JPS61123835A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JPS61123835A JPS61123835A JP24688384A JP24688384A JPS61123835A JP S61123835 A JPS61123835 A JP S61123835A JP 24688384 A JP24688384 A JP 24688384A JP 24688384 A JP24688384 A JP 24688384A JP S61123835 A JPS61123835 A JP S61123835A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- spironaphthoxazine
- photosensitive resin
- repeatability
- transparent resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、光照射により吸収スペクトルが可逆的に変化
する現象、すなわちフォトクロミズムを示すスピロナフ
トオキサジン誘導体を含む感光性樹脂組成物に関するも
のである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photosensitive resin composition containing a spironaphthoxazine derivative that exhibits a phenomenon in which the absorption spectrum changes reversibly upon irradiation with light, that is, photochromism. .
本発明においてフォトクロミズムなる用語は。In the present invention, the term photochromism is used.
光照射された際に、一定波長の光のｔＶ下に発色し、暗
所にもたらされれば元の状態に復帰する現象、すなわち
、可逆的に発色変化する現象に対して使用される。It is used for the phenomenon that when irradiated with light, it develops a color under the tV of light of a certain wavelength, and returns to its original state when brought to a dark place, that is, the phenomenon of reversible color change.
（従来の技術）、（発明が解決しようとする問題点）
従来からフォトクロミズムを示す物質としてスピロベン
ゾピラン類、トリフェニルメタン類、ジチゾンの水銀錯
塩類、あるいはビオロゲン類等が知られており、これら
フォトクロミック物質を適当な高分子バインダー中に溶
解分散させることにより、サングラス、光学フィルター
、カーテン等の分野への実用化が進められている。しか
しながら、これら物質はフォトクロミンク物質として要
求される性能中９発色性能については良好であるが、繰
り返し反復性、暗所放置における戻り速度といった点で
十分満足できるものではなく、そのため実用化されてい
ないのが現状である。ここで発色性能とは、光照射によ
る活性化状態での吸収極大波長の光学濃度の変化を示す
。(Prior art), (Problems to be solved by the invention) Spirobenzopyrans, triphenylmethanes, mercury complex salts of dithizone, and viologens have been known as substances exhibiting photochromism. By dissolving and dispersing photochromic substances in a suitable polymeric binder, practical application in fields such as sunglasses, optical filters, and curtains is progressing. However, although these materials have good color development performance among the performance requirements for photochromic materials, they are not fully satisfactory in terms of repeatability and return speed when left in a dark place, and therefore have not been put into practical use. The current situation is that there is no such thing. Here, the color development performance refers to a change in optical density at the absorption maximum wavelength in an activated state due to light irradiation.
一方、暗所における戻り速度が良好な物質として特公昭
４５−２８８９２号に１．３．３− トリメチルスピロ
〔インドリン−２−２，３’−［３Ｈ） −（２，１−
ｂ） −１，４−オキサジン〕が示されており、このも
のを適当な高分子バインダーに溶解させたのち支持体に
塗布し、乾燥させたものが’４．ｖｌ Ｘされている。On the other hand, 1.3.3-trimethylspiro[indoline-2-2,3'-[3H)-(2,1-
b) -1,4-oxazine], which was dissolved in a suitable polymeric binder, applied to a support, and dried to form '4. vl X has been done.
しかし、このものも実用化されていない。さらに。However, this method has not been put into practical use either. moreover.
同公報には、上記物質に対し、如何なる状態で使用する
と、優れた発色性能、繰り返し反復性が発現するかにつ
いては、−項記載されていない。This publication does not include any description of the condition under which the above-mentioned substance is used to exhibit excellent coloring performance and repeatability.
（問題点を解決するための手段）
本発明者は、かかる状況に鑑み、優れた発色性能及び繰
り返し反復性を有する感光性樹脂組成物を提供すること
を目的として鋭意研究を重ねた結果、スピロナフトオキ
サジン誘導体を透明樹脂に特定量配合することにより、
上記の目的が達成しうろことを見出し本発明に到達した
。(Means for Solving the Problems) In view of the above circumstances, the inventors of the present invention have conducted extensive research with the aim of providing a photosensitive resin composition having excellent coloring performance and repeatability. By blending a specific amount of naphthoxazine derivative into transparent resin,
The inventors have discovered that the above objects can be achieved and have arrived at the present invention.
すなわち１本発明は、一般式（１） （式中、Ｒ，、、Ｒ，は水素原子、低級アルキル基。That is, 1 the present invention is based on the general formula (1) (In the formula, R is a hydrogen atom or a lower alkyl group.
低級アルコキシ基、ハロゲン原子、ニトロ基又はシアノ
基を表す。）で示されるスピロナフトオキサジン誘導体
０．１〜５０重里％と透明樹脂９９．９〜５０重量％と
からなる感光性樹脂組成物である。Represents a lower alkoxy group, halogen atom, nitro group or cyano group. ) is a photosensitive resin composition consisting of 0.1 to 50% by weight of a spironaphthoxazine derivative represented by the formula and 99.9 to 50% by weight of a transparent resin.
本発明の感光性樹脂組成物が、優れた発明性能及び繰り
返し反復性を有するばかりか、暗所における戻り速度が
室温で数十秒以内と良好であり。The photosensitive resin composition of the present invention not only has excellent inventive performance and repeatability, but also has a good return speed in a dark place of within several tens of seconds at room temperature.
しかも紫外線照射によるスピロナフトオキサジン誘導体
の分解もほとんど認められないのは驚くべきことである
。Furthermore, it is surprising that almost no decomposition of the spironaphthoxazine derivatives was observed upon irradiation with ultraviolet rays.
本発明の感光性樹脂組成物中のスピロナフトオキサジン
誘導体の含有量は０．１〜５０重量％である。The content of the spironaphthoxazine derivative in the photosensitive resin composition of the present invention is 0.1 to 50% by weight.
スピロナフトオキサジン誘導体の含有量がｏ、ｔｔｉ量
％未溝になると十分な発色を得るのに樹脂組成物の厚み
が要求され、そのようなものでは実用上利用することが
不可能となるうえ、スピロナフトオキサジン誘Ｗ体の単
位重量当りの発色性能も悪化する。一方、含有量が５０
重景％をこえると樹脂媒体中にスピロナフトオキサジン
誘導体の結晶が散在し、その結果、満足できる発色が得
られず。If the content of the spironaphthoxazine derivative is o,tti% ungrooved, the thickness of the resin composition is required to obtain sufficient color development, and such a composition is not practically usable. The coloring performance per unit weight of the spironaphthoxazine diluted W product also deteriorates. On the other hand, the content is 50
If the weight ratio exceeds %, spironaphthoxazine derivative crystals will be scattered in the resin medium, and as a result, satisfactory color development will not be obtained.
いずれの場合も本発明の目的を達成することができない
。これに対し本発明の樹脂塑性物は感光性樹脂組成物と
して繰り返し反復性試験を行うと驚くべきことに１万回
繰り返しを行った後でもフォトクロミズムなる性質を有
している。In either case, the object of the present invention cannot be achieved. On the other hand, when the resin plastic material of the present invention is subjected to a repeatability test as a photosensitive resin composition, surprisingly it has a property of photochromism even after repeating the test 10,000 times.
本発明の感光性樹脂組成物の一成分である透明樹脂とし
ては１例えばポリメチルメタアクリレートのようなアク
リル系ポリマー、ポリスチレンのようなスチレン系ポリ
マー、ポリカーボネートのようなポリエステル系ポリマ
ー、ポリエチレンオキシドのようなポリエーテル系ポリ
マー、ナイロン１２のようなポリアミド系ポリマー、ポ
リエチレンのようなオレフィン系ポリマー、エチルセル
ロースのようなセルロース系ポリマー、ポリビニルアル
コール、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ酢
酸ビニル、ポリビニルブチラール、ポリグリシジルメタ
アクリレートポリ−Ｎ−ビニルカルバゾールとこれらの
共重合体等をあげることができる。これらの樹脂は、必
要に応じ、硬化させたものであってもよい。Examples of the transparent resin that is a component of the photosensitive resin composition of the present invention include acrylic polymers such as polymethyl methacrylate, styrene polymers such as polystyrene, polyester polymers such as polycarbonate, and polyethylene oxide. polyether polymers, polyamide polymers such as nylon 12, olefin polymers such as polyethylene, cellulose polymers such as ethyl cellulose, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl butyral, Examples include glycidyl methacrylate poly-N-vinylcarbazole and copolymers thereof. These resins may be cured if necessary.
本発明の感光性樹脂組成物を調製するには、上記のごと
き透明樹脂の成形時に溶融状態でスピロナフトオキサジ
ン誘導体を混練してもよいし、また、上記のごとき透明
樹脂とスピロナフトオキサジン誘導体の両成分を溶解し
うる適当な溶媒に両成分を、溶解し、しかるのち溶媒だ
けを蒸発させるキャスティング方法を採用することもで
きる。さらには、透明樹脂を成形後１例えば浸染法、パ
ッド染色法、捺染法等で着色させることにより本発明の
感光性樹脂組成物を調製することもできる。To prepare the photosensitive resin composition of the present invention, the spironaphthoxazine derivative may be kneaded in a molten state during molding of the above transparent resin, or the spironaphthoxazine derivative may be mixed with the above transparent resin and the spironaphthoxazine derivative. It is also possible to adopt a casting method in which both components are dissolved in a suitable solvent capable of dissolving both components, and then only the solvent is evaporated. Furthermore, the photosensitive resin composition of the present invention can also be prepared by coloring the transparent resin by, for example, a dip dyeing method, a pad dyeing method, a textile printing method, etc. after molding.
本発明の感光性樹脂組成物は、メガネレンズ。The photosensitive resin composition of the present invention is used as a spectacle lens.
日光遮断用フィルム材、塗料、衣服のプリント加工用樹
脂といった使節用に、また、複写材料、レーザー用感光
材料、ホログラフィ−用感光材料などの記録材料として
、さらには光学フィルター。Used as sunscreen film materials, paints, resins for printing on clothes, recording materials such as copying materials, laser light-sensitive materials, holography light-sensitive materials, and optical filters.
ディスプレイ材料としても利用できる。It can also be used as a display material.
（実施例）
以下に実施例をあげて本発明をさらに具体的に説明する
。(Example) The present invention will be described in more detail with reference to Examples below.
実施例１〜６．比較例１〜３
透明樹脂とし′ζポリメチルメタアクリレートを用い、
以下のようにして１．３．３−トリメチルスピし１ナフ
トオー１−サジンのそれぞの濃度に対する飽和吸光度の
（ｒ！ｑ定を行った。Examples 1-6. Comparative Examples 1 to 3 Using 'ζ polymethyl methacrylate as a transparent resin,
The saturated absorbance (r!q determination) for each concentration of 1.3.3-trimethylspisyl-1-naphtho-1-sazine was determined as follows.
すなわら、 ０．１１：の１，３．３− トリメチル
スピロナフトオキサジンと第１表に示す種々の量のポリ
メチルメタアクリレ−］・とをアセトンに溶解し。Specifically, 0.11: of 1,3,3-trimethylspironaphthoxazine and various amounts of polymethylmethacrylate shown in Table 1 were dissolved in acetone.
３０ｃｍ Ｘ ３０ｃｍのガラス１反」二に二１−ヤス
トし°ζフィルムを作成した。光照射は５００ Ｗ超高
圧水銀灯（牛用７Ｈｇ１社製）及びカッＩ・フィルター
ＵＶ−２９（東芝硝了損製）を用い°１ｌｒ３０秒間行
った。測定波長は発色した際の吸収極大波長 ｍａｙで
ある６１３ｎｍで行った。得られた飽和光学濃度の値を
第１表に示す。A piece of glass measuring 30 cm x 30 cm was cast twice and twice to form a film. Light irradiation was carried out at 1lr for 30 seconds using a 500 W ultra-high pressure mercury lamp (manufactured by 7Hg1 Co., Ltd. for cattle) and a Ka-I filter UV-29 (manufactured by Toshiba Nitsuroro). The measurement wavelength was 613 nm, which may be the maximum absorption wavelength when color was developed. The obtained saturated optical density values are shown in Table 1.
第１表から明らかなようにスピロナフトオキサジンＬＳ
、 ８体の発色を有効に利用できる濃度は０．１〜５０
重量％であった。なお１発色したフィルムを暗所に移す
といずれも約１０秒で元の無色の状態に戻った。As is clear from Table 1, Spironaphthoxazine LS
, The density that can effectively utilize the color development of 8 bodies is 0.1 to 50.
% by weight. When the films that developed one color were moved to a dark place, they all returned to their original colorless state in about 10 seconds.
第１表
実施例７．比較例４，５
透明樹脂として、ポリメチルメタアクリレートのｌｏｇ
を用い、これと１．３．３−１−リンチルスピロナフト
オキサジン、 １．３．３−１−ジメチル−６゛ニト
ロー８°−メトキシスピロ〔インドリン−２，２“−ベ
ンゾピラン〕あるいはジチゾン水銀錯塩の０．１ｇとを
アセトン１５０ｍ１に溶解し、厚みが５０ミクロンにな
るようにフィルムを作製し、得られたフィルムについて
繰り返し反復性試験を行った。光照射方法は実施例１と
同様であって、３０秒間照射の後。Table 1 Example 7. Comparative Examples 4 and 5 Log of polymethyl methacrylate as transparent resin
and 1.3.3-1-lyntylspironaphthoxazine, 1.3.3-1-dimethyl-6'nitro8'-methoxyspiro [indoline-2,2''-benzopyran] or dithizone mercury. A film with a thickness of 50 microns was prepared by dissolving 0.1 g of the complex salt in 150 ml of acetone, and a repeatability test was conducted on the obtained film.The light irradiation method was the same as in Example 1. After 30 seconds of irradiation.
３０秒間暗所に放置するのを１サイクルとした。測定波
長は、それぞれの物質の光照射により発色した際の第２
表に示す吸収極大波長で行った。その結果を第１図るこ
ボす。第１図から明らかなように１．３．３− トリメ
チルスピロナフトオキサジンを用いたフィルムは優れた
繰り返し反復性を有しており、１万回後でもフォトクロ
ミズム性は保たれていた。One cycle was defined as leaving the sample in the dark for 30 seconds. The measurement wavelength is the second wavelength when each substance is colored by light irradiation.
The measurement was carried out at the maximum absorption wavelength shown in the table. The results are shown in the first diagram. As is clear from FIG. 1, the film using 1.3.3-trimethylspironaphthoxazine had excellent repeatability, and photochromism was maintained even after 10,000 cycles.
第２表
（発明の効果）
本発明によれば、スピロナフトオキサジン誘導体の発色
性能を最大限に利用することができるうえ、従来から提
案されているフォトクロミック感光性樹脂組成物の繰り
返し反復性、暗所における戻り速度といった問題点が一
挙に解消され、フォトクロミンク感光性樹脂組成物を用
いた商品の提供が可能となる。Table 2 (Effects of the Invention) According to the present invention, the coloring performance of the spironaphthoxazine derivative can be utilized to the maximum, and the repeatability and darkness of the photochromic photosensitive resin compositions proposed in the past can be improved. Problems such as the return speed at places are solved at once, and it becomes possible to provide products using photochromink photosensitive resin compositions.
第１図は、スピロナフトオキサジン（実施例７）、スビ
ロヘンゾピラン（比較例４）、ジチゾン水ｆ！錯塩（比
較例５）をそれぞれ含むポリメチルメタアクリレートフ
ィルムの繰り返し特性を示すグラフである。
特許出廓人 ユニ子力株式会社
腋 １闇
くリリ（Ｌ圓劉（Figure 1 shows spironaphthoxazine (Example 7), subirohenzopyran (Comparative Example 4), dithizone water f! 2 is a graph showing the repeating characteristics of polymethyl methacrylate films each containing a complex salt (Comparative Example 5). Patent distributor Unico Power Co., Ltd. Armpit 1 Dark Lily (L Enryu)
Claims (1)
低級アルコキシ基、ハロゲン原子、ニトロ基又はシアノ
基を表す。）で示されるスピロナフトオキサジン誘導体
０．１〜５０重量％と透明樹脂９９．９〜５０重量％と
からなる感光性樹脂組成物。(1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 are hydrogen atoms, lower alkyl groups,
Represents a lower alkoxy group, halogen atom, nitro group or cyano group. ) A photosensitive resin composition comprising 0.1 to 50% by weight of a spironaphthoxazine derivative represented by the following formula and 99.9 to 50% by weight of a transparent resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24688384A JPS61123835A (en) | 1984-11-20 | 1984-11-20 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24688384A JPS61123835A (en) | 1984-11-20 | 1984-11-20 | Photosensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61123835A true JPS61123835A (en) | 1986-06-11 |
Family
ID=17155157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24688384A Pending JPS61123835A (en) | 1984-11-20 | 1984-11-20 | Photosensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61123835A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6327837A (en) * | 1986-07-22 | 1988-02-05 | Nissan Motor Co Ltd | Photochromic material |
| WO2006095705A1 (en) * | 2005-03-09 | 2006-09-14 | National University Corporation Yokohama National University | Method of forming pattern |
| JP2010174135A (en) * | 2009-01-29 | 2010-08-12 | Mitsubishi Plastics Inc | Polyester film |
-
1984
- 1984-11-20 JP JP24688384A patent/JPS61123835A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6327837A (en) * | 1986-07-22 | 1988-02-05 | Nissan Motor Co Ltd | Photochromic material |
| WO2006095705A1 (en) * | 2005-03-09 | 2006-09-14 | National University Corporation Yokohama National University | Method of forming pattern |
| JP2010174135A (en) * | 2009-01-29 | 2010-08-12 | Mitsubishi Plastics Inc | Polyester film |
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