JPH0317875B2 - - Google Patents
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- Publication number
- JPH0317875B2 JPH0317875B2 JP61035321A JP3532186A JPH0317875B2 JP H0317875 B2 JPH0317875 B2 JP H0317875B2 JP 61035321 A JP61035321 A JP 61035321A JP 3532186 A JP3532186 A JP 3532186A JP H0317875 B2 JPH0317875 B2 JP H0317875B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- formula
- derivative
- substituted
- 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.)
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- -1 4,4-dimethylhexyl group Chemical group 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 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 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical compound C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 description 1
- HMJPSXRANHDJOF-UHFFFAOYSA-N 10-nitrosophenanthren-9-ol Chemical compound C1=CC=C2C(O)=C(N=O)C3=CC=CC=C3C2=C1 HMJPSXRANHDJOF-UHFFFAOYSA-N 0.000 description 1
- FAQVDANXTSFXGA-UHFFFAOYSA-N 2,3-dihydro-1h-benzo[g]indole Chemical group C1=CC=CC2=C(NCC3)C3=CC=C21 FAQVDANXTSFXGA-UHFFFAOYSA-N 0.000 description 1
- 125000003163 2-(2-naphthyl)ethyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(C([H])=C([H])C2=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 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
- 239000002253 acid Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane 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
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- VIIKBNGEMDPDAE-UHFFFAOYSA-N spiro[1,3-dihydrobenzo[g]indole-2,3'-benzo[f][1,4]benzoxazine] Chemical compound C1=CC=CC2=C(N=CC3(NC4=C5C=CC=CC5=CC=C4C3)O3)C3=CC=C21 VIIKBNGEMDPDAE-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は印写用フオトクロミツク材料、光学機
器用フオトクロミツク材料、記録材料用フオトク
ロミツク材料または衣料、装飾品用フオトクロミ
ツク材料として有用なフオトクロミツク材料に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photochromic material useful as a photochromic material for printing, a photochromic material for optical instruments, a photochromic material for recording materials, or a photochromic material for clothing and ornaments.
［従来の技術］
フオトクロミツク化合物の代表的なものに、ス
ピロピラン化合物があり、多くの化合物が知られ
ている（ジー・エイチ・ブラウン著、“フオトク
ロミズム”、ウイリーインターサイエンス社、ニ
ユーヨーク）、（G.H.Brown，
“Photochromism”，Wiley Inter science，New
York（1971））。[Prior Art] A typical photochromic compound is a spiropyran compound, and many compounds are known (G. H. Brown, "Photochromism", Willy Interscience, New York), (GH Brown ，
“Photochromism”, Wiley Inter science, New
York (1971)).
またスピロオキサジン化合物としては特公昭45
−28892号公報、特公昭49−48631号公報、特開昭
48−23787号公報、特開昭55−36284号公報、東独
特許0153−690、東独特許1563−72に開示されて
いる。 In addition, as a spirooxazine compound,
-28892 Publication, Japanese Patent Publication No. 49-48631, Japanese Patent Application Publication No.
It is disclosed in JP-A No. 48-23787, Japanese Patent Application Laid-Open No. 55-36284, East German Patent No. 0153-690, and East German Patent No. 1563-72.
［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使用
における耐疲労性に問題があつた。また公知のス
ピロオキサジン化合物は耐疲労性は前記化合物に
比べ向上している。[Problems to be Solved by the Invention] Spiropyran compounds have a problem in fatigue resistance during repeated use of light-emitting and decoloring. Furthermore, known spirooxazine compounds have improved fatigue resistance compared to the above-mentioned compounds.
しかしながら従来のスピロピランおよびスピロ
オキサジン化合物の発色種はマトリツクス効果が
大であり、たとえば溶媒の極性により吸収波長が
大きく変化する。 However, the coloring species of conventional spiropyran and spirooxazine compounds have a large matrix effect, and the absorption wavelength changes greatly depending on, for example, the polarity of the solvent.
そのため発色種の色調が決まると自動的に用い
られ得るマトリツクスの種類は限定された。 Therefore, the types of matrices that can be automatically used once the color tone of the coloring species is determined are limited.
［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フオトク
ロミツク材料に関するものである。すなわち本発
明により提供されるフオトクロミツク材料を構成
するスピロオキサジン化合物とは、下記一般式(A)
又は(B)で表わされるものである。[Means for Solving the Problems] The present invention relates to a photochromic material for solving the above problems. That is, the spirooxazine compound constituting the photochromic material provided by the present invention has the following general formula (A).
or (B).
（式中、R2，R3，R4，R5は炭素数１〜４のア
ルキル基、炭素数１または２のハロゲン置換アル
キル基、炭素数１〜４のアルコキシ基、ハロゲン
基、ニトロ基から選ばれた置換基を表わし、ｎは
０〜２の整数、ｍおよびｔは０〜４の整数、ｌは
式(A)にあつては０〜２の整数、式(B)にあつては０
〜４の整数であり、R2，R3，R4，R5はそれぞれ
同種であつても異種であつてもよい。R1は炭素
数１〜20の無置換または置換アルキル基、炭素数
３〜10の無置換または置換シクロアルキル基、炭
素数７〜20の無置換または置換アラルキル基、炭
素数６〜14の無置換または置換アリール基から選
ばれた置換基を表わす。）
かかる式(A)又は(B)における置換基R1の具体例
としては、メチル基、エチル基、プロピル基、オ
クチル基、ヘキサデシル基、エイコシル基などの
炭素数１〜20の鎖状アルキル基；iso−プロピル
基、tert−ブチル基、４，４−ジメチルヘキシル
基、５，７−ジエチルヘキサジル基などの炭素数
３〜20の分枝状アルキル基；シクロプロピル基、
シクロヘキシル基、シクロオクチル基、シクロデ
シル基などの炭素数３〜10のシクロアルキル基；
ベンジル基、２−フエニルエチル基、（１−ナフ
チル）メチル基、２−（１−ナフチル）エチル基、
（２−ナフチル）メチル基、２−（２−ナフチル）
エチル基、（９−アントラシル）メチル基、（９−
フエナントリル）メチル基、（５−ナフタシル）
エチル基などの炭素数７〜20のアラルキル基；フ
エニル基、１−ナフチル基、２−ナフチル基、９
−アントラシル基などの炭素数６〜14のアリール
基が挙げられる。かかるR1が非環状アルキル基
である場合、その置換基誘導体に含まれる置換基
の具体例としては、ヒドロキシ基；アミノ基；メ
チルアミノ基、ジエチルアミノ基などの有機置換
アミノ基；メトキシ基、エトキシ基、tert−ブト
キシ基などの炭素数１〜４のアルコキシ基；ベン
ジロキシ基などの炭素数７〜15のアラルコキシ
基；フエノキシ基、１−ナフトキシ基などの炭素
数６〜14のアリーロキシ基；フルオロ基、クロロ
基、ブロモ基などのハロゲン基；シアノ基；カル
ボキシ基；エトキシカルボニル基などの炭素数２
〜10のアルコキシカルボニル基；アセチル基、ベ
ンゾイル基などの炭素数２〜10のアシル基；ニト
ロ基などが挙げられる。 (In the formula, R 2 , R 3 , R 4 , R 5 are an alkyl group having 1 to 4 carbon atoms, a halogen-substituted alkyl group having 1 or 2 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen group, a nitro group) represents a substituent selected from, n is an integer of 0 to 2, m and t are integers of 0 to 4, l is an integer of 0 to 2 in formula (A), and in formula (B) is 0
It is an integer of ~4, and R 2 , R 3 , R 4 , and R 5 may be the same or different. R 1 is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 10 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, or an unsubstituted or substituted aralkyl group having 6 to 14 carbon atoms. Represents a substituent selected from substituted or substituted aryl groups. ) Specific examples of the substituent R 1 in the formula (A) or (B) include a chain alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an octyl group, a hexadecyl group, and an eicosyl group. ; Branched alkyl groups having 3 to 20 carbon atoms such as iso-propyl group, tert-butyl group, 4,4-dimethylhexyl group, 5,7-diethylhexazyl group; cyclopropyl group;
Cycloalkyl groups having 3 to 10 carbon atoms such as cyclohexyl group, cyclooctyl group, cyclodecyl group;
benzyl group, 2-phenylethyl group, (1-naphthyl)methyl group, 2-(1-naphthyl)ethyl group,
(2-naphthyl)methyl group, 2-(2-naphthyl)
Ethyl group, (9-anthrasyl)methyl group, (9-
(phenanthryl) methyl group, (5-naphthasil)
Aralkyl group having 7 to 20 carbon atoms such as ethyl group; phenyl group, 1-naphthyl group, 2-naphthyl group, 9
-Aryl groups having 6 to 14 carbon atoms such as anthracyl group can be mentioned. When R 1 is an acyclic alkyl group, specific examples of substituents included in the substituent derivative include hydroxy group; amino group; organic substituted amino groups such as methylamino group and diethylamino group; methoxy group, ethoxy alkoxy groups having 1 to 4 carbon atoms such as tert-butoxy groups; aralkoxy groups having 7 to 15 carbon atoms such as benzyloxy groups; aryloxy groups having 6 to 14 carbon atoms such as phenoxy groups and 1-naphthoxy groups; fluoro groups , halogen group such as chloro group, bromo group; cyano group; carboxy group; carbon number 2 such as ethoxycarbonyl group
-10 alkoxycarbonyl groups; C2-10 acyl groups such as acetyl groups and benzoyl groups; nitro groups, and the like.
さらにかかるR1がシクロアルキル基、アラル
キル基またはアリール基である場合、シクロアル
キル基、アラルキル基のアリール部およびアリー
ル基の置換基誘導体に含まれる置換基の具体例と
しては、ヒドロキシ基；メチルアミノ基、ジエチ
ルアミノ基などの有機置換アミノ基；メトキシ
基、エトキシ基、tert−ブトキシ基などの炭素数
１〜４のアルコキシ基；ベンジロキシ基などの炭
素数７〜15のアラルコキシ基；フエノキシ基、１
−ナフトキシ基などの炭素数６〜14のアリーロキ
シ基；メチル基、エチル基、tert−ブチル基など
の炭素数１〜４の低級アルキル基；フルオロ基、
クロロ基、ブロモ基などのハロゲン基；シアノ
基；カルボキシ基；エトキシカルボニル基などの
炭素数２〜10のアルコキシカルボニル基；アセチ
ル基、ベンゾイル基などの炭素数２〜10のアシル
基；トリフルオロメチル基などの炭素数１または
２のハロゲン置換アルキル基；ニトロ基などが挙
げられる。また、これらの置換基は１置換体とし
て含まれるもののみならず、２置換以上の複数個
の置換基を有する多置換体として含まれてもよ
い。さらには、多置換体における置換基は同種で
あつても、異種であつても何ら支障はない。また
置換基の位置については、目的あるいは用途に応
じて変えられるべきである。 Further, when R 1 is a cycloalkyl group, an aralkyl group, or an aryl group, specific examples of substituents included in the cycloalkyl group, the aryl part of the aralkyl group, and the substituent derivative of the aryl group include a hydroxy group; organic substituted amino groups such as methoxy, ethoxy and tert-butoxy groups; aralkoxy groups having 7 to 15 carbon atoms such as benzyloxy; phenoxy groups, 1
- Aryloxy group having 6 to 14 carbon atoms such as naphthoxy group; Lower alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, tert-butyl group; Fluoro group,
Halogen groups such as chloro group and bromo group; Cyano group; Carboxy group; Alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl group; Acyl group having 2 to 10 carbon atoms such as acetyl group and benzoyl group; Trifluoromethyl A halogen-substituted alkyl group having 1 or 2 carbon atoms, such as a nitro group, and the like. Furthermore, these substituents are not only included as monosubstituted products, but may also be included as polysubstituted products having two or more substituents. Furthermore, there is no problem whether the substituents in the polysubstituted product are the same or different. Furthermore, the positions of substituents should be changed depending on the purpose or use.
次に一般式(A)又は(B)におけるR2，R3，R4，R5
は前述のとおりであるが、それぞれ同種であつて
も異種であつてもよい。 Next, R 2 , R 3 , R 4 , R 5 in general formula (A) or (B)
As described above, they may be of the same type or different types.
かかる式(A)又は(B)の化合物は、従来知られてい
るスピロオキサジン化合物がインドリン環を構成
要素とするのに対し、ベンズ(g)インドリン環を構
成要素とする点で異なる。すなわち従来のスピロ
オキサジン化合物よりベンゼン環が一つ増加して
いるため、その立体構造により、発色種がマトリ
ツクス効果を受けにくい。例えばメタノールのよ
うな極性溶媒中でもトルエンのような非極性溶媒
中でも、発色種の色調にはほとんど差が認められ
ないという大きな特徴を有するものである。 The compound of formula (A) or (B) differs in that the conventionally known spirooxazine compounds have an indoline ring as a constituent, whereas the compound has a benz(g) indoline ring as a constituent. That is, since it has one more benzene ring than conventional spirooxazine compounds, its steric structure makes the colored species less susceptible to matrix effects. For example, it has the great feature that there is almost no difference in the color tone of the colored species, whether in a polar solvent such as methanol or a non-polar solvent such as toluene.
かかる式(A)又は(B)で表わされる化合物の代表的
な具体例としては、スピロ［ベンズ(g)インドリン
−２，3′−［3H］−ナフト［２，１−ｂ］（１，
４）オキサジン］、又はスピロ［ベンズ(g)インド
リン−２，2′−［2H］−フエナンスロ［９，10−
ｂ］（１，４）オキサジン］の
１，３，３−トリメチル誘導体
１−ヘキシル−３，３−ジメチル−５−クロロ誘
導体
１−（３−ブロモオクデシル）−３，３−ジメチル
−５−トリフルオロメチル誘導体
１−（10−フエニルエイコシル）−３，３−ジメチ
ル−５−メトキシ誘導体
１−イソプロピル−３，３，５−トリメチル誘導
体
１−tert−ブチル−３，３−ジメチル−5′−カル
ボキシ誘導体
１−（４−クロロシクロヘキシル）−３，３−ジメ
チル−8′−ニトロ誘導体
１−（３−アミノシクロオクチル）−３，３−ジメ
チル−8′−ブロモ誘導体
１−ベンジル−３，３−ジメチル−9′−フルオロ
誘導体
１−（３−メチルベンジル）−３，３−ジメチル−
7′−エトキシ誘導体
１−（４−アセチルベンジル）−３，３−ジメチル
−５−エトキシ−8′−ブチル誘導体
１−（３，５−ビストリフルオロメチルベンジル）
−３，３−ジメチル−５−クロロ誘導体
１−（２，３，４，５，６−ペンタフルオロベン
ジル）−３，３−ジメチル−５−トリフルオロメ
チル誘導体
１−（２−ナフチル）メチル−３，３−ジメチル
−５−メトキシ誘導体
１−（３−メトキシ−２−ナフチル）メチル−３，
３，５−トリメチル誘導体
１−（５−tert−ブチル−１−ナフチル）エチル
−３，３−ジメチル−5′−カルボキシ誘導体１−
（９−アントラシル）メチル−３，３−ジメチル
−8′−ニトロ誘導体
１−（９−フエナントリル）メチル−３，３−ジ
メチル−8′−ブロモ誘導体
１−フエニル−３，３−ジメチル−9′−フルオロ
誘導体
１−（４−ニトロフエニル）−３，３−ジメチル−
7′−エトキシ誘導体
１−（２，４，６−トリメチルフエニル）３，３
−ジメチル−５−エトキシ−8′−ブチル誘導体
１−（１−ナフチル）−３，３−ジメチル−５−ク
ロロ誘導体
１−（４−ブロモ−２−ナフチル）−３，３−ジメ
チル−５−トリフルオロメチル誘導体
１−（９−シアノ−１−アントラシル）−３，３ジ
メチル−５−メトキシ誘導体などが挙げられる。 Typical specific examples of compounds represented by formula (A) or (B) include spiro[benz(g)indoline-2,3'-[3H]-naphtho[2,1-b](1,
4) Oxazine], or spiro[benz(g)indoline-2,2'-[2H]-phenanthro[9,10-
1,3,3-trimethyl derivative 1-hexyl-3,3-dimethyl-5-chloro derivative 1-(3-bromoocdecyl)-3,3-dimethyl-5-trifluoro of [b](1,4)oxazine] Methyl derivative 1-(10-phenyleicosyl)-3,3-dimethyl-5-methoxy derivative 1-isopropyl-3,3,5-trimethyl derivative 1-tert-butyl-3,3-dimethyl-5'- Carboxy derivative 1-(4-chlorocyclohexyl)-3,3-dimethyl-8'-nitro derivative 1-(3-aminocyclooctyl)-3,3-dimethyl-8'-bromo derivative 1-benzyl-3,3 -dimethyl-9'-fluoro derivative 1-(3-methylbenzyl)-3,3-dimethyl-
7'-ethoxy derivative 1-(4-acetylbenzyl)-3,3-dimethyl-5-ethoxy-8'-butyl derivative 1-(3,5-bistrifluoromethylbenzyl)
-3,3-dimethyl-5-chloro derivative 1-(2,3,4,5,6-pentafluorobenzyl)-3,3-dimethyl-5-trifluoromethyl derivative 1-(2-naphthyl)methyl- 3,3-dimethyl-5-methoxy derivative 1-(3-methoxy-2-naphthyl)methyl-3,
3,5-trimethyl derivative 1-(5-tert-butyl-1-naphthyl)ethyl-3,3-dimethyl-5'-carboxy derivative 1-
(9-Anthracyl)methyl-3,3-dimethyl-8'-nitro derivative 1-(9-phenanthryl)methyl-3,3-dimethyl-8'-bromo derivative 1-phenyl-3,3-dimethyl-9' -Fluoro derivative 1-(4-nitrophenyl)-3,3-dimethyl-
7'-Ethoxy derivative 1-(2,4,6-trimethylphenyl)3,3
-dimethyl-5-ethoxy-8'-butyl derivative 1-(1-naphthyl)-3,3-dimethyl-5-chloro derivative 1-(4-bromo-2-naphthyl)-3,3-dimethyl-5- Examples include trifluoromethyl derivatives, 1-(9-cyano-1-anthracil)-3,3 dimethyl-5-methoxy derivatives, and the like.
式(A)によつて表わされる本発明の新規スピロオ
キサジン化合物は光による発消色の耐疲労性に優
れ、さらに発色種の吸収波長がマトリツクスの影
響をほとんど受けないフオトクロミツク化合物で
ある。 The novel spirooxazine compound of the present invention represented by formula (A) is a photochromic compound that has excellent fatigue resistance to color development and fading due to light, and furthermore, the absorption wavelength of the colored species is hardly affected by the matrix.
本発明のかかる式(A)の化合物は、例えば次の製
造方法に従つて製造される。 The compound of formula (A) of the present invention is produced, for example, according to the following production method.
一般式（）
で表わされる２−メチレンベンズ(g)インドリン化
合物と、一般式（）
で表わされるニトロソナフトール化合物を反応さ
せて式(A)の化合物を製造する。 General formula () 2-methylenebenz(g)indoline compound represented by and general formula () A compound of formula (A) is produced by reacting a nitrosonaphthol compound represented by formula (A).
また一般式(B)の化合物は、上記製造プロセスに
おいて式（）の替わりに次式（）
で表わされるニトロソフエナンスロール化合物を
用いる。 In addition, the compound of general formula (B) can be prepared by the following formula () instead of formula () in the above manufacturing process. A nitrosophenanthrol compound represented by is used.
本発明の式(A)又は(B)の化合物の他の製造法の例
としては、一般式（）
で表わされるトリメチルベンズ(g)インドレニン化
合物、四級化剤R1−Ｘ（Ｘはアニオン性脱離基）、
塩基および一般式（）または（）の化合物を
任意の順序で加え反応させる方法も挙げることが
できる。 Examples of other methods for producing compounds of formula (A) or (B) of the present invention include general formula () trimethylbenz(g) indolenine compound represented by, quaternizing agent R 1 -X (X is an anionic leaving group),
A method in which a base and a compound of general formula () or () are added in any order and reacted can also be mentioned.
また製造段階における精製方法としては各種溶
剤による再結晶法、シリカラムなどによるカラム
クロマト分離あるいは活性炭処理などが好適な例
として挙げることができる。 Preferred examples of purification methods in the manufacturing stage include recrystallization using various solvents, column chromatography using a silica column, and treatment with activated carbon.
本発明フオトクロミツク材料は光学的に透明な
樹脂類、たとえばジエチレングリコールビスアリ
ルカーボネートポリマー、ポリメタアクリレート
およびその共重合体、セルロース類、ポリ酢酸ビ
ニル、ポリビニルアルコール、ポリビニルブチラ
ール、ポリエステル樹脂、ポリカーボネート、ポ
リスチレンおよびその共重合体、エポキシ樹脂、
（ハロゲン化）ビスフエノールＡのジ（メタ）ア
クリレートポリマーおよびその共重合体、（ハロ
ゲン化）ビスフエノールＡのウレタン変性ジ（メ
タ）アクリレートポリマーおよびその共重合体、
ナイロン樹脂、ポリウレタンなどに配合して好ま
しく使用される。配合された樹脂類は光による変
色性を有する光学素子として使用することが可能
である。光学素子としてはサングラスレンズ、ス
キー用ゴーグル、保護メガネレンズ、さらにはカ
ーテン、衣服、玩具等が好適な例として挙げられ
る。 The photochromic material of the present invention is made of optically transparent resins such as diethylene glycol bisallyl carbonate polymer, polymethacrylate and its copolymers, celluloses, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyester resin, polycarbonate, polystyrene and its copolymers. copolymer, epoxy resin,
Di(meth)acrylate polymer of (halogenated) bisphenol A and its copolymer, urethane-modified di(meth)acrylate polymer of (halogenated) bisphenol A and its copolymer,
It is preferably used in combination with nylon resin, polyurethane, etc. The blended resins can be used as optical elements that change color due to light. Suitable examples of optical elements include sunglass lenses, ski goggles, protective glasses lenses, curtains, clothes, toys, and the like.
樹脂類への本発明フオトクロミツク材料の配合
方法としては、染色方法、キヤステイング法、配
合されたポリマー溶液のコーテイング法など各種
の方法が適用できる。 Various methods can be used to blend the photochromic material of the present invention into resins, including dyeing, casting, and coating with a blended polymer solution.
また樹脂中への配合量としては目的および使用
方法などによつて決められるべきものであるが、
視覚に対する感度という観点からは0.01〜20重量
％の添加量が好ましい。 In addition, the amount to be added to the resin should be determined depending on the purpose and method of use.
From the viewpoint of visual sensitivity, the amount added is preferably 0.01 to 20% by weight.
実施例 １
１，３，３−トリメチルスピロ［ベンズ(g)イ
ンドリン−２，3′−［3H］−ナフト［２，１−
ｂ］（１，４）オキサジン］の合成
１，３，３−トリメチル−２−メチレンベンズ
(g)インドリン５ｇおよび１−ニトロソ−２−ナフ
トール５ｇを100mlのエタノールに溶解し、窒素
気流中２時間還流する。反応後、冷却すると結晶
が析出して来る。これに少量のエタノールを加え
取し、得られた粗結晶をエタノールに溶解した
溶液を50−60℃まで加熱した後、活性炭10ｇを加
え十分に撹拌する。その後過し、液を濃縮し
て得られた淡黄色固体をエタノールから再結晶し
１，３，３−トリメチルスピロ［ベンズ(g)インド
リン−２，3′−［3H］−ナフト［２，１−ｂ］
（１，４）オキサジン］の淡黄色の結晶を得た。Example 1 1,3,3-trimethylspiro[benz(g)indoline-2,3'-[3H]-naphtho[2,1-
b] Synthesis of (1,4)oxazine] 1,3,3-trimethyl-2-methylenebenz
(g) 5 g of indoline and 5 g of 1-nitroso-2-naphthol are dissolved in 100 ml of ethanol and refluxed for 2 hours in a nitrogen stream. After the reaction, when it is cooled, crystals start to precipitate. A small amount of ethanol is added to this, and a solution of the resulting crude crystals dissolved in ethanol is heated to 50-60°C, then 10 g of activated carbon is added and thoroughly stirred. After that, the pale yellow solid obtained by filtration and concentration of the liquid was recrystallized from ethanol. -b]
(1,4)oxazine] were obtained as pale yellow crystals.
分析結果
（融点） 218℃
（元素分析値） 実測値(%) 計算値(%)
Ｃ 82.8 82.5
Ｈ 5.7 5.8
Ｎ 7.3 7.4
実施例 ２
１，３，３−トリメチルスピロ［ベンズ(g)イ
ンドリン−２，2′−［2H］−フエナンスロ［９，
10−ｂ］（１，４）オキサジン］の合成
１，３，３−トリメチル−２−メチレンベンズ
(g)インドリン５ｇおよび10−ニトロソ−９−フエ
ナンスロール６ｇを100mlのエタノールに溶解し、
窒素気流中５時間還流する。反応後冷却すると、
結晶が析出して来る。これに少量のエタノールを
加え取し、得られた粗結晶をエタノールに溶解
した溶液を50〜60℃まで加熱した後、活性炭10ｇ
を加え十分に撹拌する。その後過し、３液を濃
縮して得られた淡黄色固体をエタノールから再結
晶し、１，３，３−トリメチルスピロ［ベンズ(g)
インドリン−２，2′−［2H］−フエナンスロ［９，
10−ｂ］（１，４）オキサジン］の淡緑色結晶を
得た。 Analysis result (melting point) 218℃ (Elemental analysis value) Actual value (%) Calculated value (%) C 82.8 82.5 H 5.7 5.8 N 7.3 7.4 Example 2 1,3,3-trimethylspiro[benz(g)indoline-2 ,2′-[2H]-Fuenanthro[9,
Synthesis of 10-b](1,4)oxazine] 1,3,3-trimethyl-2-methylenebenz
(g) Dissolve 5 g of indoline and 6 g of 10-nitroso-9-phenanthrol in 100 ml of ethanol,
Reflux for 5 hours in a nitrogen stream. When cooled after the reaction,
Crystals begin to precipitate. Add a small amount of ethanol to this, and heat the solution of the obtained crude crystals in ethanol to 50-60℃, and then add 10g of activated carbon.
Add and stir thoroughly. After that, the pale yellow solid obtained by concentrating the three liquids was recrystallized from ethanol.
Indoline-2,2′-[2H]-fuenanthro[9,
10-b](1,4)oxazine] was obtained.
分析結果
（融点） 218℃
（元素分析値） 実測値(%) 計算値(%)
Ｃ 84.2 84.1
Ｈ 5.5 5.6
Ｎ 6.5 6.5
応用例
本化合物(A)又は(B)をメチルアルコール中に0.1
重量％の濃度で溶解させた。溶液にケミカルラン
プを使用して紫外線を照射させた溶液は直ちに水
色（淡青色）に変化した。また、このものは光照
射を除くと速やかにもとの無色に戻つた。このよ
うな発色および消色テストは50回繰り返し行つて
も、第１回目とまつたく同様のフオトクロミツク
特性を示し、耐疲労性に優れていた。 Analysis result (melting point) 218℃ (Elemental analysis value) Actual value (%) Calculated value (%) C 84.2 84.1 H 5.5 5.6 N 6.5 6.5 Application example Compound (A) or (B) in methyl alcohol at 0.1
It was dissolved at a concentration of % by weight. When the solution was irradiated with ultraviolet rays using a chemical lamp, the solution immediately turned light blue (pale blue). Moreover, this material quickly returned to its original colorless color when light irradiation was removed. Even when such coloring and decoloring tests were repeated 50 times, the photochromic properties were exactly the same as those in the first test, and the fatigue resistance was excellent.
つぎに溶媒をメチルアルコールからトルエンに
変えて行つたところ、まつたく同様の現象が認め
られ、マトリツクスの影響をほとんど受けないこ
とが判つた。 Next, when the solvent was changed from methyl alcohol to toluene, a similar phenomenon was observed, and it was found that it was hardly affected by the matrix.
［発明の効果］
本発明の材料は、溶媒、マトリツクスポリマー
の種類によらず、一般的な状態では無色である
が、紫外線の照射を受けると直ちに可視光領域に
吸収波長を有する材料に変化し、紫外線の照射を
やめると速やかにもとの無色に戻る。[Effects of the Invention] The material of the present invention is colorless in its general state, regardless of the type of solvent or matrix polymer, but when irradiated with ultraviolet rays, it immediately changes into a material that has an absorption wavelength in the visible light region. However, when UV irradiation is stopped, it quickly returns to its original colorless state.
本発明の材料は、発色速度が大きく、かつ消色
速度が大きく、かつ発色種の吸収波長がマトリツ
クスによる影響を受けにくく、かつ耐疲労性が良
いという特性を有しているフオトクロミツク材料
である。また本発明の材料は耐酸性に優れ、オル
ガノポリシロキサン系への添加が容易である。 The material of the present invention is a photochromic material that has a high color development rate and a high color decolorization rate, the absorption wavelength of the colored species is not easily affected by the matrix, and has good fatigue resistance. Furthermore, the material of the present invention has excellent acid resistance and can be easily added to organopolysiloxane systems.
Claims (1)
ン化合物からなるフオトクロミツク材料。 （式中、R2，R3，R4，R5は炭素数１〜４のア
ルキル基、炭素数１または２のハロゲン置換アル
キル基、炭素数１〜４のアルコキシ基、ハロゲン
基、ニトロ基から選ばれた置換基を表わし、ｎは
０〜２の整数、ｍおよびｔは０〜４の整数、ｌは
式(A)にあつては０〜２の整数、式(B)にあつては０
〜４の整数であり、R2，R3，R4，R5はそれぞれ
同種であつても異種であつてもよい。R1は炭素
数１〜20の無置換または置換アルキル基、炭素数
３〜10の無置換または置換シクロアルキル基、炭
素数７〜20の無置換または置換アラルキル基、炭
素数６〜14の無置換または置換アリール基から選
ばれた置換基を表わす。）[Claims] 1. A photochromic material comprising a spirooxazine compound represented by general formula (A) or (B). (In the formula, R 2 , R 3 , R 4 , R 5 are an alkyl group having 1 to 4 carbon atoms, a halogen-substituted alkyl group having 1 or 2 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen group, a nitro group) represents a substituent selected from, n is an integer of 0 to 2, m and t are integers of 0 to 4, l is an integer of 0 to 2 in formula (A), and in formula (B) is 0
It is an integer of ~4, and R 2 , R 3 , R 4 , and R 5 may be the same or different. R 1 is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 10 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, or an unsubstituted or substituted aralkyl group having 6 to 14 carbon atoms. Represents a substituent selected from substituted or substituted aryl groups. )
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61035321A JPS62195075A (en) | 1986-02-21 | 1986-02-21 | Novel spirooxazine compound |
| JP4016946A JP2503145B2 (en) | 1986-02-21 | 1992-01-31 | Photochromic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61035321A JPS62195075A (en) | 1986-02-21 | 1986-02-21 | Novel spirooxazine compound |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4016946A Division JP2503145B2 (en) | 1986-02-21 | 1992-01-31 | Photochromic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62195075A JPS62195075A (en) | 1987-08-27 |
| JPH0317875B2 true JPH0317875B2 (en) | 1991-03-11 |
Family
ID=12438547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61035321A Granted JPS62195075A (en) | 1986-02-21 | 1986-02-21 | Novel spirooxazine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62195075A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0826031B2 (en) * | 1987-04-23 | 1996-03-13 | セイコーエプソン株式会社 | Photochromic compound |
| US4931219A (en) * | 1987-07-27 | 1990-06-05 | Ppg Industries, Inc. | Photochromic compound and articles containing the same |
| US5021196A (en) * | 1988-01-25 | 1991-06-04 | Ppg Industries, Inc. | Method for preparing variable-light transmittance article |
| US4968454A (en) * | 1988-01-25 | 1990-11-06 | Ppg Industries, Inc. | Variable-light transmittance article and method for preparing same |
| US4936995A (en) * | 1988-05-17 | 1990-06-26 | Ppg Industries, Inc. | Photochromic compound and articles containing the same |
-
1986
- 1986-02-21 JP JP61035321A patent/JPS62195075A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62195075A (en) | 1987-08-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |