JPH01230034A - Photochromic optical recording medium - Google Patents
Photochromic optical recording mediumInfo
- Publication number
- JPH01230034A JPH01230034A JP5717488A JP5717488A JPH01230034A JP H01230034 A JPH01230034 A JP H01230034A JP 5717488 A JP5717488 A JP 5717488A JP 5717488 A JP5717488 A JP 5717488A JP H01230034 A JPH01230034 A JP H01230034A
- Authority
- JP
- Japan
- Prior art keywords
- film
- clay
- optical recording
- photochromic
- recording
- 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 description 25
- 239000004927 clay Substances 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 5
- 125000000129 anionic group Chemical group 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 16
- 230000008859 change Effects 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000005562 fading Methods 0.000 description 10
- 239000003012 bilayer membrane Substances 0.000 description 8
- 230000007704 transition Effects 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 230000007774 longterm Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052901 montmorillonite Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005342 ion exchange Methods 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
- SKVLBFICUWJKDV-UHFFFAOYSA-N 5-oxaspiro[2.4]heptane-4,6-dione Chemical class O=C1OC(=O)CC11CC1 SKVLBFICUWJKDV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000005266 casting Methods 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
- 230000010365 information processing Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000002093 peripheral effect Effects 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000001484 Trigonella foenum graecum Nutrition 0.000 description 1
- 244000250129 Trigonella foenum graecum Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- -1 cationic organic compound Chemical class 0.000 description 1
- 150000001768 cations Chemical class 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
- PSLWZOIUBRXAQW-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC PSLWZOIUBRXAQW-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000004584 polyacrylic acid Substances 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
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
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録装置、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
光記録材料に関するものである。DETAILED DESCRIPTION OF THE INVENTION - Industrial Application Field 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 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、別の光の波長
の光をあ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、現像処理が不用で繰
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１ｅｆｆｌ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、各方面から注目される
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 the original color when heat or light of a different wavelength is applied, do not require development processing. In addition to being reusable, it has high resolution and, in principle, can increase the recording density by 10 times beyond the limit of conventional recording methods, which is 100 million bits per effl. , has recently been attracting attention from various quarters.
このようなフォトクロミック系光記録材料には、フォト
クロミック性を有する化合物、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
ゼン類などが知られている。ｊｌそ゛して、これらの中
でスピロペンゾピ、７．１ｊ二ｉ工よ。や収ユイ９＋ｔ
ｂＯ）１カきいうえに、着色体の分子吸光係数が致方に
も及び、発色効率がよく、読みだし精度が高いなどの長
所を有するために、光記録材料の素材として特に望まし
いものである。Such photochromic optical recording materials require a compound having photochromic properties, a so-called photochromic compound, and so far, photochromic compounds such as dimethylene succinic anhydride derivatives, dimethylene succinic anhydride derivatives,
Known examples include spirobenzopyrans, spirooxazines, and azobenzenes. So, among these, Spiropenzopi, 7.1j Second Engineer. Yasui Yui 9+t
It is particularly desirable as a material for optical recording materials because it has the advantage of having a molecular extinction coefficient of 1,000,000 bO), an extremely wide range of molecular extinction coefficients, high color development efficiency, and high readout accuracy. .
しかしながら、このスピロベンゾピラン類は、閉環型
開環型（無色） 可視光ま
たは熱 （着色）で示される形式のフォトクロミズム
性を有し、光による記録、読みだし、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、熱により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, these spirobenzopyrans are ring-closed type
Ring-opened type (colorless) Has photochromism in the form of visible light or heat (coloring), and can be recorded, read, and erased with light, but when used as a recording material, it is recorded as a colored type. Even if it is stored, it has the disadvantage that it is not suitable for long-term record storage because it returns to a colorless closed ring form 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
ベンゾピ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できた。しかしながらこ
の方法では、樹脂中において該スピロピラン類の熱運動
が著しく束縛されるために、その熱退色速度を溶液中の
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、読みだし、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 spirobenzopyrans in a suitable binder resin such as polystyrene, polymethyl acrylate, polymethyl methacrylate, or the like. However, in this method, the thermal movement of the spiropyrans in the resin is severely restricted, so the rate of thermal fading can be suppressed to several tenths to several hundred times of that in the solution; This is inevitably disadvantageous in terms of rapid recording, reading, and erasing, which is another desirable property of recording materials.
このような、迅速な記録、読みだし、消去と、記録の長
期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
該スピロベンゾピラン類を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 spirobenzopyrans are added to the binder. This cannot be achieved by distributing the information.
・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
みだし、消去を迅速に行いうる上に、記録の長期保存が
可能な、スピロベンゾピラン類をもちいたフォトクロミ
ック系光材料を提供することを目的として成されたもの
である。・Problems to be Solved by the Invention Under these circumstances, the present invention provides spirobenzopyrans that can be rapidly recorded, read out, and erased by light, and can be stored for a long period of time. The purpose of this work was to provide a photochromic optical material using .
Φ問題点を解決するための手段
本発明者゛らは、迅速な記録、読みだし、消去と、長期
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Ｉｌｌ＆、、例えば熱などにより、フィ
ルム状バインダーの物理状態に変化をおこさせ、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
に制御するようにすればよいこと、及びこれには二分子
膜を粘土層間に形成させた複合層状構造を有するフィル
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、前記目的を達成しうろことを見
いだし、この知見に基づいて本発明を完成するに至った
。ΦMeans for solving the problem The inventors of the present invention have conducted extensive research in order to develop a new photochromic recording material that simultaneously satisfies the conflicting requirements of rapid recording, reading, and erasing, and long-term storage. As a result of stacking, the physical state of the film binder is changed by means other than light, such as heat, and the state in which the photochromic reaction progresses and the state in which it is reversed can be arbitrarily controlled. , and found that the above objective could be achieved by dispersing spirobenzopyrans as a photochromic compound in a film having a composite layered structure in which a bilayer membrane was formed between clay layers, and based on this knowledge, Based on this, the present invention has been completed.
すなわち、本発明は、フィルム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て成る光記録
材料において、該フィルムとして、直鎮状の高級アルキ
ル基２個を有するカチオン性−界面活性剤とアニオン性
層状粘土化合物とのイオンコンプレックスより得られた
二分子膜−粘土複合層状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を提供
するものである。That is, the present invention provides an optical recording material comprising spirobenzopyrans as a photochromic compound dispersed in a film, in which the film comprises a cationic surfactant having two straight higher alkyl groups and an anionic layered The present invention provides a photochromic optical recording material characterized by using a film having a bilayer membrane-clay composite layered structure obtained from an ion complex with a clay compound.
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
として知られるスピロベンゾピラン類は、例えば一般式
（式中のＲ，は水素原子、ハロゲン原子、低級アルキル
基、低級アルコキシル基、アミノ基、または置換基を有
するアミノ基、Ｒ２はアルキル基、Ｒ３はアシル基、Ｒ
９はニトロ基、またはハロゲン原子である）で表される
化合物を挙げることができる。In the optical recording material of the present invention, spirobenzopyrans known as photochromic compounds have the general formula (wherein R represents a hydrogen atom, halogen atom, lower alkyl group, lower alkoxyl group, amino group, or amino group, R2 is an alkyl group, R3 is an acyl group, R
9 is a nitro group or a halogen atom).
このようなスピロベンゾピラン類は公知であり、例えば
、式
（ＣＬＬｔ
Ｈ３
Ｈ３
で示されるものがある。Such spirobenzopyrans are known, and for example, there is one represented by the formula (CLLt H3 H3).
これらのスピロベンゾピラン類は、紫外光を当てると無
色の閉環型から着色した開環型に変換し、また、この開
環型は可視光また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ック性を有している。When exposed to ultraviolet light, these spirobenzopyrans convert from a colorless closed-ring type to a colored open-ring type, and this open-ring type changes to a colorless closed-ring type when exposed to visible light or heat, which is a so-called photochromic property. have.
本発明の光記録材料においては、フィルムとして、直鎖
状の高級アルキル基２個を有するカチオン性界面活性剤
とアニオン性層状粘土化合物とのイオンコンプレックス
より１尋られた二分子膜と粘土の複合層状構造を有する
フィルムが用いられる。In the optical recording material of the present invention, as a film, a composite of a bilayer membrane and clay formed by an ionic complex of a cationic surfactant having two linear higher alkyl groups and an anionic layered clay compound is used. A film with a layered structure is used.
該カチオン性界面活性剤残基としては、例えば、一般式
（式中のＲ３およびＲ２は、それぞれ炭素数１２以上の
直鎮状アルキル基であって、これらは同一であってもよ
いし３．互いに異なっていてもよ＜、Ｒ３およ、１
びＲ１は、それぞれ低級アルキル基であり、これらは同
一であ、讐もよいし、互いに異な９ていてもよい）で示
されるものを挙げることはできるが、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２個を有するも
のであれば、他の構造のものを使用することができる。The cationic surfactant residue may be, for example, one represented by the general formula (in which R3 and R2 are each a straight alkyl group having 12 or more carbon atoms, and they may be the same or 3. may be different from each other <, R3, 1 and R1 are each a lower alkyl group, and these may be the same and may be opposites or may be different from each other). However, the structure is not limited to these, and other structures can be used as long as they have two linear higher alkyl groups.
一方、層状粘土化合物としては、イオン交換性ケイ酸塩
でカチオン性有機化合物を層間に挿入できるものが用い
られる。このような、層状粘土化合物としては、例えば
、モンモリロナイト、サポナイト、ヘクトライト、バー
ミキュライト、バイデライトなどを挙げることができ、
天然または人工のものを使用できる。On the other hand, as the layered clay compound, an ion-exchange silicate capable of intercalating a cationic organic compound between layers is used. Examples of such layered clay compounds include montmorillonite, saponite, hectorite, vermiculite, beidellite, etc.
Can be natural or artificial.
本発明において用いられる層状粘土化合物と二分子膜と
のイオンコンプレックスは、水中またはエタノール中に
おけるイオン交換によって得られる。また、光記録材料
は、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ピラン類および粘
土と二分子膜の複合材料を所望の割合で溶解したのち、
この溶液を支持体上に流延または塗布し、乾燥すること
によって、層状複合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 ion complex of the layered clay compound and the bilayer membrane used in the present invention is obtained by ion exchange in water or ethanol. Further, optical recording materials are usually manufactured by a casting method. For example, after dissolving the above-mentioned spirobenzopyrans and clay-bilayer membrane composite material in a suitable organic solvent in a desired ratio,
By casting or coating this solution onto a support and drying it, the optical recording material of the present invention comprising the spirobenzopyran dispersed in a layered composite film can be obtained.
この際、使用する有機溶媒としては、例えば、クロロホ
ルムやジクロロエタンなどの塩素系溶媒、各種アルコー
ル、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望ましい。At this time, the organic solvents used include, for example, chlorinated solvents such as chloroform and dichloroethane, various alcohols, and alkanes such as hexane and decane.
Chloroform is particularly desirable.
これらの溶媒はそれぞれ単独で用いても良いし、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／ｌ
ｚ、ポリメタクリル酸メチル、ホリカーボネート、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。These solvents may be used alone or in combination of two or more. As the support, for example,
Glass plate, quartz plate, metal plate, polyacrylic acid methi/l
z, a plastic plate made of polymethyl methacrylate, polycarbonate, polyamide, polyester, etc. can be used.
さらに、粘土と二分子膜の複合材料と、スピロベンゾピ
ラン類との割合については、通常酸複合体１００重量部
に対し、スピロベンゾピラン類が、０．０５〜５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ｏ、 ｏｏｉ〜０．１ｍｍの範囲で選ばれる。Furthermore, regarding the ratio of the clay and bilayer membrane composite material to the spirobenzopyrans, the spirobenzopyrans are usually used in a ratio of 0.05 to 5 parts by weight per 100 parts by weight of the acid complex. . Further, the film thickness of the optical recording material is usually selected within the range of o, ooi to 0.1 mm.
このようにして得られた本発明の光記録材料は、粘土と
二分子１膜＾の複合屑状構造を有するフィル−ニー、′
ムにスピロベンゾピラン類が分散したものであり、該二
分子膜構造はＸ線回折により確認することができる。ま
た、該フィルム中で、二分子膜は粘土層間で相転移挙動
を示すが（相転移温度をＴｃ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、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
メクチック液晶状態をとる。The optical recording material of the present invention thus obtained is one in which spirobenzopyrans are dispersed in a film having a composite scrap-like structure of clay and one bimolecule. The membrane structure can be confirmed by X-ray diffraction. Furthermore, in the film, the bilayer membrane exhibits phase transition behavior between the clay layers (the phase transition temperature is referred to as Tc), which can be confirmed by differential scanning calorimetry measurement. In this material, at low temperatures below Tc, the film assumes a lamellar crystalline state with low molecular mobility, while at high temperatures above Tc, the film assumes a smectic liquid crystalline state with high mobility.
従って、この光記録材料の紫外光照射後の熱退色反応速
度は、Ｔｃ前後付近で不連続的に大きく変化し、Ｔｃを
挟んだ４０〜５０℃の温度差をとると約１０００倍の反
応度変化となる。この反応性変化は、Ｔｃ以上＃Ｔｃ以
下の繰り返しで、可逆的であった。Therefore, the thermal fading reaction rate of this optical recording material after irradiation with ultraviolet light changes discontinuously and largely around Tc, and if a temperature difference of 40 to 50°C between Tc is taken, the reactivity increases approximately 1000 times. It becomes a change. This reactivity change was reversible by repeating Tc or more and #Tc or less.
本発明の光記録材料は、前記のような性質を有している
ので、Ｔｃ以下の温度で可視光また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り安定
に行うことができる。Since the optical recording material of the present invention has the above-mentioned properties, visible light or recording can be performed quickly at a temperature below Tc, and recording can be stably stored by keeping it at a low temperature below Tc. be able to.
・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
！！の物理的刺激により応答するものであって、記録、
読みだし、消去を任意にかつ迅速に、行いうるうえに、
記録の長期保存が可能であり、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。また
、熱応答性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。・Effects of the invention The photochromic optical recording material of the invention has two effects: light and heat.
! ! A device that responds to a physical stimulus, recording,
In addition to being able to read and erase data arbitrarily and quickly,
It enables long-term storage of records, and is suitable for use in fields such as 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. Can be used. It can also be used for applications such as thermoresponsive optical filters and toys.
・実施例
次に実施例により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
水に分散したジオクタデシルジメチルアンモニウムプロ
ミドとモンモリロナイト（おもにカチオンとしてナトリ
ウムを含む）を７０℃で混合してイオン交Ｑ７いジオク
タデシルジメチルアンモニウムとモン、Ｍ ）：ｉ−ト
ナイトの複合材料の沈澱を得、これを真空下で乾燥した
。Example 1 Dioctadecyldimethylammonium bromide dispersed in water and montmorillonite (mainly containing sodium as a cation) were mixed at 70°C to produce a composite material of diotadecyldimethylammonium and montmorillonite (Mon, M): i-tonite with ion exchange Q7. A precipitate was obtained which was dried under vacuum.
クロロホルム１−中に、上で得た複合材料５０■および
１°、１′、３’−）ジメチル−６−二トロスピ口（２
Ｈ−１−ベンゾピラン−２，２°−インドリン）０．２
３ｍｇ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．Ｏｌｍの透明なフィルムか
ら成る光記録材料を得た。この材料はＸ線回折において
二分子膜とモンモリロナイト複合のラメラに起因する４
０人の回折像が明確に観測され、また示差走査熱量測定
での昇温過程における吸熱ピークは５４℃にシャープに
観測された（エンタルピー変化ΔＨ＝ １０．４ｋｃａ
ｌ／ｍｏｌ ）。In chloroform, 50 μm and 1°, 1′, 3′-) dimethyl-6-nitrospirate (2
H-1-benzopyran-2,2°-indoline) 0.2
3 mg was dissolved and cast on a quartz plate for 3 to 4 hours at room temperature to a thickness of 0. An optical recording material consisting of a transparent film of Olm was obtained. In X-ray diffraction, this material has 4
The diffraction image of 0 person was clearly observed, and the endothermic peak during the temperature rising process in differential scanning calorimetry was observed sharply at 54 °C (enthalpy change ΔH = 10.4 kca).
l/mol).
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ー、７−５１および
３−７３を用いて紫外光および可視光を交互に照射する
と、紫外光照射時には波長５５５ｎｍにピークをもつ可
視吸収（赤〜紫色）が現れ、可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,
When ultraviolet light and visible light are alternately irradiated using colored glass filters 7-51 and 3-73 manufactured by Corning, visible absorption (red to purple) with a peak at a wavelength of 555 nm appears during ultraviolet light irradiation. Upon light irradiation, 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よりも数
十から数百分の−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わかる。The coloring after irradiation with ultraviolet light also fades due to heat, but the rate of thermal fading in the film is several tens to hundreds of times lower than that of organic solvents such as acetone, and it is clear that the spirobenzopyran compound It can be seen that the photochromic reaction of is suppressed by constraints from the film material.
この二分子膜構造を有する複合フィルムは、５４℃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、Ｔｃ以下の４５℃か
らＴｃ以下の５５℃への１０℃の温度変化で３．２Ｘ１
０−’１５６．８Ｘ１０−’／Ｓ ヘと２０倍増加した
。一方、相転移温度を外した温度領域における１０℃の
温度変化では約３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、二分子膜の相転移に起因するこ
とは明白である。この大きな退色速度変化はＴＣ以上＃
Ｔｃ以下の温度変化を繰り返しおこなっても再現性もく
認められた。Ｔｃ温度上下における大きな退色速度変化
のめたに、例えば、２５℃では７０℃に比較して約１０
００倍着色形が安定されることになる二；これに対して
、相転移挙動を示メチル中ではこの温度差で約１０倍の
安定化にすぎない。This composite film having a bilayer membrane structure exhibited a crystal-liquid crystal phase transition at 54° C., but the rate of thermal fading from coloring changed significantly above and below this temperature. The first order reaction rate constant of the main component during color fading is 3.2X1 for a 10°C temperature change from 45°C below Tc to 55°C below Tc
0-'156.8X10-'/S, an increase of 20 times. On the other hand, since a temperature change of 10° C. in a temperature range outside the phase transition temperature causes a change of only about three times, it is clear that the large speed change near Tc is caused by the phase transition of the bilayer membrane. This large change in fading speed is greater than TC#
Good reproducibility was also observed even when temperature changes below Tc were repeated. Due to the large change in fading rate above and below the Tc temperature, e.g.
In contrast, in methyl, which exhibits phase transition behavior, this temperature difference only stabilizes the colored form by a factor of about 10.
添付図面は温度の逆数に対する、−次速度定数の関係を
示すグラフ（アレニウスプロット）であり、上記記録材
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 between the -order rate constant and the reciprocal of temperature, and the recording material described above is shown as a solid line.
また、スピロベンゾピラン化合物として、下記の化合物
を用いるとＴｃ温度付近での退色速度変化の大きさは９
，５倍であり、２５℃では７０℃より１００倍の着色体
の安定化がみられた。Furthermore, when the following compound is used as a spirobenzopyran compound, the magnitude of the change in fading rate near the Tc temperature is 9
, 5 times, and the colored bodies were stabilized 100 times more at 25°C than at 70°C.
（ｃＨｄ）Ｉ？
Ｈ３
比較例
トルエンとベンゼンとの混合溶媒２蔵中に、ポリメタク
リル酸メチル１００■と、１′−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） ０．２ｇとを溶解し、これをガラ
ス板上に１１０００ｒｐでスピナーで塗布し、室温にて
３時間減圧乾燥した。(cHd)I? H3 Comparative Example In 2 volumes of a mixed solvent of toluene and benzene, 100 μm of polymethyl methacrylate and 1'-1"-3°-trimethyl-6-nitrospiro (2H-1-benzopyran-2,
2'-indoline) was dissolved and applied onto a glass plate using a spinner at 11,000 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℃の温度範囲で、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 temperature range of 30-60°C, 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を
画面に破線で示す。The Arrhenius plot for the recording material obtained in this example is shown as a dashed line on the screen.
【図面の簡単な説明】
図面は、実施例及び比較例における二分子膜−モンモリ
ロナイト複合フィルム及びポリメタクリル酸メチルフィ
ルム中でのスピロベンゾピランの着色型から無色型への
反応速度のアレニウスプロットを示すグラフである。[Brief Description of the Drawing] The drawing shows an Arrhenius plot of the reaction rate of spirobenzopyran from a colored form to a colorless form in a bilayer membrane-montmorillonite composite film and a polymethyl methacrylate film in Examples and Comparative Examples. It is a graph.
Claims (1)
を分散させて成る光記録材料において、該フィルムとし
て、直鎖状の高級アルキル基を有するカチオン性界面活
性剤とアニオン性層状粘土化合物とのイオンコンプレッ
クスより得られた粘土と二分子膜の複合層状構造を有す
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。In an optical recording material comprising spirobenzopyrans dispersed as a photochromic compound, the film is a clay obtained from an ionic complex of a cationic surfactant having a linear higher alkyl group and an anionic layered clay compound. A photochromic optical recording material characterized by using a film having a composite layered structure of a bilayer film and a bilayer film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5717488A JPH01230034A (en) | 1988-03-10 | 1988-03-10 | Photochromic optical recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5717488A JPH01230034A (en) | 1988-03-10 | 1988-03-10 | Photochromic optical recording medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01230034A true JPH01230034A (en) | 1989-09-13 |
| JPH0416776B2 JPH0416776B2 (en) | 1992-03-25 |
Family
ID=13048175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5717488A Granted JPH01230034A (en) | 1988-03-10 | 1988-03-10 | Photochromic optical recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01230034A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5474715A (en) * | 1992-09-10 | 1995-12-12 | Tdk Corporation | Photochromic material, photochromic thin film, clay thin film, and their preparation |
-
1988
- 1988-03-10 JP JP5717488A patent/JPH01230034A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5474715A (en) * | 1992-09-10 | 1995-12-12 | Tdk Corporation | Photochromic material, photochromic thin film, clay thin film, and their preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0416776B2 (en) | 1992-03-25 |
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