JP2000284475A - Color developable composition and recording material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material of a negative type with which a color image may be obtained by a simple dry processing and which has a high sensitivity by incorporating a polymerizable monomer having a nucleophilic group, an acid generative polymerizable monomer and material which is capable of developing color in the presence of an acid into a composition. SOLUTION: This composition contains the polymerizable monomer having the nucleophilic group, the acid generative polymerizable monomer and the material which is capable of developing color in the presence of the acid. The composition generates the acid at a degree of polymerization and develops color in correspondence to the generated acid accompanying the copolymerization of these monomers. The polymerizable monomer having the nucleophilic group is preferably expressed by formula I. The acid generative monomer is preferably expressed by formula II. In the formulas I and II, X denotes a bivalent linkage group; Nu denotes a group having a nucleophilic site (nucleophilic group) and n denotes 0 or 1. R1 to R6 respectively denote hydrogen atmosphere or substituents; E denotes a group having a electrophilic group and A denotes the group which generates the acid as a result of the copolymerization of the polymerizable monomer having the nucleophilic group and the acid generative polymerizable monomer expressed by the formula II and the reaction of this nucleophilic group with E.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a novel recording material from which an image can be obtained by a simple dry process.

[0002]

2. Description of the Related Art Using an acid and a substance that develops a color in the presence of the acid,
A method of producing a recording material by a simple dry process is widely known, including pressure-sensitive paper and thermal paper. There is also known an example in which a photosensitive material is produced by using a similar combination. Among them, Japanese Patent Application Laid-Open Nos. 57-179835 and 57-1975 disclose a method of obtaining a photosensitive material having high sensitivity by using a polymerization reaction.
No. 38 and US Pat. No. 4,842,976 use microcapsules containing a photopolymerization initiator, a monomer, and a leuco dye of an acid-coloring type, and after imagewise curing the microcapsules by imagewise exposure, pressure is applied. To release the inclusions from the uncured microcapsules and contact them with an acidic substance to develop color. JP-A-61-275742 and JP-A-61-275742 disclose higher sensitivity.
No. 2,788,491 uses a microcapsule containing a silver halide, a reducing agent, a monomer, and a leuco dye of an acid-coloring type. The microcapsule is cured imagewise by imagewise exposure and heat development. A method is described in which the encapsulated material is released from the uncured microcapsules and is brought into contact with an acidic substance to form a color. These methods are
It is also possible to obtain a color image by a simple dry process.

JP-A-3-72358 discloses an imagewise exposure method using a thermoresponsive microcapsule containing an acid coloring type leuco dye, an emulsion containing a photopolymerization initiator and a monomer containing an acidic moiety. Thereafter, a method is described in which an uncured acidic portion-containing monomer is brought into contact with a leuco dye in a thermoresponsive microcapsule to form a color by heat treatment. All of the above-mentioned methods are positive types in which unexposed portions develop color. When performing exposure by scanning exposure such as laser,
To form an image with many white areas such as documents,
A negative type in which the exposed portion develops a color is more suitable.

[0004] US Pat. No. 5,395,736 discloses that after a superacid precursor is exposed to light and a superacid is generated, the superacid is brought into contact with a second acid generator (oxalic acid diester) and heated. The generation method is described. When this is combined with, for example, an acid-forming type leuco dye, a negative photosensitive material can be obtained. However, this method (acid multiplication), as described above,
It is unclear how much sensitivity can be obtained compared to a method of gaining sensitivity by amplification by a polymerization reaction.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel color-forming composition and a recording material using a novel acid generation method, and in particular, to provide a high-sensitivity and negative-working photosensitive material. It is.

[0006]

The object of the present invention has been attained by the following means. (1) A color-forming composition comprising at least one polymerizable monomer having a nucleophilic group, at least one acid-generating polymerizable monomer, and a substance capable of forming a color in the presence of an acid. (2) A photosensitive chromogenic composition containing a polymerizable monomer having at least one nucleophilic group, at least one acid-generating polymerizable monomer, a substance capable of forming a color in the presence of an acid, and a photopolymerization initiator. Composition.

(3) A recording material containing a polymerizable monomer having at least one nucleophilic group on a support, at least one acid-generating polymerizable monomer, and a substance capable of coloring in the presence of an acid. . (4) A polymerizable monomer having at least one nucleophilic group and at least one acid-generating polymerizable monomer on a support, a substance capable of coloring in the presence of an acid, and a photopolymerization initiator. Photosensitive material. (5) A polymerizable monomer having at least one nucleophilic group on a support, at least one acid-generating polymerizable monomer, a photopolymerization initiator, and a compound represented by the following general formula (6) Photosensitive material containing

[0008]

DETAILED DESCRIPTION OF THE INVENTION The composition of the present invention comprises two monomers, a monomer having a nucleophilic group and a monomer capable of generating an acid, and a substance capable of forming a color in the presence of an acid. With the polymerization, an acid is generated in accordance with the degree of polymerization, and color is generated in accordance with the generated acid. The details of these two monomers are described below. The monomer having a nucleophilic group is preferably represented by the following general formula (1).

[0009]

Embedded image

In the formula (1), X represents a divalent linking group;
u represents a group having a nucleophilic site (nucleophilic group). n is 0
Or represents 1. R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₁ and R ₃ , R ₂ and-
(X) and _n -Nu and R ₃ - (X) _n -Nu ring may be bound to each other to form.

X represents a divalent linking group, which links the polymerizable unsaturated group to Nu. Specific examples of X are preferably a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -O-, -S-, -COO-, -CON.
_{(R) -, - SO 2} -, - SO -, - SO 2 N (R) -,
-OCON (R)-, -N (R)-, -N (R) CON
(R ′) —, —CO— and a combination thereof, more preferably a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, —O—,
-S-, -COO-, -CON (R)-, -CO- and combinations thereof, and most preferably a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -COO- , -CON (R)-, -C
O- and combinations thereof.
Here, R and R 'represent a hydrogen atom, an alkyl group, an aryl group,
Represents a heterocyclic group or a mere bond.

Nu represents a group having a nucleophilic site. The nucleophilic site has at least one lone pair of a heteroatom, and the conjugate acid has a pKa of 7 or less from the requirement that this lone pair does not neutralize the generated acid. Preferably -CR (R ')-OH, -COOH, -CONH
_{R, -SH, -SOH, -SO 2} H, -CON (R) O
H, -N (OH) COR, -SO 2 NHR, -N (O
H) SO ₂ R, more preferably —CR (R ′) —
OH, -COOH, -CONHR, -CON (R) O
H, -N (OH) COR, most preferably -CR
(R ')-OH, -CON (R) OH, -N (OH) C
OR, and Nu represents two or more of these nucleophilic sites.
Or two or more may be the same or different. Here, R and R 'represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or a mere bond.

R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent. R ₁ and R ₂ are each preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, _{COOR, -CONRR ', - SO 2} R, -S
_{O 2 NRR ', - SR,} -SOR, -OR, -NRR'
Or-(X) _n -Nu, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group, -COOR, -C
ONRR ′ or — (X) _n —Nu, most preferably a hydrogen atom or a substituted or unsubstituted alkyl group. Here, R and R 'represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or a mere bond.

R ₃ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,-
_{COOR, -CONRR ', - SO 2} R, -SO 2 NR
R ', -SR, -SOR, -OR, -NRR' or-
(X) _n- Nu, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, -COOR, -CONRR ', most preferably a hydrogen atom, substituted or unsubstituted An alkyl group of -CO
OR, -CONRR '. Here, R and R 'represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or a mere bond. R ₁ and R ₂ , R ₁ and R ₃ , R ₂ and −
(X) and _n -Nu and R ₃ - (X) _n -Nu ring may be bound to each other to form.

On the other hand, the acid-generating monomer is a monomer which, after copolymerizing with a monomer having a nucleophilic group, reacts with a nucleophilic group derived from the monomer having a nucleophilic group to generate an acid, It is preferably represented by the following general formula (2).

[0016]

Embedded image

In the formula (2), X represents a linking group of a divalent group, and E represents a group having a nucleophilic (electrophilic) site.
A is a polymerizable monomer having a nucleophilic group and an acid-generating polymerizable monomer represented by the general formula (2) are copolymerized, and a nucleophilic group derived from the polymerizable monomer having a nucleophilic group is generally used. Represents a group that generates an acid as a result of reacting with E in the formula (2). n represents 0 or 1. R ₄ , R ₅ and R ₆ each represent a hydrogen atom or a substituent, and R ₄ and R ₅ , R ₄ and R ₆ , R ₅ and — (X) _n -EA, and R ₆ and — (X) _n −
EA may combine with each other to form a ring.

X has the same meaning as described in the general formula (1). E represents a group having a nucleophilic (electrophilic) site, preferably -CO-, -COO-, -CON
(R ″) —, —O—CO—O—, SO ₂ —, or —SO ₃ —, and most preferably —COO— or —CON.
(R ″) −.

A is a polymerizable monomer having a nucleophilic group and an acid
A polymerizable monomer having a nucleophilic group
A nucleophilic group derived from a compatible monomer is represented by E in the general formula (2).
Represents a group that generates an acid as a result of a reaction, but is generated
The preferred acid is HO-SO_Two-R, HO-SO_Two−
Ar, HO-SO_Two-OR, HO-SO_Two-OAr, HC
1, HBr, HI, HO-COR, HO-COAr, H
SO_Two-R, HSO_Two-Ar, more preferably HO
-SO_Two-R, HO-SO_Two-Ar, HO-SO _Two-O
R, HO-SO_Two-OAr, HO-COR, HO-CO
Ar, most preferably HO-SO_Two-R, HO-
SO_Two—Ar. Here, R and R ″ are the aforementioned R and R ′
And Ar represents an aryl group. Also occurs
Acids refer to those having a pKa of 10 or less and -10 or more.
Hereinafter, it is preferably -10 or more, more preferably
Is preferably 4 or less and -8 or more, most preferably
It is 3 or less and -5 or more.

An example of a mechanism in which Nu and E react after the monomers of the general formulas (1) and (2) are copolymerized to generate an acid from A is described in, for example, US Pat. No. 4,146. , U.S. Pat. No. 4,248,96, U.S. Pat. No. 4,248,96, U.S. Pat.
No. 2, 4,847,185, 4,912,028
Or a group capable of causing a cleavage reaction using an intramolecular nucleophilic substitution reaction described in U.S. Pat. Nos. 4,409,323 and 5,034,311;
5,055,385 or 4,421,845
No. 4,546,073, which causes a cleavage reaction by utilizing the hydrolysis of imino ketals, or a group disclosed in the United Kingdom. Japanese Patent No. 1,531,927 includes a group which causes a cleavage reaction by utilizing an ester hydrolysis reaction. Among the acid-generating monomers represented by the general formula (2), the present invention The acid-generating monomer which can be used most effectively in the following general formula (3):
It is represented by general formula (4) or general formula (5).

[0021]

Embedded image

[0022]

Embedded image

In the general formulas (3), (4) and (5), R ₄ , R ₅ and R ₆ have the same meanings as those described in the general formula (2). R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent.

R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are preferably a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms, a straight chain having 2 to 50 carbon atoms. Chain or branched, chain or cyclic alkenyl group, having 2 to 50 carbon atoms in total
An alkynyl group, an aryl group having 6 to 50 carbon atoms, an acyloxy group having 1 to 50 carbon atoms, a carbamoyloxy group having 1 to 50 carbon atoms, a carbonamide group having 1 to 50 carbon atoms, and a sulfonamide having 1 to 50 carbon atoms A carbamoyl group having 1 to 50 carbon atoms, a sulfamoyl group having 0 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, an aryloxy group having 6 to 50 carbon atoms, an aryloxycarbonyl group having 7 to 50 carbon atoms, An alkoxycarbonyl group having 2 to 50 carbon atoms, an N-acylsulfamoyl group having 1 to 50 carbon atoms,
50 alkylsulfonyl groups, arylsulfonyl groups having 6 to 50 carbon atoms, alkoxycarbonylamino groups having 2 to 50 carbon atoms, aryloxycarbonylamino groups having 7 to 50 carbon atoms, amino groups having 0 to 50 carbon atoms, cyano groups Nitro group, carboxyl group, hydroxy group, sulfo group, mercapto group, alkylsulfinyl group having 1 to 50 carbon atoms, arylsulfinyl group having 6 to 50 carbon atoms, alkylthio group having 1 to 50 carbon atoms, 6 to 50 carbon atoms Arylthio group, ureido group having 1 to 50 carbon atoms, 2 to 50 carbon atoms
A heterocyclic group having at least one heteroatom such as nitrogen, oxygen or sulfur;
A two-membered monocyclic or condensed ring), an acyl group having 1 to 50 carbon atoms,
C0-50 sulfamoylamino group, C3-3
50 silyl groups and halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom). The above substituents may further have a substituent, and examples of the substituent include the substituents mentioned here. R ₇ , R ₈ ,
R ₉ , R ₁₀ , R ₁₁ and R ₁₂ may be combined with each other to form a ring, if possible.

A ₁ and A ₂ include the acid residues of the acids generated from A after being released.
R ₁₃ is preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an aryloxy group, more preferably an alkyl group, an aryl group, or a heterocyclic group, and most preferably an alkyl group or an aryl group.

Next, specific examples of the general formulas (1) and (2) used in the present invention are shown, but the scope of the present invention is not limited to these specific examples.

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

A method for synthesizing a polymerizable monomer having a nucleophilic group and an acid-generating polymerizable monomer will be described.

The monomer having a nucleophilic group can be generally synthesized by the following two typical synthetic methods. One is a method of obtaining amines and alcohols having a nucleophilic group by reacting an acid halide of a carboxylic acid having a polymerizable group, and the other is a Baylis-Hillman reaction (B).
acrylis esters, acrylamides and aldehydes known as aylis-Hillman reaction) in the presence of 1,4-diazabicyclo [2.2.2] octane (hereinafter abbreviated as DABCO). . For the Baylis-Hillman reaction, see Tetrahedron, Vol. 52, No. 24,
Details are described on pages 8001 to 8062.

Hereinafter, specific examples of the two synthesizing methods will be described. Synthesis Example 1 Synthesis of Compound Example N-01 (1-1) Synthesis of 2-hexyldecylhydroxylamine 69 g of hydroxylamine hydrochloride, 30.5 g of 2-hexyldecylbromide, 0.5 g of EDTA, methanol 5
Then, 84 g of sodium hydrogen carbonate was added, and the mixture was refluxed under heating for 3 hours. The reaction mixture was concentrated, ethyl acetate and water were added, and the mixture was separated and extracted. The organic phase was dried over magnesium sulfate. The organic phase after drying was concentrated, and the product was formed using silica gel column chromatography except for bis (2-hexyldecyl) hydroxylamine which was a by-product. The product was a colorless liquid. Yield 10.5g, 40.9%

(1-2) Synthesis of N-hexyldecyl-N-hydroxymethacrylamide (N-01) 20 g of sodium hydrogencarbonate was added to a mixture of 50 ml of water, 100 ml of ethyl acetate and 10.3 g of 2-hexyldecylhydroxylamine. In addition, 50 g of ice was added, followed by stirring and cooling. To this mixture, 5 g of methacrylic chloride was added dropwise over 2 minutes, and after completion of the addition, the mixture was stirred for 1 hour. After liquid separation, the organic phase was dried over magnesium sulfate, a small amount of p-methoxyphenol was added as a polymerization inhibitor to the dried organic phase, and the mixture was concentrated under reduced pressure. The concentrate was produced using silica gel column chromatography. The desired product was a colorless liquid. 6.8 g, 52.1% yield

Synthesis Example 2 Synthesis of Compound Example N-06 DABCO was added to a mixture of 120 g of dodecyl acrylate, 50 g of formalin, and 200 ml of THF under ice-cooling.
20 g were added. After 30 minutes, heat and raise the reaction temperature to 40 ° C.
And The reaction was carried out for 7 days, and 500 ml of water and 800 ml of ethyl acetate were added to carry out liquid separation and extraction. The organic phase was concentrated and produced by silica gel column chromatography. The desired product was a colorless liquid. 82.0 g, 60.8% yield

Specific examples of the method for synthesizing the acid-generating polymerizable monomer will be described as Synthesis Examples 3 to 5. Synthesis Example 3 Synthesis of Compound Example A-01 (3-1) Synthesis of 4-formylphenyl methacrylate 400 ml in 61 g of 4-hydroxybenzaldehyde
Acetonitrile and 84 ml of triethylamine were added and dissolved. The mixture was cooled to 0 ° C with ice-methanol, and 48.4 ml of methacrylic acid chloride was slowly added dropwise. Two hours later, liquid separation and extraction were performed with water and ethyl acetate, and the mixture was generated by silica gel column chromatography. The obtained target product was used immediately for the next reaction.

(3-2) Synthesis of 4-hydroxymethylphenyl methacrylate The total amount of the compound obtained in (3-1) was added to 300 ml of THF and 1 part of water.
00 ml was added and stirred. Under ice cooling, sodium borohydride was added little by little to this solution. TL for each addition
C confirmed the disappearance of the raw materials. After the disappearance of the raw materials, water and ethyl acetate were added, and liquid separation extraction was performed. The organic phase was dried over magnesium sulfate, concentrated, and produced by silica gel column chromatography. The desired product was obtained as a slightly brown oil. Yield 40.1 g, 41.7% (4
-Two steps from hydroxybenzaldehyde)

(3-3) Synthesis of 4- (p-toluenesulfonyloxymethyl) phenyl methacrylate (A-01) 37 g of 4-hydroxymethylphenyl methacrylate was dissolved in 250 ml of THF, and 32.4 of triethylamine was dissolved.
After adding ml, the mixture was cooled to 5 ° C and stirred. To this solution, 64 g of paratoluenesulfonic anhydride was added in 10 portions. After the addition was completed, the reaction was allowed to proceed for 1 hour at 5 ° C. or lower, and the temperature was gradually raised to room temperature. After leaving overnight, water and ethyl acetate were added to carry out liquid separation extraction. The organic phase was dried over magnesium sulfate, concentrated and then produced by column chromatography. The desired product was obtained as a slightly yellowish oil. Yield 1
7.7 g, 26.6% yield

Synthesis Example 4 Synthesis of Compound Example A-05 12.7 g of N-hydroxymethylmaleimide, 2,5-
150 ml of acetonitrile was added to 27.1 g of dichlorobenzenesulfonyl chloride and stirred. Then, 15 ml of pyridine and 1 g of 4-dimethylaminopyridine were added to the reaction mixture. After standing overnight, water and ethyl acetate were added for extraction, and the mixture was extracted by short silica gel column chromatography. Then, ethyl acetate was added for crystallization.
The desired product was a colorless solid. 6 g, 17.8% yield

Synthesis Example 5 Synthesis of Compound Example A-10 (5-1) Synthesis of exo-N-hydroxy-7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide 139 g of hydroxylamine hydrochloride A solution prepared by dissolving in 650 ml of methanol and dissolving 112 g of potassium hydroxide in 280 ml of methanol was added dropwise thereto under ice cooling. The precipitated inorganic salt was removed by suction filtration using Celite. 332 g of exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride was added to the obtained methanol solution of hydroxylamine. After heat generation, crystals precipitated. After stirring for 2 hours, the precipitated crystals were collected by filtration. After washing three times with methanol, it was dried. Yield 30
2g, 83.3%

(5-2) exo-N- (2,4,6-triisopropylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-
Synthesis of dicarboximide exo-N-hydroxy-7-oxabicyclo [2.
2.1] 100 g of hept-5-ene-2,3-dicarboximide and 500 ml of acetonitrile were mixed,
0.5 g of 2,4,6-triisopropylbenzenesulfonyl chloride was added and stirred. To this reaction mixture, 60 ml of pyridine was added dropwise, heated to 60 ° C., and reacted for 2 hours. After cooling, the obtained crystals were collected by filtration and recrystallized from methanol. Yield 191,7 g, yield 77.6%

(5-3) Synthesis of N- (2,4,6-triisopropylbenzenesulfonyloxy) maleimide (Compound Example A-10) Exo-N- (2,4,6-triisopropylbenzenesulfonyloxy) -7-oxabicyclo [2.2.
1] Hept-5-ene-2,3-dicarboximide 3
0 g was dispersed in 200 ml of xylene, and heated to 130 ° C. while gently blowing nitrogen gas. The reaction was carefully followed by TLC to confirm the disappearance of the starting materials. After about 3 hours of reaction time, upon cooling, colorless crystals precipitated. The crystals were collected by filtration and dried. 15.2 g, 59.7% yield

As the polymerizable monomer having a nucleophilic group and the acid-generating polymerizable monomer of the present invention, any monomer can be selected as necessary. The mixing ratio of these two types of monomers can be arbitrarily selected according to the purpose, but is usually preferably 1: 1000 to 1000: 1, more preferably 1: 100 to 100: 1 in molar ratio. ,
Most preferably, it is 1:10 to 10: 1.

In the present invention, a substance that develops a color by reaction with an acid is used. Examples thereof include leuco dyes having a partial structure such as lactone, lactam, and spiropyran used in pressure-sensitive paper and thermal paper. More preferred acid coloring substances include the following coloring agents.
Hereinafter, this color former is referred to as BLD. A preferred BLD in the present invention is represented by the general formula (6).

[0049]

Embedded image

In the general formula (6), D represents a hydroxyl group or
-NR₁₈R₁₉Represents R₁₈And R ₁₉Are hydrogen sources
Or a substituent, examples of which are carbon
Linear or branched, chain or cyclic alk of 1-50
Group, straight or branched, chain or ring having 2 to 50 carbon atoms
Alkenyl group, alkynyl group having 2 to 50 carbon atoms in total,
C6-C50 aryl group, C1-C50 carba
Moyl group, sulfamoyl group having 0 to 50 carbon atoms, carbon number
7 to 50 aryloxycarbonyl groups, 2 to 5 carbon atoms
0 alkoxycarbonyl group, alkyl having 1 to 50 carbon atoms
Rusulfonyl group, arylsulfonyl having 6 to 50 carbon atoms
Group, a heterocyclic group having 2 to 50 carbon atoms (as a hetero atom,
For example, at least one nitrogen, oxygen or sulfur, etc.
Including 3 to 12-membered monocyclic ring and condensed ring), having 1 carbon atom
To 50 acyl groups. More preferably hydrogen source
, Linear or branched, chain or cyclic having 1 to 50 carbon atoms
Alkyl group, linear or branched, chain having 2 to 50 carbon atoms
Or a cyclic alkenyl group, an alkyl having 2 to 50 carbon atoms in total
And an aryl group having 6 to 50 carbon atoms. Up
The substituents described above may further have a substituent,
Examples of the substituent include R represented by the general formulas (3) to (5).₇~
R₁₂Examples are given.

R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ each represent a hydrogen atom or a substituent, and examples of the substituent include the examples of R _{7 to} R ₁₂ shown in formulas (3) to (5). And R
₁₄ and R ₁₅ , R ₁₅ and R ₁₈ (or R ₁₉ ), R ₁₇ and R ₁₈ (or R ₁₉ ), and R ₁₆ and R ₁₇ may form a ring.

BL represents a block group bonded to a nitrogen atom. Here, the blocking group represents a -CONR ₂₀ R _201, or other acid-removable group. R ₂₀ and R ₂₀₁ each represent a hydrogen atom or a substituent, and examples of the substituent include:
A linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms, a linear or branched, chain or cyclic alkenyl group having 2 to 50 carbon atoms, an alkynyl group having 2 to 50 carbon atoms, a carbon number An aryl group having 6 to 50, a carbonamide group having 1 to 50 carbon atoms, a sulfonamide group having 1 to 50 carbon atoms,
A carbamoyl group having 1 to 50 carbon atoms, a sulfamoyl group having 0 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, an aryloxy group having 6 to 50 carbon atoms, an aryloxycarbonyl group having 7 to 50 carbon atoms, and a carbon number 2 to 50 alkoxycarbonyl groups, C1 to C50 alkylsulfonyl groups, C6 to C50 arylsulfonyl groups, C2
~ 50 alkoxycarbonylamino groups, 0-5 carbon atoms
0 amino group, cyano group, hydroxy group, sulfo group, alkylthio group having 1 to 50 carbon atoms, arylthio group having 6 to 50 carbon atoms, ureido group having 1 to 50 carbon atoms, 2 to 2 carbon atoms
50 heterocyclic groups (for example, nitrogen,
A 3- to 12-membered monocyclic or condensed ring containing at least one oxygen or sulfur or the like), an acyl group having 1 to 50 carbon atoms, a sulfamoylamino group having 0 to 50 carbon atoms, and 3 to 50 carbon atoms Silyl group. The above substituents may further have a substituent, and examples of the substituent include the examples of R _{7 to} R ₁₂ shown in formulas (3) to (5), and more preferably hydrogen. atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having from 1 to 30 carbon atoms, R ₂₀ and R
More preferably, any of ₂₀₁ is a hydrogen atom.

The acid-removable group means a group that can be removed by an acid generated from the acid-generating polymerizable monomer represented by the general formula (2). GR
EEN, PETER G. WUTS co-authored, PROTE
CTIVE GROUP IN ORGANIC SY
NTHESIS (Protective Group in Organic Synthesis) Second Edition, (1991) (J
OHN WILEY & SONS, INC. ) 309
On pages 405 to 405, amino group blocking groups are described in detail. Among them, those which are described as being removable with an acid are preferably used. Particularly preferred is a tert-butoxycarbonyl group (BOC group). Representative tertiary alkoxycarbonyl groups are exemplified.

L is a leaving group, and L and BL are released by the action of an acid to form a chromogenic compound (dye).

When BL is an acid-removable group other than -CONR _{20 R201} , L is a heterocyclic group (containing at least one nitrogen, oxygen or sulfur as a hetero atom,
A saturated or unsaturated 5- to 7-membered monocyclic or condensed ring, for example, succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole , Benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-
Dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one, 2-
Pyridone, etc.), halogen atom (fluorine, chlorine atom, bromine atom, iodine atom), aryloxy group (eg, phenoxy, 4-cyanophenoxy, etc.), heterocyclic oxy group (eg, pyridyloxy, pyrazolyloxy, etc.), acyloxy group (Eg, acetoxy, benzoyloxy, etc.), alkoxy group (eg, methoxy, dodecyloxy, etc.), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy group (eg, Phenoxycarbonyloxy, etc.), alkoxycarbonyloxy groups (eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), heterocyclic thio groups (eg, tetrazolyl E, 1,3,4-thiadiazolylthio, 1,3,4-oxadiazolylthio, benzimidazolylthio, etc.), alkylthio groups (eg, methylthio, octylthio, hexadecylthio, etc.), alkylsulfonyloxy groups (eg, Methanesulfonyloxy, etc.), arylsulfonyloxy group (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), carbonamide group (eg, acetamide, trifluoroacetamide, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfone) Amide), an alkylsulfonyl group (eg, methanesulfonyl), an arylsulfonyl group (eg, benzenesulfonyl), an alkylsulfinyl group (eg, methanesulfinyl), an arylsulfinyl group (eg, Zensurufiniru etc.), an arylazo group (e.g., phenylazo, naphthylazo etc.), carbamoylamino group (e.g., N- methylcarbamoyl amino, etc.) and the like.

When BL is an acid-removable group other than -CONR _{20 R201} , L is more preferably a heterocyclic group, a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group. , An aryloxycarbonyloxy group, an alkoxycarbonyloxy group, an arylthio group, a heterocyclic thio group, an alkylsulfonyloxy group, and an arylsulfonyloxy group.

[0057] If the BL is -CONR ₂₀ R _201, L is preferably a basic group undergoing protonation by the acid produced from the acid generator of the polymerized monomer, imidazole as particularly preferred groups, pyrazole, triazole, And tetrazole. These may be arbitrarily substituted for the purpose of adjusting the susceptibility to protonation or the releasability. Examples of the substituent include general formulas (3) to (3).
Examples of R _{7 to} R ₁₂ shown in (5) are given.

CPA and CPB together with the carbon atom to which they bond (C in formula (6)) represent the atomic groups necessary to form a color coupler well known in the silver halide photographic art. The partial structure (coupler) formed by CPA, CPB and carbon atom C will be described below.

The partial structure called a coupler is described in Theory of Photographic Process (4th Ed., Edited by TH James, Mac).
millan, 1977) pages 291-334, and 3
54-361, JP-A-58-12353, 58-
No. 149046, No. 58-149047, No. 59-1
Nos. 1114, 59-124399, 59-174
No. 835, No. 59-231539, No. 59-2315
No. 40, No. 60-2951, No. 60-14242,
Nos. 60-23474 and 60-66249.

The coupler preferably used in the present invention has a structure represented by the following general formulas (7) to (18). These are couplers generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively.
In the structural formula, L of the general formula (6) is also described, and an asterisk (*) represents a bond bonded to N in the general formula (6).

[0061]

Embedded image

[0062]

Embedded image

Formulas (7) to (10) represent couplers referred to as active methylene couplers, wherein R ₂₁ represents an optionally substituted acyl group, cyano group, nitro group, aryl group, A heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas (7) to (9), R ₂₂ is an optionally substituted alkyl group, aryl group or heterocyclic residue. In the general formula (10), R ₂₃ is an aryl group or a heterocyclic residue which may have a substituent.
Examples of the substituent which R ₂₁ , R ₂₂ and R ₂₃ may have include those described for R _{7 to} R ₁₂ shown in the aforementioned general formulas (3) to (5). R ₂₁ , R ₂₂ and R ₂₃ may be bonded to each other to form a ring.

The formula (11) represents a coupler called a 5-pyrazolone coupler, wherein R ₂₄ represents an alkyl group, an aryl group, an acyl group or a carbamoyl group. R ₂₅ is a phenyl group or one or more halogen atoms,
Represents a phenyl group substituted by an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group or an acylamino group. Among the 5-pyrazolone couplers represented by the general formula (11), those in which R ₂₄ is an aryl group or an acyl group, and R ₂₅ is a phenyl group substituted by one or more halogen atoms are preferable.

To describe these preferred groups in detail, R ₂₄ is a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 2-chloro-5-tetradecanamidophenyl group, a 2-chloro-5- (3-octadecenyl) group. -1-succinimide) phenyl group, 2-chloro-5-
An aryl group such as an octadecylsulfonamidophenyl group or a 2-chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group or an acetyl group, 2- (2,4-di-t) -Pentylphenoxy) butanoyl group, benzoyl group, 3- (2,
Acyl groups such as 4-di-t-amylphenoxyacetamido) benzoyl group, and these groups may further have a substituent, and these groups are organic groups linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is a substituent or a halogen atom. R ₂₅ is preferably a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group and a 2-chlorophenyl group.

The formula (12) represents a coupler called a pyrazoloazole coupler, wherein R ₂₆ represents a hydrogen atom or a substituent. Q ₃ contains 2 to 4 nitrogen atoms 5
Represents a group of nonmetallic atoms necessary for forming a membered azole ring, and the azole ring may have a substituent (including a condensed ring). Among the pyrazoloazole couplers represented by the general formula (12), imidazo [1,2] described in U.S. Pat.
-B] pyrazoles, pyrazolo [1,5-b] -1,2,4-triazoles described in U.S. Pat. No. 4,500,654, and pyrazolo [US Pat. No. 3,725,067]. 5,1-c] -1,2,4-triazoles are preferred.

For details of the substituent of the azole ring represented by the substituents R ₂₆ and Q ₃ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of the pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 201443 is a pyrazolotriazole coupler having a carboxamide group in the molecule.

The general formulas (13) and (14) are
Caps known as knol-based couplers and naphthol-based couplers
Is a puller, where R₂₇Is a hydrogen atom or -CONR
₃₂R ₃₃, -SO_TwoNR₃₂R₃₃, -NHCOR₃₂, -NH
CONR₃₂R₃₃, -NHSO _TwoNR₃₂R₃₃Chosen from
Represents a group. R₃₂, R₃₃Represents a hydrogen atom or a substituent.
In the general formulas (13) and (14), R₂₈Represents a substituent
And l is an integer selected from 0 to 2; m is selected from 0 to 4
Represents an integer. When l and m are 2 or more, R₂₈Each
They may be different. R₂₈, R₃₂, R₃₃As a substituent of
R represented by the general formulas (3) to (5)₇~ R₁₂Examples of
I can do it.

Preferred examples of the phenolic coupler represented by the general formula (13) include US Pat. No. 2,369,
No. 929, No. 2,801,171, No. 2,77
No. 2,162, No. 2,895,826, No. 3,7
72-002 and the like, 2-acylamino-5-alkylphenols, U.S. Pat. No. 2,772,162,
No. 3,758,308, No. 4,126,396
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729,
9,166,956 and the like, U.S. Patent Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427. , 767, and the like.

A preferred example of the naphthol coupler represented by the general formula (14) is described in US Pat. No. 2,474,2.
No. 93, 4,052, 212, 4,146
No. 396, No. 4,282,233, No. 4,29
Examples thereof include 2-carbamoyl-1-naphthols described in US Pat. No. 6,200 and the like and 2-carbamoyl-5-amido-1-naphthols described in U.S. Pat. No. 4,690,889.

Formulas (15) to (18) are couplers called pyrrolotriazoles, and R ₂₉ , R ₃₀ and R ₃₁ each represent a hydrogen atom or a substituent. As the substituent for R ₂₉ , R ₃₀ , and R ₃₁ , R ₇ represented by the aforementioned general formulas (3) to (5) can be used.
Examples of to R ₁₂ can be mentioned. Preferred examples of the pyrrolotriazole-based couplers represented by the general formulas (15) to (18) include European Patent Nos. 488,248A1 and 49.
Couplers in which at least one of R ₃₂ and R ₃₃ described in 1,197 A1 and 545,300 is an electron-withdrawing group.

Other couplers having structures such as fused phenol, imidazole, pyrrole, 3-hydroxypyridine, active methylene, active methine, 5,5-fused heterocycle, and 5,6-fused heterocycle can be used.

Examples of fused phenol couplers include US Pat. Nos. 4,327,173 and 4,564,586.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used. As the imidazole coupler, couplers described in U.S. Pat. Nos. 4,818,672 and 5,051,347 can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used.

As active methylene and active methine couplers, US Pat. Nos. 5,104,783 and 5,16
The couplers described in 2,196 and the like can be used. 5,5
-As a fused heterocyclic coupler, US Pat.
Pyrrolopyrazole couplers described in JP-A-4,289, and pyrroleimidazole couplers described in JP-A-4-174429 can be used. Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585 and JP-A-4-20473.
No. 0, pyrrolotriazine couplers described in EP-A-556700, and the like can be used.

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260, 64-32261, JP-A-2-29747, JP-A-2-44340, and 2-
No. 110555, No. 3-7938, No. 3-16044
No. 0, No. 3-172839, No. 4-17247,
4-179949, 4-182645, 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
And the couplers described in JP-A Nos. 4-207473 and 4-204732 can also be used.

Hereinafter, specific examples of the BLD that can be preferably used in the present invention will be described.

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image

[0081]

Embedded image

[0082]

Embedded image

[0083]

Embedded image

The two monomers of the present invention can be polymerized simply by heating, but can be combined with a thermal polymerization initiator. Those used as (thermal) polymerization initiators for vinyl monomers include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl- 2,2'-azobis (2-methylpropionate), dimethyl-2,2 '
Azo initiators such as azobisisobutyrate, lauryl peroxide, benzoyl peroxide, tert-
A peroxide initiator such as butyl peroctoate is used. In the azo-based initiator, an initiator system such as radiation and electron beam can be used in addition to heat. The amount of the initiator to be added is not particularly limited, but may be in a range suitable for each polymerization method, and a person skilled in the art can appropriately select the amount. There is no limitation on the method of adding the initiator, and it can be selected as appropriate, such as batch addition or divided addition. As the polymerization temperature, an appropriate temperature can be selected and adopted depending on the type of the initiator and the monomer used.

In the present invention, a heat-sensitive material can be prepared by combining a thermal polymerization initiator, a polymerizable monomer having a nucleophilic group, a polymerizable monomer capable of generating an acid, and a substance which develops a color in combination with an acid. .

In the present invention, when a heat-sensitive material is prepared, the recording temperature is preferably from 80 ° C. to 350 ° C., more preferably from 100 ° C. to 300 ° C., most preferably from 150 ° C. to 250 ° C. Although the time varies depending on the heat source and the application, it is preferably 0.1 μsec to 60 sec, more preferably 1 μsec to 10 sec, and most preferably 1 μsec to 100 msec when used as a normal recording material.

Further, in the present invention, a photopolymerization initiator can be combined. Many known compounds can be used as the photopolymerization initiator. 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 compounds that directly decompose photo-oxides such as oxide compounds, aromatic ketones that generate ketyl radicals by hydrogen abstraction reaction of benzophenone, and ketones and amines. 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
Hemcal Review, Vol. 93 (1993)
The compounds described on pages 435 to 446 can also be used.

Some of the above-mentioned photopolymerization initiators have sensitivity in the visible region, and they are visible lasers, LEs.
D, which is excellent in that various visible light sources such as a white fluorescent lamp can be used. Patent Publication No. 2726258 discloses that
A photopolymerization initiator composed of a cationic dye / anionic boron compound complex is described as having such sensitivity in the visible region, and can be particularly preferably used in the present invention. In the present invention, a substance that develops a color by reaction with an acid can be used. Examples thereof include leuco dyes having a partial structure such as lactone, lactam, and spiropyran used in pressure-sensitive paper and thermal paper.

In the present invention, the above-mentioned materials, that is, a photopolymerization initiator, a polymerizable monomer having a nucleophilic group, an acid-generating polymerizable monomer, and a substance which forms a color in combination with an acid are combined to form a photosensitive material. Can be created.
These combinations are optional.

In the present invention, the rate of acid generation and the rate of dye formation can be increased by preparing a photosensitive material and heating it after exposure. Heating temperature is 40 ° C ~ 200
C is preferred, more preferably from 70C to 180C, most preferably from 80C to 160C. As a heating method at this time, a heating method using a hot plate, a heat roller, infrared irradiation, a heat drum, or the like can be used. The heating time is preferably from 0.1 to 100 seconds, more preferably
It is preferably from 0.5 to 30 seconds, and most preferably from 1 to 20 seconds.

In the present invention, a polymerization inhibitor may be added for the purpose of stabilizing the composition of the present invention or controlling the amount of generated acid. Known polymerization inhibitors such as phenols, nitro compounds, and quinones can be appropriately selected and used as the polymerization inhibitor.

When preparing a light-sensitive material and a heat-sensitive material in the present invention, all the materials may be applied together on a support. Further, an oil-soluble binder such as polystyrene, polyvinyl alcohol, polyvinyl butyral, and polymethyl methacrylate may be used. Further, these materials may be used as oil droplets scattered in the hydrophilic binder. Examples of the hydrophilic binder in this case include gelatin, polyvinyl alcohol, modified polyvinyl alcohol, cellulose derivatives, polyacrylamide, and the like. Necessary materials may be used in microcapsules.

[0093]

The present invention will be illustrated below by way of examples, but the present invention is not limited to these examples. Example 1 0.03 g of BLD-11 and 0.12 of compound N-05
g, 0.11 g of compound A-11 and 1.73 g of a 10% solution of polystyrene in methyl ethyl ketone were mixed to form a uniform solution. This solution was applied on a polyethylene terephthalate film coated with gelatin at a coating amount of 35 cc / m ² and dried. A mixture of 10 g of a 16% aqueous solution of PVA205 (manufactured by Kuraray) and 1 g of a 5% aqueous solution of compound (A) was applied thereon at a coating amount of 21 cc / m ² and dried.
Sample 1 was used. Sample 2 was 0.0005 g of 2,2'-azobisisobutyronitrile as a thermal polymerization initiator.
Was prepared in exactly the same manner as in Sample 1, except that was added to the polystyrene solution. When only half of each of Samples 1 and 2 was brought into contact with the back surface for 30 seconds on a heat block heated to 130 ° C., only the portion of Sample 2 that was in contact with the heat block developed magenta.
It is considered that the acid was generated at the portion where the monomer having a nucleophilic group and the acid-generating monomer were polymerized, resulting in color development.

[0094]

Embedded image

Example 2 0.021 g of BLD-13 and 0.1% of Compound N-06
g, 0.09 g of compound A-09, 0.0033 g of compound (B) and 0.03 g of compound (C) as a photopolymerization initiator.
067 g and 1.73 g of a 10% methyl ethyl ketone solution of polystyrene were mixed to obtain a uniform solution. This solution was applied on a polyethylene terephthalate film coated with gelatin at a coating amount of 35 cc / m ² and dried. A mixture of 10 g of a 16% aqueous solution of PVA205 (manufactured by Kuraray) and 1 g of a 5% aqueous solution of the compound (A) was applied thereon.
It was applied at 1 cc / m ² and dried. The sample was exposed through a wedge having a transmission density of 0 to 4 using a halogen lamp under the condition of 100,000 lux for 40 seconds.
Then, when heated from the back at 150 ° C for 20 seconds,
A negative type image in which the exposed portion developed magenta was obtained.

[0096]

Embedded image

Example 3 0.033 g of BLD-18, 0.15 g of compound N-06, 0.137 g of compound A-09, 0.005 g of compound (B), and 0.01 g of compound (C) And 0.3 g of ethyl acetate were mixed and dissolved to obtain an oil phase.
On the other hand, 0.86 g of a 14% aqueous solution of gelatin and 0.08% of a 5% aqueous solution of sodium dodecylbenzenesulfonate were added.
g and water were mixed to form an aqueous phase. The aqueous phase was added to the oil phase, and emulsified and dispersed using a micronizer. After adding an equal amount of water to this emulsion and mixing, the mixture was coated on a polyethylene terephthalate film subbed with gelatin at a coating amount of 35 cc / m ² and dried. The same liquid as the aqueous phase was applied thereon at a coating amount of 21 cc / m ² and dried. Using a halogen lamp, this sample was
100,000 lux 4 through a wedge with a transmission density of 4
Exposure was performed under 0 second conditions. Thereafter, when heated from the back surface at 150 ° C. for 20 seconds, a negative image in which the exposed portion developed cyan was obtained.

[0098]

According to the present invention, a color image can be obtained by simple dry processing (exposure and / or heating). In particular, a highly sensitive and negative photosensitive material can be obtained by the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shunichi Ishikawa 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film F-term (reference) 2H025 AA00 AA01 AB20 AC01 AC08 AD01 BC12 BC14 BC18 BC31 BC32 BC34 BC35 BC37 BC38 BC83 BC84 BC85 BC86 CA00 CC14 2H026 AA07 AA21 BB02 BB24 BB48 FF01 2H111 HA12 HA13 HA14 HA23 HA35

Claims (7)

[Claims] 1. A color-forming composition comprising a polymerizable monomer having at least one nucleophilic group, at least one acid-generating polymerizable monomer, and a substance capable of forming a color in the presence of an acid. 2. A photosensitive composition comprising a polymerizable monomer having at least one nucleophilic group, at least one acid-generating polymerizable monomer, a substance capable of forming a color in the presence of an acid, and a photopolymerization initiator. Chromogenic composition. 3. The color-forming composition according to claim 1, wherein the polymerizable monomer having a nucleophilic group is represented by the following general formula (1). Embedded image In the formula (1), X represents a divalent linking group, and Nu represents a group having a nucleophilic site. n represents 0 or 1. R ₁ , R ₂
And R ₃ each represent a hydrogen atom or a substituent, R ₁
And R ₂ , R ₁ and R ₃ , R ₂ and — (X) _n —Nu and R ₃ and —
(X) _n -Nu may combine with each other to form a ring. 4. The color-forming composition according to claim 1, wherein the acid-generating polymerizable monomer is represented by the following general formula (2). Embedded image In the formula (2), X represents a linking group of a divalent group, and E represents a group having a nucleophilic (electrophilic) site. A is a polymerizable monomer having a nucleophilic group and an acid-generating polymerizable monomer represented by the general formula (2) are copolymerized, and a nucleophilic group derived from the polymerizable monomer having a nucleophilic group is generally used. Represents a group that generates an acid as a result of reacting with E in the formula (2). n is 0 or 1
Represents R ₄ , R ₅ and R ₆ each represent a hydrogen atom or a substituent, and R ₄ and R ₅ , R ₄ and R ₆ , R ₅ and — (X) _n −
E-A and the _{R 6 - (X) n -E} -A ring may be bound to each other to form. 5. A recording material containing a polymerizable monomer having at least one nucleophilic group on a support, at least one acid-generating polymerizable monomer, and a substance capable of coloring in the presence of an acid. 6. A polymerizable monomer having at least one nucleophilic group and at least one acid-generating polymerizable monomer on a support, a substance capable of forming a color in the presence of an acid, and a photopolymerization initiator. Recording material to be included. 7. A substance capable of coloring in the presence of an acid is represented by the following general formula (6).
Recording material described in 1. Embedded image Wherein (6), D represents a hydroxyl group or -NR ₁₈ R _19. R
₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each represent a hydrogen atom or a substituent. R ₁₄ and R ₁₅ , R ₁₅ and R ₁₈ (or R ₁₉ ), R ₁₇ and R ₁₈ (or R ₁₉ ), and R ₁₆ and R ₁₇ may form a ring. BL represents a blocking group bonded to a nitrogen atom. -CONR is here in block group ₂₀ R ₂₀₁
Or other acid-removable groups. L represents a leaving group. CPA and CPB represent an atomic group necessary for forming a color coupler together with a carbon atom to which they are bonded (C in the general formula (6)).