JPH0529899B2 - - Google Patents
Info
- Publication number
- JPH0529899B2 JPH0529899B2 JP63126988A JP12698888A JPH0529899B2 JP H0529899 B2 JPH0529899 B2 JP H0529899B2 JP 63126988 A JP63126988 A JP 63126988A JP 12698888 A JP12698888 A JP 12698888A JP H0529899 B2 JPH0529899 B2 JP H0529899B2
- Authority
- JP
- Japan
- Prior art keywords
- phb
- group
- porphine
- guest
- tetra
- 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 - Lifetime
Links
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 27
- 125000003010 ionic group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 description 20
- 239000001307 helium Substances 0.000 description 16
- 229910052734 helium Inorganic materials 0.000 description 16
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 16
- 239000000523 sample Substances 0.000 description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- -1 cationic porphine derivatives Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical group C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 4
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000001768 cations Chemical group 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- AQPPOLXYUQPDOD-UHFFFAOYSA-N 5,10,15,20-tetraphenyl-21,22-dihydroporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C2=CC=C(N2)C(C=2C=CC=CC=2)=C2C=CC3=N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 AQPPOLXYUQPDOD-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- OWMJAQBUFVTERI-UHFFFAOYSA-N n-(2-formylphenyl)acetamide Chemical compound CC(=O)NC1=CC=CC=C1C=O OWMJAQBUFVTERI-UHFFFAOYSA-N 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 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
- G11B7/246—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 dyes
- G11B7/248—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 dyes porphines; azaporphines, e.g. phthalocyanines
Landscapes
- 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、光化学ホールバーニング現象を利用
して、同一材料の同一場所に異なる波長の光で多
量に記録可能な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 an optical recording material that can record a large amount of light of different wavelengths at the same location on the same material by utilizing the photochemical hole burning phenomenon. .
[従来の技術]
光化学ホールバーニング(PHB)現象は、液
体ヘリウム温度程度の極低温において光化学反応
を起こす材料に単色性の良い光を照射することに
より、その光を吸収するゲスト分子のみを選択的
に励起し、光化学変化を生じさせるものである。
この光化学変化により材料の吸収スペクトルに鋭
いホールが形成できることから、ホールの有無に
よりフオトンモードでの光記録が可能である。し
かも、照射する光の波長を変えて順次記録するこ
とにより、同一材料の同一場所に波長多重記録を
行うことができる。このPHB現象を利用すると、
従来用いられてきた光学式デジタル記録媒体であ
るコンパクトデイスクやレーザーデイスクなどに
比べて約1000倍の記録密度向上の可能性がある。[Conventional technology] The photochemical hole burning (PHB) phenomenon is a method in which monochromatic light is irradiated onto a material that undergoes a photochemical reaction at an extremely low temperature similar to the temperature of liquid helium, and only guest molecules that absorb the light are selectively absorbed. It excites and causes photochemical changes.
This photochemical change can form sharp holes in the material's absorption spectrum, so optical recording in photon mode is possible depending on the presence or absence of holes. Furthermore, by sequentially recording while changing the wavelength of the irradiated light, wavelength multiplexing recording can be performed at the same location on the same material. Using this PHB phenomenon,
It has the potential to improve recording density by approximately 1000 times compared to conventional optical digital recording media such as compact discs and laser discs.
このようなPHB現象を用いる光記録材料は、
光反応性化合物であるゲスト分子と、それを分散
するためのホストとから構成される。光記録に際
して波長多重度を大きくするためには、ゲストの
分散状態に多様性を持たせる意味から、ホストと
して非晶質を用いるのがよい。この目的から、従
来ホストとして、有機ポリマーが好適に用いら
れ、例えば、ゲストをテトラフエニルポルフイ
ン、ホストをポリメチルメタクリレートとする材
料(光学、14(4)263−269)が知られている。 Optical recording materials that use this PHB phenomenon are
It consists of a guest molecule, which is a photoreactive compound, and a host for dispersing it. In order to increase the wavelength multiplicity during optical recording, it is preferable to use an amorphous host as a host in order to provide diversity in the dispersion state of the guest. For this purpose, conventionally, organic polymers have been suitably used as the host; for example, materials are known in which the guest is tetraphenylporphin and the host is polymethyl methacrylate (Optics, 14 (4) 263-269). .
また、PHB材料の特性については、Thijssen
らによつて、30K以下でのホールの形成につい
て、(Chem.Phys.Lett.、92(2)7−12)、また谷ら
によつて60K以下でのホールの保存について(J.
Appl.Phys.、58(9)3559−3565)の報告がある。 Also, regarding the properties of PHB materials, please refer to Thijssen
on the formation of holes below 30K (Chem.Phys.Lett., 92(2)7-12), and on the preservation of holes below 60K by Tani et al. (J.
Appl. Phys., 58(9)3559-3565).
[本発明が解決しようとする課題]
しかしながら、従来のPHB材料は、液体ヘリ
ウム温度よりも高温になると不安定になり、記録
の書込み・保存・読出しが不確実となるという欠
点を有していた。これは、PHB材料中において
不可逆的な構造変化が熱的に誘起され、各々のゲ
スト分子周辺のミクロ構造が異なつてしまうこと
に一因がある。[Problems to be solved by the present invention] However, conventional PHB materials have the disadvantage that they become unstable at temperatures higher than the liquid helium temperature, making writing, saving, and reading of records uncertain. . One reason for this is that irreversible structural changes are thermally induced in the PHB material, resulting in different microstructures around each guest molecule.
また、従来のPHB材料では、液体チツ素温度
でのホール形成が不可能であつた。そのため、冷
却コストが大幅に低減されるといつた実用の上で
重要なメリツトを有する液体チツ素温度でのホー
ル形成が可能なPHB材料が望まれていた。 Furthermore, with conventional PHB materials, it has been impossible to form holes at the temperature of liquid nitrogen. Therefore, there has been a desire for a PHB material that can form holes at the temperature of liquid nitrogen, which has important practical advantages such as a significant reduction in cooling costs.
本発明は、かかる従来技術の欠点を解消しよう
とするものであり、熱的な不可逆変化を抑え、熱
的に安定な記録材料、さらには、液体チツ素温度
においてもホール形成を期待し得る光記録材料を
提供することを目的とする。 The present invention aims to eliminate the drawbacks of the prior art, and aims to provide a recording material that suppresses irreversible thermal changes and is thermally stable, and furthermore, an optical material that can be expected to form holes even at the temperature of liquid nitrogen. The purpose is to provide recording materials.
[課題を解決するための手段]
上記目的を達成するために、本発明は下記の構
成を有する。[Means for Solving the Problems] In order to achieve the above object, the present invention has the following configuration.
「ゲスト成分とホスト成分を主成分としてなる
組成物であつて、
(イ) ゲスト成分が、下記一般式[A]で示される
イオン性基を有するポルフイン誘導体であり、
(ロ) ホスト成分が、上記のゲスト成分と相溶する
有機ポリマである
ことを特徴とするポルフイン系PHB記録材料。 "A composition comprising a guest component and a host component as main components, wherein (a) the guest component is a porphyne derivative having an ionic group represented by the following general formula [A], and (b) the host component is A porphine-based PHB recording material characterized by being an organic polymer that is compatible with the above guest component.
(式中、X1、X2、X3、X4から選ばれる少なくと
も1つは、イオン性基を有するアリール基、また
は炭素数1〜6のアルキル基を有するイオン性ヘ
テロ環基であり、その他は、水素原子または非イ
オン性基である。)」
すなわち、従来のポルフイン系ゲストを用いた
記録材料と比べ、イオン性基を有するポルフイン
誘導体と有機ポリマとからなる材料の場合には、
前者の有する電荷に基づく相互作用のためにゲス
ト・ホスト間の親和性がよく、したがつて、昇温
時の不可逆的な構造変化が少なくなると推定され
る。この結果、材料の吸収スペクトルに形成され
たホールの半値幅の増大が抑制され、記録の熱安
定性が向上する。 (In the formula, at least one selected from X 1 , X 2 , X 3 , and X 4 is an aryl group having an ionic group or an ionic heterocyclic group having an alkyl group having 1 to 6 carbon atoms, (Others are hydrogen atoms or nonionic groups.)" In other words, compared to recording materials using conventional porphin-based guests, in the case of materials made of porphin derivatives having ionic groups and organic polymers,
It is presumed that the affinity between the guest and host is good due to the interaction based on the charge of the former, and therefore irreversible structural changes occur less when the temperature is increased. As a result, an increase in the half width of a hole formed in the absorption spectrum of the material is suppressed, and the thermal stability of recording is improved.
本発明においては、X1、X2、X3、X4から選ば
れる少なくとも1つは、イオン性基を有するアリ
ール基、または炭素数1〜6のアルキル基を有す
るイオン性ヘテロ環基であり、それ以外のX1〜
X4は水素原子または非イオン性基である。 In the present invention, at least one selected from X 1 , X 2 , X 3 , and X 4 is an aryl group having an ionic group or an ionic heterocyclic group having an alkyl group having 1 to 6 carbon atoms. , otherwise X 1 ~
X 4 is a hydrogen atom or a nonionic group.
ゲスト成分の有するイオン性基は、カチオン性
基、アニオン性基、両性イオン性基のいずれであ
つてもよい。 The ionic group that the guest component has may be any of a cationic group, anionic group, and amphoteric ionic group.
カチオン性基としては、4級アミノ基やN−ア
ルキルピリジニウム基などが好ましく用いられ
る。ホスト中で安定に電離状態を保つからであ
る。特に好ましくは、一般式[B]
(ただし、式中R1〜R12はアルキル基である。)
で表される5,10,15,20−テトラ(4−N,
N,N−トリアルキルアミノフエニル)ポルフイ
ン、または、一般式[C]
(ただし、式中R13〜R16は炭素数1〜6のアル
キル基である。)で表される5,10,15,20−テ
トラ(4−N−アルキルピリジニウム)ポルフイ
ンが用いられる。これは、一般式[B]のポルフ
イン誘導体においてはポルフイン環と4級アミノ
基がフエニル基により隔てられていることから、
また一般式[C]のポルフイン誘導体においては
ピリジニウム基の電荷が共役系に分散することか
ら、カチオン部の影響がポルフイン環の光化学反
応性に及びにくいからである。一般式[B]の1
〜R12、および、一般式[C]のR13〜R16で表さ
れたアルキル基はメチル基であることが更に好ま
しい。これは、メチル基が最も構造がコンパクト
であり、ホストに分散したときの運動の自由度が
小さく、低温で不可逆的構造変化を起こすことが
少ないと推定されるからである。 As the cationic group, a quaternary amino group, an N-alkylpyridinium group, etc. are preferably used. This is because it maintains a stable ionized state in the host. Particularly preferably, general formula [B] (However, in the formula, R 1 to R 12 are alkyl groups.) 5,10,15,20-tetra(4-N,
N,N-trialkylaminophenyl)porphine or general formula [C] (However, in the formula, R 13 to R 16 are alkyl groups having 1 to 6 carbon atoms.) 5,10,15,20-tetra(4-N-alkylpyridinium)porphine is used. This is because in the porphine derivative of general formula [B], the porphine ring and the quaternary amino group are separated by a phenyl group.
Further, in the porphine derivative of general formula [C], the charge of the pyridinium group is dispersed in the conjugated system, so that the photochemical reactivity of the porphine ring is hardly influenced by the cation moiety. General formula [B] 1
It is more preferable that ~R 12 and the alkyl group represented by R 13 to R 16 in general formula [C] are methyl groups. This is because the methyl group has the most compact structure, has a small degree of freedom of movement when dispersed in the host, and is presumed to be less likely to undergo irreversible structural changes at low temperatures.
これらのカチオン性ポルフイン誘導体は材料中
では適当なアニオンとともに存在する。アニオン
の選択はホスト成分との相溶性の観点からなされ
るべきものであるが、p−トルエンスルフオネー
トイオン、I-、Br-、Cl-、ClO4 -、CH3CO2 -、
BF4 -などが好ましく用いられる。 These cationic porphine derivatives are present in the material together with appropriate anions. The anion should be selected from the viewpoint of compatibility with the host component, but p-toluenesulfonate ion, I - , Br - , Cl - , ClO 4 - , CH 3 CO 2 - ,
BF 4 - etc. are preferably used.
5,10,15,20−テトラ(4−N,N,N−ト
リアルキルアミノフエニル)ポリフインは、アセ
トアミノベンズアルデヒドとピロールから合成し
た5,10,15,20−テトラ(4−アセトアミノフ
エニル)ポルフインを酸で加水分解した後、ヨウ
化アルキルなどの4級化剤と反応させて得られ
る。また、5,10,15,20−テトラ(4−N−ア
ルキルピリジニウム)ポルフインは、5,10,
15,20−テトラ(4−N−ピリジル)ポルフイン
をヨウ化アルキルなどの4級化剤で4級化して得
られる。 5,10,15,20-tetra(4-N,N,N-trialkylaminophenyl)polyphine is a 5,10,15,20-tetra(4-acetaminophenyl) polyphine synthesized from acetaminobenzaldehyde and pyrrole. It is obtained by hydrolyzing (enyl)porphine with an acid and then reacting it with a quaternizing agent such as an alkyl iodide. In addition, 5,10,15,20-tetra(4-N-alkylpyridinium)porphine is 5,10,
It is obtained by quaternizing 15,20-tetra(4-N-pyridyl)porphine with a quaternizing agent such as alkyl iodide.
アニオン性基としては、SO3 -基、CO2 -基、O-
基などが好ましく用いられる。ホスト中で安定に
電離状態を保つからである。また、一般式[D]
(ただし、式中R17〜R20はアニオン性基であ
る。)で表されるポルフイン誘導体が好ましく用
いられる。これは、一般式[D]のポルフイン誘
導体においては、ポルフイン環とアニオン性基が
フエニル基により隔てられていることから、アニ
オン部の影響がポルフイン環の光化学反応性に及
びにくいからである。 Examples of anionic groups include SO 3 - group, CO 2 - group, O -
and the like are preferably used. This is because it maintains a stable ionized state in the host. Also, general formula [D] (However, in the formula, R 17 to R 20 are anionic groups.) Porphine derivatives represented by the following are preferably used. This is because, in the porphine derivative of general formula [D], the porphine ring and the anionic group are separated by the phenyl group, so that the anion moiety is less likely to affect the photochemical reactivity of the porphine ring.
このアニオン性基を有するポルフイン誘導体は
材料中では適当なカチオンとともに存在する。カ
チオンの選択はホスト成分との相溶性の観点から
なされるべきものであるが、アルカリ金属イオ
ン、水素イオン、アルカリ土類金属イオン、アン
モニウムイオンが好ましく用いられる。 This porphine derivative having an anionic group is present in the material together with a suitable cation. The cation should be selected from the viewpoint of compatibility with the host component, and alkali metal ions, hydrogen ions, alkaline earth metal ions, and ammonium ions are preferably used.
また、一般式[D]で示されるアニオン性基を
有するポルフイン誘導体は、5,10,15,20−テ
トラフエニルポルフインを多塩基酸と反応させる
か、または、アニオン性基となりうる基を有する
ベンズアルデヒド誘導体とピロールとから合成し
た前駆体から得られる。 In addition, the porphine derivative having an anionic group represented by the general formula [D] can be obtained by reacting 5,10,15,20-tetraphenylporphin with a polybasic acid or by reacting a group that can become an anionic group. It is obtained from a precursor synthesized from a benzaldehyde derivative and pyrrole.
両性イオン性基を有するポルフイン誘導体とし
ては、テトラ[3−(N−スルフオナトアルキル
−N−アルキルアミノ)フエニル]ポルフイン、
テトラ[3−(N−カルボナトアルキル−N−ア
ルキルアミノ)フエニル]ポルフイン、テトラ
[4−(N−スルフオナトアルキル)ピリジニウ
ム]ポルフイン、テトラ[4−(N−カルボナト
アルキル)ピリジニウム]ポルフインなどが好ま
しく用いられる。 Examples of porphin derivatives having a zwitterionic group include tetra[3-(N-sulfonatoalkyl-N-alkylamino)phenyl]porphin,
Tetra[3-(N-carbonatoalkyl-N-alkylamino)phenyl]porphine, Tetra[4-(N-sulfonatoalkyl)pyridinium]porphine, Tetra[4-(N-carbonatoalkyl)pyridinium]porphine etc. are preferably used.
本発明における有機ポリマとしては、ゲスト成
分であるイオン性基を有するポルフイン誘導体と
相溶するものであればよいが、ポリエチレンオキ
サイド、ポリビニルピリジン、ポリビニルピロリ
ドン、ポリヒドロキシエチルメタクリレート、ポ
リメタクリル酸、ポリアクリル酸、ポリメタクリ
ルアミド、ポリアクリルアミド、セルロースアセ
テート、ポリビニルスルホン酸ナトリウムなどの
水溶性ポリマが好ましく用いられるが、特に好ま
しくは、ポリビニルアルコール、または、ポリス
チレンスルホン酸ナトリウムが用いられる。ゲス
ト成分であるイオン性基を有するポルフイン誘導
体は極性溶媒に可溶であるので、これらの水溶性
ポリマとも相溶し、分散が容易だからである。特
に、ポリビニルアルコールは強い水素結合性を有
するので低温において熱的な構造変化を起こしに
くいと推定されること、また、ポリスチレンスル
ホン酸ナトリウムは側鎖にベンゼン環を有するの
でゲストであるポルフイン誘導体との親和性がた
かいことから、ホスト成分としては最も好まし
い。 The organic polymer used in the present invention may be one that is compatible with the porphyne derivative having an ionic group as a guest component, such as polyethylene oxide, polyvinylpyridine, polyvinylpyrrolidone, polyhydroxyethyl methacrylate, polymethacrylic acid, polyacrylic acid, etc. Water-soluble polymers such as acid, polymethacrylamide, polyacrylamide, cellulose acetate, and sodium polyvinylsulfonate are preferably used, and particularly preferably, polyvinyl alcohol or sodium polystyrenesulfonate is used. This is because the porphine derivative having an ionic group, which is a guest component, is soluble in a polar solvent, so it is compatible with these water-soluble polymers and can be easily dispersed. In particular, polyvinyl alcohol has strong hydrogen bonding properties, so it is estimated that it is unlikely to undergo thermal structural changes at low temperatures.Also, sodium polystyrene sulfonate has a benzene ring in its side chain, so it is difficult to interact with the guest porphin derivative. It is most preferred as a host component because of its high affinity.
本発明の光記録材料中におけるゲスト成分の濃
度は、これが高すぎるとゲスト分子間でのエネル
ギ移動によりホール生成特性が劣化し、また、低
すぎると記録読取時のS/Nが小さくなることか
ら制限を受ける。したがつて、好ましいゲスト濃
度はホストである有機ポリマの体積を基準として
10-1〜10-5Mであり、特に、10-2〜10-4Mである
ことが好ましい。 If the concentration of the guest component in the optical recording material of the present invention is too high, hole generation characteristics will deteriorate due to energy transfer between guest molecules, and if it is too low, the S/N during recording and reading will decrease. subject to restrictions. Therefore, the preferred guest concentration is based on the volume of the host organic polymer.
10 -1 to 10 -5 M, particularly preferably 10 -2 to 10 -4 M.
また、本発明の記録材料には、イオン性基を有
するポルフイン誘導体の吸収帯に重なる吸収帯を
もたない安定剤などの添加物を加えてもよいが、
ゲスト成分とホスト成分が主成分として、全体の
95%以上含まれていることが好ましい。これは、
添加物によつて、ホスト・ゲスト間の相互作用が
損なわれないようにするためである。 Furthermore, additives such as stabilizers that do not have an absorption band that overlaps with the absorption band of the porphine derivative having an ionic group may be added to the recording material of the present invention;
The guest component and host component are the main components, and the total
It is preferable that the content is 95% or more. this is,
This is to prevent the interaction between host and guest from being impaired by the additive.
[実施例]
以下に、実施例に基づいてさらに詳細に説明す
るが、本発明はこれに限定されるものではない。[Example] The present invention will be described in more detail based on Examples below, but the present invention is not limited thereto.
実施例 1
ポリビニルアルコール(重合度=2000、鹸化度
=100%)10gを蒸留水100mlに溶解させた後、
5,10,15,20−テトラ(4−N,N,N−トリ
メチルアミノフエニル)ポルフインテトラ(p−
トルエンスルフオネート)(同仁化学研究所製)
0.13gを加えた。この溶液をシヤーレ中で乾燥さ
せて、ゲスト濃度10-2M、厚さ0.5mmのフイルム
を得た。このフイルムを液体ヘリウム温度まで冷
却後、波長646nm、強度1mW/cm2のレーザー
光を1分間照射してPHBホールを形成した。こ
の後、フイルムを所定の温度まで昇温し、再び液
体ヘリウム温度まで冷却してPHBホールの半値
幅を測定した。Example 1 After dissolving 10 g of polyvinyl alcohol (degree of polymerization = 2000, degree of saponification = 100%) in 100 ml of distilled water,
5,10,15,20-tetra(4-N,N,N-trimethylaminophenyl)porphinetetra(p-
toluene sulfonate) (manufactured by Dojindo Laboratories)
Added 0.13g. This solution was dried in a shear dish to obtain a film with a guest concentration of 10 -2 M and a thickness of 0.5 mm. After cooling the film to liquid helium temperature, it was irradiated with a laser beam having a wavelength of 646 nm and an intensity of 1 mW/cm 2 for 1 minute to form PHB holes. After this, the film was heated to a predetermined temperature, cooled again to liquid helium temperature, and the half-value width of the PHB hole was measured.
実施例 2
ポリビニルアルコール(重合度=2000、鹸化度
=100%)10gを蒸留水100mlに溶解させた後、
5,10,15,20−テトラ(4−N−メチルピリジ
ニウム)ポルフインテトラアイオダイド(和光純
薬製)0.1gを加えた。この溶液をシヤーレ中で
乾燥させて、ゲスト濃度10-2M、厚さ0.5mmのフ
イルムを得た。このフイルムを液体ヘリウム温度
まで冷却後、波長646nm、強度1mW/cm2のレ
ーザー光を1分間照射してPHBホールを形成し
た。この後、フイルムを所定の温度まで昇温し、
再び液体ヘリウム温度まで冷却してPHBホール
の半値幅を測定した。Example 2 After dissolving 10 g of polyvinyl alcohol (degree of polymerization = 2000, degree of saponification = 100%) in 100 ml of distilled water,
0.1 g of 5,10,15,20-tetra(4-N-methylpyridinium)porphine tetraiodide (manufactured by Wako Pure Chemical Industries, Ltd.) was added. This solution was dried in a shear dish to obtain a film with a guest concentration of 10 -2 M and a thickness of 0.5 mm. After cooling the film to liquid helium temperature, it was irradiated with a laser beam having a wavelength of 646 nm and an intensity of 1 mW/cm 2 for 1 minute to form PHB holes. After this, the film is heated to a predetermined temperature,
After cooling to liquid helium temperature again, the half width of the PHB hole was measured.
比較例 1
アイソタクテイツクポリメチルメタクリレート
(分子量=400000)10gをトルエン120mlを溶解さ
せた後、テトラフエニルポルフイン0.05gを加え
た。この溶液をシヤーレ中で乾燥させることによ
り、ゲスト濃度10-2M、厚さ0.5mmのフイルムを
作り、これを対照試料とした。上と同様にして液
体ヘリウム温度でPHBホールを形成した後、フ
イルムを所定の温度まで昇温、再び液体ヘリウム
温度まで冷却してPHBホールの半値幅を測定し
た。Comparative Example 1 After dissolving 10 g of isotactic polymethyl methacrylate (molecular weight = 400,000) in 120 ml of toluene, 0.05 g of tetraphenylporphine was added. By drying this solution in a shear dish, a film with a guest concentration of 10 -2 M and a thickness of 0.5 mm was prepared, which was used as a control sample. After forming PHB holes at liquid helium temperature in the same manner as above, the film was heated to a predetermined temperature, cooled again to liquid helium temperature, and the half-width of the PHB holes was measured.
第1図は、レーザー光を照射した直後のPHB
ホールの半値幅(〓0)と、昇温、再冷却後の半
値幅(〓)との差を昇温温度に対して図示したも
のである。5,10,15,20−テトラ(4−N,
N,N−トリメチルアミノフエニル)ポルフイン
テトラ(p−トルエンスルフオネート)をポリビ
ニルアルコールに分散させた実施例1の試料を用
いた場合を●で、5,10,15,20−テトラ(4−
N−メチルピリジニウム)ポルフインテトラアイ
オダイドをポリビニルアルコールに分散させた実
施例2の試料を用いた場合を○で、テトラフエニ
ルポルフインをアイソタクテイツクポリメチルメ
タクリレートに分散させた比較例1の試料を用い
た場合を×で、それぞれ示した。実施例1および
実施例2の試料の方が昇温、再冷却後のPHBホ
ールの半値幅の増大が少なく、熱安定性に優れて
いることが分かる。 Figure 1 shows the PHB immediately after being irradiated with laser light.
The difference between the half-width of a hole (〓 0 ) and the half-width after heating and recooling (〓) is illustrated as a function of the heating temperature. 5,10,15,20-tetra (4-N,
When using the sample of Example 1 in which N,N-trimethylaminophenyl)porphinetetra(p-toluenesulfonate) was dispersed in polyvinyl alcohol, ● indicates that 5,10,15,20-tetra(p-toluenesulfonate) was dispersed in polyvinyl alcohol. 4-
N-Methylpyridinium) porphine The sample of Example 2 in which tetraiodide was dispersed in polyvinyl alcohol was used, and the sample in Comparative Example 1 in which tetraphenylporphine was dispersed in isotactic polymethyl methacrylate was ○. Cases in which samples were used are indicated with an x. It can be seen that the samples of Examples 1 and 2 show less increase in the half width of PHB holes after heating and recooling, and have superior thermal stability.
実施例 3
還流したプロピオン酸中で4−カルボキシベン
ズアルデヒド30gとピロール13.4gを反応させ
て、5,10,15,20−テトラ(4−カルボキシフ
エニル)ポルフイン6.9gを得た。ポリビニルア
ルコール(重合度=2000、鹸化度=100%)10g
を蒸留水200mlとメタノール300mlの混合溶媒に溶
解させた後、5,10,15,20−テトラ(4−カル
ボキシフエニル)ポルフイン0.066gを加えた。
この溶液をシヤーレ中で乾燥させて、ゲスト濃度
10-2M、厚さ0.5mmのフイルムを得た。このフイ
ルムを液体ヘリウム温度まで冷却後、波長645n
m、強度1mW/cm2のレーザー光を30秒間照射し
てPHBホールを形成した。この後、フイルムを
所定の温度まで昇温し、再び液体ヘリウム温度ま
で冷却してPHBホールの半値幅を測定した。Example 3 30 g of 4-carboxybenzaldehyde and 13.4 g of pyrrole were reacted in refluxed propionic acid to obtain 6.9 g of 5,10,15,20-tetra(4-carboxyphenyl)porphine. Polyvinyl alcohol (degree of polymerization = 2000, degree of saponification = 100%) 10g
was dissolved in a mixed solvent of 200 ml of distilled water and 300 ml of methanol, and then 0.066 g of 5,10,15,20-tetra(4-carboxyphenyl)porphine was added.
This solution was dried in a shear dish to determine the guest concentration.
A film of 10 -2 M and a thickness of 0.5 mm was obtained. After cooling this film to liquid helium temperature, the wavelength is 645n.
PHB holes were formed by irradiating laser light with an intensity of 1 mW/cm 2 for 30 seconds. After this, the film was heated to a predetermined temperature, cooled again to liquid helium temperature, and the half-value width of the PHB hole was measured.
実施例 4
ポリスチレンスルホン酸ナトリウム10gを蒸留
水100mlに溶解させた後、5,10,15,20−テト
ラ(4−N−メチルピリジニウム)ポルフインテ
トラアイオダイド(和光純薬製)0.1gを加えた。
この溶液をシヤーレ中で乾燥させて、ゲスト濃度
10-2M、厚さ0.5mmのフイルムを得た。このフイ
ルムを液体ヘリウム温度まで冷却後、波長645n
m、強度1mW/cm2のレーザー光を30秒間照射し
てPHBホールを形成した。この後、フイルムを
所定の温度まで昇温し、再び液体ヘリウム温度ま
で冷却してPHBホールの半値幅を測定した。Example 4 After dissolving 10 g of sodium polystyrene sulfonate in 100 ml of distilled water, 0.1 g of 5,10,15,20-tetra(4-N-methylpyridinium)porphine tetraiodide (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Ta.
This solution was dried in a shear dish to determine the guest concentration.
A film of 10 -2 M and a thickness of 0.5 mm was obtained. After cooling this film to liquid helium temperature, the wavelength is 645n.
PHB holes were formed by irradiating laser light with an intensity of 1 mW/cm 2 for 30 seconds. After this, the film was heated to a predetermined temperature, cooled again to liquid helium temperature, and the half-value width of the PHB hole was measured.
第2図は、レーザー光を照射した直後のPHB
ホールの半値幅(〓0)と、昇温、再冷却後の半
値幅(〓)との差を昇温温度に対して図示したも
のである。5,10,15,20−テトラ(4−カルボ
キシフエニル)ポルフインをポリビニルアルコー
ルに分散させた実施例3の試料を用いた場合を●
で、5,10,15,20−テトラ(4−N−メチルピ
リジニウム)ポルフインテトラアイオダイドをポ
リスチレンスルホン酸ナトリウムに分散させた実
施例4の試料を用いた場合を○で、テトラフエニ
ルポルフインをアイソタクテイツクポリメチルメ
タクリレートに分散させた比較例1の試料を用い
た場合を×でそれぞれ示した。実施例3および実
施例4の試料の方が昇温、再冷却後のPHBホー
ルの半値幅の増大が少なく、熱安定性に優れてい
ることが分かる。 Figure 2 shows the PHB immediately after being irradiated with laser light.
The difference between the half-width of a hole (〓 0 ) and the half-width after heating and recooling (〓) is illustrated as a function of the heating temperature. When using the sample of Example 3 in which 5,10,15,20-tetra(4-carboxyphenyl)porphine was dispersed in polyvinyl alcohol, ●
○ indicates the case where the sample of Example 4 in which 5,10,15,20-tetra(4-N-methylpyridinium)porphine tetraiodide was dispersed in sodium polystyrene sulfonate is used; The cases in which the sample of Comparative Example 1 in which ink was dispersed in isotactic polymethyl methacrylate were used are indicated by x. It can be seen that the samples of Examples 3 and 4 show less increase in the half width of PHB holes after heating and recooling, and have superior thermal stability.
実施例 5
ポリビニルアルコール(重合度=2000、鹸化度
=100%)10gを蒸留水100mlに溶解させた後、テ
トラソデイウム5,10,15,20−テトラ(4−ス
ルフオナトフエニル)ポルフイン12水和物0.1g
を加えた。この溶液をシヤーレ中で乾燥させて、
ゲスト濃度10-2M、厚さ0.5mmのフイルムを得た。
このフイルムを液体ヘリウム温度まで冷却後、波
長646nm、強度1mW/cm2のレーザー光を1分
間照射してPHBホールを形成した。この後、フ
イルムを所定の温度まで昇温し、再び液体ヘリウ
ム温度まで冷却してPHBホールの半値幅を測定
した。Example 5 After dissolving 10 g of polyvinyl alcohol (degree of polymerization = 2000, degree of saponification = 100%) in 100 ml of distilled water, tetrasodium 5,10,15,20-tetra(4-sulfonatophenyl)porphin dodecahydrate was prepared. 0.1g of material
added. Dry this solution in a shear dish,
A film with a guest concentration of 10 -2 M and a thickness of 0.5 mm was obtained.
After cooling the film to liquid helium temperature, it was irradiated with a laser beam having a wavelength of 646 nm and an intensity of 1 mW/cm 2 for 1 minute to form PHB holes. After this, the film was heated to a predetermined temperature, cooled again to liquid helium temperature, and the half-value width of the PHB hole was measured.
実施例 6
実施例3で合成した5,10,15,20−テトラ
(4−カルボキシフエニル)ポルフインに、4当
量の水酸化ナトリウムを含む水溶液を反応させて
テトラソデイウム5,10,15,20−テトラ(4−
カルボナトフエニル)ポルフインを得た。ポリビ
ニルアルコール(重合度=2000、鹸化度=100%)
10gを蒸留水100mlに溶解させた後、テトラソデ
イウム5,10,15,20−テトラ(4−カルボナト
フエニル)ポルフイン0.07gを加えた。この溶液
をシヤーレ中で乾燥させて、厚さ0.5mmのフイル
ムを得た。このフイルムを液体ヘリウム温度まで
冷却後、波長646nm、強度1mW/cm2のレーザ
ー光を1分間照射してPHBホールを形成した。
この後、フイルムを所定の温度まで昇温し、再び
液体ヘリウム温度まで冷却してPHBホールの半
値幅を測定した。Example 6 Tetrasodium 5,10,15,20- Tetra (4-
Carbonatophenyl) porphin was obtained. Polyvinyl alcohol (degree of polymerization = 2000, degree of saponification = 100%)
After dissolving 10 g in 100 ml of distilled water, 0.07 g of tetrasodium 5,10,15,20-tetra(4-carbonatophenyl)porphine was added. This solution was dried in a shear dish to obtain a film with a thickness of 0.5 mm. After cooling the film to liquid helium temperature, it was irradiated with a laser beam having a wavelength of 646 nm and an intensity of 1 mW/cm 2 for 1 minute to form PHB holes.
After this, the film was heated to a predetermined temperature, cooled again to liquid helium temperature, and the half-value width of the PHB hole was measured.
第3図は、レーザー光を照射した直後のPHB
ホールの半値幅(〓0)と、昇温、再冷却後の半
値幅(〓)との差を昇温温度に対して図示したも
のである。5,10,15,20−テトラ(4−スルフ
オナトフエニル)ポルフインをポリビニルアルコ
ールに分散させた実施例5の試料を用いた場合を
●で、テトラソデイウム5,10,15,20−テトラ
(4−カルボナトフエニル)ポルフインをポリビ
ニルアルコールに分散させた実施例4の試料を用
いた場合を○で、テトラフエニルポルフインをア
イソタクテイツクポリメチルメタクリレートに分
散させた比較例1の試料を用いた場合を×で、そ
れぞれ示した。実施例5および実施例6の試料の
方が昇温、再冷却後のPHBホールの半値幅の増
大が少なく、熱安定性に優れていることが分か
る。 Figure 3 shows the PHB immediately after being irradiated with laser light.
The difference between the half-width of a hole (〓 0 ) and the half-width after heating and recooling (〓) is illustrated as a function of the heating temperature. ● indicates the case where the sample of Example 5 in which 5,10,15,20-tetra(4-sulfonatophenyl)porphin was dispersed in polyvinyl alcohol is used. - The sample of Example 4 in which carbonatophenylporphine was dispersed in polyvinyl alcohol was used, and the sample of Comparative Example 1 in which tetraphenylporphine was dispersed in isotactic polymethyl methacrylate was used. Each case is indicated by ×. It can be seen that the samples of Examples 5 and 6 show less increase in half width of PHB holes after heating and recooling, and have superior thermal stability.
実施例 7
実施例5と同じ試料について、種々の試料温度
でレーザー光を照射してPHBホールを形成し、
ホール半値幅を測定した。Example 7 The same sample as in Example 5 was irradiated with laser light at various sample temperatures to form PHB holes,
The half width of the hole was measured.
実施例 8
実施例6と同じ試料について、種々の試料温度
でレーザー光を照射してPHBホールを形成し、
ホール半値幅を測定した。Example 8 The same sample as in Example 6 was irradiated with laser light at various sample temperatures to form PHB holes,
The half width of the hole was measured.
第4図に、実施例7と実施例8の試料につい
て、試料温度と生成したホールの半値幅の関係
を、それぞれ●と○で示す。実施例7では80Kで
も、実施例8では110Kでもホールを形成するこ
とができた。 FIG. 4 shows the relationship between the sample temperature and the half-width of the generated holes for the samples of Examples 7 and 8 with ● and ◯, respectively. In Example 7, holes could be formed even at 80K, and in Example 8, holes could be formed even at 110K.
実施例 9
ポリスチレンスルホン酸ナトリウム10gを蒸留
水100mlに溶解させた後、5,10,15,20−テト
ラ(4−N−メチルピリジニウム)ポルフインテ
トラアイオダイド(和光純薬製)0.01gを加え
た。この溶液をシヤーレ中で乾燥させて、ゲスト
濃度10-3M、厚さ0.5mmのフイルムを得た。この
フイルムを30Kまで冷却後、波長646nmのレーザ
ー光を照射することにより、PHBホールを形成
することができた。Example 9 After dissolving 10 g of sodium polystyrene sulfonate in 100 ml of distilled water, 0.01 g of 5,10,15,20-tetra(4-N-methylpyridinium)porphine tetraiodide (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Ta. This solution was dried in a shear dish to obtain a film with a guest concentration of 10 -3 M and a thickness of 0.5 mm. After cooling this film to 30K, we were able to form PHB holes by irradiating it with laser light with a wavelength of 646 nm.
実施例 10
ポリビニルアルコール(重合度=2000、鹸化度
=100%)10gを蒸留水100mlに溶解させた後、テ
トラソデイウム5,10,15,20−テトラ(4−ス
ルフオナトフエニル)ポルフイン12水和物(和光
純薬製)0.001gを加えた。この溶液をシヤーレ
中で乾燥させて、ゲスト濃度10-4M、厚さ0.5mm
のフイルムを得た。このフイルムを40Kまで冷却
後、波長646nmのレーザー光を照射することに
より、PHBホールを形成することができた。Example 10 After dissolving 10 g of polyvinyl alcohol (degree of polymerization = 2000, degree of saponification = 100%) in 100 ml of distilled water, tetrasodium 5,10,15,20-tetra(4-sulfonatophenyl)porphin dodecahydrate was prepared. (manufactured by Wako Pure Chemical Industries, Ltd.) 0.001 g was added. The solution was dried in a shear dish to a guest concentration of 10 -4 M and a thickness of 0.5 mm.
I got this film. After cooling this film to 40K, we were able to form PHB holes by irradiating it with laser light with a wavelength of 646 nm.
[本発明の効果]
本発明のポルフイン系PHB記録材料は、従来
の光記録材料に比べて、熱安定性が増大し、昇温
後のホール回復率が高い。[Effects of the Present Invention] The porphine-based PHB recording material of the present invention has increased thermal stability and a high hole recovery rate after temperature rise, compared to conventional optical recording materials.
さらに、従来ホール形成が不可能であつた液体
チツ素温度においても、ホール形成が可能となつ
た。 Furthermore, it has become possible to form holes even at liquid nitrogen temperatures, which were conventionally impossible.
第1図は、実施例1、実施例2、比較例1につ
いて、昇温、再冷却後のPHBホールの半値幅の
増加量を図示したものである。実施例1の結果を
●、実施例2の結果を○、比較例1の結果を×で
示した。第2図は、実施例3、実施例4、比較例
1について、昇温、再冷却後のPHBホールの半
値幅の増加量を図示したものである。実施例3の
結果を●、実施例4の結果を○、比較例1の結果
を×で示した。第3図は、実施例5、実施例6、
比較例1について、昇温、再冷却後のPHBホー
ルの半値幅の増加量を図示したものである。実施
例5の結果を●、実施例6の結果を○、比較例1
の結果を×で示した。第4図は、実施例7、実施
例8について、試料温度とPHBホールの半値幅
の関係を図示したものである。実施例7の結果を
●、実施例8の結果を○で示した。
FIG. 1 illustrates the amount of increase in the half width of the PHB hole after heating and recooling for Example 1, Example 2, and Comparative Example 1. The results of Example 1 are indicated by ●, the results of Example 2 are indicated by ○, and the results of Comparative Example 1 are indicated by ×. FIG. 2 illustrates the amount of increase in the half-width of the PHB hole after heating and recooling for Example 3, Example 4, and Comparative Example 1. The results of Example 3 are indicated by ●, the results of Example 4 are indicated by ○, and the results of Comparative Example 1 are indicated by ×. FIG. 3 shows Example 5, Example 6,
4 is a diagram illustrating the amount of increase in the half-width of PHB holes after heating and recooling for Comparative Example 1. The results of Example 5 are ●, the results of Example 6 are ○, and Comparative Example 1
The results are indicated by ×. FIG. 4 illustrates the relationship between the sample temperature and the half width of the PHB hole for Examples 7 and 8. The results of Example 7 are shown by ●, and the results of Example 8 are shown by ○.
Claims (1)
組成物であつて、 (イ) ゲスト成分が、下記一般式[A]で示される
イオン性基を有するポルフイン誘導体であり、 (ロ) ホスト成分が、上記のゲスト成分と相溶する
有機ポリマである ことを特徴とするポルフイン系PHB記録材料。 (式中、X1、X2、X3、X4から選ばれる少なくと
も1つは、イオン性基を有するアリール基または
炭素数1〜6のアルキル基を有するイオン性ヘテ
ロ環基であり、その他は、水素原子または非イオ
ン性基である。)[Scope of Claims] 1. A composition comprising a guest component and a host component as main components, wherein (a) the guest component is a porphyne derivative having an ionic group represented by the following general formula [A], ( b) A porphine-based PHB recording material, characterized in that the host component is an organic polymer that is compatible with the above-mentioned guest component. (In the formula, at least one selected from X 1 , X 2 , X 3 , and X 4 is an aryl group having an ionic group or an ionic heterocyclic group having an alkyl group having 1 to 6 carbon atoms, and is a hydrogen atom or a nonionic group.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12698888A JPH0245A (en) | 1987-06-10 | 1988-05-26 | Porphin type recording material |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62-143291 | 1987-06-10 | ||
JP14329187 | 1987-06-10 | ||
JP62-309448 | 1987-12-09 | ||
JP62-309449 | 1987-12-09 | ||
JP12698888A JPH0245A (en) | 1987-06-10 | 1988-05-26 | Porphin type recording material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0245A JPH0245A (en) | 1990-01-05 |
JPH0529899B2 true JPH0529899B2 (en) | 1993-05-06 |
Family
ID=26463045
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12698888A Granted JPH0245A (en) | 1987-06-10 | 1988-05-26 | Porphin type recording material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0245A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4715752B2 (en) | 2004-12-09 | 2011-07-06 | コニカミノルタエムジー株式会社 | Ink set, ink jet recording method and ink jet recording apparatus using photocurable ink |
US8888262B2 (en) | 2008-11-07 | 2014-11-18 | Konica Minolta Holdings, Inc. | Actinic energy radiation curable inkjet ink and inkjet recording method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6132051A (en) * | 1984-07-23 | 1986-02-14 | Nippon Telegr & Teleph Corp <Ntt> | Wavelength selecting optical storage material |
-
1988
- 1988-05-26 JP JP12698888A patent/JPH0245A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6132051A (en) * | 1984-07-23 | 1986-02-14 | Nippon Telegr & Teleph Corp <Ntt> | Wavelength selecting optical storage material |
Also Published As
Publication number | Publication date |
---|---|
JPH0245A (en) | 1990-01-05 |
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