JP2001064532A - Light-achromatic material, light-achromatic resin composition, indication label for exposure quantity, light-achromatic ink and light-recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize excellent achromatism and preservability in a dark place by containing a pigment for a specified light-achromatic material and a specified compound as an additive. SOLUTION: This light-achromatic material is obtained by containing a pigment for a light-achromatic material represented by formula I and least one of compounds represented by formulas II and III (wherein Z is an atomic group required for a 5-membered aromatic heterocyclic formation; R is a substitutable group on an aromatic heterocycle; (m) is 0 to 3; CP is a group to totally form a chromophoric group by binding the aromatic heterocycle through a methylene group; R11 is H, a hydroxyl group, an alkyl group, an alkenyl group, a heterocyclic group or the like; Z11 and Z12 are each a 1-3C alkylene group; R12 is a substitutable group on Z11 and Z12; n11 is 0 to 4; X11 is -CR16R17-, -NR18-, -O-, -S- or the like; R16 and R17 are each H or -OCOR20; R20 is an alkyl group, an alkyl group or the like; R18 is H, an alkyl group, an alkenyl group or the like; R12 is H, an alkyl group, an acyl group or a trialkylsilyl group; and R22 to R26 are each H, an alkyl group, an alkyoxy group, an aryl group, an aryloxy group or the like).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photobleachable material containing a dye for a specific photobleachable material, a photobleachable resin composition containing a specific compound as an additive, an optical recording material, and a photobleachable material. The present invention relates to a functional ink and an exposure amount label.

[0002]

2. Description of the Related Art Dyes used for photobleaching are:
Japanese Unexamined Patent Publication (Kokai) No. 5-100421, a combination of a leuco dye or an azomethine dye and an acid generator, and Japanese Unexamined Patent Publication (Kokai) No. 9-279081, a sensitizing dye and an organic boron salt are known. JP-A-5-96868 discloses a guanidine salt dye of a pyrazolotriazole nucleus. Further, as an exposure amount display label, a photosensitive material is disclosed in JP-A-7-219115,
Japanese Patent Application Laid-Open No. Hei 9-111161 discloses an ultraviolet ray detection ink. All of these are color display labels that combine a leuco dye and a color former, and are suitable for measurement in a relatively short time because they are easily affected by temperature. The reliability of the quantity display decreases. Further, a decoloring type exposure amount indicating material as in the present invention has not been conventionally known.

[0003] Leuco dyes are easily decolored by light, but their storage stability in a colored state is not sufficient. In addition, since the coloring properties change depending on the temperature, the measurement can be performed in a short time or only in a place where the temperature is controlled. Further, since the color is easily developed by heat, the preservation before the color development must be stored in a refrigerator, and handling is troublesome.

Although azomethine dyes have sufficient storage stability,
Unless combined with an acid generator or the like, sufficient decoloring properties cannot be obtained. The sensitizing dye also has insufficient storage stability. Further, the dye disclosed in JP-A-5-96868 has a low solubility in a binder resin and has problems such as precipitation from the binder resin, so that a sufficient concentration cannot be provided.

[0005]

Accordingly, the first aspect of the present invention is as follows.
An object of the present invention is to provide a photo-decolorable material containing a photo-decolorable dye having excellent decolorability and storage stability. A second object of the present invention is to provide a photo-decolorable ink having excellent decolorability and storage stability. A third object of the present invention is to provide a photobleachable resin composition which is dissolved at a high concentration and is excellent in storability and storage stability. A fourth object of the present invention is to provide an optical recording material using a photobleachable resin composition having excellent decolorability and storage stability.

A fifth object of the present invention is to provide a decoloring property on a support,
An object of the present invention is to provide an exposure amount indicating label having a dye layer for a photo-decolorable material having excellent storage stability.

The dye for a photo-decolorable material of the present invention is a dye characterized in that the concentration of the main absorption portion in the visible portion of the dye is reduced by irradiation with ultraviolet light or visible light. The display material of the present invention is characterized in that the change can be recognized particularly under irradiation of a white fluorescent lamp (approximately 50 hours or more at 500 Lux) when a product is displayed. Furthermore, the dye of the present invention is less likely to deteriorate during storage in a dark place, and its density is reduced only by light.

Furthermore, the present inventors have found that by adding a specific additive to the dye of the present invention, the exposure time display time can be controlled, and the storage stability in a dark place is improved.

[0009]

The above object of the present invention is attained by the following constitutions.

[0010] 1. A dye for a photobleaching material represented by the following general formula (1) and the following general formula (I) or the following general formula (I
A photobleachable material comprising at least one compound represented by the formula (I).

[0011]

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In the formula, Z represents an atomic group necessary for forming a 5-membered aromatic heterocyclic ring. R represents a group that can be substituted on an aromatic heterocyclic ring. m represents an integer of 0 to 3, and when m is 2 or more, Rs may be the same or different. CP represents a group which forms a chromophore as a whole by bonding to an aromatic heterocycle through a methylene group.

[0013]

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Wherein R ¹¹ is a hydrogen atom, a hydroxyl group,
—SOR ¹³ , —SO ₂ R ¹⁴ , an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a —COR ¹⁵ group. R ¹³ and R ¹⁴ each represent an alkyl group or an aryl group. R ¹⁵ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
Z ¹¹ and Z ¹² each represent an alkylene group having 1 to 3 carbon atoms. ^However, the total number of carbon atoms of the alkylene group represented by ^{Z 11} and ^{Z 12} are 3-6. R ¹² represents Z ¹¹ or a group that can be substituted on Z ¹² , and n ₁₁ represents an integer of 0 to 4. X ¹¹ is ^{-CR 16 R 17 -, - NR} 18 -, - O -, -
S -, - SO -, - SO 2 -, - PO (OR 19) 2 - represents a. R ¹⁶ and R ¹⁷ each represent a hydrogen atom or a —OCOR ²⁰ group, and R ¹⁶ and R ¹⁷ may combine to form a heterocyclic ring.
R ²⁰ is an alkyl group, a cycloalkyl group, an alkenyl group,
Represents an alkynyl group, an aryl group, or a heterocyclic group. R ¹⁸ , R
¹⁹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

[0015]

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In the formula, R ²¹ represents a hydrogen atom, an alkyl group, an acyl group, or a trialkylsilyl group. R ²² , R ²³ ,
R ²⁴ , R ²⁵ , and R ²⁶ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkenyloxy group, an acylamino group, a halogen atom, an alkylthio group, an arylthio group, an alkoxy group. Represents a carbonyl group, an acyloxy group, an acyl group, a sulfonamide group, or a trialkylsilyloxy group. Two groups may form a 5- or 6-membered ring by combining one of R ²² to R ^26.

2. The dye for light decoloring material has the following general formula (2)
2. The photobleachable material according to the above item 1, wherein

[0018]

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In the formula, Z 'represents an atom group necessary for forming a 5-membered aromatic heterocyclic ring. R and R 'each represent a group that can be substituted on an aromatic heterocyclic ring. m and n are 0-3
And when m and n are each 2 or more, R and R 'may be the same or different. R ₁
Represents a hydrogen atom, a halogen atom or a substituent.

3. The dye for light decoloring material has the following general formula (3)
2. The photobleachable material according to the above item 1, wherein

[0021]

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In the formula, X represents an oxygen atom or a sulfur atom. R represents a group that can be substituted on an aromatic heterocyclic ring. m is 0
Represents an integer of 3, and when m is 2 or more, R may be the same or different. R ₁ and R ₂ each represent a hydrogen atom, a halogen atom or a substituent.

4. The dye for light decoloring material has the following general formula (4)
2. The photobleachable material according to the above item 1, wherein

[0024]

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In the formula, R represents a group which can be substituted on an aromatic heterocyclic ring. m represents an integer of 0 to 3, and when m is 2 or more, Rs may be the same or different. R ₁ and R ₂ each represent a hydrogen atom, a halogen atom or a substituent.

[5] The dye for a photobleaching material represented by the general formula (1) and the general formula (I) or the general formula (I
A photobleachable resin composition comprising at least one compound represented by I).

6. The general formula (2), (3) or (4)
At least one selected from dyes for photobleachable materials represented by
A photobleachable resin composition comprising: a kind of dye for photobleachable material and at least one of the compounds represented by formula (I) or formula (II).

7. The dye for a photobleaching material represented by the general formula (1) and the general formula (I) or the general formula (II)
A photo-decolorable ink comprising at least one compound represented by the formula:

8. The general formula (2), (3) or (4)
At least one selected from dyes for photobleachable materials represented by
What is claimed is: 1. A photo-decolorable ink comprising: a kind of dye for photo-decolorable material; and at least one compound represented by formula (I) or (II).

9. An exposure amount display label comprising the photo-decolorable material represented by 1, 2, 3 or 4.

10. 10. The exposure amount display label as described in 9 above, comprising a display material having a density change rate of 1% to 15% / 8hour in a room temperature white fluorescent lamp of 500 Lux.

11. 10. The exposure amount display label as described in 9 above, comprising a display material having a density change rate of 1.2% to 5% / 8hour in a room temperature white fluorescent lamp of 500 Lux.

12. The display material has a density change rate of 1% to 15% / 8hour in a room-temperature white fluorescent lamp 500Lux and a density change rate of 0% to 25% / month in a dark room at room temperature. 10. The exposure amount display label according to the item 9, wherein

13. The exposure amount indicating label according to any one of items 9 to 12, wherein the label has a layer structure in which a dye layer is provided on one side of the support and an adhesive layer is provided on the other side.

14. (9) The color filter according to the above (9), further comprising a dye layer on the support, and an adhesive layer on the dye layer.
13. The exposure amount display label according to any one of items 1 to 12.

15. The dye for a photobleaching material represented by the general formula (1) and the general formula (I) or the general formula (I
An optical recording material comprising at least one compound represented by I).

16. At least one dye for photo-decolorable materials selected from the dyes for photo-decolorable materials represented by the general formulas (2), (3) and (4); and the general formula (I) or the general formula (II) An optical recording material comprising at least one compound represented by the formula:

Hereinafter, the present invention will be described in more detail.

In the general formula (1), Z represents an atom group necessary for forming a 5-membered aromatic heterocycle. Examples of the aromatic heterocycle include a thiophene ring, a furan ring, and a pyrrole ring.

R represents a group which can be substituted on the aromatic heterocyclic ring represented by Z. Examples of the substitutable group include an alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, a t-butyl group, a 2-ethylhexyl group, etc.), a cycloalkyl group (eg, Cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, etc.), alkoxy group (eg, methoxy group, n-butoxy group, etc.), aryloxy group (eg, Phenoxy group), cyano group,
Acylamino group (eg, acetylamino group, propionylamino group, etc.), alkylthio group (eg, methylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, etc.), alkoxycarbonyl group (eg, methoxy group) Carbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, etc.), amino group (A methylamino group, an ethylamino group, a dimethylamino group, etc.), an imide group (eg, a phthalimide group), and a heterocyclic group (eg, a pyridyl group). Particularly preferred is a dialkylamino group.
These substituents may be further substituted.

M represents an integer of 0 to 3. When m is 2 or more, R may be the same or different.

CP is a compound having an active hydrogen capable of forming a dye by coupling with a known oxide of p-phenylenediamines.
Represents a group which forms a chromophore as a whole by bonding to an aromatic heterocycle through a methylene group. As the CP, for example,
Pyrazolone, imidazole, pyrazolopyrrole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, barbitur, thiobarbitur, rhodanine, hydantoin, thiohydantoin, oxazolone,
Examples include isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, pyrazolopyridone, ketoester, ketoamide and phenol. Among them, pyrazolotriazole is preferred from the viewpoint of decolorability and storage stability.

In the general formula (2), Z 'represents an atom group necessary for forming a 5-membered aromatic heterocyclic ring. Also,
Z ′ may form a condensed ring with another ring. As the aromatic heterocycle, a nitrogen-containing aromatic heterocycle is preferable, and examples thereof include an imidazole ring, a triazole ring, a tetrazole ring, a pyrrole ring and a benzotriazole ring. R represents a group which can be substituted on the aromatic heterocyclic ring represented by Z, and represented by the general formula (1)
Is synonymous with R. R ′ represents a group that can be substituted on the aromatic heterocyclic ring represented by Z ′, and examples of the substitutable group include an alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trimethyl group). Fluoromethyl group, t-butyl group, 2-ethylhexyl group, etc., cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, etc.) ), An alkoxy group (eg, methoxy group, n-butoxy group, etc.), an aryloxy group (eg, phenoxy group, etc.), a cyano group, an acylamino group (eg, acetylamino group, propionylamino group, etc.), an alkylthio group (eg, methylthio group, etc.) ), An arylthio group (for example, a phenylthio group), a sulfonylamino group (for example, Emissions sulfonylamino group), an alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), an aryloxycarbonyl group (e.g. phenoxycarbonyl group), a sulfonyl group (e.g., methanesulfonyl group,
Examples thereof include a butanesulfonyl group, a phenylsulfonyl group, an acyl group (eg, an acetyl group), an amino group (eg, a methylamino group, an ethylamino group, a dimethylamino group), and a heterocyclic group (eg, a pyridyl group). Preferably, it is an alkyl group or an aryl group. These substituents may be further substituted.

M and n each represent an integer of 0 to 3. When m and n are each 2 or more, R and R 'may be the same or different.

Examples of the group represented by R ₁ include a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a monovalent substituent (eg, an alkyl group, an aryl group, an acyl group, an amino group, Cyano group, acylamino group, alkoxy group, hydroxy group, alkoxycarbonyl group, sulfonyl group, sulfamoyl group, carbamoyl group).

In the general formula (3), X represents an oxygen atom or
Represents a sulfur atom. R represents a furan or thiophene ring
It represents a substitutable group and has the same meaning as R in the general formula (1).
m represents an integer of 0 to 3, and when m is 2 or more, R is the same
May also be different. R₁And R_TwoAre hydrogen sources
Atom, halogen atom (for example, fluorine atom, chlorine atom, bromine
Atom, etc.), or a substituent (eg, alkyl group, aryl)
Group, acyl group, amino group, cyano group, acylamino
Group, alkoxy group, hydroxy group, alkoxy carbonyl
Group, sulfonyl group, sulfamoyl group, carbamoyl
Group). R ₁Is preferably an alkyl having 1 to 9 carbon atoms
And R is_TwoIs preferably a substituted alkyl group.

In the general formula (4), R represents a group which can be substituted on a furan ring, and has the same meaning as R in the general formula (1). m
Represents an integer of 0 to 3, and when m is 2 or more, R may be the same or different. R ₁ and R ₂ each represent a hydrogen atom, a halogen atom or a substituent, and have the same meanings as R ₁ and R _{2 in} formula (3), respectively.

The following are examples of compounds of the coloring matter for photodecolorable materials of the present invention, but the present invention is not limited to these.

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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The dyes for photodecolorable materials represented by the general formulas (1) to (4) of the present invention are obtained, for example, by reacting various couplers known as photographic color formers with aldehyde-substituted aromatic derivatives. By doing so, it can be easily produced using a known reaction. Hereinafter, specific synthesis examples will be exemplified.

Synthesis Example 1 (Synthesis of Compound 7 of the Present Invention) 50 g (0.11 mol) of the intermediate (1) was added to toluene 75
0 ml, and the intermediate (2) 31 g (0.14 mol
l) then piperidine 23.3 g (0.27 mol)
Was added and stirred overnight. Ethyl acetate was added, washed with water, dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.
The obtained residue was separated and purified by silica gel column chromatography (elution solvent: hexane / ethyl acetate) to obtain Compound 7 of the present invention. Yield 36 g (yield 49
%), Red amorphous, NMR spectrum and Ma
The product was confirmed to be the target by the ss spectrum.

[0059]

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Synthesis Example 2 (Synthesis of Compound 28 of the Present Invention) 36 g (0.15 mol) of the intermediate (3) was dissolved in toluene 50
0 ml, and the intermediate (4) 23 g (0.18 mol
1) Then, 30 g (0.35 mol) of piperidine was added and the mixture was stirred overnight. Ethyl acetate was added, washed with water, dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained residue was separated and purified by silica gel column chromatography (elution solvent: hexane / ethyl acetate) to obtain Compound 28 of the present invention. Yield: 22 g (42% yield), red amorphous, NMR spectrum and Mass spectrum confirmed that it was the desired product.

[0061]

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In the above, typical examples of the synthesis of dyes have been described, but dyes other than those described above can be synthesized in the same manner.

Next, the compounds represented by formulas (I) and (II) will be described.

In the general formula (I), when X ¹¹ is —CR ¹⁶ R ¹⁷ —, the substituent represented by R ¹¹ is a hydrogen atom, an alkyl group, a hydroxyl group, —SOR ¹³ ,
—SO ₂ R ¹⁴ and —COR ¹⁵ are preferable, and X ¹¹ is —NR ¹⁸
-, - O -, - S -, - SO -, - SO 2 -, - PO
In the case of (OR ₁₉ ) ₂ —, an alkyl group or a phenyl group is preferred.

R ¹³ , R ¹⁴ and R ¹⁵ each represent an alkyl group,
Represents a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

R ¹⁶ and R ¹⁷ each represent a hydrogen atom or —OCO
R ²⁰ represents a group, and R ¹⁶ and R ¹⁷ may combine with each other to form a heterocyclic ring. R ²⁰ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. As the heterocyclic ring formed by combining R ¹⁶ and R ¹⁷ with each other, for example,

[0067]

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(Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl ring.).

R ¹⁸ and R ¹⁹ represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

Z ¹¹ and Z ¹² each represent an alkylene group having 1 to 3 carbon atoms. However, the total number of carbon atoms of the alkylene group represented by Z ¹¹ and Z ¹² are 3-6.

R ¹² represents Z ¹¹ or a group that can be substituted on Z ^12. Examples of the displaceable group include an alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group). Group, t-
Butyl group, 2-ethylhexyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.),
An aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), an aryl group (eg, phenyl group, etc.), an alkoxy group (eg, methoxy group, n-butoxy group, etc.), an aryloxy group (eg, phenoxy group, etc.), a cyano group, Acylamino groups (eg, acetylamino groups, propionylamino groups, etc.), alkylthio groups (eg, methylthio groups, etc.),
Arylthio group (for example, phenylthio group, etc.), sulfonylamino group (for example, methanesulfonylamino group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group,
Ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, etc.), amino group (methylamino group, etc.) Groups, an ethylamino group, a dimethylamino group, etc.), an imide group (eg, a phthalimido group), and a heterocyclic group (eg, a pyridyl group). These substituents may be further substituted.

N ₁₁ represents an integer of 0 to 4. When n ₁₁ is 2 or more, R ¹² may be the same or different.

The specific examples of the compounds represented by formula (I) are shown below, but the present invention is not limited to these.

[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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Next, the general formula (II) will be described.

R ²¹ is a hydrogen atom, an alkyl group, an acyl group,
Represents a trialkylsilyl group.

R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group,
Aryl group, aryloxy group, alkenyl group, alkenyloxy group, acylamino group, halogen atom, alkylthio group, arylthio group, alkoxycarbonyl group,
Represents an acyloxy group, an acyl group, a sulfonamide group, or a trialkylsilyloxy group.

Two groups out of R ^{22 to} R ²⁶ are linked to form 5
A 6-membered ring may be formed, and examples thereof include rings of indane, spiroindane, chroman, spirochroman and the like.

The following are typical examples of the compound represented by formula (II), but the present invention is not limited to these.

[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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The photo-decolorable ink of the present invention can be obtained by dissolving the dye for a photo-decolorable material of the present invention in a solvent.
The solvent to be used may be any solvent that is soluble in the dye for photo-decolorable material of the present invention, and generally used ketones (eg, acetone, methyl ethyl ketone, methyl isopropyl ketone, etc.) and alcohols (eg, ethanol) , Isopropanol, etc.), cellosolves (eg, methylcellosolve), esters (eg, ethyl acetate, ethyl lactate, etc.), aromatics (eg, toluene, xylene, chlorobenzene), and ethers (eg, tetrahydrofuran, dioxane). .

When dissolving the dye for photochromic material and the additive of the present invention in a solvent, if the amount is small, a sufficient concentration will not be obtained. Therefore, the content is preferably 0.01 to 30%, more preferably 0.05 to 10%, based on the solvent.

The photobleachable resin composition of the present invention can be obtained by dissolving the dye for a photobleachable material of the present invention and an additive in a solvent, if necessary, and then dissolving in a binder resin. The solvent to be used may be any one having solubility in both the binder resin and the dye for the photo-decolorable material of the present invention,
Commonly used ketones (eg, acetone, methyl ethyl ketone, methyl isopropyl ketone, etc.), alcohols (eg, methanol, ethanol, isopropanol, etc.), cellosolves (eg, methyl cellosolve), esters (eg, ethyl acetate, ethyl lactate) And the like, aromatics (eg, toluene, xylene, chlorobenzene), ethers (eg, tetrahydrofuran, dioxane), and chlorinated solvents (eg, chloroform, trichloroethylene).

When dissolving the dye for photo-decoloring material and the additive of the present invention in a binder resin, if the amount is small, the concentration is not sufficient, and if the amount is large, the dye is precipitated or the photo-decoloring property is deteriorated. 0.1 to the binder resin
-20% is preferable, and 1-10% is more preferable.

Examples of the binder resin include water-soluble polymers such as cellulose, polyacrylic, polyvinyl alcohol and polyvinylpyrrolidone, acrylic resins, methacrylic resins, silicone resins, polystyrene, and the like.
Although a polymer soluble in an organic solvent such as polycarbonate, polysulfone, polyethersulfone, and ethyl cellulose can be mentioned, a polymer soluble in an organic solvent is preferable. When a polymer soluble in an organic solvent is used, it may be used in the form of a latex dispersion as well as being dissolved in an organic solvent.

The optical recording material of the present invention can be obtained by preparing a resin composition containing a dye for an optical decoloring material and an additive, applying the resin composition on a support, and drying.

The support may be any as long as it has good dimensional stability and can withstand light irradiation at the time of recording. However, heat-resistant materials such as condenser paper, thin paper such as glassine paper, polyethylene terephthalate, polyamide, and polycarbonate can be used. Is preferably used.

The thickness of the support is preferably from 10 to 200 μm, more preferably from 1 to 100 μm. Further, the support preferably has an undercoat layer made of a polymer selected for the purpose of preventing adhesion to the photodecolorable resin composition and preventing dye from adhering to the support. Further, a slipping layer is provided on the back surface of the support (the side opposite to the photosensitive layer) for the purpose of preventing the optical recording material of the present invention from sticking to the support when the optical recording material is overlaid, or for the purpose of preventing abrasion. May have. Further, for the same purpose, a protective layer may be provided further above the photobleachable binder resin composition layer.

The amount of the dye for photo-decolorable material of the present invention is preferably 0.05 g to 10 g per 1 m ² of the support.

The amount of the additive of the present invention is preferably 0.01 g to ²⁰ g per 1 m ² of the support.

To record on the optical recording material of the present invention, a mask is placed on the optical recording material of the present invention, and the recording is performed by irradiating ultraviolet rays or performing scanning exposure with a He-Ne laser or the like. Arbitrary information can be recorded. On this occasion,
Since the area irradiated with light is erased, a positive image is obtained.

The exposure amount indicating label of the present invention is produced by forming a dye layer by coating or printing on a support using the photobleachable ink or the photobleachable resin composition. This is a layer configuration (A) or (B).

The layer structure (A) comprises a dye layer, a support, and a pressure-sensitive adhesive layer from the upper layer.

The dye layer is obtained from the photo-decolorable ink or the photo-decolorable resin composition.

The support is selected from those similar to the support described in the optical recording material.

For the purpose of preventing the optical recording material of the present invention from sticking to the support when laminated, or the purpose of preventing abrasion, a protective layer is further formed on the above-mentioned photo-decolorable binder resin composition layer. May be provided. The material used for the protective layer is selected in consideration of light transmittance, oxygen permeability and the like, and includes the binder resin, OP varnish, or polypropylene treatment.

Either the support or the protective layer needs to transmit light, and by exposing from the light transmitting side, the dye is decolorized, and the exposure amount can be determined. The protective layer preferably transmits light.

Examples of the pressure-sensitive adhesive layer include rubber-based, PVC-based, and acrylic-based copolymer resins.

Further, a release layer may be provided below the pressure-sensitive adhesive layer. The release layer includes silicone paper, a release-treated polyester film, etc., and the exposure amount of the sample is measured by peeling the release layer from the exposure amount label of the present invention immediately before use and attaching the release layer to a sample for measuring the exposure amount. You can judge.

The layer structure (B) comprises a transparent support, a dye layer and a pressure-sensitive adhesive layer in order from the upper layer.

Examples of the support include those described in the layer constitution (A).

It is preferable that one of the support and the pressure-sensitive adhesive layer transmits light. Exposing from the light transmitting side causes decoloration of the dye, and the amount of exposure can be determined. It is preferable that the body layer transmits light.
For example, a heat-resistant plastic film such as polyethylene terephthalate, polyamide, or polycarbonate is preferably used.

Examples of the pressure-sensitive adhesive include those similar to the pressure-sensitive adhesive in the layer constitution (A), and it is preferable to select and use a pressure-sensitive adhesive which does not affect the decoloring property or the storage stability in a dark place on the dye layer.

FIG. 1 is a sectional view showing an example of the layer structure of the exposure amount indicating label of the present invention.

FIG. 2 is a sectional view showing another example of the layer structure of the exposure amount indicating label of the present invention.

[0130]

EXAMPLES The present invention will now be described specifically with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 <Preparation of photo-decolorable ink> Dye 7 of the present invention (0.1 g)
Was dissolved in 50 ml of ethanol to prepare a photo-decolorable ink.

After the ink of a commercially available felt pen was removed and the ink was replenished by absorbing the photo-decolorable ink into the felt, the optical density of the synthetic paper (YUPO FPG-150 manufactured by Oji Oil Chemical Synthetic Paper) was 1. The sample 1 was prepared by drawing so as to obtain a sample No. 5.

<Evaluation of Photodecolorable Ink> Sample 1 was adjusted so that the illuminance of a fluorescent lamp was 600 Lux, and the sample was irradiated for 100 hours. The density was 55% of the initial density. It was confirmed by visual inspection that the color had been clearly erased.

When Sample 1 was stored at 40 ° C. for 120 hours, the concentration became 93% of the initial concentration. It could not be confirmed by visual inspection that the color had been erased.

Samples 2 to 9 were prepared and evaluated in the same manner as in Sample 1 except that the type of dye and additives were changed as shown in Table 1. The results are shown in Table 1.

Light resistance was expressed by (density after light irradiation) / (initial density) × 100 (%).

Heat resistance (concentration after storage) / (initial concentration)
× 100 (%).

[0138]

[Table 1]

[0139]

Embedded image

From the above, it can be seen that the photobleachable ink of the present invention has improved storage stability while maintaining high decolorability even when compared to a photobleachable ink containing no additive. On the other hand, in Samples 10 to 12 using the comparative dyes, the storage stability was slightly inferior even when the additive was added, the decoloration ratio upon irradiation with light was small, and it was difficult to visually discriminate.

Example 2 <Preparation of Photodecolorable Resin Composition>
A photobleachable resin composition of the present invention was prepared.

Dye 7 0.3 mmol Polyvinyl butyral resin (ESLEX BX-1) 100 mg Methyl ethyl ketone 3.0 ml Next, the obtained resin composition was synthesized with a wire bar using synthetic paper (YUPO FPG-150 Oji Oil Chemical Synthetic Paper). Sample 13 was prepared by applying the solution to a concentration of 1.5.

<Evaluation of Photodecolorable Resin Composition> Sample 13 was adjusted such that the illuminance of a fluorescent lamp was 500 Lux.
When irradiated for 0 hours, the concentration becomes 65% of the initial concentration,
It was confirmed by visual inspection that the color had been clearly erased.

Further, the sample 13 was treated at 40 ° C. and 80% RH for 16 hours.
When stored for 0 hours, the concentration was 92% of the initial concentration. It could not be confirmed by visual inspection that the color had been erased.

Sample 1 was used except that the type of dye and / or the additive (the amount added was 0.3 mmol) was changed as shown in Table 2.
Samples 14 to 24 were prepared and evaluated in the same manner as in No. 3. The results are shown in Table 2.

The light resistance was represented by (density after light irradiation) / (initial density) × 100 (%).

Heat resistance (concentration after storage) / (initial concentration)
× 100 (%).

[0148]

[Table 2]

[0149]

Embedded image

From the above, it can be seen that the photobleachable resin composition of the present invention has excellent erasability and good storage stability.

Example 3 <Preparation of Optical Recording Material> The photobleachable binder resin composition of Sample 13 was dried on a 100 μm-thick PET film with a wire bar at a coating amount of 2.5 g / m 2. ^An optical recording material sample 25 in which a photo-decolorable layer was formed on a PET film was prepared by coating and drying so as to obtain No. 2. Note that a nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichi Seika Co., Ltd.) is provided as a sticking prevention layer on the back surface of the PET film.

Samples 25 to 37 were prepared in the same manner as described above except that the coloring matter or the additive was changed, and the photobleachability and the storage stability were evaluated.

Table 3 shows the results.

Evaluation method (optical decoloring property): UGRA plate control wedge PCW was applied to the produced optical recording material.
Using Sample No. 82 (manufactured by Mika Denshi Co., Ltd.), the sample 13 was irradiated with ultraviolet rays, and the irradiation amount of the ultraviolet rays was adjusted so that the number of decolored steps became the eighth step. Next, the same amount of ultraviolet light was irradiated, and the evaluation was made based on the number of wedges that were erased. The larger the number of steps, the better the decoloring property.

Evaluation method (storability): A sample wrapped in black paper and shielded from light was stored in a thermostat at 50 ° C. for 150 hours. The storability was expressed as (density / initial density) × 100 (%) after storage.

[0156]

Embedded image

[0157]

[Table 3]

It can be seen that the optical recording material of the present invention can control the light decoloring property by an additive and has good storage stability.

Example 4 <Production of Exposure Label> 0.5 g of Dye 7 was dissolved in 10 g of a commercially available medium (PSY-T manufactured by Tokyo Ink).
An ink was prepared by adding 10 ml of MEK and 5 ml of toluene, and a wedge stripe of 0.1 in increments of 0.1 to 1.5 was printed on a 38 μm pet film using a gravure printer. An adhesive (Ricabond AP-202 manufactured by Chuo Rika Kogyo Co., Ltd.) is applied to the printed surface of the obtained printed matter, and after drying, a release paper is pasted and the printed stripe is cut out to produce an exposure amount display label sample 38. did.

FIG. 3 is a schematic view showing another example of the exposure amount display label of the present invention.

<Evaluation of Exposure Amount Display Label> The prepared sample 38 was peeled off from the release paper and stuck to a glass plate, and a fluorescent lamp was applied from the pet film side at a temperature of 10 ° C. and an illumination of 6
After adjusting to 00 Lux, irradiating for 8 hours and then irradiating for 16 hours was repeated until the total irradiation time became 120 hours, the concentration became 70% of the initial concentration,
It was confirmed by visual inspection that the color had been clearly erased.

When the sample 38 was shielded from light with black paper and stored at 20 degrees for 720 hours, the initial density was 91% of the initial density.
It could not be confirmed by visual inspection that the color had been erased.

Similarly, samples 38 to 50 were prepared and evaluated.
Table 4 shows the results.

[0164]

[Table 4]

The light residual ratio was calculated as density after light irradiation / initial density × 1.
It was shown as 00 (%). () Shows the rate of change of the concentration when converted to 8 hours. Density change rate = (100−light remaining rate) / (120/8) The heat remaining rate was represented by density after storage / initial density × 100 (%).

From the above, it can be seen that the exposure amount indicating label of the present invention has excellent storage properties while having excellent decoloring properties.

Example 5 <Preparation of Exposure Amount Display Label> 70.5 g of a dye was dissolved in 10 g of a commercially available medium (PSY-T manufactured by Tokyo Ink).
An ink was prepared by adding 10 ml of EK and 5 ml of toluene, and a gravure printing machine was used to coat a paper support with polyethylene on both sides of a paper support at a concentration of 0.1 to 1.5.
The wedge stripes were printed in increments of 0.1 until the end. A commercially available OP varnish (70 g of Dainippon Ink and Chemicals, Die Reducer PA No. 20 on 30 g of Ultimame Medium manufactured by Dainippon Ink and Chemicals) was applied on the printing surface of the obtained printed matter.
Was diluted using a wire bar and dried such that the coating amount after drying was 1.5 g / m ² . Next, an adhesive (Licabond AP-202 manufactured by Chuo Rika Kogyo Co., Ltd.) is applied to the back side of the printed surface, dried, a release paper is pasted, the printed stripe is cut out, and an exposure amount display label sample 5 is prepared.
1 was produced.

FIG. 4 is a schematic view showing another example of the exposure amount indicating label of the present invention.

<Evaluation of Exposure Amount Display Label> The prepared sample 51 was peeled off from the release paper and adhered to a glass plate, and a fluorescent lamp was applied from the OP varnish layer side at a temperature of 10 ° C. and an illuminance of 600 °.
Lux was adjusted, and after irradiation for 8 hours, non-irradiation was repeated for 16 hours. When the total irradiation time reached 120 hours, the density was 73% of the initial density, and the color was clearly erased visually. Was confirmed.

When the sample 51 was shielded from light with black paper and stored at 20 degrees for 720 hours, it became 94% of the initial density.
It could not be confirmed by visual inspection that the color had been erased.

Samples 52 to 61 were prepared and evaluated in the same manner except that the dyes and additives were changed as shown in Table 5. Table 5 shows the results
Shown in

[0172]

[Table 5]

[0173] The light residual ratio was calculated as density after light irradiation / initial density x 1
It was shown as 00 (%). () Shows the rate of change of the concentration when converted to 8 hours. Density change rate = (100−light remaining rate) / (120/8) The heat remaining rate was represented by density after storage / initial density × 100 (%).

As described above, the exposure amount indicating label of the present invention may have excellent erasability and good storage stability. Further, the decoloring property can be controlled by selecting the additive.

[0175]

The photobleachable material, the photobleachable ink, the photobleachable resin composition dissolved at a high concentration, and the photobleachable resin composition containing the photobleachable dye according to the present invention are used. The decoloring type exposure amount display label having the optical recording material and the dye layer for the light decoloring material on the support has excellent effects on decoloring property and storage stability.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a layer configuration of an exposure amount indicating label of the present invention.

FIG. 2 is a cross-sectional view illustrating another example of the layer configuration of the exposure amount indicating label of the present invention.

FIG. 3 is a schematic diagram showing an example of an exposure amount display label of the present invention.

FIG. 4 is a schematic diagram showing another example of the exposure amount display label of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Dye layer 2 Support 3 Adhesive layer 4 Wedge stripe 5 Pet film 6 Ink layer 7 Release layer 8 OP varnish layer 9 Paper support (laminated on both sides)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 23/00 C09B 23/00 LM C09K 9/02 C09K 9/02 B G03C 1/73 G03C 1/73 // C09K 3/00 C09K 3/00 Y F term (reference) 2H123 AE00 AE01 CA00 CA15 CA17 CB00 CB02 EA14 EA17 FA12 4H056 CA01 CC02 CC08 CE03 CE07 DD06 DD12 DD15 DD19 FA05 4J002 AA001 AB011 BC031 BF011 BG021 BG021 BG021 EJ017 EJ027 EJ037 EJ067 EL067 EL087 EL107 EP017 EU037 EU107 EU137 EU146 EU166 EU187 EV077 EV216 EV286 EV306 EV307 EW047 EX037 FD096 FD097 GH00

Claims (16)

[Claims] 1. A dye for a photo-decolorable material represented by the following general formula (1) and the following general formula (I) or the following general formula (II)
A photo-decolorable material comprising at least one compound represented by the formula: Embedded image [In the formula, Z represents an atom group necessary for forming a 5-membered aromatic heterocyclic ring. R represents a group that can be substituted on an aromatic heterocyclic ring. m represents an integer of 0 to 3, and when m is 2 or more, Rs may be the same or different. CP represents a group which forms a chromophore as a whole by bonding to an aromatic heterocycle through a methylene group. [Chemical formula 2] Wherein R ¹¹ is a hydrogen atom, a hydroxyl group, -SO
R ¹³ , —SO ₂ R ¹⁴ , an alkyl group, a cycloalkyl group,
Represents an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a —COR ¹⁵ group. R ¹³ and R ¹⁴ each represent an alkyl group or an aryl group. R ¹⁵ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Z ¹¹
And Z ¹² each represent an alkylene group having 1 to 3 carbon atoms. However, the total number of carbon atoms of the alkylene group represented by Z ¹¹ and Z ¹² are 3-6. R ¹² is Z ¹¹ or Z ¹²
And n ₁₁ represents an integer of 0 to 4. X
^{11 -CR 16 R 17 -, - NR} 18 -, - O -, - S -, -
_{SO -, - SO 2 -,} - PO (OR 19) 2 - represents a.
R ¹⁶ and R ¹⁷ each represent a hydrogen atom or a —OCOR ²⁰ group, and R ¹⁶ and R ¹⁷ may combine to form a heterocyclic ring. R
²⁰ represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. R ¹⁸ , R ¹⁹
Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. [Chemical formula 3] [In the formula, R ²¹ represents a hydrogen atom, an alkyl group, an acyl group, or a trialkylsilyl group. ^{R 22, R 23, R 24} , R 25, R
²⁶ is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkenyloxy group, an acylamino group, a halogen atom, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an acyloxy group, and an acyl group, respectively. Group, a sulfonamide group, and a trialkylsilyloxy group. R ²² ~R ²⁶
And two of the groups may be linked to form a 5- to 6-membered ring. ] 2. The photo-decolorizable material according to claim 1, wherein the dye for a photo-decolorable material is represented by the following general formula (2). Embedded image [In the formula, Z ′ represents an atom group necessary for forming a 5-membered aromatic heterocyclic ring. R and R 'each represent a group that can be substituted on an aromatic heterocyclic ring. m and n represent an integer of 0 to 3, and when m and n are each 2 or more, R and R 'may be the same or different. R ₁ represents a hydrogen atom, a halogen atom or a substituent. ] 3. The photobleachable material according to claim 1, wherein the dye for a photobleachable material is represented by the following general formula (3). Embedded image [In the formula, X represents an oxygen atom or a sulfur atom. R represents a group that can be substituted on an aromatic heterocyclic ring. m represents an integer of 0 to 3, and when m is 2 or more, Rs may be the same or different. R ₁ and R ₂ each represent a hydrogen atom, a halogen atom or a substituent. ] 4. The photobleachable material according to claim 1, wherein the dye for a photobleachable material is represented by the following general formula (4). Embedded image [In the formula, R represents a group that can be substituted with an aromatic heterocyclic ring. m represents an integer of 0 to 3, and when m is 2 or more, Rs may be the same or different. R ₁ and R ₂ are each a hydrogen atom,
Represents a halogen atom or a substituent. ] 5. A dye for a photo-decolorable material represented by the general formula (1) and the general formula (I) or the general formula (II)
A photobleachable resin composition comprising at least one compound represented by the formula: 6. A dye for a photo-decolorable material selected from the dyes for a photo-decolorable material represented by the general formula (2), (3) or (4) and the general formula (I) or A photobleachable resin composition comprising at least one compound represented by the general formula (II). 7. A photo-decoloring material dye represented by the general formula (1) and at least one compound represented by the general formula (I) or the general formula (II). Light decolorable ink. 8. A dye for a photo-decolorable material selected from the dyes for a photo-decolorable material represented by the general formula (2), (3) or (4) and the general formula (I) or A photo-decolorable ink comprising at least one compound represented by the general formula (II). 9. An exposure amount indicating label comprising the photo-decolorable material according to claim 1, 2, 3, or 4. 10. The exposure amount display label according to claim 9, comprising a display material having a density change rate of 1% to 15% / 8hour in a room temperature white fluorescent lamp of 500 Lux. 11. The exposure amount display label according to claim 9, further comprising a display material having a density change rate of 1.2% to 5% / 8hour in a room-temperature white fluorescent lamp of 500 Lux. 12. A display material having a density change rate of 1% to 15% / 8hour in a room temperature white fluorescent lamp 500 Lux and a density change rate of 0% to 25% / month in a dark place at room temperature. The exposure amount indicating label according to claim 9, wherein the label is provided. 13. A support having a dye layer on one side of a support,
The exposure amount indicating label according to any one of claims 9 to 12, wherein the label has a layer structure having an adhesive layer on the other surface. 14. A layer structure having a dye layer on a support and an adhesive layer on the dye layer.
13. The exposure amount display label according to any one of items 1 to 12. 15. A dye for a photo-decolorable material represented by the general formula (1) and the general formula (I) or the general formula (II)
An optical recording material comprising at least one compound represented by the formula: 16. The general formula (2), (3) or (4)
At least one selected from dyes for photobleachable materials represented by
An optical recording material comprising: a kind of dye for a photo-decolorable material; and at least one of the compounds represented by the general formula (I) or the general formula (II).