JP2587676B2 - Photosensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photosensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support.

BACKGROUND OF THE INVENTION A photosensitive material having a photosensitive layer containing a silver halide, a reducing agent, and a polymerizable compound on a support is an image forming method in which a latent image of silver halide is formed and the polymerizable compound is polymerized. Can be used for

Examples of the image forming method are described in JP-B Nos. 45-11149 and 47-207.
No. 41, 49-10697, JP-A-57-138632, 57-142
No. 638, No. 57-176033, No. 57-211146, No. 58-10752
No. 9, No. 58-121031, and No. 58-169143. In these methods, when the exposed silver halide is developed using a developer, a coexisting polymerizable compound (eg, a vinyl compound) starts to polymerize to form an image-like polymer compound. Therefore, the above method requires a developing process using a liquid, and the process requires a relatively long time.

As an improvement of the above method, JP-A-61-69062 and JP-A-61-7
No. 3145, No. 61-183640, No. 61-188535, No. 61-2284
No. 41 discloses a method capable of forming a polymer compound by dry treatment. The above method uses a recording material (photosensitive material) in which a photosensitive layer comprising a photosensitive silver salt (silver halide), a reducing agent, a crosslinkable compound (polymerizable compound) and a binder is supported on a support. is there.

The image forming method described above is a method of polymerizing a polymerizable compound in a portion where a latent image of silver halide is formed.

Furthermore, a method capable of polymerizing a polymerizable compound in a portion where a silver halide latent image is not formed is disclosed in
-260241. In this method, by heating, a reducing agent acts on the portion where the latent image of silver halide is formed to suppress the polymerization of the polymerizable compound and promote the polymerization of the other portion.

As one embodiment of a photosensitive material that can be used in the image forming method as described above, a photosensitive material having a constitution in which constituent parts of a photosensitive layer such as silver halide and a polymerizable compound are contained in microcapsules is disclosed in JP-A-61-1986. No. 275742. The light-sensitive material of the embodiment using the above-described microcapsules (hereinafter, referred to as photosensitive microcapsules) has an advantage that a clear image, particularly excellent in sharpness, can be obtained.

On the other hand, the polymerization reaction in the developing treatment of the above-described image forming method proceeds smoothly under alkaline conditions. Therefore, as an image formation accelerator in the photosensitive layer of the photosensitive material,
A base or base precursor can be included. The photosensitive material in which the photosensitive layer contains a base or a base precursor is described in Japanese Patent Application No. 60-227528.

When a base or a base precursor is added to the photosensitive material using the above-described photosensitive microcapsules, it is preferable that the base or the base precursor be contained in the photosensitive microcapsules in view of the image formation promoting function of the base or the base precursor. However, when a base is contained in the photosensitive microcapsule, there has been a problem that the sensitivity of the photosensitive material is reduced during the storage period from production to use. In addition, various types of base precursors such as salts of carboxylic acids and organic bases are described in JP-A-62-264041, etc., and any of the base precursors has stability during storage and image formation. The two requirements of rapid degradation (base formation) at the time were not sufficiently compatible. Furthermore, it is stable to the reaction conditions (especially the reaction temperature, generally 30 ° C. to 80 ° C.) in the process of forming the outer shell of the photosensitive microcapsule, and heat-processes the photosensitive material (heating temperature is usually
80-200 ° C, generally 50-120 ° C above the above reaction temperature
(A very high temperature), a base precursor that rapidly produces a base was not found.

For the above reasons, in the conventional image formation using a photosensitive material, a method in which a base or a base precursor is added to the photosensitive layer outside the photosensitive microcapsule and the base penetrates into the photosensitive microcapsule during development. Was generally adopted.

[Summary of the Invention] It is an object of the present invention to provide a light-sensitive material having good storage stability and capable of obtaining a very clear image.

The present invention is a photosensitive material having a photosensitive layer containing a silver halide, a microcapsule containing a reducing agent and a polymerizable compound on a support, and a base precursor consisting of a salt of a carboxylic acid and an organic base, The organic base constituting the base precursor has two to four partial structures corresponding to an atomic group obtained by removing one or two hydrogen atoms from guanidine represented by the following formula (I), and a linking group of the partial structures Wherein the base precursor is contained in the microcapsule.

[In the above formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic ring. A monovalent group selected from the group consisting of residues (each group may have one or more substituents), and selected from R ¹ , R ² , R ³ , R ⁴ and R ⁵ Any two groups may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring.] Preferred embodiments of the present invention are described below.

(1) The organic base constituting the base precursor is represented by the following formula (II): R ⁶ (-B) _l (II) [In the above formula (II), R ⁶ is a l-valent linking group, and B is A monovalent group corresponding to an atomic group obtained by removing one hydrogen atom from guanidine represented by the formula (I);
And an integer of from 4 to 4].

(2) The linking group of the organic base constituting the base precursor is a hydrocarbon residue or a heterocyclic residue.

(3) R ⁶ in the above formula (II) is an alkylene group or an arylene group (each group may have one or more substituents).

(4) The organic base represented by the formula (II) has symmetry.

(5) l in the above formula (II) is 2.

(6) The carboxyl group of the carboxylic acid constituting the base precursor has a property of being decarboxylated under heating conditions of 50 to 200 ° C.

(7) The carboxylic acid constituting the base precursor has an aryl group or an arylene group.

(8) The carboxylic acid constituting the base precursor is represented by the following formula (III-1): [In the above formula (III-1), R ⁷ and R ⁸ are each monovalent selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic residue. (Each group may have one or more substituents), m is 1 or 2, and when m is 1, Y is an alkyl group, a cycloalkyl group, an alkenyl group Is a monovalent group selected from the group consisting of an alkynyl group, an aralkyl group, an aryl group and a heterocyclic residue (each group may have one or more substituents), and m is 2. In this case, Y is a divalent group selected from the group consisting of an alkylene group, an arylene group and a heterocyclic residue (each group may have one or more substituents).

(9) The melting point of the base precursor is 50 ° C to 200 ° C.

(10) The base precursor is contained in a microcapsule in the form of a fine particle dispersion.

(11) The photosensitive layer contains the above base precursor in an amount of 0.01 to 40% by weight.

(12) The photosensitive layer further contains a color image forming substance.

(13) For thermal development.

[Effect of the Invention] The photosensitive material of the present invention is characterized in that a salt of the above carboxylic acid and an organic base is used as a base precursor, and the salt is contained in a photosensitive microcapsule.

According to the study of the present inventor, by setting the organic base constituting the base precursor to the above-described diacid or tetraacid base, the temperature is kept at a certain level or less (for example, the reaction temperature and It was found that the base precursor was very stable at the storage temperature of the light-sensitive material, and a base precursor that rapidly released a base was obtained when the temperature was raised to the above-mentioned constant value (that is, the heating temperature during the development of the light-sensitive material). The reason can be presumed as follows.

In the salt composed of a carboxylic acid and an organic base, a salt in which the organic base is a diacid to a tetraacid base has a more stable crystal structure than a salt in which the organic base is a monoacid base.
In particular, when the diacid to tetraacid base has symmetry,
The crystal structure becomes remarkably stable.

In addition, a carboxylic acid constituting the above-mentioned base precursor often introduces a decarboxylation promoting group such as an aryl group.
Therefore, the carboxylic acid generally has a hydrophobic residue. In a salt in which a carboxylic acid has a hydrophobic residue and the organic base is a diacid to a tetraacid base, the hydrophobic residues of a plurality of carboxylic acids are located around the organic base via an ionic bond. . As described above, the structure in which the organic base is located at the center surrounded by the hydrophobic residues of the carboxylic acid is such that the organic base is a monoacid base, and the organic base and the hydrophobic residue of the carboxylic acid are linked via an ionic bond. The crystal structure becomes more stable as compared with the case where it is located at both ends.

According to the study of the present inventor, after a base precursor comprising a salt of a carboxylic acid and an organic base is melted during heating or dissolved in a binder or the like contained in a photosensitive material, a decarboxylation reaction of the carboxylic acid is started. . As described above, the base precursor composed of a salt having a stable crystal structure maintains the crystal structure until the temperature rises to a certain value, and when the crystal structure collapses due to melting or dissolution, the carboxylic acid is rapidly removed. Carbonation occurs and releases the base.

When the carboxylic acid has a hydrophobic residue, the organic base of the base precursor used in the present invention and the carboxyl group of the carboxylic acid are blocked by the hydrophobic residue. That is, dissolution in a binder (generally hydrophilic) is hindered, while stabilization is achieved by the intermolecular interaction of hydrophobic residues. Therefore, when the carboxylic acid has a hydrophobic residue, the base precursor in the photosensitive material of the present invention shows more excellent stability.

Further, the base precursor used in the present invention has a diacid to tetraacid base derived from guanidine represented by the above formula (I) as an organic base. Therefore,
Since the above-mentioned base precursor releases a guanidine derivative having strong basicity, the action of a base during development (image formation accelerating action) is excellent.

By using the base precursor having the excellent characteristics as described above, the base precursor can be accommodated in the photosensitive microcapsule. That is, since the base precursor has a relatively clear decomposition point (base generation temperature), the reaction temperature for forming the outer shell of the photosensitive microcapsule and the heating temperature for heat development are relatively narrow. Temperature differences can also significantly alter the behavior with respect to base formation.

Since the light-sensitive material of the present invention contains a base precursor in the inside of the photosensitive microcapsule, the base generated at the time of development acts immediately on each component inside the photosensitive microcapsule as an image formation accelerator.

As a result, according to the photosensitive material of the present invention, a very clear image with high sensitivity can be obtained even after storage for a long period of time or after storage under severe conditions.

[Detailed Description of the Invention] The base precursor used in the light-sensitive material of the present invention comprises a salt of a carboxylic acid and an organic base. The organic base has two to four partial structures in a molecule corresponding to an atomic group obtained by removing one or two hydrogen atoms from guanidine represented by the following formula (I).

R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the above formula (I) are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic residue. And a monovalent group selected from the group consisting of Among them, a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group and an aryl group are preferred. Note that each group may have one or more substituents. The alkyl group, alkenyl group and alkynyl group preferably have 1 to 6 carbon atoms. Examples of the cycloalkyl include a cyclohexyl group. An example of the aralkyl group is a benzyl group. Examples of the aryl group include:
A phenyl group can be mentioned.

Any two groups selected from R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring.

The organic base constituting the base precursor used in the present invention has two to four partial structures corresponding to an atomic group obtained by removing one or two hydrogen atoms from guanidine represented by the above formula (I), And a diacid or tetraacid base comprising at least one hydrocarbon residue or heterocyclic residue as a linking group of the partial structure.

The partial structure is preferably present as a monovalent substituent of a hydrocarbon or a heterocyclic ring constituting the linking group, as represented by the formula (II) described later. That is, the partial structure preferably corresponds to an atomic group obtained by removing one hydrogen atom from guanidine represented by the formula (I) as described above. However, the above partial structure may correspond to an atomic group obtained by removing two hydrogen atoms from guanidine represented by the formula (I). In this case, the organic base constituting the base precursor used in the present invention can constitute a nitrogen-containing heterocyclic ring (for example, a piperazine ring).

The diacid to tetraacid base represented by the following formula (II) can be preferably used as a base precursor.

R ⁶ (-B) ₁ (II) In the above formula (II), R ⁶ is a monovalent hydrocarbon residue or a heterocyclic residue, and 1 is an integer of 2 to 4. l is preferably 2 or 4, and more preferably 2. When 1 is 2, the hydrocarbon residue that can constitute R ⁶ is preferably an alkylene group (more preferably 1 to 6 carbon atoms) and an arylene group (more preferably a phenylene group). Examples of the heterocyclic residue that can constitute R ⁶ include a residue derived from a pyridine ring.

The diacid to tetraacid base represented by the above formula (II) preferably has symmetry. In the present specification, the symmetry of the organic base means that all 1 Bs are equivalent in the molecule of the organic base. Specifically, it means that even if each of 1 B is replaced with a different group, no isomer is generated.

B in the above formula (II) is a monovalent group corresponding to an atomic group obtained by removing one hydrogen atom from guanidine represented by the above formula (I).

Preferred specific examples of the organic base constituting the base precursor used in the present invention are described below.

The carboxylic acid constituting the base precursor of the present invention is:
The carboxyl group must have the property of being decarboxylated under certain conditions. However, since a carboxyl group generally has the above properties, various kinds of carboxylic acids can be used as the base precursor of the present invention.

When the base precursor of the present invention is applied to a heat-developable recording material or the like, the carboxyl group preferably has a property of being decarboxylated under heating conditions. The heating temperature required for the decarboxylation of the carboxyl group is preferably 50 to 200 ° C, more preferably 80 to 160 ° C.

Examples of carboxylic acids satisfying the above conditions include:
There are trichloroacetic acid, propiolic acid, sulfonylacetic acid and the like described in the above-mentioned publications. As described above, the carboxylic acid preferably has an aryl group or an arylene group as a decarboxylation promoting group. As the carboxylic acid described above, sulfonylacetic acid represented by the following formula (III-1) and propiolic acid represented by the following formula (III-2) are particularly preferable.

R ⁷ and R ⁸ in the above formula (III-1) are each a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic residue. It is. Among these, a hydrogen atom, an alkyl group and an aryl group are preferred, and a hydrogen atom is particularly preferred. Note that each group may have one or more substituents. The alkyl group, alkenyl group and alkynyl group preferably have 1 to 8 carbon atoms.

m is 1 or 2, and when m is 1, Y is
It is a monovalent group selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group and a heterocyclic residue. Among these, an aryl group and a heterocyclic residue are preferable, and an aryl group is particularly preferable. Note that each group may have one or more substituents. Examples of the substituent that can substitute the aryl group include a halogen atom, an alkyl group, an alkoxyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, a carbamoyl group, a sulfamoyl group, and the like.

When m is 2, Y is a divalent group selected from the group consisting of an alkylene group, an arylene group and a heterocyclic residue. Among these, an arylene group and a heterocyclic residue are preferable, and an arylene group is particularly preferable. Note that each group may have one or more substituents. Examples of the substituent capable of substituting the arylene group are the same as the above-described substituent of the aryl group.

Z (—C≡C—CO ₂ H) _n (III-2) In the above formula (III-2), n is 1 or 2,
When n is 1, Z is a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic residue and a carboxyl group. is there. Among these, an aryl group is particularly preferred. Note that each group may have one or more substituents.

When n is 2, Z is a divalent group selected from the group consisting of an alkylene group, an arylene group and a heterocyclic residue. Among these, an arylene group is particularly preferred. Note that each group may have one or more substituents.

 The following are specific examples of preferred carboxylic acids.

The base precursor of the present invention comprises a salt of a carboxylic acid and an organic base as described above. There is no particular limitation on the combination of the carboxylic acid and the organic base. However, the melting point of the salt of the carboxylic acid and the organic base is preferably from 50 ° C to 200 ° C, more preferably from 80 ° C to 120 ° C.

The following shows specific examples of the base precursor of the present invention,
The present invention is not limited to these.

 The method for synthesizing guanidines is described in Methodend
er Organischen Chemie (Houbenn-Weyl) 4th edition,8
(1952), pp. 180-195, and ibid.E4(1983), 608
Page 624, and use of these methods.
Can be.

The photosensitive material of the present invention comprises the above-described base precursor contained in a photosensitive microcapsule described below.

The photosensitive material of the present invention uses the above-mentioned base precursor in the photosensitive layer.
Preferably, it is contained in the range of 50% by weight or less, and 0.01 to 40% by weight.
More preferably, it is contained in the range of weight%. Further, two or more kinds of the above base precursors may be used in combination.

The base precursor is preferably contained in the photosensitive microcapsules as a solid particulate dispersion. The base precursor can be added at any stage in the process of producing a photosensitive microcapsule described below.

Next, the silver halide, the reducing agent, the polymerizable compound, and the support contained in the photosensitive layer other than the base precursor described above will be described in order.

In the light-sensitive material, any of silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide can be used as silver halide. .

The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. Regarding silver halide grains having multiple structures having different compositions on the surface and in the interior, JP-A-57-154232, JP-A-58-108533, and JP-A-59-48
Nos. 755, 59-52237, U.S. Pat. No. 4,433,048 and European Patent No. 100984. Also,
As in the light-sensitive material described in JP-A-62-183453, silver halide grains having a high silver iodide ratio in the shell portion may be used.

There is no particular limitation on the crystal habit of the silver halide grains.
For example, tabular grains having an aspect ratio of 3 or more, such as a photosensitive material described in JP-A-61-55509, may be used.

The silver halide grains are described in Japanese Patent Application No. 61-2145.
It is preferable to use silver halide grains having a relatively low fog value as in the light-sensitive material described in the specification of JP-A-80.

The silver halide used for the photosensitive material includes a halogen composition,
Two or more kinds of silver halide grains having different crystal habits, grain sizes and the like can be used in combination.

There is no particular limitation on the grain size distribution of the silver halide grains. For example, monodisperse silver halide grains having a substantially uniform grain size distribution may be used, such as a photosensitive material described in JP-A-62-210448.

In the light-sensitive material, the average grain size of the silver halide grains is preferably from 0.001 to 5 μm, and more preferably from 0.001 to 2 μm.

The amount of silver halide contained in the photosensitive layer is 0.1 mg to 10 g / m 2 in terms of silver containing an organic silver salt which is an optional component described later.
It is preferred to be in the range of ² . Further, in terms of silver equivalent of only silver halide, it is preferably 1 g / m ² or less, and 1 mg / m ² or less.
It is particularly preferred that the concentration be in the range of from 500 to 500 mg / m ² .

The reducing agent that can be used in the light-sensitive material has a function of reducing silver halide and / or a function of accelerating (or suppressing) polymerization of a polymerizable compound. There are various kinds of substances as the reducing agent having the above function. Examples of the reducing agent include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, and 4-amino-5.
-Pyrazolones, 5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonaminophenols, o- or p-sulfonamidonaphthols,
2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamidopyrazolobenzimidazoles, sulfonamidopyrazolotriazoles, α-sulfonamidoketones, hydrazines and the like There is. By adjusting the type and amount of the reducing agent, the polymerizable compound in a portion where a latent image of silver halide is formed or a portion where a latent image is not formed can be polymerized. In a system in which a polymerizable compound in a portion where a latent image of silver halide is not formed is polymerized, it is particularly preferable to use 1-phenyl-3-pyrazolidones as a reducing agent.

The various reducing agents having the above functions are described in JP-A-61-183640, JP-A-61-188535, JP-A-61-228441, and JP-A-62-70836 and JP-A-62-86354. ,same
Nos. 62-86355, 60-227528, and 62-86355, each of which is described in the specification or the specification (including those described as a developing agent or a hydrazine derivative). The reducing agent is described in “The Theory of the Photographic Pr.” By T. James.
ocess ", 4th edition, pp. 291-334 (1977), Research Disclosure Magazine, Vol. 170, No. 17029, June 1978 (9
Pp. 15 to 15), and in the same magazine, Vol. 176, No. 17643, December 1978 (pp. 22 to 31). Also, JP-A-62-210446
A reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base or the like may be used in place of the reducing agent as in the photosensitive material described in Japanese Patent Application Laid-Open Publication No. H11-139,036. The reducing agent and the reducing agent precursor described in each of the above specifications and literatures can also be effectively used for the photosensitive material in this specification. Therefore, the “reducing agent” in the present specification includes the reducing agent and the reducing agent precursor described in each of the above publications, the specification and the literature. These reducing agents may be used alone, or as described in the above-mentioned respective specifications, two or more reducing agents may be mixed and used. When two or more types of reducing agents are used in combination, the reducing agents interact firstly by promoting reduction of silver halide (and / or organic silver salt) by so-called superadditivity. Causing the polymerization of the polymerizable compound via an oxidation-reduction reaction with another reducing agent coexisting with an oxidized form of the first reducing agent generated by the reduction of silver halide (and / or organic silver salt) (Or to suppress polymerization). However, at the time of actual use, since the above-mentioned reactions can occur at the same time, it is difficult to specify which action it is.

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p- (N, N-diethylamino) phenol, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenyl Sulfonylamino-4-t-butyl-5-hexadecyloxyphenol, 2- (N-butylcarbamoyl) -4-phenylsulfonylaminonaphthol, 2- (N-methyl-N-octadecylcarbamoyl) -4-sulfonylaminonaphthol , 1-acetyl-2-phenylhydrazine, 1-acetyl-2-
{(P or o) -aminophenyl} hydrazine, 1-
Formyl-2-{(p or o) -aminophenyl} hydrazine, 1-acetyl-2-{(p or o) -methoxyphenyl} hydrazine, 1-lauroyl-2-
{(P or o) -aminophenyl} hydrazine, 1-
Trityl-2- (2,6-dichloro-4-cyanophenyl) hydrazine, 1-trityl-2-phenylhydrazine, 1-phenyl-2- (2,4,6-trichlorophenyl) hydrazine, 1- {2- (2,5-di-t-pentylphenoxy) butyroyl {-2-} (p or o) -aminophenyl} hydrazine, 1- {2- (2,5-di-t
-Pentylphenoxy) butyroyl {-2-} (p or o) -aminophenyl} hydrazine pentadecylfluorocaprylate, 3-indazolinone, 1- (3,5
-Dichlorobenzoyl) -2-phenylhydrazine, 1
-Trityl-2-[{(2-N-butyl-N-octylsulfamoyl) -4-methanesulfonyl} phenyl]
Hydrazine, 1- {4- (2,5-di-t-pentylphenoxy) butyroyl} -2-{(p or o) -methoxyphenyl} hydrazine, 1- (methoxycarbonylbenzohydryl) -2-phenyl Hydrazine, 1-formyl-2- [4- {2- (2,4-di-t-pentylphenoxy) butylamido} phenyl] hydrazine, 1-acetyl-2- [4- {2- (2,4-di -T-pentylphenoxy) butylamido {phenyl] hydrazine, 1-trityl-2-[{2,6-dichloro-4- (N, N-di-2-)
Ethylhexyl) carbamoyl {phenyl] hydrazine, 1- (methoxycarbonylbenzohydryl) -2-
(2,4-dichlorophenyl) hydrazine, 1-trityl-2-[{2- (N-ethyl-N-octylsulfamoyl) -4-methanesulfonyl} phenyl] hydrazine, 1-benzoyl-2-tritylhydrazine, 1-
(4-butoxybenzoyl) -2-tritylhydrazine, 1- (2,4-dimethoxybenzoyl) -2-tritylhydrazine, 1- (4-dibutylcarbamoylbenzoyl) -2-tritylhydrazine, and 1- (1-naphthoyl) ) -2-tritylhydrazine and the like.

In the light-sensitive material, the above-mentioned reducing agent is 1 mol of silver (including the above-described silver halide and an organic silver salt as an optional component).
It is preferably used in the range of 0.1 to 1500 mol% based on the total amount.

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and a known polymerizable compound can be used. In addition,
As a method of using the photosensitive material, when a heat development process is scheduled, a high boiling point (for example, having a boiling point of 80
(° C. or more). Further, since the mode in which the photosensitive layer contains a color image-forming substance as an optional component described later aims to immobilize the color image-forming substance by polymerization and curing of the polymerizable compound, the polymerizable compound has a plurality of molecules in the molecule. It is preferably a crosslinkable compound having a polymerizable functional group. When a transfer image is formed using an image receiving material, it is preferable to use a high-viscosity material as a polymerizable compound, as in a photosensitive material described in Japanese Patent Application No. 61-150079.

The polymerizable compound that can be used for the photosensitive material is described in the above-mentioned and later-described series of photosensitive material application specifications.

The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having addition polymerizability includes a compound having an ethylenically unsaturated group, and the compound having ring-opening polymerizability includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable.

Compounds having an ethylenically unsaturated group that can be used in the photosensitive material include acrylic acid and salts thereof, acrylic esters, acrylamides, methacrylic acid and salts thereof, methacrylic esters, methacrylamides, and maleic anhydride. Acids, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers,
There are allyl esters and their derivatives.

Specific examples of the polymerizable compound that can be used in the photosensitive material include acrylates, such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, and dicyclohexyloxy. Ethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate,
Neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, diacrylate of polyoxyethylenated bisphenol A, 2,2-dimethyl-3-hydroxypropionaldehyde And dimethyl of trimethylolpropane condensate, triacrylate of 2,2-dimethyl-3-hydroxypropionaldehyde and pentaerythritol condensate, polyacrylate of hydroxypolyether, polyester acrylate and polyurethane acrylate.

As other specific examples, methacrylates, methyl methacrylate, butyl methacrylate,
Ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate,
Examples thereof include pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and dimethacrylate of polyoxyalkylenated bisphenol A.

The above polymerizable compounds may be used alone or in combination of two or more. Photosensitive materials using two or more polymerizable compounds in combination are described in JP-A-62-210445. In addition, a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of the above-mentioned reducing agent or a color image forming substance which is an optional component described later can also be used as the polymerizable compound. As described above, the use of a substance which also serves as a reducing agent and a polymerizable compound or a substance which also serves as a color image forming substance and a polymerizable compound is included in the embodiment of the photosensitive material.

In the light-sensitive material, the polymerizable compound is silver halide 1
It is preferable to use 50,000 to 120,000 parts by weight based on parts by weight. A more preferred use range is from 12 to 12,000 parts by weight.

The components of the photosensitive layer are contained in microcapsules.

Various known techniques can be applied to the microcapsules without any particular limitation. An example of a photosensitive material in which oil droplets of a polymerizable compound are in the form of microcapsules is described in JP-A-61-278441.

There is no particular limitation on the wall material constituting the outer shell of the microcapsule. For a photosensitive material using a microcapsule having an outer shell made of a polyamide resin and / or a polyester resin, Japanese Patent Application Laid-Open No. 62-209437 discloses a microcapsule having an outer shell made of a polyurea resin and / or a polyurethane resin. Japanese Patent Application Laid-Open No. 62-209438 discloses a photosensitive material used, and Japanese Patent Application Laid-Open No. 62-209439 discloses a photosensitive material using a microcapsule having an outer shell made of an amino-aldehyde resin. Japanese Patent Application Laid-Open No. 62-209440 discloses a photosensitive material using microcapsules having epoxy resin, and Japanese Patent Application Laid-Open No. 62-209441 discloses a photosensitive material using microcapsules having an outer shell made of epoxy resin. For photosensitive materials using microcapsules having a composite resin shell containing urea resin and polyurea resin 094
Japanese Patent Application Laid-Open No. 62-209442 discloses a photosensitive material using a microcapsule having a composite resin shell containing a polyurethane resin and a polyester resin.

When containing silver halide in microcapsules,
It is preferable that silver halide is present in the wall material constituting the outer shell of the microcapsule. For photosensitive materials containing silver halide in the wall material of microcapsules, see
No. 169147.

The average particle size of the microcapsules is preferably 3 to 20 μm. The particle size distribution of the microcapsules is preferably uniformly distributed to a certain value or more, as in the photosensitive material described in Japanese Patent Application No. 61-150080.
The thickness of the microcapsules is preferably within a certain range with respect to the particle diameter, as in the case of the photosensitive material described in Japanese Patent Application No. 61-227767.

When silver halide is contained in the microcapsules, the average grain size of the silver halide grains described above is preferably set to 1/5 or less of the average size of the microcapsules, and is set to 1/10 or less. Is more preferred. By setting the average grain size of the silver halide grains to 1/5 or less of the average size of the microcapsules,
A uniform and smooth image can be obtained.

The photosensitive material is obtained by providing a photosensitive layer containing the components described above on a support. Although there is no particular limitation on the support, when a heat-development process is scheduled as a method of using the photosensitive material, it is preferable to use a material that can withstand the processing temperature of the development process. Materials that can be used for the support include glass, paper, woodfree paper, coated paper, cast-coated paper, synthetic paper, metal and analogs thereof, polyester, acetylcellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, and polyethylene. Examples include films such as terephthalate, and paper laminated with a resin material or a polymer such as polyethylene.

When the support is made of a porous material such as paper,
Like a support used for a light-sensitive material described in JP-A-62-209529, the support preferably has a certain degree of smoothness according to a method defined by waviness. In the case of using a paper support, a paper support having a low water absorption such as a light-sensitive material described in Japanese Patent Application No. 61-183050 may be used.
Paper support having a constant Beck smoothness as in the light-sensitive material described in Japanese Patent Application No. 61-227766, paper support having a low shrinkage as in the light-sensitive material described in Japanese Patent Application No. 61-227766, Japanese Patent Application No. 61-227766. 227768
Paper support having low air permeability as described in the specification of Japanese Patent Application No. 61-243552.
A paper support or the like having a pH value of 5 to 9 can also be used.

 Arbitrary components can be contained in the photosensitive layer.

Optional components that can be included in the photosensitive layer of the photosensitive material include a color image forming substance, a sensitizing dye, an organic silver salt, a radical generator, various image formation accelerators, a thermal polymerization inhibitor, a thermal polymerization initiator, Development stop agents, fluorescent brighteners, anti-fading agents, dyes or pigments for preventing halation or irradiation, dyes having the property of decoloring by heating or light irradiation, matting agents, anti-smudge agents, plasticizers, water releasing agents, Examples include a binder, a photopolymerization initiator, a solvent for a polymerizable compound, and a water-soluble vinyl polymer.

The photosensitive material can obtain a polymer image by the constitution of the photosensitive layer described above, but can also form a color image by including a color image forming substance as an optional component in the photosensitive layer.

There is no particular limitation on the color image forming substance that can be used for the photosensitive material, and various types can be used. In other words, substances that are themselves colored (dyes and pigments), are themselves colorless or pale, but have external energy (heating, pressurizing, light irradiation, etc.) and other components (developers) A substance that develops color upon contact (color former) is also included in the color image forming substance. The general photosensitive material using a color image forming substance is described in the above-mentioned JP-A-61-73145. Further, a photosensitive material using a dye or a pigment as a color image forming substance is disclosed in JP-A-62-187346, and a photosensitive material using a leuco dye is disclosed in JP-A-62-209436. Japanese Patent Application Nos. 61-96339 and 61-133091 and 61-133302 disclose cyan-sensitive leuco dyes. Are described in Japanese Patent Application No. 61-197963.

The color image forming substance is based on 100 parts by weight of the polymerizable compound.
It is preferably used in a proportion of 0.5 to 20 parts by weight, more preferably in a proportion of 2 to 7 parts by weight. When a color developer is used, it is preferably used in a ratio of about 0.3 to 80 parts by weight with respect to 1 part by weight of the color former.

When two types of substances that cause a color reaction in a contact state are used as the solid color image forming substances, one of the substances that cause the color reaction and a polymerizable compound are contained in a microcapsule. However, a color image can be formed on the photosensitive layer by allowing another substance among the substances that cause the color-forming reaction to exist outside the microcapsules containing the polymerizable compound. The photosensitive material from which a color image can be obtained without using an image receiving material as described above is described in JP-A-62-209444.

The sensitizing dye that can be used in the light-sensitive material is not particularly limited, and a silver halide sensitizing dye known in photographic technology or the like can be used.

The amount of the sensitizing dye to be added is generally per mole of silver halide.
It is about 10 ^{-8 to} 10 ^-2 mol.

The sensitizing dye is preferably added at the stage of preparing a silver halide emulsion described below. A photosensitive material obtained by adding a sensitizing dye in the stage of forming silver halide grains is described in JP-A-62-947, in which a sensitizing dye is added to a silver halide emulsion after forming silver halide grains. Regarding the photosensitive material obtained by adding at the preparation stage,
These are described in the specification of JP 61-55510 A, respectively. Further, specific examples of sensitizing dyes that can be used in photosensitive materials are described in JP-A-62-947 and JP-A-61-55510. Further, as in the light-sensitive material described in Japanese Patent Application No. 61-208786, an infrared light-sensitive sensitizing dye may be used in combination.

The addition of an organic silver salt to a light-sensitive material is particularly effective in a heat development process. The organic silver salt is generally used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of silver halide. The same effect can be obtained by adding an organic compound (for example, benzotriazole) constituting the organic silver salt to the photosensitive layer instead of the organic silver salt. A photosensitive material using an organic silver salt is described in JP-A-62-3246. The above-mentioned organic silver salt is used per mole of silver halide.
Preferably used in the range of 0.1 to 10 mol, 0.01
More preferably, it is used in the range of 1 to 1 mol.

To the photosensitive layer, a radical generator that participates in the above-described polymerization promotion (or polymerization inhibition) reaction of the reducing agent may be added. The photosensitive material using triazene silver as the radical generator is described in JP-A-62-15639, and the photosensitive material using diazotate silver is disclosed in Japanese Patent Application No. 61-195640.
Japanese Patent Application Laid-Open No. Sho 62-195641 discloses a photosensitive material using an azo compound.

Various image formation accelerators can be used for the photosensitive material. Examples of the image formation accelerator include the promotion of an oxidation-reduction reaction between a silver halide (and / or an organic silver salt) and a redox agent with a reducing agent, and the conversion of a photosensitive material to an image receiving material or an image receiving layer (these will be described later). It has a function of promoting the transfer of the image forming substance. From the viewpoint of physicochemical functions, the image formation accelerators include oils, surfactants, antifoggant functions and / or
Alternatively, they are further classified into compounds having a development accelerating function, thermal solvents, compounds having a function of removing oxygen, and the like. However,
These substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Therefore, the above classification is a matter of convenience, and in practice, one compound often has a plurality of functions.

As the oil, a high-boiling organic solvent used as a solvent for emulsifying and dispersing a hydrophobic compound can be used.

Examples of the surfactant include pyridinium salts, ammonium salts, phosphonium salts, and polyalkylene oxides (JP-A-59-74547 and JP-A-59-572).
No. 31).

The compound having an antifogging function and / or a development accelerating function can be used for the purpose of obtaining a clear image having a high maximum density and a low minimum density (an image having a high S / N ratio). JP-A-62-151838 discloses a photosensitive material using an antifoggant as a compound having an antifogging function and / or a development accelerating function, and discloses a light-sensitive material using a compound having a cyclic amide structure. JP-A-62-151841 discloses a photosensitive material using a thioether compound in JP-A-62-151842. A photosensitive material using a polyethylene glycol derivative is described in JP-A-62-151843. Japanese Patent Application Laid-Open No. 62-151844 discloses a photosensitive material using acetylene compound, and Japanese Patent Application Laid-Open No. 62-1782 describes a photosensitive material using acetylene compound.
No. 32, a photosensitive material using a sulfonamide derivative is described in JP-A-62-183450, and a photosensitive material using a quaternary ammonium salt is described in Japanese Patent Application No. 61-238871. is there.

As the thermal solvent, a compound that can be used as a solvent for a reducing agent, and a compound having a high dielectric constant that is known to promote physical development of a silver salt are useful (see JP-A-62-86355). ).

The compound having an oxygen removing function can be used for the purpose of eliminating the influence of oxygen during development (oxygen has a polymerization inhibiting effect). Examples of the compound having an oxygen removing function include a compound having two or more mercapto groups (see JP-A-62-209443).

The thermal polymerization initiator is generally a compound that is thermally decomposed under heating to generate a polymerization initiation species (particularly a radical), and is generally used as an initiator for radical polymerization. The thermal polymerization initiator is described in “Addition Polymerization and Ring-Opening Polymerization” edited by the Editing Committee of Polymer Experiments of the Society of Polymer Science, 1983, Kyoritsu Shuppan, No. 6.
Page 18 to page 18. The thermal polymerization initiator is used preferably in the range of 0.1 to 120% by weight, more preferably 1 to 10% by weight, based on the polymerizable compound. In a system for polymerizing a polymerizable compound in a portion where a silver halide latent image is not formed, it is preferable to add a thermal polymerization initiator to the photosensitive layer. Also,
Japanese Patent Application Laid-Open No. 62-70 describes a photosensitive material using a thermal polymerization initiator.
It is described in JP-A-836.

A development terminator that can be used in photosensitive materials is a compound that neutralizes a base or reacts with a base immediately after proper development to reduce the base concentration in the film and to interact with a compound that stops development and silver and silver salts. Is a compound that suppresses development.

As the anti-smudge agent used in the light-sensitive material, solid particles at room temperature are preferable. The average particle size of the particles is preferably in the range of 3 to 50 μm, more preferably 5 to 40 μm in terms of volume average diameter. As described above, when the oil droplets of the polymerizable compound are in the form of microcapsules, it is more effective that the particles are larger than the microcapsules.

The binder that can be used in the photosensitive material can be contained alone or in combination in the photosensitive layer. It is preferable to use a hydrophilic binder mainly as the binder (see JP-A-61-69062 and JP-A-62-209525).

A photopolymerization initiator may be added to the photosensitive layer of the photosensitive material for the purpose of polymerizing an unpolymerized polymerizable compound after image transfer (see JP-A-62-161149).

When a solvent for a polymerizable compound is used for the light-sensitive material, it is preferable to use the solvent encapsulated in a microcapsule different from the microcapsule containing the polymerizable compound. A photosensitive material using an organic solvent miscible with the polymerizable compound encapsulated in the microcapsule is described in JP-A-62-209524.

A water-soluble vinyl polymer may be adsorbed on the silver halide grains described above before use. The photosensitive material using a water-soluble vinyl polymer as described above is described in Japanese Patent Application No. 61-238870.

In addition to the examples described above, examples of optional components that can be included in the photosensitive layer and usage modes thereof are also described in the above-described application specification relating to the series of photosensitive materials,
Disclosure Magazine, Vol. 170, June, 1978, No. 17029 (pages 9 to 15).

Incidentally, the photosensitive layer of the photosensitive material comprising the above-mentioned components preferably has a pH value of 7 or less as in the photosensitive material described in Japanese Patent Application No. 61-104226.

Examples of layers that can be optionally provided on the photosensitive material include an image receiving layer, a heating element layer, an antistatic layer, an anti-curl layer, a peeling layer, a cover sheet or a protective layer, a layer containing a base or a base precursor, a base barrier layer, An antihalation layer (colored layer) can be used.

Instead of using an image receiving material described later as a method of using the photosensitive material, the image receiving layer may be provided on the photosensitive material to form an image on this layer. The image receiving layer provided on the photosensitive material can have the same configuration as the image receiving layer provided on the image receiving material. Details of the image receiving layer will be described later.

 Hereinafter, a method for producing a photosensitive material will be described.

Various methods can be used as a method for producing a photosensitive material, but a general production method uses constituents of a photosensitive layer,
After dissolving, emulsifying or dispersing in a suitable solvent to prepare a photosensitive composition, the composition is microencapsulated to prepare a coating liquid containing a microcapsule dispersion, and the coating liquid is supported as described above. It comprises a step of obtaining a photosensitive material by applying it to a body and drying it.

Generally, the coating liquid is prepared by preparing a liquid composition containing each component for each component, and then mixing each liquid composition. The liquid composition may be prepared to include a plurality of components. Some of the components of the photosensitive layer can be added to the liquid composition or the coating solution during or after the preparation. Further, as described below, a method of preparing a secondary composition by further emulsifying an oily (or aqueous) composition containing one or more components in an aqueous (or oily) solvent may be used. .

With respect to the main components contained in the photosensitive layer, methods for preparing a liquid composition and a coating solution are described below.

The preparation of the halogenated emulsion can be carried out by any of known methods such as an acidic method, a neutral method and an ammonia method.

The reaction between the soluble silver salt and the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. An inverse mixing method in which grains are formed under silver ion excess conditions and a controlled double jet method in which pAg is kept constant can also be employed. Further, in order to accelerate the grain growth, the concentration, amount or rate of silver salt and halogen salt to be added may be increased (JP-A-55-158124).
Nos. 55-158124 and U.S. Pat. No. 3,650,57).

Silver halide emulsions used in the production of photosensitive materials are surface latent image types in which a latent image is mainly formed on the grain surface,
An internal latent image type formed inside the grains may be used. A direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used. Internal latent image emulsions suitable for this purpose are:
It is described in U.S. Pat. Nos. 2,592,250 and 3,761,276, Japanese Patent Publication No. 58-3534, and Japanese Patent Application Laid-Open No. 58-136641. Preferred nucleating agents for combining with the above emulsions are
U.S. Pat.Nos. 3,227,552, 4,425,037, 4,255,511
No. 4,260,613, No. 4,276,364 and West German Patent Publication (OLS) No. 2,635,316.

In the silver halide emulsion, at the stage of forming silver halide grains, ammonia, an organic thioether derivative (see JP-B-47-386) and a sulfur-containing compound (see JP-A-53-144319) as a silver halide solvent. Etc. can be used. In the process of particle formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, and the like may coexist. Further, for the purpose of improving high illuminance failure and low illuminance failure, a water-soluble iridium salt such as iridium chloride (III or IV) and ammonium hexachloroiridium salt, or a water-soluble rhodium salt such as rhodium chloride can be used.

The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening. In this case, it can be carried out according to the Nudel washing method or the sedimentation method. Although the silver halide emulsion may be used as it is after unripe, it is usually used after chemical sensitization. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method and the like can be used alone or in combination in the emulsion for a normal type light-sensitive material. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 58-1983).
-126526 and 58-215644).

When a sensitizing dye is added to a silver halide emulsion, the method described in JP-A-62-947 and Japanese Patent Application No. 61-555 described above may be used.
It is preferably added during the preparation of a silver halide emulsion as in the light-sensitive material described in JP-A No. 10 (1994). When a nitrogen-containing heterocyclic compound is added as a compound having an antifogging function and / or a development accelerating function described above, it may be added at the stage of forming or ripening silver halide grains in the preparation of a silver halide emulsion. Is preferred. A method for producing a light-sensitive material in which a nitrogen-containing heterocyclic compound is added at the stage of forming or ripening silver halide grains is described in JP-A-62-161144.

When the above-mentioned organic silver salt is contained in the photosensitive layer, an organic silver salt emulsion can be prepared by a method similar to the above-mentioned method for preparing a silver halide emulsion.

In the production of a photosensitive material, the polymerizable compound can be used as a medium for preparing a composition of other components in the photosensitive layer. For example, a silver halide (including a silver halide emulsion), a reducing agent, a color image forming substance, and the like can be dissolved, emulsified, or dispersed in a polymerizable compound and used in the production of a photosensitive material. In particular, when a color image forming substance is added, it is preferable to include the compound in a polymerizable compound.
Further, as described below, when microdrops of oil droplets of the polymerizable compound are microencapsulated, components such as a wall material necessary for microencapsulation may be included in the polymerizable compound.

A photosensitive composition containing a polymerizable compound containing silver halide can be prepared using a silver halide emulsion.
In addition, in addition to the silver halide emulsion, a silver halide powder prepared by freeze-drying or the like can be used for the preparation of the photosensitive composition. These photosensitive compositions containing silver halide can be obtained by stirring with a homogenizer, a blender, a mixer, or another commonly used stirrer.

The polymerizable compound used for preparing the photosensitive composition preferably has a copolymer of a hydrophilic repeating unit and a hydrophobic repeating unit dissolved therein. The photosensitive composition containing the above copolymer is disclosed in
No. 209449 describes this.

Further, instead of using the above copolymer, a photosensitive composition may be prepared by dispersing microcapsules having a silver halide emulsion as a core substance in a polymerizable compound. The photosensitive composition containing microcapsules containing the above silver halide emulsion as a core substance is described in JP-A-62-164041.

The polymerizable compound (including the one containing other components like the above-mentioned photosensitive composition) is preferably used as an emulsion emulsified in an aqueous solvent. In addition, JP
In the case where oil droplets of a polymerizable compound are microencapsulated as in the light-sensitive material described in -275742, a wall material necessary for microencapsulation is added to the emulsion, and the outer shell of the microcapsule is further added. Can be carried out at the stage of this emulsion. Further, a reducing agent or other optional components may be added at the stage of the emulsion.

Examples of the above microencapsulation method include a method utilizing coacervation of a hydrophilic wall-forming material described in U.S. Pat. Nos. 2,800,457 and 2,800,458; U.S. Pat. No. 3,287,154 and British Patent No. 990443. Each statement,
And JP-B Nos. 38-19574, 42-446 and 42-77
No. 1, No. 3,418,250 and No. 3,660,304, by a polymer precipitation method; US Pat. No. 3,796,669, using an isocyanate-polyol wall material: US Patent No. 391451
A method using the isocyanate wall material described in No. 1;
U.S. Pat.Nos. 4001140, 4087376 and 408980
No. 2, a method using a urea-formaldehyde-based or urea-formaldehyde-resylcinol-based wall-forming material; a method using a melamine-formaldehyde resin, hydroxypropylcellulose, or the like described in U.S. Pat. No. 4,025,455. An in situ method by polymerization of monomers described in JP-B-36-9168 and JP-A-51-9079; a polymerization dispersion cooling method described in British Patent Nos. 927807 and 965074; U.S. Pat. The spray drying method described in the specifications of 3111407 and British Patent No. 930422 can be exemplified. The method of microencapsulating oil droplets of the polymerizable compound is not limited to the above, but a method of emulsifying a core substance and then forming a polymer film as a microcapsule wall is particularly preferable.

The dispersion of microcapsules containing the base precursor, silver halide, reducing agent and polymerizable compound obtained as described above can be used as it is as a coating solution for a photosensitive material. The addition of other components at the stage of this coating solution can be carried out in the same manner as in the above-mentioned emulsion.

The coating material for the photosensitive layer prepared as described above is applied to a support and dried to produce a photosensitive material. The application of the coating solution to the support can be easily carried out according to a known technique.

 Hereinafter, a method of using the photosensitive material will be described.

The photosensitive material is used after being subjected to a development treatment simultaneously with or after the imagewise exposure.

As the above-mentioned exposure method, various exposure means can be used. In general, a latent image of silver halide is obtained by imagewise exposure to radiation containing visible light. The type of light source and the exposure amount can be selected according to the photosensitive wavelength of silver halide (in the case of dye sensitization, the sensitized wavelength) and the sensitivity. The original image may be a black and white image or a color image.

The photosensitive material is subjected to a development treatment simultaneously with or after the imagewise exposure. Photosensitive material: Japanese Patent Publication No. 45-11149
Development processing using a developing solution described in Japanese Patent Application Laid-Open Publication No. HEI 7-163, etc. may be performed. Incidentally, as described above, Japanese Patent Application Laid-Open No.
The method described in Japanese Patent No. 69062 has an advantage that the operation is simple and the processing can be performed in a short time because it is a dry processing. Therefore, the latter is particularly excellent as a developing process for the photosensitive material.

As the heating method in the thermal development treatment, various conventionally known methods can be used. Further, as in the case of the photosensitive material described in JP-A-61-294434, a heating element layer may be provided on the photosensitive material and used as a heating means.
Further, as in the image forming method described in Japanese Patent Application Laid-Open No. Sho 62-210461, the heat development may be performed while suppressing the amount of oxygen present in the photosensitive layer. Heating temperature is generally 80 ℃ ~ 20
0 ° C., preferably 100 ° C. to 160 ° C. The heating time is generally 1 second or more, preferably 1 to 5 minutes, and further,
Preferably, it is 1 second to 1 minute.

The photosensitive material is subjected to the heat development treatment as described above to polymerize the polymerizable compound in the portion where the silver halide latent image is formed or in the portion where the silver halide latent image is not formed. In the case of a light-sensitive material, the polymerizable compound in the portion where the latent image of silver halide is formed generally polymerizes in the above-mentioned heat development process.
As in the light-sensitive material described in JP-A-70836, by adjusting the type and amount of the reducing agent, it is possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is not formed.

As described above, the photosensitive material can obtain a polymer image on the photosensitive layer. Alternatively, a dye or pigment can be fixed to the polymer to obtain a dye image.

When the photosensitive material is configured as described in JP-A-62-209444 described above, two types of photosensitive materials that have been subjected to development processing are pressed to break microcapsules and cause a color-forming reaction. A color image can be formed on a photosensitive material by bringing the above substances into contact.

Further, an image can be formed on the image receiving material by using the image receiving material.

Next, the image receiving material will be described. A general image forming method using an image receiving material or an image receiving layer is described in JP-A-61-278849.

As the support for the image receiving material, baryta paper can be used in addition to the support that can be used for the photosensitive material described above. When a porous material such as paper is used as the support of the image receiving material, it is preferable that the image receiving material has a certain degree of smoothness like the image receiving material described in JP-A-62-209530. An image receiving material using a transparent support is described in JP-A-62-209531.

The image receiving material generally has an image receiving layer provided on a support. The image receiving layer is in accordance with the above-described color image forming material color forming system and the like.
It can be configured in any form using various compounds. When a polymer image is formed on an image receiving material, or when a dye or a pigment is used as a color image forming substance, the image receiving material may be composed of only the above-mentioned support.

For example, when a color developing system including a color former and a developer is used, the image receiving layer can contain a developer.
Further, the image receiving layer may be configured as a layer containing at least one mordant. The mordant may be selected from compounds known in photographic technology and the like in consideration of conditions such as the type of a color image forming substance and used. If necessary, two or more image receiving layers may be constituted by using a plurality of mordants having different mordant powers.

The image receiving layer preferably has a structure containing a polymer as a binder. As the binder, the binder that can be used in the photosensitive layer of the photosensitive material described above can be used. Further, as in the image receiving material described in JP-A-62-209454, a polymer having low oxygen permeability may be used as a binder.

The image receiving layer may contain a thermoplastic compound. When a thermoplastic compound is contained in the image receiving layer, the image receiving layer itself is preferably constituted as an aggregate of fine particles of the thermoplastic compound (Japanese Patent Application Nos. 61-12552 and 61-12553).

The image receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator (JP-A-62-161149 and JP-A-62-210444).
Reference).

The image receiving layer may be configured as two or more layers according to the functions described above. The thickness of the image receiving layer is 1 to
It is preferably 100 μm, more preferably 1 to 10 μm.

Note that a protective layer may be further provided on the image receiving layer. Further, a layer composed of an aggregate of fine particles of a thermoplastic compound may be provided on the image receiving layer.

The photosensitive material is subjected to development processing as described above, and by applying pressure while the image receiving material is superimposed, an unpolymerized polymerizable compound is transferred to the image receiving material, thereby obtaining a polymer image on the image receiving material. it can. Various known methods can be used for the pressurizing means.

After forming an image on the image receiving material as described above,
As in the image forming method described in JP-A-62-210459,
The image receiving material may be heated. The above method also has an advantage that the unpolymerized polymerizable compound transferred onto the image receiving material is polymerized, and the preservability of the obtained image is improved.

The present applicant has already filed patent applications for various image recording apparatuses suitable for performing the above-described series of image forming methods using photosensitive materials (Japanese Patent Application No. 60-2874).
No. 92, etc.).

Photosensitive materials include black-and-white or color photographing and printing materials, printing materials, printing plates, X-ray materials, medical materials (for example, ultrasonic diagnostic CRT photography materials), computer graphic hardcopy materials, There are many uses such as photosensitive materials for copying machines.

The present invention will be more specifically described by the following examples.
However, the present invention is not limited to this.

[Example 1] [Preparation of photosensitive material] Preparation of silver halide emulsion Stirring aqueous gelatin solution (24 g of gelatin in 1200 ml of water)
And pH 1.2 with 1N sulfuric acid containing 1.2 g of sodium chloride and kept at 60 ° C.), 600 ml of an aqueous solution containing 117 g of potassium bromide and an aqueous solution of silver nitrate (0.74 ml of silver nitrate in 600 ml of water)
Mol dissolved) at the same time and over 15 minutes at an equal flow rate. One minute after this was completed, 47 cc of a 1% methanol solution of the following sensitizing dye was added.
In 15 minutes, 200 ml of an aqueous solution containing 4.3 g of potassium iodide were added at a constant flow rate over 5 minutes. To this emulsion, 1.2 g of poly (isobutylene-monosodium comaleate) was added to precipitate, washed with water and desalted. 24 g of gelatin was added to dissolve the emulsion, and 5 mg of sodium thiosulfate was added.
For 15 minutes to obtain a silver halide emulsion having a yield of 1000 g.

Preparation of Photosensitive Composition To 100 g of trimethylolpropane triacrylate (Aronix M-309, manufactured by Toa Gosei Chemical Co., Ltd.), 0.40 g of the following copolymer and Purgas Script Red I-
10.00 g of 6-B (manufactured by Ciba Geigy) was dissolved. Next, 15.0 g of the following base precursor (7) was dispersed in the above solution using a Dynomill. In 24.00 g of the above dispersion,
1.29 g of the following hydrazine derivative (reducing agent), 1.22 g of the following developing agent (reducing agent), 0.001 g of the following antifoggant, and 0.36 of Emarex NP-8 (manufactured by Nippon Emulsion Co., Ltd.)
g, and 4.00 g of methylene chloride were further added to obtain a uniform solution.

On the other hand, the silver halide emulsion prepared as described above 3.
To 100 g, 0.46 of a 10% aqueous solution of potassium bromide was added, followed by stirring for 5 minutes. The mixed solution containing the silver halide emulsion was added to the above-mentioned homogeneous solution, and the homogenizer was used for 1500 minutes per minute.
The mixture was stirred at 0 rotation for 5 minutes to obtain a photosensitive composition comprising a W / O emulsion.

Preparation of photosensitive microcapsule solution Sodium salt of polyvinylbenzenesulfonic acid (Vers
a TL 500, manufactured by National Starch Co., Ltd.) was adjusted to pH 3.5 using a 20% aqueous solution of phosphoric acid. on the other hand,
0.90 g of Takenate D110N (a polyvalent isocyanate compound, a product of Takeda Pharmaceutical Co., Ltd.) was added to the above W / O emulsion, and this was added to the above aqueous solution. The mixture was heated to 40 ° C. and stirred at 7000 rpm for 30 minutes using a monogenizer to obtain a W / O / W emulsion.

Separately, 13.20 g of melamine in 37% formaldehyde aqueous solution
21.6 g and 70.8 g of distilled water were added, heated to 60 ° C., and stirred for 30 minutes to obtain a transparent aqueous solution of a melamine-formaldehyde precondensate.

13.00 g of this aqueous solution of the initial condensate is added to the above W / O / W emulsion, and the pH is adjusted to 6.5 using a 20% aqueous solution of phosphoric acid.
Was adjusted. It was then heated to 60 ° C. and stirring was continued for 120 minutes. Further, the pH was adjusted to 7.0 using a 1N aqueous solution of sodium hydroxide to obtain a photosensitive microcapsule solution having a melamine / formaldehyde resin as a capsule wall.

Preparation of photosensitive material (A) 5% of Emarex NP-8 (manufactured by Nippon Emulsion Co., Ltd.) was added to 2.50 g of the microcapsule solution prepared as described above.
0.33 g of an aqueous solution, 0.83 g of a 20% aqueous dispersion of corn starch, and 3.19 g of distilled water were added, and the mixture was stirred well to prepare a coating solution. Using a # 40 wire bar, apply this coating solution to 100μ
The composition was coated on a m-thick polyethylene terephthalate film and dried at 40 ° C. for 1 hour to prepare a light-sensitive material (A) according to the present invention.

[Example 2] Preparation of photosensitive material (B) Except that the following base precursor (22) was used in the same amount in place of 15.0 g of the base precursor (7) used in the preparation of the photosensitive material of Example 1, In the same manner as in Example 1, a light-sensitive material (B) according to the present invention was prepared.

Preparation of image receiving material 125g of water 40% sodium hexametaphosphate aqueous solution 11
g, and then 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of a 55% calcium carbonate slurry were mixed and coarsely dispersed by a mixer. The liquid was dispersed with a dynamill disperser, and 50% SBR latex 6 was added to 200 g of the obtained liquid.
g and 55 g of 8% polyvinyl alcohol were added and mixed uniformly. 30 μm of this mixed solution was weighed on a baryta paper weighing 43 g / m ^2.
And then dried to obtain an image receiving material.

Evaluation of photosensitive material Each photosensitive material obtained in Examples 1 and 2 was stored at room temperature (25 ° C.) and room temperature (60%) for 12 hours. After storage, each photosensitive material was passed through a continuous filter having a transmission density of 0 to 3.0 using a tungsten bulb, exposed at 2000 lux for 1 second, and then heated on a hot plate heated to 140 ° C. for 10 seconds. Next, each photosensitive material was superimposed on the above-mentioned image receiving material and passed through a pressure roller of 500 kg / cm ² , and the maximum density and the minimum density of the positive magenta color image obtained on the image receiving material were measured with a Macbeth densitometer.

In addition, each of the above photosensitive materials is used at high temperature (40 ° C) and low humidity (5%).
After storing for 12 hours under the conditions described above, the image forming process was performed as described above, and the maximum density and the minimum density of the magenta positive color image obtained on the image receiving material were measured with a Macbeth densitometer.

 The above measurement results are shown in Table 1 below.

As is clear from the results shown in Table 1, the photosensitive material according to the present invention can provide a clear image with high contrast even after storage under severe conditions.

Claims (1)

(57) [Claims] 1. A photosensitive material comprising a support and a photosensitive layer containing a microcapsule containing a silver halide, a reducing agent and a polymerizable compound, and a base precursor comprising a salt of a carboxylic acid and an organic base. The organic base constituting the base precursor has two to four partial structures corresponding to an atomic group obtained by removing one or two hydrogen atoms from guanidine represented by the following formula (I), and a connection of the partial structures: A light-sensitive material, which is a diacid to tetraacid base comprising a base, and wherein the base precursor is contained in the microcapsule: [In the above formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic ring. A monovalent group selected from the group consisting of residues (each group may have one or more substituents), and selected from R ¹ , R ² , R ³ , R ⁴ and R ⁵ Any two groups may be linked together to form a 5- or 6-membered nitrogen-containing heterocycle].