 g of crude crystals. 10.0 g of this crude crystal was recrystallized with isopropyl alcohol to obtain 6.4 g of compound (b). The yield was 23% (based on 5-carboxy-2-(2,4-dihydroxyphenyl)-2H-benzotriazole), and the melting point was 174°C.

[0043] Furthermore, the purity of compound (b) was measured by HPLC analysis. <Measurement conditions> Equipment: L-2400 (Hitachi High-Technologies Corporation) Column used: SUMIPAX ODS A-212 6.0 x 150 mm 5 μm Column temperature: 40℃ Mobile phase: methanol / water = 6 / 4 (phosphoric acid 3 ml / L) Flow rate: 1.0ml / min Detection: UV 250 nm <Measurement results> HPLC surface purity: 98.3%

[0044] Furthermore, when the ultraviolet-visible absorption spectrum of compound (b) was measured, the maximum absorption wavelength λmax was 358.1 nm, and the molar absorption coefficient ε at that wavelength was 25800. The spectrum is shown in FIG.

[0045] Furthermore, NMR analysis of compound (b) provided results supporting the above structure. The obtained 1H-NMR spectrum is as follows: δ=10.59(br,1H,phenolic OH),8.74(s,1H,benzotriazole-H),8.12(d,J=9.2 Hz,1H,phenol-H),8.03(dd,J=8.5,1.5Hz,1H,phenol-H),7.70(d,J=8.4Hz,1H,benzotriazole-H),6.68(d,2H,phenol-H),6.63(dd,J=8.8,2.7Hz,1H,phenol-H),5.03(t, J=5.0Hz,1H,methylene-OH),4.94(t,J=5.0Hz,1H,methylene-OH),4.33(t,2H,J=5.0Hz,methylene-H),4.03(m,2H,J=5.0Hz,methylene-H),3.7-3.76(m,4H,methylene-H)

[0046] Example 3 [Compound (c): 5-(2-hydroxyethoxy)-2-[5-(2-hydroxyethyl)-2H-benzotriazol-2-yl]phenol] [ka] Compound (c)

[0047] A 500 ml four-neck flask equipped with a ball condenser, a thermometer, and a stirrer was added. 10.0 g (0.0369 mol) of 5-(2-hydroxyethyl)-2-(2,4-dihydroxyphenyl)-2H-benzotriazole (synthesized by conventional methods), 80 ml of methyl isobutyl ketone, 9.0 g (0.112 mol) of 2-chloroethanol, 8.0 g (0.0755 mol) of sodium carbonate, 1.0 g of potassium iodide, and 1.5 g of PEG-400 were added and refluxed for 24 hours at 110-120 ° C. The mixture was then left to stand at 70 ° C. to separate and remove the lower aqueous layer. 80 ml of isopropyl alcohol was then added and the mixture was cooled to 10 ° C. after recovering the methyl isobutyl ketone under reduced pressure. The precipitated crystals were filtered, washed with 40 ml of isopropyl alcohol, and dried to obtain 2.4 g of crude crystals. The crude crystals were recrystallized from isopropyl alcohol to obtain 1.6 g of compound (c). The yield was 14% (based on 5-(2-hydroxyethyl)-2-(2,4-dihydroxyphenyl)-2H-benzotriazole). The melting point was 138°C.

[0048] Furthermore, the purity of compound (c) was measured by HPLC analysis. <Measurement conditions> Equipment: LC-20A (Shimadzu Corporation) Column used: SUMIPAX ODS A-212 6.0 x 150 mm 5 μm Column temperature: 40℃ Mobile phase: acetonitrile / water = 6 / 4 (phosphoric acid 3 ml / L) Flow rate: 1.0ml / min Detection: UV 250 nm <Measurement results> HPLC surface purity: 97.8%

[0049] Furthermore, when the ultraviolet-visible absorption spectrum of compound (c) was measured, the maximum absorption wavelength λmax was 344.3 nm, and the molar absorption coefficient ε at that wavelength was 21200. The spectrum is shown in FIG.

[0050] Furthermore, NMR analysis of compound (c) provided results supporting the above structure. The obtained 1H-NMR spectrum is as follows: δ=10.62(s, 1H, phenolic OH),7.90(d,J=9.2Hz,1H,phenol-H),7.78(s,1H,benzotriazole-H),7.72(d,J=9.2Hz,1H,benzotriaz ole-H),7.39(dd,J=9.2,1.5Hz,1H,benzotriazole-H),6.67(d,J=3.1Hz,1H,phenol-H),6.62(dd,J=8. 8,2.7Hz,1H,phenol-H),4.92(t,J=5.7Hz,1H,methylene-OH),4.71(t,J=5.0Hz,1H,methylene-OH),4. 03(t,J=5.0Hz,2H,methylene-H),3.74-3.67(m,4H,methylene-H),2.89(t,J=6.9Hz,2H,methylene-H)

[0051] [Preparation of polyvinyl alcohol film] 2 g of polyvinyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.: n = approximately 2000, saponification degree approximately 80 mol%) and 38 g of water were added to a 100 ml screw tube and stirred at 25 °C for 48 hours to prepare aqueous polyvinyl alcohol solutions. Compounds (a), (b), and (c) obtained in Examples 1 to 3, as well as compound (d), 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, a conventional UV absorber used as a comparative example, and compound (e), 2,4-dihydroxybenzophenone, a conventional UV absorber used in polyvinyl alcohol, were added in an amount of 0.002 g to 40 g of separate aqueous polyvinyl alcohol solutions and stirred at 25 °C for 1 hour to disperse the dispersion. 3.6 g of each dispersion was added to a 4.8 cm diameter Petri dish and dried at room temperature for 96 hours to obtain a 0.05 mm thick polyvinyl alcohol film containing 0.1% dispersion of the UV absorber.

[0052] [UV-Visible Absorption Spectrum Measurement] The ultraviolet-visible absorption spectrum of the polyvinyl alcohol film obtained above was measured under the following conditions. The absorbance at each wavelength is shown in Table 1.

[0053] <Measurement conditions> Equipment: UV-1850 (Shimadzu Corporation) Measurement wavelength: 300~450nm

[0054] [Table 1]

[0055] From Table 1, it can be seen that the product of the present invention has a higher absorbance at the maximum absorption wavelength in polyvinyl alcohol film and is well dispersed in polyvinyl alcohol compared to conventional ultraviolet absorbents. It also has a high absorbance in the 380-390 nm range, and can absorb the entire ultraviolet region. [Industrial Applicability]

[0056] The benzotriazole derivative compound of the present invention exhibits excellent ultraviolet absorption properties in a polyvinyl alcohol film, absorbing strongly throughout the entire ultraviolet region, and can be suitably used in display applications, agricultural applications, packaging applications, and the like.

Claims

1. A benzotriazole derivative compound represented by the following general formula (1): 【Chemistry 1】 General formula (1) [In the formula, R １ represents an alkylene group having 1 to 8 carbon atoms or an alkylenecarbonyl group having 1 to 8 carbon atoms, R ２ represents an alkylene group having 1 to 8 carbon atoms, an alkyleneoxy group having 1 to 8 carbon atoms, an alkylenecarbonyl group having 1 to 8 carbon atoms, an alkylenecarbonyloxy group having 1 to 8 carbon atoms, or an alkyleneoxycarbonyl group having 1 to 8 carbon atoms.

2. R in the above general formula (1) １ is an alkylene group having 1 to 2 carbon atoms or an alkylenecarbonyl group having 1 to 2 carbon atoms, and R ２ is an alkylene group having 1 to 2 carbon atoms, an alkyleneoxy group having 1 to 2 carbon atoms, an alkylenecarbonyl group having 1 to 2 carbon atoms, an alkylenecarbonyloxy group having 1 to 2 carbon atoms, or an alkyleneoxycarbonyl group having 1 to 2 carbon atoms.

3. R in the above general formula (1) １ is an alkylene group having 1 to 2 carbon atoms, and R ２ 2. The benzotriazole derivative compound according to claim 1, wherein is an alkylene group having 1 to 2 carbon atoms, an alkyleneoxy group having 1 to 2 carbon atoms, or an alkyleneoxycarbonyl group having 1 to 2 carbon atoms.

4. An ultraviolet absorber containing the benzotriazole derivative compound according to any one of claims 1 to 3.

5. A polyvinyl alcohol resin composition comprising a polyvinyl alcohol resin and the benzotriazole derivative compound according to any one of claims 1 to 3 blended therein.

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