JPH01163740A - Porphin type recording material - Google Patents

Abstract

PURPOSE:To reduce a half-width of hole of a recording material permitting high density recording and to improve the heat stability by using a specific porphin deriv. for a guest component. CONSTITUTION:A porphin deriv. expressed by formula I is used as a guest component in the title material, and a polymer contg. no active proton which can be exchanged with heavy hydrogen of said component is used as a host component. Each compd. expressed by formula II and III may be used as a cationic and anionic porphin deriv. respectively. In the formulas, D is heavy hydrogen; at least one among X1-X4 is aryl group having an ionic group, and others are H or anionic group; each R13-R16 is 1-6C alkyl; each R17-R20 is anionic group. Polyvinyl alcohol having a proton activated by transforming it to deuterium may be used for the polymer.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an optical recording material that is capable of multiplex recording with light of different wavelengths at the same location on the same material by utilizing the photochemical hole burning phenomenon. .

[Prior art] 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 exposed. 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. By utilizing this PHB phenomenon, there is a possibility of improving the recording density by about 1000 times compared to conventionally used optical digital recording media such as compact discs and laser discs.

An optical recording material using such a PHB phenomenon is composed of guest molecules, which are photoreactive compounds, and a host for dispersing the guest molecules. 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 or inorganic polymers have been suitably used as the host, such as materials in which the guest is tetraphenylporphine and the host is polymethyl methacrylate (Optics, 14-(4) 2B3-269), Materials with quinizarin as the guest and silicate glass as the host (J, Appl, phys, 5B(9)3559-
3565) is known.

[Problems to be solved by the present invention] However, the conventional PH8 material has the disadvantage that it becomes 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 PH8 material, resulting in different microstructures around each guest molecule. Furthermore, the recording density was also insufficient.

The present invention aims to solve the drawbacks of the conventional technology, and by using an ionic porphine derivative in which the active proton is deuterated as a guest, the half width of the hole is small and high density recording is possible. Another object of the present invention is to provide a wavelength multiplexing recording medium that is highly thermally stable.

[Means for Solving the Problems] In order to achieve the above object, the present invention has the following configuration.

"A composition comprising a guest component and a host component as main components, (a) the guest component is a porphine derivative having an ionic group represented by the following general formula [A], (b) the host component is A porphine-based recording material characterized in that it is a polymer having no active protons that can be exchanged with deuterium as the guest component.

(In the formula, D is deuterium, and at least one selected from Xl, X2, X3, and X4 is an aryl group having an ionic group or an ionic heterocyclic ring having an alkyl group having 1 to 6 carbon atoms. group, and the others are hydrogen atoms or nonionic groups.) In other words, compared to recording materials that use conventional porphine-based guests, we use ionic porphine derivatives with deuterated active protons and active protons. In the case of materials consisting of polymers that do not contain polymers, the affinity between guest and host is good due to the interaction based on the charge of the former, and the active protons of the porphine rings are deuterated, resulting in thermal resistance. Less susceptible to disturbance. Therefore, it is presumed that irreversible structural changes upon temperature rise will be reduced. 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.

In the present invention, at least one selected from ×1, x2, X3, and ×4 is an aryl group having an ionic group,
Alternatively, it is an ionic heterocyclic group having an alkyl group having 1 to 6 carbon atoms, and the other groups x1 to x4 are hydrogen atoms or nonionic groups.

The ionic group contained in the guest component may be a cationic group, an anionic group, or an amphoteric ionic group.

As the cationic group, a quaternary amino group, an N-alkylpyridinium group, etc. are preferably used.

This occurs because it maintains a stable ionized state in the host. Particularly preferably, 5,10,15.20-tetra(4-N,N,
5, 10.15.20 represented by deuterium substitution of N-trialkylaminophenyl) porphine (in the formula, R13 to R16 are alkyl groups having 1 to 6 carbon atoms)
A deuterated product of -tetra(4-N-alkylpyridinium)porphine is used. This is because in the porphine derivative of the general formula [8], the porphine ring and the quaternary amino group are separated by a phenyl group, and in the porphine derivative of the general formula [CI], the charge of the pyridinium group is dispersed in the conjugated system. Therefore, the influence of the cation moiety is unlikely to affect the photochemical reactivity of the porphine ring. R1-R12 of general formula [B], and general formula [CI
It is more preferable that the alkyl group represented by R13 to R16 is a methyl group. 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.

These cationic porphine derivatives are present in the material together with appropriate anions. The selection of anion should be made from the viewpoint of compatibility with the host component,
p-toluenesulfonate ion, l-1Br-, C
I-, Cl0a-, CH3CO2-, BF4-, etc. are preferably used.

The deuterated product of 5.10,15.20-tetra(4-N,N,N-trialkylaminophenyl)porphine is 5,10.15.20-tetra(4) synthesized from acetaminobenzaldehyde and virol. -acetaminophenyl)porphine is hydrolyzed with an acid, reacted with a quaternizing agent such as alkyl iodide, and then reacted with heavy water. Also, 5.10.15.20-tetra(4
-N-alkylpyridinium) porphine is produced by quaternizing 5.10.15.20-tetra(4-N-pyridyl)porphine with a quaternizing agent such as alkyl iodide, and then adding it to heavy water. Obtained by reaction.

Anionic groups include SO3- group, CO2- group, 〇-
and the like are preferably used. This is because it maintains a stable ionized state in the host. In addition, the general formula (wherein R1
□ to R20 are anionic groups.

) are preferably used.

This means that in the porphine derivative of general formula [D],
This is because since the porphine ring and the anionic group are separated by the phenyl group, the anion moiety is less likely to affect the photochemical reactivity of the porphine ring.

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, deuterium ions, alkaline earth metal ions, and ammonium ions are preferably used.

In addition, a porphine derivative having an anionic group represented by the general formula [0] can be prepared by reacting 5,10,15.20-tetraphenylporphine with a polybasic acid and then reacting it with heavy water, or It is obtained from a precursor synthesized from a benzaldehyde derivative having a group that can serve as a base and pyrrole.

Examples of porphine derivatives having a zwitterionic group include deuterated derivatives of tetra[3-(N-sulfonatoalkyl-N-alkylamino)phenylcoborfin, tetra[3-(N-carbonatoalkyl-N- Deuterated product of alkylamino) phenylcoborfin, tetra[4-
Deuterium-substituted products of (N-sulfonatoalkyl)pyridinium]porphine, deuterium-substituted products of tetra[4-(N-carbonatoalkyl)pyridinium]porphine, and the like are preferably used.

Also, in the present invention, among Xl, x2, X3, x4,
Aryl group having the above ionic group, or having 1 carbon number
Other than the ionic heterocyclic group having ~6 alkyl groups, it is a hydrogen atom or a nonionic group, and examples of the nonionic group include a phenyl group, a methoxyphenyl group, a nitrophenyl group, a naphthyl group, Examples include methoxynaphthyl group.

The polymer used in the present invention may be any polymer that is compatible with the porphine derivative having an ionic group as a guest component and does not have active protons that can be exchanged with deuterium. Examples of polymers that are compatible with porphine derivatives include polyethylene oxide, polyvinylpyridine, polyvinylpyrrolidone, polyhydroxyethyl methacrylate, polymethacrylic acid, polyacrylic acid, polymethacrylamide, polyacrylamide, cellulose acetate, and sodium polyvinylsulfonate. Water-soluble organic polymers and inorganic polymers such as silicate glass are preferably used, and polyvinyl alcohol or sodium polystyrene sulfonate is particularly preferred. Among these, in the case of a polymer having active protons that can be exchanged with deuterium as a guest component, such as polyvinyl alcohol, the active protons are deuterated and used. Porphine derivatives with ionic groups, which are guest components, are soluble in polar solvents, so these water-soluble polymers, sol,
It is also compatible with silicate glass synthesized by the gel method and is easily dispersed. In particular, since polyvinyl alcohol has strong hydrogen bonding properties, it is estimated that it is unlikely to undergo thermal structural changes at low temperatures, and sodium polystyrene sulfonate has a benzene ring in its side chain, so it is difficult to interact with guest polyfin derivatives. It is most preferred as a host component because of its high affinity.

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 10-1 to 10'M based on the volume of the host polymer, especially 10-2 to 10'M.
Preferably it is 10-4M.

Furthermore, the recording material of the present invention may contain 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, but the guest component and the host component may be the main components. , preferably 95% or more of the total. This is mainly to prevent the interaction between host and guest from being impaired by the additive.

[Examples] The present invention will be described in detail below based on Examples, but the present invention is not limited thereto.

5, 10.15.20-tetra(4-N-methylpyridinium)porphine tetraiodide (Wako l1I4
ia＞o.

After heating and dissolving 2 g in 4 g of Tarumi water, it was dried to obtain a deuterated porphine in which active protons were deuterated. Separately, polyvinyl alcohol (degree of polymerization = 2000,
Degree of saponification = 100%>1 g was dissolved in 15 g of heavy water by heating, and then dried to obtain deuterated polyvinyl alcohol in which active protons were deuterated. This deuterated porphine and deuterated polyvinyl alcohol were dissolved in heavy water and dried to obtain a film of deuterated porphine/deuterated polyvinyl alcohol with a guest concentration of 20 mM.

After cooling this film to liquid helium temperature, the wavelength of 64
A PH8 hole with an absorption rate change of 40% was formed by irradiating a laser beam with a wavelength of 0 nm and an intensity of 1 m/-. At this time, the half width of the hole was 0.25 cm'.

On the other hand, a film of non-deuterated 5,10,15.20-tetra(4-N-methylpyridium)porphine tetraiodide/polyvinyl alcohol also contains PH8 holes with an absorption rate change of 40%. When formed, the half width of the hole was 1.10 cm'.

The half-width of the hole was reduced to 1/4.4 times by deuteration of the active proton. As a result, the number of holes that can be formed in the same absorption band increased by 4.4 times, that is, the multiplicity increased by 4.4 times.

(Example 2) 5.10,15.20-tetra(4-N-methylpyridinium)porphine tetraiodide (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.)
4.6 mg of sodium polystyrene sulfonate and 5 g of sodium polystyrene sulfonate were heated and dissolved in 50 ml of heavy water, and then dried in a dry nitrogen atmosphere to obtain a film of heavy hydration porphine/sodium polystyrene sulfonate with a guest concentration of 1 m+.

A PH8 hole was formed by irradiating this film with a laser beam having a wavelength of 645 nm and an intensity of 1 ml/d. FIG. 1 illustrates the relationship between the temperature of the sample and the half-width of the generated holes. In this sample, holes could be formed even at 60 holes.

(Example 3) Tetrasodium 5,10,15.20-tetra(4-
Sul 1 phonatophenyl) porphine (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) 4
A film of deuterated porphine/sodium polystyrene sulfonate with a guest concentration of 1 mH was obtained by heating and dissolving 8 mg of deuterated porphine and 5 g of sodium polystyrene sulfonate in 50 ml of heavy water, followed by drying in a dry nitrogen atmosphere.

This film has a wavelength of 645 and a strength of 11IIIll/C.
A PH8 hole was formed by irradiating the laser beam d. FIG. 2 illustrates the relationship between the sample length and the half-width of the generated holes. In this sample, holes could be formed even at 60 holes.

(Example 4) 5,10.15.20-tetra(4-N,N,N-trimethylaminophenyl)porphinetetra(p-toluenesulfonate) (manufactured by Isotope Kagaku Kenkyusho) 5.9 mg
and 5 g of sodium polystyrene sulfonate in 50 m of heavy water.
1 and then drying in a dry nitrogen atmosphere to dissolve deuterated porphine/
A film of sodium polystyrene sulfonate was obtained.

This film has a wavelength of 645 nm and an intensity of 1 mW/CIi.
By irradiating with laser light at 60°C, PH8 holes were able to be formed.

<Example 5> 30 Cl of 4-carboxybenzaldehyde and 13.4 Cl of pyrrole were reacted in refluxed propionic acid, and 5.
10.15.20-tetra(4-carboxyphenyl)
6.9 g of porphine was obtained. This was reacted with an aqueous solution containing 4 equivalents of sodium hydroxide to form tetrasodium 5
,10,15.20-tetra(4-carbonatophenyl)porphine was obtained.

This tetrasodium 5,10,15.20-tetra(
Deuterated porphine/sodium polystyrene sulfonate with a guest concentration of 1 mH was prepared by heating and dissolving 3.4 mg of 4-carbonatophenyl)porphine and 5 g of sodium polystyrene sulfonate in 50 ml of heavy water and drying it under a dry nitrogen atmosphere. Got the film.

This film has a wavelength of 645 and a strength of 1m1Il/CId.
By irradiating the laser beam at 60 degrees, Pi-f
I was able to form the B hole.

(Example 6) Tetrasodium 5,10,15.20-tetra(4-
Sulfonatophenyl) porphine (Wako Tsumugi Pharmaceutical Co., Ltd.) 40
mg, tetramethoxysilane (manufactured by Shin-Etsu Chemical) 10
ml, methanol 201 with deuterated active protons,
After dissolving in a mixed solution of 20ml of heavy water and 0.1
Gelation was carried out using 0.51111 N aqueous ammonia as a catalyst. By drying this in a dry nitrogen atmosphere,
A film of deuterated porphine/silicate glass was obtained.

By irradiating this film with a laser beam having a wavelength of 645 and an intensity of 1 mW/ci at 60, it was possible to form PH8 holes.

[Effects of the Invention] The porphine-based recording material of the present invention has a narrow half-width of holes generated at liquid helium temperature and a high recording multiplicity. Further, holes can be formed even at a temperature of about 60°C.

[Brief explanation of the drawing]

FIG. 1 illustrates the relationship between the sample temperature and the half width of the PI-IB hole in Example 2. FIG. 2 illustrates the relationship between the sample temperature and the half-value width of the PHB hole for Example 3.

Claims (1)

[Claims] (1) A composition comprising a guest component and a host component as main components, (a) the guest component is a porphine derivative having an ionic group represented by the following general formula [A], and (b) the host A porphine-based recording material characterized in that the component is a polymer having no active protons that can be exchanged with deuterium of the guest component. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[A] (In the formula, D is deuterium, X_1, X_2, X_3,
At least one selected from 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 the others are hydrogen atoms or nonionic groups. )