JPH01291239A - Photosensitive material - Google Patents

Abstract

PURPOSE:To improve the shelf life of image quality of the title material by incorporating a compd. which makes a silver halide to inactive, in a photosensitive layer. CONSTITUTION:The photosensitive layer contains the silver halide, a reducing agent, a polymerizable compd. and two kinds of substances capable of inducing a coloring reaction by allowing said substances to contact with each other, and one of the substances and the polymerizable compd. are housed in a microcapsule. The photosensitive layer is mounted on a supporting body. In this case, a substance capable of being released by heating the compd. which makes the silver halide to inactive, is incorporated in the photosensitive layer in an amount of 0.2-20mol.% per 1mol. of the silver halide. Namely, as a stabilizing agent contd. in the photosensitive layer releases a compd. capable of allowing it to react with the silver halide by thermal development after exposing the material, the unreacted silver halide remained in the photosensitive layer forms a stabilized compd. Thus, the reduction of the image quality of the material after forming an image is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a self-coloring photosensitive material capable of producing a color image on the photosensitive material. More specifically, the present invention includes:
The present invention relates to a self-coloring photosensitive material for thermal development, which contains a substance that releases a compound capable of inactivating silver halide when heated.

[Background of the Invention] A photosensitive material having a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support uses a latent image of silver halide to polymerize a polymerizable compound by the action of a reducing agent. It can be used in image forming methods.

Examples of image forming methods include, for example, Japanese Patent Publication No. 45-11
No. 149, No. 47-20741, No. 49-10697
No., JP-A-57-138632, JP-A No. 58-16914
There are methods described in various publications such as No. 3. In these methods, when exposed silver halide is developed using a developer, the reducing agent is oxidized and at the same time coexisting polymerizable compounds (e.g. vinyl compounds) start polymerizing, resulting in high image quality. It is a method of forming molecular compounds. Therefore, the above method requires a development process using a liquid, and the process requires a relatively long time.

As an improvement on the above method, Japanese Patent Application Laid-Open No. 61-69062 discloses a method in which a polymer compound can be formed by dry treatment. This method uses a photosensitive silver salt (silver halide), a reducing agent, a crosslinking compound (polymerizable compound)
A recording material (photosensitive material) comprising a photosensitive layer supported on a support and a binder is imagewise exposed to form a latent image, and then heated to form a latent image of the photosensitive silver salt on the area where the latent image of the photosensitive silver salt has been formed. , is a method of forming a polymer compound.

It should be noted that a method of polymerizing a polymerizable compound in areas where a silver halide latent image is not formed is already known (Japanese Unexamined Patent Publication No. 6
2-70836). In this method, a reducing agent is applied to a portion where a silver halide latent image has been formed by heating to suppress the polymerization of the polymerizable compound, while at the same time promoting polymerization in other portions.

As a photosensitive material that can easily obtain a desired color image using the above-described image forming method, the present applicant has prepared silver halide, a reducing agent, a polymerizable compound, and a color image-forming material on a support. A patent application has already been filed for a photosensitive material having a photosensitive layer containing a substance, and in which a polymerizable compound and a color image forming substance are housed in the same microcapsule (Japanese Patent Laid-Open No. 61-275742). This light-sensitive material is advantageous when a substance that forms a so-called two-component color system, which develops color by utilizing a reaction between two components, is used as a color image-forming substance. That is, by microcapsulating one of the color image-forming substances (components), it can be easily separated from the other substance (component), and especially when the two components are mixed together in the same photosensitive layer. It is also possible to create a photosensitive material (self-coloring type or monosheet type photosensitive material) in which the two types of photosensitive materials coexist.・With the photosensitive material having the above structure, a color image can be obtained on the photosensitive material with a simple operation. However, if the photosensitive material is left in a place exposed to indoor light after image formation, the image area (unused part) Color turbidity may occur in the exposed areas (exposed areas), or staining may occur in the background (non-image areas, exposed areas).
In some cases, the contrast of the image was reduced.

[Summary of the Invention] The present invention is characterized by providing a photosensitive material with improved image quality and storage stability. An object of the present invention is to provide a monosheet-type photosensitive material with improved reduction in .

The present invention includes a support, silver halide, a reducing agent, a polymerizable compound, and two types of substances that cause a color reaction when they come into contact with each other, which are provided on the support, and among the substances that cause a color reaction, In a photosensitive material having a photosensitive layer in which one of the substances and the polymerizable compound are housed in microcapsules, a substance that releases a compound that deactivates the silver halide upon heating is contained in the photosensitive layer. The object of the present invention is to provide a photosensitive material characterized in that the content is in the range of 0.2 to 20 moles per mole of silveride.

The photosensitive material of the present invention preferably has the following embodiments.

(1) A substance that releases the compound that inactivates the silver halide upon heating is contained in an amount ranging from 0.5 to 10 moles.

(2) The substance that releases the compound that inactivates silver halide upon heating is a compound containing sulfur in its molecular structure.

(3) The substance that releases the compound that inactivates silver halide upon heating is a compound containing sulfur in its molecular structure, and the sulfur-containing compound is an intiuronium compound.

(4) The substance that releases the compound that inactivates silver halide upon heating is a compound containing sulfur in its molecular structure, and the sulfur-containing compound is a carboxylate,
Alternatively, it is a sulfonylacetate.

(5) The two types of substances that cause the above-mentioned color-forming reaction are a color former and a color developer, and one of the substances that causes the above-mentioned color-forming reaction is a color former.

(6) The silver halide is contained in the microcapsule.

(7) The reducing agent is contained in the microcapsule.

(8) The photosensitive layer contains a base precursor.

(9) The heating temperature is in the range of 80 to 200'C.

[Effects of the Invention] Since the light-sensitive material of the present invention contains a specific amount of a stabilizer precursor, this removes unreacted silver halide remaining in the light-sensitive material after image formation (exposure/thermal development). is fixed and the above-mentioned influence on light is suppressed, so that an image with excellent contrast is formed on the photosensitive material.

That is, since the stabilizer precursor contained in the photosensitive layer of the present invention releases a compound that can react with silver halide by heat development after exposure, unreacted silver halide remaining in the photosensitive layer is removed by this compound. Reacts immediately with the released compound to form a stable compound (silver compound). Therefore, it is possible to suppress the formation of metallic silver caused by unreacted silver halide light after image formation, which is thought to cause a deterioration in image quality, as described above, and to reduce color turbidity in the image area or background. The occurrence of stains will be suppressed.

From the above, according to the photosensitive material of the present invention, an image with good contrast is maintained without deterioration of the image quality due to light after image formation.

[Detailed Description of the Invention] A compound that inactivates silver halide (also referred to as a stabilizer precursor), which is a characteristic component of the present invention, is a compound capable of reacting with silver halide by heating. Any compound that releases can be used without particular limitation.

In the present invention, the substance is preferably a compound containing sulfur in its molecular structure.

Typical examples of compounds containing sulfur in their molecular structure are:
Intiuronium compounds represented by the following (1) to (5) can be mentioned.

Below Margin (1) Compound represented by the following formula [1-I] or [1-II] H In the above formulas [1-I and [1-nl], R1 and R4 each have 1 carbon number ~5 lower alkylene groups (e.g., methylene, ethylene, propylene, butylene, imbutylene, amidino, etc.), R2, R3, R5
and R6 each represent a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, or an aryl group (eg, phenyl group, naphthyl group), and an aryl group having the substituent shown below.

D Here, D represents a nitro group, a hydroxy group, a chlorine atom, a bromine atom, a lower alkyl group having 1 to 5 carbon atoms, or an alkoxy group (the alkyl portion is the same lower alkyl group as above).

or -valent anions or chloride, bromide, nitrate, formate, trichloroacetate, perchlorate,
Represents acid residues such as acetate and aminoacetate.

A represents a hydroxy group, a group shown below.

Below margin 11i10 In the above formula, R7, R8, R9, R10, R11,
and RI2 each represent a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, or an aryl group represented by R2, R3, R5 and R6 described above.

Typical specific examples of the compound represented by the above formula are shown below.

2-Hydroxyethyl inthiuronium chloride salt, 2-hydroxyethyl inthiuronium nitrate salt, 2-hydroxyethyl inthiuronium trichloroacetate, 2-
Hydroxyethyl inthiuronium salt, 3-hydroxypropyl intiuronium salt, 2-hydroxyethyl isothiuronium formate, 2-hydroxyethyl isothiuronium perchloride, 2-hydroxyethyl inthiuronium perchloride, Inchureidoacetic acid, 2-inchureidopropionic acid, 3-inchureidoacetic acid, 2-hydroxyethylisothiuronium acetate, 2-hydroxyethylisothiuronium-
N-(p-hydroxyphenyl)-aminoacetate,
β-(2-morpholinoethylthio)-β-phenylpropiophenone hydrochloride and the like.

For details about the above compound, see US Patent No. 3301.
It is described in the specification of No. 678.

(2) Inthiourea derivative 2N\N represented by the following general formula [2-Il] In the above formula [2-Il, R21 is an alkylene group, or an alkylene substituted with an alkyl group or an aryl group (e.g., phenol) represents a group.

Y represents an anion or an acid group such as -803H, which forms a so-called intramolecular acid salt. In the present invention, Y is preferably a sulfonic acid group that forms an intramolecular acid salt with the isothiuronium moiety in the above structure. For example, the inner salt has the formula shown below.

2N A preferred specific example can be represented by the formula shown below.

2N \ N In the above formula, R22 represents an alkylene group, and j is
represents an integer of at least 1, preferably 1 to 4;

Typical examples of isourea derivatives represented by the above formula include 3-3-thiuronium propanesulfone fused salt, 2-3
-thiuronium ethanesulfonate, 4-S-thiuronium butanesulfonate, and the like.

For details regarding the above compound, please refer to US Patent No. 3506.
It is described in the specification of No. 444.

(3) Sulfonylalkyl intiuronium compounds and sulfonamide alcohol intiuronium compounds represented by the following formula [3,-Il; In the above formula [3-Il, R31 has 1 to 5 carbon atoms] Alkyl group, carbon number 6-12
represents an aryl group or , k represents O or l, Y represents =NR32 or 2502 (Z represents l~5
divalent hydrocarbon having carbon atoms or -C-O-
represents a carbon chain containing C-.

R32 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following formula.

The sentence is 2 or 3 and X- is a nonmetal anion. Examples of nonmetal anions include anions containing halogens such as chloride, bromide, and iodide.

Specific compounds represented by the above formula are illustrated below.

2.2'-Sulfonylbis(ethylisothiuronium chloride salt), 2.2'-methylsulfonyliminobis(ethylisothiuronium-p-toluenesulfonate), 2
．． These include 2'-methylsulfonyliminobis (ethyl inthiuronium methanesulfonate), 3-methylsulfonylpropylisothiuronium trifluoroacetate, and the like.

For details regarding the above compound, please refer to U.S. Patent No. 3844.
It is described in the specification of No. 788.

(4) S-carbamoyl compound represented by the following general formula [4-IF N-C-3-R43[4-Il / In the above formula [4-Il], R41 and R42 are a hydrogen atom, an alkyl group ( Preferably, it represents an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, propyl, butyl, pentyl), or an aryl group such as phenyl or tolyl.

3 1 (43 is sulfur containing a moiety that has the property of forming a compound with silver halide immediately after heating or contact with an alkali.

Further, the above Ha+, R42 and S R43 are, for example, methyl, ethyl, propyl, isopropyl, ter
It may have a substituent such as t-butyl or n-butyl, and may also contain a salt made of a compound such as an amine salt.

The above S R43 is R45゜ -3-C-R44 It is preferable that

The above R44 is an amino group, an alkyl group having 1 to 4 carbon atoms (
methyl, ethyl, propyl, butyl), carboxyl group, carboxyalkyl group having an alkyl moiety with 2 to 5 carbon atoms, aminomethyl group, sulfoalkyl group with carbon e 1 to 4 (methyl, ethyl), morpholinomethyl, or the following It is a group represented by the formula.

(2) -CH2NHCNH-R47 The above R47 represents an alkyl group having 1 to 4 carbon atoms (methyl, ethyl, propyl, butyl).

R45 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R46 represents a hydrogen atom or a carboxyl group.

Specific examples of the above-mentioned sulfur-containing moieties include those shown below.

(i) -3-CHCOOH H2 (ii) -3-CH2CHCOOH ViewH2 (iii) (ii) -S -CH2-CH2-CH2-S O3N a(V
) -3-CH2CH2COO○ ■ N H2(C6H13)2 (Mai) Shif13 (Ma1i) CH3 -3-CH2-C-COOH CH3 (Ma1ii) COOH 飄(iri■ -3-CH2CH2NH3 (X) -3-CHCOOH CH3 (Xi) -S , CH2CH2CH2S O3N a(Xii) -3-CH2CH2N HCN HCH2CH3(Xi
ii) \CH3 CH3 / 1'5-CH2CH2N \CH3 (XVi) ■ -S -CH2CH2N HC-CH3 (XVii) So-3-CH2CH2NHCNHCH3 Next, preferred groups constituting the carbamoyl group are shown below.

(i) 10NHCH2CH3 (ii) (iii) -CN H-C-CH3 H3 (V) C-N \ H2CH3 (Vi) -CN HCH2CH2CH2CH3 (1ii) -CNHCH3 Next, S expressed by the above formula - Specific examples of carbamoyl compounds are shown.

S-ethylcarbamoyl-N-acetyl-2-mercaptoethylamine, 5-N-ethylaminocarbonyl-L
- cysteine, S-ethylcarbamoyl-2-mercaptopropionic acid-dicyclohexylamine salt, and S-carbamoyl compounds including polymers of vinyl methyl ether-N-ethylcarbamoyl (thioether) maleic acid.

For details regarding the above compound, please refer to U.S. Patent No. 3824.
It is described in the specification of No. 103.

(5) Compound represented by the following formula [5-Il] [5-Il
.

1 (51, R52 and R53 each have 1 to 1 carbon atoms)
5 alkylene group (for example, methylene, ethylene, propylene, 1,3-)limethylene, 1,4-tetramethylene, 1,5-pentamethylene, etc.).

Y represents a sulfur atom, an oxygen atom, or a urelene group represented by the following formula.

-HN-C-NH- n represents 0, l, or 2, and when n is O and Y is an oxygen atom or a sulfur atom, R5+ and 1 (the total number of carbon atoms in 53 is at least 2) Two.

X represents an anion. For example, chloride, bromide, p-
) JL/ensulfone salt, s>Iy*7 salt, trifluoroacetate, acetate, chloroacetate, ethyl sulfate or formate (preferably p-toluenesulfonate).

m represents l or 2.

Preferred specific examples of the compound represented by the above formula are described below.

1.8-(3,6-thioxaoctane)bis(trifluoroacetic acid intiuronium salt), 1.8-(3,6-
thioxaoctane)bis(intiuronium chloride salt)・
1 Wood salt, 1.8-(3,6-thioxaoctane) bis(
intiuronium acetate salt), 1,8-(3,6-thioxaoctane)bis(intiuronium chloroacetate salt),
1.8-(3,6-thioxaoctane)bis(isothiuronium formate salt), 1,8-(3,6-thioxaoctane)bis(p-)rueneacetic acid isothiuronium salt), 1
．． 8-(3,6-thioxaoctane)bis(inchuronium nitrate salt), 1.7-(4-oxaheptane)bis(inchuronium chloride salt) dihydrate, 1.9-(oxanonan) Bis(inchuronium chloride salt), 1.12
-bis(isothiuronium)-4,9-dioxo-3°5.8.10-tetraazadodecane dichloride and the like.

For details about the above compound, see US Pat. No. 3,669.
It is described in the specification of No. 670.

Examples of sulfur-containing compounds other than the above-mentioned thiuronium compounds include compounds represented by the following (6).

(6) Compounds represented by the following formulas [6-Il and [6-III] In the above formulas [6-Il and [6-III], R63 and R67 have the same meaning as R1 in the above-mentioned [1-Il, R61, ) i62 and R64 are R2. It has the same meaning as R3, R5 and R6. R65 and 1 (66 is each a cyano group,
It represents an alkoxycarbonyl group containing an alkyl moiety having 1 to 5 carbon atoms or an amine group.

M and Z are a hydroxy group, a carboxy group,
Represents an amino group (primary amine, tertiary amine, tertiary amine consisting of morpholino, piperidino, pyrrolidino, alkylamino having 1 to 5 carbon atoms, etc.). The compounds represented by the above formulas [6-III] and [6-III] are used in the form of salts.

Specific examples and details of the compounds represented by the above formulas [6-Il and [6-nl] are described in the above-mentioned US Pat. No. 3,301,678.

Another stabilizer precursor that can be used in the present invention is carboxylate (7) represented by the following formula.

(7) Carboxylic acid salt represented by the following general formula [7-Il In the above formula [7-Il], B represents an alkylene having an alkylene chain having 2 to 3 carbon atoms.

R7+ represents a hydrogen atom, alkyl having 1 to 3 carbon atoms (methyl, ethyl, propyl), cycloalkyl having 5 to 6 carbon atoms (cyclopentyl, cyclohexyl), or aralkyl having 7 to 10 carbon atoms (benzyl).

R72C00- represents an acid anion that can be decarboxylated at a temperature of 80°C or higher.

The compound represented by the above formula includes tautomers.

A preferred carboxylate represented by the above formula is an ethylene group (wherein B forms a thiazoline ring).
The following can be mentioned.

The above formula is a case where R7+ is a hydrogen atom and 1li72 is a trichloromethyl group in the formula [7-1,].

Preferred examples other than those mentioned above include the following.

Bis(2-amino-2-thiazolinium)oxaloacetate, 2-amino-2-thiazolium tribromide salt, 2-amino-2-cyanoacetic acid thiazolium salt, 2-amino-5
-bromomethyl-2-trichloroacetic acid thiazolium salt, 4
, 5-dihydro-6H-1,3-thiazin-3-im trichloroacetate, and the like.

Specific examples and details of the compound represented by the above formula [7-II are described in US Pat. No. 4,012,260.

In addition, Research Disclosure magazine No. 15109,
151.1976 (November) edition may also be used.

The substance (silver halide stabilizer precursor) that releases the compound that inactivates silver halide by heating is added to the photosensitive layer in an amount of 0.2 to 20 moles per mole of silver halide. include.

The content is further preferably in the range of 0.5 to 10 moles.

The above stabilizer precursors may be used alone or in appropriate combinations. In order to include the stabilizer precursor in the photosensitive layer, a solution in which the precursor is dissolved using an appropriate solvent is prepared, and this is added to the coating solution for forming the photosensitive layer, or it is used to form the coating solution. This is done by directly adding it to the liquid ingredients.

The stabilizer precursor can be present at any position in the photosensitive layer using the method described above.

Preferably, a stabilizer precursor is included in the microforce decel. When contained in microcapsules, the polymerizable compound and/or silver halide (silver halide is usually present in the wall material of the capsule or in a phase near the wall material in many cases). It may exist in either.

It is believed that the above stabilizer precursor releases a compound that can easily react with silver halide upon heating (temperature range of thermal development) to generate a silver compound (mercaptide). As a result, unreacted silver halide remaining after exposure and development is fixed, and deterioration in image quality is suppressed. Furthermore, among the stabilizer precursors, the formula [1-I
The compounds represented by l, [1-III and [2-Il] are
Since activation is further promoted (increased release amount) in the presence of a base, the photosensitive layer preferably contains a base precursor (a compound that releases a base upon heating). Note that the base precursor will be described later.

The monosheet-type photosensitive material of the present invention is a photosensitive material in which two types of substances that produce a coloring reaction upon contact coexist in the same photosensitive layer via microcapsules. Other monosheet-type photosensitive materials contain two types of substances that produce a color reaction when they come into contact with each other, separated into an image-receiving layer and a photosensitive layer, and the support, image-receiving layer, and photosensitive layer are laminated. It is also possible to make a photosensitive material having the following structure.A photosensitive material having such a structure is described in the above-mentioned Japanese Patent Laid-Open Publication No. 61-275742.

Below, in the margin, the silver halide, reducing agent, polymerizable compound, and substances that cause a coloring reaction when they come into contact with the light-sensitive material,
and the support will be explained in turn.

Light-sensitive materials contain silver chloride, silver bromide, silver halide,
Any grains of silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide can be used.

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 with different compositions on the surface and inside, Japanese Patent Application Laid-open Nos. 57-154232 and 58-10853 disclose
No. 3, No. 59-48755, No. 59-52237, U.S. Patent No. 4433048 and European Patent No. 1
It is described in the 00984 specification. Silver halide grains with a high proportion of silver iodide in the shell portion may also be used (
(See Japanese Patent Application Laid-open No. 183453/1983).

There is also no particular restriction on the crystal habit of the silver halide grains. For example, tabular grains having an aspect ratio of 3 or more may be used (Japanese Patent Application No. 55509/1982).

The above-mentioned silver halide grains are disclosed in Japanese Patent Application No. 61-2
It is preferable to use silver halide grains having a relatively low fog value, such as the photosensitive material described in No. 14580.

For the silver halide used in the photosensitive material, two or more types of silver halide grains having different halogen compositions, crystal habits, grain sizes, etc. can be used in combination.

There are no particular restrictions on the grain size distribution of silver halide grains. For example, monodisperse silver halide grains having a substantially uniform grain size distribution may be used (JP-A-61-2
(See Publication No. 10448).

In the light-sensitive material, the average grain size of the silver halide grains is preferably from o, ooi to 5 ILm, and from 0 to 5 ILm.
．． 001 to 2. More preferably, it is wm.

The amount of silver halide contained in the photosensitive layer is 0.1 mg to L in terms of silver, including organic silver salt, which is an optional component described below.
The range is preferably Og/rn'. Further, when converting only silver halide into silver, it is preferably 1 g/rn' or less, and particularly preferably 1 mg to 5 oomg/rn'.

A reducing agent that can be used in a light-sensitive material has a function of reducing silver halide and/or a function of promoting (or suppressing) polymerization of a polymerizable compound. There are various types of reducing agents having the above functions. The reducing agents include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-
Pyrazolones, 5-aminouracils, 4゜5-dihydroxy-6-aminopyrimidines, reductones, amylreductones, 0- or p-sulfonamidophenols, 0- or p-sulfonamidonaphthols,
2-sulfonamide indanones, 4-sulfonamide-5-pyrazolones, 3-sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide ketones, hydrazines, etc. There is. By adjusting the type, amount, etc. of the reducing agent, it is possible to polymerize the polymerizable compound in either the area where the silver halide latent image is formed or the area where no latent image is formed. In addition, in a system in which a polymerizable compound is polymerized in a portion where a silver halide latent image is not formed, it is particularly preferable to use 1-phenyl-3-pyrazolidones as the reducing agent.

Regarding various reducing agents having the above functions, please refer to JP-A-61-183640, JP-A No. 61-188535, and JP-A-61-188535.
No. 1-228441, No. 62-70836, No. 62-
No. 863544, No. 62-86355, No. 62-19
Publications such as No. 8849, and patent application No. 60-22752
8 (including those described as developing agents or hydrazine derivatives). Regarding the above-mentioned reducing agent, please refer to “The Theory” by T. James.
f the Photo-graphic Process
ss” 4th edition, pp. 291-334 (1977), Research Disclosure Magazine Vol. 1.170.1978
No. 17029 (pages 9-15), June 2015, O and V
o1.176, No. 17643 of December 1978 (2
There is also a description on pages 2-31). Further, instead of the reducing agent, a reducing agent precursor that can release the reducing agent under heating conditions or in contact with a base may be used (Japanese Patent Application Laid-Open No. 62-210446); The reducing agents and reducing agent precursors described in the above-mentioned specifications and literatures can also be effectively used in photosensitive materials. Therefore, the "reducing agent" in this specification includes the reducing agents and reducing agent precursors described in each of the above-mentioned publications, specifications, and literature. These reducing agents may be used alone, but as described in each of the above specifications, two or more types of reducing agents may be used in combination. When two or more types of reducing agents are used together, the interaction of the reducing agents is, first, to promote the reduction of silver halide (and/or organic silver salt) through so-called superadditivity; silver halide (and/
or an organic silver salt) to cause polymerization of a polymerizable compound (or to suppress polymerization) through a redox reaction with other reducing agents in which the oxidized form of the first reducing agent is produced by reduction. etc. are possible. However, in actual use, the reactions described above can occur simultaneously, so it is difficult to specify which effect is occurring.

Specific examples of the reducing agent include pesotadecylnohydroquinone, 5-t-butylcatechol, p-(N,N-diethylamino)phenol, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l- Phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamine-4-hexadecyloxy-5-t-octylphenol, 2-phenylsulfonylamine-4-t-butyl-5- Hexadecyloxyphenol, 2-(N-butylcarbamoyl)-4-phenylsulfonylaminonaphthol, 2-(N-methyl-N-octadecylcarbamoyl)-4-sulfonylaminonaphthol, l-acetyl-2-phenylhydrazine, 1-acetyl-2-(
Cp or 0)-aminophenyl)hydrazine, 1-formyl-2-((p or 0)-aminophenyl)hydrazine, l-acetyl-2-((p or O)-methoxyphenyl)hydrazine, 1-lauroyl- 2-((p
or 0)-aminophenyl)hydrazine, l-)lythyl-2-(2,6-dichloro-4-cyanophenyl)
hydrazine, 1-) lotyl-2-phenylhydrazine,
1-Phenyl-2-(2,4,6-drichlorophenyl)hydrazine, 1-(2-(2,5-di-t-pentylphenoxy)butyroyl)-2-((p or 0)-
aminophenyl)hydrazine, 1-(2-(2,5-di-t-pentylphenoxy)butyroyl)-2-((P
or 0)-aminophenyl)hydrazine pentadecylfluorocaprylate, 3-indazolinone, 1. −
(3,5-dichlorobenzoyl)-2-phenylhydrazine, 1-trityl-2-[((2-N-butyl-N-
octylsulfamoyl)-4-methanesulfonyl)phenyl 1-hydrazine, 1-(4-(2,5-di-t-pentylphenoxy)butyroyl)-2-((p or 0
)-methoxyphenyl)hydrazine, t-(methoxycarbonylbenzohydryl)-2-phenylhydrazine,
1-Formyl-2-[4-(2-(2,4-di-t-pentylphenoxy)butyramido)phenyl]hydrazine, l-acetyl-2-[4-(2-(2,4-di-t
-pentylphenoxy)butyramido)phenyl 1hydrazine, 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, ■-benzoyl-2-tritylhydrazine, 1-(4-butoxybenzoyl)-2 -) Lythylhydrazine, 1-(2,4-dimethoxybenzoyl)-2
-1 lytylhydrazine, 1-(4-dibutylcarbamoylbenzoyl)-2-1 lytylhydrazine, and 1-
(1-naphthoyl)=2-tritylhydrazine and the like can be mentioned.

In the light-sensitive material, the reducing agent is preferably used in an amount of 0.1 to 1,500 mol % based on 1 mol of silver (including the aforementioned silver halide and optional organic silver salt).

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and any known polymerizable compound can be used. If heat development is planned as a method of using the photosensitive material, it should be noted that materials with a high boiling point (e.g. 80
℃ or higher) is preferably used. Furthermore, in the embodiment in which the photosensitive layer contains a color image forming substance as an optional component described later, the color image forming substance is immobilized by polymerization and curing of the polymerizable compound, so the polymerizable compound has a plurality of molecules in the molecule. A crosslinkable compound having a polymerizable functional group is preferable. Moreover, a highly viscous substance can be used as the polymerizable compound.

Note that polymerizable compounds that can be used in photosensitive materials are described in the application specifications for the series of photosensitive materials described above and below.

Polymerizable compounds used in photosensitive materials generally have addition polymerizability or ring-opening polymerizability. Examples of the compound having addition polymerizability include compounds having an ethylenically unsaturated group, and compounds having ring-opening polymerizability include compounds having an epoxy group, and compounds having an ethylenically unsaturated group are particularly preferred.

Compounds with ethylenically unsaturated groups that can be used in photosensitive materials include acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, and maleic anhydride. Examples include acids, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof.

Specific examples of polymerizable compounds that can be used in photosensitive materials include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, Dicyclohexyloxyethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, to dipentaerythritol Kisa acrylate,
Examples include diacrylate of polyoxyethylated bisphenol A, polyacrylate of hydroxypolyether, polyester acrylate, and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, Methacrylate and dimethacrylate of polyoxyalkylenated bisphenol A can be mentioned.

The above polymerizable compounds may be used alone or in combination of two or more. A photosensitive material using a combination of two or more types of polymerizable compounds is described in JP-A-62-210444. Note that a substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the above-mentioned reducing agent or a substance that causes a coloring reaction described below can also be used as the polymerizable compound.

In the light-sensitive material, the polymerizable compound is preferably used in an amount of 50,000 to 120,000 parts by weight per 1 part by weight of silver halide. A more preferable usage range is 12 to 120
00 parts by weight.

Examples of substances that develop color when in contact with another component include acid-base reactions between two or more components, redox reactions,
Various systems that develop color through coupling reactions, chelate formation reactions, etc. are included. For example, pressure-sensitive copying paper (pp. 29-58), Azography (p.
-95 pages), heat-sensitive color development by chemical change (118-120
Pages 26-32, (19
The coloring system described in June 19, 1980) can be used.

Specifically, a coloring system consisting of a coloring agent with a partial structure such as lactone, lactam, or spiropyran used in pressure-sensitive paper and an acidic substance (coloring agent) such as acid clay or thunols: aromatic diazonium salt, Systems that utilize azo coupling reactions between diazotate, diazosulfonates, naphthols, anilines, active methylenes, etc.; reactions between hexamethylenetetramine and ferric ions and gallic acid; and reactions between phenolphthalein and combreculanes. Chelate-forming reactions such as reactions with alkaline earth metal ions; redox reactions such as reactions between ferric stearate and pyrogallol and reactions between silver behenate and 4-methoxy-1-naphthol can be used.

Among the coloring systems described above, it is preferable to use a so-called coloring agent/coloring agent system. Color formers in the color former/color developer system include (1) triarylmethane type, (2) diphenylmethane type, and (3)
These include xanthine-based, (4) thiazine-based, and (5) spiropyran-based compounds.
Examples include those described in Publication No. 27253 and the like. Among these, (1) triarylmethane-based and (3) xanthine-based color formers have less fog and
Many of them are preferable because they provide high color density. Specific examples of the coloring agent include crystal violet lactone, 3-diethylamino-6-chloro-7-(β-
ethoxyethylamino)fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-triethylamino-6-methyl-7-anilinofluorane, 3
-cyclohexylmethylamino-6-methyl-7-ani, riffluorane, 3-diethylamino-7-o-chloroanilinofluorane, and the like. These coloring agents may be used alone or in combination.

Color developers for systems using color formers as described above include phenolic compounds, organic acids or metal salts thereof, oxybenzoic acid esters, acid clay, and the like.

Specific examples of the above phenol compounds include 4゜4'-isopropylidene-diphenol (bisphenol A)
, p-tert-butylphenol, 2,4-dinitrophenol, 3,4-dichlorophenol, 4,4
'-methylene-bis(2°6-tert-butylphenol), p-phenylphenol, 1,1-bis(
4-hydroxyphenyl)-2-ethylhexane, 2,
2-bis(4-hydroxyphenyl)phthane, 2.2'
-methylenebis(4-tert-butylphenol),
2.2'-methylenebis(α-phenyl-p-cresol)thiodiphenol, 4.4'-thiobis(6-te
In addition to rt-butyl-m-cresol)sulfonyldiphenol, p-tert-butylphenol-formalin condensate, p-phenylphenol-formalin condensate, and the like can be mentioned.

Specific examples of the organic acids or metal salts thereof include phthalic acid, phthalic anhydride, maleic acid, benzoic acid, gallic acid, o-toluic acid, p-)ruic acid, salicylic acid, 3-
tert-butylsalicylic acid, 3,5-di-tert
-butylsalicylic acid, 5-α-methylbenzylsalicylic acid, 3.5-(α-methylbenzyl)salicylic acid, 3-
tert-octylsalicylic acid and its zinc, lead,
Examples include aluminum salts, magnesium salts, nickel salts, and the like. Among these, salicylic acid derivatives and their zinc and aluminum salts have color developing ability,
It is excellent in terms of the fastness of color images and the storage stability of photosensitive materials.

Examples of the oxybenzoate esters include ethyl p-oxybenzoate, butyl p-oxybenzoate, heptyl p-oxybenzoate, benzyl p-oxybenzoate, and the like.

Among the above-mentioned color developers, there are some that take part in the color-forming reaction after melting at a certain temperature or higher. When such a color developer is used, it is added as a eutectic with a low melting point thermofusible substance, or the low melting point compound is added in a state fused to the surface of the color developer particles. It is preferable.

Specific examples of the above-mentioned low melting point compounds include higher fatty acid amides such as stearic acid amide, erucic acid amide, palmitic acid amide, ethylene bisstearamide; waxes such as higher fatty acid esters; phenyl benzoate derivatives; aromatic ethers. Derivatives; urea derivatives and the like can be mentioned.

Color formers/developer systems other than the above-mentioned (1) to (5) include phenolphthalein, fluorescein,
2', 4', 5°, 7'-tetrabromo-3,4,5,
There are systems that use 6-titrachlorofluorescein, tetrabromophenolphthalein, eosin, alarin cresol red, 2-naphtholphenolphthalein, etc. as color formers.

Color developers for systems using the above color formers include inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, There are nitrogen-containing compounds such as indoles, imidazoles, imidacillines, triazoles, morpholines, piperidines, amidines, formazines, and pyridines. Specific examples of these include ammonium acetate, tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allyl urea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenyl Imidazole, 2-phenyl-4-methyl-imidazole, 2-undecyl-imidacillin, 2,4.5-)refry-2-imidacillin, 1,2-diphenyl-4,
4-dimethyl-2-imidacyline, 2-phenyl-2-
imidacilline, 1,2.3-1 rifenylguanidine,
1,2-ditolylguanidine, 1,2-dicyclohexylguanidine, ■.

2-dicyclohexyl-3-phenylguanidi 7.1,
2.3-Tricyclohexylguanidine, guanidine trichloroacetate, N,N'-dibenzylpiperazine, 4
, 4'-dithiomorpholine, morpholinium trichloroacetate, 2-amino-benzothiazole, 2-benzoylhydrazino-benzothiazole and the like.

In the light-sensitive material of the present invention, one of the substances that cause a color-forming reaction as described above is contained in a microcapsule together with the polymerizable compound, and the other substance that causes a color-forming reaction is contained in a microcapsule. It exists outside the capsule.

When using a color former/S color agent system as a coloring system, it is more common to use the substance contained in the microcapsules as the coloring agent and the substance existing outside the microcapsules as the color developer. be.

Note that a color developer can also be accommodated in microcapsules, and in this case, an oil-absorbing white pigment can be used in combination with the color developer to diffuse and fix the contents of the capsule.

Furthermore, a plurality of coloring systems as described above may be used. In this case, by combining at least three types of silver halide emulsions (silver halide emulsions will be described later) that are sensitive to different spectral regions, each microcapsule is used in a manner corresponding to each emulsion. , can easily form full-color images.

In the light-sensitive material of the present invention, when a color former/color developer system is used as the color forming system, the color former is preferably used in a proportion of 0.5 to 20 parts by weight based on 100 parts by weight of the polymerizable compound. More preferably, it is used in a proportion of 2 to 7 parts by weight. Further, when a color developer is used, it is preferably used in a proportion of about 0.3 to 80 parts by weight per 1 part by weight of the color former.

Regarding photosensitive materials in general that use substances that cause a color reaction upon contact, the above-mentioned Japanese Patent Application Laid-Open No. 61-73
There is also a description in Publication No. 145.

Note that the substance j accommodated in the r microcapsules means a substance present in the core substance and/or wall material constituting the microcapsules.

Regarding the above-mentioned microcapsules, various known techniques can be used without particular limitation, and the details will be described later.

In the light-sensitive material of the present invention, the microcapsules preferably also contain the above-mentioned silver halide and reducing agent.

The photosensitive material is formed by providing a photosensitive layer containing the above-mentioned components on a support. There are no particular restrictions on this support, but if heat development is planned as a method of using the photosensitive material, it is preferable to use a material that can withstand the processing temperature of the development. Materials that can be used for the support include glass, paper, high-quality paper, coated paper, cast coated paper, synthetic paper, metals and their analogs,
Examples include films of polyester, cellulose acetate, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, etc., and papers laminated with resin materials and polymers such as polyethylene.

In addition, when the support is made of a porous material such as paper, it is preferable that it has a certain level of smoothness according to the method defined by waviness (see JP-A No. 62-209529).
. In addition, when using a paper support, a paper support with low water absorption (see JP-A No. 63-3893'4), a paper support with Beck smoothness (see JP-A-63-47754), ), a paper support with a low shrinkage rate like the photosensitive material described in Japanese Patent Application No. 61-227766, Japanese Patent Application No. 61-227
A paper support with low air permeability such as the photosensitive material described in the specification of Japanese Patent Application No. 27768, a paper support with a pH value of 5 to 9 such as the photosensitive material described in the specification of Japanese Patent Application No. 61-243552, etc. may be used. You can also do it.

In the photosensitive material of the present invention, as described above, the polymerizable compound is contained in the photosensitive layer in the form of microcapsules together with one of the substances that cause a coloring reaction.

There are no particular limitations on the wall material that constitutes the outer shell of the microcapsules. Furthermore, regarding photosensitive materials using microcapsules having outer shells made of polyamide resin and/or polyester resin, Japanese Patent Application Laid-Open No. 62-20943
No. 7 describes a photosensitive material using microcapsules having an outer shell made of polyurea resin and/or polyurethane resin, and JP-A-62-209438 describes microcapsules having an outer shell made of amino aldehyde resin. Regarding the photosensitive material used, see JP-A-62-2.
No. 09439 describes a photosensitive material using microcapsules having an outer shell made of gelatin.
No. 09440 discloses a photosensitive material using microcapsules having an outer shell made of epoxy resin, and JP-A-62-209441 discloses a photosensitive material using microcapsules having a composite resin outer shell containing polyamide resin and polyurea resin. For photosensitive materials, see JP-A No. 62-209447.
JP-A-62-209442 describes a photosensitive material using microcapsules having a composite resin shell containing a polyurethane resin and a polyester resin.

In addition, when using aldehyde-based microcapsules, it is preferable to keep the amount of residual aldehyde below a certain value, as in the photosensitive material described in JP-A-63-32535.

When silver halide is contained in microcapsules, it is preferable that silver halide be present in the wall material constituting the outer shell of the microcapsules. Regarding photosensitive materials containing silver halide in the wall material of microcapsules, JP-A-62
There is a description in the publication No.-169147.

Furthermore, two or more microcapsules containing at least one different component such as silver halide, a reducing agent, a polymerizable compound, and one of the substances that cause a color reaction may be used in combination. good. In particular, when forming a full-color image, it is preferable to use three or more types of microcapsules containing different color image-forming substances in different hues. For photosensitive materials containing two or more types of microcapsules, JP-A-62-19
There is a description in Publication No. 8850.

The average particle size of the microcapsules is preferably 3 to 20 gm. It is preferable that the particle size distribution of the microcapsules is uniformly distributed over a certain value, as in the photosensitive material described in JP-A No. 63-5334. In addition, the film thickness of the microcapsules is
As in the photosensitive material described in No. 67, the particle size is preferably within a certain range.

Nao, when storing silver halide in microcapsules, it is preferable that the average particle size of the silver halide grains mentioned above be one-fifth or less of the average size of the microcapsules, and one-tenth or less. is even more preferable. A uniform and smooth image can be obtained by setting the average particle size of the silver halide grains to one-fifth or less of the average size of the microcapsules.

Optional components that can be included in the photosensitive layer of the photosensitive material include sensitizing dyes, organic silver salts, radical generators, various image formation accelerators, thermal polymerization inhibitors, thermal polymerization initiators, development terminators, silicon Optical brighteners, anti-fading agents, anti-halation or irradiation dyes or pigments, pigments that bleach when heated or exposed to light, matting agents, anti-smudge agents, plasticizers, water-releasing agents, binders, photopolymerization Examples include initiators, solvents for polymerizable compounds, and water-soluble vinyl polymers.

The sensitizing dye that can be used in the light-sensitive material is not particularly limited, and silver halide sensitizing dyes known in the photographic technology can be used. In addition, a dye that itself does not have a spectral sensitizing effect, or a substance that does not substantially absorb visible light but exhibits supersensitization may be used in combination with the sensitizing dye. The amount of the sensitizing dye added is generally about 10-8 to 10-2 mol per mol of silver halide.

The above-mentioned sensitizing dye is preferably added at the stage of preparing a silver halide emulsion, which will be described later. Regarding a light-sensitive material obtained by adding a sensitizing dye at the stage of forming silver halide grains, JP-A-62-947 discloses that a sensitizing dye is added to a silver halide emulsion after the formation of silver halide grains. The photosensitive materials obtained by adding these materials in the preparation stage are described in JP-A No. 62-210449. Further, specific examples of sensitizing dyes that can be used in light-sensitive materials are also described in the above-mentioned Japanese Patent Application Laid-Open No. 62-947. Further, as in the photosensitive material described in Japanese Patent Application No. 61-208786, a sensitizing dye sensitive to infrared light may be used in combination.

Addition of organic silver salts to photosensitive materials is particularly effective in thermal development processing. That is, when heated to a temperature of 80° C. or higher, the organic silver salt is considered to participate in an oxidation-reduction reaction catalyzed by the latent image of silver halide. In this case, the silver halide and the organic silver salt are preferably in contact or in close proximity. The above-mentioned organic silver salt is generally 0.0. Ol to 10 mol, preferably o, oi to 1 mol is used. Note that 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. For photosensitive materials using organic silver salts, see JP-A-62-3246.
There is a description in the bulletin.

The organic silver salt as described above is preferably used in an amount of 0.1 to 10 mol, more preferably 0.01 to 1 mol, per mol of silver halide. - A radical generator that participates in the above-mentioned polymerization promotion (or polymerization inhibition) reaction of the reducing agent may be added to the photosensitive layer.

A photosensitive material using silver triazene as the radical generator is described in JP-A-62-195639, and a photo-sensitive material using silver diazotate is described in JP-A-62-1956.
No. 195640 describes a photosensitive material using an azo compound, and JP-A-62-195641 describes a photosensitive material using an azo compound.

Various image formation accelerators can be used in the photosensitive material. The image formation accelerator has functions such as promoting the redox reaction between silver halide (and/or organic silver salt) and a reducing agent. In terms of physicochemical functions, image formation accelerators include base precursors, oils, surfactants, compounds with antifogging and/or development accelerating functions, thermal solvents, compounds with oxygen removal functions, etc. being classified. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Therefore, the above classification is for convenience, and in reality, one compound often has multiple functions.

Examples of various image formation accelerators are shown below.

Examples of base precursors include salts of organic acids and bases that decarboxylate when heated, compounds that release amines through reactions such as intramolecular nucleophilic substitution, Rossen rearrangement, and Beckmann rearrangement. Compounds that emit bases and compounds that generate bases by electrolysis or the like are preferably used. Specific examples of base precursors include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-)luidine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine phenylsulfonylacetate, 4-chlorophenylsulfonylacetate guanidine, and 4-chlorophenylsulfonylacetate. Examples include guanidine methyl-sulfonylphenylsulfonylacetate and guanidine 4-acetylaminomethylpropiolate.

In photosensitive materials, base precursors can be used in a wide range of amounts. The base precursor is suitably used in an amount of 100% by weight or less in terms of weight of the coating film of the photosensitive layer, and more preferably in a range of 0.1% to 40% by weight.

Incidentally, a photosensitive material using a base or a base precursor is described in JP-A-60-227528. Further, for a photosensitive material using a tertiary amine as a base, see JP-A-62-170954, and for a photosensitive material using a fine particle dispersion of a hydrophobic organic base compound with a melting point of 80 to 180°C. Japanese Patent Publication No. 62-20952
No. 3 describes a photosensitive material using a guanidine derivative with a solubility of 0.1% or less in Japanese Patent Application No. 61-215637.
Regarding photosensitive materials using hydroxides or salts of alkali metals or alkaline earth metals, a patent application filed in 1983
Each of these is described in the specification of No. 1-96341.

Furthermore, regarding a photosensitive material using an acetylide compound as a base precursor, JP-A-63-24242 discloses a photosensitive material using a propiolate as a base precursor.
Furthermore, regarding photosensitive materials containing silver, copper, silver compounds, or copper compounds as catalysts for base-forming reactions, JP-A-63-46
Japanese Patent Application No. 4'46 discloses a photosensitive material containing the propiolic acid salt and the silver, copper, silver compound, or copper compound separated from each other in Japanese Patent Application No. 61-227769. Regarding photosensitive materials containing silver, copper, a silver compound, or a ligand in a free state in addition to a copper compound, Japanese Patent Application No. 61-243555 describes the use of a propiolic acid salt as a base precursor and the use of a heat-fusible compound. Regarding the kyōsho material containing as a reaction accelerator for the base production reaction, see JP-A-63-46447, using sulfonylacetate as the base precursor,
Furthermore, regarding a photosensitive material containing a heat-melting compound as a reaction accelerator for a base production reaction, JP-A-63-48543 describes a photosensitive material using a compound in which incyanate or isothiocyanate is bonded to an organic base as a base precursor. Each of these is described in Japanese Patent Application Laid-Open No. 63-24242.

When a base precursor is used in a photosensitive material, it is preferable that silver halide, a reducing agent, a polymerizable compound, etc. are contained in the microcapsules described above, and the base precursor is present in the photosensitive layer outside the microcapsules. Alternatively, the base precursor may be contained in a separate microcapsule, as in the photosensitive material described in JP-A-62-209521.

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

Examples of the surfactant include pyridinium salts, ammonium salts, and phosphonium salts described in JP-A-59-74547, and polyalkylene oxides described in JP-A-59-57231.

A compound having an antifogging function and/or a development accelerating function can be used for the purpose of obtaining a clear image (an image with a high S/N ratio) having a high maximum density and a low minimum density. Note that a photosensitive material using an antifoggant as a compound having an antifogging function and/or a development accelerating function is described in JP-A-62-151838, and a photosensitive material using a compound having a cyclic amide structure is described in JP-A-62-151838. For photosensitive materials using thioether compounds, see Japanese Patent Application Laid-open No. 62-151841.
No. 151842 describes photosensitive materials using polyethylene glycol derivatives, and Japanese Patent Application Laid-Open No. 151843/1983
For photosensitive materials using thiol derivatives, see JP-A-62-151844, and for photosensitive materials using acetylene compounds, see JP-A-62-178232.
For photosensitive materials using sulfonamide derivatives, see JP-A-62-183450, and for photosensitive materials using quaternary ammonium salts, see Japanese Patent Application No. 61-23.
Each of these is described in the specification of No. 8871.

Useful examples of the thermal solvent include compounds that can serve as solvents for reducing agents, and compounds with high dielectric constants that are known to accelerate the physical development of silver salts.

Note that a photosensitive material using a hot solvent is described in JP-A-62-86355.

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

Thermal polymerization initiators that can be used in photosensitive materials are generally compounds that are thermally decomposed under heating to generate polymerization initiating species (particularly radicals), and are commonly used as radical polymerization initiators.

Thermal polymerization initiators are described in pages 6 to 18 of "Addition Polymerization/Ring-Opening Polymerization J" edited by the Editorial Committee of Polymer Experiments, Japan Society of Polymer Science and Technology (1983, Kyoritsu Publishing). The thermal polymerization initiator is 0.1 to 120% by weight based on the polymerizable compound.
It is preferably used in a range of 1 to 10% by weight, and more preferably in a range of 1 to 10% by weight. In addition, in a system in which a polymerizable compound is polymerized 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. Furthermore, a photosensitive material using a thermal polymerization initiator is described in JP-A-62-70836.

A development stopper that can be used in photosensitive materials is a compound that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development immediately after proper development, or a compound that interacts with silver and silver salts. It is a compound that suppresses development. Specific examples include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Examples of acid precursors include JP-A-60-1
Oxime esters described in JP-A No. 08837 and JP-A-60-192939, and compounds that release acid by Rossen rearrangement described in JP-A No. 60-230133 can be mentioned.

Examples of electrophilic compounds that undergo a substitution reaction with a base upon heating include compounds described in JP-A-60-230134.

Binders that can be used in photosensitive materials can be contained in the photosensitive layer alone or in combination. It is preferable to use a mainly hydrophilic binder. A typical example of the wood-loving binder is a transparent or semi-transparent wood-loving binder. Incidentally, a photosensitive material using a binder is described in the above-mentioned Japanese Patent Laid-Open No. 61-69062. Regarding photosensitive materials using binders together with microcapsules, JP-A-62-2
There is a description in Publication No. 09525.

When a solvent for a polymerizable compound is used in a photosensitive material, it is preferable to encapsulate it in a microcapsule separate from the microcapsule containing the polymerizable compound. Regarding photosensitive materials using organic solvents that are miscible with polymerizable compounds encapsulated in microcapsules, Japanese Patent Application Laid-Open No. 62-2095
There is a description in Publication No. 34.

A water-soluble vinyl polymer may be adsorbed onto the silver halide grains described above. Regarding photosensitive materials using water-soluble vinyl polymers as mentioned above, Japanese Patent Application No. 61-2388
It is described in the specification of No. 70.

In addition to those mentioned above, examples of optional components that can be included in the photosensitive layer and how they are used can also be found in the application specifications related to the above-mentioned series of photosensitive materials and Research Disclosure Magazine Vol.

No. 17029, June 1978 (pages 9-15).

Layers that can be optionally provided on the photosensitive material include an image receiving layer, a heating layer, an antistatic layer, an anticurl layer, a peeling layer, a cover sheet or protective layer, a layer containing a base or a base precursor, and a base barrier layer. , antihalation layer (
colored layer), etc.

Regarding photosensitive materials using a heating layer, Japanese Patent Application Laid-Open No. 1986-
For photosensitive materials provided with a cover sheet or a protective layer, see JP-A-62-210447, and for photosensitive materials provided with a layer containing a base or base precursor, see Japanese Patent Application No. 61-96340. To,
Photosensitive materials provided with a colored layer as an antihalation layer are described in Japanese Patent Application No. 61-246901. A photosensitive material provided with a base barrier layer is also described in the above-mentioned Japanese Patent Application No. 61-96340. Furthermore, examples of other auxiliary layers and their usage are also described in the application specifications relating to the above-mentioned series of photosensitive materials.The method for producing the photosensitive materials will be described below in the margins.

Various methods can be used to produce photosensitive materials, but a common method is to prepare a photosensitive composition by dissolving, emulsifying, or dispersing the components of the photosensitive layer in an appropriate solvent. , a step of microcapsulating this to prepare a coating solution containing a capsule dispersion, and a step of coating the coating solution on a support and drying it.

Generally, the above-mentioned coating liquid is prepared by preparing a liquid composition containing each component and then mixing the respective liquid compositions. The liquid composition may be prepared to contain multiple components. Some of the components of the photosensitive layer can also be added during or after the preparation of the liquid composition or coating solution. Furthermore, as described below, a method of preparing a secondary composition by further emulsifying an oil-based (or aqueous) composition containing one or more components in an aqueous (or oil-based) solvent can also be used. .

Regarding the main components contained in the photosensitive layer, methods for preparing a liquid composition and a coating solution are shown below.

Preparation of the halogenated emulsion can be carried out using any known method such as an acid method, a neutral method or an ammonia method.

The reaction method between the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. A back-mixing method in which particles are formed under conditions in excess of silver ions and a Chondrold double-jet method in which pAg is kept constant can also be employed. Furthermore, in order to accelerate grain growth, the concentration, amount, or rate of addition of silver salts and halogen salts may be increased (Japanese Patent Laid-Open No. 55-158
No. 124, No. 55-158124, and U.S. Pat. No. 3,650,757).

The silver halide emulsion used in the production of light-sensitive materials may be of the surface latent image type, in which latent images are mainly formed on the grain surfaces, or of the internal latent image type, in which the latent images are formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used. Internal latent image emulsions suitable for this purpose are disclosed in U.S. Pat. No. 2,592,250, U.S. Pat.
No. 6641, various publications, etc., contain detailed information. A preferred nucleating agent for combination with the above emulsion is U.S. Pat. No. 3,227,552.
No. 4245037, No. 4255511, No. 4266013, No. 4276364, and OLS No. 2635316.

In the preparation of silver halide emulsions used in the production of light-sensitive materials, it is preferable to use wood-philic colloids as protective colloids.

Silver halide emulsions are prepared by using ammonia, organic thioether derivatives (see Japanese Patent Publication No. 47-386), and sulfur-containing compounds (see Japanese Patent Application Laid-Open No. 144319-1987) as silver halide solvents in the stage of forming silver halide grains.
etc. can be used. Further, in the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be allowed to coexist. Furthermore, for the purpose of improving high-light failure and low-light failure, iridium chloride (■ or ■),
Water-soluble iridium salts such as ammonium hexachloroiridium salt, or water-soluble rhodium salts 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 Tardel water washing method or the sedimentation method. Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. In emulsions for conventional sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (Japanese Patent Laid-Open No. 58
-126526, No. 58-215644).

In addition, when adding a sensitizing dye to a silver halide emulsion,
The aforementioned Japanese Patent Application Laid-open No. 62-947 and No. 62-21
It is preferable to add it at the stage of preparing a silver halide emulsion as in the light-sensitive material described in Japanese Patent No. 0449. Also,
When a nitrogen-containing heterocyclic compound is added as a compound having the above-mentioned antifogging function and/or development accelerating function, it is preferably added at the stage of forming or ripening silver halide grains in the preparation of a silver halide emulsion. . 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 organic silver salt described above is included in the photosensitive layer, the organic silver salt emulsion can be prepared by a method similar to the method for preparing the silver halide emulsion described above.

In the production of photosensitive materials, the polymerizable compound can be used as a medium in preparing the composition of other components in the photosensitive layer. For example, photosensitive materials are manufactured by dissolving, emulsifying, or dispersing silver halide (including silver halide emulsions), a reducing agent, one of the substances that cause a color-forming reaction (e.g., a color former), etc. in a polymerizable compound. It can be used for. In particular, when adding one of the substances that cause a coloring reaction, it is preferable to include a polymerizable compound. Furthermore, as will be described later, when the 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 silver halide in a polymerizable compound can be prepared using a silver halide emulsion. In addition to the silver halide emulsion, silver halide powder prepared by freeze-drying or the like can also be used to prepare the photosensitive composition.

Photosensitive compositions containing these silver halides can be obtained by stirring with a homogenizer, blender, mixer, or other commonly used stirrers.

In addition, it is preferable that a copolymer consisting of a hydrophilic repeating unit and a hydrophobic repeating unit is dissolved in the polymerizable compound used for preparing the photosensitive composition. Regarding photosensitive compositions containing the above-mentioned copolymers, JP-A-62-
There is a description in No. 209449.

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

It is preferable to use the polymerizable compound (including those containing other constituent components like the above photosensitive composition) in the form of an emulsion in an aqueous solvent. It is also possible to add a wall material necessary for microcapsulation to this emulsion and further perform a treatment to form the outer shell of the microcapsules at the stage of this emulsion. Furthermore, a reducing agent or other optional components may be added at the stage of the emulsion.

Examples of the above-mentioned microencapsulation method include a method using coacervation of aromatic wood-philic wall-forming materials as described in U.S. Pat. No. 2,800,457 and U.S. Pat. No. 2,800,458; U.S. Pat. Specification of contents and Special Publication No. 38-1957
No. 4, No. 42-446, and No. 42-771; Interfacial polymerization method described in US Pat. No. 3,418,250 and US Pat. No. 3,860,304; Method by precipitation of aromatic polymer; US Pat. No. 3,796,669 Method using the incyanate-polyol wall material described in U.S. Pat. No. 3,914,511; U.S. Pat. No. 4,001,140;
No. 087376 and No. 4,089,802 A method using an aromatic urea-formaldehyde-based or urea-formaldehyde-resircinol-based wall-forming material; a wall-forming material such as melamine-formaldehyde resin or hydroxypropyl cellulose described in U.S. Pat. No. 4,025,455 Methods using forming materials: In-5-itu method by polymerization of monomers described in Japanese Patent Publication Nos. 36-9168 and 51-9079; polymerization described in British Patent Nos. 927807 and 965074 Distributed cooling method; US Patent No. 3,111,407 and British Patent No. 930
Examples include the spray drying method described in the specification of No. 422 Yoyo. Although the method for microcapsulating oil droplets of a polymerizable compound is not limited to the above, a method in which a core substance is emulsified and then a polymer film is formed as a microcapsule wall is particularly preferred.

A photosensitive composition is microencapsulated using the above microencapsulation technique to prepare a microcapsule dispersion.

When the capsule dispersion contains the silver halide stabilizer precursor according to the present invention (it may be present in the capsule), it can be used as it is as a coating solution for the photosensitive layer. Furthermore, a coating solution for forming a photosensitive layer can be prepared by adding the silver halide stabilizer precursor according to the present invention to the capsule dispersion. The photosensitive material can be produced by applying the above-mentioned coating liquid onto the above-mentioned support and drying it. The coating liquid can be easily applied to the support according to known techniques.

Below, remaining white The method of using the photosensitive material will be described below.

The photosensitive material can be used simultaneously with imagewise exposure or after imagewise exposure.
Perform development processing and use.

Although various exposure means can be used as the above-mentioned exposure method, a latent image of silver halide is generally obtained by imagewise exposure to radiation including visible light. The type of light source and amount of exposure
Sensitive wavelength of silver halide (if dye sensitization is performed,
It can be selected depending on the sensitized wavelength) and sensitivity. Further, the original image may be a black and white image or a color image.

The photosensitive material is developed at the same time as the imagewise exposure or after the imagewise exposure. The photosensitive material was published under the Special Publication Act in 1977-111.
Development processing using a developer described in Japanese Patent No. 49 or the like may be performed. As mentioned above, the method described in Japanese Patent Application Laid-Open No. 61-69062 which performs heat development treatment is a dry treatment, and therefore has the advantage of being simple to operate and capable of processing in a short time. Therefore, the development process for photosensitive materials is as follows:
The latter is especially good.

As the heating method in the above heat development treatment, various conventionally known methods can be used. Further, as in the photosensitive material described in the above-mentioned Japanese Patent Application Laid-open No. 61-294434, a heat generating layer may be provided on the photosensitive material and used as a heating means. Further, as in the image forming method described in JP-A-62-210461, the heat development treatment may be carried out while suppressing the amount of oxygen present in the photosensitive layer. The heating temperature is generally 80°C to 200°C, preferably 100°C to 1
The temperature is 60°C. The heating time is generally 1 second to 5 minutes.
Preferably it is 5 seconds to 1 minute.

Incidentally, instead of including the above-mentioned base or base precursor in the photosensitive material, development may be carried out while or immediately after adding the base or base precursor to the photosensitive layer. As a method for adding a base or a base precursor, a method using a sheet (base sheet) containing a base or a base precursor is easiest and preferred. Regarding the image forming method using the above base sheet, JP-A No. 6
There is a description in Publication No. 2-32546.

The photosensitive material can be thermally developed as described above to polymerize the polymerizable compound in the area where the silver halide latent image is formed or the area where the silver halide latent image is not formed. In light-sensitive materials, the polymerizable compound in the area where the latent image of silver halide is generally polymerized in the heat development process described above.
As in the photosensitive material described in Japanese Patent No. 70836, by adjusting the type, amount, etc. of the reducing agent, it is also possible to polymerize the polymerizable compound in the area where the silver halide latent image is not formed.

In the manner described above, a polymer image can be obtained on the photosensitive layer of the photosensitive material.

After the photosensitive material is developed as described above, it is pressurized by a commonly used pressurizing means to destroy microcapsules containing unpolymerized polymerizable compounds and the like. In addition, two types of substances that cause a color reaction at the same time as the microcapsules are destroyed also come into contact with each other and develop color. In this way, a hardened color image can be obtained on the photosensitive material.

Additionally, the applicant has already filed patent applications for various image recording devices suitable for carrying out the above-described series of image forming methods using photosensitive materials (Japanese Patent Application No. 1986-28
9703 specification, etc.).

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

The present invention will be explained in more detail with reference to Examples below. However, the present invention is not limited to this.

[Example 1] [Preparation of photosensitive material] Preparation of a silver halide emulsion A gelatin aqueous solution (containing 25 g of gelatin and 3 g of potassium bromide in 1200 ml of water and adjusted to pH 3 with IN sulfuric acid)
, 2 and kept warm at 60'0), 600 ml of an aqueous solution containing 117 g of potassium bromide and a silver nitrate stock solution (0.74 mol of silver nitrate dissolved in 600 m of water) were added at the same time at 45 ml. Added at equal flow rates over a period of minutes. 5 minutes after this ends, potassium iodide 4.3
200 ml of an aqueous solution containing g were added at equal flow rates over 5 minutes. After washing this emulsion with water and desalting it, 24 g of gelatin was added and stirred at 50'0 for 15 minutes to obtain a silver halide emulsion with a yield of 1000 g.

Preparation of W10 emulsion 100 g of trimethylolpropane triacrylate, 0.4 g of the following copolymer, Burger Script Red l-
6-B (manufactured by Ciba Geigy) was dissolved. Add 18g of this solution to the surfactant: NS 20
Dissolve 0.36 g of the following hydrazine derivative (reducing agent), 1.22 g of the following current drug (reducing agent) and the following thiol derivative o.
, 0015g dissolved in 4g of methylene chloride was added to form an oil phase (0).

On the other hand, 0.45 g of a 10% aqueous solution of potassium bromide was added to 2.0 g of the silver halide emulsion obtained above to form an aqueous phase (W).

Next, add the water phase (W) to the above oil phase (0),
Using a homogenizer, the mixture was stirred at 15,000 revolutions per minute for 5 minutes to obtain a W10 emulsion.

' Space below (copolymer) GO2CH2GH20HGO2CzHs (hydrazine derivative) (t) [5H++ 2H5 (developer) (thiol derivative) R Partial sodium salt of polyvinylbenzenesulfonic acid (V
ER3A, Tl2O3, manufactured by National Starch) 5
% aqueous solution was adjusted to pH 3.5 with a 20% phosphoric acid aqueous solution. To 40 g of this aqueous solution, 0.9 g of Bamboo DIION (polyvalent incyanate compound, manufactured by Narita Pharmaceutical Co., Ltd.) was added to the W10 emulsion and mixed well, and the mixture was heated at 700 per minute using a homogenizer at 40°C.
The mixture was stirred at 0 rotations for 30 minutes. A thin shell of polyurea resin was formed around the oil phase of the W10/W emulsion produced here.

Separately, 13.2 g of melamine, 21.6 g of a 37% formaldehyde aqueous solution, and 70.8 g of water were heated and stirred at 60° C., and after 30 minutes, a transparent melamine/formaldehyde initial condensate was obtained.

Add and mix 10 g of the above initial condensate to the above W/0/W emulsion (covered with a thin polyurea film), adjust the pH to 6.0 with a 20% phosphoric acid aqueous solution while stirring, and raise the liquid temperature to 65 ° C. The mixture was raised and stirred for 90 minutes to prepare a microcapsule liquid in which melamine autoformaldehyde resin was deposited on the outer shell of the polyurea membrane.

Preparation of color developer solution 11 g of 40% sodium hexametaphosphate aqueous solution was added to 125 g of water, and further mixed with 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry, and coarsely mixed with a mixer. Dispersed. The liquid was dispersed using a Dynamil splitter, and 6 g of 50% SBR latex and 55 g of 8% polyvinyl alcohol were added to 200 g of the obtained liquid and mixed uniformly to prepare a color developer liquid.

Preparation of photosensitive material (I) Microcapsule liquid prepared above 15. Mix Og and 15 g of the above color developer solution, and add 0.23 g (4.7 mol/A) of the following stabilizer precursor (a) to this mixed solution.
g X 1 mol), 4 ml of 5% aqueous solution of the following polyethylene glycol derivative, 1 guanidine trichloroacetate
0% solution (water/ethanol = 50750 volume ratio) 8+
nJJ and 40 ml of water were added to prepare a coating solution for forming a photosensitive layer.

Next, the above coating solution was applied onto a 100Ji, m-thick polyethylene terephthalate sheet (support) using a #40 coating rod to a wet film thickness of 60mg, and dried at about 40°C to form a film according to the present invention. Photosensitive material (
I) was created.

(Stabilizer precursor a) CH3GH2-NH-C-3-C:H2-CH-COO
H In Example 1, instead of using the stabilizer precursor a described above when preparing the photosensitive material, 0.28 g (4.7 mol/A) of the stabilizer precursor (b) shown below was used.
g x 1 mol), (c) 0.38 g (4,7 mol/A g x 1-E nyl), and (d) 0.2
By operating in the same manner as in Example 1 except that 4 (4.7 mol/A gX 1 mol) was used, photosensitive materials 1 to 2 according to the present invention were prepared correspondingly.

(Stabilizer precursor b) \ NH2 (Stabilizer precursor C) (Stabilizer precursor d) NH2 〉 C-3-CH2-CH2-3031 ( / NH2 [Comparative example 1] In Example 1, the photosensitive material A comparative photosensitive material V was prepared in the same manner as in Example 1 except that the stabilizer precursor a was not used during the preparation.

[Evaluation as a photosensitive material] Next, each photosensitive material (IV) obtained as described above
An image was formed by the following operations and evaluated.

The photosensitive material was imagewise exposed for 1 second at 2000 lux using a tungsten bulb, then placed on a hot plate heated to 140° C. and subjected to heat development for 20 seconds.

Next, the photosensitive material was passed through a pressure roller of 350 kg/crn'' to obtain a magenta positive color image on the photosensitive material.
■ax) and minimum concentration (I)+in) were immediately measured.

Furthermore, after exposing the color image for 30 minutes under a 500 lux fluorescent lamp, the density of the lowest density (Dmin) portion was measured again in the same manner as above.

The above measurement results are summarized in Table 1.

Table 1 with margins below Maximum concentration of stabilizer Minimum concentration change Material Added amount (g) (Dmax) (Dmin) I
O, 230,760,20→ 0.22II
O, 280,740,19→ 0.20m 0,
38 0.72 0.19→ 0.211V
O, 240,740,21→ 0.22V −
0,800,23+0.40 As is clear from the results in Table 1, the light-sensitive materials (I to ■) according to the present invention to which a specific amount of a stabilizer precursor is added are those to which a stabilizer precursor is added. Photosensitive materials for comparison (V
), there is almost no change in the image density in the lowest density area,
It was stable and no staining occurred.

Furthermore, the same effects as described above were obtained in a light-sensitive material in which a stabilizer precursor was contained in the micropressure.

Claims (1)

[Claims] 1. Contains a support, silver halide, a reducing agent, a polymerizable compound, and two types of substances that cause a color reaction when they come into contact with each other, provided on the support, and one of the substances that cause a color reaction. In a photosensitive material having a photosensitive layer in which a substance and at least the above-mentioned polymerizable compound are housed in microcapsules, a substance that releases a compound that deactivates the silver halide upon heating is added to the photosensitive layer. A photosensitive material characterized in that silver is contained in a range of 0.2 to 20 moles per mole of silver.