JP6991497B2 - Benzotriazole derivative compounds and their polymers - Google Patents
Benzotriazole derivative compounds and their polymers Download PDFInfo
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- JP6991497B2 JP6991497B2 JP2017029521A JP2017029521A JP6991497B2 JP 6991497 B2 JP6991497 B2 JP 6991497B2 JP 2017029521 A JP2017029521 A JP 2017029521A JP 2017029521 A JP2017029521 A JP 2017029521A JP 6991497 B2 JP6991497 B2 JP 6991497B2
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- -1 Benzotriazole derivative compounds Chemical class 0.000 title claims description 111
- 229920000642 polymer Polymers 0.000 title description 40
- 238000006243 chemical reaction Methods 0.000 claims description 85
- 239000000463 material Substances 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 40
- 229920001577 copolymer Polymers 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 34
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 33
- 238000000034 method Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000005259 measurement Methods 0.000 description 17
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
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- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 3
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- HNWDFLSODFEDIT-UHFFFAOYSA-N n-(1,2,2,6,6-pentamethylpiperidin-3-yl)prop-2-enamide Chemical compound CN1C(C)(C)CCC(NC(=O)C=C)C1(C)C HNWDFLSODFEDIT-UHFFFAOYSA-N 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 150000002988 phenazines Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920005671 poly(vinyl chloride-propylene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920002098 polyfluorene Chemical class 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000004322 quinolinols Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- OZTYRAWXWCSOAF-DIYDOPDJSA-N tetramethylsilane;trichloro(deuterio)methane Chemical compound [2H]C(Cl)(Cl)Cl.C[Si](C)(C)C OZTYRAWXWCSOAF-DIYDOPDJSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
Description
本発明は、新規なベンゾトリアゾール誘導体化合物、及びそれらの重合体に関し、さらに、これらを含有する波長変換材料、及びそれを用いた農業用波長変換フィルムと太陽電池用波長変換フィルムに関する。さらに詳しくは、340nm付近の紫外線を強く吸収して410nm付近で強い青色発光を示す、優れた波長変換性を示す波長変換材料、及びそれを用いた農業用波長変換フィルムと太陽電池用波長変換フィルムに関する。 The present invention relates to novel benzotriazole derivative compounds and polymers thereof, and further to wavelength conversion materials containing them, and wavelength conversion films for agriculture and wavelength conversion films for solar cells using the same. More specifically, a wavelength conversion material exhibiting excellent wavelength conversion property that strongly absorbs ultraviolet rays in the vicinity of 340 nm and emits strong blue light in the vicinity of 410 nm, and a wavelength conversion film for agriculture and a wavelength conversion film for solar cells using the same. Regarding.
波長変換材料は照射された特定の波長の光を吸収して別の波長の光を放出する材料であり、単体、有機溶媒中、樹脂中などで用いられ、幅広い分野で使用されている。 The wavelength conversion material is a material that absorbs the irradiated light of a specific wavelength and emits light of another wavelength, is used as a simple substance, in an organic solvent, in a resin, or the like, and is used in a wide range of fields.
波長変換材料を含有したフィルムを農作物の周辺に設置することで、特定の波長の光をより多く農作物に当て、農作物の生育を促進させることが実施されている。また、太陽電池は一般的に紫外域の感度が低く、太陽光に含まれる紫外線を十分活用できていないため、紫外線を可視光に変換することができる波長変換材料を含有したフィルムを太陽電池表面に取り付けることで、感度が高い可視光域の光をより多く取り入れて、太陽電池の効率を向上させることが実施されている。 By installing a film containing a wavelength conversion material around the crop, more light of a specific wavelength is applied to the crop to promote the growth of the crop. In addition, since solar cells generally have low sensitivity in the ultraviolet region and cannot fully utilize the ultraviolet rays contained in sunlight, a film containing a wavelength conversion material capable of converting ultraviolet rays into visible light is used on the surface of the solar cell. By attaching it to the solar cell, it is possible to improve the efficiency of the solar cell by taking in more light in the visible light region with high sensitivity.
上記の各用途で使用される波長変換材料には、紫外線を十分吸収して強い可視光を発する優れた波長変換性があることが求められている。すなわち、物質が光を吸収する程度を示す指標であるモル吸光係数が高く、吸収された光子数に対する放出された光子数の比で表される蛍光量子効率が高い波長変換材料が求められており、モル吸光係数及び蛍光量子効率が高いほど優れた波長変換材料となる。 The wavelength conversion material used in each of the above applications is required to have excellent wavelength conversion property of sufficiently absorbing ultraviolet rays and emitting strong visible light. That is, there is a demand for a wavelength conversion material having a high molar absorption coefficient, which is an index indicating the degree to which a substance absorbs light, and a high fluorescence quantum efficiency expressed by the ratio of the number of emitted photons to the number of absorbed photons. , The higher the molar absorption coefficient and the fluorescence quantum efficiency, the better the wavelength conversion material.
波長変換フィルムの波長変換性は、物体に特定の波長の光を当てたときに吸収される光の程度を示す吸光度と、蛍光量子効率で評価することができ、吸光度及び蛍光量子効率が高いほど優れた波長変換フィルムとなる。 The wavelength conversion property of a wavelength conversion film can be evaluated by the absorbance indicating the degree of light absorbed when light of a specific wavelength is applied to an object and the fluorescence quantum efficiency. The higher the absorbance and the fluorescence quantum efficiency, the higher the absorbance and the quantum efficiency. It is an excellent wavelength conversion film.
波長変換材料はフィルム等の樹脂中で使用されることが多く、固体状態で波長変換性が優れていることが求められており、さらに、波長変換材料自体のブリードが起こらないような、樹脂との相溶性が高い波長変換材料が求められている。また、波長変換材料は、フィルムの表面に成膜して使用されることが多く、成膜時に有機溶媒に溶解させる必要があり、有機溶媒に溶解しやすい波長変換材料が求められている。 Wavelength conversion materials are often used in resins such as films, and are required to have excellent wavelength conversion properties in the solid state. Furthermore, with resins that do not cause bleeding of the wavelength conversion materials themselves. There is a demand for a wavelength conversion material having high compatibility with the above. Further, the wavelength conversion material is often used by forming a film on the surface of a film and needs to be dissolved in an organic solvent at the time of film formation, and there is a demand for a wavelength conversion material that is easily dissolved in an organic solvent.
これまで各種の波長変換材料が提案されており、それを用いたフィルムを取り付けることで、植物の生育促進や太陽電池の効率向上が示されている。しかしながら、モル吸光係数及び蛍光量子効率ともに優れた波長変換材料や、吸光度及び蛍光量子効率ともに優れた波長変換フィルムは少なく、特に紫外線を410nm付近の青色光に効率よく変換する波長変換材料や波長変換フィルムはほとんどない。 Various wavelength conversion materials have been proposed so far, and it has been shown that the growth of plants and the efficiency of solar cells are improved by attaching a film using the materials. However, there are few wavelength conversion materials with excellent molar absorbance coefficient and fluorescence quantum efficiency, and wavelength conversion films with excellent absorbance and fluorescence quantum efficiency. In particular, wavelength conversion materials and wavelength conversion that efficiently convert ultraviolet rays into blue light near 410 nm. There is almost no film.
波長変換材料としては一般的に有機蛍光色素が用いられており、例えば非特許文献1に記載されているように、オキサジアゾール誘導体、トリアゾール誘導体等が提案されている。しかし、これらの化合物のモル吸光係数及び蛍光量子効率はすべてが十分大きいと言えず、特に青色蛍光色素フィルムの蛍光量子効率が不十分であり、波長変換性が高いとは言えない。 Organic fluorescent dyes are generally used as the wavelength conversion material, and for example, as described in Non-Patent Document 1, oxadiazole derivatives, triazole derivatives and the like have been proposed. However, it cannot be said that the molar absorption coefficient and the fluorescence quantum efficiency of these compounds are all sufficiently large, and in particular, the fluorescence quantum efficiency of the blue fluorescent dye film is insufficient, and it cannot be said that the wavelength conversion property is high.
農業用及び太陽電池用の波長変換フィルムでは、例えば特許文献1~4に記載されているように、フェナジン誘導体、オキサゾール誘導体、ベンゾ複素環誘導体、キノリノール誘導体の金属錯体、ベンゾチアジアゾール誘導体等を波長変換材料として使用することが提案されており、それらを添加した波長変換フィルムを用いることで、植物の生育促進及び太陽電池の効率向上が示されている。しかしながら、これら波長変換材料のモル吸光係数や、波長変換フィルムの吸光度の記載がない。 In wavelength conversion films for agriculture and solar cells, for example, as described in Patent Documents 1 to 4, wavelength conversion of a phenazine derivative, an oxazole derivative, a benzoheterocyclic derivative, a metal complex of a quinolinol derivative, a benzothiazol derivative and the like is performed. It has been proposed to use it as a material, and it has been shown that the use of a wavelength conversion film to which they are added promotes the growth of plants and improves the efficiency of solar cells. However, there is no description of the molar extinction coefficient of these wavelength conversion materials or the absorbance of the wavelength conversion film.
特許文献5~6では、本発明でも用いられているベンゾトリアゾール誘導体が提案されており、最大発光波長440~460nm程度の化合物が示されている。これらを波長変換材料として使用することは可能であるが、農作物の生育促進や太陽電池の効率向上に最適な波長は、農作物や太陽電池の種類によって異なっており、410nm付近で発光する波長変換材料も必要である。 Patent Documents 5 to 6 propose benzotriazole derivatives also used in the present invention, and show compounds having a maximum emission wavelength of about 440 to 460 nm. Although it is possible to use these as wavelength conversion materials, the optimum wavelength for promoting the growth of crops and improving the efficiency of solar cells differs depending on the type of crop and solar cell, and is a wavelength conversion material that emits light at around 410 nm. Is also needed.
このような状況下、本発明における課題は、溶液中、又はフィルム状態において、紫外線を410nm付近の青色光に効率よく変換する優れた波長変換性を示す波長変換材料を提供することにある。 Under such circumstances, an object of the present invention is to provide a wavelength conversion material exhibiting excellent wavelength conversion property that efficiently converts ultraviolet rays into blue light in the vicinity of 410 nm in a solution or in a film state.
本発明では、下記一般式(1)で示されるベンゾトリアゾール誘導体化合物、及びそれらを有する重合体を、波長変換材料、農業用波長変換フィルム、及び太陽電池用波長変換フィルムに用いることを上記課題の主要な解決手段とする。
一般式(1)
[式中R1は、炭素数1~18のアルキル基であり、R
2
がアルキル炭素数1~4のアクリロイルオキシアルキル基、アルキル炭素数1~4のアクリロイルオキシヒドロキシアルキル基、アルキル炭素数1~4のメタクリロイルオキシアルキル基もしくはアルキル炭素数1~4のメタクリロイルオキシヒドロキシアルキル基である]
In the present invention, it is an object of the above-mentioned subject to use the benzotriazole derivative compound represented by the following general formula (1) and the polymer having them as a wavelength conversion material, an agricultural wavelength conversion film, and a wavelength conversion film for a solar cell. It is the main solution.
General formula (1)
[In the formula, R 1 is an alkyl group having 1 to 18 carbon atoms, R 2 is an acryloyloxyalkyl group having 1 to 4 alkyl carbon atoms, an acryloyloxyhydroxyalkyl group having 1 to 4 alkyl carbon atoms, and an alkyl carbon number. It is a methacryloyloxyalkyl group of 1 to 4 or a methacryloyloxyhydroxyalkyl group having 1 to 4 alkyl carbon atoms].
上記一般式(1)で示されるベンゾトリアゾール誘導体化合物は、好ましくは、R1が炭素数1~8のアルキル基であり、R 2 がアルキル炭素数1~2のアクリロイルオキシアルキル基もしくはアルキル炭素数1~2のメタクリロイルオキシアルキル基である。 In the benzotriazole derivative compound represented by the general formula (1), R 1 is preferably an alkyl group having 1 to 8 carbon atoms, and R 2 is an acryloyloxyalkyl group or an alkyl carbon having an alkyl carbon number of 1 to 2. It is a methacryloyloxyalkyl group of the number 1-2.
本発明の一般式(1)で示されるベンゾトリアゾール誘導体化合物、及びそれらを有する重合体は、340nm付近の紫外線を強く吸収して410nm付近で強い青色発光を示し、溶液のモル吸光係数が約30000で蛍光量子効率が約70%であり、フィルム状態で高い吸光度を示して蛍光量子効率は53~60%であることから、紫外線を青色光に変換する波長変換性が高く、従来技術の課題を解決し得る波長変換材料、農業用波長変換フィルム、及び太陽電池用波長変換フィルムとして有用である。 The benzotriazole derivative compound represented by the general formula (1) of the present invention and the polymer having them strongly absorb ultraviolet rays in the vicinity of 340 nm and exhibit strong blue emission in the vicinity of 410 nm, and the molar absorbance coefficient of the solution is about 30,000. The fluorescence quantum efficiency is about 70%, and the fluorescence quantum efficiency is 53 to 60%, showing high absorbance in the film state. Therefore, the wavelength conversion property for converting ultraviolet light into blue light is high, which poses a problem of the prior art. It is useful as a wavelength conversion material that can be solved, a wavelength conversion film for agriculture, and a wavelength conversion film for solar cells.
以下に本発明につき詳細に説明する。本発明は波長変換材料、及び波長変換フィルムとして、下記一般式(1)で示されるベンゾトリアゾール誘導体化合物、及びそれらを有する重合体を用いたものである。以下に下記一般式(1)において表される化合物について説明する。
一般式(1)中、R1はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ヘキシル基、オクチル基、2-エチルヘキシル基、ドデシル基、オクタデシル基等の炭素数1~18の直鎖または分岐のアルキル基;カルボキシエチル基、カルボキシヘプチル基等のアルキル炭素数1~7のカルボキシアルキル基;メトキシカルボニルエチル基、オクチルオキシカルボニルヘプチル基等の各アルキルの炭素数の合計が2~15のアルキルオキシカルボニルアルキル基;ヒドロキシエチル基、ヒドロキシオクチル基等の炭素数1~8のヒドロキシアルキル基;メチルカルボニルオキシエチル基、ヘプチルカルボニルオキシオクチル基等の各アルキルの炭素数の合計が2~15のアルキルカルボニルオキシアルキル基;ホルミル基;アセチル基、プロピオニル基、ブチリル基、イソブチリル基、オクタノイル基、2-エチルヘキサノイル基等のアルキル炭素数1~7の直鎖又は分岐のアルキルカルボニル基;ベンゾイル基;トルオイル基;アクリロイル基;メタクリロイル基;アクリロイルオキシエチル基、アクリロイルオキシブチル基等のアルキル炭素数1~4のアクリロイルオキシアルキル基;アクリロイルオキシ-2-ヒドロキシプロピル基等のアルキル炭素数1~4のアクリロイルオキシヒドロキシアルキル基;メタクリロイルオキシエチル基、メタクリロイルオキシブチル基等のアルキル炭素数1~4のメタクリロイルオキシアルキル基;メタクリロイルオキシ-2-ヒドロキシプロピル基等のアルキル炭素数1~4のメタクリロイルオキシヒドロキシアルキル基が挙げられ、R2は水素原子;メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ヘキシル基、オクチル基、2-エチルヘキシル基、ドデシル基、オクタデシル基等の炭素数1~18の直鎖または分岐のアルキル基;フェニル基;トリル基;アクリロイルオキシエチル基、アクリロイルオキシブチル基等のアルキル炭素数1~4のアクリロイルオキシアルキル基;アクリロイルオキシ-2-ヒドロキシプロピル基等のアルキル炭素数1~4のアクリロイルオキシヒドロキシアルキル基;メタクリロイルオキシエチル基、メタクリロイルオキシブチル基等のアルキル炭素数1~4のメタクリロイルオキシアルキル基;メタクリロイルオキシ-2-ヒドロキシプロピル基等のアルキル炭素数1~4のメタクリロイルオキシヒドロキシアルキル基が挙げられ、
かつ、R1がアクリロイル基、メタクリロイル基、アルキル炭素数1~4のアクリロイルオキシアルキル基、アルキル炭素数1~4のアクリロイルオキシヒドロキシアルキル基、アルキル炭素数1~4のメタクリロイルオキシアルキル基もしくはアルキル炭素数1~4のメタクリロイルオキシヒドロキシアルキル基であるか、および/またはR2がアルキル炭素数1~4のアクリロイルオキシアルキル基、アルキル炭素数1~4のアクリロイルオキシヒドロキシアルキル基、アルキル炭素数1~4のメタクリロイルオキシアルキル基もしくはアルキル炭素数1~4のメタクリロイルオキシヒドロキシアルキル基である。
In the general formula (1), R 1 is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a dodecyl. A linear or branched alkyl group having 1 to 18 carbon atoms such as a group and an octadecyl group; a carboxyalkyl group having 1 to 7 alkyl carbon atoms such as a carboxyethyl group and a carboxyheptyl group; a methoxycarbonylethyl group and an octyloxycarbonylheptyl group. Alkyloxycarbonylalkyl groups having a total carbon number of 2 to 15 for each alkyl such as, etc .; hydroxyalkyl groups having 1 to 8 carbon atoms such as hydroxyethyl groups and hydroxyoctyl groups; methylcarbonyloxyethyl groups, heptylcarbonyloxyoctyl groups, etc. Alkylcarbonyloxyalkyl groups having a total carbon number of 2 to 15 for each alkyl such as; formyl group; acetyl group, propionyl group, butyl group, isobutylyl group, octanoyl group, 2-ethylhexanoyl group, etc. Up to 7 linear or branched alkylcarbonyl groups; benzoyl groups; toluoil groups; acryloyl groups; methacryloyl groups; acryloyloxyethyl groups, acryloyloxybutyl groups, and other alkylloyloxyalkyl groups with 1 to 4 alkyl carbon atoms; acryloyloxy- Acryloyloxyhydroxyalkyl group having 1 to 4 alkyl carbon atoms such as 2-hydroxypropyl group; Methacryloyloxyalkyl group having 1 to 4 alkyl carbon atoms such as methacryloyloxyethyl group and methacryloyloxybutyl group; Methacryloyloxy-2-hydroxypropyl Examples thereof include methacryloyloxyhydroxyalkyl groups having 1 to 4 alkyl carbon atoms such as groups, and R2 is a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-. A linear or branched alkyl group having 1 to 18 carbon atoms such as a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, an octadecyl group; a phenyl group; a trill group; an acryloyloxyethyl group or an acryloyloxybutyl group. Acryloyloxyalkyl groups having 1 to 4 alkyl carbon atoms such as; acryloyloxyhydroxyalkyl groups having 1 to 4 alkylcarbons such as acryloyloxy-2-hydroxypropyl groups; alkylcarbons such as methacryloyloxyethyl groups and methacryloyloxybutyl groups. Methacryloyloxyalkyl groups of numbers 1 to 4; Examples thereof include a methacryloyloxyhydroxyalkyl group having 1 to 4 alkyl carbon atoms such as a methacryloyloxy-2-hydroxypropyl group.
In addition, R 1 is an acryloyl group, a methacryloyl group, an acryloyloxyalkyl group having 1 to 4 alkyl carbon atoms, an acryloyloxyhydroxyalkyl group having 1 to 4 alkyl carbon atoms, a methacryloyloxyalkyl group or an alkyl carbon having 1 to 4 alkyl carbon atoms. It is a methacryloyloxyhydroxyalkyl group having the number 1 to 4, and / or an acryloyloxyalkyl group having an alkyl carbon number of 1 to 4, an acryloyloxyhydroxyalkyl group having an alkyl carbon number of 1 to 4, and an alkyl carbon number of 1 to 4. It is a methacryloyloxyalkyl group of 4 or a methacryloyloxyhydroxyalkyl group having 1 to 4 alkyl carbon atoms.
上記一般式(1)で示されるベンゾトリアゾール誘導体化合物は、好ましくは、R1が炭素数1~8のアルキル基、アルキル炭素数1~2のアクリロイルオキシアルキル基、またはアルキル炭素数1~2メタクリロイルオキシアルキル基であり、R2が炭素数1~8のアルキル基、アルキル炭素数1~2のアクリロイルオキシアルキル基、またはアルキル炭素数1~2のメタクリロイルオキシアルキル基であり、
かつ、R1がアルキル炭素数1~2のアクリロイルオキシアルキル基もしくはアルキル炭素数1~2メタクリロイルオキシアルキル基であるか、および/またはR2がアルキル炭素数1~2のアクリロイルオキシアルキル基もしくはアルキル炭素数1~2のメタクリロイルオキシアルキル基である化合物である。
The benzotriazole derivative compound represented by the general formula (1) is preferably an alkyl group having 1 to 8 carbon atoms, an acryloyloxyalkyl group having 1 to 2 alkyl carbon atoms, or a methacryloyl having 1 to 2 alkyl carbon atoms. It is an oxyalkyl group, and R 2 is an alkyl group having 1 to 8 carbon atoms, an acryloyloxyalkyl group having 1 to 2 alkyl carbon atoms, or a methacryloyloxyalkyl group having 1 to 2 alkyl carbon atoms.
And, R 1 is an acryloyloxyalkyl group having 1 to 2 alkyl carbon atoms or an alkyl methacryloyloxyalkyl group having 1 to 2 alkyl carbon atoms, and / or R 2 is an acryloyloxyalkyl group or alkyl having 1 to 2 alkyl carbon atoms. It is a compound which is a methacryloyloxyalkyl group having 1 to 2 carbon atoms.
本発明のベンゾトリアゾール誘導体化合物一般式(1)としては、例えば、次に示すものを挙げることができる。
2-メタクリロイルオキシエチル 2-(4-メトキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレート、2-メタクリロイルオキシエチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレート、2-メタクリロイルオキシエチル 2-(4-アセトキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレート、2-メタクリロイルオキシエチル 2-(4-メタクリロイルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレート、2-メタクリロイルオキシエチル 2-[4-(2-メタクリロイルオキシエトキシ)フェニル]-2H-ベンゾトリアゾール-5-カルボキシレート、4-メタクリロイルオキシブチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレート、2-アクリロイルオキシエチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレート、オクチル 2-[4-(2-アクリロイルオキシエトキシ)フェニル]-2H-ベンゾトリアゾール-5-カルボキシレート、メチル 2-[4-(2-メタクリロイルオキシエトキシ)フェニル]-2H-ベンゾトリアゾール-5-カルボキシレート、オクチル 2-[4-(2-メタクリロイルオキシエトキシ)フェニル]-2H-ベンゾトリアゾール-5-カルボキシレート。
Examples of the benzotriazole derivative compound general formula (1) of the present invention include those shown below.
2-methacryloyloxyethyl 2- (4-methoxyphenyl) -2H-benzotriazole-5-carboxylate, 2-methacryloxyethyl 2- (4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate, 2 -Methacloyloxyethyl 2- (4-acetoxyphenyl) -2H-benzotriazole-5-carboxylate, 2-methacryloyloxyethyl 2- (4-methacryloyloxyphenyl) -2H-benzotriazole-5-carboxylate, 2- Methacyoyloxyethyl 2- [4- (2-methacyloxyethoxy) phenyl] -2H-benzotriazole-5-carboxylate, 4-methacryloxybutyl 2- (4-octyloxyphenyl) -2H-benzotriazole-5- Carboxylate, 2-acryloyloxyethyl 2- (4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate, octyl 2- [4- (2-acryloxyethoxy) phenyl] -2H-benzotriazole-5 -Carboxylate, methyl 2- [4- (2-methacryloyloxyethoxy) phenyl] -2H-benzotriazole-5-carboxylate, octyl 2- [4- (2-methacryloyloxyethoxy) phenyl] -2H-benzotriazole -5-Carboxyrate.
本発明のベンゾトリアゾール誘導体化合物一般式(1)を合成する方法に特に限定はなく、従来公知の反応原理を広く用いることができ、たとえば、下記(化2~化9)に示した反応式を経て合成することができる。ただし、Xはハロゲン原子を表す。
本発明のベンゾトリアゾール誘導体化合物の重合体は、単独重合体であれば一般式(1)におけるR1が炭素数1~8のアルキル基、アルキル炭素数1~2のアクリロイルオキシアルキル基、またはアルキル炭素数1~2のメタクリロイルオキシアルキル基であり、R2が炭素数1~8のアルキル基、アルキル炭素数1~2のアクリロイルオキシアルキル基、又はアルキル炭素数1~2のメタクリロイルオキシアルキル基であるとともに、R1がアルキル炭素数1~2のアクリロイルオキシアルキル基もしくはアルキル炭素数1~2メタクリロイルオキシアルキル基であるか、および/またはR2がアルキル炭素数1~2のアクリロイルオキシアルキル基もしくはアルキル炭素数1~2のメタクリロイルオキシアルキル基であるベンゾトリアゾール誘導体化合物の単独重合体である。また共重合体であれば前記ベンゾトリアゾール誘導体化合物と(メタ)アクリロイル基、ビニル基、アリル基といったラジカル重合性不飽和二重結合を有する化合物との共重合体である。 If the polymer of the benzotriazole derivative compound of the present invention is a homopolymer, R 1 in the general formula (1) is an alkyl group having 1 to 8 carbon atoms, an alkylloyloxyalkyl group having 1 to 2 carbon atoms, or an alkyl. It is a methacryloyloxyalkyl group having 1 to 2 carbon atoms, and R2 is an alkyl group having 1 to 8 carbon atoms, an acryloyloxyalkyl group having 1 to 2 alkyl carbon atoms, or a methacryloyloxyalkyl group having 1 to 2 alkyl carbon atoms. In addition, R 1 is an acryloyloxyalkyl group having 1 to 2 alkyl carbons or an alkylloyloxyalkyl group having 1 to 2 alkyl carbons, and / or R 2 is an acryloyloxyalkyl group having 1 to 2 alkyl carbons. It is a homopolymer of a benzotriazole derivative compound which is a methacryloyloxyalkyl group having 1 to 2 alkyl carbon atoms. Further, if it is a copolymer, it is a copolymer of the benzotriazole derivative compound and a compound having a radically polymerizable unsaturated double bond such as a (meth) acryloyl group, a vinyl group and an allyl group.
共重合体とする場合の共重合対象となる化合物は、具体的には、例えばメチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート等の(メタ)アクリル酸アルキルエステル類;グリシジル(メタ)アクリレート等のエポキシ基含有の不飽和単量体;(メタ)アクリルアミド、ダイアセトンアクリルアミド、ジメチルアクリルアミド、N‐イソプロピルアクリルアミド、ヒドロキシエチルアクリルアミド、N,N'-ジメチルアミノエチル(メタ)アクリレート、アクリロイルモルホリン、2-ビニルピリジン、4-ビニルピリジン、1-ビニルイミダゾール、N-ビニルカルバゾール、(4-ビニルフェニル)-ジフェニルアミン等の含窒素不飽和単量体;塩化ビニル、塩化ビニリデン等のハロゲン元素含有の不飽和単量体;スチレン、α-メチルスチレン、ビニルトルエン等の芳香族不飽和単量体;酢酸ビニル等のビニルエステル;ビニルエーテル;(メタ)アクリロニトリル等の不飽和シアン化合物単量体;4-(メタ)アクリロイルオキシ-2,2,6,6- テトラメチルピペリジン、4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルオキシ-1,2,2,6,6-ペンタメチルピペリジン、4-(メタ)アクリロイルアミノ-1,2,2,6,6-ペンタメチルピペリジン、4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジン、4-クロトノイルアミノ-2,2,6,6‐テトラメチルピペリジン、1-(メタ)アクリロイル-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、1-(メタ)アクリロイル-4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、1-クロトノイル-4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジン等の光安定性単量体;ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、カプロラクトン変性ヒドロキシ(メタ)アクリレート等の水酸基含有単量体;(メタ)アクリル酸、クロトン酸、イタコン酸、マレイン酸、無水マレイン酸等のカルボキシル基含有不飽和単量体;ビニルスルホン酸、スチレンスルホン酸、スルホエチル(メタ)アクリレート等のスルホン酸基含有不飽和単量体;2-(メタ)アクリロイルオキシエチルアシッドホスフェート、2-(メタ)アクリロイルオキシプロピルアシッドホスフェート、2-(メタ)アクリロイルオキシ-3-クロロプロピルアシッドホスフェート、2-メタクリロイルオキシエチルフェニルリン酸等の酸性リン酸エステル系不飽和単量体等が挙げられるが、特に限定されるものではなく、共重合体に要求される種々の物性を付与し、必要な物性を損なわない化合物であればよい。また、一種類のみを用いてもよく、また、二種類以上を適宜混合して用いてもよい。 Specific examples of the compound to be copolymerized in the case of a copolymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and other (meth) acrylic acid alkyl esters; glycidyl (meth) acrylate Epoxy group-containing unsaturated monomers such as (meth) acrylamide, diacetone acrylamide, dimethyl acrylamide, N-isopropyl acrylamide, hydroxyethyl acrylamide, N, N'-dimethylaminoethyl (meth) acrylate, acryloyl morpholine, 2 -Nitrogen-containing unsaturated monomers such as vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, N-vinylcarbazole, (4-vinylphenyl) -diphenylamine; unsaturated elements containing halogen elements such as vinyl chloride and vinylidene chloride. Monomer; Aromatic unsaturated monomer such as styrene, α-methylstyrene, vinyltoluene; Vinyl ester such as vinyl acetate; Vinyl ether; Unsaturated cyan compound monomer such as (meth) acryloylnitrile; 4- (Meta) ) Acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidin, 4- (meth) acryloyloxy-1,2,2 6,6-Pentamethylpiperidin, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidin, 4-cyano-4- (meth) acryloylamino-2,2,6,6- Tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-( Meta) Acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- Photostable monomers such as clotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, caprolactone-modified hydro Hydroxyl group-containing monomers such as xy (meth) acrylate; carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride; vinyl sulfonic acid, styrene sulfonic acid, Sulfuric acid group-containing unsaturated monomers such as sulfoethyl (meth) acrylate; 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloro Examples thereof include acidic phosphate ester-based unsaturated monomers such as propyl acid phosphate and 2-methacryloyloxyethylphenyl phosphate, but the present invention is not particularly limited and imparts various physical properties required for the copolymer. However, any compound may be used as long as it does not impair the required physical properties. Further, only one type may be used, or two or more types may be appropriately mixed and used.
重合体を得る際の重合方法は、特に限定されるものではなく、従来公知の種々の重合方法、例えば、ラジカル重合、イオン重合による連鎖重合反応を用いた溶液重合法、塊状(バルク)重合法、懸濁(パール)重合法、光重合法等を採用することができる。 The polymerization method for obtaining the polymer is not particularly limited, and various conventionally known polymerization methods such as radical polymerization, solution polymerization method using chain polymerization reaction by ion polymerization, and bulk polymerization method. , Suspension (pearl) polymerization method, photopolymerization method and the like can be adopted.
溶液重合法を採用して重合体を得る場合において用いることができる溶媒としては、具体的には、例えば、トルエン、キシレン、その他の高沸点の芳香族系溶媒;酢酸エチル、酢酸ブチル、セロソルブアセテート等のエステル系溶媒;メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒;メタノール、エタノール、2-プロパノール等のアルコール系溶媒等が挙げられるが、特に限定されるものではない。これら溶媒は、一種類のみを用いてもよく、また、二種類以上を適宜混合して用いてもよい。また、溶媒の使用量は、特に限定されるものではない。 Specific examples of the solvent that can be used when the solution polymerization method is adopted to obtain a polymer include toluene, xylene, and other high-boiling aromatic solvents; ethyl acetate, butyl acetate, and cellosolve acetate. Etc.; Ester-based solvent such as: Methyl ethyl ketone, Methyl isobutyl ketone and the like; Alcohol-based solvent such as methanol, ethanol and 2-propanol, and the like, but the present invention is not particularly limited. Only one kind of these solvents may be used, or two or more kinds may be appropriately mixed and used. Further, the amount of the solvent used is not particularly limited.
塊状(バルク)重合法を採用して重合体を得る場合において用いることができる重合開始剤としては、後述に列記する重合開始剤が挙げられる。 Examples of the polymerization initiator that can be used in the case of obtaining a polymer by adopting the bulk polymerization method include the polymerization initiators listed below.
懸濁(パール)重合法を採用して重合体を得る場合において用いることができる分散剤としては、具体的には、例えば、ポリビニルアルコール、 ポリ(メタ)アクリル酸またはその塩、スチレンとマレイン酸共重合体の塩、α-メチルスチレンとアクリル酸共重合体の塩、ポリビニルピロリドン、ポリ(メタ)アクリルアミド、メチルセルロース、エチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシブチルメチルセルロース、カルボキシメチルセルロース、ゼラチン、デンプン、トラガント、ペクチン、グルー、アルギン酸またはその塩等の高分子界面活性剤;ポリエチレンオキサイド、ポリプロピレンオキサイド等のポリオキシアルキレン系分散剤;ポリオキシエチレン-アルキルエーテル、ポリオキシエチレン-アルキルフェノール、ポリオキシエチレン-多価アルコールエステル、多価アルコールと脂肪酸とのエステル、オキシエチレン・オキシプロピレンブロック縮合物等の非イオン系界面活性剤等が挙げられる。また、これら分散剤は、一種類のみを用いてもよく、また、二種類以上を適宜混合して用いてもよい。また、分散剤の使用量は、特に限定されるものではない。 Specific examples of the dispersant that can be used in the case of obtaining a polymer by adopting the suspension (pearl) polymerization method include polyvinyl alcohol, poly (meth) acrylic acid or a salt thereof, styrene and maleic acid. Copolymer salt, α-methylstyrene and acrylic acid copolymer salt, polyvinylpyrrolidone, poly (meth) acrylamide, methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, carboxymethylcellulose, gelatin , Polymer surfactants such as starch, tragant, pectin, glue, alginic acid or salts thereof; polyoxyalkylene-based dispersants such as polyethylene oxide and polypropylene oxide; polyoxyethylene-alkyl ethers, polyoxyethylene-alkylphenols, polyoxy Examples thereof include an ethylene-polyhydric alcohol ester, an ester of a polyhydric alcohol and a fatty acid, and a nonionic surfactant such as an oxyethylene / oxypropylene block condensate. Further, only one kind of these dispersants may be used, or two or more kinds of these dispersants may be appropriately mixed and used. Further, the amount of the dispersant used is not particularly limited.
また、溶液重合法、塊状重合法、懸濁重合法を採用して重合体を得る際には、重合開始剤を用いることができる。重合開始剤としては、具体的には、例えば、 2,2'-アゾビス-(2-メチルブチロニトリル) 、2,2'-アゾビスイソブチロニトリル、1,1’ -アゾビス(シクロヘキサン-1-カルボニトリル)、ベンゾイルパーオキサイド、ジ-t- ブチルパーオキサイド、t-ブチルパーオキシ-2-エチルヘキサノエート等の油溶性のラジカル重合開始剤;過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム、t-ブチルパーオキサイド、2,2-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]・二塩酸塩、2,2-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]・二硫酸・二水和物、2,2-アゾビス(2-アミジノプロパン)・二塩酸塩 、2,2-アゾビス〔N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]水和物、2,2-アゾビス{2-[1-(2-ヒドロキシエチル)-2-イミダゾリン-2-イル]プロパン}・二塩酸塩、2,2-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]、2,2-アゾビス(1-イミノ-1-ピロリジノ-2-エチルプロパン)・二塩酸塩、2、2-アゾビス{2-メチル-N-[1,1-ビス(ヒドロキシメチル)-2-ヒドロキシエチル]プロピオンアミド}、2,2-アゾビス[2-メチル-N-(2-ヒドロキシエチル)プロピオンアミド]、2,2-アゾビス(N-ヒドロキシエチルイソブチルアミド)、4,4-アゾビス(4-シアノペンタン酸)等の水溶性のラジカル重合開始剤;過硫酸塩類や有機過酸化物類の重合開始剤にナトリウムスルホオキシレートホルムアルデヒド、亜硫酸水素ナトリウム、亜硫酸水素アンモニウム、チオ硫酸ナトリウム、チオ硫酸アンモニウム、過酸化水素、ヒドロキシメタンスルフィン酸ナトリウム、L-アスコルビン酸、およびその塩、第一銅塩、第一鉄塩などの還元剤を重合開始剤に組み合わせて用いるレドックス系開始剤;ベンゾフェノン、N,N′-テトラアルキル-4,4′-ジアミノベンゾフェノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノ-プロパノン-1、4,4′-ビス(ジメチルアミノ)ベンゾフェノン(ミヒラーケトン)、4,4′-ビス(ジエチルアミノ)ベンゾフェノン、4-メトキシ-4′-ジメチルアミノベンゾフェノン等の芳香族ケトン類、アルキルアントラキノン、フェナントレンキノン等のキノン類、ベンゾイン、アルキルベンゾイン等のベンゾイン化合物、ベンゾインアルキルエーテル、ベンゾインフェニルエーテル等のベンゾインエーテル化合物、ベンジルジメチルケタール等のベンジル誘導体、2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-クロロフェニル)-4,5-ジ(m-メトキシフェニル)イミダゾール二量体、2-(o-フルオロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体、2,4-ジ(p-メトキシフェニル)-5-フェニルイミダゾール二量体、2-(2,4-ジメトキシフェニル)-4,5-ジフェニルイミダゾール二量体等の2,4,5-トリアリールイミダゾール二量体、N-フェニルグリシン、N-フェニルグリシン誘導体、9-フェニルアクリジン等のアクリジン誘導体、1,2-オクタンジオン,1-[4-(フェニルチオ)-,2-(o-ベンゾイルオキシム)]等のオキシムエステル類、7-ジエチルアミノ-4-メチルクマリン等のクマリン系化合物、2,4-ジエチルチオキサントン等のチオキサントン系化合物、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド等のアシルホスフィンオキサイド系化合物等の光(主として紫外線)開裂型ラジカル重合開始剤が挙げられるが、特に限定されるものではない。また、これら重合開始剤は、一種類のみを用いてもよく、また、二種類以上を適宜混合して用いてもよい。また、重合開始剤の使用量は、特に限定されるものではない。 Further, when a polymer is obtained by adopting 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-). Oil-soluble radical polymerization initiators such as 1-carbonitrile), benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxy-2-ethylhexanoate; ammonium persulfate, potassium persulfate, sodium persulfate , T-butyl peroxide, 2,2-azobis [2- (2-imidazolin-2-yl) propane], dihydrochloride, 2,2-azobis [2- (2-imidazolin-2-yl) propane]・ Disulfate / dihydrate, 2,2-azobis (2-amidinopropane) / dihydrochloride, 2,2-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2-Azobisisobuty {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-hydroxyethylisobutyamide), 4,4-azobis Water-soluble radical polymerization initiators such as (4-cyanopentanoic acid); sodium sulfooxylate formaldehyde, sodium hydrogen sulfite, ammonium hydrogen sulfite, sodium thiosulfate, thio as polymerization initiators for persulfates and organic peroxides. A redox-based initiator that uses a reducing agent such as ammonium sulfate, hydrogen peroxide, sodium hydroxymethanesisobutyate, L-ascorbic acid, and salts thereof, ferrous salt, and ferrous salt in combination with the polymerization initiator; benzophenone, N. , N'-Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-Molholino-propanone-1, 4,4'-bis (dimethylamino) benzophenone (Michlerketone), 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminoben Aromatic ketones such as zophenone, quinones such as alkylanthraquinone and phenanthrenquinone, 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-Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-Dimethoxyphenyl) -4,5-diphenylimidazole dimer, etc. 2,4,5-Triarylimidazole dimer, N-phenylglycine, N-phenylglycine derivative, 9-phenylacridin, etc. Aclysine derivatives, 1,2-octanedione, oxime esters such as 1- [4- (phenylthio)-, 2- (o-benzoyloxime)], coumarin compounds such as 7-diethylamino-4-methylcoumarin, 2, , 4-dixanthone-based compounds such as 4-diethylthioxanthone, and light (mainly ultraviolet) cleavage-type radical polymerization initiators such as acylphosphine oxide-based compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide. Not limited. Further, only one kind of these polymerization initiators may be used, or two or more kinds thereof may be appropriately mixed and used. Further, the amount of the polymerization initiator used is not particularly limited.
反応温度は、特に限定されるものではないが、室温~200℃の範囲が好ましく、50℃~150℃の範囲がより好ましい。尚、反応時間は、反応温度、或いは、用いる単量体組成物の組成や重合開始剤の種類等に応じて、重合反応が完結するように、適宜設定すればよい。 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 so that the polymerization reaction is completed according to the reaction temperature, the composition of the monomer composition used, the type of the polymerization initiator, and the like.
光重合法を採用して重合体を得る場合において共重合対象となる化合物は、前述の他に分子内に2個以上のエチレン性不飽和基を有する(メタ)アクリレートなどが挙げられる。分子内に2個以上のエチレン性不飽和基を有する(メタ)アクリレートとしては、例えば、1,3-ブタンジオールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ビスフェノールAジ(メタ)アクリレート、トリシクロデカンジメタノールジ(メタ)アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリス(2-アクリロキシエチル)イソシアヌレート、グリセリントリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、及びこれらのエチレンオキシドまたはプロピレンオキシドまたはε-カプロラクトン変性(メタ)アクリレート、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート、ポリエステル(メタ)アクリレートなどを挙げることができる。これらは単独で用いてもよいし、または2種以上を組わせて用いてもよい。 In addition to the above, examples of the compound to be copolymerized when the polymer is obtained by the photopolymerization method include (meth) acrylate having two or more ethylenically unsaturated groups in the molecule. Examples of the (meth) acrylate having two or more ethylenically unsaturated groups in the molecule include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,9. -Nonandiol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, bisphenol A di ( Meta) acrylate, tricyclodecanedimethanol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, trimethylol ethanetri (meth) acrylate, trimethylol propanetri (meth) acrylate, tris (2-acrylate) Roxyethyl) isocyanurate, glycerintri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylates and these ethylene oxides or propylene oxides or ε-caprolactone-modified (meth) acrylates, epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates and the like can be mentioned. These may be used alone or in combination of two or more.
光重合法を採用して重合体を得る場合において用いる光重合開始剤としては、活性エネルギー線の照射によって光重合開始作用を示す公知の光重合開始剤のいずれもが使用できる。例えば、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]-フェニル}-2-メチル-プロパン-1-オン、フェニルグリオキシリックアシッドメチルエステル、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、2-ジメチルアミノ-2-(4-メチル-ベンジル)-1-(4-モルフォリン-4-イル-フェニル)-ブタン-1-オン、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイドなどを挙げることができ、また、ベンゾフェノンおよび/または2-イソプロピルチオキサントンと重合促進剤の2-エチルヘキシル-4-ジメチルアミノベンゾエートおよび/またはエチル-4-ジメチルアミノベンゾエートといった組み合わせも使用できる。本発明で、これらの光重合開始剤を単独で用いてもよいし、または2種以上を組み合わせて用いてもよい。 As the photopolymerization initiator used when the polymer is obtained by adopting the photopolymerization method, any known photopolymerization initiator that exhibits a photopolymerization initiator action by irradiation with active energy rays can be used. For example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[ 4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4- [4- (2-hydroxy-2-methyl-propionyl) ) -Phenyl] -Phenyl} -2-Methyl-Propane-1-one, Phenylglycylic acid methyl ester, 2-Methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropane-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl) -Phenyl) -butane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like, as well as benzophenone and / or 2-isopropylthioxanthone and 2-isopropylthioxanthone as a polymerization accelerator. 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.
そのうちでも、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オンおよび/または2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]-フェニル}-2-メチル-プロパン-1-オンが、硬化膜の黄変が少なく、表面硬化性に優れる点から好ましく用いられる。 Among them, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and / or 2-hydroxy-1- {4- [ 4- (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1-one is preferably used because it causes less yellowing of the cured film and is excellent in surface curability.
波長変換材料はフィルムに配合したり、フィルムの表面又は中間層に成膜して、波長変換フィルムとして使用されることが多く、本発明のベンゾトリアゾール誘導体化合物、及びそれらを有する重合体も同様に、波長変換フィルムに使用できる。本発明のベンゾトリアゾール誘導体化合物、及びそれらを有する重合体を使用できるフィルムの樹脂素材は特に限定されるわけではないが、例えば、ポリエチレン、ポリプロピレン、ポリブテン、ポリペンテン、ポリ-3-メチルブチレン、ポリメチルペンテンなどのα-オレフィン重合体またはエチレン-酢酸ビニル共重合体、エチレン-プロピレン共重合体などのポリオレフィン、ポリ塩化ビニル、ポリ臭化ビニル、ポリフッ化ビニル、塩素化ポリエチレン、塩素化ポリプロピレン、臭素化ポリエチレン、塩化ゴム、塩化ビニル-酢酸ビニル共重合体、塩化ビニル-エチレン共重合体、塩化ビニル-プロピレン共重合体、塩化ビニル-スチレン共重合体、塩化ビニル-イソブチレン共重合体、塩化ビニル-塩化ビニリデン共重合体、塩化ビニル-スチレン-無水マレイン酸三元共重合体、塩化ビニル-スチレン-アクリロニトリル三元共重合体、塩化ビニル-ブタジエン共重合体、塩化ビニル-イソブチレン共重合体、塩化ビニル-塩素化プロピレン共重合体、塩化ビニル-塩化ビニリデン-酢酸ビニル三元共重合体、塩化ビニル-アクリル酸エステル共重合体、塩化ビニル-マレイン酸エステル共重合体、塩化ビニル-メタクリル酸エステル共重合体、塩化ビニル-アクリロニトリル共重合体、内部可塑性ポリ塩化ビニルなどの含ハロゲン合成樹脂、石油樹脂、クマロン樹脂、ポリスチレン、スチレンと他の単量体(無水マレイン酸、ブタジエン、アクリロニトリルなど)との共重合体、アクリロニトリル-ブタジエン-スチレン樹脂、アクリル酸エステル-ブタジエン-スチレン樹脂、メタクリル酸エステル-ブタジエン-スチレン樹脂などのスチレン系樹脂、ポリ酢酸ビニル、ポリビニルアルコール、ポリビニルホルマール、ポリビニルブチラール、アクリル樹脂、メタクリレート樹脂、ポリアクリロニトリル、ポリフェニレンオキシド、ポリカーボネート、変性ポリフェニレンオキシド、ポリアセタール、フェノール樹脂、尿素樹脂、メラミン樹脂、エポキシ樹脂、シリコン樹脂、ポリエチレンテレフタレート、強化ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリスルホン系樹脂、ポリエーテルスルホン、ポリフェニレンスルフィド、ポリエーテルケトン、ポリエーテルイミド、ポリオキシベンゾイル、ポリイミド、ポリマレイミド、ポリアミドイミド、アルキド樹脂、アミノ樹脂、ビニル樹脂、水溶性樹脂、粉体塗料用樹脂、ポリアミド樹脂、ポリウレタン樹脂、不飽和ポリエステル樹脂等を挙げることができる。 The wavelength conversion material is often used as a wavelength conversion film by blending it in a film or forming a film on the surface or an intermediate layer of the film, and the benzotriazole derivative compound of the present invention and the polymer having them are also used. , Can be used for wavelength conversion film. The resin material of the film in which the benzotriazole derivative compound of the present invention and the polymer containing the same can be used is not particularly limited, but for example, polyethylene, polypropylene, polybutene, polypentene, poly-3-methylbutylene, and polymethyl. Α-olefin polymer such as penten or ethylene-vinyl acetate copolymer, polyolefin such as ethylene-propylene copolymer, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, chlorinated polyethylene, chlorinated polypropylene, brominated Polyethylene, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-chloride Vinylidene copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, vinyl chloride-styrene-acrylonitrile ternary copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride- Chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer , Vinyl chloride-acrylonitrile copolymer, halogen-containing synthetic resin such as internal plastic polyvinyl chloride, petroleum resin, kumaron resin, polystyrene, styrene and co-weight with other monomers (maleic anhydride, butadiene, acrylonitrile, etc.) Combined, styrene resin such as acrylonitrile-butadiene-styrene resin, acrylic acid ester-butadiene-styrene resin, methacrylic acid ester-butadiene-styrene resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic resin, methacrylate resin , Polyacrylonitrile, Polyphenylene oxide, Polycarbonate, Modified polyphenylene oxide, Polyacetal, Phenolic resin, Urea resin, Melamine resin, Epoxy resin, Silicon resin, Polyethylene terephthalate, Reinforced polyethylene terephthalate, Polybutylene terephthalate, Polysulfone resin, Polyethersulfone, Polyphenylene Sulfur, polyether ketone, polyetherimide, polyoxybenzoyl, polyimide, polymerimide, polyamideimide, alkyd resin, amino resin, vinyl Examples thereof include resins, water-soluble resins, powder paint resins, polyamide resins, polyurethane resins, unsaturated polyester resins and the like.
本発明のベンゾトリアゾール誘導体化合物、及びそれらを有する重合体を波長変換フィルムに使用する場合、波長変換材料としては本発明のベンゾトリアゾール誘導体化合物、及びそれらを有する重合体のみ、あるいは他の波長変換材料と組合せて使用できる。本発明のベンゾトリアゾール誘導体化合物、及びそれらを有する重合体以外の波長変換機能を有する化合物としては、一般に市場で入手できるもので紫外線領域に励起帯を有し可視光領域に発光ピークを有するものあれば特に限定されない。例えば、ペリレン誘導体、クマリン誘導体、有機金属錯体、ピラン誘導体、スチルベン誘導体、アクリドン誘導体、オキサゾン誘導体、キナクリドン誘導体、ベンゾオキサゾール誘導体、ポリフルオレン誘導体、ポリフェニレンビニレン誘導体、ナフタルイミド誘導体等、一般的な低分子蛍光材料、低分子リン光材料、ポリマー発光材料等が用いられる。これらの波長変換材料は、一種類のみを用いてもよく、また、二種類以上を適宜混合して用いてもよい。 When the benzotriazole derivative compound of the present invention and the polymer having them are used for the wavelength conversion film, the wavelength conversion material is only the benzotriazole derivative compound of the present invention and the polymer having them, or another wavelength conversion material. Can be used in combination with. Examples of the benzotriazole derivative compound of the present invention and compounds having a wavelength conversion function other than the polymers having them are those that are generally available on the market and have an excitation band in the ultraviolet region and an emission peak in the visible light region. There is no particular limitation. For example, general low molecular weight fluorescence such as perylene derivative, coumarin derivative, organic metal complex, pyrane derivative, stylben derivative, acridone derivative, oxazone derivative, quinacridone derivative, benzoxazole derivative, polyfluorene derivative, polyphenylene vinylene derivative, naphthalimide derivative and the like. Materials, low molecular weight phosphorescent materials, polymer light emitting materials and the like are used. Only one kind of these wavelength conversion materials may be used, or two or more kinds may be appropriately mixed and used.
本発明のベンゾトリアゾール誘導体化合物、及びそれらを有する重合体をフィルムに配合する場合、樹脂に対して少なすぎると十分な発光が得られず、また、多すぎると濃度消光が起こるため、0.001~20重量%、好ましくは0.005~10重量%の範囲で使用されることが好ましい。 When the benzotriazole derivative compound of the present invention and the polymer having them are blended in a film, sufficient light emission cannot be obtained if the amount is too small with respect to the resin, and concentration quenching occurs if the amount is too large. It is preferably used in the range of about 20% by weight, preferably 0.005 to 10% by weight.
本発明のベンゾトリアゾール誘導体化合物、及びそれらを有する重合体をフィルムに成膜する方法として、例えば、湿式塗布法が挙げられる。湿式塗布法は複雑な工程を必要とせず、製造コストが低く、大面積化が容易という利点があり、湿式塗布法として、例えば、インクジェット法、スピンコート法、キャスト法やディップコート法がある。湿式塗布法を行うには波長変換材料を有機溶媒に溶解させる必要があり、有機溶媒に溶解しやすい波長変換材料を用いることが望ましい。本発明のベンゾトリアゾール誘導体化合物、及びそれらを有する重合体は、有機溶媒に溶解しやすく、例えばキャスト法によって、波長変換膜を形成することができる。 As a method for forming a film of the benzotriazole derivative compound of the present invention and a polymer having them on a film, for example, a wet coating method can be mentioned. The wet coating method does not require a complicated process, has the advantages of low manufacturing cost and easy increase in area, and examples of the wet coating method include an inkjet method, a spin coating method, a casting method and a dip coating method. In order to perform the wet coating method, it is necessary to dissolve the wavelength conversion material in an organic solvent, and it is desirable to use a wavelength conversion material that is easily dissolved in the organic solvent. The benzotriazole derivative compound of the present invention and the polymer having them are easily dissolved in an organic solvent, and a wavelength conversion film can be formed by, for example, a casting method.
本発明のベンゾトリアゾール誘導体化合物、及びそれらを有する重合体を湿式塗布法によりフィルムに成膜する際、ベンゾトリアゾール誘導体化合物、及びそれらを有する重合体を溶解させる有機溶媒として、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素;シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素;石油エーテル、石油ベンジン等の石油系溶媒;四塩化炭素、クロロホルム、1,2-ジクロロエタン等のハロゲン化炭化水素;エチルエーテル、イソプロピルエーテル、アニソール、ジオキサン、テトラヒドロフラン等のエーテル;アセトン、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン、アセトフェノン、イソフォロン等のケトン;酢酸エチル、酢酸ブチル等のエステル;ジメチルホルムアミド、ジメチルアセトアミド等のアミド;アセトニトリル;ジメチルスルフォキシド;クロロベンゼン、ジクロロベンゼン等のハロゲン化ベンゼン等が挙げられる。これらは一種類のみを用いてもよく、また、二種類以上を適宜混合して用いてもよい。 When the benzotriazole derivative compound of the present invention and the polymer having them are formed on a film by a wet coating method, as an organic solvent for dissolving the benzotriazole derivative compound and the polymer having them, pentane, hexane, heptane, etc. Hydrocarbons; Aromatic hydrocarbons such as benzene, toluene and xylene; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Petroleum solvents such as petroleum ether and petroleum benzine; Carbon tetrachloride, chloroform, 1, 2 -Halogenated hydrocarbons such as dichloroethane; ethers such as ethyl ether, isopropyl ether, anisole, dioxane, tetrahydrofuran; ketones such as acetone, methylisobutylketone, methylethylketone, cyclohexanone, acetophenone, isophorone; esters such as ethyl acetate, butylacetate; Examples thereof include amides such as dimethylformamide and dimethylacetamide; acetonitrile; dimethylsulfoxide; and hydrocarbonated benzenes such as chlorobenzene and dichlorobenzene. Only one kind of these may be used, or two or more kinds may be appropriately mixed and used.
本発明のベンゾトリアゾール誘導体化合物を有する重合体は、単独で波長変換フィルムにすることができる。例えば、フィルムや硝子板の表面に成膜し、波長変換フィルムを剥がし取ることで得られる。 The polymer having the benzotriazole derivative compound of the present invention can be used alone as a wavelength conversion film. For example, it can be obtained by forming a film on the surface of a film or a glass plate and peeling off the wavelength conversion film.
以下に本発明で実施したベンゾトリアゾール誘導体化合物、及びその重合体の合成法と特性を示す。ただし、合成方法はこれらに限定されるものではない。 The synthetic method and characteristics of the benzotriazole derivative compound and its polymer carried out in the present invention are shown below. However, the synthesis method is not limited to these.
(実施例1)
[中間体;5-カルボキシ -2-(4-ヒドロキシフェニル)-2H-ベンゾトリアゾール]の合成
Synthesis of [Intermediate; 5-carboxy-2- (4-hydroxyphenyl) -2H-benzotriazole]
1000ml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-(4-カルボキシ-2-ニトロフェニルアゾ)フェノールを111.6g(0.389モル)、イソプロピルアルコール250ml、水200ml、水酸化ナトリウム24.7g(0.618モル)、ハイドロキノン0.6gを入れて溶解させ、60%ヒドラジン一水和物19.8g(0.237モル)を60~65℃で1時間で滴下し、同温度で2時間撹拌させ、62.5%硫酸でpH4に調整し、生成した沈殿物をろ過、水洗、乾燥し、5-カルボキシ -2-(4-ヒドロキシフェニル)-2H-ベンゾトリアゾール N-オキシドを87.0g得た。 A condenser with a ball, a thermometer, and a stirrer were attached to a 1000 ml four-necked flask, and 111.6 g (0.389 mol) of 4- (4-carboxy-2-nitrophenylazo) phenol, 250 ml of isopropyl alcohol, and 200 ml of water were added. , 24.7 g (0.618 mol) of sodium hydroxide and 0.6 g of hydroquinone are added and dissolved, and 19.8 g (0.237 mol) of 60% hydrazine monohydrate is added dropwise at 60 to 65 ° C. in 1 hour. Then, the mixture was stirred at the same temperature for 2 hours, adjusted to pH 4 with 62.5% sulfuric acid, and the resulting precipitate was filtered, washed with water, dried, and 5-carboxy-2- (4-hydroxyphenyl) -2H-benzotriazole. 87.0 g of N-oxide was obtained.
1000ml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、5-カルボキシ -2-(4-ヒドロキシフェニル)-2H-ベンゾトリアゾール N-オキシドを87.0g(0.321モル)、イソプロピルアルコール350ml、水350ml、水酸化ナトリウム57.6g(1.440モル)を入れて溶解させ、亜鉛末31.4g(0.480モル)を60~65℃で30分で添加し、同温度で1時間撹拌させ、同温度でろ過して固形分を取り除き、ろ液を62.5%硫酸でpH4に調整し、生成した沈殿物をろ過、水洗、乾燥して粗結晶を得た。この粗結晶をイソプロピルアルコールで再結晶して、5-カルボキシ -2-(4-ヒドロキシフェニル)-2H-ベンゾトリアゾールを37.5g得た。収率34%(4-アミノ-3-ニトロ-安息香酸から)であった。 A condenser with a ball, a thermometer, and a stirrer were attached to a 1000 ml four-necked flask, and 87.0 g (0.321 mol) of 5-carboxy-2- (4-hydroxyphenyl) -2H-benzotriazole N-oxide was added. Add 350 ml of isopropyl alcohol, 350 ml of water and 57.6 g (1.440 mol) of sodium hydroxide to dissolve, and add 31.4 g (0.480 mol) of zinc powder at 60 to 65 ° C. in 30 minutes at the same temperature. The mixture was stirred at the same temperature for 1 hour, filtered at the same temperature to remove solids, the filtrate was adjusted to pH 4 with 62.5% sulfuric acid, and the produced precipitate was filtered, washed with water and dried to obtain crude crystals. The crude crystals were recrystallized from isopropyl alcohol to obtain 37.5 g of 5-carboxy-2- (4-hydroxyphenyl) -2H-benzotriazole. The yield was 34% (from 4-amino-3-nitro-benzoic acid).
(実施例2)
[化合物(a);2-メタクリロイルオキシエチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートの合成]
[Compound (a); Synthesis of 2-methacryloxyethyl 2- (4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate]
500ml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、5-カルボキシ -2-(4-ヒドロキシフェニル)-2H-ベンゾトリアゾールを22.3g(0.087モル)、N,N-ジメチルホルムアミド45ml、炭酸ナトリウム9.5g(0.090モル)、ヨウ化カリ1.3g、オクチルクロライド24.2g(0.163モル)を仕込み、120~130℃で2時間還流撹拌した。メチルイソブチルケトン150ml、酢酸20ml、水200mlを仕込み、70℃で下層の水層を分液して取り除いた。減圧で溶媒を回収し、イソプロピルアルコール100mlを加えて、生成した沈殿物をろ過、洗浄、乾燥して粗結晶を得た。この粗結晶をイソプロピルアルコールで再結晶して、オクチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートを23.2g得た。 A condenser with a ball, a thermometer, and a stirrer were attached to a 500 ml four-necked flask, and 22.3 g (0.087 mol) of 5-carboxy-2- (4-hydroxyphenyl) -2H-benzotriazole was added to N, N. -45 ml of dimethylformamide, 9.5 g (0.090 mol) of sodium carbonate, 1.3 g of potassium iodide and 24.2 g (0.163 mol) of octyl chloride were charged and stirred at 120 to 130 ° C. for 2 hours. 150 ml of methyl isobutyl ketone, 20 ml of acetic acid, and 200 ml of water were charged, and the lower aqueous layer was separated and removed at 70 ° C. The solvent was recovered under reduced pressure, 100 ml of isopropyl alcohol was added, and the resulting precipitate was filtered, washed and dried to obtain crude crystals. The crude crystals were recrystallized from isopropyl alcohol to obtain 23.2 g of octyl 2- (4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate.
500ml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、オクチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートを13.8g(0.029モル)、イソプロピルアルコール140ml、水140ml、水酸化ナトリウム4.5g(0.113モル)を仕込んで75℃で2時間撹拌させ、62.5%硫酸でpH4に調整し、生成した沈殿物をろ過、水洗、乾燥して粗結晶を得た。この粗結晶をメチルイソブチルケトンで再結晶して、5-カルボキシ -2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾールを9.2g得た。 A condenser with a ball, a thermometer, and a stirrer were attached to a 500 ml four-necked flask, and 13.8 g (0.029 mol) of octyl 2- (4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate was added. Add 140 ml of isopropyl alcohol, 140 ml of water and 4.5 g (0.113 mol) of sodium hydroxide, stir at 75 ° C. for 2 hours, adjust the pH to 4 with 62.5% sulfuric acid, and filter and wash the resulting precipitate with water. It was dried to obtain coarse crystals. The crude crystals were recrystallized from methyl isobutyl ketone to obtain 9.2 g of 5-carboxy-2- (4-octyloxyphenyl) -2H-benzotriazole.
300ml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、5-カルボキシ -2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾールを7.6g(0.021モル)、トルエン40ml、塩化チオニル3.8g(0.032モル)、N,N-ジメチルホルムアミド0.4mlを仕込み、65℃で1時間撹拌した。減圧で溶媒を回収し、トルエン100ml、メタクリル酸2-ヒドロキシエチル13.3g(0.102モル)を仕込み、115℃で4時間還流撹拌した。水100mlを仕込んで、70℃で下層の水層を分液して取り除き、さらに水100mlを仕込んで、70℃で下層の水層を分液して取り除いた。減圧でトルエンを回収し、イソプロピルアルコール75mlを加えて、生成した沈殿物をろ過、洗浄、乾燥して、粗結晶を7.9g得た。この粗結晶をイソプロピルアルコールで再結晶して、化合物(a)を6.7g得た。収率33%(5-カルボキシ -2-(4-ヒドロキシフェニル)-2H-ベンゾトリアゾールから)であった。融点83℃。 A condenser with a ball, a thermometer, and a stirrer were attached to a 300 ml four-necked flask, and 7.6 g (0.021 mol) of 5-carboxy-2- (4-octyloxyphenyl) -2H-benzotriazole was added to 40 ml of toluene. , 3.8 g (0.032 mol) of thionyl chloride and 0.4 ml of N, N-dimethylformamide were charged, and the mixture was stirred at 65 ° C. for 1 hour. The solvent was recovered under reduced pressure, 100 ml of toluene and 13.3 g (0.102 mol) of 2-hydroxyethyl methacrylate were charged, and the mixture was stirred under reflux at 115 ° C. for 4 hours. 100 ml of water was charged and the lower aqueous layer was separated and removed at 70 ° C., and 100 ml of water was further charged and the lower aqueous layer was separated and removed at 70 ° C. Toluene was recovered under reduced pressure, 75 ml of isopropyl alcohol was added, and the resulting precipitate was filtered, washed and dried to obtain 7.9 g of crude crystals. The crude crystals were recrystallized from isopropyl alcohol to obtain 6.7 g of compound (a). The yield was 33% (from 5-carboxy-2- (4-hydroxyphenyl) -2H-benzotriazole). Melting point 83 ° C.
また、HPLC分析により、化合物(a)の純度を測定した。
<測定条件>
装置:L-2130((株)日立ハイテクノロジーズ製)
使用カラム:SUMIPAX ODS A-212 6.0×150mm 5μm
カラム温度:40℃
移動相: メタノール/水=99/1
流速:1.0ml/min
検出:UV250nm
<測定結果>
HPLC面百純度99.0%
In addition, the purity of compound (a) was measured by HPLC analysis.
<Measurement conditions>
Equipment: L-2130 (manufactured by Hitachi High-Technologies Corporation)
Column used: SUIMPAX ODS A-212 6.0 x 150 mm 5 μm
Column temperature: 40 ° C
Mobile phase: Methanol / water = 99/1
Flow velocity: 1.0 ml / min
Detection: UV250nm
<Measurement result>
HPLC surface 100 purity 99.0%
また、化合物(a)のNMR測定を行った結果、上記構造を支持する結果が得られた。測定条件は次のとおりである。
<測定条件>
装置:JEOL-ECX400
共振周波数:400MHz(1H-NMR)
溶媒:クロロホルム-d
1H-NMRの内部標準物質として、テトラメチルシランを用い、ケミカルシフト値はδ値(ppm)、カップリング定数はHertzで示した。またsはsinglet、dはdoublet、tはtriplet、mはmultipletの略とする。以下の実施例3においても同様である。得られたNMRスペクトルの内容は以下のとおりである。
σ=8.71(s,1H,benzotriazole-H),8.28(m,2H,benzotriazole-H),8.05(d,1H,J=8.0Hz,benzene-H),7.95(d,1H,J=8.0Hz,benzene-H),7.06(m,2H,benzene-H),6.17(s,1H,C=CH2-H),5.61(s,1H,C=CH2-H),4.64(t,2H,benzotriazole-CO-O-CH2-H),4.54(t,2H,methacryloyl-O-CH2-H),4.05(t,2H,benzene-O-CH2-H),1.97(s,3H,CH2-C-CH3-H),1.83(m,2H,O-CH2-CH2-H),1.48(m,2H,O-CH2-CH2-CH2-H),1.33(m,8H,(CH2)4-H),0.89(t,3H,CH3-H)
Further, as a result of NMR measurement of compound (a), a result supporting the above structure was obtained. The measurement conditions are as follows.
<Measurement conditions>
Equipment: JEOL-ECX400
Resonance frequency: 400MHz (1H-NMR)
Solvent: Chloroform-d
Tetramethylsilane was used as an internal standard substance for 1H-NMR, the chemical shift value was shown in δ value (ppm), and the coupling constant was shown in Hertz. Further, s is an abbreviation for singlet, d is an abbreviation for doublet, t is an abbreviation for triplet, and m is an abbreviation for multiplet. The same applies to the following Example 3. The contents of the obtained NMR spectrum are as follows.
σ = 8.71 (s, 1H, benzoliazole-H), 8.28 (m, 2H, benzoliazole-H), 8.05 (d, 1H, J = 8.0Hz, bendene-H), 7.95 (D, 1H, J = 8.0Hz, benzene-H), 7.06 (m, 2H, benzene-H), 6.17 (s, 1H, C = CH2 -H), 5.61 (s) , 1H, C = CH2 -H), 4.64 (t, 2H, benzoliazole-CO-O- CH2 -H), 4.54 (t, 2H, meshryloyl-O- CH2 -H), 4 .05 (t, 2H, benzene-O-CH 2 -H), 1.97 (s, 3H, CH 2 -C-CH 3 -H), 1.83 (m, 2H, O-CH 2 -CH) 2 -H), 1.48 (m, 2H, O-CH 2 -CH 2 -CH 2 -H), 1.33 (m, 8H, (CH 2 ) 4-H), 0.89 (t, 3H, CH 3 -H)
(実施例3)
[化合物(b);メチル 2-[4-(2-メタクリロイルオキシエトキシ)フェニル]-2H-ベンゾトリアゾール-5-カルボキシレートの合成]
[Compound (b); Synthesis of Methyl 2- [4- (2-methacryloyloxyethoxy) phenyl] -2H-benzotriazole-5-carboxylate]
1000ml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、5-カルボキシ -2-(4-ヒドロキシフェニル)-2H-ベンゾトリアゾールを15.0g(0.059モル)、N,N-ジメチルホルムアミド250ml、炭酸カリウム16.3g(0.118モル)、ヨウ化メチル8.4g(0.059モル)を仕込み、19~20℃で5時間撹拌した。トルエン500ml、酢酸30ml、水100mlを仕込み、60℃で下層の水層を分液して取り除いた。減圧で溶媒を回収し、イソプロピルアルコール250mlを加えて、生成した沈殿物をろ過、洗浄、乾燥して、メチル 2-(4-ヒドロキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートを8.5g得た。 A condenser with a ball, a thermometer, and a stirrer were attached to a 1000 ml four-necked flask, and 15.0 g (0.059 mol) of 5-carboxy-2- (4-hydroxyphenyl) -2H-benzotriazole was added to N, N. -250 ml of dimethylformamide, 16.3 g (0.118 mol) of potassium carbonate and 8.4 g (0.059 mol) of methyl iodide were charged, and the mixture was stirred at 19 to 20 ° C. for 5 hours. Toluene (500 ml), acetic acid (30 ml), and water (100 ml) were charged, and the lower aqueous layer was separated and removed at 60 ° C. The solvent is recovered under reduced pressure, 250 ml of isopropyl alcohol is added, and the resulting precipitate is filtered, washed and dried to give 8.5 g of methyl 2- (4-hydroxyphenyl) -2H-benzotriazole-5-carboxylate. Obtained.
1000ml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、メチル 2-(4-ヒドロキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートを7.6g(0.028モル)、N,N-ジメチルホルムアミド160ml、炭酸ナトリウム6.0g(0.057モル)、2-クロロエタノール7.9g(0.098モル)、ヨウ化カリウム0.8g(0.005モル)を仕込み、140℃で24時間還流撹拌した。トルエン200ml、酢酸12ml、水80mlを仕込み、70℃で下層の水層を分液して取り除いた。減圧で溶媒を回収し、イソプロピルアルコール400mlを加えて、生成した沈殿物をろ過、洗浄、乾燥して、メチル 2-[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-カルボキシレートを6.8g得た。 A condenser with a ball, a thermometer, and a stirrer were attached to a 1000 ml four-necked flask, and 7.6 g (0.028 mol) of methyl 2- (4-hydroxyphenyl) -2H-benzotriazole-5-carboxylate, N. , N-dimethylformamide 160 ml, sodium carbonate 6.0 g (0.057 mol), 2-chloroethanol 7.9 g (0.098 mol), potassium iodide 0.8 g (0.005 mol), and charged at 140 ° C. The mixture was refluxed and stirred for 24 hours. 200 ml of toluene, 12 ml of acetic acid, and 80 ml of water were charged, and the lower aqueous layer was separated and removed at 70 ° C. The solvent is recovered under reduced pressure, 400 ml of isopropyl alcohol is added, and the resulting precipitate is filtered, washed and dried to methyl 2- [4- (2-hydroxyethoxy) phenyl] -2H-benzotriazole-5-carboxy. A rate of 6.8 g was obtained.
1000ml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、メチル 2-[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-カルボキシレートを6.8g(0.022モル)、トルエン200ml、メタクリル酸2.0g(0.023モル)、メタンスルホン酸0.6g(0.006モル)を仕込み、110~113℃で8時間還流脱水した。水80ml、炭酸ナトリウム4.0g(0.038モル)を仕込んで60℃で下層を分液した後、水80ml、酢酸8mlを仕込んで60℃で下層を分液した。減圧で溶媒を回収し、メチルアルコール800mlを加えて、生成した沈殿物をろ過、洗浄、乾燥して、粗結晶を4.0g得た。この粗結晶をメチルアルコールで再結晶して、化合物(b)を3.0g得た。収率15%(5-カルボキシ -2-(4-ヒドロキシフェニル)-2H-ベンゾトリアゾールから)であった。融点123℃。 A condenser with a ball, a thermometer, and a stirrer were attached to a 1000 ml four-necked flask, and 6.8 g (0.) of methyl 2- [4- (2-hydroxyethoxy) phenyl] -2H-benzotriazole-5-carboxylate was added. 022 mol), 200 ml of toluene, 2.0 g (0.023 mol) of methacrylic acid and 0.6 g (0.006 mol) of methanesulfonic acid were charged, and reflux dehydrated at 110 to 113 ° C. for 8 hours. After charging 80 ml of water and 4.0 g (0.038 mol) of sodium carbonate and separating the lower layer at 60 ° C., 80 ml of water and 8 ml of acetic acid were charged and the lower layer was separated at 60 ° C. The solvent was recovered under reduced pressure, 800 ml of methyl alcohol was added, and the resulting precipitate was filtered, washed and dried to obtain 4.0 g of crude crystals. The crude crystals were recrystallized from methyl alcohol to obtain 3.0 g of compound (b). The yield was 15% (from 5-carboxy-2- (4-hydroxyphenyl) -2H-benzotriazole). Melting point 123 ° C.
また、HPLC分析により、化合物(b)の純度を測定した。
<測定条件>
装置:L-2130((株)日立ハイテクノロジーズ製)
使用カラム:SUMIPAX ODS A-212 6.0×150mm 5μm
カラム温度:40℃
移動相: メタノール/水=95/5
流速:1.0ml/min
検出:UV250nm
<測定結果>
HPLC面百純度99.8%
In addition, the purity of compound (b) was measured by HPLC analysis.
<Measurement conditions>
Equipment: L-2130 (manufactured by Hitachi High-Technologies Corporation)
Column used: SUIMPAX ODS A-212 6.0 x 150 mm 5 μm
Column temperature: 40 ° C
Mobile phase: Methanol / water = 95/5
Flow velocity: 1.0 ml / min
Detection: UV250nm
<Measurement result>
HPLC surface 100 purity 99.8%
また、化合物(b)のNMR測定を行った結果、上記構造を支持する結果が得られた。測定条件は次のとおりである。
<測定条件>
装置:JEOL-ECX400
共振周波数:400MHz(1H-NMR)
溶媒:DMSO-d
得られたNMRスペクトルの内容は以下のとおりである。
σ=8.65(s,1H,benzotriazole-H),8.27(m,2H,benzotriazole-H),8.14(d,1H,J=9.2Hz,benzene-H),8.01(d,1H,J=1.2Hz,benzene-H),7.25(m,2H,benzene-H),6.06(s,1H,C=CH2-H),5.71(s,1H,C=CH2-H),4.49(t,2H,methacryloyl-O-CH2-H),4.39(t,2H,benzene-O-CH2-H),3.93(s,3H,benzotriazole-CO-O-CH3-H),1.89(s,3H,CH2-C-CH3-H)
Further, as a result of NMR measurement of compound (b), a result supporting the above structure was obtained. The measurement conditions are as follows.
<Measurement conditions>
Equipment: JEOL-ECX400
Resonance frequency: 400MHz (1H-NMR)
Solvent: DMSO-d
The contents of the obtained NMR spectrum are as follows.
σ = 8.65 (s, 1H, benzoliazole-H), 8.27 (m, 2H, benzoliazole-H), 8.14 (d, 1H, J = 9.2Hz, bendene-H), 8.01 (D, 1H, J = 1.2Hz, benzene-H), 7.25 (m, 2H, benzene-H), 6.06 (s, 1H, C = CH2 -H), 5.71 (s) , 1H, C = CH2 -H), 4.49 (t, 2H, methacrylloyl-O- CH2 -H), 4.39 (t, 2H, benzene-O- CH2 -H), 3.93. (S, 3H, benzoliazole-CO-O-CH 3 -H), 1.89 (s, 3H, CH 2 -C-CH 3 -H)
(実施例4)
[重合体(a);2-メタクリロイルオキシエチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートを有する重合体の合成]
100ml4つ口フラスコにジムロート冷却器、水銀温度計、窒素ガス吹き込み管、撹拌装置を取り付け、重合性化合物としての化合物(a);2-メタクリロイルオキシエチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートを0.125g、メチルメタクリレート(以下、「MMA」と記す。)を4.875g、および、溶媒としてのトルエン10g、メチルエチルケトン(以下、「MEK」と記す。)を10g、および、重合開始剤としての1,1’-アゾビス(シクロヘシサン-1-カルボニトリル)(以下、「ACN」と記す。)を0.1g仕込み、撹拌しながら窒素ガス流量5ml/minで1時間フラスコ内を窒素置換後に昇温を行い、反応液温度88~91℃で10時間還流状態にて重合反応を行い、重合体(a)の溶液25.1gを得た。
(Example 4)
[Polymer (a); Synthesis of polymer having 2-methacryloxyethyl 2- (4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate]
A Dimroth condenser, a mercury thermometer, a nitrogen gas blowing tube, and a stirrer were attached to a 100 ml 4-necked flask, and the compound as a polymerizable compound (a); 2-methacryloxyethyl 2- (4-octyloxyphenyl) -2H- 0.125 g of benzotriazole-5-carboxylate, 4.875 g of methyl methacrylate (hereinafter referred to as "MMA"), 10 g of toluene as a solvent, and 10 g of methyl ethyl ketone (hereinafter referred to as "MEK"). , And 0.1 g of 1,1'-azobis (cyclohesisan-1-carbonitrile) (hereinafter referred to as "ACN") as a polymerization initiator was charged, and the nitrogen gas flow rate was 5 ml / min for 1 hour with stirring. After substituting nitrogen in the flask, the temperature was raised, and the polymerization reaction was carried out in a reflux state at a reaction solution temperature of 88 to 91 ° C. for 10 hours to obtain 25.1 g of a solution of the polymer (a).
(実施例5)
[重合体(b);2-メタクリロイルオキシエチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートを有する重合体の合成
100ml4つ口フラスコにジムロート冷却器、水銀温度計、窒素ガス吹き込み管、撹拌装置を取り付け、重合性化合物としての化合物(a);2-メタクリロイルオキシエチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートを0.125g、MMAを1.875g、シクロヘシキルメタクリレート(以下、「CHMA」と記す。)2.0g、スチレン1.0g、および、溶媒としてのトルエン10g、MEKを10g、および、重合開始剤としてのACNを0.05g仕込み、撹拌しながら窒素ガス流量5ml/minで1時間フラスコ内を窒素置換後に昇温を行い、反応液温度88~91℃で10時間還流状態にて重合反応を行い、重合体(b)の溶液25.05gを得た。
(Example 5)
[Polymer (b); Synthesis of polymer having 2-methacryloxyethyl 2- (4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate 100 ml 4-necked flask with Dimroth condenser, mercury thermometer, A nitrogen gas blowing tube and a stirrer were attached, and the compound (a) as a polymerizable compound; 0.125 g of 2-methacryloxyethyl 2- (4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate, MMA. 1.875 g, cyclohexyl methacrylate (hereinafter referred to as “CHMA”) 2.0 g, styrene 1.0 g, and toluene as a solvent 10 g, MEK 10 g, and ACN as a polymerization initiator 0. The polymer (b) was charged with 0.05 g, and the temperature was raised after replacing the nitrogen in the flask for 1 hour with a nitrogen gas flow rate of 5 ml / min while stirring, and the polymerization reaction was carried out at a reaction solution temperature of 88 to 91 ° C. in a reflux state for 10 hours. ) Was obtained in 25.05 g.
(実施例6)
[重合体(c);2-メタクリロイルオキシエチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートを有する重合体の合成
100ml4つ口フラスコにジムロート冷却器、水銀温度計、窒素ガス吹き込み管、撹拌装置を取り付け、重合性化合物としての化合物(a);2-メタクリロイルオキシエチル 2-(4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートを0.125g、MMAを2.125g、CHMAを2.25g、2-ヒドロキシエチルメタクリレート(以下、「HEMA」と記す。)0.5g、および、溶媒としてのトルエン10g、MEKを10g、および、重合開始剤としてのACNを0.1g仕込み、撹拌しながら窒素ガス流量5ml/minで1時間フラスコ内を窒素置換後に昇温を行い、反応液温度88~91℃で10時間還流状態にて重合反応を行い、重合体(c)の溶液25.1gを得た。
(Example 6)
[Polymer (c); Synthesis of polymer having 2-methacryloxyethyl 2- (4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate 100 ml 4-necked flask with Dimroth condenser, mercury thermometer, A nitrogen gas blowing tube and a stirrer were attached, and the compound (a) as a polymerizable compound; 0.125 g of 2-methacryloxyethyl 2- (4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate, MMA. 2.125 g, CHMA 2.25 g, 2-hydroxyethyl methacrylate (hereinafter referred to as "HEMA") 0.5 g, toluene as a solvent 10 g, MEK 10 g, and ACN as a polymerization initiator. 0.1 g of the mixture was charged, and the temperature was raised after replacing the nitrogen in the flask for 1 hour with a nitrogen gas flow rate of 5 ml / min while stirring, and the polymerization reaction was carried out at a reaction solution temperature of 88 to 91 ° C. in a reflux state for 10 hours to carry out the polymerization reaction. 25.1 g of the solution of (c) was obtained.
[重合体の分子量]
上記の実施例4~6により得られた重合体(a)~(c)の合成処方仕込み量と分子量を表1に示す。共重合体の分子量はGPCシステムHLC-8320GPC EcoSEC(東ソー株式会社)を用い、溶離液をテトラヒドロフラン、分離カラムをTSKgelGMHXL-L(東ソー株式会社)として、ポリスチレン検量線を用いたポリスチレン換算の重量平均分子量(Mw)、数平均分子量(Mn)、多分散度(Mw/Mn)を測定した。
[Molecular weight of polymer]
Table 1 shows the amounts and molecular weights of the polymers (a) to (c) obtained in the above Examples 4 to 6 in the synthetic formulation. The molecular weight of the copolymer is GPC system HLC-8320GPC EcoSEC (Tosoh Co., Ltd.), the eluent is tetrahydrofuran, the separation column is TSKgelGMHXL-L (Tosoh Co., Ltd.), and the polystyrene-equivalent weight average molecular weight using a polystyrene calibration line is used. (Mw), number average molecular weight (Mn), and polydispersity (Mw / Mn) were measured.
(比較例)
従来に提案されているベンゾトリアゾール誘導体化合物であり、一般式(1)と異なる構造である、化合物(c);2-メタクリロイルオキシエチル 2-(3-メトキシ-4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレート、化合物(d);2-メタクリロイルオキシエチル 2-(3,5-ジメトキシ-4-オクチルオキシフェニル)-2H-ベンゾトリアゾール-5-カルボキシレートを比較例として合成した。また、従来の一般的な青色発光材料であり、ナフタルイミド誘導体である化合物(e);N-[2-(4-tert-ブチルフェニル)-1,3-ジオキソ-2,3-ジヒドロ-1H-ベンゾ[de]イソキノリン-6-イル]アセトアミドを比較例として合成した。
(Comparative example)
Compound (c); 2-methacryloyloxyethyl 2- (3-methoxy-4-octyloxyphenyl) -2H-, which is a conventionally proposed benzotriazole derivative compound and has a structure different from that of the general formula (1). Benzotriazole-5-carboxylate, compound (d); 2-methacryloyloxyethyl 2- (3,5-dimethoxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate was synthesized as a comparative example. In addition, the compound (e) which is a conventional general blue light emitting material and is a naphthalimide derivative; N- [2- (4-tert-butylphenyl) -1,3-dioxo-2,3-dihydro-1H -Benzo [de] isoquinoline-6-yl] acetamide was synthesized as a comparative example.
[溶液の吸収及び発光特性]
上記の実施例及び比較例で得られた化合物(a)~(e)のクロロホルム中での吸収及び発光特性を表2に示す。
[Solution absorption and emission characteristics]
Table 2 shows the absorption and emission characteristics of the compounds (a) to (e) obtained in the above Examples and Comparative Examples in chloroform.
[波長変換フィルムの作製]
上記の比較例で得られた化合物(e)を0.05g、ポリメタクリル酸メチル1.95g、メチルエチルケトン4.00g、トルエン4.00gを混合し、波長変換材料を有した樹脂組成物の溶液を得た。得られた波長変換材料を有した樹脂組成物の溶液、及び実施例4~6で得られた重合体(a)、(b)、(c)の溶液を、バーコーターNo.20を用いてガラス板(セントラル社製「フロートガラス板」、厚み=2mm)に塗布し、加熱乾燥90℃を2分、120℃を3分の順で行った後、減圧乾燥40℃を24時間実施して溶媒を除去、波長変換材料が2.5%添加された膜厚4μmのフィルムを得た。
[Making a wavelength conversion film]
0.05 g of the compound (e) obtained in the above comparative example, 1.95 g of polymethyl methacrylate, 4.00 g of methyl ethyl ketone, and 4.00 g of toluene were mixed to prepare a solution of a resin composition having a wavelength conversion material. Obtained. The solution of the resin composition having the obtained wavelength conversion material and the solutions of the polymers (a), (b) and (c) obtained in Examples 4 to 6 were mixed with the bar coater No. 20 was applied to a glass plate (“float glass plate” manufactured by Central Co., Ltd., thickness = 2 mm), heat-dried at 90 ° C for 2 minutes, 120 ° C for 3 minutes, and then vacuum-dried at 40 ° C at 24. After a period of time, the solvent was removed to obtain a film having a film thickness of 4 μm to which 2.5% of the wavelength conversion material was added.
[フィルムの吸収及び発光特性]
上記で得られた化合物(e)、重合体(a)、(b)、(c)のフィルムでの吸収及び発光特性を表3に示す。
[Film absorption and emission characteristics]
Table 3 shows the absorption and emission characteristics of the compound (e), the polymer (a), (b) and (c) obtained above in the film.
表2より、本発明のベンゾトリアゾール誘導体化合物の溶液は、約30000のモル吸光係数及び約70%の蛍光量子効率であり、従来の一般的な青色発光材料である化合物(e)よりはるかに高いモル吸光係数及び蛍光量子効率を示している。さらに表3より、本発明品を用いたフィルムは、従来の一般的な波長変換材料である化合物(e)を用いたフィルムよりはるかに高い吸光度を示しており、蛍光量子効率は53~60%で従来品より高い値を示していることから、優れた波長変換性をもつと言え、有用な波長変換材料及び波長変換フィルムであることがわかる。また、表2より、従来に提案されているベンゾトリアゾール誘導体化合物である化合物(c)、(d)は、440~460nm程度に最大発光波長を示すが、本発明品は約410nmに最大発光波長を示すことから、本発明品は、410nm付近の光で生育が促進される農作物や、410nm付近の光の感度が高い太陽電池に最適に使用できることがわかる。なお、実施例1~6及び比較例により得られた化合物(a)、(b)、(c)、(d)、(e)、重合体(a)、(b)、(c)及びそれらを用いたフィルムの吸収スペクトル、発光スペクトル、励起スペクトル、蛍光量子効率の測定条件は次の通りである。 From Table 2, the solution of the benzotriazole derivative compound of the present invention has a molar extinction coefficient of about 30,000 and a fluorescence quantum efficiency of about 70%, which is much higher than that of the conventional general blue light emitting material (e). It shows the molar extinction coefficient and the fluorescence quantum efficiency. Further, from Table 3, the film using the product of the present invention shows much higher absorbance than the film using the compound (e), which is a conventional general wavelength conversion material, and the fluorescence quantum efficiency is 53 to 60%. Since it shows a higher value than the conventional product, it can be said that it has excellent wavelength conversion property, and it can be seen that it is a useful wavelength conversion material and wavelength conversion film. Further, from Table 2, the compounds (c) and (d), which are the conventionally proposed benzotriazole derivative compounds, show a maximum emission wavelength of about 440 to 460 nm, but the product of the present invention has a maximum emission wavelength of about 410 nm. It can be seen that the product of the present invention can be optimally used for agricultural products whose growth is promoted by light near 410 nm and solar cells having high sensitivity to light around 410 nm. The compounds (a), (b), (c), (d), (e), polymers (a), (b), (c) obtained in Examples 1 to 6 and Comparative Examples and them are used. The measurement conditions of the absorption spectrum, emission spectrum, excitation spectrum, and fluorescence quantum efficiency of the film using the above are as follows.
<溶液の吸収スペクトル測定条件>
装置:UV-2450((株)島津製作所製)
測定波長:250~ 500nm
溶媒:クロロホルム
濃度:10ppm
セル:1cm石英
<Measurement conditions for absorption spectrum of solution>
Equipment: UV-2450 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-500 nm
Solvent: Chloroform Concentration: 10 ppm
Cell: 1 cm quartz
<フィルムの吸収スペクトル測定条件>
装置: U-3900H((株)日立ハイテクサイエンス製)
測定波長:310~510nm
<Measurement conditions for film absorption spectrum>
Equipment: U-3900H (manufactured by Hitachi High-Tech Science Corporation)
Measurement wavelength: 310-510 nm
<溶液の発光スペクトル、励起スペクトル及び蛍光量子効率測定条件>
装置:FP-8500(日本分光(株)製)
測定波長:200~850nm
溶媒:クロロホルム
濃度:10ppm
セル:1cm石英
<Solution emission spectrum, excitation spectrum and fluorescence quantum efficiency measurement conditions>
Equipment: FP-8500 (manufactured by JASCO Corporation)
Measurement wavelength: 200 to 850 nm
Solvent: Chloroform Concentration: 10 ppm
Cell: 1 cm quartz
<フィルムの発光スペクトル、励起スペクトル及び蛍光量子効率測定条件>
装置:FP-8500(日本分光(株)製)
測定波長:200~ 850nm
<Film emission spectrum, excitation spectrum and fluorescence quantum efficiency measurement conditions>
Equipment: FP-8500 (manufactured by JASCO Corporation)
Measurement wavelength: 200 to 850 nm
本発明のベンゾトリアゾール誘導体化合物は、モル吸光係数及び蛍光量子効率が従来品より大きく、さらに本発明品のベンゾトリアゾール誘導体化合物を用いた波長変換フィルムは、吸光度及び蛍光量子効率が従来品より大きく、優れた波長変換性を示すことから、波長変換材料及び波長変換フィルムとして、好適に利用できる。さらに、従来品にない約410nmで最大発光波長を示すことから、410nm付近の光で生育が促進される農作物や、410nm付近の光の感度が高い太陽電池に最適に利用できる。 The benzotriazole derivative compound of the present invention has a higher molar absorption coefficient and fluorescence quantum efficiency than the conventional product, and the wavelength conversion film using the benzotriazole derivative compound of the present invention has higher absorbance and fluorescence quantum efficiency than the conventional product. Since it exhibits excellent wavelength conversion properties, it can be suitably used as a wavelength conversion material and a wavelength conversion film. Furthermore, since it exhibits a maximum emission wavelength at about 410 nm, which is not found in conventional products, it can be optimally used for agricultural products whose growth is promoted by light near 410 nm and solar cells with high light sensitivity around 410 nm.
Claims (8)
一般式(1)
[式中R1は、炭素数1~18のアルキル基であり、R 2 がアルキル炭素数1~4のアクリロイルオキシアルキル基、アルキル炭素数1~4のアクリロイルオキシヒドロキシアルキル基、アルキル炭素数1~4のメタクリロイルオキシアルキル基もしくはアルキル炭素数1~4のメタクリロイルオキシヒドロキシアルキル基である] A benzotriazole derivative compound represented by the following general formula (1).
General formula (1)
[In the formula, R 1 is an alkyl group having 1 to 18 carbon atoms, R 2 is an acryloyloxyalkyl group having 1 to 4 alkyl carbon atoms, an acryloyloxyhydroxyalkyl group having 1 to 4 alkyl carbon atoms, and an alkyl carbon number. It is a methacryloyloxyalkyl group of 1 to 4 or a methacryloyloxyhydroxyalkyl group having 1 to 4 alkyl carbon atoms].
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JP2014144931A (en) | 2013-01-29 | 2014-08-14 | Shipro Kasei Kaisha Ltd | Benzotriazole derivative compound |
JP2014144932A (en) | 2013-01-29 | 2014-08-14 | Shinnakamura Kagaku Kogyo Kk | Benzotriazole derivative compounds and polymers thereof |
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JP2014144931A (en) | 2013-01-29 | 2014-08-14 | Shipro Kasei Kaisha Ltd | Benzotriazole derivative compound |
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