JPH0416776B2 - - Google Patents
Info
- Publication number
- JPH0416776B2 JPH0416776B2 JP5717488A JP5717488A JPH0416776B2 JP H0416776 B2 JPH0416776 B2 JP H0416776B2 JP 5717488 A JP5717488 A JP 5717488A JP 5717488 A JP5717488 A JP 5717488A JP H0416776 B2 JPH0416776 B2 JP H0416776B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- optical recording
- recording material
- photochromic
- spirobenzopyrans
- 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.)
- Expired
Links
- 239000000463 material Substances 0.000 claims description 31
- 230000003287 optical effect Effects 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- 239000004927 clay Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 230000008859 change Effects 0.000 description 10
- 238000005562 fading Methods 0.000 description 10
- 239000003012 bilayer membrane Substances 0.000 description 9
- 230000007704 transition Effects 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 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 5
- 229910052901 montmorillonite Inorganic materials 0.000 description 5
- 238000000034 method Methods 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
- 239000011230 binding agent Substances 0.000 description 3
- -1 cationic organic compound Chemical class 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 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
- 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
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000010365 information processing Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000010453 quartz Substances 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
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene 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
- 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
- 230000008033 biological extinction 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
- 150000001768 cations Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 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
- 230000000694 effects Effects 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
- 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
- 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
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 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
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 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)
Description
【発明の詳細な説明】
・ 産業上の利用分野
本発明は新規なフオトクロミツク系光記録材料
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ユ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イス
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、フオ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１cm2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
になつてきた。- 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, cannot be developed. Not only is it unnecessary and can be used repeatedly, it also has high resolution and, in principle, can increase the recording density by 10 times over the 100 million bits per cm2 , which is the limit of conventional recording methods. For this reason, it has recently been attracting attention from various quarters.
このようなフオトクロミツク系光記録材料に
は、フオトクロミツク性を有する化合物、いわゆ
るフオトクロミツク化合物が必要であるが、この
フオトクロミツ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。そして、これらの中でスピロベ
ンゾピラン類は、光照射前後の吸収スペクトルの
差が大きいうえに、着色体の分子吸光係数が数万
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 compounds with photochromic properties, so-called photochromic compounds. Until now, photochromic compounds such as dimethylene succinic anhydride derivatives, spirobenzopyrans, and spirooxazines have been used. , azobenzenes, etc. Among these, spirobenzopyrans have a large difference in absorption spectra before and after light irradiation, and the molecular extinction coefficient of the colored substance is in the tens of thousands, and has good coloring efficiency and high readout accuracy. These advantages make it particularly desirable as a material for optical recording materials.
しかしながら、このスピロベンゾピラン類は、
閉環型
（無色） 紫外線
――――――――→
←――――――――
可視光又は熱 開環型
（着色）
で示される形式のフオ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 exhibit photochromism in the form of ring-closed type (colorless) ultraviolet light --------→ ← --------- Visible light or heat ring-opened type (colored) However, even if it is recorded as a colored type when used as a recording material, it will return to the colorless ring-closed type due to heat, so it will take a long time to record, read, and erase. It has the disadvantage that it is not suitable for record keeping.
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
の一ないし数百分の一に抑制することができる
が、光記録材料にとつて、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 shortcomings, so far,
Attempts have been made to disperse the spirobenzopyrans in suitable binder resins such as polystyrene, polymethyl acrylate, polymethyl methacrylate, and the like. However, in this method, the thermal movement of the spiropyrans in the resin is significantly restricted, so the rate of thermal fading can be suppressed to one-tenth to one-hundredth 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。 Such quick recording, reading, erasing,
Balancing the theoretically contradictory properties of long-term preservation of records cannot be realized by using a conventionally known polymer binder and dispersing the spirobenzopyrans therein.
・ 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
もちいたフオトクロミツ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 quickly 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 .
・ 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
新規なフオトクロミツ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、フイルム状バインダーの物理状
態に変化をおこさせ、フオトクロミツク反応が進
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イル
ム中に、フオトクロミツ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
うることを見いだし、この知見に基づいて本発明
を完成するに至つた。・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 storage. As a result, it is possible to change the physical state of the film-like 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 was discovered 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, The present invention has now been completed.
すなわち、本発明は、フイルムにフオトクロミ
ツ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、該フイルムとし
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
イオンコンプレツ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イルムを用いたことを
特徴とするフオトクロミツ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 linear higher alkyl groups and an anionic layered clay. The present invention provides a photochromic optical recording material characterized by using a film having a bilayer membrane-clay composite layered structure obtained by ion complex with a compound.
以下、本発明を詳細に説明する。 The present invention will be explained in detail below.
本発明の光記録材料において、フオトクロミツ
ク化合物として用いられるスピロベンゾピラン類
は、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、R4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。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
で示されるものがある。 In the optical recording material of the present invention, spirobenzopyrans used as photochromic compounds have the general formula: (R 1 in the formula is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxyl group, an amino group, or an amino group having a substituent, R 2 is an alkyl group,
R 3 is an acyl group, R 4 is a nitro group, or a halogen atom). Such spirobenzopyrans are known and, for example, have the formula There is something indicated by .
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つて
無色の閉環型になるという、いわゆるフオトクロ
ミツク性を有している。 When these spirobenzopyrans are exposed to ultraviolet light, they convert from a colorless ring-closed form to a colored ring-opened form, and this ring-opened form changes to a colorless ring-closed form when exposed to visible light or heat. It has photochromic properties.
本発明の光記録材料においては、フイルムとし
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
イオンコンプレツクスより得られた二分子膜と粘
土の複合層状構造を有するフイルムが用いられ
る。 In the optical recording material of the present invention, the film is composed of a bilayer membrane obtained from an ionic complex of a cationic surfactant having two linear higher alkyl groups and an anionic layered clay compound, and a clay composite. A film having 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R1およびR2は、それぞれ炭素数12以
上の直鎖状アルキル基であつて、これらは同一で
あつてもよいし、互いに異なつていてもよく、
R3およびR4は、それぞれ低級アルキル基であり、
これらは同一であつてもよいし、互いに異なつて
いてもよい）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。 As the cationic surfactant residue, for example, the general formula (R 1 and R 2 in the formula are each a linear alkyl group having 12 or more carbon atoms, and these may be the same or different from each other,
R 3 and R 4 are each a lower alkyl group,
These may be the same or different from each other), but are not limited to these, and include those having two linear higher alkyl groups. If so, other structures can be used.
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、バーミキユライト、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, and beidellite, and natural or artificial ones can be used.
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ツクスは、水中または
エタノール中におけるイオン交換によつて得られ
る。また、光記録材料は、通常キヤスト法によつ
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
によつて、層状複合フイ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, this solution is cast or coated onto a support and dried. Thus, the optical recording material of the present invention is obtained, which comprises a layered composite film in which the spirobenzopyran is dispersed.
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。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ツク板などを用いることがで
きる。 At this time, the organic solvent used is, for example,
Examples include chlorine-based solvents such as chloroform and dichloroethane, various alcohols, and alkanes such as hexane and decane, with chloroform being particularly desirable. 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、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、通常該複合
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0.001〜0.1mmの範囲で選
ばれる。 Furthermore, regarding the ratio of spirobenzopyrans to the composite material of clay and bilayer membrane, the ratio of spirobenzopyrans to 100 parts by weight of the composite is usually as follows:
It is used in a proportion of 0.05 to 5 parts by weight. Further, the film thickness of the optical recording material is usually selected within the range of 0.001 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、粘土と二分子膜との複合層状構造を有するフ
イル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、該フイルム中で、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
イルムは、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
メクチツク液晶状態をとる。 The optical recording material of the present invention obtained in this way has spirobenzopyrans dispersed in a film having a composite layered structure of clay and a bilayer film, and the bilayer structure is determined by X-ray diffraction. It can be confirmed. Furthermore, in the film, the bilayer membrane exhibits phase transition behavior between the clay layers (the phase transition temperature is
Tc), which can be confirmed by differential scanning calorimetry measurements. 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, it assumes a smectic liquid crystalline state with high mobility.
従つて、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
つた。 Therefore, the thermal fading reaction rate of this optical recording material after irradiation with ultraviolet light changes significantly discontinuously around Tc, and if a temperature difference of 40 to 50°C between Tc is taken, the reaction is about 1000 times faster. The degree changes. 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以上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 above Tc, and recording can be stably stored by keeping it at a low temperature below Tc. be able to.
・ 発明の効果
本発明のフオトクロミツク系光記録材料は、光
と熱の２種の物理的刺激により応答するものであ
つて、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、超大型コンピユ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イス
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、熱応答性光フイ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 present invention responds to two types of physical stimuli, light and heat, and can record, read, and erase arbitrarily and quickly. It is possible to preserve records for a long time, 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 for It can also be used for applications such as heat-responsive 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つてなんら限定さ
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
ウムブ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
オン交換を行いジオクタデシルジメチルアンモニ
ウムとモンモリロ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 and montmorillonite (mainly containing sodium as a cation) dispersed in water were mixed at 70°C and ion exchanged to obtain a precipitate of a composite material of diotadecyldimethylammonium and montmorillonite.
This was dried under vacuum.
クロロホルム１ml中に、上で得た複合材料50mg
および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〕0.23mgを溶解し、これを石英板上に３〜４時
間かけて室温にてキヤストし、厚み0.01mmの透明
なフイ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40Å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度過程に
おける吸熱ピークは54℃にシヤープに観測された
（エンタルピー変化ΔH＝10.4kcal／mol）。 50 mg of the composite material obtained above in 1 ml of chloroform
and 0.23 mg of 1',1',3'-trimethyl-6-nitrospiro [2H-1-benzopyran-2,2'-indoline] and spread it on a quartz plate for 3 to 4 hours at room temperature. An optical recording material consisting of a transparent film with a thickness of 0.01 mm was obtained by casting. In X-ray diffraction of this material, a 40 Å diffraction image due to the lamellae of the bilayer membrane and montmorillonite composite was clearly observed, and in differential scanning calorimetry, the endothermic peak during the temperature rising process was observed to sharply rise to 54°C. (Enthalpy change ΔH = 10.4 kcal/mol).
さらに、この光記録材料は良好なフオトクロミ
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イルタ
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つた。 Furthermore, this optical recording material showed good photochromism. In other words, when the light from a 500W ultra-high pressure mercury lamp is alternately irradiated with ultraviolet light and visible light using colored glass filters manufactured by Corning, 7-51 and 3-73, the wavelength changes during ultraviolet light irradiation.
A visible absorption (red to purple) with a peak at 555 nm appeared, and the material became colorless again upon visible light irradiation.
紫外光照射後の着色は熱によつても退色する
が、フイ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一に低下してお
り、明らかに、スピロベンゾピラン化合物のフオ
トクロミツク反応はフイ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 spirobenzo It can be seen that the photochromic reaction of the pyran compound is suppressed by the constraint from the film material.
この二分子膜構造を有する複合フイルムは、54
℃において結晶−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
ｋは、Tc以下の45℃からTc以上の55℃への10℃
の温度変化で3.2×10-4／S6.8×10-3／Ｓへと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つ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1000
倍着色形が安定されることになる。これに対し
て、相移転挙動を示さない高分子バインダーであ
るポリメタクリル酸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 with bilayer structure is 54
Although it exhibits a crystal-liquid crystal phase transition at ℃, the rate of thermal fading from coloring varied greatly above and below this temperature. The first-order reaction rate constant k of the main components during color fading is 10°C from 45°C below Tc to 55°C above Tc.
It increased 20 times to 3.2×10 -4 /S6.8×10 -3 /S with a temperature change of . On the other hand, since a temperature change of 10°C 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 rate was observed with good reproducibility even when the temperature was repeatedly changed from Tc to Tc. Due to large fading rate changes above and below Tc temperature, for example, approximately 1000% at 25°C compared to 70°C.
The double colored form will be stabilized. On the other hand, in polymethyl methacrylate, which is a polymeric binder that does not exhibit phase transition behavior, this temperature difference causes approximately
It's just a 10x stabilization.
添付図面は温度の逆数に対する、一次速度定数
の関係を示すグラフ（アレニウスプロツト）であ
り、上記記録材料については実線で示されてい
る。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。 The accompanying drawing is a graph (Arrhenius plot) showing the relationship of the first-order rate constant to the reciprocal of temperature, and the recording material described above is shown as a solid line. In addition, when the following compound is used as a spirobenzopyran compound, the change in fading rate near the Tc temperature is 9.5 times larger, and at 25°C it is 9.5 times larger than at 70°C.
A 100-fold stabilization of colored bodies was observed.
比較例
トルエンとベンゼンとの混合溶媒２ml中に、ポ
リメタクリル酸メチル100mg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〕0.2mgとを溶解し、
これをガラス板上に1000rpmでスピナーで塗布
し、室温にて３時間減圧乾燥した。 Comparative Example In 2 ml of a mixed solvent of toluene and benzene, 100 mg of polymethyl methacrylate and 1',-1',-3'-trimethyl-6-nitrospiro [2H-1-benzopyran-2,2'-indoline] Dissolve 0.2mg and
This was applied onto a glass plate using a spinner at 1000 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
リル酸メチルフイルムは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
は観測されなかつた。 For this sample, 30 to 60
The fading rate was measured over a temperature range of °C. Polymethyl methacrylate film has a temperature range of 30~60℃,
No rapid fading rate change was observed since it did not exhibit phase transition behavior.
この例で得た記録材料についてのアレニウスプ
ロツトを図面に破線で示す。 The Arrhenius plot for the recording material obtained in this example is shown in the drawing by a dashed line.
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イルム及びポリメタクリ
ル酸メチルフイ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
ツトを示すグラフである。
The drawings show bilayer membranes in Examples and Comparative Examples.
1 is a graph showing an Arrhenius plot of the reaction rate of spirobenzopyran from a colored type to a colorless type in a montmorillonite composite film and a polymethyl methacrylate film.
Claims (1)
ラン類を分散させて成る光記録材料において、該
フイルムとして、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ツ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イルムを用
いたことを特徴とするフオトクロミツク系光記録
材料。 In an optical recording material comprising spirobenzopyrans dispersed as a photochromic compound, the film is 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 clay 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 JPH01230034A (en) | 1989-09-13 |
| JPH0416776B2 true 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) |
Families Citing this family (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
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01230034A (en) | 1989-09-13 |
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