JPS63267784A - photochromic compounds - Google Patents
photochromic compoundsInfo
- Publication number
- JPS63267784A JPS63267784A JP62100461A JP10046187A JPS63267784A JP S63267784 A JPS63267784 A JP S63267784A JP 62100461 A JP62100461 A JP 62100461A JP 10046187 A JP10046187 A JP 10046187A JP S63267784 A JPS63267784 A JP S63267784A
- Authority
- JP
- Japan
- Prior art keywords
- group
- oxazine
- photochromic
- polymerization
- added
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 19
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- -1 oxazine compound Chemical class 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 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 2
- 125000001309 chloro group Chemical class Cl* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000004262 preparative liquid chromatography Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-O 1H-indol-1-ium Chemical compound C1=CC=C2[NH2+]C=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-O 0.000 description 1
- WAOPPELONVRRKQ-UHFFFAOYSA-N 1h-indol-1-ium;iodide Chemical compound [I-].C1=CC=C2[NH2+]C=CC2=C1 WAOPPELONVRRKQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 241001481824 Indri Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、衣料、装飾品用の７オトクロミツク材料、記
録材料用フォトクロミック材料または光学機器用として
有用な新規フォトクロミック化合物に閃する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is directed to a novel photochromic compound useful as a photochromic material for clothing, ornaments, a photochromic material for recording materials, or an optical device.
（従来の技術〕
フォトクロミック化合物物質のなかで、スピロ炭素を存
するインドリノスピロピラン化合物は、発消色速度に優
れ、モル吸光係数も大きく、バラエティ−に富んだ色調
の変化を示すことより、数多くの研究が報告されている
。(Prior art) Among photochromic compound substances, indolinospiropyran compounds containing spirocarbons have an excellent rate of color development and fading, a large molar extinction coefficient, and exhibit a wide variety of color changes. Research has been reported.
しかし、前述のスピロピラン化合物は耐久性に大きな問
題点が有る。 その原因は、ピラン骨格のＣ１Ｃ二重結
合が容易にし１項酸素の攻撃を受け、分解するためであ
る。これに対し、オキサジン骨格のＣ，Ｎ二ｍ結合は、
酸素分解反応に対して強固である。However, the above-mentioned spiropyran compound has a major problem in durability. The reason for this is that the C1C double bond in the pyran skeleton is easily attacked by 1-term oxygen and decomposed. On the other hand, the C,N dim bond in the oxazine skeleton is
Robust against oxygen decomposition reactions.
そこで、本発明はこのように問題点を解決するもので、
その目的とするところは、発消色速度を任意に制御が可
能であり、 モル吸光係数が大きく、バラエティ−に富
んだ色調の変化を示し、耐久性に富んだフォトクロミッ
ク化合物を提携することにある。Therefore, the present invention solves the problems as described above.
The aim is to develop photochromic compounds that can control the rate of color development and fading, have a large molar extinction coefficient, exhibit a wide variety of color changes, and are highly durable. .
すなわち本発明の７オトクａミック化合物は、下記一般
式で示されることを特徴とする。That is, the 7-otochomic compound of the present invention is characterized by being represented by the following general formula.
〔式中 Ｒ＋〜Ｒ１６は、 水素、アルキル基、アルコ
キシ基、ベンジル基、アリール基、ハロゲン、ニトロ基
、アルコキシアルキル基、 シアノ基、アルキルアミノ
基、カルボキシ基、カルボキシアルキル基、Ｓｏ、Ｍ
（Ｍはアルカリ金屑）、Ｒ１とＲ”とで飽和炭化水素環
もしくは不飽和炭化水素環、 重合もしくは縮合可能な
置換基から選ばれる同種または異種の一種以上の置換基
を示す。〕
本発明のフォトクロミック化合物は、オキサジン骨格の
Ｃ１Ｎ二重結合が、−同項酸素の攻撃に対して、反応し
難い為、耐久性が向上する。 また、置換基が電子吸引
基、電子倶与基と様々であるため、深色効果、浅色効果
による色調の変化を可能である。さらに、分子中に重合
や綜合が可能な置換基を付与した場合、他の成分との反
応や、自分自身との反応により、ポリマー化され、 ７
オトクロミツク物質の流出を防ぐことも可能となる。[In the formula, R+ to R16 are hydrogen, alkyl group, alkoxy group, benzyl group, aryl group, halogen, nitro group, alkoxyalkyl group, cyano group, alkylamino group, carboxy group, carboxyalkyl group, So, M
(M is alkali metal scrap), R1 and R'' represent one or more substituents of the same or different types selected from saturated hydrocarbon rings, unsaturated hydrocarbon rings, and substituents capable of polymerization or condensation.] The present invention The photochromic compound has improved durability because the C1N double bond in the oxazine skeleton is difficult to react to the attack of -isomer oxygen.In addition, the substituent group is various, such as an electron-withdrawing group or an electron-donating group. Therefore, it is possible to change the color tone by bathochromic effect or hypsochromic effect.Furthermore, if a substituent that can polymerize or synthesize is added to the molecule, it may react with other components or react with itself. Polymerized by reaction, 7
It also becomes possible to prevent the outflow of otochromic substances.
このように、本発明では、前述の問題点を解決するに至
った。In this way, the present invention has solved the above-mentioned problems.
本発明のフォトクロミック物質は、合成樹脂や紙への練
り込み法や浸漬法、昇華転写法、コーティング材料 （
ブライマー、バインダー、ハードコートなど）へ溶解も
しくは分散させ基材に塗布する方法、高分子を溶解した
溶液へ溶解もしくは分散させ、フィルムにする方法、他
のモノマーやフボリマーに入れ、重合もしくは共重合す
る方法など適用方法は様々である。The photochromic substance of the present invention can be applied to synthetic resins or paper by kneading or dipping, sublimation transfer, coating materials (
(brimer, binder, hard coat, etc.) and apply it to the substrate; dissolve or disperse it in a solution containing a polymer and make a film; add it to other monomers or fuborimers and polymerize or copolymerize it. There are various methods of application.
また、本発明における重合もしくは縮合可能な置換基と
は、ビニル基、アリル基、アクリル基、メタクリル基、
エポキシ基などの重合性置換基や水酸基、メルカプト基
、ハロゲンなどのように他成分と綜合反応可能な置換基
などがあげられる。In addition, the substituents capable of polymerization or condensation in the present invention include vinyl groups, allyl groups, acrylic groups, methacrylic groups,
Examples include polymerizable substituents such as epoxy groups, and substituents capable of synthetic reactions with other components such as hydroxyl groups, mercapto groups, and halogens.
フォトクロミック化合物のポリマー化反応としては、ラ
ジカル重合、イオン重合、異性化重合、環化重合、脱ｌ
ｆｆ１ｍ合、重縮合、付加縮合反応などがあり、フォト
クロミック物質のみのポリマー化や他成分とフォトクロ
ミック物質との共重合などの適用方法がある。Polymerization reactions of photochromic compounds include radical polymerization, ionic polymerization, isomerization polymerization, cyclization polymerization, and desulfurization.
There are ff1m reactions, polycondensation, and addition condensation reactions, and there are application methods such as polymerization of only the photochromic substance and copolymerization of other components and the photochromic substance.
さらに、フォトクロミック物質と酸化防止剤、−重項酸
素クエンチャー、紫外線吸収剤を加えることはフォトク
ロミック物質の寿命延長や色調変化に効果的である。Furthermore, adding a photochromic substance, an antioxidant, a doublet oxygen quencher, and an ultraviolet absorber is effective in extending the life of the photochromic substance and changing its color tone.
以下、実施例により、本発明を更に詳しく説明するが、
本発明は、これ等に限定されるものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these.
〔実施例１〕
１．３．３−トリノチルスピロ〔ベンズ（ｇ）インドリ
ノ−２，３’ −（２１−Ｉ）−（９’−メトキシナフ
ト）（２，１−ｂ）（１，４）オキサジン）の合成及び
その応用例。[Example 1] 1.3.3-trinotylspiro[benz(g)indolino-2,3'-(21-I)-(9'-methoxynaphtho)(2,1-b)(1,4 ) Oxazine) synthesis and its application examples.
１．２．３．３−テトラメチルベンズ（ｇ）インドリウ
ムのヨウ素塩３．３７ｇ （０，Ｏｌｍ。1.2.3.3-Tetramethylbenz(g) Indolium iodide salt 3.37g (0,Olm.
］）及び］１−ヒドロキシー２−二トロン−７メドキシ
ナフタレン２．０３ｇ （０，０１ｍｏ １）とをエタ
ノール１００ｍ１に加えた後、さらにトリエチルアミｙ
１．２１２ｇ （０，Ｏｌｍｏ ＋）を添加し、窒素気
流中５時間還流を行なった。溶媒除去後、水を加え、塩
化メチレンで抽出を行なった。この塩化メチレン溶液を
活性炭で処理した後、溶媒除去をし、分取液体クロマト
グラフィーで目的とする１、３．３−）リメチルスピロ
〔ベンズ（ｇ）インドリノ−２，３’ −（２Ｈ） −
（９′−メトキシナフト）（２，１−ｂ）（１，４）オ
キサジン〕を３．２４ｇ（収率６０％）得た。]) and ]1-hydroxy-2-nitrone-7 medoxynaphthalene (2.03 g (0.01 mo 1)) were added to 100 ml of ethanol, and then triethylamine y
1.212 g (0, Olmo +) was added and refluxed in a nitrogen stream for 5 hours. After removing the solvent, water was added and extraction was performed with methylene chloride. After treating this methylene chloride solution with activated carbon, the solvent was removed, and the target 1,3.3-)limethylspiro[benz(g)indolino-2,3'-(2H)-]
(9'-methoxynaphtho)(2,1-b)(1,4)oxazine] was obtained in an amount of 3.24 g (yield: 60%).
得られたオキサジン化合物０．Ｌｇｚ メタクリル酸メ
チル４９．９ｇ及びＡＩＢＮＯ，Ｉｇとを６０℃で２０
時間かけて重合を行ない、得られたポリマーを厚さ０．
１曽ｌのフィルムとなように成形１．た。このフィルム
は、室内では無色で紫外線を照射すると青色に着色した
。The obtained oxazine compound 0. Lgz 49.9 g of methyl methacrylate and AIBNO, Ig were heated at 60°C for 20
Polymerization is carried out over a period of time, and the resulting polymer has a thickness of 0.
1. Molding it into a 1-piece film. Ta. This film was colorless indoors, but turned blue when exposed to ultraviolet light.
フォトクロミック性能の評価は次のようにして行ない表
１に示した。Evaluation of photochromic performance was carried out as follows and is shown in Table 1.
（鳳）透過率
光照射前後の４００〜７００ｎｍの平均透過率を表１に
示した。なお、光照射の光源は、５００Ｗ超高圧水銀灯
（ウシオ電気社製）を用い、測定時の温度は２５℃とし
た。(Otori) Transmittance The average transmittance of 400 to 700 nm before and after light irradiation is shown in Table 1. Note that a 500 W ultra-high pressure mercury lamp (manufactured by Ushio Electric Co., Ltd.) was used as the light source for light irradiation, and the temperature at the time of measurement was 25°C.
（２）耐久性
キセノンロングライフ７エードメーダー（スガ試験機社
製ＦＡＬ−２５ＡＸ）に５０時間後の透過率の性能評価
を行い表１に示した。(2) Durability A performance evaluation of transmittance after 50 hours was performed using a xenon long life 7 aedameder (FAL-25AX, manufactured by Suga Test Instruments Co., Ltd.), and the results are shown in Table 1.
〔実施例２〕
１−ベンジル−３、３−ジメチルスピロ〔ベンズ（ｆ）
インドリノ−２、３’ −（２Ｈ）−（９′−メタクリ
ロオキシナフト） （２，１−ｂ）（１，４）オキサ
ジン）の合成及びその応用例
２．３．３−トリメチルベンズ（ｆ）インドリＬ／７２
．０９ｇ （０，Ｏｌｍｏｌ）と、ベンジルブｏｖイド
１．７１ｇ （０，Ｏｌｍｏｌ）とエタノール１０ｍ１
とを封管し、８０℃で４時間反応させた後、生成物をエ
ーテルで洗浄し、１−ベンジル−２，３，３−トリメチ
ルベンズ（ｆ）インドリウムの臭素塩の結晶を３．３８
ｇ （収率８９％）で得た。 ２．７−ジヒドロキ
シナフタレンと亜硝酸ナトリウムより合成した１−ニト
ロン−２，７−シヒドロキシナフタレン０．９４５ｇ（
５Ｘ１０””ｍｏｌ）と上記臭素塩１．９ｇとをエタノ
ール５０ｍ１に加えた後、さらにトリエチルアミン０．
Ｅ３０Ｂｇ （８Ｘ１０− ” ｍｏ １）を添加し、
窒素気流中５時間還流を行なった。溶媒除去後、水を加
え、塩化メチレンで抽出を行なった。この塩化メチレン
溶液を活性炭で処理した後、溶媒除去をし、分取液体ク
ロマトグラフィーにより、１−ベンジル−３，３−ジメ
チルスピロ〔ベンズ（ｆ）インドリノ−２，３’ −（
２Ｈ）−（９′−ヒドロキシナフト） （２，１−
ｂ）（１，４）オキサジン〕を０．９４２ｇ （収率４
０％）で得た。このオキサジン化合物０．４７１ｇ（Ｉ
ＸＩＯ−”ｍｏｌ）とメタクリル酸クロリド０．１０４
５ｇ （ＩＸＩＯ−” ｍｏｌ）とを乾燥ベンゼン１０
ｍ１に加えた後、トリエチルアミ７０．１２１２ｇ （
１，２Ｘ１０−” ｍｏｌ）を加え、窒素気流中、室温
で１時間か（拌を行なった。この後、水を加え、存ｖＡ
届を分離し、溶媒除去をし、薄層クロマトグラフィーで
目的とするｌ−ベンジル−３，３−ジメチルスピロ 〔
ベンズ（ｆ）インドリノ−２，３’ （２Ｈ）−（９
’ −メタクリロオキシナフト）（２，１−ｂ）（１，
４）オキサジン〕を０．５１２ｇ（収率９５％）を得た
。[Example 2] 1-benzyl-3,3-dimethylspiro[benz(f)
Synthesis of indolino-2,3'-(2H)-(9'-methacrylooxynaphtho)(2,1-b)(1,4)oxazine) and its application example 2.3.3-Trimethylbenz(f ) Indri L/72
．． 09g (0,Olmol), 1.71g (0,Olmol) of benzyl alcohol and 10ml of ethanol
After sealing the tube and reacting at 80°C for 4 hours, the product was washed with ether, and the crystals of 1-benzyl-2,3,3-trimethylbenz(f) indolium bromine salt were 3.38
g (yield 89%). 0.945 g of 1-nitrone-2,7-dihydroxynaphthalene synthesized from 2,7-dihydroxynaphthalene and sodium nitrite (
After adding 1.9 g of the above bromine salt to 50 ml of ethanol, 0.5 x 10"mol of triethylamine was added to 50 ml of ethanol.
Add E30Bg (8X10-” mo 1),
Refluxing was carried out for 5 hours in a nitrogen stream. After removing the solvent, water was added and extraction was performed with methylene chloride. After treating this methylene chloride solution with activated carbon, the solvent was removed, and preparative liquid chromatography was performed to detect 1-benzyl-3,3-dimethylspiro[benz(f)indolino-2,3'-(
2H)-(9'-hydroxynaphtho) (2,1-
b) 0.942 g (yield 4) of (1,4)oxazine]
0%). This oxazine compound 0.471g (I
XIO-”mol) and methacrylic acid chloride 0.104
5g (IXIO-” mol) and 10% of dry benzene
After adding to m1, 70.1212 g of triethylamine (
1.2 x 10-" mol) was added and stirred at room temperature in a nitrogen stream for 1 hour. After this, water was added and the remaining vA
The target l-benzyl-3,3-dimethylspiro product was separated using thin layer chromatography.
Benz (f) indolino-2,3' (2H)-(9
'-methacrylooxynaphtho)(2,1-b)(1,
4) Oxazine] was obtained in an amount of 0.512 g (yield: 95%).
得られたオキサジン化合物０．１ｇ％ ２．２−ビス（
３，５−ジブロモ−４−メタクリロオキシエトキシフェ
ニル）フロパン２５ｇ１スチレン２０ ｇ １ ジエ
チレングリコールビスアリルヵーボネー）５ｇｓ
ｔｅｒｔ＝ブチルパーオキシネオカーボネート０．５ｇ
とを混合し、醋酸ビニルーポリエチレン共重合体のガス
ケット及シ、２枚のフラットなガラス型より構成される
中心厚２１．のモールドに注入し、４０℃３時間、 ６
０°Ｃ８時間、８０℃２時間で重合を行なった。得られ
たフラット板は、室内で無色で、紫外線を照射すると青
紫色に着色した。Obtained oxazine compound 0.1g% 2.2-bis(
3,5-dibromo-4-methacrylooxyethoxyphenyl)furopane 25 g 1 Styrene 20 g 1 Diethylene glycol bisallyl carbonate) 5 gs
tert=butyl peroxy neocarbonate 0.5g
and a gasket of vinyl acetate-polyethylene copolymer and two flat glass molds with a center thickness of 21. Pour into a mold and heat at 40°C for 3 hours. 6
Polymerization was carried out at 0°C for 8 hours and at 80°C for 2 hours. The obtained flat plate was colorless indoors, but turned blue-purple when irradiated with ultraviolet light.
フォトクロミック性能の評価は実施例１の評価方法と同
様に行ない表１に示した。Evaluation of photochromic performance was performed in the same manner as in Example 1 and is shown in Table 1.
〔実施例３〕
１−（ｐ−アリルベンジル）−３，３−ジメチルスピロ
（ベンズ〔ｇ〕インドトリ−２，３’ −（２Ｈ）−（
８’−ブロモナフト） 〔２、■−ｂ）（１，４）オ
キサジン〕の合成及びその応用例
２．３．３−）リンチルベンズ（ｇ）インドレニン２．
０９ｇ （０，Ｏ１ｍｏ ｌ）とｐ−クロロメチルスチ
レン１．５２５ｇ （０，Ｏｌｍｏｌ）とヒドロキノン
０．２ｇ及びエタノール１ ’Ｏｍ １を封管し、８０
℃で４時間反応させた後、生成物をエーテルで洗浄し、
１−（ｆ）−アリルベンジル’）−２，３，３−）リン
チルベンズ（ｇ）インドリウムの塩素塩の結晶を、３．
０７ｇ（収率８５％）で得た。[Example 3] 1-(p-allylbenzyl)-3,3-dimethylspiro(benz[g]indotri-2,3'-(2H)-(
Synthesis of 8'-bromonaphtho) [2,■-b) (1,4) oxazine] and its application example 2.3.3-) lyntylbenz (g) indolenine 2.
09g (0,01mol), p-chloromethylstyrene 1.525g (0,01mol), hydroquinone 0.2g and ethanol 1'Om1 were sealed in a tube, and 80
After reacting for 4 hours at °C, the product was washed with ether and
3. Crystals of chlorine salt of 1-(f)-allylbenzyl')-2,3,3-)lyntylbenz(g) indolium;
07 g (yield 85%).
上記塩素塩１．８０８ｇ （５Ｘ１０−” ｍ。1.808g of the above chlorine salt (5X10-”m.
ｌ）と１−二トロン−２−ヒドロキシ−６−プロモナフ
タンン１．２６ｇ（５ＸｆＯ−” ｍｏ ｌ）ヒドロキ
ノン０．１ｇとをエタノール５０ｍ１に加えた後、さら
にトリエチルアミン０．６０６ｇ（６Ｘ１０−’ｍｏｌ
）を添加し、窒素気流中２時間還流を行なった。溶媒除
去後、水を加え、塩化メチレンで抽出を行なった。この
塩化メチレノ溶液を活性炭で処理した後、溶媒除去し、
分取液体クロマトグラフィーで目的とする １−（ｐ−
アリルベンジル）−３，３−ジメチルスピロ〔ベンズ（
ｇ）インドリ／−２、３’−（２Ｈ）−（８′−ブロモ
ナフト）（２，１−ｂ） （１，４）オキサジン〕
を０．９２４ｇ（収率３３％）で得た。1) and 1.26 g (5XfO-'mol) of 1-nitrone-2-hydroxy-6-promonaphthane and 0.1g of hydroquinone in 50ml of ethanol, and then 0.606g of triethylamine (6X10-'mol
) was added thereto and refluxed for 2 hours in a nitrogen stream. After removing the solvent, water was added and extraction was performed with methylene chloride. After treating this methylene chloride solution with activated carbon, the solvent was removed,
The target in preparative liquid chromatography is 1-(p-
allylbenzyl)-3,3-dimethylspiro[benz(
g) indoli/-2,3'-(2H)-(8'-bromonaphtho)(2,1-b) (1,4)oxazine]
was obtained in an amount of 0.924 g (yield 33%).
得られたオキサジン化合物０−Ｌｇｓスチレン４９．９
ｇ、 ビス７！／−ｋＡｏ、１ｇ及びＡＩＢＮＯ，Ｉｇ
とを８０°Ｃで２０時間かけ重合を行ない、得られたポ
リマーを厚さ０．１１のフィルムとなよう成形した。室
内ではうすい緑色で、紫外線を照射すると緑青色に着色
した。Obtained oxazine compound 0-Lgs styrene 49.9
g, screw 7! /-kAo, 1g and AIBNO, Ig
Polymerization was carried out at 80°C for 20 hours, and the resulting polymer was molded into a film with a thickness of 0.11. It was pale green indoors, but turned green-blue when exposed to ultraviolet light.
フォトクロミック性能の評価は実施例１の評価方法と同
様に行ない結果を表１に示した。Evaluation of photochromic performance was carried out in the same manner as in Example 1, and the results are shown in Table 1.
〔実施例４〕
１−（γ−アクリルオキシブａピル）−３，３−ジメチ
ルスピロ 〔ベンズ〔ｆ〕インドトリ−２、３’（２Ｈ
） −す フ ト 〔２、１−ｂ）（１，４）
オキサジン〕の合成及び応用例。[Example 4] 1-(γ-acryloxybu-a-pyr)-3,3-dimethylspiro [benz[f]indotri-2,3'(2H
) -Sft [2, 1-b) (1, 4)
Synthesis and application examples of [Oxazine].
２．３．３−）リンチルベンズ（ｆ）インドレ二ｙ２．
０９ｇ （０，０１ｍｏ １）と３−ブＣ７モー１−プ
ロパツール１．３９ｇ （０，ＯＩｒｎ。2.3.3-) lynchilbenz (f) indoreni y2.
09g (0,01mo 1) and 3-buC7mo1-Propertool 1.39g (0,OIrn.
１）とりＯＯホルム１０ｍ１とを封管し、６０°Ｃで２
００時間反応せた後、生成物をエーテルで洗浄し１−（
γ−ヒドロジプロピル） ２．３．３−トリメチルベ
ンズ（ｆ）インドリウムの臭素塩の結晶を２．１６ｇ（
収率７５％）で得た。1) Seal the tube with 10ml of OO form and heat at 60°C for 2 hours.
After reacting for 00 hours, the product was washed with ether and 1-(
2.16 g of 3-trimethylbenz(f) indolium bromine salt crystals (
Yield: 75%).
上記臭素塩１．７４ｇ （５Ｘ１０−’ ｍｏｌ）と１
−二トンー２−ナフトール０．８６５ｇ （５ＸＩＯ−
’ ｍｏ １）とをエタノール５０ｍ１に加えた後、さ
らに、トリエチルアミンｏ、ｅｏ６ｇ（ｅＸｌｏ−’ｍ
ｏｌ）を添加し、窒素気流中２時間還流を行なった。溶
媒除去後、水を加え、塩化メチレンで抽出を行なった。1.74 g (5X10-' mol) of the above bromine salt and 1
-2ton-2-naphthol 0.865g (5XIO-
'mo 1) was added to 50ml of ethanol, and then 6g of triethylamine o, eo (eXlo-'m
ol) was added and refluxed for 2 hours in a nitrogen stream. After removing the solvent, water was added and extraction was performed with methylene chloride.
この塩化メチレノ溶液を活性炭で処理した後、溶媒除去
し、分取液体クロマトグラフィーで、１−（γ−ヒドロ
キシプロピル’）−３、３−ジメチルスピロ〔ベンズ〔
「〕〕インドリノー２３’ −（２Ｈ）−ナフト（２，
１−ｂ）（１，４）オキサジン〕を０．７３９ｇ（収率
３５％）で得た。After treating this methylene chloride solution with activated carbon, the solvent was removed, and 1-(γ-hydroxypropyl')-3,3-dimethylspiro[benz[
"]]Indolino23'-(2H)-naphtho(2,
1-b) (1,4)oxazine] was obtained in an amount of 0.739 g (yield 35%).
このオキサジン化合物０．４２２ｇ （ＩＸＩＯ−”
ｍｏ １）とアクリル酸クロリド０．０９１ｇ（ＩＸＩ
Ｏ−”ｍｏｌ）とを乾燥ベンゼン１０ｍ１に加えた後、
トリエチルアミン０．１２１ｇ（ＩＸＩＯ−”ｍｏ
ｌ）を加え、窒素気流中、置屋で１時間かく拌を行なっ
た。 この後、水を加え、仔ｊａ届を分離し、溶媒除去
し、薄層クロマトグラフィーで目的とする１−（γ−ア
クリルオキシプロピル）−３，３−ジメチルスピロ〔ベ
ンズ（ｆ）インドリノ−２，３’ −（２）１）−ナフ
ト〔２，１−ｂ）（１，４）オキサジン〕を０．３８２
ｇ（収率８０％）で得た。0.422g of this oxazine compound (IXIO-”
mo 1) and 0.091 g of acrylic acid chloride (IXI
After adding O-”mol) to 10ml of dry benzene,
Triethylamine 0.121g (IXIO-”mo
1) was added, and the mixture was stirred for 1 hour in an oven in a nitrogen stream. After this, water was added to separate the larvae, the solvent was removed, and the target 1-(γ-acryloxypropyl)-3,3-dimethylspiro[benz(f)indolino-2] was purified by thin layer chromatography. ,3'-(2)1)-naphtho[2,1-b)(1,4)oxazine] at 0.382
g (yield 80%).
このオキサジ／化合物０．１ｇをダイヤビーム（三菱レ
イヨン（株）製）１００ｇに溶解させ、アクリル板に塗
布し、高圧水銀灯（８０Ｗ ／ ａｍ ）で３０秒照射
した。得られた塗膜の膜厚は２５μｍであり、室内では
無色で、紫外線を照射することにより紫色に着色した。0.1 g of this oxazi/compound was dissolved in 100 g of Diabeam (manufactured by Mitsubishi Rayon Co., Ltd.), applied to an acrylic plate, and irradiated with a high-pressure mercury lamp (80 W/am) for 30 seconds. The resulting coating film had a thickness of 25 μm and was colorless indoors, but was colored purple by irradiation with ultraviolet light.
フォトクロミック性能の評価は実施例１の評価方法と同
様に行ない結果を表１に示した。Evaluation of photochromic performance was carried out in the same manner as in Example 1, and the results are shown in Table 1.
〔実施例５〕
実施例１で得られた、 １．３．３−）ジメチルスピ
ロ〔ベンズ（ｇ）インドリノ−２，３’ −（２Ｈ）−
（９’ メトキシナフト）（２，１−ｂ）（１，４）オ
キサジン〕２０ｇをジエチレングリコール８０ｇに溶か
した溶液を１００℃に加熱し、との溶液に、 厚さ２■
■のジエチレングリコールビスアリルカーボネート樹脂
製フラット板を３０分間浸漬し、イソプロピルアルコー
ルで洗浄した。このフラット板に、真空蒸着により、５
ｓｏｎ、ＺｒＯ＊、５ｉｎｓの順序で光学的膜厚λ／４
（λ＝５２０ｎｍ）の膜を設けた。[Example 5] 1.3.3-)dimethylspiro[benz(g)indolino-2,3'-(2H)- obtained in Example 1
(9'Methoxynaphtho)(2,1-b)(1,4)oxazine] A solution of 20g dissolved in 80g of diethylene glycol was heated to 100°C, and the solution was poured into a 2cm thick solution.
The flat plate made of diethylene glycol bisallyl carbonate resin (2) was immersed for 30 minutes and washed with isopropyl alcohol. On this flat plate, 5
optical film thickness λ/4 in the order of son, ZrO*, 5ins
(λ=520 nm) was provided.
フォトクロミック性能の評価は実施例１の評価方法と同
様に行ない結果を表１に示した。Evaluation of photochromic performance was carried out in the same manner as in Example 1, and the results are shown in Table 1.
〔実施例６〕
実施例１で得られた、 １．３．３−トリエチルアミ
ン（ベンズ（ｇ）インドリノ−２，３’−（２Ｈ）−（
９’−メトキシナフト）（２，１−ｂ）（１，４）オキ
サジン）Ｉｇを、γ−グリシドキシプロピルトリメトキ
シシラン２８ｇ１エタ／−ル６４ｇ、０．０５規定塩酸
７ｇｓフローコントロール剤０．０２ｇ、塩化第１スズ
０．０７ｇで調整したコーテイング液に溶した。この溶
液をポリカーボネート板に塗布し、１００℃で３時間乾
燥をした（膜厚５μｍ）。[Example 6] 1.3.3-triethylamine (benz(g)indolino-2,3'-(2H)-(
9'-Methoxynaphtho)(2,1-b)(1,4)oxazine) Ig was mixed with 28 g of γ-glycidoxypropyltrimethoxysilane, 64 g of ethyl, 7 g of 0.05 N hydrochloric acid, and 0.0 g of flow control agent. 0.02 g and 0.07 g of stannous chloride. This solution was applied to a polycarbonate plate and dried at 100° C. for 3 hours (film thickness: 5 μm).
フォトクロミック性能の評価は実施例１の評価方法と同
様に行ない結果を表１に示した。Evaluation of photochromic performance was carried out in the same manner as in Example 1, and the results are shown in Table 1.
表１
〔発明の結果〕
以上に述べたように本発明は、オキサジン骨格ををする
ために、耐久性に優れている。また、分子中に重合もし
くは縮合可能な置換基を有する化合物は、他成分もしく
は自分自身でポリマー化させることにより、フォトクロ
ミック物質の流出という問題点を解決することが可能で
ある。Table 1 [Results of the Invention] As described above, the present invention has excellent durability due to the oxazine skeleton. Further, a compound having a substituent that can be polymerized or condensed in its molecule can solve the problem of outflow of photochromic substances by polymerizing other components or itself.
このため、本発明は、サングラス、窓ガラス、記録材料
、繊維、装飾品への応用が可能である。Therefore, the present invention can be applied to sunglasses, window glasses, recording materials, textiles, and ornaments.
以 上that's all
Claims (1)
ック化合物。 ▲数式、化学式、表等があります▼または▲数式、化学
式、表等があります▼ 〔式中、Ｒ＾１〜Ｒ＾１＾６は、水素、アルキル基、ア
ルコキシ基、ベンジル基、アリール基、ハロゲン、ニト
ロ基、アルコキシアルキル基、シアノ基、アルキルアミ
ノ基、カルボキシ基、カルボキシアルキル基、ＳＯ＿３
Ｍ（Ｍはアルカリ金属）、Ｒ＾２とＲ＾３とで飽和炭化
水素環もしくは不飽和炭化水素環、重合もしくは縮合可
能な置換基から選ばれる同種または異種の一種以上の置
換基を示す。）[Scope of Claims] A photochromic compound characterized by being represented by the following general formula. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 to R^1^6 are hydrogen, alkyl group, alkoxy group, benzyl group, aryl group, Halogen, nitro group, alkoxyalkyl group, cyano group, alkylamino group, carboxy group, carboxyalkyl group, SO_3
M (M is an alkali metal), R^2 and R^3 represent one or more of the same or different substituents selected from saturated hydrocarbon rings, unsaturated hydrocarbon rings, and substituents capable of polymerization or condensation. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62100461A JPH0826031B2 (en) | 1987-04-23 | 1987-04-23 | Photochromic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62100461A JPH0826031B2 (en) | 1987-04-23 | 1987-04-23 | Photochromic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63267784A true JPS63267784A (en) | 1988-11-04 |
| JPH0826031B2 JPH0826031B2 (en) | 1996-03-13 |
Family
ID=14274548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62100461A Expired - Fee Related JPH0826031B2 (en) | 1987-04-23 | 1987-04-23 | Photochromic compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0826031B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4936995A (en) * | 1988-05-17 | 1990-06-26 | Ppg Industries, Inc. | Photochromic compound and articles containing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62195075A (en) * | 1986-02-21 | 1987-08-27 | Toray Ind Inc | Novel spirooxazine compound |
-
1987
- 1987-04-23 JP JP62100461A patent/JPH0826031B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62195075A (en) * | 1986-02-21 | 1987-08-27 | Toray Ind Inc | Novel spirooxazine compound |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4936995A (en) * | 1988-05-17 | 1990-06-26 | Ppg Industries, Inc. | Photochromic compound and articles containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0826031B2 (en) | 1996-03-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |