JPH0423884A - Photochromic material - Google Patents
Photochromic materialInfo
- Publication number
- JPH0423884A JPH0423884A JP2126826A JP12682690A JPH0423884A JP H0423884 A JPH0423884 A JP H0423884A JP 2126826 A JP2126826 A JP 2126826A JP 12682690 A JP12682690 A JP 12682690A JP H0423884 A JPH0423884 A JP H0423884A
- Authority
- JP
- Japan
- Prior art keywords
- group
- trifluoromethyl
- derivative
- groups
- hydrocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 33
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 125000003277 amino group Chemical group 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 125000001391 thioamide group Chemical group 0.000 claims description 4
- 125000000101 thioether group Chemical group 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 28
- -1 nitroso-hydroxy Chemical class 0.000 abstract description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract description 8
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 abstract description 4
- 235000010288 sodium nitrite Nutrition 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 abstract description 3
- 238000006783 Fischer indole synthesis reaction Methods 0.000 abstract description 2
- 150000002429 hydrazines Chemical class 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract description 2
- 235000010265 sodium sulphite Nutrition 0.000 abstract description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 230000009935 nitrosation Effects 0.000 abstract 1
- 238000007034 nitrosation reaction Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012769 display material Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- HCJDAAXIBIPERT-UHFFFAOYSA-N 6-(trifluoromethyl)naphthalen-2-ol Chemical compound C1=C(C(F)(F)F)C=CC2=CC(O)=CC=C21 HCJDAAXIBIPERT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001093 holography Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- ODGIMMLDVSWADK-UHFFFAOYSA-N 4-trifluoromethylaniline Chemical compound NC1=CC=C(C(F)(F)F)C=C1 ODGIMMLDVSWADK-UHFFFAOYSA-N 0.000 description 1
- KWIKEUOFWNWERV-UHFFFAOYSA-N 6-iodonaphthalen-2-ol Chemical compound C1=C(I)C=CC2=CC(O)=CC=C21 KWIKEUOFWNWERV-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate 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
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は窓用調光ガラス、カーテン、サングラス、スキ
ー用ゴーグル等の調光材料、再生使用可能なコピー用紙
等の印写用感光材料、複写材料、または各種の記録・記
憶材料、表示材料、レーザー用感光材料、ホログラフィ
−用感光材料、あるいは光学フィルター、マスキング用
材料、光量計、デイスプレー用材料、または塗料、衣料
、玩具、スポーツ用品、化粧品、装飾品用材料として有
用な新規フォトクロミック材料に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to light control materials for windows, curtains, sunglasses, ski goggles, etc., photosensitive materials for printing such as recyclable copy paper, Copying materials, various recording/memory materials, display materials, photosensitive materials for lasers, photosensitive materials for holography, optical filters, masking materials, photometers, display materials, or paints, clothing, toys, sporting goods. This invention relates to a novel photochromic material useful as a material for cosmetics and ornaments.
［従来の技術］
フォトクロミック化合物は数多く知られており、代表的
なものにスピロピラン化合物がある。（Ｇ、Ｈ，Ｂｒｏ
ｗｎ、” Ｐｈｏｔｏｃｈｒｏｍｉｓｍ 、Ｗｉｌｅ
ｙ Ｉｎｔｅｒｓｃｉｅｎｃｅ、Ｎｅｗ Ｙｏｒｋ
（１９７１））またスピロオキサジン化合物が紫外光に
より発色、熱または可視光により消色するフォトクロミ
ック性を有することは知られている。例えば、特公昭４
５−２８８９２号、特公昭４９−４８６３１号、特開昭
５５−３６２８４号、特開昭６１”−５３２８８号、特
開昭６１−２６３９８２号、特開昭６２−３３１８４号
、ＵＳＰ４３４２６６８にはスピロナフトオキサジン系
化合物の置換誘導体および該化合物を含有するフォトク
ロミック材料が提案されている。[Prior Art] Many photochromic compounds are known, and a typical example is a spiropyran compound. (G, H, Bro
wn,” Photochromism, Wile
y Interscience, New York
(1971)) It is also known that spirooxazine compounds have photochromic properties in which they develop color when exposed to ultraviolet light and disappear when exposed to heat or visible light. For example,
5-28892, JP 49-48631, JP 55-36284, JP 61''-53288, JP 61-263982, JP 62-33184, and USP 4342668. Substituted derivatives of oxazine compounds and photochromic materials containing the compounds have been proposed.
また、特開昭６０−５３５８６号、特開昭６２−２８８
６８２号にはベンゼン環、ナフタレン環にトリフルオロ
メチル基を有するスピロナフトオキサジン系化合物を用
いたフォトクロミック材料が開示されている。Also, JP-A No. 60-53586, JP-A No. 62-288
No. 682 discloses a photochromic material using a spironaphthoxazine compound having a trifluoromethyl group on a benzene ring or a naphthalene ring.
また、特開昭６０−１１２８８０号、特開昭６２−１５
３２９２号にはスピロピリドベンゾオキサジン系化合物
および該化合物を用いたフォトクロミック材料が提案さ
れている。Also, JP-A-60-112880, JP-A-62-15
No. 3292 proposes a spiropyridobenzoxazine compound and a photochromic material using the compound.
また、特開昭６２−１６４６８５号、特開昭６３−３０
４８９号にはスピロフェナンスロオキサジン系化合物お
よび該化合物を使用した感光材料が提案されている。Also, JP-A-62-164685, JP-A-63-30
No. 489 proposes a spirophenanthrooxazine compound and a photosensitive material using the compound.
［発明が解決しようとする問題点］
スピロピラン化合物は光発消色の繰り返し耐久性に問題
があった。また公知のスピロオキサジン化合物は前記化
合物に比べて繰り返し耐久性は向上しているものの、実
用化レベルにおいてはまだまだ不十分であった。[Problems to be Solved by the Invention] Spiropyran compounds have a problem in durability over repeated photo-emission and decolorization. Further, although the known spirooxazine compounds have improved repeat durability compared to the above-mentioned compounds, they are still insufficient for practical use.
Ｅ問題点を解決するための手段］
本発明は前記問題点を解決するための新規フォトクロミ
ック材料に関するものである。Means for Solving Problem E] The present invention relates to a novel photochromic material for solving the above problem.
本発明のフォトクロミック材料は下記の一般式（ｂ）で
表されるＸ、Ｙにトリフルオロメチル基またはフッ素原
子を導入した新規スピロオキサジン系化合物を含有する
ことにより上記の問題点を解決するものである。The photochromic material of the present invention solves the above problems by containing a novel spirooxazine compound in which a trifluoromethyl group or a fluorine atom is introduced into X and Y represented by the following general formula (b). be.
（式中、Ｘ、Ｙはトリフルオロメチル基またはフッ素原
子を示す。環Ａ、ＢはＸ、Ｙ以外にも置換されていても
よい炭化水素芳香環または複素環系芳香環を示す。Ｒ１
、Ｒ２、Ｒ３、Ｒ４は水素原子、あるいは炭素数１〜２
５の炭化水素基、あるいはアルコキシ基、Ｆ、またはｃ
ｌ、Ｂｒ、工等のハロゲン原子、エステル基、シアノ基
、ニトロ基、エーテル基、チオエーテル基、カルボニル
基、スルホニル基、アミノ基、置換アミノ基、イミノ基
、アミド基、チオアミド基 ウレタン基、ウレア基、イ
ンシアネート基、アゾ基、またはヒドロキシ基、チオー
ル基、カルボキシル基、スルホン駿基およびその金属塩
基を有する炭化水素基を示す。Ｒ１、Ｒ２、Ｒ３、Ｒ４
はそれぞれ同一もしくは異なる置換基であり、Ｒ２、Ｒ
３は互いに結合し環化していてもよい。）
上記式（ｂ）において、Ｘ、Ｙはトリフルオロメチル基
またはフッ素原子を示し、それぞれ同一もしくは異なっ
ていてもよい。好ましくはＸ、Ｙが両方ともトリフルオ
ロメチル基である。(In the formula, X and Y represent a trifluoromethyl group or a fluorine atom. Rings A and B represent a hydrocarbon aromatic ring or a heterocyclic aromatic ring which may be substituted in addition to X and Y. R1
, R2, R3, R4 are hydrogen atoms or have 1 to 2 carbon atoms
5 hydrocarbon group, or alkoxy group, F, or c
Halogen atoms such as L, Br, and engineering, ester groups, cyano groups, nitro groups, ether groups, thioether groups, carbonyl groups, sulfonyl groups, amino groups, substituted amino groups, imino groups, amide groups, thioamide groups, urethane groups, urea group, incyanate group, azo group, or a hydrocarbon group having a hydroxy group, thiol group, carboxyl group, sulfone group, and its metal base. R1, R2, R3, R4
are the same or different substituents, R2, R
3 may be bonded to each other and cyclized. ) In the above formula (b), X and Y represent a trifluoromethyl group or a fluorine atom, and may be the same or different. Preferably, both X and Y are trifluoromethyl groups.
また上記式（ｂ）で表される化合物において環Ａ、Ｂの
Ｘ、Ｙ以外にも置換されていてもよい炭化水素芳香環ま
たは複素環系芳香環としては、ベンゼン環、ナフタレン
環、キノリン環、フェナンスレン環、アントラセン環、
ピリジン環等が挙げられる。好ましくはｆｆ１Ａはベン
ゼン環、ピリジン環であり、ｆｉＢはナフタレン環、キ
ノリン環、フェナンスレン環である。これらのＸ、Ｙ以
外の置換基としてはジフル才口メチル基、フルオロメチ
ル基、Ｃ１，Ｂｒ、■等のハロゲン原子、エステル基、
シアノ基、ニトロ基、エーテル基、チオエーテル基、カ
ルボニル基、スルホニル基、アミノ基、置換アミノ基、
イミノ基、アミド基、チオアミド基、ウレタン基、ウレ
ア基、インシアネート基、アゾ基、またはヒドロキシ基
、チオール基、カルボキシル基、スルホン酸基およびそ
の金属塩基、炭素数１〜２５の炭化水素基、あるいはア
ルコキシ基、Ｆ、またはＣ１、Ｂｒ、■等のハロゲン原
子、エステル基、シアノ基、ニド四基、エーテル基、チ
オエーテル基、カルボニル基、スルホニル基、アミノ基
、置換アミノ基、イミノ基、アミド基、チオアミド基
ウレタン基、ウレア基、インシアネート基、アゾ基、ま
たはヒドロキシ基、チオール基、カルボキシル基、スル
ホン酸基およびその金属塩基を有する炭化水素基等が挙
げられる。In addition, in the compound represented by the above formula (b), examples of the hydrocarbon aromatic ring or heterocyclic aromatic ring which may be substituted in addition to X and Y of rings A and B include a benzene ring, a naphthalene ring, and a quinoline ring. , phenanthrene ring, anthracene ring,
Examples include pyridine ring. Preferably, ff1A is a benzene ring or a pyridine ring, and fiB is a naphthalene ring, a quinoline ring, or a phenanthrene ring. These substituents other than X and Y include difluoromethyl group, fluoromethyl group, halogen atoms such as C1, Br, ■, ester group,
Cyano group, nitro group, ether group, thioether group, carbonyl group, sulfonyl group, amino group, substituted amino group,
imino group, amide group, thioamide group, urethane group, urea group, incyanate group, azo group, or hydroxy group, thiol group, carboxyl group, sulfonic acid group and its metal base, hydrocarbon group having 1 to 25 carbon atoms, Or an alkoxy group, F, or a halogen atom such as C1, Br, ■, an ester group, a cyano group, a nido tetragroup, an ether group, a thioether group, a carbonyl group, a sulfonyl group, an amino group, a substituted amino group, an imino group, an amide group. group, thioamide group
Examples thereof include a urethane group, a urea group, an incyanate group, an azo group, a hydroxy group, a thiol group, a carboxyl group, a sulfonic acid group, and a hydrocarbon group having a metal base thereof.
またＲ’、 Ｒ”、Ｒ３としては、アルキル基、アルキ
レン基等を介してもう一つのスピロオキサジン環と結合
し、全体として２量体の化合物を形成したものも挙げら
れる。また１ｌｔ１． Ｒ２、Ｒ３、Ａ環、Ｂ環に二重
結合、シランカップリング基等の反応性基を導入し、マ
トリックス材料と結合させることも出来る。Further, examples of R', R'', and R3 include those that are bonded to another spirooxazine ring via an alkyl group, an alkylene group, etc. to form a dimer compound as a whole.Also, 1lt1.R2, It is also possible to introduce a reactive group such as a double bond or a silane coupling group into R3, the A ring, and the B ring to bond them to the matrix material.
本発明の新規フォトクロミック材料は、一般式（ａ）の
Ｘ、Ｙにトリフルオロメチル基またはフッ素原子を導入
することにより光発消色の繰り返し耐久性に極めて優れ
、実用化レベルにおいて使用可能であるという特徴を有
する。The novel photochromic material of the present invention has extremely excellent durability against repeated light-emitting and decoloring by introducing a trifluoromethyl group or a fluorine atom into X and Y in general formula (a), and can be used at a practical level. It has the following characteristics.
本発明の化合物は、例えば次のようにして製造すること
が出来る。下記一般式（ｃ）（式中、Ｘ、及び環Ａは前
記定義に同じ。）で表されるアミノ誘導体にＮａＮ０＊
にょるジアゾ化、Ｎａ＊ＳＯｓによる還元を行い、下記
一般式（ｄ）
（式中、Ｘ、及び環Ａは前記定義に同じ、）で表される
ヒドラジン誘導体を得た。これを下記般式（ｅ）
（式中、Ｒ２、Ｒ１、Ｒ４は前記定義に同じ。）で表さ
れるケトンと反応させた後にフィッシャーインドール反
応を行うことにより下記一般式（ｆ）
（式中、Ｘ、Ｒ’、Ｒ３、Ｒ４、及びｆｆ１Ａは前記定
義に同じ。）で表されるインドレニン誘導体を得た。
また、下記一般式（ｇ）
（式中、Ｙ、環Ｂは前記定義と同じ。）で表されるヒド
ロキシ誘導体をＮａＮ０ｉにてニトロソ化することによ
り下記一般式（ｈ）
（式中、Ｙ、及び環Ｂは前記定義と同じ。）で表される
ニトロソ−ヒドロキシ誘導体を得た。The compound of the present invention can be produced, for example, as follows. NaNO* to the amino derivative represented by the following general formula (c) (wherein, X and ring A are the same as defined above)
Diazotization with Na*SOs and reduction with Na*SOs were performed to obtain a hydrazine derivative represented by the following general formula (d) (wherein X and ring A are the same as defined above). This is reacted with a ketone represented by the following general formula (e) (in which R2, R1, and R4 are the same as defined above) and then subjected to a Fischer indole reaction to perform the following general formula (f) (in the formula , X, R', R3, R4, and ff1A are the same as defined above.) An indolenine derivative was obtained.
In addition, by nitrosating a hydroxy derivative represented by the following general formula (g) (wherein Y and ring B are the same as defined above) with NaN0i, the following general formula (h) (wherein Y, and ring B are the same as defined above.) A nitroso-hydroxy derivative was obtained.
ここで先に得られたインドレニン誘導体（ｆ）を下記一
般式（ｉ）
Ｒ’Ｘ （ｉ ）（式中、Ｘは
ＩまたはＳＯ，Ｃ，Ｈ４ＣＨ３、Ｒ１は前記定義と同じ
。）と反応させた後にニトロソ−ヒドロキシ誘導体（ｈ
）と反応させることにより製造できる。Here, the previously obtained indolenine derivative (f) is reacted with the following general formula (i) R'X (i) (wherein, X is I or SO, C, H4CH3, and R1 is the same as defined above). The nitroso-hydroxy derivative (h
) can be produced by reacting with
インドレニン誘導体とニトロソ−ヒドロキシ誘導体のカ
ップリング反応はインドレニン誘導体とＲ’Ｘを無溶媒
あるいは溶媒中、０℃〜１５０℃の反応温度で１時間〜
８時間反応した後に、ニトロソ−ヒドロキシ誘導体、並
びにトリエチルアミン、ピペリジン、ピペラジン、モル
ホリン等の塩基を加え、０℃〜１５０℃の反応温度で１
時間〜８時間反応することにより実施される。好ましく
はトルエン、エタノール中、トリエチルアミンの存在下
、４０℃〜１２０℃で円滑に実施出来る。The coupling reaction between the indolenine derivative and the nitroso-hydroxy derivative is carried out by combining the indolenine derivative and R'X without a solvent or in a solvent at a reaction temperature of 0°C to 150°C for 1 hour or more.
After reacting for 8 hours, a nitroso-hydroxy derivative and a base such as triethylamine, piperidine, piperazine, morpholine, etc. were added, and the reaction temperature was 0°C to 150°C.
This is carried out by reacting for 8 hours to 8 hours. Preferably, it can be carried out smoothly at 40°C to 120°C in toluene or ethanol in the presence of triethylamine.
本発明のフォトクロミック材料のマトリックス材料とし
ては、ガラス、光学的に透明な樹脂、例えばポリビニル
ブチラール、ポリビニルアルコール、ポリエステル、ポ
リスチレン、ポリカーボネート、ポリ塩化ビニリデン、
ポリ塩化ビニル、ポリメタクリル酸メチル、ポリ酢酸ビ
ニル、酢酸セルロース、エポキシ樹脂、フェノール樹脂
、ナイロン樹脂、ポリウレタン、（ハロゲン化）ビスフ
ェノールＡの（ウレタン変性）アクリレートポリマー、
アモルファスポリオレフィン、及び上記樹脂の混合物ま
たは共重合体などを使用することが出来る。Matrix materials for the photochromic material of the present invention include glass, optically transparent resins such as polyvinyl butyral, polyvinyl alcohol, polyester, polystyrene, polycarbonate, polyvinylidene chloride,
Polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, epoxy resin, phenol resin, nylon resin, polyurethane, (urethane-modified) acrylate polymer of (halogenated) bisphenol A,
Amorphous polyolefins and mixtures or copolymers of the above resins can be used.
マトリックス材料への本発明フォトクロミック化合物の
配合方法としては染色法、キャスティング法、配合され
たポリマー溶液のコーティング法、または本発明フォト
クロミック化合物をマイクロカプセル化した後に付着す
る方法、あるいは本発明フォトクロミック化合物中の二
重結合、シランカップリング基等の反応性基とマトリッ
クス材料を反応させることにより結合する方法等、各種
の方法が適用出来る。Methods for blending the photochromic compound of the present invention into the matrix material include dyeing, casting, coating of a blended polymer solution, or attachment after microencapsulating the photochromic compound of the present invention; Various methods can be applied, such as a method of bonding by reacting a reactive group such as a double bond or a silane coupling group with a matrix material.
また、本発明のフォトクロミック材料においては、耐光
性向上のために紫外線吸収剤、酸化防止剤、ヒンダード
アミン系安定剤等を添加することも出来る。Further, in the photochromic material of the present invention, ultraviolet absorbers, antioxidants, hindered amine stabilizers, etc. can be added to improve light resistance.
［実施例］
［合成例１］
イソプロピルメチルケトン−（４−トリフルオロメチル
）フェニルヒドラゾンの合成４−トリフルオロメチルア
ニリン２５ｇをジオキサン１００ｍ１に溶解した後に水
１００ｍ１と濃塩酸４０ｍ１を加えた。水冷撹拌下、亜
硝酸ソーダｌ１ｇの水溶液１００ｍ１を滴下後、亜硫酸
ソーダ５６ｇの水溶液２００ｍ１を加えた。室温にて一
晩放置した後に８０℃まで加熱した。抽出処理の後、有
機溶媒を減圧にて留去した。得られた残渣にイソプロピ
ルメチルケトン２０ｇを加え２時間加熱還流した後、減
圧蒸留することにより表記の化合物を２０ｇ得た。[Examples] [Synthesis Example 1] Synthesis of isopropylmethylketone-(4-trifluoromethyl)phenylhydrazone After 25 g of 4-trifluoromethylaniline was dissolved in 100 ml of dioxane, 100 ml of water and 40 ml of concentrated hydrochloric acid were added. While cooling with water and stirring, 100 ml of an aqueous solution containing 1 g of sodium nitrite was added dropwise, and then 200 ml of an aqueous solution containing 56 g of sodium sulfite was added. After being left at room temperature overnight, it was heated to 80°C. After the extraction process, the organic solvent was distilled off under reduced pressure. 20 g of isopropyl methyl ketone was added to the resulting residue, heated under reflux for 2 hours, and then distilled under reduced pressure to obtain 20 g of the title compound.
［合成例２］
５−トリフルオロメチル−２，３，３−トリメチルイン
ドレニンの合成 イソプロピルメチルケトン−（４−ト
リフルオロメチル）フェニルヒドラゾン２０ｇを酢酸１
２０ｍ１に溶解し９０℃にて一晩撹拌した。抽出処理の
後、有機溶媒を減圧にて留去し得られた残渣を減圧蒸留
することにより表記の化合物を１２ｇ得た。[Synthesis Example 2] Synthesis of 5-trifluoromethyl-2,3,3-trimethylindolenine 20 g of isopropylmethylketone-(4-trifluoromethyl)phenylhydrazone was mixed with 1 acetic acid.
The solution was dissolved in 20ml and stirred at 90°C overnight. After the extraction process, the organic solvent was distilled off under reduced pressure, and the resulting residue was distilled under reduced pressure to obtain 12 g of the title compound.
ＨＮＭＲ（ＣＤ、Ｃ１）：δ １．３ｐｐｍ （ｓ
。HNMR (CD, C1): δ 1.3ppm (s
.
６ Ｈ）、 ２．３ｐｐｍ （ｓ 、 ３Ｈ） 、
７．４〜’７．７ｐｐｍ （ｍ、 ３Ｈ）
”ＦＮＭＲ（ｃＤｓ Ｃ１，ＣＦＣｌ、基準）；δ−６
２ｐｐｍ（３Ｆ）
［合成例３］
５−トリフルオロメチル−１，２，３，３テトラメチル
インドレニニウムヨードジドの合成
５−トリフルオロメチル−２，３，３−トリメチルイン
ドレニン１２ｇをクロロホルム５０ｍ１に溶解し、メチ
ルヨードシト１５ｇを加えた。６０℃にて１日撹拌した
後に反応液を濾別することにより表記の化合物を１７ｇ
得た。6H), 2.3ppm (s, 3H),
7.4~'7.7ppm (m, 3H) "FNMR (cDs C1, CFCl, standard); δ-6
2 ppm (3F) [Synthesis Example 3] Synthesis of 5-trifluoromethyl-1,2,3,3-tetramethylindoleninium iododide 12 g of 5-trifluoromethyl-2,3,3-trimethylindolenine was dissolved in 50 ml of chloroform. 15 g of methyl iodosite was added. After stirring at 60°C for one day, the reaction solution was filtered to obtain 17g of the indicated compound.
Obtained.
［合成例４］
６−トリフルオロメチル−２−ナフトールの合成
６−ヨード−２−ナフトール１６ｇをＤＭＡｃ４００ｍ
ｌに溶解し、トリフルオロ酢酸ナトリウム２７ｇとヨウ
化第−銅１９ｇを加え、１６０℃にて４時間撹拌した。[Synthesis Example 4] Synthesis of 6-trifluoromethyl-2-naphthol 16 g of 6-iodo-2-naphthol was dissolved in 400 m of DMAc.
27 g of sodium trifluoroacetate and 19 g of cupric iodide were added, and the mixture was stirred at 160° C. for 4 hours.
抽出処理の後、有機溶媒を減圧にて留去し得られた残渣
をシリカゲルカラムクロマトグラフィーにて分離精製し
、表記の化合物を５ｇ得た。After the extraction process, the organic solvent was distilled off under reduced pressure, and the resulting residue was separated and purified using silica gel column chromatography to obtain 5 g of the title compound.
’ＨＮＭＲ（ＣＤ、ＣＩ）：δ５−８ ｐｐｍ（ｂ ｓ
。'HNMR (CD, CI): δ5-8 ppm (b s
.
ＩＨ）、７．０〜８．（ｌｐｐｍ （ｍ 、 ’６
Ｈ）”ＦＮＭＲ（ＣＤ、Ｃ１，ＣＦＣｌ、基＄） ６
６１ ｐｐｍ （３Ｆ）
［合成例５］
５−トリフルオロメチル−１，３，３−トリメチル−８
°−トリフルオロメチル−スピロ［インドリン−２，３
’ −（３Ｈ）−ナフト（２，１−ｂ）（１，４）オ
キサジン〕の合成６−トリフルオロメチル−２−ナフト
ール５ｇをＩＮ水酸化ナトリウム水溶液２５ｍ１に溶解
した。水冷撹拌下、亜硝酸ソーダ５ｇの水溶液２５ｍ１
を滴下した後にｌＮ硫酸水溶液３５ｍ１を滴下し、室温
にて３時間撹拌した。抽出処理の後、有機溶媒を減圧に
て留去し得られた残渣をエタノール５０ｍ１に溶解し、
５−トリフルオロメチル−１，２，３，３−テトラメチ
ルインドレニニウムヨードジド８．７ｇとトリエチルア
ミン３２ｇを加えた。４時間加熱還流の後に溶媒を減圧
にて留去し得られた残渣をシリカゲルカラムクロマトグ
ラフィーにて分離精製し、表記の化合物を３．５ｇ得た
。この化合物を以下の実施例で用いた。IH), 7.0-8. (lppm (m, '6
H)"FNMR (CD, C1, CFCl, group $) 6
61 ppm (3F) [Synthesis Example 5] 5-trifluoromethyl-1,3,3-trimethyl-8
°-Trifluoromethyl-spiro[indoline-2,3
Synthesis of '-(3H)-naphtho(2,1-b)(1,4)oxazine] 5 g of 6-trifluoromethyl-2-naphthol was dissolved in 25 ml of IN aqueous sodium hydroxide solution. 25 ml of an aqueous solution of 5 g of sodium nitrite under water cooling and stirring
After that, 35 ml of 1N sulfuric acid aqueous solution was added dropwise, and the mixture was stirred at room temperature for 3 hours. After the extraction process, the organic solvent was distilled off under reduced pressure, and the resulting residue was dissolved in 50 ml of ethanol.
8.7 g of 5-trifluoromethyl-1,2,3,3-tetramethylindoleninium iododide and 32 g of triethylamine were added. After heating under reflux for 4 hours, the solvent was distilled off under reduced pressure, and the resulting residue was separated and purified using silica gel column chromatography to obtain 3.5 g of the title compound. This compound was used in the examples below.
λｍａｘ ＝ ６０５ ｎｍ
’ＨＮＭＲ（ＣＤ、ＣＩ） ： δ １．４ｐｐｍ
（ｓ、６Ｈ）、 ２．７ｐｐｍ（ｓ、３Ｈ）。λmax = 605 nm 'HNMR (CD, CI): δ 1.4ppm
(s, 6H), 2.7 ppm (s, 3H).
６．３〜７．９ ｐｐｍ （ｍ、 ８ Ｈ） 、 ８
．６ ｐｐｍ（ｍ、ＬＨ）
”ＦＮＭＲ（ＣＤ、ＣＩ、ＣＦＣｌ３基準）：δ−６１
ｐｐｍ （３Ｆ） 、 −６２ｐｐｍ （３Ｆ）［比
較合成例１］
５−トリフルオロメチル−１，３３−トリメチル−スピ
ロ［インドリン−２，３’ −（３Ｈ）−ナフト（２，
ｔ−ｂ）（１，４）オキサジン〕の合成
５−トリフルオロメチル−１，２，３，３テトラメチル
インドレニニウムヨ一ドジド５ｇをエタノール５０ｍ１
に溶解し、トリエチルアミン２ｇと１−ニトロソ−２−
ナフトール２．３ｇを加えた。３時間加熱還流の後に溶
媒を減圧にて留去し得られた残渣をシリカゲルカラムク
ロマトグラフィーにて分離精製し、表記の化合物を４．
１ ｇ得た。6.3-7.9 ppm (m, 8H), 8
．． 6 ppm (m, LH) "FNMR (CD, CI, CFCl3 standards): δ-61
ppm (3F), -62ppm (3F) [Comparative Synthesis Example 1] 5-Trifluoromethyl-1,33-trimethyl-spiro[indoline-2,3'-(3H)-naphtho(2,
t-b) Synthesis of (1,4)oxazine] 5-trifluoromethyl-1,2,3,3-tetramethylindoleninium iododide (5 g) was added to 50 ml of ethanol.
2 g of triethylamine and 1-nitroso-2-
2.3 g of naphthol was added. After heating under reflux for 3 hours, the solvent was distilled off under reduced pressure, and the resulting residue was separated and purified using silica gel column chromatography to obtain the compound described in 4.
I got 1g.
λｍａｘ ＝ ５８０ ｎｍ［比較合成例２
］
１．３．３−トリメチル−８°−トリフルオロメチル−
スピロ〔インドリン−２，３゜（３Ｈ）−ナフト（２，
１−ｂ）（１，４）オキサジン〕の合成 ５−トリフル
オロメチル−１，２，３，３−テトラメチルインドレニ
ニウムヨードジドの代わりに、ｌ、３．３−トリメチル
−２−メチレンインドリンを用い合成例４と同様の手法
にて表記の化合物を合成した。λmax = 580 nm [Comparative synthesis example 2
] 1.3.3-trimethyl-8°-trifluoromethyl-
Spiro[indoline-2,3°(3H)-naphtho(2,
1-b) Synthesis of (1,4)oxazine] Instead of 5-trifluoromethyl-1,2,3,3-tetramethylindoleninium iododide, l,3,3-trimethyl-2-methyleneindoline The indicated compound was synthesized using the same method as in Synthesis Example 4.
λｍａｘ ＝ ６０５ ｎｍ［比較例３コ
λｍａｘ ＝
［実施例〕
ポリビニルブチラールの３０％トルエン：イソプロビル
アルコール（４２：５ｇ）混合溶液にスピロオキサジン
化合物のトルエン溶液を加え撹拌した。この溶液からキ
ャスト製膜し約５０μの厚さのフィルムを得た。室温に
て２時間風乾、４０℃にて１時間乾燥したものを測定に
用いた。λmax = 605 nm [Comparative Example 3 λmax = [Example] A toluene solution of a spirooxazine compound was added to a 30% toluene:isopropyl alcohol (42:5 g) mixed solution of polyvinyl butyral and stirred. A film having a thickness of about 50 μm was obtained by casting from this solution. The samples were air-dried at room temperature for 2 hours and dried at 40° C. for 1 hour before being used for measurement.
色素／ポリマー＝ ０．１５ （ｍｍｏｌ／ ｇ ）結
果を第１図に示した。Dye/polymer = 0.15 (mmol/g) The results are shown in Figure 1.
［発明の効果］
本発明の新規フォトクロミック材料は光発消色の繰り返
し耐久性に極めて優れるという特徴を有し、実用レベル
において十分な耐光性を有する。[Effects of the Invention] The novel photochromic material of the present invention is characterized by extremely excellent durability against repeated light-emitting and decoloring, and has sufficient light resistance at a practical level.
このような本フォトクロミック材料は窓用調光ガラス、
カーテン、サングラス、スキー用ゴーグル等の調光材料
、再生使用可能なコピー用紙等の印写用感光材料、複写
材料、または各種の記録・記憶材料、表示材料、レーザ
ー用感光材料、ホログラフィ−用感光材料、あるいは光
学フィルター、マスキング用材料、光量計、デイスプレ
ー用材料、または衣料、装飾品用材料として使用される
。Such photochromic materials are used for window dimming glass,
Light control materials for curtains, sunglasses, ski goggles, etc., photosensitive materials for printing such as recyclable copy paper, copying materials, various recording/memory materials, display materials, photosensitive materials for lasers, photosensitive materials for holography It is used as a material for optical filters, masking materials, photometers, display materials, or clothing and decorative items.
第１図は、実施例ににおける紫外光照射時間と吸光度（
ＡＢＵ）の関係を示す図である。Figure 1 shows the ultraviolet light irradiation time and absorbance (
It is a figure showing the relationship of ABU).
Claims (1)
子を示す。環Ａ、ＢはＸ、Ｙ以外にも置換されていても
よい炭化水素芳香環または複素環系芳香環を示す。Ｒ＾
１、Ｒ＾２、Ｒ＾３、Ｒ＾４は水素原子、あるいは炭素
数１〜２５の炭化水素基、あるいはアルコキシ基、Ｆ、
またはＣｌ、Ｂｒ、Ｉ等のハロゲン原子、エステル基、
シアノ基、ニトロ基、エーテル基、チオエーテル基、カ
ルボニル基、スルホニル基、アミノ基、置換アミノ基、
イミノ基、アミド基、チオアミド基、ウレタン基、ウレ
ア基、イソシアネート基、アゾ基、またはヒドロキシ基
、チオール基、カルボキシル基、スルホン酸基およびそ
の金属塩基を有する炭化水素基を示す。Ｒ＾１、Ｒ＾２
、Ｒ＾３、Ｒ＾４はそれぞれ同一もしくは異なる置換基
であり、Ｒ＾２、Ｒ＾３は互いに結合し環化していても
よい。）で表されるスピロオキサジン系フォトクロミッ
ク材料。[Claims] General formula (a) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (a) (In the formula, X and Y represent a trifluoromethyl group or a fluorine atom. Rings A and B are X and Y Indicates a hydrocarbon aromatic ring or a heterocyclic aromatic ring which may be substituted.R^
1, R^2, R^3, R^4 are hydrogen atoms, hydrocarbon groups having 1 to 25 carbon atoms, or alkoxy groups, F,
or halogen atoms such as Cl, Br, I, ester groups,
Cyano group, nitro group, ether group, thioether group, carbonyl group, sulfonyl group, amino group, substituted amino group,
It represents an imino group, an amide group, a thioamide group, a urethane group, a urea group, an isocyanate group, an azo group, or a hydrocarbon group having a hydroxy group, a thiol group, a carboxyl group, a sulfonic acid group, and its metal base. R^1, R^2
, R^3, and R^4 are the same or different substituents, respectively, and R^2 and R^3 may be bonded to each other and cyclized. ) is a spirooxazine-based photochromic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2126826A JPH0423884A (en) | 1990-05-18 | 1990-05-18 | Photochromic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2126826A JPH0423884A (en) | 1990-05-18 | 1990-05-18 | Photochromic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0423884A true JPH0423884A (en) | 1992-01-28 |
Family
ID=14944886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2126826A Pending JPH0423884A (en) | 1990-05-18 | 1990-05-18 | Photochromic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0423884A (en) |
-
1990
- 1990-05-18 JP JP2126826A patent/JPH0423884A/en active Pending
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