JPS63241543A - Photochromic optical storage material - Google Patents
Photochromic optical storage materialInfo
- Publication number
- JPS63241543A JPS63241543A JP7679587A JP7679587A JPS63241543A JP S63241543 A JPS63241543 A JP S63241543A JP 7679587 A JP7679587 A JP 7679587A JP 7679587 A JP7679587 A JP 7679587A JP S63241543 A JPS63241543 A JP S63241543A
- Authority
- JP
- Japan
- Prior art keywords
- film
- optical recording
- recording material
- high molecular
- photochromic
- 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
- 230000003287 optical effect Effects 0.000 title claims abstract description 30
- 239000011232 storage material Substances 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 36
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 229920006254 polymer film Polymers 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000002563 ionic surfactant Substances 0.000 claims description 10
- 239000005518 polymer electrolyte Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000004321 preservation Methods 0.000 abstract description 4
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 abstract description 2
- 108010020346 Polyglutamic Acid Proteins 0.000 abstract description 2
- 108010039918 Polylysine Proteins 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 229920000669 heparin Polymers 0.000 abstract description 2
- 229960002897 heparin Drugs 0.000 abstract description 2
- 229920000083 poly(allylamine) Polymers 0.000 abstract description 2
- 229920002643 polyglutamic acid Polymers 0.000 abstract description 2
- 229920000656 polylysine Polymers 0.000 abstract description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 2
- 239000004094 surface-active agent Substances 0.000 abstract 2
- 230000008859 change Effects 0.000 description 12
- 238000005562 fading Methods 0.000 description 9
- 230000007704 transition Effects 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003012 bilayer membrane Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000010365 information processing Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PSXPTGAEJZYNFI-UHFFFAOYSA-N 1',3',3'-trimethyl-6-nitrospiro[chromene-2,2'-indole] Chemical compound O1C2=CC=C([N+]([O-])=O)C=C2C=CC21C(C)(C)C1=CC=CC=C1N2C PSXPTGAEJZYNFI-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- SKVLBFICUWJKDV-UHFFFAOYSA-N 5-oxaspiro[2.4]heptane-4,6-dione Chemical class O=C1OC(=O)CC11CC1 SKVLBFICUWJKDV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 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
- 230000008094 contradictory effect Effects 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 hexane and decane Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
-
- 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
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/245—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing a polymeric component
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
本発明は新規なフォトクロミック系光記録材料に関する
ものである。さらに詳しくいえば、本発明は、例えば超
大型コンピューターに対応した超大容量記憶装置、業務
用や家庭用の超小型ディスク装置、光情報処理周辺機器
である高解像度表示装置などに使用するための、高性能
フォトクロミック系光記録材料に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel photochromic optical recording material. More specifically, the present invention is suitable for use in, for example, ultra-large capacity storage devices compatible with ultra-large computers, ultra-small disk devices for business and home use, and high-resolution display devices that are optical information processing peripherals. This invention relates to high-performance photochromic optical recording materials.
従来の技術
光が当たると色が変化し、熱を加えたり、別の波長の光
を当てると元の色に戻る現象、すなわちフォトクロミズ
ムを利用した光記録材料は、現像処理が不要で繰り返し
使用が可能な上に、高解像度を有し、原理的には記録密
度を、従来の記録方式の限界であるl−当り1億ビツト
より、さらに10倍高めることができるという特徴を有
することから、最近各方面で注目されるようになってき
た。Conventional technology Optical recording materials that use photochromism, a phenomenon in which the color changes when exposed to light and returns to its original color when heated or exposed to light of a different wavelength, do not require development and can be used repeatedly. Not only is it possible, but it also has high resolution and, in principle, the recording density can be increased ten times higher than the limit of 100 million bits per l, which is the limit of conventional recording methods. It has started to attract attention from all walks of life.
このようなフォトクロミック系光記録材料には、フォト
クロミズム性を有する化合物、いわゆるフォトクロミッ
ク化合物が必要であるが、このフォトクロミック化合物
としては、これまでジメチレンコハク酸無水物の誘導体
、スピロベンゾピラン類、スピロオキサジン類、アゾベ
ンゼン類などが知うしている。そして、これらの中でス
ピロベンゾビラン類は、光照射前後の吸収スペクトルの
差が大きい上に1着色体の分子吸光係数が致方にもおよ
び発色効率がよく、読み出し精度が高いなどの長所を有
するために、光記録材料用の素材として特に好ましいも
のである。Such photochromic optical recording materials require compounds with photochromic properties, so-called photochromic compounds. Until now, photochromic compounds such as dimethylene succinic anhydride derivatives, spirobenzopyrans, and spirooxazines have been used. and azobenzenes. Among these, spirobenzobilanes have advantages such as a large difference in absorption spectra before and after light irradiation, an extremely high molecular extinction coefficient for a single colored substance, high coloring efficiency, and high readout accuracy. Therefore, it is particularly preferable as a material for optical recording materials.
しかしながら、このスピロベンゾビラ7Mn、で示され
る形式の7オトクロミズム性を有し、光による記録、読
み出し、消去が可能であるが、記録材料に用いる際に、
着色型として記録しておいても、熱によって無色の閉環
型に戻るために、長時間の記録保存には適さないという
欠点を有している。However, this spirobenzobira 7Mn has a type of 7 otochromism and can be recorded, read, and erased by light, but when used as a recording material,
Even if it is recorded as a colored type, it has the disadvantage that it is not suitable for long-term storage because it returns to the colorless closed ring type when heated.
このような欠点を改良するために、これまで、該スピロ
ベンゾビラン類をポリスチレン、ポリアクリル酸メチル
、ポリメタクリル酸メチルなどの適当なバインダー樹脂
中に分散させる方法が試みられてきた。しかしながら、
この方法では、樹脂中において、該スピロベンゾビラン
類の熱運動が著しく束縛されるために、その熱退色速度
全溶液中の数十分の−ないし数百分の−に抑制すること
ができるが、光記録材料にとって、もう一つの望ましい
性質である迅速な記録、読み出し、消去を行うという点
で、不利になるのを免れない。In order to improve these drawbacks, attempts have been made so far to disperse the spirobenzobilanes in a suitable binder resin such as polystyrene, polymethyl acrylate, polymethyl methacrylate, or the like. however,
In this method, the thermal movement of the spirobenzobilanes in the resin is significantly restricted, so the rate of thermal fading can be suppressed to several tenths to several hundredths of that in the total solution. , which is inevitably disadvantageous in terms of rapid recording, reading, and erasing, which is another desirable property for optical recording materials.
このような、迅速な記録、読み出し、消去と、記録の長
期間保存という原理的に相反する特性を両立させること
は、従来知られている高分子バインダーを用い、この中
に該スピロベンゾビラン類全分散させるという方法では
実現不可能である。In order to achieve both of these properties, which are contradictory in principle, such as rapid recording, reading, and erasing, and long-term preservation of records, a conventionally known polymer binder is used, and the spirobenzobilanes are added to the binder. This cannot be achieved by completely dispersing it.
発明が解決しようとする問題点
本発明はこのような事情のもとで、光による記録、読み
出し、消去を迅速に行いつる上に、記録の長期保存が可
能な、スピロベンゾピラン類を用いたフォトクロミック
系光記録材料全提供することを目的としてなされたもの
である。Problems to be Solved by the Invention Under these circumstances, the present invention uses spirobenzopyrans, which can quickly record, read, and erase with light, and can preserve records for a long time. It was developed with the aim of providing a complete range of photochromic optical recording materials.
問題点を解決するための手段
本発明者らは、迅速な記録、読み出し、消去と、記録の
長期間保存の相反する要求を同時に満足させる新規なフ
ォトクロミック系記録材料を開発するために鋭意研究を
重ねた結果、光以外の刺激、例えば熱などにより、高分
子バインダーの物理状態に変化を引き起こさせ、フォト
クロミック反応が進行する状態とその逆の状態を任意に
制御しうるようにすればよいこと及びこれには二分子膜
構造を有するある特定の高分子フィルムが効果的であり
、この高分子フィルム中に、フォトクロミック化合物と
してスピロベンゾピラン類を分散させれば、前記目的全
達成しうろことを見い出し、この知見に基づいて本発明
を完成するに至った。Means for Solving the Problems The present inventors have conducted extensive research in order to develop a new photochromic recording material that simultaneously satisfies the conflicting demands of rapid recording, reading, and erasing, and long-term preservation of records. As a result of this, it is only necessary to cause a change in the physical state of the polymer binder by stimulation other than light, such as heat, and to arbitrarily control the state in which the photochromic reaction progresses and the state in which it is reversed. It has been discovered that a particular polymer film with a bilayer membrane structure is effective for this purpose, and that if spirobenzopyrans are dispersed as a photochromic compound in this polymer film, all of the above objectives can be achieved. Based on this knowledge, the present invention was completed.
すなわち、本発明は、高分子フィルム中に、フォトクロ
ミック化合物としてスピロベンゾビラン類を分散させて
成る光記録材料において、該高分子フィルムとして、直
鎖状の高級アルキル基2@を有するイオン性界面活性剤
とその反対荷電を有する高分子電解質とのイオンコンプ
レックスより得られた二分子膜構造を有するフィルムを
用いたことを特徴とするフォトクロミック系光記録材料
全提供するものである。That is, the present invention provides an optical recording material comprising spirobenzobilanes as a photochromic compound dispersed in a polymer film, in which the polymer film is an ionic surfactant having a linear higher alkyl group 2@. The present invention provides a photochromic optical recording material characterized by using a film having a bilayer structure obtained from an ionic complex of an agent and a polymer electrolyte having an opposite charge.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の光記録材料において、フォトクロミック化合物
として用いられるスピロベンゾビラン類は1例えば一般
式
(式中のR1は水素原子、ハロゲン原子、低級アルキル
基、低級アルコキシ基、アミ7基又は置換基金有するア
ミノ基、R2はアルキル基、R3はニトロ基又はハロゲ
ン原子である)
で表わされる化合物金挙げることができる。このような
スピロベンゾピラン類は公知であり1例えば式
Q)i5
で示されるものがある。In the optical recording material of the present invention, spirobenzobilanes used as photochromic compounds have the following general formula (wherein R1 is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, an amine group, or an amino group having a substituent group). group, R2 is an alkyl group, R3 is a nitro group or a halogen atom). Such spirobenzopyrans are well known and include those represented by the formula Q)i5.
これらのスピロベンゾビラン類は、紫外光を当てると無
色の閉環型から着色し友開環型に変換し、また、この開
環型は可視光又は熱によって無色の閉環型になるという
、いわゆるフォトクロミズム性5CMしている。When these spirobenzobilanes are exposed to ultraviolet light, they change from a colorless ring-closed form to a colored open-ring form, and this open-ring form changes to a colorless closed-ring form when exposed to visible light or heat, a phenomenon known as photochromism. I'm doing sex 5CM.
本発明の光記録材料においては、高分子フィルムとして
、直鎖状の高級アルキル基2個を有するイオン性界面活
性剤とその反対荷電を有する高分子電解質とのイオンコ
ンプレックスより得られた二分子膜構造を有するフィル
ムが用いられる。In the optical recording material of the present invention, the polymer film is a bilayer film obtained from an ionic complex of an ionic surfactant having two linear higher alkyl groups and a polymer electrolyte having an opposite charge. A structured film is used.
該イオン性界面活性剤残基としては、例えば一般式
(式中のR1及びR2は、それぞれ炭素数12以の直鎖
状アルキル基であって、これらは同一でCつてもよいし
、たがいに異なっていてもよ(、R及びR4は、それぞ
れ低級アルキル基であり、こiらは同一であってもよい
し、たがいに異なって(てもよい)
で示されるものを挙げることができるが、これらに限定
されることはなく、直鎖状の高級アルキル基2fllH
−有するイオン性界面活性剤であれば、他の構造のもの
も使用することができる。The ionic surfactant residue may be, for example, a compound of the general formula (in which R1 and R2 are each a linear alkyl group having 12 or more carbon atoms, and they may be the same and C or each other may be They may be different (R and R4 are each a lower alkyl group, and they may be the same or different from each other). , but not limited to, linear higher alkyl groups 2fllH
- Ionic surfactants having other structures can also be used.
一方、高分子電解質としては、前記のイオン性界面活性
剤に対して反対荷電を有するものが用いられる。このよ
うな高分子電解質としては、例えばポリスチレン系電解
質、ポリビニル硫酸、ポリグルタミン酸、ヘパリン、ポ
リリジン、ポリアリルアミンなどを挙げることができる
。該ポリスチレン系電解質の残基としては、例えば、一
般式(ただし、mは10以上の整数である)で示される
ものが挙げられる。On the other hand, as the polymer electrolyte, one having an opposite charge to the above-mentioned ionic surfactant is used. Examples of such polymer electrolytes include polystyrene electrolytes, polyvinyl sulfate, polyglutamic acid, heparin, polylysine, and polyallylamine. Examples of the residue of the polystyrene electrolyte include those represented by the general formula (where m is an integer of 10 or more).
これらの高分子電解質は、対応するイオン性界面活性剤
の種類に応じて適宜選ばれる。These polymer electrolytes are appropriately selected depending on the type of corresponding ionic surfactant.
本発明の光記録材料は1通常キャスト法によって製造さ
れる。例えば、適当な有機溶媒中に、前記のスピロベン
ゾビラン類及びイオン性界面活性剤と高分子電解質との
イオンコンプレックス’t−所望の割合で溶解したのち
、この溶液を支持体上に流延又は塗布し、乾燥すること
によって、高分子フィルム中に該スピロベンゾピランを
分散して成る本発明の光記録材料が得られる。The optical recording material of the present invention is usually produced by a casting method. For example, after dissolving the above-mentioned ionic complex of spirobenzobilane, ionic surfactant, and polymer electrolyte in a suitable organic solvent in a desired ratio, this solution is cast or cast onto a support. By coating and drying, the optical recording material of the present invention comprising the spirobenzopyran dispersed in a polymer film can be obtained.
この際、使用する有機溶媒としては、例えばりOI)ホ
ルムやジクロロエタンなどの塩素系溶媒、ヘキサンやデ
カンなどのアルカン類などがあるが、特にクロロホルム
が好ましい。これらの溶媒はそれぞれ単独で用いてもよ
いし、2種以上を混合して用いてもよい。支持体として
は、例えばガラス板、石英板、金属板や、ポリアクリル
酸メチル、ポリメタクリル酸メチル、ポリカーボネート
、ポリアミド、ポリエステルなどのプラスチック板など
を用いることができる。At this time, the organic solvent used includes, for example, chlorinated solvents such as OIform and dichloroethane, and alkanes such as hexane and decane, with chloroform being particularly preferred. These solvents may be used alone or in combination of two or more. As the support, for example, a glass plate, a quartz plate, a metal plate, a plastic plate made of polymethyl acrylate, polymethyl methacrylate, polycarbonate, polyamide, polyester, etc. can be used.
さらに、イオン性界面活性剤と高分子電解質とのイオン
コンプレックスと、スピロベンゾビラン類との割合につ
いては、通常該イオンコンプレックス100重量部に対
し、スピロベンゾビラン類が0.05〜1重量部の割合
で用いられる。また、該光記録材料の膜厚は、通常0.
001−0.1111の範囲で選ばれる。Furthermore, regarding the ratio of the ionic complex of the ionic surfactant and the polymer electrolyte to the spirobenzobilanes, the proportion of the spirobenzobilanes to 100 parts by weight of the ionic complex is usually 0.05 to 1 part by weight. Used in percentages. Further, the film thickness of the optical recording material is usually 0.
It is selected in the range of 001-0.1111.
このようにして得られた本発明の光記録材料は、二分子
膜構造を有する高分子フィルムにスピロベンゾビラン類
が分散し九ものであり、該二分子膜構造はX線回折によ
り′1M認することができる。また、該二分子膜構造を
有する高分子フィルムは、該材料中で相転移挙動を示す
が(相転移温度’jzTcと呼ぶ)、これは示差走査熱
量の測定により確認できる。該材料中で、Tc以下の低
温では、高分子フィルムは分子運動性の低いラメラ状結
晶状態となり、一方Tc以上の高温では運動性の高いス
メクチック液晶状頭金とる。The optical recording material of the present invention obtained in this manner has spirobenzobilanes dispersed in a polymer film having a bilayer structure, and the bilayer structure has been recognized as '1M by X-ray diffraction. can do. Furthermore, the polymer film having the bilayer structure exhibits phase transition behavior in the material (referred to as phase transition temperature 'jzTc), which can be confirmed by differential scanning calorimetry measurement. In this material, at low temperatures below Tc, the polymer film assumes a lamellar crystalline state with low molecular mobility, while at high temperatures above Tc, it assumes a smectic liquid crystal-like precipitate with high mobility.
したがって、この光記録材料の紫外光照射後の熱退色反
応速度は、 Tc温度付近で不連続的に大きく変化し
、Tc以上の温度ではTc以下の温度の場合の3〜8倍
大きいことが観測された。この反応性の変化は、Tc以
上 ?−TC以下の温度の繰り返しで、可逆的であった
。Therefore, it is observed that the thermal fading reaction rate of this optical recording material after irradiation with ultraviolet light changes discontinuously and greatly around the Tc temperature, and is 3 to 8 times faster at temperatures above Tc than at temperatures below Tc. It was done. Is this change in reactivity greater than Tc? -It was reversible by repeated temperatures below TC.
また、相変化により反応性を制御するには、該高分子フ
ィルムの二分子膜構造がよりよく発達していることが必
要で、一般にキャストした状態そのままでは、二分子膜
構造の発達の程度が低いが、これをTc以上の温度で、
相対湿度100チの雰囲気下に数時間放置すると、該二
分子膜構造がよりよく発達する。In addition, in order to control reactivity through phase change, it is necessary that the bilayer structure of the polymer film is well developed, and generally speaking, the degree of development of the bilayer structure in the cast state is limited. Although it is low, at a temperature higher than Tc,
If left in an atmosphere with a relative humidity of 100 degrees for several hours, the bilayer structure will develop better.
本発明の光記録材料は、前記のような性質を有している
めで、Tc以上の高温で可視光又は紫外光を照射するこ
とにより、消去又は記録が迅速に行われ、記録の保存は
Tc以下の低温に保つことによp安定に行うことができ
る。Since the optical recording material of the present invention has the above-mentioned properties, erasing or recording can be performed quickly by irradiating visible light or ultraviolet light at a high temperature higher than Tc, and recording can be stored at Tc or higher. It can be carried out stably by keeping the temperature at the following low temperature.
発明の効果
本発明のフォトクロミック系光記録材料は、光と熱の2
種の物理的刺激により応答するものであって、記録、読
み出し、消去を任意にかつ迅速に行いうる上に、記録の
長期保存が可能であシ、例えば超大型コンピューターに
対応した超大容量記憶装置、業務用や家庭用の超小型デ
ィスク装置、光情報処理周辺機器である高解像度表示装
置などの分野において好適に使用できる。Effects of the Invention The photochromic optical recording material of the present invention has two effects: light and heat.
It responds to the physical stimulus of a species, and can be recorded, read out, and erased arbitrarily and quickly, as well as long-term storage of records, such as an ultra-large capacity storage device compatible with an ultra-large computer. It can be suitably used in fields such as ultra-small disk devices for business and home use, and high-resolution display devices that are peripheral devices for optical information processing.
また、熱応答光フィルターや玩具などの用途にも利用す
ることができる。It can also be used in applications such as heat-responsive optical filters and toys.
実施例
次に実施例によυ本発明をさらに詳細に説明するが、本
発明はこれらの例によってなんら限定されるものではな
い。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例1
クロロホルム1tnt中に、ジオクタデシルジメチルア
ンモニウムとポリスチレンスルホン酸とのイオンコンプ
レックス50■及びl’、 1’、 3’−)ツメチル
−6−二トロスピ口[:2H−1−ペンソヒランー2.
2’−インドリン]0.23■を溶解し、これを石英板
上に3〜4時間かけて室温にてキャストし、厚み0.0
1mの透明なフィルムから成る光記録材料を得た。次い
でこの材料を60℃、相対湿度100%の条件下で1時
間放置した。この熱処理により、二分子膜構造が良く発
達することがX線回折と示差走査熱量測定(DSC)よ
り確めた。Example 1 In 1 tnt of chloroform, an ionic complex of dioctadecyldimethylammonium and polystyrene sulfonic acid was prepared with 50 μl and 1', 1', 3'-)methyl-6-nitrosip[:2H-1-pensohylan-2.
2'-indoline] was dissolved and cast on a quartz plate at room temperature for 3 to 4 hours to a thickness of 0.0
An optical recording material consisting of 1 m of transparent film was obtained. This material was then left for 1 hour at 60° C. and 100% relative humidity. It was confirmed by X-ray diffraction and differential scanning calorimetry (DSC) that the bilayer structure was well developed by this heat treatment.
前記熱処理により、X線回折において二分子膜ラメラに
帰因する39Aの回折像がより明確に観測され、またp
sc測定での昇温過程における吸熱ピークが、39℃か
ら49℃と高温へ移行すると共に、エンタルピー変化(
ΔH)は2.6 kcal /molから10.4 k
cal / mol ヘと増加した。As a result of the heat treatment, the diffraction image of 39A attributed to bilayer membrane lamellae was observed more clearly in X-ray diffraction, and p
The endothermic peak during the temperature increase process in SC measurement shifts from 39°C to 49°C, and the enthalpy change (
ΔH) is 2.6 kcal/mol to 10.4 k
Cal/mol increased.
さらに、この光記録材料は良好なフォトクロミズムを示
した。すなわち、500Wの超高圧水銀灯からの光を、
コーニング社製の色ガラスフィルタ−7−51及び3−
73’i用いて紫外光及び可視光全交互に照射すると、
紫外光照射時には、波長558nmにピークをもつ可視
吸収(紫色)が現われ、’E+J視光照射で該材料は再
び無色となった。Furthermore, this optical recording material showed good photochromism. In other words, light from a 500W ultra-high pressure mercury lamp,
Corning colored glass filters -7-51 and 3-
When UV light and visible light are irradiated alternately using 73'i,
Upon irradiation with ultraviolet light, visible absorption (purple color) with a peak at a wavelength of 558 nm appeared, and upon irradiation with 'E+J visual light, the material became colorless again.
紫外光照射後の着色は熱によっても退色するが、フィル
ム中での熱退色速度はアセトンなどの有機溶媒中よりも
数十分の−に低下しており、明らかにスピロベンゾピラ
ン化合物のフォトクロミック反応はフィルム材料からの
束縛により抑制されていることが分かる。The coloring after irradiation with ultraviolet light also fades due to heat, but the rate of thermal fading in the film is several tenths of a second lower than in organic solvents such as acetone, which is clearly due to the photochromic reaction of the spirobenzopyran compound. It can be seen that this is suppressed by constraints from the film material.
この光記録材料中の二分子膜構造を有する高分子フィル
ムは、49℃において結晶一液晶の相転移を示すが、着
色からの熱退色速度は、この温度の上下で大きく変化し
た。退色の際の主要な成分の一次反応速度定数には、T
c以下の47.5℃からTc以上の52.5℃への5℃
の温度変化で1.0×10 /Sから5.5 X 1
0 /Sへと5.5倍増加した。一方、相転移温度を
外した温度領域における5℃の温度変化では、速度変化
は1.2〜2倍しか変化しないことから、Tc付近での
大きな速度変化は2二分子膜の相転移に帰因することは
明白である。この大きな退色速度変化はTc以上#Tc
以下の温度のa!ll返しにより可逆的に変化した。The polymer film having a bilayer structure in this optical recording material exhibits a crystal-liquid crystal phase transition at 49° C., but the rate of thermal fading from coloring changes significantly above and below this temperature. The first-order reaction rate constant of the main component during color fading is T
5℃ from 47.5℃ below c to 52.5℃ above Tc
From 1.0 x 10/S to 5.5 x 1 with temperature change of
It increased 5.5 times to 0/S. On the other hand, with a temperature change of 5°C in the temperature range outside the phase transition temperature, the speed change is only 1.2 to 2 times, so the large speed change near Tc is attributed to the phase transition of the bilayer membrane. It is clear that this is due to this. This large change in fading rate is greater than Tc #Tc
A of the following temperatures! The change was reversible by reversing.
添付図面は、温度の逆数に対する、−次速度定数の対数
の関係を示すグラフ(アレニウスプロット)であり、上
記の記録材料については実線で示されている。The accompanying drawing is a graph (Arrhenius plot) showing the relationship of the logarithm of the -order rate constant to the reciprocal of temperature, and is shown as a solid line for the above-mentioned recording material.
また、スピロベンゾピラン化合物として、下記の化合物
を用い、同様にして光記録材料を作製した。これらの材
料におけるTc付近での退色速度の変化の大きさは次の
とおりである。Further, an optical recording material was produced in the same manner using the following compound as a spirobenzopyran compound. The magnitude of the change in fading rate near Tc for these materials is as follows.
スピロベンゾピラン化合物 k (Tc以上)/k
(Tc以下)H5
H3
比較例
トルエンとベンゼンとの混合溶媒2fIt中に、ポリメ
タクリル酸メチル100〜と、lL、 1′、 3/−
トリメチル−6−ニトロスピロ[2H−1−ベンゾピラ
ン−2,2′−インドリン〕0.2■とを溶解し、これ
どガラス板上に1100Orpでスピナー@布し、室温
にて3時間減圧乾燥した。Spirobenzopyran compound k (Tc or more)/k
(Tc or less) H5 H3 Comparative Example In 2 fIt of a mixed solvent of toluene and benzene, polymethyl methacrylate 100~, 1L, 1', 3/-
0.2 μm of trimethyl-6-nitrospiro[2H-1-benzopyran-2,2'-indoline] was dissolved, placed on a glass plate using a spinner at 1100 rpm, and dried under reduced pressure at room temperature for 3 hours.
この試料について、実施例と同様にして30〜60℃の
温度範囲で退色速度を測定した。ポリメタクリル酸メチ
ルフィルムは、30〜60 ’CcDm度範囲で、相転
移挙動を示さないので、急速な退色速度変化は観測され
なかった。Regarding this sample, the fading rate was measured in the temperature range of 30 to 60°C in the same manner as in the examples. Polymethyl methacrylate films do not exhibit phase transition behavior in the 30-60'CcDm degree range, so no rapid fading rate changes were observed.
この例で得た記録材料についてのアレニウスプロットに
図面に破線で示す。The Arrhenius plot for the recording material obtained in this example is indicated by a dashed line in the drawing.
1面は、実施例及び比較例における高分子フィルム中で
のスピロベンゾビランの着色型から無色型へのアレニウ
スプロットヲ示すグラフである。The first page is a graph showing an Arrhenius plot from a colored type to a colorless type of spirobenzobilane in polymer films in Examples and Comparative Examples.
Claims (1)
てスピロベンゾピラン類を分散させて成る光記録材料に
おいて、該高分子フィルムとして、直鎖状の高級アルキ
ル基2個を有するイオン性界面活性剤とその反対荷電を
有する高分子電解質とのイオンコンプレックスより得ら
れた二分子膜構造を有するフィルムを用いたことを特徴
とするフォトクロミック系光記録材料。1. An optical recording material comprising a spirobenzopyran as a photochromic compound dispersed in a polymer film, in which the polymer film contains an ionic surfactant having two linear higher alkyl groups and an oppositely charged ionic surfactant. 1. A photochromic optical recording material characterized by using a film having a bilayer structure obtained by an ion complex with a polymer electrolyte having the following properties.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7679587A JPS63241543A (en) | 1987-03-30 | 1987-03-30 | Photochromic optical storage material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7679587A JPS63241543A (en) | 1987-03-30 | 1987-03-30 | Photochromic optical storage material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63241543A true JPS63241543A (en) | 1988-10-06 |
JPH0416775B2 JPH0416775B2 (en) | 1992-03-25 |
Family
ID=13615571
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7679587A Granted JPS63241543A (en) | 1987-03-30 | 1987-03-30 | Photochromic optical storage material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63241543A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03185090A (en) * | 1989-12-14 | 1991-08-13 | Agency Of Ind Science & Technol | Photochromic material of heat stability type |
-
1987
- 1987-03-30 JP JP7679587A patent/JPS63241543A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03185090A (en) * | 1989-12-14 | 1991-08-13 | Agency Of Ind Science & Technol | Photochromic material of heat stability type |
Also Published As
Publication number | Publication date |
---|---|
JPH0416775B2 (en) | 1992-03-25 |
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