JP2001261997A - Color-developing composition and photosensitive material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color-developing composition which can form a dye by a coupling reaction to develop the color without needing an oxidizing agent such as a silver halide. SOLUTION: The color-developing composition comprising a color-developing main oxidizer precursor represented by the general formula (I) (A1 and the nitrogen atom are groups for producing a dye together with the coupler; A3 is a substituent which is released together with an electron pair bound to the nitrogen atom, when the color-developing main oxidizer precursor is converted into the oxidizer; A2 is a group which is released with the production of the dye, after the oxidizer is coupled with the coupler to form the dye precursor) and a carbamoyloxy-releasing type two equivalent dye-forming coupler having an electron-attracting substituent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a color-forming composition useful for a color print material for outputting digital image information and a photosensitive material using the same.

[0002]

2. Description of the Related Art WO 90/0097, WO 94/220
52, etc., describe a color-forming composition using a dye precursor. However, a coloring composition using a dye precursor generally has a high synthesis cost due to the complex structure of the dye precursor, that the dye precursor is colored, and that the dye gradually forms during storage. There is a problem that it is difficult to prevent this from happening. As a method for solving these problems, there is a method utilizing dye formation by coupling. However, currently known,
In the dye forming method by coupling, an oxidant is generated from a color developing agent by the action of an oxidizing agent such as silver halide, and a dye is formed by coupling this with a dye forming coupler. Therefore, when these are used as printing materials, in one method, development,
Bleaching and fixing are necessary, and in some methods, it is necessary to transfer a dye to an image receiving sheet.Therefore, there is a problem that the method is used as a simple and inexpensive color print material for digital image information output. Is not enough.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a color-forming composition capable of forming a dye by coupling to form a color without requiring an oxidizing agent such as silver halide (particularly capable of forming a good yellow color). The purpose is to provide. Another object of the present invention is to provide a color forming composition, a photosensitive material, and an image forming method which are highly useful for a digital image information output color print material or the like which forms a color image at low cost with a simple operation. .

[0004]

Means for solving the above problems are as follows. That is, <1> a color-forming composition comprising an oxidized precursor of a color-forming agent represented by the general formula (I) and a carbamoyloxy-eliminable 2-equivalent dye-forming coupler having an electron-withdrawing substituent.

[0005]

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In the general formula (I), A ¹ and a nitrogen atom represent a group which forms a dye together with the coupler, and A ³
Represents a substituent that is released with a bonding electron pair with a nitrogen atom when the oxidized precursor of the coloring agent becomes an oxidized form;
² represents a group which is released with the formation of a dye after the oxidized product is coupled with the coupler to form a dye precursor.

<2> The color-forming composition according to <1>, wherein the oxidized precursor of the color-forming main agent is represented by the following general formula (II).

[0008]

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In the general formula (II), A ⁴ represents a substituent, and n represents an integer of 0 to 4. A ⁵ is -OA ⁹ or -N
(A ¹⁰ ) represents A ¹¹ , wherein A ⁷ represents —O—, —S—, —N (A
¹²⁾ - or ^{-C (A 13) (A 14} ) - represents each A ⁶ and A ⁹ to A ¹⁴ represents a hydrogen atom or a substituent, A ⁸
Represents a substituent. 2 selected from A ⁴ , A ¹⁰ and A ¹¹
The above may be mutually bonded to form a ring.

<3> The color-forming composition according to <1>, wherein the oxidized precursor of the color-forming agent is represented by the following general formula (III).

[0011]

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In the general formula (III), A^FifteenRepresents a substituent
And n represents an integer of 0 to 4. A¹⁶, A¹⁷And A¹⁸Is
Each represents a hydrogen atom or a substituent. A^Fifteen, A¹⁶and
A¹⁷Two or more selected from each other bond to form a ring
May be. A¹⁹Is -O-, -S-, -N (A^{twenty two})-Ma
Or -C (A^{twenty three}) (A^{twenty four})-, And A²⁰Is = O, =
S, = NA^{twenty five}Or = C (A²⁶) -C (A²⁷) = N−
A²⁸And A^{twenty one}Represents a substituent, and A²⁰And A^{twenty one}Is phase
They may combine with each other to form a ring. A^{twenty two}~ A ²⁸Is each
Each represents a hydrogen atom or a substituent.

<4> The color-forming composition according to any one of <1> to <3>, wherein the coupler is represented by the following general formula (IV).

[0014]

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In the general formula (IV), R ¹ and R ² each represent an alkyl group or an aryl group, and at least one of them represents an alkyl group having an electron-withdrawing substituent. Q ¹ is —COR ³ , —CN, —CON (R ⁴ ) R ⁵ , —COO
R ⁶ , —SO ₂ R ⁷ or a heterocyclic group; Q ² is an alkyl group, an aryl group, a heterocyclic group, —N (R ¹⁰ ) R ¹¹ or —
Representing the OR ^12. R ³ , R ^{5 to} R ⁷ , R ¹¹ and R ¹² each represent an alkyl group, an aryl group or a heterocyclic group;
⁴ and R ¹⁰ each represent a hydrogen atom or a substituent. Q ¹ and Q ² may combine with each other to form a ring.

<5> The color-forming composition according to any one of <1> to <3>, wherein the coupler is represented by the following general formula (V).

[0017]

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In the general formula (V), Q ³ and R ¹⁴ each represent an alkyl group, an aryl group or a heterocyclic group. R
¹³ represents a hydrogen atom or a substituent. At least one of R ¹⁵ and R ¹⁶ represents an alkyl group having an electron-withdrawing substituent, and the other represents an alkyl group or an alkyl group having an electron-withdrawing substituent.

<6> A photosensitive material containing the color-forming composition according to any one of <1> to <5>, a photopolymerization initiator, and a polymerizable compound. Incidentally, the photosensitive material of <6> includes an embodiment in which either the oxidized precursor of the color-forming agent or the coupler contained in the color-forming composition functions as a polymerizable compound. It may not contain a compound.

<7> A light-sensitive material having at least one support and a recording layer comprising at least one layer formed on the support, wherein the recording layer is from <1> to <5> A photosensitive material comprising the color-forming composition according to any one of the above, a photopolymerization initiator, and a polymerizable compound. In the photosensitive material of <7>, "the recording layer contains the color forming composition, the photopolymerization initiator, and the polymerizable compound" means that all the materials are necessarily contained in one layer. Does not mean, but also includes a form in which each material is contained in two or more layers. Further, in the photosensitive material of <7>, the recording layer does not necessarily need to be formed on one support, and the recording layer may be formed separately on different supports.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The oxidized color former precursor used in the composition and photosensitive material of the present invention will be described in detail below. [Color-forming composition]-Oxidized precursor of color-forming agent-The color-forming composition of the present invention contains the oxidized precursor of color-forming agent represented by the general formula (I). A ¹ and the nitrogen atom of the oxidized color precursor precursor represent a group that forms a dye together with the coupler, and A ³ represents a bond electron pair with a nitrogen atom when the oxidized color precursor precursor becomes an oxidized product. And A ² represents a group which is released with the formation of a dye after the oxidized product is coupled with the coupler to form a dye precursor. In the oxidized color precursor precursor, for example, A ³ is released along with a bond electron pair with a nitrogen atom due to the donation of heat or the action of another compound to generate an oxidized color main agent. A of the formed oxidized color developing agent
^{The 1} and the nitrogen atom undergo a coupling reaction with the coupler to form a dye precursor. After the dye precursor is formed, A ²
Is released and a dye is formed.

That is, in the present invention, A ³ is released from the oxidized color precursor precursor represented by the general formula (I) to form an oxidized color drug main body, and then coupled with a coupler, a ¹⁾ (a ²⁾ to yield a dye precursor having the structure of N- (coupler). With the release of A ² ,
A dye (A ¹ -N = coupler) is formed. In the conventional coupling type color developing system, an oxidizing agent such as silver halide is used, so that a processing solution or dye transfer is required. However, the precursor of the color developing agent represented by the formula (I) of the present invention is used. Since a dye can be generated by coupling without using an oxidizing agent, a processing solution or dye transfer is not required, and a color image can be formed by simple processing at low cost.

Among the oxidized precursors of the coloring agent represented by the general formula (I), the compound represented by the general formula (II) is preferable, and the compound represented by the general formula (III) is more preferable. . Hereinafter, the general formula (II) and the general formula (III) will be described, but a compound in which any one of the groups contained in each of the formulas is in a preferable range shown below is preferable as the precursor of the oxidized color developing agent. A compound in which more groups have the following preferable ranges is more preferable as the precursor of the color developing agent, and a compound in which all the groups have the following preferable ranges is most preferable as the precursor of the color developing agent.

In the above general formulas (II) and (III), A ⁴ and A ¹⁵ each represent a substituent. Examples of the substituent include a halogen atom (eg, chloro, bromo), an alkyl group (eg, methyl, ethyl, isopropyl, n-butyl, t-butyl), an aryl group (eg, phenyl, tolyl, xylyl), a heterocyclic group (Eg, 2-pyridyl, N
-Pyrrolidinyl), carbonamido groups (eg, acetylamino, propionylamino, butyroylamino, benzoylamino), sulfonamide groups (eg, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino, toluenesulfonylamino), alkoxy groups (eg, methoxy) , Ethoxy), aryloxy group (eg, phenoxy), alkylthio group (eg, methylthio, ethylthio, butylthio), arylthio group (eg, phenylthio, tolylthio), amino group (unsubstituted amino group, aliphatic group, aromatic group, etc.) Amino groups such as methylamino and phenylamino), carbamoyl groups (aliphatic groups, aromatic groups, carbamoyl groups substituted with heterocyclic groups, etc.), and carbamoyl in which nitrogen atoms are connected to form a ring , For example methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidinocarbonyl carbamoyl, morpholino carbamoyl, phenylcarbamoyl, methylphenylcarbamoyl, ethyl phenylcarbamoyl, benzyl phenylcarbamoyl)

Sulfamoyl group (aliphatic group, aromatic group,
A sulfamoyl group substituted with a heterocyclic group or the like, and a sulfamoyl group in which nitrogen atoms are connected to each other to form a ring, for example, methylsulfamoyl, dimethylsulfamoyl,
Ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidinosulfamoyl, morpholinosulfamoyl, phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl), Cyano group,
Sulfonyl group (eg, methanesulfonyl, ethanesulfonyl, phenylsulfonyl, 4-chlorophenylsulfonyl, p-toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), acyl Groups (eg, acetyl, propionyl, butyroyl, benzoyl, alkylbenzoyl), ureido groups (eg, methylaminocarbonamide, diethylaminocarbonamide), urethane groups (eg, methoxycarbonamide, butoxycarbonamide), or acyloxy groups (eg, acetyloxy, Propionyloxy, butyroyloxy) and the like.

A ⁴ and A ¹⁵ may further have a substituent, and the substituent is the same as A ⁴ and A ¹⁵ described above. The carbon number of the groups represented by A ⁴ and A ¹⁵ (including those further substituted) is preferably from 0 to 36.

Preferred as A ⁴ and A ¹⁵ are an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, a carbonamide group, a ureido group, a urethane group and a halogen atom. An atom is particularly preferred, and an alkyl group is particularly preferred.

The formula (II) and the formula (II)
In I), n represents any integer of 0-4. When n is 2 or more, two or more of A ⁴ and A ¹⁵ may be different from each other or may be the same. When n is 2 or more,
Two or more of A ⁴ and A ¹⁵ may be bonded to each other to form a ring. n is preferably 0 or 1.

In the general formula (II), A ⁵ represents -OA ⁹ or -N (A ¹⁰ ) A ¹¹ . A ⁹ to A ^{1 1} are each independently
Represents a hydrogen atom or a substituent. As the substituent, A ⁴
And include the same substituents as substituents exemplified in example A ^15. Preferred as A ^{9 to} A ¹¹ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an amino group or an alkyloxy group. Particularly preferred are alkyl groups.
These groups may further have a substituent. A ⁹
And A ⁴ , A ¹⁰ , A ¹¹ and A ⁴ may be bonded to each other to form a ring.

In the general formula (II), A ⁷ represents —O—, —S
^{-, - N (A 12)} - or ^{-C (A 1 3) (A} 14) - represents a. A ^{12 to} A ¹⁴ represent a hydrogen atom or a substituent. Examples of the substituent include the same substituents as those described in the examples of A ⁴ and A ¹⁵ .

In the general formula (II), A ⁶ represents a hydrogen atom or a substituent, and A ⁸ represents a substituent. Examples of substituents A ⁶ and the A ⁸ represents each and preferred ranges are the same synonymous the A ⁴ and A ^{1 5.}

In the general formula (III), A¹⁶And A¹⁷Is
Each independently represents a hydrogen atom or a substituent. A¹⁶And
And A¹⁷Are each a substituent represented by A^FourAnd A^FifteenExample
And the same substituents as those described above. A¹⁶And
And A¹⁷Are preferably a hydrogen atom, an alkyl group,
Reel group, heterocyclic group, acyl group, sulfonyl group, carba
Moyl group, alkyloxycarbonyl group, aryloxy
A cyclocarbonyl group, an amino group or an alkyloxy group
Particularly preferred is an alkyl group. A ¹⁶and
A¹⁷The substituent represented by may further have a substituent. Ma
A^Fifteen, A¹⁶And A¹⁷Two or more selected from each other
They may combine to form a ring.

In the general formula (III), A ¹⁸ represents a hydrogen atom or a substituent. Examples of the substituent represented by A ¹⁸ include the same substituents as those exemplified for A ⁴ and A ¹⁵ . Among them, as A ¹⁸ , when a dye precursor is formed from an oxidized color-forming agent and a coupler, it is suitable for forming a dye by releasing as an OＣC ＝ N-A ¹⁸ molecule together with a coupler leaving group. It is preferably a group. Examples of such a substituent include a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, a carbamoyl group,
Examples include an alkyloxycarbonyl group, an aryloxycarbonyl group, an amino group, an alkyloxy group, and an aryloxy group. Particularly preferred as A ¹⁸ are a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group.

In the general formula (III), A ¹⁹ represents —O—,
^{S -, - N (A 22} ) - or ^{-C (A 23) (A 24} ) - represents, A ²⁰ is = O, = S, = N -A 25 or = C
It represents ^{(A 26) -C (A 27} ) = N-A 28, A 21 represents a substituent, A ²² to A ²⁸ each represents a hydrogen atom or a substituent. When A ^{21 to} A ²⁸ represent a substituent, examples of the substituent include the same substituents as those described as examples of A ⁴ and A ¹⁵ . A ²⁰ and A ²¹ may be mutually bonded to form a ring.

In the general formula (III), -A ¹⁹ -C (= A
The group represented by ²⁰⁾ -A ^21, by the action of the donor or other compounds of heat, leaves the color oxidized precursor represented by formula (III), to produce a color oxidized Are preferable, and among them, groups represented by the following general formulas (VI) to (IX) are preferable.

[0036]

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In the above general formulas (VI) to (IX), A²⁹~ A³⁷
Each represents a substituent;³⁸Is A in the general formula (III)
²⁰Is synonymous with A²⁹~ A³⁵Is preferably
Kill group, aryl group, heterocyclic group, sulfonyl group, carba
Moyl group, alkyloxycarbonyl group, aryloxy
Cicarbonyl group, amino group, alkyloxy group or
A reeloxy group. Of these, particularly preferred are
It is an alkyl group. A ³⁶Is preferably -C (=
A³⁸) -A³⁷Or a heterocyclic group. A³⁷
Are preferably an alkyl group, an aryl group, a heterocyclic ring
Group, alkyloxy group, aryloxy group, alkyl group
It is a mino group, an arylamino group or a hydrazino group.

Among the groups represented by the general formulas (VI) to (IX), -A ¹⁹ -C (= A
²⁰ ) -A ²¹ is particularly preferably the above-mentioned general formula (VI)
Is a group represented by

Specific examples (exemplary compounds I-1 to 36) of the compound represented by the above general formula (I) are shown below. The oxidized precursor of the color developing agent used in the present invention includes the following exemplified compounds. It is not limited.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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Examples of the synthesis of the compound represented by formula (I) are shown below. Synthesis Example 1 Synthesis of Exemplified Compound (I-1) 100 g (271 mmol) of the coloring agent (A) having the following structure was dissolved in a mixture of 500 ml of ethyl acetate and 1000 ml of water, and 136 g of sodium hydrogen carbonate (1.6) was dissolved.
2 mol) and phenyl chloroformate 38.14 g (244)
Mmol). After stirring for 1 hour, the organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. 500 ml of acetonitrile and 74.68 g (256 mmol) of amine (B) having the following structure were added, and the mixture was heated under reflux for 2 hours. After the reaction solution was concentrated under reduced pressure, 1 liter of methanol and 100 ml of water were added, and the precipitated crystals were collected by filtration, and 110.4 g (18) of a coloring agent (C) having the following structure was obtained.
7 mmol).

100 g (170) of the obtained color former (C)
Mmol) was dissolved in 600 ml of ethyl acetate, and ammonium pyrrolidine-N-dithiocarbamate 55.80.
g (340 millimil) and 700 g of manganese dioxide were added and stirred for 2 hours. After the reaction solution was filtered, the reaction solution was purified by silica gel column chromatography to give Exemplified Compound (I)
-1) 65 g (88.5 mmol) were obtained.

[0049]

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Synthesis Example 2 Synthesis of Exemplified Compound (I-2) 20 g (93 mmol) of the coloring agent (D) having the following structure was dissolved in a mixture of 100 ml of ethyl acetate and 200 ml of a saturated aqueous solution of sodium hydrogen carbonate, and octadecyl isocyanate was dissolved. 27.52 g (93 mmol) were added and stirred. After 1 hour, the precipitated crystals were collected by filtration, washed with water and ethyl acetate, and then dried to obtain 40.3 g (8) of a coloring agent (E).
5.1 mmol). Color former (E) 10.0g
(21.1 mmol) and 6.93 g (42.2 mmol) of ammonium pyrrolidine-N-dithiocarbamate were dissolved in 60 ml of dichloromethane, and 60 g (690 mmol) of manganese dioxide was added and stirred for 1 hour. After the reaction solution was filtered through celite, the filtrate was purified by silica gel column chromatography to give the exemplified compound (I-
2) 4.43 g (7.16 mmol) were obtained.

[0051]

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Synthesis Example 3 Synthesis of Exemplified Compound (I-8) 10 g of a coloring agent (F) synthesized in the same manner as in Synthesis Example 2
(17.6 mmol) and 4.24 g (26.5 mmol) of potassium ethyl xanthate were suspended in methylene chloride, 40 g of manganese dioxide was added, and the mixture was stirred for 1 hour. After the reaction solution was filtered, it was purified by silica gel column chromatography to give 10 g of Exemplified Compound (I-8) (1
4.6 mmol).

[0053]

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Synthesis Example 4 Synthesis of Exemplified Compound (I-16) 20.79 g (79.27 mmol) of a coloring agent (G) having the following structure and 15 g (79.27) of a compound (H) having the following structure
Was dissolved in a mixture of 100 ml of ethyl acetate and 300 ml of a saturated aqueous solution of sodium hydrogen carbonate, and 21.71 g (95.12 mmol) of ammonium persulfate was added. The organic layer was separated, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The product was purified by alumina column chromatography to obtain 16 g (45.5 mmol) of the exemplified compound (J). 15 g of compound (J) having the following structure (42.7)
Mmol) in 30 ml of butyl isocyanate,
Stirred at 50 ° C. for 72 hours. The reaction solution was purified by silica gel column chromatography to give the exemplified compound (I-1).
6) 1.8 g (3.99 mmol) were obtained.

[0055]

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-Coupler- The coupler used in the color forming composition of the present invention includes:
Carbamoyloxy-eliminable type 2 having electron-withdrawing substituent
Equivalent dye-forming couplers are preferred. Among them, the compound represented by the general formula (IV) is preferable. Hereinafter, the general formula (IV) will be described, but a compound in which any one of the groups included in the formula is in the following preferable range is preferable as a coupler, and more groups are in the following preferable range. Compounds are more preferred as couplers, and compounds in which all groups are within the following preferred ranges are even more preferred as couplers.

In the general formula (IV), R ¹ and R ² each represent an alkyl group or an aryl group, and at least one of them represents an alkyl group having an electron-withdrawing substituent. The term “electron-withdrawing substituent” used herein means a halogen atom,
Cyano group, nitro group, sulfonyl group (for example, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group), carbonyl group (for example, alkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylcarbonyl group, arylcarbonyl group , A heterocyclic carbonyl group), and in the case of a halogen atom, those substituted by two or more are preferable. R ¹ and R ²
Examples of the alkyl group and aryl group represented by each include those exemplified as each group represented by R ³ , R ⁵ , R ^6, and R ⁷ described below. Further, the alkyl group and the aryl group may have a substituent. Among them, it is preferable that both R ¹ and R ² are alkyl groups having an electron-withdrawing substituent.

In the general formula (IV), Q¹Is -COR^Three, −
CN, -CON (R^Four) R^Five, -COOR⁶, -SO_TwoR⁷
Or a heterocyclic group. Q¹As the heterocyclic group represented by
Contain at least one of nitrogen, sulfur, and oxygen atoms
5- or 6-membered heterocyclic groups and fused heterocyclic groups are preferred.
New As the heterocyclic group, pyridine (for example, 2-py
Lysyl, 4-pyridyl group), pyrimidine (for example, 2-
Pyrimidyl, 3-pyrimidyl group), pyrazine (for example,
2-pyrazyl group), piperidine (eg, 2-piperidi
Group), piperazine (for example, 2-piperazyl group),
Ruforin (eg, 2-morpholino group), quinoline
(Eg, 2-quinolyl, 4-quinolyl, 8-quinolyl
Group), pyrrole (eg, 2-pyrrolo group), thiophene
(E.g., 2-thienyl group), furan (e.g., 2-
Ryl group), imidazole (eg, 2-imidazolyl)
Group), triazole (eg, 1,2,4-triazo-
3-yl group), tetrazole (for example, 1,2,3,4
-Tetrazo-5-yl group), thiazole (eg, 2-thio
Azolyl, 3-isothiazolyl group), thiadiazole
(Eg, 2-thiadiazolyl group), oxazole (eg,
For example, 2-oxazolyl, 3-isoxazolyl group),
Oxadiazole (for example, 2-oxadiazolyl
Group), purines (eg, 6-purinyl, 8-purinyl)
Group), pyrazolo [3,4-d] pyrimidine (e.g., 1
H-pyrazolo [3,4-d] pyrimidin-4-yl group)
Groups having a heterocyclic ring are preferred. These heterocycles are saturated
It may be either a Japanese type or an unsaturated type.
The terrorist ring may be condensed. The heterocyclic ring has one or more positions.
May have a substituent, and as the substituent, the above-mentioned general
A of formula (II) ^FifteenAnd a substituent represented by

R^Three, R^Five, R⁶And R⁷Is each alkyl
Group, an aryl group or a heterocyclic group,^FourIs a hydrogen atom
Or a substituent, which is represented by the general formula (II
I) A¹⁸Substituents similar to the substituents exemplified in
You. R^Three, R^Five, R⁶And R⁷As an alkyl group represented by
Is an alkyl group having 1 to 18 carbon atoms
Groups (eg, methyl, butyl, octyl, dodecyl,
Cutadecyl group), preferably an alkyl group having 1 to 8 carbon atoms
(Eg, methyl, ethyl, butyl, octyl groups)
And a cyclic alkyl group (eg, cyclopropyl
A cyclohexyl group). R^Three, R^Five, R⁶You
And R⁷The aryl group represented by
Reel groups (eg, phenyl, naphthyl, etc.)
Can be R^Three, R^Five, R ⁶And R⁷As a heterocyclic group represented by
Is Q¹Are the same as those exemplified as the heterocyclic group represented by
And a preferred range is also the same. Note that R
^Three, R^Five, R⁶And R⁷Represents an alkyl group or an aryl group
Or a heterocyclic group is further substituted with one or more substituents.
And the substituent may be a group represented by A in the general formula (II).^Fifteen
And the same substituents as those described above.

In the general formula (IV), Q ² represents an alkyl group,
Aryl group, a heterocyclic group, -N (R ¹⁰⁾ R ¹¹ or -OR
Represents ¹² . The alkyl group, aryl group or heterocyclic group represented by Q ² has the same meaning as the respective groups represented by R ³ , R ⁵ , R ⁶ and R ⁷ , and the preferred range is also the same. In the general formula (IV), Q ¹ and Q ² may be mutually bonded to form a ring.

As the coupler used in the present invention, those having the structure represented by formula (V) are more preferable. Hereinafter, the general formula (V) will be described.
A compound in which any one of the groups included in the formula is in the following preferred range is preferred as a coupler, a compound in which more groups are in the following preferred range is more preferred as a coupler, and all groups are in the following preferred ranges. Is most preferred as a coupler. In the general formula (V), Q ³ and R ¹⁴ each represent an alkyl group, an aryl group or a heterocyclic group. As the alkyl group, an alkyl group having 1 to 18 carbon atoms (eg, methyl, butyl, octyl, dodecyl, octadecyl group), preferably an alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, butyl, octyl group) And a cyclic alkyl group (eg, a cyclopropyl group, a cyclohexyl group) is also included. Examples of the aryl group include an aryl group having 6 to 14 carbon atoms (e.g., a phenyl and naphthyl group). Examples of the heterocyclic group include the same heterocyclic groups as those exemplified for R ⁸ . The alkyl group, the aryl group, or the heterocyclic group may be further substituted with one or more substituents, and the substituent is the same as the substituent represented by A ¹⁵ in the general formula (II). Is mentioned. Q ³
Is preferably a linear, cyclic, or branched alkyl group or aryl group. Further, R ¹⁴ is preferably an aryl group.

In the general formula (V), R ¹³ represents a hydrogen atom or a substituent. The substituent is specifically the same as that represented by Q ³ . R ¹³ is preferably a hydrogen atom.

In the general formula (V), at least one of R ¹⁵ and R ¹⁶ represents an alkyl group having an electron-withdrawing substituent, and the other represents an alkyl group or an alkyl group having an electron-withdrawing substituent. . Each of R ¹⁵ and R ¹⁶ is preferably a group having 1 to 6 carbon atoms. As the “electron-withdrawing substituent”, R ¹ and R ² of the above general formula (IV)
And the same substituents as the electron-withdrawing substituents exemplified above. The alkyl group having an electron-withdrawing substituent preferably has 1 to 2 carbon atoms from the nitrogen atom to the electron-withdrawing group, and more preferably 1 carbon atom. As the electron-withdrawing substituent, a cyano group or an alkoxycarbonyl group is particularly preferred.

Specific examples (exemplary compounds Y-1 to 17) of couplers usable in the present invention are shown below, but the couplers used in the present invention are not limited to the following specific examples.

[0065]

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[0066]

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[0067]

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[0068]

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An example of the synthesis of the compound represented by the general formula (IV) is shown below. -Synthesis Example 5 Synthesis of Exemplified Compound Y-5 Exemplified Compound Y-5 can be synthesized by the following synthetic route.

[0070]

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Synthesis of Intermediate A-2 25.6 g (50.0 mmol) of compound A-1 was added to 100 ml of dichloromethane, stirred at room temperature, and 4.03 ml (50.0 mmol) of sulfuryl chloride was added for 5 minutes. Was dropped. After stirring at room temperature for 1.5 hours, the reaction mixture was washed three times with water, and the organic layer was dried over anhydrous magnesium sulfate. Concentrate on a rotary evaporator to intermediate A
-2 crude product was obtained. This was used in the next step without purification.

Synthesis of Intermediate A-3 The total amount of Intermediate A-2 synthesized above was dissolved in 70 ml of N, N-dimethylformamide (hereinafter abbreviated as DMF),
Stir at room temperature. 22.8 ml of acetic acid (0.40
0 mol) and 19.6 g (0.200 m) of potassium acetate
ol), and the mixture was stirred at 55 ° C. for 1.5 hours under a nitrogen stream. After cooling, 300 ml of ethyl acetate and saturated aqueous sodium hydrogen carbonate 3
50 ml was added for extraction, and the organic layer was washed with saturated saline. The organic layer was dried over anhydrous magnesium sulfate and concentrated by a rotary evaporator to obtain a crude product of Intermediate A-3. This was used in the next step without purification.

Synthesis of Intermediate A-4 The entire amount of Intermediate A-3 synthesized above was converted to methanol 13
The mixture was stirred at room temperature for 10 minutes while blowing nitrogen. 29 ml of 28% aqueous ammonia was added, and the mixture was stirred at an internal temperature of 30 to 40 ° C. for 2 hours under a nitrogen stream. 300 ml of ethyl acetate and 400 ml of water were poured into the reaction mixture, and the mixture was acidified with concentrated hydrochloric acid and extracted. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated by a rotary evaporator to obtain a crude product of Intermediate A-4.
This was used in the next step without purification.

Synthesis of Exemplified Compound Y-5 1.14 g (12.0 g) of commercially available iminodiacetonitrile
mmol) was added to 20 ml of ethyl acetate, cooled with ice water and stirred. To this, 1.19 g (4.0 mmol) of commercially available bistrichloromethyl carbonate was added, and the mixture was stirred for 5 minutes. Then, 1.68 ml (12.0 mmol) of triethylamine was added.
l) was added in 10 minutes. After stirring for 10 minutes while cooling, the mixture was stirred at room temperature for 10 minutes. 30 ml of water in the reaction mixture
Was added and extracted, and the organic layer was washed with saturated saline. The organic layer was dried over anhydrous magnesium sulfate and concentrated on a rotary evaporator to obtain a crude product of Intermediate A-5.
The total amount of the intermediate A-4 synthesized above was added to 15 ml of DMF.
And stirred at room temperature. The whole amount of the intermediate A-5 previously synthesized was diluted with 8 ml of ethyl acetate and added.
Further, 4.15 g (30.0 mmol) of anhydrous potassium carbonate
l) was added and the mixture was stirred for 3 hours and left overnight. The reaction mixture was poured into 50 ml of ethyl acetate, 40 ml of water was added,
The mixture was acidified with concentrated hydrochloric acid and extracted. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated using a rotary evaporator. The residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate 4/4).
(1-7 / 3 mixed solvent) and 3.11 g (yield 4)
8%) of Exemplified Compound Y-5.

Synthesis Example 6 Synthesis of Exemplified Compound Y-3 Exemplified Compound Y-3 can be synthesized by the following synthetic route.

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Synthesis of Intermediate B-2 Compound B-1 synthesized in the same manner as in Synthesis Example 1
0 g (20.0 mmol) was added to methanol (120 ml), and the mixture was stirred at room temperature while blowing nitrogen. 20% of 28% ammonia water is added, and the internal temperature is 30 ~ under nitrogen flow.
Stirred at 40 ° C. for 2 hours. Ethyl acetate 3 was added to the reaction mixture.
00 ml and 400 ml of water were poured, and extracted with concentrated hydrochloric acid. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated with a rotary evaporator to obtain a crude product of Intermediate B-2. This was used in the next step without purification.

Synthesis of Exemplified Compound Y-3 1.14 g of commercially available ethyl iminodiacetate (6.00 mm
ol) was added to 10 ml of ethyl acetate, and the mixture was cooled with ice water and stirred. Add commercially available bistrichloromethyl carbonate.
After adding 59 g (2.0 mmol) and stirring for 5 minutes, 0.84 ml (6.0 mmol) of triethylamine was slowly added. After stirring for 30 minutes while cooling, 30 minutes at room temperature
Stirred for minutes. 20 ml of water was added to the reaction mixture for extraction, and the organic layer was washed with saturated saline. The organic layer was dried over anhydrous magnesium sulfate and concentrated on a rotary evaporator to obtain a crude intermediate B-3. The 1/4 amount of the intermediate B-2 synthesized above was dissolved in 8 ml of DMF,
Stir at room temperature. The whole amount of the intermediate B-3 previously synthesized was diluted with 2 ml of ethyl acetate and added, and 2.07 g (15.0 mmol) of anhydrous potassium carbonate was further added. The mixture was stirred for 1 hour and left overnight. The reaction mixture was poured into 30 ml of ethyl acetate, 30 ml of water was added, and the mixture was acidified with concentrated hydrochloric acid and extracted. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated using a rotary evaporator. The residue was purified by silica gel column chromatography (eluent: mixed solvent of hexane / ethyl acetate 5/1) to obtain 2.34 g (yield 50%) of Exemplified Compound Y-3.

In the color-forming composition of the present invention, the oxidized color precursor precursor and the coupler can be used in any molar ratio, but preferably the oxidized color precursor precursor / dye-forming coupler is preferably used in a molar ratio. Is from 0.01 to 100, more preferably from 0.1 to 10, and most preferably from 0.5 to 5. In the present invention, two or more types of compounds may be used in combination for the oxidized color precursor precursor and the coupler, and in that case, the total ratio of the molar amounts of the compounds used in each case is within the above range. Is preferred.

The color forming composition of the present invention may contain an activator for activating the oxidized precursor of the color forming agent and promoting the reaction with the coupler. As the activator, an electrophile described in Japanese Patent Application No. 11-240596, a metal compound described in Japanese Patent Application No. 11-275336, or the like can be used. When an activator is used, the oxidized color precursor precursor and the activator can be used in any molar ratio, but preferably the activator / oxidized color precursor precursor is 0.1 to 0.1 mol by mole ratio. 100 is preferred,
More preferably 0.2 to 20, most preferably 0.5.
10 to 10. In the present invention, when an activator is used, two or more compounds may be used in combination as the activator. In that case, the total ratio of the molar amounts of the compounds used is within the above range. preferable. The color forming composition of the present invention may contain various components such as additives in addition to the above.

The color forming composition of the present invention can be formed into a desired image by providing heat in accordance with image information or by providing an activator in accordance with image information. It can be used as a forming material.

[Light-sensitive material] The light-sensitive material of the present invention comprises the color-forming composition of the present invention, a photopolymerization initiator, and a polymerizable compound. When the light-sensitive material of the present invention is imagewise irradiated with light, the polymerizable compound in the light-irradiated portion is polymerized by the action of a photopolymerization initiator, and is added as an oxidized precursor of a coloring agent, a coupler, and if desired. It reduces the mobility of at least one of the activators. Therefore, even if heat is applied to the light-sensitive material or an activator is acted on thereafter, the coupling reaction does not proceed in the light-irradiated portion, and only the non-light-irradiated portion can be colored. The polymerizable compound may be the same molecule as any of the oxidized precursor of the coloring agent, the coupler, or the activator added as required.

-Polymerizable Compound- As the polymerizable compound, a compound having a known polymerizable group can be used. For example, a compound having a vinyl group as a polymerizable group may be used. Specifically, acrylic acid and its salts, acrylic esters, acrylamides; methacrylic acid and its salts, methacrylic esters, methacrylamides; maleic anhydride, maleic esters; itaconic acid, itaconic esters Styrenes; vinyl ethers; vinyl esters;
Vinyl heterocycles; aryl ethers; allyl esters. Among these polymerizable vinyl monomers, a polymerizable vinyl monomer having a plurality of vinyl groups in the molecule is particularly preferable, for example, an acrylate or methacrylate of a polyhydric alcohol such as trimethylolpropane or pentaerythritol; Particularly preferred are acrylic esters and methacrylic esters of polyhydric phenols such as resorcinol, pyrogallol and phloroglucinol, and bisphenols; and acrylate or methacrylate-terminated epoxy resins, and acrylate or methacrylate-terminated polyesters. Specific examples of these include ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate, and diethylene glycol dimethacrylate. Is mentioned. In the present invention, the polymerizable compound may include an activator moiety containing a metal atom in the molecule.

-Photopolymerization Initiator- As the photopolymerization initiator, compounds that generate radicals or the like upon irradiation with light and can polymerize the polymerizable compound can be widely used. For example, compounds that generate a radical by a Norrish type I reaction in which a bond between a carbonyl group and a carbon atom adjacent thereto such as benzoin alkyl ether is cleaved, oxime esters, peroxides, organic sulfur compounds, halides, phosphines Donor and acceptor form exciplexes such as ketone and amine ketone radicals that generate ketyl radicals by hydrogen abstraction reaction of compounds such as oxide compounds, benzophenones, etc. There are a combination in which radicals are generated by generation and a photo-redox system in which radicals are generated in a complex system of a dye and a weak reducing agent. In addition, Monroe et al., "C
Chemical Review "Vol. 93 (1993
Compounds described on pages 435 to 446 can also be used. The use amount of the photopolymerization initiator is preferably 0.01 to 10% by mass based on the mass of the polymerizable compound.

Some of the above-mentioned photopolymerization initiators have sensitivity in the visible region, and they include visible lasers, LEDs,
It is excellent in that various visible light sources such as a white fluorescent lamp can be used. Patent Publication No. 2726258 describes a photopolymerization initiator composed of a cationic dye / anionic boron compound complex as having such a sensitivity in the visible region, and is particularly suitable for the photosensitive material of the present invention. Can be used. Preferred cationic dye / anionic boron compound complexes include compounds represented by the following general formula (A).

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In the general formula (A), D ⁺ represents a cationic dye. R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, an alicyclic group, Or an unsubstituted aryl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aryloxyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted heterocyclic group,
Or a substituted or unsubstituted silyl group. R ²¹ , R
²² , R ²³ and R ²⁴ may be the same or different from each other, and two or more of them may combine to form a cyclic structure.

Specific examples of the organic borate anion portion in the general formula (A) include tetramethyl borate, tetraethyl borate, tetrabutyl borate, triisobutyl methyl borate, di-n-butyl-di-t-butyl borate, Tetra-n-butyl borate, tetraphenyl borate, tetra-p-chlorophenyl borate, tetra-m-chlorophenyl borate, tri-m-chlorophenyl-n-hexyl borate, triphenylmethyl borate, triphenylethyl borate, triphenylpropyl borate , Triphenyl-n-butyl borate,
Trimesityl butyl borate, tolyl isopropyl borate, triphenyl benzyl borate, tetraphenyl borate, tetrabenzyl borate, triphenyl phenethyl borate, triphenyl-p-chlorobenzyl borate, triphenylethenyl butyl borate, di (α-naphthyl) Preferable examples include borate anions such as -dipropyl borate, triphenylsilyltriphenylborate, tritolylsilyltriphenylborate, and tri-n-butyl (dimethylphenylsilyl) borate.

In the general formula (A), the cationic dye represented by D ⁺ is not particularly limited as long as it has an absorption peak in a visible light region to a wavelength region of 1100 nm. Can be selected as appropriate. For example, a methine dye, a carbonium dye, an indoline dye, a quinone imine dye, a styryl dye and the like are preferably exemplified. The methine dye is preferably a methine dye, a polymethine dye, a cyanine dye, an azamethine dye, and the like, and particularly preferably a cyanine dye, a carbocyanine dye, a dicarbocyanine dye, a tricarbocyanine dye, a hemicyanine dye, and the like. As the carbonium dye,
Triarylmethane dyes, xanthene dyes, acridine dyes and the like are preferred, and rhodamine dyes are particularly preferred.
The quinone imine dye is preferably an azine dye, an oxazine dye, a thiazine dye, a quinoline dye, a thiazole dye, or the like. One of these organic cationic dyes may be used alone, or two or more thereof may be used in combination.

As the cationic dye represented by D ⁺ ,
Among the dyes exemplified above, methine dyes, polymethine dyes, triarylmethane dyes, indoline dyes, azine dyes, xanthene dyes, oxazine dyes, organic cationic dyes selected from acridine dyes and styryl dyes are preferable, and in particular, cyanine dyes , Hemicyanine dye,
Preferred are cationic dyes selected from rhodamine dyes and azamethine dyes. Many organic cationic dyes having an absorption peak in the wavelength region of the visible light region or higher are known, for example, “chemical chemistry of functional dyes”.
In 1981, pages 393 to 416 of CMC Publishing Company,
Dyes described in “Coloring Materials”, 60 [4] 212-224 (1987) and the like can be referred to.

In the light-sensitive material of the present invention, the polymerizable compound and the oxidized precursor of the coloring agent can be used in any molar ratio. 0.1 to 1000, more preferably 1 to 100, and most preferably 2 to 50.

An embodiment of the light-sensitive material of the present invention has at least one support and a recording layer composed of one or more layers formed on the support, and the recording layer has the color-forming composition. Photosensitive material containing a compound, a polymerizable compound and a photopolymerization initiator. An example of an image forming method using the photosensitive material of this embodiment includes a step of imagewise irradiating light to a recording layer to form a cured region imagewise, and a step of applying heat to the recording layer where the cured region is formed. And / or applying pressure to form a dye in the non-light irradiated area. In the curing region forming step, radicals and the like are generated from the photopolymerization initiator by light irradiation, the polymerizable compound in the light irradiation region is polymerized, and the polymerizable compound in the light irradiation region is cured. In the color forming step, heat is applied to the recording layer in which the cured region has been formed. In the non-light-irradiated area, at least one of the oxidized color former precursor, the coupler, and the optional activator, which is added in a non-contact state in the recording layer, is brought into contact with the non-light-irradiated area to form the oxidized color precursor precursor. While the body changes to the oxidized color developing agent, the oxidized form and the coupler undergo a coupling reaction to form a dye and develop color. On the other hand, in the light irradiation region, since the polymerizable compound is cured, the mobility of any one of the oxidized color precursor precursor, the coupler, and the activator added as desired is reduced. The material remains out of contact, does not form a pigment, and remains colorless.

In the light-sensitive material of the present embodiment, the recording layer may have a multilayer structure. In this case, the precursor of the oxidized color-forming agent and the coupler, which are components of the color-forming composition, may be added if desired. The activator, polymerizable compound, and photopolymerization initiator to be used may be contained in different layers. Further, the number of the supports may be two or more. In this case, the recording layer is formed separately for each of the supports.
For example, a first layer containing an oxidized color precursor precursor, a polymerizable compound and a photopolymerization initiator is formed on a first support, and a second layer containing a coupler and an optional activator is added. Can be formed on the second support. In this embodiment, the recording layer includes a first layer and a second layer.

Also, an oxidized color precursor precursor, a coupler,
When the same layer contains an activator and an optional activator, at least one of the three materials is preferably isolated from the other materials. For example, it is preferred that one or two of the oxidized color precursor, the activator and the coupler are encapsulated (encapsulated in microcapsules) and separated from the others. By making the microcapsules heat-responsive or pressure-responsive, the two can be brought into contact by imagewise heating or pressurizing to form an image.

In the case of the photosensitive material of the present embodiment, when the recording layer is divided into two or more supports, the photosensitive material comprising the two or more supports is integrated and subjected to an image forming step. It is not necessary. For example, in the photosensitive material of the preferred embodiment, in the cured region forming step, only the first layer is irradiated with light, and in the color forming step, the first layer and the second layer are brought into contact with each other. Heat may be provided (integrating the photosensitive material).

In the recording layer, an oxidized precursor of a coloring agent, a coupler and an activator added as required (hereinafter, these two (and optionally three) materials may be referred to as “dye-forming materials”). Is disclosed in JP-A-07-104448.
By using various known dispersing methods described in Japanese Patent Laid-Open Publication No. 71 (3rd line, 3rd line, 72nd column, 11th line) and the like, it can be introduced into the recording layer. For example, the dye-forming material is made of a high-boiling organic solvent (a low-boiling organic solvent is used if necessary).
It is preferable to use an oil-in-water dispersion method of dissolving in water and emulsifying and dispersing in an aqueous gelatin solution. The details of the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027, and the method can be preferably used. Examples of the high-boiling organic solvent include phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate) which can be used in the above-described oil-in-water dispersion method. , Decyl phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (for example, diphenyl phosphate, triphenyl phosphate, triphenyl phosphate) Cresyl phosphate, 2-ethylhexyl diphenyl phosphate,
Dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate,
Tridodecyl phosphate, di-2-ethylhexylphenyl phosphate), benzoic acid esters (for example,
2-ethylhexyl benzoate, 2,4-dichlorobenzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate),

Amides (eg, N, N-diethyldodecaneamide, N, N-diethyllaurylamide), alcohols (eg, isostearyl alcohol), aliphatic esters (eg, dibutoxyethyl succinate, dibutyl succinate) -2-ethylhexyl, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate,
Isostearyl lactate, trioctyl citrate), aniline derivatives (such as N, N-dibutyl-2-butoxy-5-tert-octylaniline), chlorinated paraffins (paraffins having a chlorine content of 10% to 80%), Trimesic esters (eg, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg, 2,4-di-tert)
-Amylphenol, 4-dodecyloxyphenol,
4-dodecyloxycarbonylphenol, 4- (4-
Dodecyloxyphenylsulfonyl) phenol), carboxylic acids (eg, 2- (2,4-di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkyl phosphoric acids (eg, di-2 (ethylhexyl) phosphoric acid) , Diphenylphosphoric acid) and the like.
As an auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or more and about 160 ° C. or less (for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate, dimethylformamide) may be used in combination.

Also, US Pat. No. 4,555,470,
No. 4,536,466, No. 4,536,467, No. 4,587,206, No. 4,555,476, No. 4,599,296, No. 3-62,256, etc. A high boiling organic solvent such as
It can be used in combination with a low boiling organic solvent having a temperature of 0 ° C to 160 ° C. Two or more kinds of the above-mentioned high-boiling organic solvents can be used in combination. The high boiling point organic solvent can be used in a mass ratio of 0 to 2.0 times, preferably 0 to 1.0 times the mass of the dye-forming material. When the recording layer contains a binder together with the dye-forming material, the high-boiling organic solvent is preferably 1 ml or less, more preferably 0.5 ml or less, per 1 g of the binder. Most preferably, it is 0.3 ml or less.

The dye-forming material is described in JP-B-51-39,
No. 853, a dispersion method using a polymer described in JP-A-51-59,943 and JP-A-62-3.
No. 0,242, and the like, a method of adding a fine particle dispersion and adding it can also be contained in the recording layer.

When any of the above dye-forming materials is a compound substantially insoluble in water, it can be dispersed in fine particles in a binder and contained in a layer. When the dye-forming material is a hydrophobic compound, it can be dispersed in a hydrophilic colloid and contained in the layer. When the dye-forming material is dispersed in a hydrophilic colloid, various surfactants can be used. For example, JP-A-59
The surfactants described in JP-A-157,636, pages (37) to (38), and the surfactants described in Research Disclosure can be used.

Regarding the latex dispersion method as one of the polymer dispersion methods, the steps, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application No. (OLS) 2,541,274
No. 2,541,230, JP-B-53-41091
And European Patent Publication No. 029104, etc., and can also be used in the present invention. Regarding the dispersion method using an organic solvent-soluble polymer, see PCT International Publication No. WO8
No. 08/00723 and can be used in the present invention.

The polymerizable compound and the photopolymerization initiator are:
It is preferable that the emulsion layer is contained in the recording layer in a state of being emulsified and dispersed to form oil droplets. Two or more polymerizable compounds may be mixed and used in the oil droplets.

The recording layer may contain other additives together with the dye-forming material, the polymerizable compound and the photopolymerization initiator. As the additive, JP-A-07-1044
No. 48 (column 39, line 50 to column 70, line 9) and JP-A-07-77775 (column 61, line 50 to line 6)
A stain inhibitor described in JP-A-07-301895 (column 87, line 49 to column 88, line 48); JP-A-62-215272 (page 125, upper right column 2)
Line to page 127, lower left column, last line) Gazette, JP-A-2-3314
No. 4 (page 37, lower right column, line 14 to page 38, upper left column, line 11)
Gazette, European Patent No. 0.355.600A2 (page 85, 2
Lines 2 to 31) The ultraviolet absorber described in the specification, JP-A-07-104448 (column 70, line 10 to column 71, 2)
Line 2) Discoloration inhibitors described in the official gazette. As the anti-fading agent, a compound represented by the following general formula (B) or the following general formula (C) is preferable.

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In the general formula (B), R ⁶⁰ is an alkyl group,
Alkenyl group, aryl group, aralkyl group, heterocyclic group,
Represents a group represented by R ⁶⁸ CO—, R ⁶⁹ SO ₂ — or R ⁷⁰ NHCO—. Here, R ^{68 to} R ⁷⁰ each represent an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R ⁶¹ and R ⁶² each represent a hydrogen atom, a halogen atom,
It represents an alkyl group, an alkenyl group, an alkoxy group or an alkenoxy group, and R ^{63 to} R ⁶⁷ each represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

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In the general formula (C), E represents a group of non-metallic atoms necessary for forming a 5- to 7-membered ring together with C and N. In the general formula (C), R ⁷¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group or a hydroxyl group. In the general formula (C), R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ each represent a hydrogen atom or an alkyl group.

Formula (B) or Formula (C)
The compound represented by the formula (1) is preferably contained in an amount of 5 to 200 mol% based on the oxidized precursor of the color-forming main agent,
More preferably, the content is 0 mol%.

In the photosensitive material of this embodiment, examples of the support include paper, coated paper, laminated paper, synthetic paper, polyethylene terephthalate film, triacetate cellulose film, polyethylene film, polystyrene film, polycarbonate film and the like. And a metal plate of aluminum, zinc, copper, or the like, or a substrate obtained by subjecting the surface of a support to various treatments such as surface treatment, undercoating, or metal vapor deposition. In addition,
rch Disclosure, Vol. 200, 19
The support described in Item 800036, XVII, December 80, can also be referred to. Further, if necessary, an antihalation layer may be provided on the surface of the support, and a layer according to the purpose, such as a sliding layer, an antistatic layer, an anti-curl layer, and an adhesive layer, may be provided on the back surface of the support. Can be.

The light-sensitive material of the present embodiment can be used for forming a single-color image or a multi-color image. Examples of constitutions for multicolor image forming applications include, on a support, photopolymerization initiators having mutually different photosensitive wavelengths, and dye-forming materials combined such that the colors of the formed dyes are mutually different from each other. And an image forming material in which two or more recording layers are laminated. For example, by laminating three recording layers that can emit cyan, magenta, and yellow and have different photosensitive wavelengths, it is possible to form a full-color image. When the photosensitive material of the present embodiment has two or more recording layers, an intermediate layer can be provided between the recording layers. Further, a protective layer, a filter layer, and the like may be provided on the recording layer.

As the exposure light source used in the cured region forming step, of course, a light source suitable for the photosensitive wavelength of the photopolymerization initiator contained in the recording layer is selected, but the image information is transmitted via an electric signal. Whether or not it can be selected in consideration of the processing speed, compactness, and power consumption of the entire system. When image information is recorded via an electric signal, a light emitting diode and various lasers may be used as the image exposure device, and various devices known as an image display device (CRT, liquid crystal display, electronic device, etc.) may be used. A luminescence display, an electrochromic display, a plasma display, or the like). In this case, the image information is an image signal obtained from a video camera or an electronic still camera, a television signal represented by the Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels by a scanner or the like, and an image signal stored in a recording material such as a magnetic tape or a disk can be used.

When exposing a color image, an LED, a laser, a fluorescent tube, and the like are used in combination according to the color sensitivity of each recording layer. A plurality of the same may be used, or a combination of different types may be used. May be used. The color sensitivity of the photosensitive material is R (red), G (green), B in the photographic field.
(Blue) Photosensitivity is normal, but in recent years, UV, IR and the like are often used in combination, and the use range of light sources is expanding. For example, if the color sensitivity of the photosensitive material is (G, R,
IR) or (R, IR (short wave), IR (long wave)), (UV (short wave), UV (medium wave), UV (long wave)), (UV, B, G) Used. As the light source, another type such as a combination of two colors of LED and a laser may be combined. The light emitting tube or element may be subjected to scanning exposure using a single tube or element for each color, or an array of elements may be used to increase the exposure speed. Available arrays include LED arrays, liquid crystal shutter arrays, magneto-optical element shutter arrays, and the like. In addition, a light source using a blue light emitting diode, which has been remarkably developed recently, and a combination with a green light emitting diode or a red light emitting diode can also be used.

As the image display device described above, a CRT
There are a color display type and a monochrome display type as described above, and a method of performing exposure several times by combining a filter with a monochrome display type may be adopted. The existing two-dimensional image display device may be used in a one-dimensional manner like FOT, or one screen may be divided into several parts and used in combination with scanning.

Various means can be used as the heating means that can be used in the color forming step. For example, JP-A-61-2
As described in Japanese Patent No. 94434, a heating element layer may be provided on a surface on the support (the surface on which the recording layer is not provided), and the recording layer may be heated by the heating layer. When the photosensitive material of the present embodiment has the heat-generating layer, the surface of the support on which the recording layer is provided prevents evaporation of moisture and volatile components from the photosensitive material and releases heat. It is preferable to cover with a heat insulating material or the like in order to keep the temperature without heat.

The heating means is described in JP-A-61-14.
As described in JP-A-7244, heating can also be performed using a hot plate, an iron, and a hot roller. Further, as described in JP-A-62-144166, a method of heating by sandwiching a photosensitive material between a heat roller and a belt may be used. That is, the entire surface may be heated simultaneously by bringing the recording layer of the image forming material into contact with a heating element having a surface area larger than the area of the recording layer, or a heating element having a smaller surface area (a heating plate, a heat roller, The recording layer may be brought into contact with the recording layer, and the entire surface may be heated with time by scanning the recording layer. In addition to the method in which the heating element is brought into direct contact with the recording layer to heat the recording layer, the recording layer may be heated in a non-contact state by applying electromagnetic waves, infrared rays, hot air or the like to the recording layer.

The application of heat to the recording layer in the color forming step is as follows.
After the light irradiation in the cured region forming step is completed,
It is preferable to perform the process after 0.1 seconds or more. When a heating plate, a heat roller or a heating drum is used as the heating means in the color forming step, the heating temperature is generally 40 ° C. to 25 ° C.
0 ° C., preferably 70 ° C. to 180 ° C. The heating time is generally between 0.1 seconds and 5 minutes, preferably between 0.1 seconds and 100 seconds, more preferably between 0.5 seconds and 3 minutes.
0 seconds, most preferably 1 second to 20 seconds. Further, heating may be performed twice or more at different temperatures.

In the above-described image forming method, an example has been described in which heat is supplied in the color forming step. However, depending on the content of the dye forming material in the recording layer, color may be formed by applying pressure, or heat and pressure may be applied. May be developed by the donation.

[0118]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to the following examples. [Example 1] Oxidized precursor of a coloring agent (Exemplified compound I-
1) 10 mg, 10 mg of coupler (exemplary compound Y-3)
And a composition consisting of 0.5 ml of cumene was placed in a test tube and heated in an oil bath at 150 ° C. for 10 minutes to produce a yellow dye.

Example 2 10 mg of an oxidized precursor of a coloring agent (Exemplified Compound I-10) and a coupler (Exemplified Compound Y-)
5) A composition consisting of 10 mg and 0.5 ml of cumene was placed in a test tube and heated in an oil bath at 150 ° C. for 10 minutes to produce a yellow dye.

[Comparative Example 1] 10 mg of an oxidized color precursor precursor (Exemplified Compound I-10), a coupler having the following structure (Ex)
-1) A yellow pigment was not formed at all when a composition consisting of 10 mg and 0.5 ml of cumene was placed in a test tube and heated in an oil bath at 150 ° C. for 10 minutes.

[Comparative Example 2] 10 mg of an oxidized precursor of a coloring agent (Exemplified Compound I-10), a coupler having the following structure (Ex)
-2) A yellow pigment was not generated at all even when a composition comprising 10 mg and 0.5 ml of cumene was placed in a test tube and heated in an oil bath at 150 ° C. for 10 minutes.

[0122]

Embedded image

Example 3 An activator (K-
1) 0.195 g, coupler (exemplary compound Y-5)
173 g, oil (tricyclohexyl phosphate)
An oil phase-1 was obtained by mixing and dissolving 0.173 g and 2.0 g of ethyl acetate. On the other hand, a 16% aqueous solution of gelatin
64 g was mixed with 2.56 g of water to obtain an aqueous phase-1. After adding the aqueous phase-1 to the oil phase-1, the mixture was emulsified and dispersed with a homogenizer. To this emulsion, 3.53 g of water was added, mixed, and coated on a polyethylene terephthalate film subbed with gelatin at a coating amount of 35 ml / m ² and dried to obtain Sheet A.

On the other hand, 0.3 g of a precursor of an oxidized color developing agent (Exemplified Compound I-10), 0.9 g of a polymerizable compound (trimethylolpropane triacrylate), 0.1 g of a photopolymerization initiator (BO-1) having the following structure. 03g, the following compound (DY-
1) 0.005 g, 0.7 g of ethyl acetate, and 2 g of methyl ethyl ketone were mixed and dissolved to obtain an oil phase-2. On the other hand, 5.4 g of a 14% aqueous solution of gelatin, 1.3 g of a 5% aqueous solution of sodium dodecylbenzenesulfonate, and 8.5 g of water.
g and mixed to form an aqueous phase-2. After adding aqueous phase-2 to oil phase-2, it was emulsified and dispersed with a homogenizer. This emulsion was applied onto a polyethylene terephthalate film undercoated with gelatin at a coating amount of 70 ml / m ² and dried to obtain a sheet B.

[0125]

Embedded image

The sheet B was exposed through a wedge having a transmission density of 0 to 4 using a halogen lamp under the conditions of 100,000 lux and 40 seconds. After that, the sheets A and B are bonded together so that the application surfaces thereof are in contact with each other.
After heating at 140 ° C. for 10 seconds from the back surface of the sheet, the two sheets were peeled off, and a yellow positive image was obtained on sheet A. That is, the portion corresponding to the exposed portion of the bonded sheet B is Dmin, and the portion corresponding to the unexposed portion is Dma.
It became x. This is presumably because the polymerizable compound was polymerized in the exposed portion of the sheet B, and the mobility of the oxidized color precursor was reduced, so that an image was obtained.

[0127]

According to the present invention, there is provided a color-forming composition which can form a dye by coupling to form a color (especially a good yellow color) without requiring an oxidizing agent such as silver halide. can do. Further, according to the present invention, it is possible to provide a color forming composition, a photosensitive material, and an image forming method which are highly useful for a digital image information output color print material or the like which forms a color image at a low cost by a simple operation. .

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kensuke Morita 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. (72) Inventor Hideaki Naruse 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. Inventor: Shunichi Ishikawa 210, Nakanuma, Minamiashigara-shi, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. CA00 CA50 CC14 FA03 FA22

Claims (7)

[Claims] 1. A color-forming composition comprising an oxidized color-forming agent precursor represented by the general formula (I) and a carbamoyloxy-eliminable 2-equivalent dye-forming coupler having an electron-withdrawing substituent. Embedded image (In the general formula (I), A ¹ and a nitrogen atom represent a group that forms a dye together with the coupler, and A ³ represents a bond electron pair with a nitrogen atom when the oxidized precursor of the coloring agent becomes an oxidized product. And A ² represents a group which is released with the formation of a dye after the oxidized product is coupled with the coupler to form a dye precursor.) 2. The oxidized precursor of a coloring agent is represented by the following general formula (I)
The color forming composition according to claim 1, which is represented by I). Embedded image (In the general formula (II), A ⁴ represents a substituent, and n represents 0 to
Represents an integer of 4. A ⁵ represents -OA ⁹ or -N (A ¹⁰⁾ A ¹¹
A ⁷ represents —O—, —S—, —N (A ¹² ) — or —C (A ¹³ ) (A ¹⁴ ) —, and A ⁶ and A ^{9 to} A ¹⁴ each represent a hydrogen atom or A ⁸ represents a substituent, and A ⁸ represents a substituent. Two or more selected from A ⁴ , A ¹⁰ and A ¹¹ may be mutually bonded to form a ring. ) 3. The oxidized precursor of a coloring agent is represented by the following general formula (II)
The color development according to claim 1, characterized by being represented by I).
Composition. Embedded image(In the general formula (III), A^FifteenRepresents a substituent, and n represents 0
Represents an integer of from 4 to 4. A¹⁶, A¹⁷And A¹⁸Is hydrogen
Represents an atom or a substituent. A^Fifteen, A¹⁶And A¹⁷Choose from
Two or more groups may combine with each other to form a ring
No. A¹⁹Is -O-, -S-, -N (A^{twenty two})-Or -C
(A^{twenty three}) (A^{twenty four})-, And A²⁰Is = O, = S, = N-
A^{twenty five}Or = C (A²⁶) -C (A²⁷) = NA²⁸The table
A^{twenty one}Represents a substituent, and A²⁰And A^{twenty one}Are interconnected
To form a ring. A^{twenty two}~ A ²⁸Are hydrogen sources
Represents a child or a substituent. ) 4. The color-forming composition according to claim 1, wherein the coupler is represented by the following general formula (IV). Embedded image (In the general formula (IV), R ¹ and R ² each represent an alkyl group or an aryl group, and at least one of them represents an alkyl group having an electron-withdrawing substituent. Q ¹ represents —COR ³ ,
^{-CN, -CON (R 4) R} 5, -COOR 6, -SO 2 R
⁷ represents a heterocyclic group, and Q ² represents an alkyl group, an aryl group, a heterocyclic group, —N (R ¹⁰ ) R ¹¹ or —OR ¹² . ^{R 3, R 5 ~R 7,} R 11 and R ¹² each represents an alkyl group, an aryl group or a heterocyclic group, R ⁴ and R ¹⁰
Each represents a hydrogen atom or a substituent. Q ¹ and Q ² may combine with each other to form a ring. ) 5. The color-forming composition according to claim 1, wherein the coupler is represented by the following general formula (V). Embedded image (In the general formula (V), Q ³ and R ¹⁴ each represent an alkyl group, an aryl group, or a heterocyclic group. R ¹³ represents a hydrogen atom or a substituent. At least one of R ¹⁵ and R ¹⁶ is an electron. Represents an alkyl group having a withdrawing substituent, and the other represents an alkyl group or an alkyl group having an electron-withdrawing substituent.) 6. A photosensitive material comprising the color-forming composition according to claim 1, a photopolymerization initiator, and a polymerizable compound. 7. A photosensitive material having at least one support and a recording layer comprising at least one layer formed on the support, wherein the recording layer is any one of claims 1 to 5. A light-sensitive material comprising the color-forming composition according to claim 1, a photopolymerization initiator, and a polymerizable compound.