JPH0245A - Porphin type recording material - Google Patents

Abstract

PURPOSE:To improve the thermal stability of the title material, and to make possible to form hall at a liquid nitrogen temp. by composing a guest component of a photochemical hall burning material of a specified porphin derivative, and a host component of an org. polymer compatible to the guest component, respectively. CONSTITUTION:The porphin derivative having an ionic groups shown by the formula wherein at least one of groups X1-X4 is an ionic heterocyclic ring group comprising aryl or alkyl group having an ionic group, the another of said groups is hydrogen atom or a nonionic group. And, the host component is composed of the org. polymer compatible to the guest component. According ly, owing to the interaction between the guest component and the host compo nent due to an electric charge of the porphin derivative, the affinity between the guest component and the host component is losed, and the irreversible struc tural change of the recording material at the time of raising the temp. is lessened. Thus, the thermal stability of the material and the recovery ratio of the hall after raising temp. are improved, and the formation of the hall at the liquid nitrogen temp. makes possible.

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 (PH8) 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. By utilizing this PH8 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 PH8 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 have been suitably used as hosts, such as materials in which the guest is tetraphenylporphine and the host is polymethyl methacrylate (optics, 1
4(4)2B3-269) is known.

Mata, regarding the characteristics of PHB materials, Th1jSSen
For the formation of holes below in 30, (
Chem, Phys, Lett, 92(2) 7-12
), and on the conservation of holes in 60 by Tani et al. (J, Apl) 1. Phys., 58(9)35
59-3565) has been reported.

``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 PHB material, resulting in different microstructures around each guest molecule.

Furthermore, with conventional PHB materials, it has been impossible to form holes at liquid nitrogen temperatures. Therefore, there has been a desire for a PH8 material that can form holes at the temperature of liquid nitrogen and has the important practical advantage of significantly reducing cooling costs.

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.

[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 by being an organic polymer that is compatible with the above guest component.

(In the formula, at least one selected from xl, x2, , a hydrogen atom or a nonionic group)
In other words, compared to recording materials that use conventional porphine-based guests, in the case of materials made of porphine derivatives with ionic groups and organic polymers, the interaction between the guest and host is caused by the interaction based on the charge of the former. 1 has good affinity, and therefore it is presumed that irreversible structural changes upon increasing temperature 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.

At least one selected from the groups x1, x2, x3, and x4 of the present invention is an aryl group having an ionic group or an ionic heterocyclic group having an alkyl group having 1 to 6 carbon atoms. , the other 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 is 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 N-trialkylaminophenyl) porphine or crest needle [C] R+3 (wherein R13 to R16 are an alkyl group having 1 to 6 carbon atoms) -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, and in the porphine derivative of general formula [C], the charge of the pyridinium group is transferred to the conjugated system. This is because the cation moiety is less likely to affect the photochemical reactivity of the porphine ring since it is dispersed. R1-R12° of general formula [B] and R13-R16 of general formula [C]
It is more preferable that the alkyl group represented by 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 cause 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-1C
I-1CIO4-1CR3C02-1B F4- and the like are preferably used.

5,10.15.20-Tetra(4-N,N,N-trialkylaminophenyl)porphine was synthesized from acetaminobenzaldehyde and pyrrole5,10.
After hydrolyzing 15,20-tetra(4-acetaminophenyl)porphine with acid, 4
Obtained by reacting with a grading agent. Also, 5.10.15.
20-Tetra(4-N-alkylpyridinium)porphine is produced by converting 5,10,15.20-tetra(4-N-pyridyl)porphine with a quaternizing agent such as alkyl iodide.
Obtained by grading.

Examples of anionic groups include 303- group, CO2- group, 〇-
and the like are preferably used. This is because it maintains a stable ionized state in the host. Moreover, the general formula % formula % (However, in the formula, 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, hydrogen ions, alkaline earth metal ions, and ammonium ions are preferably used.

In addition, the porphine derivative having an anionic group represented by the general formula [D] can be obtained by reacting 5,10,15.20-tetraphenylporphine with a polybasic acid, or by reacting benzaldehyde having a group that can become an anionic group. It is obtained from a precursor synthesized from a derivative and pyrrole.

Examples of porphine derivatives having an amphoteric ionic group include tetra[3-(N-sulfonatoalkyl-N-alkylamino)phenyl]porphine, tetra[3-(N-carbonatoalkyl-N-alkylamino)phenyl] Porphine, tetra[4-(N-sulfonatoalkyl)
Pyridinium]porphine, tetra[4-(N-carbonatoalkylporphine), and the like are preferably used.

The organic polymer used in the present invention may be one that is compatible with the porphine derivative having an ionic group as a guest component, such as polyethylene oxide, polyvinylpyridine, polyvinylpyrrolidone, polyhydroxyethyl methacrylate, polymethacrylic acid, polyacrylic acid, etc. acid,
Water-soluble polymers such as polymethacrylamide, polyacrylamide, cellulose acetate, and sodium polyvinyl sulfonate are preferably used, and polyvinyl alcohol or sodium polystyrene sulfonate is particularly preferably used. This is because the porphine derivative having an ionic group, which is a guest component, is soluble in a polar solvent and is therefore compatible with these water-soluble polymers, making it easy to disperse. 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 porphine derivative. Since they have mutual affinity, they are most preferred as host components.

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, a preferable guest concentration is 10-1 to 10-'M based on the volume of the host organic polymer, particularly 10-'M.
-2 to 104M is preferable.

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 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.

(Example 1) Polyvinyl alcohol (degree of polymerization = 2000, degree of saponification = 1
After dissolving 00%>10o in 100ml of distilled water, 5
, 10, 15.20-tetra(4-N,N,N-trimethylaminophenyl)porphinetetra(p-toluenesulfonate) (manufactured by Isotope Kagaku Kenkyusho)0.

Added 13g. Dry this solution in a petri dish,
A film with a guest concentration of 10 −2 M and a thickness of 0.5 mm was obtained. After cooling this film to liquid helium temperature, the wavelength of 646 nm. A PH8 hole was formed by irradiating a laser beam with an intensity of 1 mW/a+t for 1 minute. Thereafter, the film was heated to a predetermined temperature, cooled again to liquid helium temperature, and the half width of the PHB hole was measured.

(Example 2) Polyvinyl alcohol (degree of polymerization = 2000, degree of saponification = 1
00%) 10q was dissolved in 100 ml of distilled water, and 0.10 of 5,10,15.20-tetra(4-N-methylpyridinium)porphine tetraiodide (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was added. . This solution was dried in a petri dish to give a guest concentration of 10-2M and a thickness of 0.

A 5 mm film was obtained. After cooling this film to liquid helium temperature, the wavelength was 646 nm, the intensity was 1 mW, and 10 vf.
A PH8 hole was formed by irradiating the laser beam for 1 minute. Thereafter, the film was heated to a predetermined temperature, cooled again to liquid helium temperature, and the half width of the PI-(B hole was measured).

(Comparative Example 1) After dissolving autactic polymethyl methacrylate (molecular weight = 400,000>IOg in 120 ml of toluene, 0.05 Q of tetraphenylporphine was added. By drying this solution in a Petri dish, the guest concentration was 10 -Make a film of 2M, thickness Q, 5mm,
This 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 hole was measured.

Figure 1 shows the difference between the half-width (0) of the PH8 hole immediately after laser beam irradiation and the half-width ([) after heating and recooling, as a function of temperature and humidity. .5.10.
15. When using the sample of Example 1 in which 20-tetra(4-N,N,N-trimethylaminophenyl)porphinetetra(1)-toluenesulfonate) was dispersed in polyvinyl alcohol, 5 , 10.15.20-
Q is the case where the sample of Example 2 in which tetra(4-N-methylpyridinium)porphine tetraiodide is dispersed in polyvinyl alcohol is used, and Comparative Example 1 is in which tetraphenylporphine is dispersed in tactical polymethyl methacrylate. The case where a sample of 1 was used is indicated by X. It can be seen that the samples of Examples 1 and 2 show less increase in the half width of the PHB hole after heating and recooling, and have excellent thermal stability.

(Example 3) 4-Carboxybenzaldehyde 30C1 and virol 13.4g were reacted in refluxed propionic acid to produce 5,1
0.15.20-tetra(4-carboxyphenyl)porphine 6.90 was obtained. Polyvinyl alcohol (degree of polymerization = 2000, degree of saponification = 100% > 100) with distilled water 20%
After dissolving in a mixed solvent of 0 ml and 300 ml of methanol, s, 10.15.20-tetra(4-carboxyphenyl q) was added. This solution was dried in a petri dish to give a guest concentration of 10-2 M and a thickness of Q: A 5 mm film was obtained.

After cooling this film to liquid helium temperature, the wavelength of 64
A PH8 hole was formed by irradiating a laser beam of 5 nm and intensity of 1 mW/cnf for 30 seconds.

After this, the film was heated to a predetermined temperature, cooled again to the liquid helium temperature, and the half width of the PHB hole was measured.

(Example 4) Sodium polystyrene sulfonate 10C] was added to 1 part of distilled water.
After dissolving in 00ml, 5, 10, 15. 20
- 0.1 g of 7tra(4-N-methylpyridinium)porphine tetraiodide (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was added.

This solution was dried in a Petri dish and the guest concentration was 10-
2M, thickness Q. A 5 mm film was obtained. After cooling this film to liquid helium temperature, it was irradiated with a laser beam having a wavelength of 645 nm and an intensity of 1 mW/- for 30 seconds to form PH8 holes. The film was then heated to a predetermined temperature, cooled again to liquid helium temperature, and the half width of the PHB hole was measured.

Figure 2 shows the difference between the half-width (") of a straight-change PH8 hole irradiated with laser light and the half-width (") after heating and recooling, as a function of temperature and humidity. is.5,10
, 15. When the sample of Example 3 in which 20-tetra(4-carboxyphenyl)porphine was dispersed in polyvinyl alcohol was used.

10,15.20-tetra(4-N-methylpyridinium)porphine tetraiodide is dispersed in sodium polystyrene sulfonate using the sample of Example 4. Comparative example 1 dispersed in methacrylate
The case where a sample of 1 was used is indicated by X. It can be seen that the samples of Examples 3 and 4 showed a smaller increase in the half width of the PH8 hole after heating and recooling one flame, and had better thermal stability.

(Example 5) Polyvinyl alcohol (degree of polymerization = 2000, degree of saponification = 1
After dissolving 10q of 00%) in 100ml of distilled water, tetrasodium 5,10,15.20-tetra(
4-sulfonatophenyl)porphine dodecahydrate 0.
1C] was added. Dry this solution in a petri dish,
1 film with a guest concentration of 10-2M and a thickness of 0.5 mm
It's q. After cooling this film to liquid helium temperature, it was irradiated with a laser beam having a wavelength of 646 nm and an intensity of 1 mW/- for 1 minute to form PH8 holes. Thereafter, the film was heated to a predetermined temperature, cooled again to liquid helium temperature, and the half width of the PHB hole was measured.

(Example 6) 5,10,15.20-tetra(4
-carboxyphenyl)porphine was reacted with an aqueous solution containing sodium hydroxide to obtain tetra(4-carbonatophenyl)porphine. Polyvinyl alcohol (degree of polymerization = 2000. Degree of saponification = 100% > 10q with distilled water 100%
Shun dissolved in m1, tetrandiram 5.10.15
．． 0.07 g of 20-tetra(4-carbonatophenyl)porphine was added. This solution was dried in a petri dish to obtain a film with a thickness Q of 5 mm. After cooling this film to liquid helium temperature, the wavelength was 646 nm and the intensity was 1.
PHB holes were formed by irradiating mW/Ti laser light for 1 minute. Thereafter, the film was heated to a predetermined temperature, cooled again to liquid helium temperature, and the half width of the PHB hole was measured.

Figure 3 shows the difference between the half-width ([0) of the directly restored PH8 hole irradiated with laser light and the half-width ([) after heating and recooling, as a function of temperature and humidity. be. 5.10.
15. When using the sample of Example 5 in which 20-tetra(4-sulfonatophenyl)porphine was dispersed in polyvinyl alcohol, tetrandiram 5.10.
15. Comparative Example 1 in which the sample of Example 4 in which 20-tetra(4-carbonatophenyl)porphine was dispersed in polyvinyl alcohol was used, and tetraphenylporphine was dispersed in tactical polymethyl methacrylate. The case where a sample of 1 was used is indicated by X.

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 excellent thermal stability.

(Example 7) For the same sample as in Example 5, a PHB hole was formed by irradiating laser light at various sample temperatures, and the half width of the hole was measured.

(Example Day) For the same sample as in Example 6, a PHB hole was formed by irradiating laser light at various sample temperatures, and the half width of the hole was measured.

Figure 4 shows the relationship between the sample temperature and the half-width of the generated holes for the samples of Examples 7 and 8, respectively.
Indicated by Even if it is 80 in Example 7, it is 110 in Example 8.
I was able to form a hole even in the middle.

(Example 9) 10Q of sodium polystyrene sulfonate was mixed with 10Q of distilled water.
After dissolving in 0ml, 5,10,15.20-tetra(4-N-methylpyridinium)porphinetetraiodide (Wako Tsumugi Yakuhin 117) O,O'l was added. This solution was dried in a Petri dish and the guest concentration was 10-3M.
A film with a thickness Q of 5 mm was obtained.

After cooling this film to 30K, PH8 holes were able to be formed by irradiating it with a laser beam having a wavelength of 646 nm.

(Example 10) Polyvinyl alcohol (degree of polymerization = 2000. Degree of saponification = 1
After dissolving 00%>l0CJ in 100ml of distilled water,
Tetrandiram 5,10,15.20-tetra(4-
Sulfonatophenyl)porphine dodecahydrate (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) O, OO'l were added. This solution was dried in a Petri dish to obtain a film with a guest concentration of 10-4M1 and a thickness Q of 5 mm. After cooling this film to 40K, it was irradiated with a laser beam with a wavelength of 646 nm.
It was possible to form an HB hole.

[Effects of the Present Invention] The porphine-based recording material of the present invention has increased thermal stability and a high hole recovery rate after heating, compared to conventional optical recording materials.

In general, it has become possible to form holes even at liquid nitrogen temperatures, which were previously impossible.

[Brief explanation of the drawing]

FIG. 1 illustrates the amount of increase in the half width of the PH8 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 X. FIG. 2 illustrates the increase in the half width of the PH8 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 O1, and the results of Comparative Example 1 are indicated by X. FIG. 3 illustrates the amount of increase in the half-width of PHB holes after heating and recooling for Example 5, Example 6, and Comparative Example 1. The results of Example 5 are indicated by ., the results of Example 6 are indicated by ◯, and the results of Comparative Example 1 are indicated by ×. Figure 4 shows the sample temperature and P for Examples 7 and 8.
It is a diagram illustrating the relationship between the half width of the H8 hole. The results of Example 7 are indicated by ., and the results of Example 8 are indicated by O.

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) a host component. is an organic polymer that is compatible with the above guest component. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [A] (In the formula, at least one selected from X_1, X_2, X_3, and X_4 has an aryl group having an ionic group or an alkyl group having 1 to 6 carbon atoms. (It is an ionic heterocyclic group, and the others are hydrogen atoms or nonionic groups.)