JP2002214737A - Photofixing composition, recording material containing the same and image recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photo-fixing composition with which light sources in a wide range from UV to IR regions can be used and images can be fixed without depending on the absorption wavelength of a diazo compound. SOLUTION: The photo-fixing composition contains a diazo compound, a coupler compound having releasing groups except for hydrogen atoms, and organic dyes. The oxidation potential of the coupler compound is preferably <=1 V. The organic dyes preferably have capability to produce singlet oxygen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diazo color-forming optical fixing composition which can be fixed with light in the ultraviolet to infrared region and has excellent whiteness in a non-color-forming portion, a recording material containing the same, and a recording material containing the same. The present invention relates to an image recording method using a recording material.

[0002]

2. Description of the Related Art A diazo compound is a compound having a very high chemical activity, which easily reacts with a coupler compound to form an azo dye, has photosensitivity, and is decomposed by light irradiation to reduce its activity. lose. An image forming method utilizing a color development reaction by coupling of a diazo compound and a coupler compound is widely known. In this image forming method, after a desired image is formed by heating or pressing, the diazo compound is decomposed by irradiating light corresponding to the light absorption wavelength of the remaining diazo compound without contributing to the coupling reaction. By doing so, the image can be fixed. Such a method is described in, for example, JP-A-60-49991.
JP, JP-A-4-53794, JP-A-7-96
No. 671 and the like.

In such a method, when a diazo compound having a maximum absorption wavelength (λmax) of less than 330 nm is to be used, light is absorbed by an organic coexisting component having an absorption in the wavelength region, so that an inexpensive fixing is performed. The diazo compound cannot be completely decomposed by the lamp for use. That is, the non-colored portion cannot be sufficiently fixed, and the whiteness of the non-image portion (background portion) cannot be maintained. Moreover, the light (short-wavelength light) of such a lamp is often harmful, and it can be said that it is not suitable for general use.

As described above, in a recording material of a diazo coloring system using a diazo compound and a coupler compound, an image is fixed by photolysis of the diazo compound. Available light sources were limited.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention can use a wide range of light sources in the ultraviolet to infrared region, can fix the formed image regardless of the absorption wavelength of the diazo compound, and can provide a high-contrast image excellent in background whiteness. It is an object of the present invention to provide a photo-fixable composition capable of stably forming, a recording material having a recording layer containing the photo-fixable composition, and an image recording method using the recording material.

[0006]

The object of the present invention is to provide a diazo coloring system using a diazo compound and a coupler compound,
The reactivity of the coupler compound, that is, the coupler compound is decomposed by irradiating light in the coexistence of a specific coupler compound and a specific organic dye, regardless of the absorption wavelength of the diazo compound, can be a stable non-coloring system Achieved based on Specific means for solving the above problems are as follows. That is,

<1> An optical fixing composition comprising a diazo compound, a coupler compound having a leaving group other than a hydrogen atom, and an organic dye. <2> The photo-fixable composition according to <1>, wherein the coupler compound is a coupler compound having an oxidation potential of 1 V or less.

<3> The coupler compound is a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (3), and a compound represented by the following formula: The photofixable composition according to <1> or <2>, which is at least one selected from the compounds represented by (4).

[0009]

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[In the general formulas (1) and (2), X ¹ , X ² ,
X ³ and X ⁴ each independently represent an atomic group necessary for forming a 5-membered aromatic heterocycle. Y represents a hydroxyl group, an amino group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and Y and X ¹ may be bonded to each other to form a ring. In the general formula (3), EWG ¹ and EWG
² each independently represents an electron-withdrawing group, and EWG ¹ and EWG ¹
WG ² may combine with each other to form a ring. In the general formula (4), Z represents a hydroxyl group or an amino group, and Ar ¹ is
Represents a benzene ring and a naphthalene ring. General formula (1)-
In (4), L represents a leaving group other than a hydrogen atom that can be removed during the reaction with the diazo compound. ]

<4> The photo-fixable composition according to any one of <1> to <3>, wherein the organic dye is a dye capable of generating singlet oxygen upon irradiation with light. <5> The photo-fixable composition according to <3> or <4>, wherein the leaving group other than a hydrogen atom is a halogen or a phenoxy group. <6> A recording material having a recording layer on a support, wherein the recording layer contains the photo-fixable composition according to any one of <1> to <5>.

<7> An image recording method using a recording material having a recording layer containing a photo-fixable composition on a support, wherein at least the recording layer of the recording material is imagewise exposed.
An exposure step of generating a singlet oxygen to form a latent image, and a color development step of forming an image by forming a color in accordance with the latent image by heating or pressing simultaneously or after forming the latent image in the exposure step; And the recording material is <6
<3> An image recording method, characterized by being the recording material described in (1).

<8> An image recording method using a recording material having a recording layer containing a photo-fixable composition on a support, wherein at least the recording layer of the recording material is heated or pressed imagewise to form a color. And a fixing step of irradiating the surface of the recording layer with light to generate singlet oxygen and fixing the recording layer, and wherein the recording material is the recording material according to the item <6>. An image recording method characterized by the following.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The photo-fixing composition of the present invention contains an organic dye together with a diazo compound and a coupler compound which reacts with the diazo compound to form a color. The recording material of the present invention has a recording layer containing the photo-fixable composition of the present invention, and the image recording method of the present invention uses the recording material of the present invention. Hereinafter, the photo-fixable composition of the present invention will be described in detail, and the recording material and the image recording method of the present invention will also be described in detail through the description.

<Photo-Fixing Composition> The photo-fixing composition of the present invention comprises a diazo compound as a color-forming component and a coupler compound having a leaving group other than a hydrogen atom, which forms a color by coupling reaction with the diazo compound. And an organic dye, if necessary, a coloring aid, a binder, an organic base,
It contains other components such as an organic borate compound and an organic unsaturated compound.

In the present invention, a coupler compound, which is one of the coloring components, and an organic dye are allowed to coexist, and the coupler compound is decomposed by irradiating the organic dye with light to fix a formed image. That is, the non-colored portion (background portion) and the maximum density (Dma
In the region where the color has not been formed up to x), the unreacted color forming component remains as it is, and therefore it is necessary to form the image once and then make it non-color-forming (that is, fix). In the present invention, singlet oxygen is generated by light irradiation on the organic dye,
The coupler compound is decomposed and fixed by the generated singlet oxygen. In particular, since the coupler compound according to the present invention is excellent in decomposability by singlet oxygen, it can be easily decomposed and sufficiently fixed. Therefore, any organic dye may be used as long as it has singlet oxygen generating ability, and can be arbitrarily selected regardless of the dye absorption wavelength. As described above, even when a diazo compound having low photodegradability due to short-wave absorption is used, it is possible to sufficiently fix an image, and the light source for fixing is not only ultraviolet light, but also visible to light.
A wide range of light sources that emit light in the infrared region can be used. In addition, since sufficient fixing with less fluctuation of density or the like can be performed, the whiteness of the non-image portion (background portion) is excellent, and a high-contrast image can be formed stably and held for a long time.

Next, each component constituting the photo-fixable composition of the present invention will be described. Hereinafter, the coupler compound may be simply referred to as “coupler”.

(Coupler Compound) The photo-fixable composition of the present invention contains, as a coupler compound, a coupler compound (coupler) having a leaving group other than a hydrogen atom. The coupler is a compound which forms a azo dye by a coupling reaction with a diazo compound described below when heated or pressurized to form a color.

The coupler compound used in the present invention is not particularly limited as long as it has a leaving group other than a hydrogen atom, and can be appropriately selected from coupler compounds represented by the following general formula (α).

Cp-L: General formula (α) In the general formula (α), Cp represents a mother nucleus of a coupler compound;
It may be an aliphatic compound or an aromatic compound. When Cp is an aromatic compound, it is preferably substituted with an electron-withdrawing group. In addition, because of high reactivity, the aromatic compound is preferably a heterocycle having an atom having a lone electron pair such as oxygen, nitrogen, or sulfur as a constituent element.

L in the formula represents a substituent other than a hydrogen atom which can be removed when reacting with a diazo compound (hereinafter, appropriately referred to as a "leaving group"), and among them, a halogen atom, a phenoxy group, a cyano group Are preferred. When L is a hydrogen atom, the decomposability due to singlet oxygen generated from an organic dye coexisting at the time of light fixing is low, so that it cannot be easily decomposed and sufficient light fixing cannot be performed.

Among the coupler compounds represented by the general formula (α), compounds having a structure represented by the following general formula (1), (2), (3) or (4) are preferable.

[0023]

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In the above general formulas (1) and (2), X ¹ ,
X ² , X ³ and X ⁴ each independently represent an atomic group necessary for forming a 5-membered aromatic heterocyclic ring, and examples thereof include carbon, nitrogen, oxygen, sulfur and phosphorus. In the formula, Y represents a hydroxyl group, an amino group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and Y and X ¹ may be bonded to each other to form a ring.

An amino group, an alkyl group represented by the aforementioned Y,
The aryl group, alkoxy group, and aryloxy group may be unsubstituted or substituted with a substituent. Examples of the substituent when substituted include, for example, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a nitro group, a cyano group, a substituted carbamoyl group, a substituted sulfamoyl group, a substituted amino group, a substituted oxycarbamoyl group, Examples include an oxysulfonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group, a hydroxy group, an acyl group, an acyloxy group, a substituted sulfonyloxy group, a substituted aminocarbonyloxy group, and a substituted phosphoryloxy group.

The alkyl group represented by Y is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl, trifluoromethyl, ethyl, butyl, hexyl, octyl, 2-ethylhexyl. Group, decyl group, dodecyl group, octadecyl group, propyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, isopentyl group, heptyl group , Nonyl group, undecyl group, propenyl group, heptadecenyl group, t-octyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyl group, 1- (ethoxycarbonyl) ethyl group, 2 ′, 4 ′ -Diisopentylphenyloxymethyl group, 2 ', 4'- Di-t-butylphenyloxymethyl group, ethoxycarbonylethyl group, 2-ethylhexyloxycarbonylethyl group, butyldecyloxycarbonylethyl group, dibutylaminocarbonylmethyl group, dibenzylaminocarbonylethyl group, ethyloxycarbonylpropyl group,

2-ethylhexyloxycarbonylpropyl group, 2,4-di-t-amylphenyloxypropyl group, 1- (2 ', 4'-di-t-amylphenyloxy) propyl group, 2,4-di -T-butylphenyloxypropyl group, acetylaminoethyl group, N, N-dihexylaminocarbonylethyl group, 2,4-di-t-amyloxyethyloxycarbonylpropyl group, isostearyloxycarbonylpropyl group, 1- ( 2,4-
Di-t-pentylphenyloxy) propyl group, 2,4
-Di-t-pentylphenyloxyethyloxycarbonylpropyl group, naphthyloxyethyloxycarbonylethyl group, N-methyl-N-phenylethyloxycarbonylethyl group, methanesulfonylaminopropyl group and the like.

The aryl group represented by Y is preferably an aryl group having 6 to 30 carbon atoms, for example, a phenyl group, a 2-methylphenyl group, a 2-chlorophenyl group,
2-methoxyphenyl group, 2-ethoxyphenyl group, 2
-Propoxyphenyl group, 2-isopropoxyphenyl group, 2-butoxyphenyl group, 2- (2-ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 2-undecyloxyphenyl group, 2-trifluoromethylphenyl Group, 2- (2-ethylhexyloxy) -5-chlorophenyl group, 2- (2-ethylhexyloxy) -3,5-dichlorophenyl group, 3- (2,
4-di-t-pentylphenoxyethoxy) phenyl group, 2- (dibutylaminocarbonylethoxy) phenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,4,6-trimethylphenyl group, 3-
Chlorophenyl group, 3-nitrophenyl group, 3-cyanophenyl group,

3-trifluoromethylphenyl group, 3-
Methoxyphenyl group, 3-ethoxyphenyl group, 3-butoxyphenyl group, 3- (2-ethylhexyloxy)
Phenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 3,4-dimethoxyphenyl group,
3,5-dibutoxyphenyl group, 3-octyloxyphenyl group, 3- (dibutylaminocarbonylmethoxy)
A phenyl group, a 3- (di-2-ethylhexylaminocarbonylmethoxy) phenyl group, a 3-dodecyloxyphenyl group, a 4-chlorophenyl group, a 4-cyanophenyl group, a 4-nitrophenyl group, a 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-isopropoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group, 4-isopentyloxyphenyl group, 4- (octadecyloxy) Phenyl group, 4-benzylphenyl group,

4-aminosulfonylphenyl group, 4-
N, N-dibutylaminosulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4- (2-ethylhexyloxycarbonyl) phenyl group, 4-t-octylphenyl group, 4-fluorophenyl group, 3-acetylphenyl group, 2 -Acetylaminophenyl group, 2,4-di-
t-pentylphenyl, 4- (2-ethylhexyloxy) carbonylphenyl, 4-methylthiophenyl, 4- (4-chlorophenylthio) phenyl, hydroxyphenyl, phenylsulfonylphenyl, phenylsulfonyloxy Examples include a phenyl group, a phenylcarbonyloxyphenyl group, a dimethylaminocarbonyloxyphenyl group, a butylcarbonyloxyphenyl group, and the like.

The alkoxy group represented by Y is preferably an alkoxy group having 1 to 20 carbon atoms, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, an isobutyloxy group and an n-hexyloxy group. , 2-ethylhexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group and the like. As the aryloxy group represented by Y, an aryloxy group having 7 to 30 carbon atoms is preferable, and examples thereof include a phenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, and a 4-chlorophenoxy group. .

When Y represents a substituted amino group having a substituent, the substituted amino group is preferably a substituted amino group having 1 to 30 carbon atoms, for example, isopropylamino, isobutylamino, n-hexyl. Amino group, 2-
Ethylhexylamino group, n-octylamino group, n-
Decylamino group, acylamino group, ethanoylamino group, propanoylamino group, butanoylamino group, hexanoylamino group, 2-hexylhexanoylamino group,
n-octanoylamino group, n-decanoylamino group,
n-dodecanoylamino group, methanesulfonylamino group, ethanesulfonylamino group, propanesulfonylamino group, butanesulfonylamino group, hexanesulfonylamino group, 2-ethylhexanesulfonylamino group,
Examples thereof include an n-octanesulfonylamino group, an n-decanesulfonylamino group, and an n-dodecanesulfonylamino group.

In the general formula (3), EWG ¹ and EWG ²
Each independently represents an electron withdrawing group, and examples of the electron withdrawing group include a nitro group, a carboxyl group, a carbonyl group, and a cyano group. EWG ¹ and EWG
² may combine with each other to form a ring.

The ring formed by Y and X ¹ and EWG ¹ and EWG ² includes a 5- or 6-membered aromatic or heterocyclic ring. The aromatic (heterocyclic) ring preferably has at least one electron-withdrawing group as a substituent, from the viewpoint of facilitating dissociation of the coupler compound.
Here, examples of the electron-withdrawing group include a nitro group, a carboxyl group, a carbonyl group, and a cyano group.

In the general formula (4), Z represents a hydroxyl group or an amino group, and the amino group may be unsubstituted or substituted with a substituent. The amino group has the same meaning as the above-mentioned substituted amino group represented by Y. Ar ¹ in the formula represents a benzene ring or a naphthalene ring, and each of them may be unsubstituted or substituted with a substituent, and as the substituent, Y is substituted. The same substituents as in the above case are exemplified.

In the above general formulas (1) to (4), L represents a leaving group other than a hydrogen atom which can be removed during the reaction with a diazo compound, and among them, a halogen atom, a phenoxy group, a cyano group and the like are preferable. , From the point of high reactivity, a fluorine atom,
Chlorine, bromine and iodine are particularly preferred.

In the present invention, a coupler compound having an oxidation potential of 1 V or less is preferable in that it has high decomposability due to singlet oxygen generated from an organic dye coexisting during light fixing and is easily decomposable. In the present invention, the oxidation potential refers to a half-wave potential measured by the following method. That is, first, as a supporting electrolyte, a supporting electrolyte solution in which an aqueous solution containing 2.5 × 10 ⁻² mol each of Na ₂ CO ₃ and NaHCO ₃ and acetonitrile is mixed at a ratio of 1: 1 is prepared.
In this supporting electrolyte solution, the coupler compound was dissolved so as to have a concentration of 1 × 10 ⁻³ mol, and a carbon electrode and a saturated calomel electrode as a reference electrode were arranged in the solution, and cyclic voltammetry was performed. The oxidation potential can be measured by the method. For example, the oxidation potential of the following exemplary compound (C-1) of the coupler compound is 0.38 V, and the oxidation potential of the following exemplary compound (C-13) is 0.5.
9V.

Specific examples of preferred coupler compounds (exemplary compounds (C-1) to (C-39)) are shown below, but the present invention is not limited thereto.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The coupler compound may be used by adding a water-soluble polymer (binder described later) together with other components described below and solid-dispersing it with a sand mill or the like. It can also be used as a product. Here, as a method of solid dispersion or emulsification,
The method is not particularly limited, and a conventionally known method can be used. For details of these methods, see JP-A-59-190886, JP-A-2-141279,
It is described in JP-A-7-17145.

The coupler compounds may be used alone or in a combination of two or more. As the content of the coupler compound, the following diazo compound 1
The amount is preferably 0.5 to 20% by mass, and
10% by mass is more preferred. The content is 0.5% by mass.
When the amount is less than the above, the coloring density may be reduced. When the amount exceeds 20% by mass, for example, when a layer is formed on a support or the like, the suitability for coating may be deteriorated.

(Organic Dye) In the present invention, the organic dye is a compound that generates singlet oxygen by light irradiation.
The organic dye can be appropriately selected from known compounds, and among them, an organic dye having a maximum absorption wavelength (λmax) at 300 to 1000 nm is preferable.
Specific examples of the organic dye include “Research”.
Disclogure, Vol. 200, 1980 1
February, Item 20036 ”and“ Sensitizer ”(p.160
~ P.163, Kodansha; Katsumi Tokumaru, Shin Okawara / ed., 198
7 years). The organic dye contained in the photo-fixable composition of the present invention may be any of a cationic type, an anionic type and a nonionic type organic dye.

Specifically, 3-ketocoumarin compounds described in JP-A-58-15603, JP-A-58-40
No. 302, JP-B-59-
No. 28328, No. 60-53300, naphthothiazole merocyanine compounds, JP-B-61-9
621, 62-3842, and JP-A-59-842.
Nos. 89303 and 60-60104, merocyanine compounds described in JP-A-62-150242, JP-A-64-59345, and JP-B-8-964.
No. 3, Japanese Patent Application No. 11-20089, Japanese Patent Application No. 1
No. 1-323838, Japanese Patent Application No. 11-368432.
Specification, Japanese Patent Application No. 2000-34935, Japanese Patent Application No. 2000-34935
000-38861, Japanese Patent Application No. 2000-3887.
No. 2, Japanese Patent Application No. 2000-142112, a merocyanine dye containing thiobarbituric acid, a hemioxanol dye, a cyanine having an indolenine nucleus,
Hemicyanine, merocyanine dyes, and the like.

Further, “Chemistry of functional dyes” (1981)
Year, CMC Publishing Co., p.393-p.416) and "Colorants"
(60 [4] 212-224 (1987)). Specific examples thereof include a cationic methine dye, a cationic carbonium dye, a cationic quinone imine dye, a cationic indoline dye, and a cationic dye. And the like.

The organic dye includes keto dyes such as coumarin (including ketocoumarin or sulfoncoumarin) dyes, merostyril dyes, oxonol dyes and hemioxonol dyes; non-ketopolymethine dyes, triarylmethane dyes, xanthene dyes, anthracene dyes Non-keto dyes such as dyes, rhodamine dyes, acridine dyes, aniline dyes and azo dyes; non-ketopolymethine dyes such as azomethine dyes, cyanine dyes, carbocyanine dyes, dicarbocyanine dyes, tricarbocyanine dyes, hemicyanine dyes and styryl dyes; It includes quinone imine dyes such as azine dyes, oxazine dyes, thiazine dyes, quinoline dyes, and thiazole dyes.

As described above, in the present invention, from the viewpoint of performing light fixing by decomposing the coupler compound, a dye capable of generating singlet oxygen by irradiation light is preferable as the organic dye. . Regarding the singlet oxygen generating ability of an organic dye, for example, in a mixed solution of diphenylisobenzofuran and the organic dye, only the organic dye is irradiated with light, and the absorption intensity of diphenylisobenzofuran, which is reduced by the reaction with the generated singlet oxygen ( It can be confirmed by measuring the waveform variation of the absorption wavelength). When the absorption wavelength of the organic dye overlaps with that of diphenylisobenzofuran, the emission intensity (1270 nm) of singlet oxygen when the mixed solution is irradiated with light may be measured. These measurement methods are described in "J. Amer. Chem. So.
c. "(105, 5756 (1983))," J. Ph.
ys. Chem. "(91, 4599 (1987)).

Specific examples of the above-mentioned cationic, anionic or nonionic organic dyes (exemplified compounds 1-1 to 3-
12, Exemplified Compounds 1 to 115), but are not limited thereto.

(Cation type organic dye)

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[0053]

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[0054]

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[0055]

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(Anionic Organic Dye)

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(Nonionic organic dye)

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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The organic dye is the same as the coupler compound described above.
A water-soluble polymer (binder described below) may be added together with the coupler compound and other components described below, and solid-dispersed using a sand mill or the like, or emulsified with a suitable emulsifying aid and used as an emulsion. The method of solid dispersion or emulsification is as described above.

The organic dyes may be used alone or in combination of two or more. The content of the organic dye is, based on the coupler compound, 0.0
1-10 mass% is preferable, and 0.02-5 mass% is more preferable. If the content is less than 0.01% by mass, the coupler compound may not be sufficiently decomposed. If the content is more than 10% by mass, the organic dye may not be sufficiently decolorized after image formation. There is.

(Diazo Compound) The photo-fixable composition of the present invention contains a diazo compound as a color-forming component, and forms a color image by coupling with the above-mentioned coupler compound. The diazo compound is not particularly limited, and can be arbitrarily selected from diazo compounds represented by the following general formula (β). _{^{Ar-N 2 + · X -}} ... In the general formula (beta) Formula (beta), Ar represents a substituted or unsubstituted aryl group, X ^- represents an acid anion.

Among them, Ar in the general formula (β) represents an unsubstituted aryl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group because of high color-forming reactivity and easy post-treatment of the reaction. And a diazo compound which is an aryl group substituted with an arylthio group or a substituted amino group, and a diazo compound represented by the following general formula (5), (6) or (7) is particularly preferable.

[0079]

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In the general formula (5), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group;
Each of the alkyl group and the aryl group may be unsubstituted or have a substituent. R ¹ and R ² are not hydrogen atoms at the same time and may be linked to each other to form a heterocyclic ring.

R in the general formula (5)^ThreeAnd R^FourRespectively
Independently hydrogen, alkyl, alkoxy, aryl
Oxy group, alkylthio group, arylthio group, alkyl
Represents a sulfonyl group or an arylsulfonyl group. The archi
Group, alkoxy group, aryloxy group, alkylthio
Group, arylthio group, alkylsulfonyl group, aryl
Each of the sulfonyl groups has a substituent even if it is unsubstituted.
May be. Also, X ^-Represents an acid anion.

[0082]

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In the general formula (6), R ⁵ is an alkyl group,
Represents an aryl group, each of which may be unsubstituted or may have a substituent; R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, or an arylsulfonyl group. The alkyl group,
Each of the alkoxy group, the aryloxy group, the alkylthio group, the arylthio group, the alkylsulfonyl group, and the arylsulfonyl group may be unsubstituted or have a substituent. Wherein X ^- represents an acid anion.

[0084]

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In the general formula (7), Ar ² represents an aryl group which may be unsubstituted or have a substituent. Also, R ⁸
And R ⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, or an arylsulfonyl group. Each of the alkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, and arylsulfonyl group may be unsubstituted or have a substituent. Wherein X ^- represents an acid anion.

In the general formulas (5) to (7), R¹~ R⁹
When represents an alkyl group, the alkyl group has the general formula
Has the same meaning as the alkyl group represented by Y in (1) and (2)
Yes, R¹, R^Two, R^FiveOr Ar^TwoWhen represents an aryl group
In this case, the aryl group is represented by Y in the general formulas (1) and (2).
Has the same meaning as the aryl group represented by^Three, R^Four, R⁶,
R⁷, R⁸Or R⁹Is an alkoxy group,
The xy group is represented by Y in the general formulas (1) and (2).
Has the same meaning as the alkoxy group,^Three, R^Four, R⁶, R⁷, R ⁸
Or R⁹Represents an aryloxy group,
The xy group is represented by Y in the general formulas (1) and (2).
It has the same meaning as the aryloxy group.

In the general formulas (5) to (7), R ³ ,
When R ⁴ , R ⁶ , R ⁷ , R ⁸ or R ⁹ represents an alkylthio group, the alkylthio group is preferably an alkylthio group having 1 to 20 carbon atoms, for example, a methylthio group, an ethylthio group, a propylthio group, Isopropylthio group, isobutylthio group, n-hexylthio group, 2-ethylhexylthio group, n-octylthio group, n-decylthio group,
and an n-dodecylthio group.

When R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ or R ⁹ represents an arylthio group, the arylthio group is preferably an arylthio group having 7 to 30 carbon atoms.
Examples include a phenylthio group, a 4-methylphenylthio group, a 4-methoxyphenylthio group, and a 4-chlorophenylthio group.

When R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ or R ⁹ represents an alkylsulfonyl group, the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. Sulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, octylsulfonyl, 2-
Examples include an ethylhexylsulfonyl group, a decanoylsulfonyl group, a dodecanoylsulfonyl group, an octadecanoylsulfonyl group, a cyanomethylsulfonyl group, and the like.

When R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ or R ⁹ represents an arylsulfonyl group, the arylsulfonyl group is preferably an arylsulfonyl group having 6 to 30 carbon atoms. Phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3- (2-ethylhexyloxy) phenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-chlorophenylsulfonyl group, 4- Methylphenylsulfoni And a 4-cyanophenylsulfonyl group, a 4-butoxyphenylsulfonyl group, a 4- (2-ethylhexyloxy) phenylsulfonyl group, and a 4-octadecylphenylsulfonyl group.

When each of the groups represented by R ^{1 to} R ⁹ in the general formulas (5) to (7) has a substituent, the substituent includes:
The same substituents as in the case where Y in the general formulas (1) and (2) are substituted can be exemplified. Examples of the acid anion represented by X ⁻ in the general formulas (5) to (7) include inorganic anions such as hexafluorophosphate ion (PF ₆ ⁻ ) and borofluoride ion (B
F ₄ ⁻ ), chloride ion, sulfate ion, hydrogen sulfate ion. Examples of the organic anion include polyfluoroalkylsulfonic acid ion, polyfluoroalkylcarboxylic acid ion, tetraphenylborate ion, and aromatic carboxylic acid. Ions, aromatic sulfonic acid ions and the like. Of these, hexafluorophosphate ion (PF ₆ ^-),
Borofluoride ion (BF ₄ ⁻ ) is preferred.

Specific examples of preferred diazo compounds (or diazo moieties) are shown below (exemplified compounds (2) -1 to (4) -1 and exemplified compounds (5) -1 to (5) -13). In the present invention,
It is not limited to these.

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The diazo compounds may be used alone or in combination of two or more. The content of the diazo compound is preferably from 0.5 to 40% by mass of the total solid content (mass) of the photo-fixable composition, and from 1 to 20%.
% Is more preferred. If the content is less than 0.5% by mass, the coloring density may decrease, and if it exceeds 40% by mass, the background whiteness may decrease. In the diazo coloring system using the diazo compound and the coupler compound described above, in order to control the desired maximum color density, the type of the diazo compound or the coupler compound is appropriately selected, or when a layer is formed as described below. The application amount may be adjusted.

-Microencapsulation-The diazo compound can be used in the form of a solid dispersion in the same manner as the coupler compound, but the storage stability (raw storage and image storage) of the recording material is further improved. From the viewpoint, it is preferable to use the microcapsules. The method for encapsulating the diazonium salt in the microcapsules is not particularly limited, and a known method using a wall material such as gelatin, polyurea, polyurethane, polyimide, polyester, polycarbonate, or melamine can be employed. Details are described in JP-A-2-141279.

For example, an oil phase prepared by dissolving or dispersing a diazonium salt compound, which is one of the color-forming components, in an organic solvent that is hardly soluble or insoluble in water is mixed with an aqueous phase in which a water-soluble polymer is dissolved, and then homogenized. After emulsifying and dispersing by such means as above, a heating reaction causes a polymer formation reaction at the oil droplet interface to form a microcapsule wall of a polymer substance. According to the interfacial polymerization method, a capsule having a uniform particle size can be formed in a short time, and a recording material having excellent raw storability can be obtained.

As the organic solvent, a high-boiling organic solvent may be used. The organic solvent is not particularly limited, and includes, for example, known solvents such as alkyl phthalate, phosphate, citrate, benzoate, alkylamide, aliphatic ester, trimesate, and the like. Are described in JP-A-7-17145.

Examples of the water-soluble polymer include water-soluble polymers such as polyvinyl alcohol. Examples thereof include polyvinyl alcohol, silanol-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amino-modified polyvinyl alcohol, itaconic acid-modified polyvinyl alcohol, and styrene. -Maleic anhydride copolymer, butadiene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer,
Examples thereof include polyacrylamide, polystyrenesulfonic acid, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, and gelatin. Among them, carboxy-modified polyvinyl alcohol is preferable.

The water-soluble polymer may be used in combination with a hydrophobic polymer emulsion or latex.
Examples of the emulsion or latex include a styrene-butadiene copolymer, a carboxy-modified styrene-butadiene copolymer, and an acrylonitrile-butadiene copolymer. At this time, a conventionally known surfactant or the like may be added as necessary.

Examples of the polymer substance constituting the microcapsule wall include polyurethane resin, polyurea resin, polyamide resin, polyester resin, polycarbonate resin, aminoaldehyde resin, melamine resin, polystyrene resin, styrene-acrylate copolymer resin,
Styrene-methacrylate copolymer resin, gelatin, polyvinyl alcohol and the like. Among them, polyurethane / polyurea resins are particularly preferred.

For example, when a polyurethane / polyurea resin is used as a capsule wall material, a microcapsule wall precursor such as polyvalent isocyanate is encapsulated and mixed in an oily medium (oil phase) to be used as a core substance. A second substance (for example, polyol or polyamine) which forms a capsule wall by reacting with a capsule wall precursor is mixed in a water-soluble polymer aqueous solution (aqueous phase), and the oil phase is emulsified and dispersed in an aqueous phase. By heating, a polymer formation reaction occurs at the oil droplet interface, and a microcapsule wall can be formed.

Hereinafter, specific examples of the polyvalent isocyanate compound will be shown. However, it is not limited to these. For example, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-
4,4'-diisocyanate, 3,3'-diphenylmethane-4,4'-diisocyanate, xylene-1,4
-Diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate,

Diisocyanates such as cyclohexylene-1,4-diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, toluene-2,
Triisocyanates such as 4,6-triisocyanate, 4,4′-dimethylphenylmethane-2,2 ′,
Tetraisocyanates such as 5,5′-tetraisocyanate, adducts of hexamethylene diisocyanate with trimethylolpropane, adducts of 2,4-tolylenediisocyanate with trimethylolpropane, and xylylenediisocyanate with trimethylolpropane And isocyanate prepolymers such as adducts and adducts of tolylene diisocyanate and hexanetriol. If necessary, two or more types may be used in combination. Among them, particularly preferable are. It has three or more isocyanate groups in the molecule.

In the microencapsulation method, the coupler compound, the organic dye, other components such as a coloring aid, and the organic solvent for dissolving the microcapsule wall precursor and the second substance which reacts with the precursor are as described above. And the same as the organic solvent. The particle size of the microcapsules is 0.1-1.
0 μm is preferable, and 0.2 to 0.7 μm is more preferable.

(Other Components) In addition to the above components, the photo-fixing composition of the present invention may contain other components such as a coloring aid, a binder, an organic base, and an organic borate compound.

[Color-forming Aid] In the present invention, a color-forming aid can be added for the purpose of accelerating the color-forming reaction.
Examples of the coloring aid include phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, hydroxy compounds, carboxylic acid amide compounds, and sulfonamide compounds. Since these compounds have an effect of lowering the melting point of the coupler compound or the basic substance or improving the heat permeability of the microcapsule wall, it is considered that a high color density can be obtained.

[Binder] A binder is used, for example, when the recording material is formed in a layer form as in the case of forming a recording material described later. The binder is not particularly limited, and includes conventionally known binders such as polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, and styrene-acrylic acid copolymer. The details are described in JP-A-2-141279.

[Organic base] It is also preferable to add an organic base for the purpose of promoting the coupling reaction between the diazonium salt and the coupler. The organic base is preferably contained in the light and heat sensitive recording layer together with the diazonium salt and the coupler, and may be used alone or in combination of two or more. Examples of the organic base include nitrogen-containing compounds such as tertiary amines, piperidines, piperazines, amidines, formamidines, pyridines, guanidines, and morpholines.

These are described in JP-A-57-123086, JP-A-60-49991, and JP-A-60-94.
381, JP-A-9-71048, and 9-7
Nos. 7729 and 9-77737.

[Organic borate compound] The photo-fixing composition of the present invention contains an organic dye.
When an organic dye having an absorption on the longer wavelength side than m is contained, the photofixable composition is colored by the base dye, so that the color remains even after image formation and the whiteness of the non-image area is reduced. May not be maintained. In such a case, by using an organic borate compound or an organic unsaturated compound such as diarylethylene in combination, irradiation with light can eliminate the coloring due to the organic dye. The description of Japanese Patent Application No. 11-36308 can be applied to the organic borate compound, the amount of the organic borate compound to be used, the decoloring method, and the preferred embodiment.

[Others] Organic or inorganic pigments, various stabilizers, antioxidants and the like, and organic or inorganic salts can also be added for the purpose of accelerating the color-forming reaction. The salts include acetate, lactate, carbonate, sulfate, nitrate,
Secondary ammonium salts and the like. Specifically, there are calcium acetate, magnesium acetate, ammonium acetate, potassium acetate, barium acetate and the like as acetates, and sodium carbonate, potassium carbonate, calcium carbonate and the like as carbonates, and other triethanolamine hydrochloride and the like. is there. Although the action of promoting the color-forming reaction by these organic or inorganic salts is unknown, it is thought that the effect of accelerating the color-forming reaction itself is obtained. The content of the organic or inorganic salt is preferably from 0.01 to 1 times the mol of the above-mentioned coupler compound from the viewpoint of accelerating the coloring reaction.

<Recording Material> Next, the recording material of the present invention will be described. The recording material of the present invention comprises at least a recording layer on a support, specifically, a light- and heat-sensitive recording material having a light- and heat-sensitive recording layer on a support, or a light- and heat-sensitive recording material on a support. This is a photosensitive pressure-sensitive recording material having a pressure recording layer. The recording layer may be a single layer or a multilayer including a plurality of layers, and may have other layers such as an intermediate layer and a protective layer as needed.

(Recording Layer) The recording layer contains the above-described photo-fixable composition of the present invention, and develops a color by application of heat or pressure, and develops a color by irradiation with light having an absorption wavelength of an organic dye. This is a layer that loses reactivity (photosensitive / thermosensitive recording layer, photosensitive / pressure sensitive recording layer). The photo-fixing composition constituting the recording layer is as described above. In some cases, the diazo compound, the coupler compound, and the organic dye may be contained in the same layer (when the recording layer has a multilayer structure, one layer thereof) or may be contained in different layers. It may be.

The coating amount of the photo-fixing composition in one recording layer is preferably ² to 30 g / m ² , and 3 to 20 g / m ^2.
/ M ² is more preferred. The thickness of one recording layer is preferably 1 to 20 μm.

The contents of the diazo compound, coupler compound and organic dye contained in one recording layer are preferably in the following ranges. The coating amount of the diazo compound of the recording layer one layer is preferably from ^{0.02~3.0g / m 2, 0.1~2.0g / m} 2 is more preferable. If the coating amount is less than 0.02 g / m ² , a sufficient color density may not be obtained. If the coating amount is more than 3.0 g / m ² , it takes a long time for light fixing and a non-image area. (Fixed portion) coloring after fixing may increase.

The coating amount of the coupler compound in one recording layer is preferably 0.02 to 5 g / m ² , and 0.1 to 4 g / m ^2.
g / m ² is more preferred. When the coating amount is 0.02 g / m ²
If it is less than 5, sufficient color density may not be obtained, and if it exceeds 5 g / m ² , the suitability for coating on a support may be reduced. The coating amount of the organic dye in one recording layer is 0.001 to 1.0 g / m ^2.
Is preferable, and 0.01 to 0.5 g / m ² is more preferable. If the coating amount is less than 0.001 g / m ² , the coupler compound may not be sufficiently decomposed in some cases.
If it exceeds 0 g / m ² , the color of the organic dye may not be sufficiently erased after image formation.

The recording material of the present invention can be produced, for example, as follows. That is, a coating solution (coating solution for recording layer) containing the diazo compound, the coupler compound, the organic dye, and other components such as a binder is prepared,
The recording layer coating solution is applied onto a support by a known coating method such as bar coating, blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating, curtain coating, or the like to obtain a solid content of 2 to 30 g / m2. It can be prepared by applying so as to be ² and drying. Also,
When an intermediate layer is provided between the support and the recording layer and a protective layer is provided on the recording layer, a coating solution for forming the intermediate layer and a coating solution for forming the protective layer (a coating solution for the intermediate layer, a coating solution for the protective layer, respectively) ) May be prepared beforehand, and the coating solution for the intermediate layer and the coating solution for the protective layer may be multi-layer coated together with the coating solution for the recording layer, or the coating solution for the intermediate layer, the coating solution for the recording layer, and the coating solution for the protective layer. You may apply | coat in order of a liquid.

(Support) As the support, a conventionally known support can be used. Specifically, neutral paper,
Acidic paper, recycled paper, polyolefin resin laminated paper, synthetic paper, polyester films, cellulose derivative films such as cellulose triacetate film, polystyrene films, polyolefin films such as polypropylene films and polyethylene films, and the like, or these alone or It can be used by bonding. The thickness of the support is preferably 20 to 200 μm.

(Other Layers) -Intermediate Layer- An intermediate layer can be provided between the support and the recording layer. The intermediate layer is disclosed in, for example, JP-A-61-5.
No. 4980, and the like. —Protective Layer— It is preferable to provide a protective layer on the recording layer. The protective layer usually includes a water-soluble polymer compound, a pigment, and the like. From the viewpoint of achieving both light resistance and light fixing property, it is preferable that the protective layer contains a compound having an ultraviolet transmittance adjusting function. The thermosensitive recording material containing the compound having the function of adjusting the ultraviolet transmittance is described in detail in JP-A-7-276808.

The recording material of the present invention can be made into a multicolor recording material by laminating a plurality of monochromatic recording layers that develop colors different from each other. Multicolor recording materials are disclosed in JP-A-4-135787 and JP-A-4-144.
No. 784, No. 4-144785, No. 4-19
Nos. 4842, 4-24747 and 4-2
Nos. 47448, 4-340540, 4-
It is described in, for example, JP-A-340541 and JP-A-5-34860.

For example, the recording material may be a recording material having the following three-layer structure (aspect X). That is, a recording layer containing a diazonium salt compound having a maximum absorption wavelength of 340 ± 20 nm or less and a coupler that undergoes a color reaction with the diazonium salt compound (first recording layer (A layer)), A recording layer (second recording layer (B layer)) containing a diazonium salt compound having a maximum absorption wavelength of 360 ± 20 nm and a coupler which reacts with the diazonium salt compound to form a color, and has a maximum absorption wavelength of 400 ± 20 nm. A recording layer (third recording layer (C layer)) containing a diazonium salt compound and a coupler that reacts with the diazonium salt compound to produce a color, and a recording layer formed by laminating the recording layers in this order. And a recording material provided with a light transmittance adjusting layer and a protective layer as necessary.

<Image Recording Method> In the first image recording method of the present invention, the recording material of the present invention described above (recording material having a recording layer containing the photo-fixable composition of the present invention) on a support. An image recording method using an image forming method, wherein at least a recording layer of the recording material is imagewise exposed to generate singlet oxygen to form a latent image, and a latent image is formed simultaneously with or at the time of latent image formation in the exposure step. A color forming step of forming a color according to the latent image by heating or pressing after image formation to form an image. The second image recording method of the present invention is an image recording method using the above-described recording material of the present invention (a recording material having a recording layer containing the photo-fixable composition of the present invention) on a support. A color forming step of forming an image by heating or pressurizing at least the recording layer of the recording material imagewise to form an image, and a fixing step of irradiating the surface of the image-formed recording layer with light to generate singlet oxygen and fixing the image. An image recording method comprising:

In the image recording method of the present invention, the color-forming component can be obtained by performing a development process by heating or pressurizing (1) simultaneously with or after exposure for forming a latent image, or (2) before exposure. Can be colored to form an image. When the recording material of the present invention is a photosensitive and heat-sensitive recording material, a visible image can be obtained by a developing process by heating, and when the recording material is a photosensitive and pressure-sensitive recording material, a visible image can be obtained by a developing process by pressure.

The first image recording method is according to the above (1). In the exposure step, for example, by performing imagewise exposure using a laser beam, a photomask, or the like before heating or pressing, in the light irradiation area, the organic dye in the area generates singlet oxygen and coexists. Decomposes the coupler compound and loses color development (that is, forms a latent image).
In this step, a latent image is formed by imagewise exposure and light fixing is performed at the same time. In the subsequent color forming step, when heating or pressurizing, only the unirradiated area develops color, the irradiated area does not develop color, the whiteness is maintained, and a clear image with high contrast can be formed. In this method, since the image is light-fixed at the same time as the imagewise exposure, the process is simplified, and furthermore, the density stability of the non-image area (image density change, increase in fog density, etc.) is prevented after image formation, and storage stability is improved. (Especially image storage stability).

Further, the second image recording method is characterized in that
According to (2). In the color forming step, for example, a heating element such as a thermal head is used to directly apply heat on the recording layer in an image-like manner, so that only the heated area develops a color and an image can be formed. Here, a color-forming component exists in the non-color-forming portion and the region where the color is not formed to the maximum density. For this reason, in the fixing step, by further irradiating the entire surface of the recording layer with light, the organic dye in the recording layer generates singlet oxygen, decomposes the coupler compound remaining in the recording layer, and loses the coloring property. . As described above, it is possible to prevent a density fluctuation (a change in image density, an increase in fog density, etc.) in a non-image portion or the like after image formation, and to provide excellent storage stability (especially, image storage stability).
In addition, a clear image with high contrast can be formed.

The second image recording method is described in JP-A-59-190886, JP-A-2-141279,
The method described in JP-A-7-17145 can be applied.

An example of the specific method of the second image recording method will be described below using the recording material having the three-layer structure of the embodiment X. First, the third recording layer (C layer) is heated so that the diazo compound and the coupler compound contained in the layer are colored. Next, light of a wavelength corresponding to the organic dye in the C layer is irradiated to decompose the unreacted coupler compound contained in the C layer and fix it by light, and then the second recording layer (B layer) is colored. To give a color to the diazo compound and coupler compound contained in the layer. At this time, the C layer is also strongly heated at the same time, but the coupler compound has already been decomposed (fixed by light) and does not develop color because its coloring ability has been lost. Further, after irradiating light having a wavelength corresponding to the organic dye in the B layer to decompose and fix the coupler compound contained in the B layer, finally, the first recording layer (A layer) is sufficiently colored so that the color can be formed. Apply heat to develop color. At this time, the recording layers C and B are also heated strongly at the same time, but do not develop color as described above.
As described above, a multicolor image can be formed.

Light sources used for exposure in the exposure step in the first image recording method and light irradiation in the fixing step in the second image recording method include fluorescent lamps, xenon lamps, and the like.
Mercury lamps, blue to infrared lasers, and the like. Japanese Patent Application No. 10-287808 discloses a method using these light sources.
No., Japanese Patent Application No. 11-36308, WO95 / 31745
And the method described in JP-A-60-195568.

The maximum absorption wavelength of the diazo compound used is 29
When it is on the longer wavelength side than 0 nm, after the exposure step or the fixing step is completed, it is further irradiated with light using a fluorescent lamp, a xenon lamp, a mercury lamp or the like having an emission spectrum in the above wavelength region, and remains in the recording layer. It is preferable to decompose the coupler compound in order to maintain the whiteness of the non-image area (background area).

As a heating method in the color forming step in the first image recording method, a known method can be applied, and generally, a processing method using a hot plate, a heating roller, or the like can be used.
The heating temperature during the heating is preferably from 80 to 200 ° C., and the heating time is preferably from 3 to 60 seconds. In addition, as the pressing method, a known method can be applied, and in general, a processing method using a pressing platen roller, a point contact ball, or the like can be mentioned.
0 kg / cm ² is preferred.

As described above, when the recording layer contains an organic borate compound or an organic unsaturated compound such as diarylethylene, after forming an image (exposure step-color-forming step / color-forming step-fixing step) By irradiating the entire recording layer with a light source such as a mercury lamp, a xenon lamp, a tungsten lamp, a metal halide lamp, and a fluorescent lamp, the organic dye can be decolorized and the contrast of the formed image can be improved.

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EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Hereinafter, “parts” and “%” in the examples represent “parts by mass” and “% by mass”, respectively.

(Example 1) <Preparation of coating solution for light- and heat-sensitive recording layer>-Preparation of microcapsule solution A containing diazo compound-2.8 parts of the following diazo compound (a-1) was added to ethyl acetate 1
9.0 parts, and further mixed with 5.9 parts of isopropyl biphenyl, which is a high boiling point solvent, and tricresyl phosphate.
5 parts and stirred uniformly.

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To the obtained mixture, xylylene diisocyanate / trimethylolpropane adduct (Takenate D110N, 75% ethyl acetate solution,
7.6 parts (manufactured by Takeda Pharmaceutical Co., Ltd.) was added, and the mixture was further uniformly stirred to obtain a liquid I.

Separately, 64 parts of a 6% aqueous solution of gelatin (MGP-9066, manufactured by Nippi Gelatin Industries Co., Ltd.) to which 2.0 parts of a 10% aqueous solution of sodium dodecyl sulfonate were added was prepared. Was added and emulsified and dispersed with a homogenizer. After adding 20 parts of water to the obtained emulsion and homogenizing, an encapsulation reaction was performed for 3 hours while stirring at 40 ° C. Subsequently, the liquid temperature was set to 3
Lower to 5 ° C and ion-exchange resin Amberlite IRA68
6.5 parts (manufactured by Organo Corporation) and Amberlite IR
13 parts of C50 (manufactured by Organo Corporation) was added, and the mixture was further stirred for 1 hour. Thereafter, the ion exchange resin was filtered to obtain a diazo compound-encapsulated microcapsule solution A.

—Preparation of Coupler Emulsion B— 10.5 parts of ethyl acetate was mixed with the following coupler compound (b-
1) 3.0 parts, 0.5 part of organic dye (C-1), 4,
6.6 parts of 4 '-(p-phenylenediisopropylidene) diphenol was dissolved, and 0.48 part of tricresyl phosphate, which is a high boiling point solvent, and 0.2 ml of diethyl maleate were dissolved.
24 parts and Bionin A41C (manufactured by Takemoto Yushi Co., Ltd.)
After adding 1.27 parts, the mixture was heated and uniformly mixed to obtain a liquid II.

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Solution II was added to 93 parts of an aqueous 8% gelatin solution (# 750 gelatin, manufactured by Nitta Gelatin Co., Ltd.), and the mixture was stirred at 40 ° C. and 10,000 rpm using a homogenizer.
The mixture was emulsified and dispersed at 10 rpm for 10 minutes. The remaining ethyl acetate was removed by evaporation from the obtained emulsion to obtain a coupler emulsion B.

-Preparation of Coating Solution for Light- and Heat-Sensitive Recording Layer- The diazo compound-encapsulated microcapsule solution A, coupler emulsion B, and styrene-butadiene rubber (SBR; SN307, manufactured by Sumitomo Nogatta Co., Ltd.) obtained above were used. ,
In each case, the ratio of diazo compound / coupler compound is 1/2.
And the ratio of diazo compound / SBR is 1 / 6.4
To prepare a coating solution (1) for a light and heat sensitive recording layer.

<Preparation of Coating Solution for Protective Layer> 5.0% Itaconic Acid-Modified Polyvinyl Alcohol (KL-318, Inc.)
To 61 parts of an aqueous solution of Kuraray, 2.0 parts of a 20.5% zinc stearate dispersion (Hydrin F115, manufactured by Chukyo Yushi Co., Ltd.) was added, and sodium (4-nonylphenoxytrioxyethylene) butylsulfonate was added. 7. 2% aqueous solution
4 parts, fluorine release agent (ME-313, Daikin Co., Ltd.)
8.0 parts) and 0.5 part wheat flour starch (KF-4, Kagoshima Starch Co., Ltd.) were added and uniformly stirred. This is hereinafter referred to as “mother liquor”.

Separately, 12.5 parts of an ion-exchanged 20% aqueous solution of chaogloss (manufactured by Shiraishi Industry Co., Ltd.), 0.06 part of Poise 532A (manufactured by Kao Corporation), and Hydrin Z-
7 (manufactured by Chukyo Yushi Co., Ltd.) 1.87 parts, 10% polyvinyl alcohol (PVA105, manufactured by Kuraray Co., Ltd.) 1.25
Parts and a 2% aqueous solution of sodium dodecylsulfonate at 0.
39 parts were mixed and finely dispersed by a dyno mill to obtain a pigment liquid. To 80 parts of the mother liquor, 4.4 parts of the pigment liquid was added and stirred for 30 minutes or more. After that, Wetmaster5
2.8 parts (made by Toho Chemical Co., Ltd.).
After stirring for at least one minute, a coating solution for a protective layer was prepared.

<Preparation of Recording Material (1)> The coating solution (1) for the light- and heat-sensitive recording layer obtained above and the protective layer were coated on a photographic paper support obtained by laminating polyethylene on woodfree paper using a Meyer bar. Apply the coating solution in this order, dry,
A recording material (1) of the present invention was prepared in which a light and heat sensitive recording layer and a protective layer were provided in this order on a support. Incidentally, the coating amount of the solid content of the coating solution for the light and heat sensitive recording layer and the coating solution for the protective layer is
Each 8.33 g / m ^2, was 1.23 g / m ^2.

<Image Recording and Evaluation> The recording material (1) obtained above was imagewise exposed from the protective layer side using a semiconductor laser having a wavelength of 405 nm and an output of 40 mW to form a latent image (exposure). Process). After the exposure, the recording material on which the latent image is formed is heated by a hot plate at a temperature of 110 ° C. for 10 seconds,
An image was formed by coloring the unexposed area (color developing step).
The maximum absorption wavelength (λmax) of the colored region was 558 nm.

With respect to the obtained image, the density (Dmax) of the colored portion and the density (Dmin) of the uncolored portion were measured using a Macbeth reflection densitometer RD-918 (manufactured by Macbeth Co., Ltd.). The index was used to evaluate the whiteness of a non-colored portion (background portion) and image contrast. The measurement results are shown in Table 1 below.

(Example 2) The recording material (1) produced in Example 1 was prepared, and the recording material (1) was recorded with a KST type thermal head (manufactured by Kyocera Corporation) at a recording energy per unit area of 50 mJ. / Mm ² to adjust the voltage applied to the thermal head and the pulse width to perform thermal printing (color developing step). After that, wavelength 405nm, output 40m
The entire surface was exposed using a W semiconductor laser (fixing step).
For the obtained image, the density (Dmax) of the heat-printed portion (colored portion) and the density (Dmin) of the uncolored portion were measured in the same manner as in Example 1, and the non-colored portion (background portion) in the image was measured. ) Was used as an index for evaluating the whiteness and image contrast. The measurement results are shown in Table 1 below.

(Example 3) In Example 1, 2.8 parts of the diazo compound (a-1) used for preparing the diazo compound-encapsulated microcapsule solution A was replaced with the following diazo compound (a-2)
3.1 parts and the following organic borate compound (d
-1) A diazo compound-encapsulated microcapsule solution C was prepared in the same manner as in Example 1 except that 5.0 parts was added.
In addition, the organic dye (C-
1) Coupler emulsion D was prepared in the same manner as in Example 1 except that 0.7 part of the following organic dye (C-2) was used instead of 0.5 part.
Was prepared. Then, in the same manner as in Example 1 except that the diazo compound-containing microcapsule liquid C and the coupler emulsion D were used in place of the diazo compound-containing microcapsule liquid A and the coupler emulsion B used in Example 1, respectively. The recording material (2) of the present invention was produced.

[0153]

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-Image Recording and Evaluation- The recording material (2) obtained above was imagewise exposed from the protective layer side using a semiconductor-excited YLF solid-state laser having a wavelength of 657 nm to form a latent image ( Exposure step). After the exposure, the recording material on which the latent image is formed is heated for 10 seconds with a hot plate at a temperature of 110 ° C. to form a color in the unexposed area to form an image (color forming step). Then, a 38000 lux fluorescent lamp irradiator is used. The entire surface of the light and heat sensitive recording layer was irradiated for 30 seconds (decoloring). The maximum absorption wavelength (λma
x) was 572 nm.

The density (Dmax) of the color-developed portion and the density (Dmin) of the uncolored portion of the obtained image were measured in the same manner as in Example 1. The measurement results are shown in Table 1 below.

(Example 4) In Example 1, 2.8 parts of the diazo compound (a-1) used for preparing the diazo compound-encapsulated microcapsule solution A was replaced with the following diazo compound (a-3)
A diazo compound-encapsulated microcapsule solution E was prepared in the same manner as in Example 1, except that 2.9 parts was used. Then, the recording material (3) of the present invention was prepared in the same manner as in Example 1 except that the diazo compound-containing microcapsule solution E used in Example 1 was used instead of the diazo compound-containing microcapsule solution A. Produced.

[0157]

Embedded image

-Image Recording and Evaluation- The recording material (3) obtained above was imagewise exposed from the protective layer side using a semiconductor laser having a wavelength of 405 nm and an output of 40 mW to form a latent image (exposure). Process). After exposure,
The recording material on which the latent image has been formed is heated for 10 seconds by a hot plate at a temperature of 110 ° C. to form a color in the unexposed area to form an image (color forming step).
The entire surface of the photosensitive and heat-sensitive recording layer was irradiated for 60 seconds on a UV lamp having a power of 40 mW (color erasing). The maximum absorption wavelength (λmax) of the colored region was 640 nm.

The density of the color-developed portion (Dmax) and the density of the uncolored portion (Dmin) of the obtained image were measured in the same manner as in Example 1. The measurement results are shown in Table 1 below.

(Comparative Example 1) Coupler compound (b-1) used in preparation of coupler emulsion B in Example 1
A coupler emulsion F was prepared in the same manner as in Example 1, except that 0 parts was replaced with 3.0 parts of the following coupler compound (b-2). Then, the coupler emulsion B used in Example 1 was used.
In the same manner as in Example 1 except that the above-mentioned coupler emulsion F was used, a recording material (4) of Comparative Example was produced. Then, in the same manner as in Example 1, image recording and density (Dmax, Dmi) were performed using the recording material (4).
n) was measured and evaluated. The maximum absorption wavelength (λmax) of the colored region was 558 nm (purple).
Purple color development was also observed in the exposed area. The measurement results are shown in Table 1 below.

[0161]

Embedded image

(Comparative Example 2) The recording material (4) produced in Comparative Example 1 was prepared, and the recording material (4) was used in Example 2
In the same manner as described above, image recording and density (Dmax, Dm
in) was measured and evaluated. The measurement results are shown in Table 1 below.

[0163]

[Table 1]

From the results shown in Table 1, the recording material (1) having a light- and heat-sensitive recording layer containing a coupler compound having a leaving group other than a hydrogen atom and an organic dye together with the diazo compound
In (3) to (3), the coupler compound was decomposed by exposure to ultraviolet to visible light (light irradiation), and sufficient light fixing properties were exhibited regardless of the absorption wavelength of the diazo compound. Therefore, the obtained image was excellent in whiteness of the non-colored portion (background portion), high in contrast, and sharp. On the other hand, in the recording material (4) using a coupler compound having a hydrogen atom as a leaving group, which contains an organic dye together with the diazo compound, the coupler compound is not sufficiently decomposed, and the diazo compound is not decomposed by ultraviolet light. As a result, light fixation by light irradiation was insufficient, and the fog density (Dmin) could not be kept low. Therefore, the obtained image had low contrast and poor clarity.

[0165]

According to the present invention, it is possible to use a wide range of light sources in the ultraviolet to infrared region, to fix a formed image irrespective of the absorption wavelength of a diazo compound, and to have excellent background whiteness. , A recording material having a recording layer containing the photo-fixable composition, and an image recording method using the recording material. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/61 502 B41M 5/18 102T F-term (Reference) 2H026 AA07 BB43 2H123 AC00 AC04 AC12 AC22 AC23 BB00 BB23 CB00 CB03 CB05 CB12 DA06 DA08 FA01

Claims (7)

[Claims] 1. A photo-fixing composition comprising a diazo compound, a coupler compound having a leaving group other than a hydrogen atom, and an organic dye. 2. The photo-fixable composition according to claim 1, wherein the coupler compound has an oxidation potential of 1 V or less. 3. A compound represented by the following general formula (1), a compound represented by the following general formula (2),
The photo-fixing composition according to claim 1, which is at least one selected from a compound represented by the following general formula (3) and a compound represented by the following general formula (4). Embedded image [In general formulas (1) and (2), X ¹ , X ² , X ³ and X
⁴ independently represents an atomic group necessary to form a 5-membered aromatic heterocycle. Y represents a hydroxyl group, an amino group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and Y and X ¹ may be bonded to each other to form a ring. In the general formula (3), EWG ¹ and EWG ² each independently represent an electron-withdrawing group, and EWG ¹ and EWG ² may be bonded to each other to form a ring. In the general formula (4),
Z represents a hydroxyl group or an amino group, Ar ¹ represents a benzene ring,
Represents a naphthalene ring. In the general formulas (1) to (4), L is
It represents a leaving group other than a hydrogen atom which can be removed at the time of reaction with a diazo compound. ] 4. The photo-fixable composition according to claim 1, wherein the organic dye is a dye capable of generating singlet oxygen by light. 5. A recording material comprising a recording layer on a support, wherein the recording layer contains the photo-fixable composition according to claim 1. Description: 6. An image recording method using a recording material having a recording layer containing a photo-fixable composition on a support, comprising exposing at least the recording layer of the recording material imagewise to reduce singlet oxygen. Having an exposure step of generating a latent image to form a latent image, and simultaneously or after forming the latent image in the exposure step, a color forming step of forming a color in accordance with the latent image by heating or pressing to form an image. An image recording method, wherein the recording material is the recording material according to claim 5. 7. An image recording method using a recording material having a recording layer containing a photo-fixable composition on a support, wherein at least the recording layer of the recording material is imagewise heated or pressed to form a color. 6. The recording method according to claim 5, further comprising: a color forming step of forming an image; and a fixing step of irradiating the surface of the recording layer on which the image is formed with light to generate singlet oxygen and fixing the recording medium. An image recording method characterized by being a material.