JPH0428725B2 - - Google Patents
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- Publication number
- JPH0428725B2 JPH0428725B2 JP56213255A JP21325581A JPH0428725B2 JP H0428725 B2 JPH0428725 B2 JP H0428725B2 JP 56213255 A JP56213255 A JP 56213255A JP 21325581 A JP21325581 A JP 21325581A JP H0428725 B2 JPH0428725 B2 JP H0428725B2
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- JP
- Japan
- Prior art keywords
- color
- photoreversible
- producing
- compound
- formula
- 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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- 150000001875 compounds Chemical class 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 230000008859 change Effects 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 238000002845 discoloration Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 4
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000002656 Distearyl thiodipropionate Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019305 distearyl thiodipropionate Nutrition 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- USVKSIGZJOSBMX-UHFFFAOYSA-N phenyl 6-(6-oxo-6-phenoxyhexyl)sulfanylhexanoate Chemical compound C1(=CC=CC=C1)OC(CCCCCSCCCCCC(=O)OC1=CC=CC=C1)=O USVKSIGZJOSBMX-UHFFFAOYSA-N 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- NNWNNQTUZYVQRK-UHFFFAOYSA-N 5-bromo-1h-pyrrolo[2,3-c]pyridine-2-carboxylic acid Chemical compound BrC1=NC=C2NC(C(=O)O)=CC2=C1 NNWNNQTUZYVQRK-UHFFFAOYSA-N 0.000 description 1
- 229920002574 CR-39 Polymers 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は光照射によつて化学的に発色し光照射
を断つことによつて消色するスピロピラン化合物
を安定化した状態で含有する樹脂成形体に関す
る。
［従来の技術］
光に感応して発色し光透過性が変化する物質は
その機能を利用してサングラスに使用されてい
る。例えば無機成分を用いたものとして感光性の
銀化合物を含有させ、戸外においては色が濃くな
り室内においては無色になるものがあるが、サン
グラスはフアツシヨン性が要求されるから単に光
に感応して黒つぽく変色するだけでなくカラフル
な色に変色するものが望まれる。そこで光、特に
紫外線によつて発色する有機成分である光可逆変
色性色素を含有する種々の樹脂成形体の開発が試
みられているが一般にこの種の色素は化学的に不
安定であるため耐久性がなく実用に供するには困
難があつた。
このような光可逆変色性樹脂成形体をサングラ
スまたはコンタクトレンズに利用した場合は、太
陽に晒すと瞬時に変色し室内に入つたときは瞬時
に無色透明になるような光感応性の良いものが好
ましく、更に、度の有無に拘わらずレンズとして
の諸機能を満足するものでなければならない。
［発明が解決しようとする課題］
本発明の目的は太陽光線下（紫外線）で直ちに
発色し室内では速やかに消色する光可逆変色性樹
脂成形体を提供することであり、更に詳しくはス
ピロピラン化合物を含有する樹脂成形体において
消発色繰返しに伴うスピロピラン化合物の光可逆
変色性の劣化を防止し、耐光性に優れたこの種の
樹脂成形体を提供することである。
スピロピラン化合物は紫外線照射により青又は
赤紫に発色し、紫外線を除くと消色する特性（光
可逆変色性）を持つている有機化合物である。し
かしながら、スピロピラン化合物は繰返し消発色
させているうちに比較的短時間で光可逆変色性の
劣化が起こる。すなわち、スピロピラン化合物は
耐光性が著しく悪いという欠点がある。例えば、
１，３，３−トリメチル−6′−ニトロスピロ
（2′H′−1′−ベンゾピラン−２，2′−インドリン）
のメチルエチルケトン溶液は真夏の直射日光下で
１時間以内に光可逆変色性を失う。従つて長時間
の寿命を必要とするような用途にあつては商品価
値が著しく劣るため、未だ実用化されていないの
が現状である。
［課題を解決するための手段］
本発明者らは上記の問題点を解決すべく種々の
検討を行なつた結果、樹脂成形体の原料である重
合又は共重合可能な単量体に光可逆変色性を有す
るスピロピラン化合物（その塩を含まず）を混合
し、その後にこの単量体を重合又は共重合させる
ことによつて、得られた光可逆変色性樹脂成形体
が長期寿命を持つようになることを見出し本発明
を完成した。カチオン重合開始剤としてある種の
スピロピラン化合物の塩を用いることが知られて
いるが（例えば、特公昭55−7841号）、本発明に
用いるスピロピラン化合物にはその塩は含まれな
い。ただし、付加的に塩を用いることはできる。
以下に本発明を更に詳しく説明する。
本発明に用いられるスピロピラン化合物は
一般式〔１〕
（式中、R1，R2，R3はアルキル基を示す。）
で表されるもので、例えば１，３，３−トリメチ
ル−５−メチルスルホニル−6′−ニトロ−8′−メ
トキシスピロ（2′H′−1′−ベンゾピラン−２，
2′−インドリン）、１−ブチル−３，３−ジメチ
ル−５−メチルスルホニル−6′−ニトロ−8′−エ
トキシスピロ（2′H−1′−ベンゾピラン−２，
2′−インドリン）、１，３，３−トリメチル−５
−ブチルスルホニル−6′−ニトロ−8′−メトキシ
スピロ（2′H−1′−ベンゾピラン−２，2′−イン
ドリン）等を挙げることができる。これらの化合
物は５位にアルキルスルホニル基を有し、6′位に
ニトロ基、8′位にアルコキシル基を有しているこ
とを特徴とする。アルキルスルホニル基を有する
化合物は極性の影響を受け難く溶剤中で自然着色
してこない。このために消色発色の変化が極めて
顕著で優れた光可逆変色性を示す。また、8′位の
アルコキシル基は光可逆変色性の劣化防止に有益
であることが挙げられる。これはアルコキシル基
が隣接位にあるスピロ環の−Ｏ−を他の副反応か
ら保護する為であると考えられる。
スピロピラン化合物の光発色機構は光イオン化
（又は光ラジカル化）に基づく光解離によつてス
ピロ環が開環する為であると説明されている。又
同時にシスートランス異性化を起こす事も知られ
ており、そのトランス型（発色種）に酸素付加が
起こり分解が始まると考えられ、その機構は下記
のように推測されるが、実際には分解物として得
られたアルデヒドやカルボン酸どうしが更に複雑
に反応しあつて分解着色物を形成していくものと
考えられる。
一般式〔１〕で示されるスピロピラン化合物は
従来のこの種の他の色素と比較して光可逆変色性
の寿命が長いが、これと、ポリスチレン，ポリビ
ニルアセテート，ポリメチルメタクリレート及び
ポリビニルブチラール等の樹脂とを適当な溶媒で
溶かし、溶媒を揮散させて得た光可逆変色性樹脂
成形体では実用に供するまでの寿命を持ち得な
い。ところが、これらの樹脂の原料である単量体
に先ずスピロピラン化合物を溶かしてから樹脂原
料の単量体を重合させたものは著しく光可逆変色
性の寿命が改善された。更に、本発明者らは上記
スピロピラン化合物と共に、酸化防止剤を前記単
量体に混合してから前記単量体を重合又は共重合
させることによつて光可逆変色性の寿命を飛躍的
に延ばすことが出来ることを見出した。酸化防止
剤は上記機構に基づく光酸化分解を抑制して光可
逆変色性の寿命のより長期化を達成するものと推
測される。
酸化防止剤は好ましくは
一般式〔２〕
（式中、Ｒは６乃至20個の炭素原子を有する炭
化水素基であり、ｎは１乃至20好ましくは１乃至
６の整数である。）
で表されるカルボン酸エステルのチオエーテルで
あり、これらの化合物としては、ジラウリルチオ
ジプロピオネート、ジステアリルチオジプロピオ
ネート、ジヘキシルチオジブチレート、ジフエニ
ルチオジカプロエート等が挙げられる。代表的に
はジラウリルチオジプロピオネートである。
本発明の効果は、スピロピラン化合物又はこれ
と酸化防止剤を、これらを含有させるべき樹脂の
原料である単量体に混合してからその後に単量体
を重合又は共重合させ、スピロピラン化合物又は
これと酸化防止剤を樹脂中に封じ込めることによ
つて得られるものであるから、含有させるべき樹
脂の種類は特に限定されるものではないが、スピ
ロピラン化合物はその無色種、発色種によつて樹
脂との相溶性が異なるため、消発色を繰返し行な
うとスピロピラン化合物が析出し、光可逆変色性
が消失する原因となる。従つて、本発明によつて
得られる樹脂は無色種、発色種共に相溶性の良い
ものが好ましい。プラスチツクレンス素材として
一般的に用いられているメチルメタクリレート樹
脂又はこれを成分とする共重合体は、無色種、発
色種いずれとも相溶性が良く、析出による光可逆
変色性の消失がないので好ましい。このほかヒド
ロキシエチルメタクリレート、Ｎ−ビニルピロリ
ドン、シロキサン、シランカツプリング剤、アリ
ルジグリコールカーボネート等も他の成分として
使用することが出来る。
スピロピラン化合物及び酸化防止剤の添加量は
用途及び化合物の種類によつて異なるが、通常
は、スピロピラン化合物の添加量は、0.05乃至
5.0w／ｖ％好ましくは0.2乃至2.0w／ｖ％であり、
酸化防止剤の添加量は、0.02乃至2.5w／ｖ％、好
ましくは0.1乃至1.0w／ｖ％である。更に他の酸
化防止剤を添加したり、又、発色に必要な紫外線
量を除く過剰の紫外線をカツトする為、紫外線防
止剤を添加するか又は樹脂成形体表面にコーテイ
ングするなど、必要に応じて常識的な操作を加え
ることができるのは云うまでもない。
［作用］
本発明の光可逆変色性樹脂成形体は光感応性が
良好で、光（紫外線）の照射によつて短時間で発
色し、光（紫外線）の照射を断つと短時間で無色
透明となる。更に、本発明をサングラス、コンタ
クトレンズ又は義眼等に利用した場合は従来数日
間で劣化してしまつた光可逆変色性樹脂成形体の
耐用期間を約２年以上にもすることが可能であ
り、充分実用的なこの種製品を提供することがで
きる。本発明の光可逆変色性樹脂成形体はこの特
異な性質を利用してこの他にも多種多様の用途に
供し得ることは云うまでもない。
［実施例］
以下に、本発明の実施例を示す。
実施例 １
１，３，３−トリメチル−５−メチルスルホニ
ル−6′−ニトロ−8′−メトキシスピロ（2′H−1′−
ベンゾピラン−２，2′−インドリン）１ｇをメチ
ルメタクリレート100c.c.に溶解し、更に重合開始
剤としてアゾイソブチロニトリル0.2ｇを加えて
充分均一に混合した後試験管に入れて60℃４時
間、65℃16時間重合反応を行なつた。得られた棒
状重合体を直径10mm、厚さ３mmの円板状サンプル
にして、下記の条件で耐光性テストを行なつた。
このサンプルをＡとして実験結果を表１に示し
た。
使用装置：キセノンフエードテスター（島津
XF−15N型）
試験方法：温度43乃至48℃、湿度40乃至５％の
条件下、約1.5KWキセノン光を１cm
角の受光面に連続照射する。一定時間
毎に取り出し、光可逆変色性の有無を
調べた。
比較例 １
１，３，３−トリメチル−５−メチルスルホニ
ル−6′−ニトロ−8′−メトキシスピロ（2′H−1′−
ベンゾピラン−２，2′−インドリン）１ｇとメチ
ルメタクリレート重合体100c.c.とをクロロホルム
に均一に溶解し、クロロホルムを揮散させて実施
例１と同様のサンプルを作製した。実施例１と同
様の耐光性テストを行なつた結果をサンプルＢと
して表１に示した。比較例のサンプルＢが２時間
以内に光可逆変色性を消失してしまうのに対し
て、本発明に係るサンプルＡは200時間以上の照
射においても充分変色性を有していた。
比較例 ２
実施例１のスピロピラン化合物に対して５位に
メチルスルホニル基のない化合物、即ち１，３，
３−トリメチル−6′−ニトロ−8′−メトキシスピ
ロ（2′H−1′−ベンゾピラン−２，2′−インドリ
ン）を用いて実施例１と同様のサンプルを作製し
たところ、作製時に青色になつてしまい、光可逆
変色性を示さなかつた。
実施例 ２
１−ブチル−３，３−ジメチル−５−メチルス
ルホニル−6′−ニトロ−8′−エトキシスピロ
（2′H−1′−ベンゾピラン−２，2′−インドリン）
１ｇと、酸化防止剤としてジラウリルチオジプロ
ピオネート0.5ｇをメチルメタクリレート単量体
100c.c.に溶解し、更に重合開始剤としてアゾイソ
ブチロニトリル0.2ｇを加えて充分均一に混合し
た後試験管に入れて60℃４時間、65℃16時間重合
反応を行なつて実施例１と同様のサンプルを作製
した。実施例１と同様の耐光性テストを行なつた
結果をサンプルＣとして表１に示した。サンプル
Ａと比較して初期発色時の青色を長時間維持でき
るようになつた。
【表】[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a resin molding containing a spiropyran compound in a stabilized state, which chemically develops color when exposed to light and disappears when exposed to light. Regarding the body. [Prior Art] Substances that develop color and change their light transmittance in response to light are used in sunglasses by utilizing this function. For example, there are inorganic products that contain a photosensitive silver compound and become dark in color outdoors and colorless indoors, but sunglasses require fashionability and are simply sensitive to light. What is desired is something that not only turns black but also turns colorful. Therefore, attempts have been made to develop various resin moldings containing photoreversible color-changing pigments, which are organic components that develop color when exposed to light, especially ultraviolet rays; however, these types of pigments are generally chemically unstable and therefore have limited durability. It was difficult to put it into practical use due to the lack of functionality. When such photoreversible color-changing resin moldings are used in sunglasses or contact lenses, they must be highly photosensitive, changing color instantly when exposed to the sun, and instantly becoming colorless and transparent when indoors. Preferably, it must also satisfy various functions as a lens, regardless of whether it has a prescription or not. [Problems to be Solved by the Invention] The purpose of the present invention is to provide a photoreversible color-changing resin molded product that immediately develops color under sunlight (ultraviolet light) and quickly discolors indoors. An object of the present invention is to prevent deterioration of the photoreversible discoloration of a spiropyran compound due to repeated decoloring and developing in a resin molded product containing the same, and to provide a resin molded product of this type that has excellent light resistance. Spiropyran compounds are organic compounds that develop a blue or reddish-purple color when irradiated with ultraviolet rays and disappear when the ultraviolet rays are removed (photoreversible discoloration). However, when a spiropyran compound is repeatedly decolored and developed, its photoreversible color change property deteriorates in a relatively short period of time. That is, spiropyran compounds have a drawback of extremely poor light resistance. for example,
1,3,3-trimethyl-6'-nitrospiro (2'H'-1'-benzopyran-2,2'-indoline)
A methyl ethyl ketone solution loses its photoreversible color change within an hour under direct sunlight in midsummer. Therefore, in applications that require a long service life, the commercial value is significantly inferior, and as a result, it has not yet been put into practical use. [Means for Solving the Problems] The present inventors conducted various studies in order to solve the above problems, and as a result, the present inventors added photoreversible monomers to polymerizable or copolymerizable monomers, which are raw materials for resin moldings. By mixing a color-changing spiropyran compound (not including its salt) and then polymerizing or copolymerizing this monomer, the resulting photoreversible color-changing resin molded product can have a long service life. The present invention was completed based on this discovery. Although it is known that salts of certain spiropyran compounds are used as cationic polymerization initiators (for example, Japanese Patent Publication No. 7841/1983), the spiropyran compounds used in the present invention do not include such salts. However, it is possible to additionally use salt. The present invention will be explained in more detail below. The spiropyran compound used in the present invention has the general formula [1] (In the formula, R 1 , R 2 and R 3 represent an alkyl group.) For example, 1,3,3-trimethyl-5-methylsulfonyl-6'-nitro-8'-methoxyspiro (2′H′−1′-benzopyran-2,
2'-indoline), 1-butyl-3,3-dimethyl-5-methylsulfonyl-6'-nitro-8'-ethoxyspiro (2'H-1'-benzopyran-2,
2'-indoline), 1,3,3-trimethyl-5
-butylsulfonyl-6'-nitro-8'-methoxyspiro (2'H-1'-benzopyran-2,2'-indoline) and the like. These compounds are characterized by having an alkylsulfonyl group at the 5-position, a nitro group at the 6'-position, and an alkoxyl group at the 8'-position. Compounds having an alkylsulfonyl group are not easily affected by polarity and do not naturally become colored in a solvent. For this reason, the change in decolorization and color development is extremely remarkable and exhibits excellent photoreversible color change properties. Furthermore, the alkoxyl group at the 8' position is useful for preventing deterioration of photoreversible color change. This is considered to be because the alkoxyl group protects the -O- of the spiro ring at the adjacent position from other side reactions. It is explained that the photocoloring mechanism of spiropyran compounds is due to the ring opening of the spiro ring due to photodissociation based on photoionization (or photoradicalization). It is also known that cis-trans isomerization occurs at the same time, and it is thought that oxygen is added to the trans form (coloring species) and decomposition begins.The mechanism is speculated as follows, but in reality, decomposition occurs. It is thought that the aldehydes and carboxylic acids obtained as products react with each other in a more complex manner to form decomposed colored products. The spiropyran compound represented by the general formula [1] has a longer photoreversible discoloration life than other conventional dyes of this type, but it is also used with resins such as polystyrene, polyvinyl acetate, polymethyl methacrylate, and polyvinyl butyral. A photoreversibly color-changing resin molded product obtained by dissolving the above in a suitable solvent and volatilizing the solvent does not have a lifespan long enough to be put to practical use. However, when the spiropyran compound was first dissolved in the monomer as the raw material for these resins and then the monomer as the resin raw material was polymerized, the life of the photoreversible color change property was significantly improved. Furthermore, the present inventors have dramatically extended the life of photoreversible color change by mixing an antioxidant with the monomer and then polymerizing or copolymerizing the monomer together with the spiropyran compound. I discovered that it is possible. It is presumed that the antioxidant suppresses photooxidative decomposition based on the above mechanism and achieves a longer life of photoreversible color change. Antioxidants are preferably A carboxylic acid ester represented by the general formula [2] (wherein, R is a hydrocarbon group having 6 to 20 carbon atoms, and n is an integer of 1 to 20, preferably 1 to 6). It is a thioether, and examples of these compounds include dilaurylthiodipropionate, distearylthiodipropionate, dihexylthiodibutyrate, diphenylthiodicaproate, and the like. A typical example is dilaurylthiodipropionate. The effects of the present invention are obtained by mixing a spiropyran compound or an antioxidant with a monomer that is a raw material for a resin containing these, and then polymerizing or copolymerizing the monomer, and then producing a spiropyran compound or an antioxidant. The type of resin that should be contained is not particularly limited, but spiropyran compounds can be used as resins depending on whether they are colorless or colored. Since the compatibility of the two is different, repeating decoloring and developing will cause the spiropyran compound to precipitate, causing loss of photoreversible discoloration. Therefore, it is preferable that the resin obtained by the present invention has good compatibility with both the colorless species and the colored species. Methyl methacrylate resin or a copolymer containing it, which is commonly used as a plastic lens material, is preferred because it has good compatibility with both colorless and colored species and does not lose photoreversible discoloration due to precipitation. In addition, hydroxyethyl methacrylate, N-vinylpyrrolidone, siloxane, silane coupling agent, allyl diglycol carbonate, etc. can also be used as other components. The amount of spiropyran compound and antioxidant added varies depending on the use and the type of compound, but usually the amount of spiropyran compound added is 0.05 to 0.05.
5.0w/v% preferably 0.2 to 2.0w/v%,
The amount of antioxidant added is 0.02 to 2.5 w/v%, preferably 0.1 to 1.0 w/v%. Furthermore, other antioxidants may be added, or ultraviolet rays may be added or coated on the surface of the resin molded product to block excess ultraviolet rays other than those necessary for color development, as necessary. Needless to say, common sense operations can be added. [Function] The photoreversible color-changing resin molded article of the present invention has good photosensitivity, develops color in a short time when irradiated with light (ultraviolet light), and becomes colorless and transparent in a short time when irradiation with light (ultraviolet light) is interrupted. becomes. Furthermore, when the present invention is applied to sunglasses, contact lenses, artificial eyes, etc., it is possible to extend the useful life of photoreversible color-changing resin moldings, which conventionally deteriorated within a few days, to about 2 years or more, This type of product can be provided with sufficient practicality. It goes without saying that the photoreversibly color-changing resin molded article of the present invention can be used for a wide variety of other uses by utilizing this unique property. [Example] Examples of the present invention are shown below. Example 1 1,3,3-trimethyl-5-methylsulfonyl-6'-nitro-8'-methoxyspiro(2'H-1'-
Dissolve 1 g of benzopyran-2,2'-indoline in 100 c.c. of methyl methacrylate, add 0.2 g of azoisobutyronitrile as a polymerization initiator, mix thoroughly, and then place in a test tube at 60°C. The polymerization reaction was carried out at 65°C for 16 hours. The obtained rod-shaped polymer was made into a disk-shaped sample with a diameter of 10 mm and a thickness of 3 mm, and a light resistance test was conducted under the following conditions.
This sample was designated as A and the experimental results are shown in Table 1. Equipment used: Xenon fade tester (Shimadzu)
XF-15N type) Test method: Approximately 1.5KW xenon light for 1cm under conditions of temperature 43 to 48℃ and humidity 40 to 5%.
Continuously irradiates the light receiving surface at the corner. It was taken out at regular intervals and examined for photoreversible color change. Comparative Example 1 1,3,3-trimethyl-5-methylsulfonyl-6'-nitro-8'-methoxyspiro(2'H-1'-
A sample similar to that in Example 1 was prepared by uniformly dissolving 1 g of benzopyran-2,2'-indoline and 100 c.c. of methyl methacrylate polymer in chloroform and volatilizing the chloroform. The same light resistance test as in Example 1 was conducted and the results are shown in Table 1 as Sample B. While sample B of the comparative example lost its photoreversible color change within 2 hours, sample A according to the present invention had sufficient color change even after irradiation for 200 hours or more. Comparative Example 2 A compound without a methylsulfonyl group at the 5-position with respect to the spiropyran compound of Example 1, that is, 1, 3,
When a sample similar to Example 1 was prepared using 3-trimethyl-6'-nitro-8'-methoxyspiro (2'H-1'-benzopyran-2,2'-indoline), it turned blue during preparation. It faded and did not exhibit photoreversible color change. Example 2 1-Butyl-3,3-dimethyl-5-methylsulfonyl-6'-nitro-8'-ethoxyspiro (2'H-1'-benzopyran-2,2'-indoline)
1g of methyl methacrylate monomer and 0.5g of dilauryl thiodipropionate as an antioxidant.
Dissolved in 100 c.c., added 0.2 g of azoisobutyronitrile as a polymerization initiator, mixed thoroughly and uniformly, then placed in a test tube and polymerized at 60°C for 4 hours and at 65°C for 16 hours. A sample similar to Example 1 was prepared. The same light resistance test as in Example 1 was conducted and the results are shown in Table 1 as Sample C. Compared to Sample A, the initial blue color can be maintained for a longer period of time. 【table】
Claims (1)
成形体の製造方法であつて、 該樹脂成形体の原料であるメチルメタクリレー
ト又はこれを成分とする単量体に一般式 （式中、R1、R2、R3はアルキル基を示す。） で表される光可逆変色性を有するスピロピラン化
合物（その塩を含まず）を混合し、その後該単量
体を重合又は共重合させることを特徴とする光可
逆変色性樹脂成形体の製造方法。 ２ 光可逆変色性を有する化合物を含有する樹脂
成形体の製造方法であつて、 該樹脂成形体の原料であるメチルメタクリレー
ト又はこれを成分とする単量体に一般式 （式中、R1、R2、R3はアルキル基を示す。） で表される光可逆変色性を有するスピロピラン化
合物（その塩を含まず）及び酸化防止剤を混合
し、その後該単量体を重合又は共重合させること
を特徴とする光可逆変色性樹脂成形体の製造方
法。 ３ 前記酸化防止剤が一般式 （式中、Ｒは６乃至20個の炭素原子を有する炭
化水素基であり、ｎは１乃至20好ましくは１乃至
６の整数である。） で表されるカルボン酸エステルのチオエーテルか
ら選ばれた少なくとも一種の化合物である特許請
求の範囲第２項に記載の光可逆変色性樹脂成形体
の製造方法。 ４ 前記カルボン酸エステルのチオエーテルが、
ジラウリルチオジプロピオネート、ジステアリル
チオジプロピオネート、ジヘキシルチオジブチレ
ート、ジフエニルチオジカプロエートである特許
請求の範囲第３項に記載の光可逆変色性樹脂成形
体の製造方法。[Scope of Claims] 1. A method for producing a resin molding containing a compound having photoreversible color change, wherein methyl methacrylate, which is a raw material for the resin molding, or a monomer containing the same as a component has the general formula (In the formula, R 1 , R 2 , and R 3 represent an alkyl group.) A spiropyran compound (not including its salt) having photoreversible color change represented by the formula is mixed, and then the monomer is polymerized or A method for producing a photoreversibly color-changing resin molded article, which comprises copolymerization. 2. A method for producing a resin molding containing a compound having photoreversible color change, wherein methyl methacrylate, which is a raw material for the resin molding, or a monomer containing the same as a component has the general formula (In the formula, R 1 , R 2 , and R 3 represent an alkyl group.) A spiropyran compound (not including its salt) having photoreversible discoloration represented by the formula and an antioxidant are mixed, and then the monomer 1. A method for producing a photoreversibly color-changing resin molded article, which comprises polymerizing or copolymerizing a resin molded article. 3 The antioxidant has the general formula (In the formula, R is a hydrocarbon group having 6 to 20 carbon atoms, and n is an integer of 1 to 20, preferably 1 to 6.) The method for producing a photoreversibly color-changing resin molded article according to claim 2, which is at least one type of compound. 4 The thioether of the carboxylic acid ester is
The method for producing a photoreversibly color-changing resin molded article according to claim 3, which is dilaurylthiodipropionate, distearylthiodipropionate, dihexylthiodibutyrate, or diphenylthiodicaproate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21325581A JPS58113203A (en) | 1981-12-28 | 1981-12-28 | Manufacture of photo-reversible color changeable resin formed body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21325581A JPS58113203A (en) | 1981-12-28 | 1981-12-28 | Manufacture of photo-reversible color changeable resin formed body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58113203A JPS58113203A (en) | 1983-07-06 |
| JPH0428725B2 true JPH0428725B2 (en) | 1992-05-15 |
Family
ID=16636065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21325581A Granted JPS58113203A (en) | 1981-12-28 | 1981-12-28 | Manufacture of photo-reversible color changeable resin formed body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58113203A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL69939A0 (en) * | 1983-10-10 | 1984-01-31 | Yeda Res & Dev | Quasi liquid crystals |
| AU637868B2 (en) * | 1990-07-04 | 1993-06-10 | Lintec Corporation | Photochromic composition |
| US5213733A (en) * | 1991-06-03 | 1993-05-25 | Industrial Technology Research Institute | Method of making synthetic fibers containing photochromic pigment |
| EP0896685A4 (en) * | 1996-04-30 | 2000-07-19 | Corning Inc | Organic photochromic contact lens compositions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS514958A (en) * | 1974-06-06 | 1976-01-16 | Ise Electronics Corp | TAKETAKEIKOHYOJIKAN |
| JPS557841A (en) * | 1978-06-30 | 1980-01-21 | Kanegafuchi Chem Ind Co Ltd | Graft polymer for reinforcing vinyl chloride resin |
-
1981
- 1981-12-28 JP JP21325581A patent/JPS58113203A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS514958A (en) * | 1974-06-06 | 1976-01-16 | Ise Electronics Corp | TAKETAKEIKOHYOJIKAN |
| JPS557841A (en) * | 1978-06-30 | 1980-01-21 | Kanegafuchi Chem Ind Co Ltd | Graft polymer for reinforcing vinyl chloride resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58113203A (en) | 1983-07-06 |
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