JPH0675330A - Porphin type recording material - Google Patents

Abstract

(57) [Summary] [Structure] A composition comprising a guest component and a host component as main components, wherein the guest component is a nonionic porphine derivative, and the host component is an organic polymer compatible with the guest component. And a hydrogen atom constituting a host component is deuterium-substituted, a porphine-based recording material. [Effect] The porphine-based recording material of the present invention has a narrower half-value width of the hole than the conventional optical recording material using a porphine derivative.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical recording material capable of multiple recording with the light of different wavelengths at the same place of the same material by utilizing the photochemical hole burning phenomenon.

[0002]

2. Description of the Related Art The photochemical hole burning (PHB) phenomenon is caused by irradiating a material that causes a photochemical reaction at an extremely low temperature of about the temperature of liquid helium with light of good monochromaticity.
Only the guest molecule that absorbs the light is selectively excited to cause a photochemical change. Since a sharp hole can be formed in the absorption spectrum of the material by this photochemical change, optical recording in the photon mode is possible depending on the presence or absence of the hole. Moreover, wavelength-multiplexed recording can be performed at the same location on the same material by changing the wavelength of the emitted light and recording sequentially. By utilizing this PHB phenomenon, there is a possibility that the recording density will be improved about 1000 times as compared with the conventionally used optical digital recording media such as compact disk (CD) and laser disk (LD).

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 medium as a host in order to make the dispersed state of the guest diverse. For this purpose, an organic polymer, silicate glass, or the like has been conventionally used as a host. For example, a material in which the guest is tetraphenylporphine and the host is polymethylmethacrylate (Optics, 14 (4) 263-269 (1985))
And materials that use quinizarin as the guest and silicate glass as the host (Journal of Applied Physics, 58 (9) 3559-3565.
(1985)) are known.

[0004]

However, in general, the width of the hole formed in the PHB material composed of the porphine / polymer system is, in part, due to tunneling of hydrogen, which is the lightest element constituting the host polymer, in the host polymer. Is considered to increase with the relaxation rate of the two-level system (TLS). Therefore, it has a drawback that the generated hole has a wide half-value width, and the wavelength multiplicity expected of the PHB material is reduced.

The present invention is intended to solve the drawbacks of the prior art, and is an organic polymer in which a nonionic porphine as a guest component is compatible with a guest component as a host component and a hydrogen atom is substituted with deuterium. The purpose of the present invention is to provide a recording material in which the full width at half maximum of generated holes is small.

[0006]

In order to achieve the above object, the present invention has the following constitution.

"A composition comprising a guest component and a host component as main components, the guest component is a nonionic porphine derivative, the host component is an organic polymer compatible with the guest component, and the host component A porphine-based recording material characterized in that the hydrogen atoms constituting the are replaced by deuterium. ”That is, in comparison with a recording material using a conventional porphine derivative, a material using a polymer deuterium-substituted for a host, Since the deuteration of hydrogen atoms suppresses the tunneling of hydrogen, the full width at half maximum of generated holes can be reduced.

The guest component can be used without limitation as long as it is a nonionic porphine derivative soluble in a general organic solvent, and a porphine derivative represented by the following formula (I) is particularly preferable. Used.

[0009]

[Chemical 2]

(In the formula, X _{1 to} X ₄ are an aryl group or a heterocyclic group.) The aryl group is an unsubstituted phenyl group or its 1 as having good compatibility with the host component. Substitute, 2
Substitutes, tri-substitutes and the like are preferably used. The porphine derivative having an aryl group is represented by the formula (II)

[0011]

[Chemical 3]

(Wherein R _{1 to} R ₅ are all hydrogen atoms or at least one of R _{1 to} R ₅ is an alkyl group such as a methyl group or an ethyl group, an alkoxyl group such as a methoxy group or an ethoxy group). , A methylthio group, an alkylthio group such as an ethylthio group, a halogen group such as a fluoro group and a chloro group, a cyano group, a nitro group, and a dialkylamino group.), 5,10,15,20-tetraphenylporphine, 5,10,15,20-tetrakis (alkylphenyl)
Porphine, 5,10,15,20-tetrakis (dialkylphenyl) porphine, 5,10,15,20-tetrakis (trialkylphenyl) porphine, 5,10,15,20-tetrakis (alkoxyphenyl) porphine, 5, 10,15,20-Tetrakis (dialkoxyphenyl) porphine, 5,10,15,
20-Tetrakis (trialkoxyphenyl) porphine, 5,10,15,20-Tetrakis (alkylthiophenyl)
Porphine, 5,10,15,20-tetrakis (halogenophenyl) porphine, 5,10,15,20-tetrakis (cyanophenyl) porphine and the like are preferably used.

As the heterocyclic group, a pyridine ring and a thiophene ring are preferably used. The porphine derivative having a heterocyclic group is represented by the formula (III)

[0014]

[Chemical 4]

5,10,15,20-tetrapyridylporphine represented by the formula (IV)

[0016]

[Chemical 5]

5,10,15,20-tetrathienylporphine represented by: is preferably used. The nonionic porphine derivative having an aryl group or a heterocyclic group at the 5,10,15,20-position can be synthesized by condensing the corresponding benzaldehyde derivative and pyrrole with an acid catalyst and then oxidizing the condensed product.

Further, as shown in formulas (II) to (IV), in addition to the porphine derivative in which the substituents X _{1 to} X ₄ in formula (I) are all the same, the substitution in formula (I) A porphine derivative in which at least one of the groups X _{1 to} X ₄ is a different substituent may be used.

The organic polymer in the present invention may be any one that is compatible with the guest component, and is a deuterated polyethylene oxide polymerized from a deuterium-substituted monomer, deuterated polyvinyl pyridine, or deuterium, respectively. Deuterated polymethylmethacrylate, deuterated polyhydroxyethylmethacrylate, deuterated polymethylacrylate,
Organic polymers soluble in organic solvents such as chloroform, toluene and tetrahydrofuran such as deuterated polystyrene and deuterated polyvinyl acetate are preferably used.
This is because the nonionic porphine derivative, which is a guest component, is also soluble in a solvent such as chloroform and can be easily dispersed in these polymers. Deuterated polymethyl methacrylate is particularly preferably used. This is because the sample using deuterated polymethylmethacrylate as the host polymer has good transparency and is easy to handle. Deuterated polymethyl methacrylate - DOO commercial monomer - can be obtained by radical polymerization using an initiator such as is methyl methacrylate -d ₈ azobisisobutyronitrile (AIBN).

When the concentration of the guest component in the optical recording material of the present invention is too high, the hole transfer property is deteriorated due to energy transfer between guest molecules, and when it is too low, the S / N at the time of recording and reading is small. Be restricted. Therefore, the preferred guest concentration is 10 ^-1 to 10 ^-6 mol / l based on the volume of the organic polymer that is the host.
And particularly preferably 10 ⁻² to 10 ⁻⁴ mol / l.

[0021]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Example 1 20 g of methyl methacrylate-d ₈ (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 25 ml of methyl ethyl ketone, 120 mg of azobisisobutylnitrile was further added, and then degassed to 7
Polymerization was carried out at 0 ° C. for 8 hours. The polymer was isolated by reprecipitation with methanol to obtain deuterated polymethyl methacrylate (PMMA-d ₈ ) in a yield of 12.4 g and a yield of 62%.

After dissolving 1 g of PMMA-d ₈ obtained above in 15 ml of chloroform, 6 mg of 5,10,15,20-tetraphenylporphine was added and mixed with stirring. The solution was dried to give a guest concentration of 1 × 10 ^-2 mol / l and a thickness of 0.4 m.
m film was obtained. This film is used to irradiate laser light at helium temperature and 15K to form holes,
The half width was measured. The absorption spectrum of the film at this temperature is shown in the drawing.

Comparative Example 1 5 g of isotactic polymethylmethacrylate (molecular weight = 40,000) was dissolved in 80 ml of chloroform, and then 5,
31 mg of 10,15,20-tetraphenylporphine was added and mixed with stirring. This solution is dried to a guest concentration of 1 × 1
0 ^-2 mol / l, to obtain a film having a thickness of 0.5 mm. Using this film, holes were formed by irradiating laser light at a liquid helium temperature and 15 K, and the half width was measured.

The liquid helium temperature of Example 1 and Comparative Example 1 and the full width at half maximum at 15 K were both narrower in Example 1.

Example 2 After dissolving 500 mg of PMMA-d ₈ obtained in Example 1 in 7 ml of chloroform, 3.6 mg of 5,10,15,20-tetrakis (4-methoxyphenyl) porphine was added and mixed with stirring. This solution is dried to a guest concentration of 1 × 10 ^-2 mo
A film having a l / l and a thickness of 0.4 mm was obtained. Using this film, holes were formed by irradiating laser light at 5K and 12K, and the full width at half maximum was measured.

Comparative Example 2 10 g of isotactic polymethylmethacrylate (molecular weight = 40,000) was dissolved in 120 ml of toluene, and then 5,
73 mg of 10,15,20-tetrakis (4-methoxyphenyl) porphine was added and mixed with stirring. The solution is dried to give a guest concentration of 1 × 10 ^-2 mol / l and a thickness of 0.5 mm.
I got a film of. 5K and 1 with this film
A hole was formed by irradiating a laser beam at 2K, and the half width was measured.

5K and 12K of Example 2 and Comparative Example 2
The half value widths in Example 2 were narrower in Example 2 in both cases.

[0029]

According to the porphine-based recording material of the present invention, the hole half width can be narrowed and the recording multiplicity can be improved as compared with the conventional optical recording material using the porphine derivative.

[0030]

[Brief description of drawings]

[0031]

FIG. 1 shows the absorption spectrum of the recording material obtained in Example 1 measured at a hole formation temperature and shown in the drawing. In the drawing, the horizontal axis represents wavelength (unit is nm),
The vertical axis represents absorption intensity.

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[Procedure amendment]

[Submission date] September 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical recording material capable of multiple recording with the light of different wavelengths at the same place of the same material by utilizing the photochemical hole burning phenomenon.

[0002]

2. Description of the Related Art The photochemical hole burning (PHB) phenomenon is caused by irradiating a material that causes a photochemical reaction at an extremely low temperature of about the temperature of liquid helium with light of good monochromaticity.
Only the guest molecule that absorbs the light is selectively excited to cause a photochemical change. Since a sharp hole can be formed in the absorption spectrum of the material by this photochemical change, optical recording in the photon mode is possible depending on the presence or absence of the hole. Moreover, wavelength-multiplexed recording can be performed at the same location on the same material by changing the wavelength of the emitted light and recording sequentially. By utilizing this PHB phenomenon, there is a possibility that the recording density will be improved about 1000 times as compared with the conventionally used optical digital recording media such as compact disk (CD) and laser disk (LD).

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 medium as a host in order to make the dispersed state of the guest diverse. For this purpose, an organic polymer, silicate glass, or the like has been conventionally used as a host. For example, a material in which the guest is tetraphenylporphine and the host is polymethylmethacrylate (Optics, 14 (4) 263-269 (1985))
And materials that use quinizarin as the guest and silicate glass as the host (Journal of Applied Physics, 58 (9) 3559-3565.
(1985)) are known.

[0004]

However, in general, the width of the hole formed in the PHB material composed of the porphine / polymer system is, in part, due to the tunneling of hydrogen, which is the lightest element constituting the host polymer, in the host polymer. Is considered to increase with the relaxation rate of the two-level system (TLS). Therefore, it has a drawback that the generated hole has a wide half-value width, and the wavelength multiplicity expected of the PHB material is reduced.

The present invention is intended to solve the drawbacks of the prior art, and is an organic polymer in which a nonionic porphine as a guest component is compatible with a guest component as a host component and a hydrogen atom is substituted with deuterium. The purpose of the present invention is to provide a recording material in which the full width at half maximum of generated holes is small.

[0006]

In order to achieve the above object, the present invention has the following constitution.

"A composition comprising a guest component and a host component as main components, the guest component is a nonionic porphine derivative, the host component is an organic polymer compatible with the guest component, and the host component A porphine-based recording material characterized in that the hydrogen atoms constituting the are replaced by deuterium. ”That is, in comparison with a recording material using a conventional porphine derivative, a material using a polymer deuterium-substituted for a host, Since the deuteration of hydrogen atoms suppresses the tunneling of hydrogen, the full width at half maximum of generated holes can be reduced.

The guest component can be used without limitation as long as it is a nonionic porphine derivative soluble in a general organic solvent, and a porphine derivative represented by the following formula (I) is particularly preferable. Used.

[0009]

[Chemical 2] (In the formula, X _{1 to} X ₄ are an aryl group or a heterocyclic group.) The aryl group is an unsubstituted phenyl group or a monosubstituted product thereof, which has good compatibility with the host component. Two
Substitutes, tri-substitutes and the like are preferably used. The porphine derivative having an aryl group is represented by the formula (II)

[Chemical 3] (Wherein, R _{1 to} R ₅ are all hydrogen atoms or at least one of R _{1 to} R ₅ is an alkyl group such as a methyl group or an ethyl group, an alkoxyl group such as a methoxy group or an ethoxy group, or a methylthio group. , Alkylthio groups such as ethylthio group, halogen groups such as fluoro group and chloro group,
A cyano group, a nitro group and a dialkylamino group. ) 5,10,15,20-tetraphenylporphine, 5,1
0,15,20-tetrakis (alkylphenyl) porphine, 5,10,15,20-tetrakis (dialkylphenyl) porphine, 5,10,15,20-tetrakis (trialkylphenyl) porphine, 5,10,15, 20-tetrakis (alkoxyphenyl) porphine, 5,10,15,20-tetrakis (dialkoxyphenyl) porphine, 5,10,15,20-tetrakis (trialkoxyphenyl) porphine, 5,10,15,
20-tetrakis (alkylthiophenyl) porphine,
5,10,15,20-Tetrakis (halogenophenyl) porphine, 5,10,15,20-tetrakis (cyanophenyl) porphine and the like are preferably used.

As the heterocyclic group, a pyridine ring and a thiophene ring are preferably used. The porphine derivative having a heterocyclic group is represented by the formula (III)

[Chemical 4] 5,10,15,20-tetrapyridylporphine represented by the formula (IV)

[Chemical 5] 5,10,15,20-tetrathienylporphine represented by is preferably used.

An aryl group or a heterocyclic group is added to 5,10,15,20
The nonionic porphine derivative at the − position can be synthesized by condensing the corresponding benzaldehyde derivative and pyrrole with an acid catalyst and then oxidizing the condensed benzaldehyde derivative.

Further, as shown in formulas (II) to (IV), in addition to the porphine derivative in which the substituents X _{1 to} X ₄ in formula (I) are all the same, the substitution in formula (I) A porphine derivative in which at least one of the groups X _{1 to} X ₄ is a different substituent may be used.

The organic polymer in the present invention may be any one that is compatible with the guest component, and is a deuterated polyethylene oxide polymerized from a deuterium-substituted monomer, deuterated polyvinyl pyridine, or deuterium, respectively. Deuterated polymethylmethacrylate, deuterated polyhydroxyethylmethacrylate, deuterated polymethylacrylate,
Organic polymers soluble in organic solvents such as chloroform, toluene and tetrahydrofuran such as deuterated polystyrene and deuterated polyvinyl acetate are preferably used.
This is because the nonionic porphine derivative, which is a guest component, is also soluble in a solvent such as chloroform and can be easily dispersed in these polymers. Deuterated polymethyl methacrylate is particularly preferably used. This is because the sample using deuterated polymethylmethacrylate as the host polymer has good transparency and is easy to handle. Deuterated polymethyl methacrylate - DOO commercial monomer - can be obtained by radical polymerization using an initiator such as is methyl methacrylate -d ₈ azobisisobutyronitrile (AIBN).

If the concentration of the guest component in the optical recording material of the present invention is too high, the hole transfer property is deteriorated due to energy transfer between guest molecules, and if it is too low, the S / N during recording and reading is small. Be restricted. Therefore, the preferred guest concentration is 10 ^-1 to 10 ^-6 mol / l based on the volume of the organic polymer that is the host.
And particularly preferably 10 ⁻² to 10 ⁻⁴ mol / l.

[0015]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Example 1 20 g of methyl methacrylate-d ₈ (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 25 ml of methyl ethyl ketone, 120 mg of azobisisobutylnitrile was further added, and then degassed to 7
Polymerization was carried out at 0 ° C. for 8 hours. The polymer was isolated by reprecipitation with methanol to obtain deuterated polymethyl methacrylate (PMMA-d ₈ ) in a yield of 12.4 g and a yield of 62%.

After dissolving 1 g of PMMA-d ₈ obtained above in 15 ml of chloroform, 6 mg of 5,10,15,20-tetraphenylporphine was added and mixed with stirring. The solution was dried to give a guest concentration of 1 × 10 ^-2 mol / l and a thickness of 0.4 m.
m film was obtained. This film is used to irradiate laser light at helium temperature and 15K to form holes,
The half width was measured. The absorption spectrum of the film at this temperature is shown in the drawing.

Comparative Example 1 5 g of isotactic polymethylmethacrylate (molecular weight = 40,000) was dissolved in 80 ml of chloroform,
31 mg of 10,15,20-tetraphenylporphine was added and mixed with stirring. This solution is dried to a guest concentration of 1 × 1
0 ^-2 mol / l, to obtain a film having a thickness of 0.5 mm. Using this film, holes were formed by irradiating laser light at a liquid helium temperature and 15 K, and the half width was measured.

The liquid helium temperature of Example 1 and Comparative Example 1 and the full width at half maximum at 15 K were both narrower in Example 1.

Example 2 After dissolving 500 mg of PMMA-d ₈ obtained in Example 1 in 7 ml of chloroform, 3.6 mg of 5,10,15,20-tetrakis (4-methoxyphenyl) porphine was added and mixed with stirring. This solution is dried to a guest concentration of 1 × 10 ^-2 mo
A film having a l / l and a thickness of 0.4 mm was obtained. Using this film, holes were formed by irradiating laser light at 5K and 12K, and the full width at half maximum was measured.

Comparative Example 2 10 g of isotactic polymethylmethacrylate (molecular weight = 40,000) was dissolved in 120 ml of toluene, and then 5,
73 mg of 10,15,20-tetrakis (4-methoxyphenyl) porphine was added and mixed with stirring. The solution is dried to give a guest concentration of 1 × 10 ^-2 mol / l and a thickness of 0.5 mm.
I got a film of. 5K and 1 with this film
A hole was formed by irradiating a laser beam at 2K, and the half width was measured.

5K and 12K of Example 2 and Comparative Example 2
The half value widths in Example 2 were narrower in Example 2 in both cases.

[0023]

According to the porphine-based recording material of the present invention, the hole half width can be narrowed and the recording multiplicity can be improved as compared with the conventional optical recording material using the porphine derivative.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 shows the absorption spectrum of the recording material obtained in Example 1 measured at a hole formation temperature and shown in the drawing. In the drawing, the horizontal axis represents wavelength (unit is nm),
The vertical axis represents absorption intensity.

Claims (2)

[Claims] 1. A composition comprising a guest component and a host component as main components, the guest component being a nonionic porphine derivative, the host component being an organic polymer compatible with the guest component, and the host. A porphine-based recording material, wherein hydrogen atoms constituting the component are replaced with deuterium. 2. The guest component is of the formula (I): The porphine-based recording material according to claim 1, which is a nonionic porphine derivative represented by the formula: wherein X _{1 to} X ₄ are aryl groups or heterocyclic groups.