JP5518613B2 - Benzotriazole derivative compounds - Google Patents

Description

  The present invention relates to a novel benzotriazole derivative compound, and also relates to an ultraviolet absorber which exhibits high absorption in a long wavelength ultraviolet region of 350 nm or more containing the novel compound.

  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. In addition, a sheet or film to which an ultraviolet absorber is added is used for the purpose of blocking ultraviolet rays generated from sunlight or lighting equipment. As such ultraviolet absorbers, for example, benzophenone-based, benzotriazole-based, benzoate-based, salicylate-based, or triazine-based compounds are known.

  However, the conventional UV absorbers have the property of producing volatilization and bleed of themselves, so when the amount of addition is increased in response to bleed and volatilization, it will be exposed to the light irradiation environment. The coloring also increased, and the added resin was not yet satisfactory in terms of light resistance, thermal discoloration and the like.

  In order to suppress bleeding and volatilization of the ultraviolet absorber, attempts to make a ultraviolet absorber polymer by introducing a polymerizable group into the ultraviolet absorber and homopolymerizing or copolymerizing are proposed in Patent Documents 1 to 5.

JP 60-38411 A

JP-A 63-185969

JP-A 63-227575

Japanese Patent Application Laid-Open No. 3-28185

Japanese Patent Laid-Open No. 9-34057

  However, although the ultraviolet absorbent polymers described in these documents were effective in preventing bleeding and volatilization, the ability to absorb ultraviolet rays in a long wavelength region of 350 nm or more is not sufficient, or absorption in visible light of 400 nm or more is not achieved. For this reason, there is a problem that the added resin is colored yellow.

  Therefore, an object of the present invention is to provide a polymerizable new compound that enhances absorption in a long wavelength region of 350 nm or more and eliminates visible light absorption of 400 nm or more.

一般式（１）

［式中、Ｒ_１は水素原子、炭素数１〜８のアルキル基、アリール基又はアシル基を表す。Ｒ_２は炭素数１〜８のアルキレン基を表す。Ｒ_３は水素原子又はメチル基を表す。］ In order to solve the above-described problems, the present invention mainly uses a novel benzotriazole derivative compound represented by the following general formula (1) as an ultraviolet absorber monomer.

General formula (1)

[Wherein, R ₁ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, or an acyl group. R ₂ represents an alkylene group having 1 to 8 carbon atoms. R ₃ represents a hydrogen atom or a methyl group. ]

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

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

  In the benzotriazole derivative compound general formula (1) of the present invention, the maximum absorption wavelength λmax is 350 or more, the absorbance ε at that time is about 30000, and at the same time, there is no absorption in the visible light region of 400 nm or more. That is, the ability to absorb ultraviolet rays in the long wavelength region is sufficient, and when added to the resin, the resin is not colored yellow.

  In addition, since it has a polymerizable double bond, it can be homopolymerized or copolymerized, and can be easily polymerized in experiments, so that it can solve the problems of the prior art. Useful as an absorbent monomer.

  The present invention will be described in detail below. In the present invention, a compound represented by the following general formula (1) is used as an ultraviolet absorber monomer. The compounds represented by the following general formula (1) will be described below.

一般式（１）

General formula (1)

In the general formula (1), as an example of the optional substituent, R ₁ is a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl. Group, n-hexyl group, n-octyl group, 2-ethylhexyl group and the like, optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms; phenyl group, benzyl group, tolyl group, xylyl group, etc. Aryl group; acyl groups such as formyl group, acetyl group, propionyl group, butyryl group, benzoyl group and the like can be mentioned.

  Among the above substituents, an alkyl group is preferable.

As an example of the optional substituent, R ₂ is an optionally substituted linear or branched alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Can be mentioned.

  Among the above substituents, an ethylene group is preferable.

R ₃ represents a hydrogen atom or a methyl group.

  As benzotriazole derivative compound general formula (1) of this invention, the following can be mentioned, for example. 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.

The method for synthesizing the general formula (1) of the benzotriazole derivative compound of the present invention is not particularly limited, and conventionally known methods can be widely used. For example, the reaction formulas shown in the following (Chemical Formula 2 to Chemical Formula 5) are used. Can be synthesized. However, X represents a halogen atom.

  The polymerization method of the benzotriazole derivative compound of the present invention may be homopolymerization or copolymerization. Other polymerizable monomers that can be copolymerized are not particularly limited. For example, acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, methyl methacrylate, And methacrylic acid esters such as ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate and octyl methacrylate.

  The homopolymer or copolymer of the benzotriazole derivative compound of the present invention may be added to the resin or coated on the resin. The resin that can be added or applied is not particularly limited. For example, an α-olefin polymer such as polyethylene, polypropylene, polybutene, polypentene, poly-3-methylbutylene, polymethylpentene, or ethylene-vinyl acetate copolymer. Polyolefins such as coalesced ethylene-propylene copolymer, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, chlorinated Vinyl-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary Copolymer, vinyl chloride-styrene-acrylic Nitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride- Acrylic ester copolymer, vinyl chloride-maleic ester copolymer, vinyl chloride-methacrylic ester copolymer, vinyl chloride-acrylonitrile copolymer, halogen-containing synthetic resin such as internal plastic polyvinyl chloride, petroleum resin, Coumarone resin, polystyrene, copolymer of styrene and other monomers (maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene resin, acrylate ester-butadiene-styrene resin, methacrylate ester-butadiene- Styrene such as styrene resin Fat, 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 resin, polyurethane resin, unsaturated A polyester resin etc. can be mentioned.

  Although the use of the homopolymer or copolymer of the benzotriazole derivative compound of the present invention is not particularly limited, for example, optical films such as polarizing plate protective films and antireflection films, plastic lenses such as glasses and contact lenses, pharmaceuticals, foods , Packaging materials for packaging cosmetics, clothing, etc., agricultural films for greenhouses, insect repellent sheets, laminated films for dye-sensitized solar cells, and the like.

  The synthesis method of the benzotriazole derivative compound implemented by this invention and the characteristic of a compound are shown below. However, the synthesis method is not limited to this.

Example 1
[Intermediate; Synthesis of 2- [5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl] -5-octyloxyphenol]
4- (5-methoxy-2H-benzotriazol-2-yl) benzene-1,3-diol synthesized by a conventional method with a condenser with a ball, a thermometer, and a stirrer attached to a 1000 ml four-necked flask 176. 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, Reflux dehydration at ~ 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 10 L four-necked flask was equipped with a condenser with a ball, a thermometer, and a stirring device, and 216.9 g (0.587 mol) of 2- (5-methoxy-2H-benzotriazol-2-yl) -5-octyloxyphenol. 47% hydrobromic acid (125.8 g, 0.731 mol) and sulfolane (1800 ml) were added, and the mixture was 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 was 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. , 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 were added and refluxed at 113 to 118 ° C. for 10 hours. Dehydrated. 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 the mixture was cooled to 10 ° C., and the precipitated crystals were filtered, washed with 50 ml of isopropyl alcohol, dried in a dryer, and 2- [5- (2- 95.3 g of hydroxyethoxy) -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）
(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 ball condenser, a thermometer, and a stirring device, and 95.3 g of 2- [5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl] -5-octyloxyphenol ( 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 reflux dehydrated 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.

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 is shown in FIG. 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 Examples 3 to 5 below, ultraviolet to visible absorption spectra were measured under the same measurement conditions as in this example.

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%
In Example 3 below, HPLC measurement was performed under the same measurement conditions as in this example.

Moreover, the infrared absorption spectrum of the compound (a) was also measured. The measurement conditions are as follows.
<Measurement conditions>
Apparatus: FTIR-8400S (manufactured by Shimadzu Corporation)
Sample: 1/200 (KBr)
The obtained infrared absorption spectrum is shown in FIG. In the following examples, infrared absorption spectrum measurement was performed under the same measurement conditions as in this example.

Moreover, as a result of conducting NMR measurement 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. Further, s is a singlet, d is a doublet, t is a triplet, dd is a doublet doublet, b is a broadcast singlet, and m is an abbreviation of multiplet. The same applies to all the following examples.
The contents of the obtained NMR spectrum are as follows.
δ 11.3 (s, OH), 8.19 (d, 1H, J = 9.9 Hz, benzotriazol-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, benzotriazol-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, 1 H, 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, _{H, CH 2 -H), 1.2-1.6} (m, 10H, (CH 2) 5 -H), 0.89 (s, 3H, CH 3 -H)

化合物（ｂ）

メタクリル酸をアクリル酸とした以外は実施例２と同様にして、化合物（ｂ）を収率４３％（２−［５−（２−ヒドロキシエトキシ）−２Ｈ−ベンゾトリアゾール−２−イル］−５−オクチルオキシフェノールから）で得た。融点８６℃、最大吸収波長λｍａｘが３５１ｎｍの時の吸光度εは２９７００、ＨＰＬＣ面百純度９８．７％であった。紫外〜可視吸収スペクトルを図２に示す。赤外線吸収スペクトルを図６に示す。 (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 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. -From octyloxyphenol). When the melting point was 86 ° C. and the maximum absorption wavelength λmax was 351 nm, the absorbance ε was 29700, and the HPLC surface purity was 98.7%. The ultraviolet to visible absorption spectrum is shown in FIG. An infrared absorption spectrum is shown in FIG.

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. In the following examples, NMR measurement was performed under the same measurement conditions as in this example.
δ 11.3 (b, OH), 8.21 (d, 1H, J = 9.07 Hz, benzotriazol-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 = 10.5Hz , 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）

２００ｍｌの４つ口フラスコに玉付きコンデンサー、温度計、撹拌装置を取り付け、４−（５−メトキシ−２Ｈ−ベンゾトリアゾール−２−イル）ベンゼン−１，３−ジオール１７．０ｇ（０．０６６モル）、メチルイソブチルケトン３５ｍｌ、１−ブロモブタン９．２ｇ（０．０６７モル）、炭酸ナトリウム５．６ｇ（０．０５３モル）、ヨウ化カリウム４．９ｇを入れて１０５〜１１５℃で４時間還流撹拌した。水３５ｍｌを加え、静置して下層部の水層を分離して除去し、温水３５ｍｌで洗浄した。メチルイソブチルケトン３５ｍｌを減圧で回収後にイソプロピルアルコール１００ｍｌを加え、析出した結晶をろ過し、イソプロピルアルコール２０ｍｌで洗浄し、乾燥して、５−ブトキシ−２−（５−メトキシ−２Ｈ−ベンゾトリアゾール−２−イル）フェノールを１５．０ｇ得た。 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 mol) of 4- (5-methoxy-2H-benzotriazol-2-yl) benzene-1,3-diol. ), 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 stirred at reflux at 105 to 115 ° C. for 4 hours. did. 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 was equipped with a ball 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, 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 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, a thermometer and a stirring device, and 6.2 g (0.021 mol) of 5-butoxy-2- (5-hydroxy-2H-benzotriazol-2-yl) phenol, 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 reflux dehydrated at 113 to 118 ° C. for 10 hours. . 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 stirrer, and 5-butoxy-2- (5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl) phenol 3.4 g (0 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 at 110 to 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. The ultraviolet to visible absorption spectrum is shown in FIG. An infrared absorption spectrum is shown in FIG.

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%
In the following examples, HPLC measurement was performed under the same measurement conditions as in this example.

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, benzotriazol-H), 7.80 (dd, 1H, J = 9.1 Hz, J = 0.66 Hz, J = 0.66 Hz, benzotriazol-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, benzotriazol-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）

２００ｍｌの４つ口フラスコに玉付きコンデンサー、温度計、撹拌装置を取り付け、４−（５−メトキシ−２Ｈ−ベンゾトリアゾール−２−イル）ベンゼン−１，３−ジオール１０．０ｇ（０．０３９モル）、メチルイソブチルケトン４０ｍｌ、ブロモエタン６．４ｇ（０．０５９モル）、炭酸ナトリウム３．３ｇ（０．０３１モル）、ヨウ化カリウム３．０ｇを入れて９５〜１１０℃で６時間還流撹拌した。水２０ｍｌを加え、静置して下層部の水層を分離して除去し、温水２０ｍｌで洗浄した。メチルイソブチルケトン４０ｍｌを減圧で回収後にイソプロピルアルコール１００ｍｌを加え、析出した結晶をろ過し、イソプロピルアルコール２５ｍｌで洗浄し、乾燥して、５−エトキシ−２−（５−メトキシ−２Ｈ−ベンゾトリアゾール−２−イル）フェノールを８．２ｇ得た。 (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 mol) of 4- (5-methoxy-2H-benzotriazol-2-yl) benzene-1,3-diol ), 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, 47 g of hydrobromic acid (6.2 g, 0.036 mol) and 82 ml of sulfolane 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 was equipped with a ball condenser, a thermometer, and a stirrer, and 4.6 g (0.017 mol) of 5-ethoxy-2- (5-hydroxy-2H-benzotriazol-2-yl) phenol, 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 refluxed at 113 to 118 ° C. for 8 hours. did. 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 a solid content of 5.0 g of 5-ethoxy-2- [5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl] phenol.

  4. A 300 ml four-necked flask is equipped with a ball condenser, a thermometer, and a stirrer, and the solid content of 5-ethoxy-2- [5- (2-hydroxyethoxy) -2H-benzotriazol-2-yl] phenol 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 reflux 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). When the melting point was 156 ° C. and the maximum absorption wavelength λmax was 350 nm, the absorbance ε was 29000, and the HPLC surface purity was 98.1%. The ultraviolet to visible absorption spectrum is shown in FIG. An infrared absorption spectrum is shown in FIG.

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, benzotriazol-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 6)
[Synthesis of copolymer (e); compound (a) / methyl methacrylate copolymer (50 wt% / 50 wt%)]
A 200 ml four-necked flask is equipped with a condenser with a ball, a thermometer, a stirrer, and a gas blowing tube, 20 g of compound (a), 20 g of methyl methacrylate, 40 g of ethyl acetate, 2,2′-azobis (2-methylbutyro (Nitrile) 0.6 g was added, the inside of the flask was purged with nitrogen at a nitrogen gas flow rate of 10 ml / min for 1 hour, and then the polymerization reaction was carried out at 78 to 88 ° C. for 10 hours under reflux. After completion of the polymerization reaction, 20 g of ethyl acetate was added to obtain a solution of copolymer (e). The solution had a non-volatile content of 40.2%, a viscosity of 1190 mPa · s / 25 ° C., a polymer weight average molecular weight (Mw) of 75400, a number average molecular weight (Mn) of 19100, and a polydispersity (Mw / Mn) was 3.95.

When the ultraviolet to visible absorption spectrum of the copolymer (e) obtained by removing the solvent from the above solution under reduced pressure was measured, the maximum absorption wavelength λmax was 349 nm. The spectrum is shown in FIG. The spectrum measurement conditions are as follows.
<Measurement conditions>
Apparatus: UV-2450 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-450 nm
Solvent: Chloroform Concentration: 20 ppm
Cell: 1 cm quartz In the following examples, ultraviolet to visible absorption spectra were also measured under the same measurement conditions as in this example.

(Example 7)
[Synthesis of Copolymer (f); Compound (b) / Methyl Methacrylate Copolymer (50 wt% / 50 wt%)]
A solution of the copolymer (f) was obtained in the same manner as in Example 6 except that the compound (a) was changed to the compound (b). The weight average molecular weight (Mw) of the polymer was 57100, the number average molecular weight (Mn) was 24700, and the polydispersity (Mw / Mn) was 2.32. Moreover, when the ultraviolet-visible absorption spectrum of the copolymer (f) was measured, the maximum absorption wavelength (lambda) max was 350 nm. The spectrum is shown in FIG.

(Example 8)
[Synthesis of Copolymer (g); Compound (c) / Methyl Methacrylate Copolymer (50 wt% / 50 wt%)]
A solution of the copolymer (g) was obtained in the same manner as in Example 6 except that the compound (a) was changed to the compound (c). The weight average molecular weight (Mw) of the polymer was 73500, the number average molecular weight (Mn) was 25400, and the polydispersity (Mw / Mn) was 2.89. Further, when the ultraviolet to visible absorption spectrum of the copolymer (g) was measured, the maximum absorption wavelength λmax was 349 nm. The spectrum is shown in FIG.

  The benzotriazole derivative of the present invention exhibits high absorption in a long wavelength ultraviolet region of 350 nm or more, and at the same time, has no absorption in the visible light region of 400 nm or more, and has a polymerizable double bond. It is effective as a UV absorber monomer. The ultraviolet absorber polymer obtained by homopolymerization or copolymerization of this ultraviolet absorber monomer can be suitably used as an ultraviolet absorber for resins, among which optical films, plastic lenses, packaging materials, agricultural films, insect repellents. It can be suitably used for sheets, laminated films for dye-sensitized solar cells, and the like.

It is an ultraviolet-visible absorption spectrum of a compound (a). It is an ultraviolet-visible absorption spectrum of a compound (b). It is an ultraviolet-visible absorption spectrum of a compound (c). It is an ultraviolet-visible absorption spectrum of a compound (d). It is an infrared absorption spectrum of a compound (a). It is an infrared absorption spectrum of a compound (b). It is an infrared absorption spectrum of a compound (c). It is an infrared absorption spectrum of a compound (d). It is an ultraviolet-visible absorption spectrum of a copolymer (e). It is an ultraviolet-visible absorption spectrum of a copolymer (f). It is an ultraviolet-visible absorption spectrum of a copolymer (g).

Claims (4)

A benzotriazole derivative compound represented by the following general formula (1):

General formula (1)

[Wherein, R ₁ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, or an acyl group. R ₂ represents an alkylene group having 1 to 8 carbon atoms. R ₃ represents a hydrogen atom or a methyl group. ] The benzotriazole derivative compound according to claim 1, wherein R ₁ in the general formula (1) is an alkyl group having 2 to 8 carbon atoms. The benzotriazole derivative compound according to claim 1, wherein R ₁ in the general formula (1) is an alkyl group having 2 to 8 carbon atoms, and R ₂ is an ethylene group. The ultraviolet absorber containing the benzotriazole derivative compound of any one of Claims 1-3.

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