JPH04116659A - Photosensitive material - Google Patents

Abstract

PURPOSE:To obtain bright full-color images and to improve preservable stability by incorporating at least one of specific compds. into the above photosensitive material. CONSTITUTION:At least one of the compds. expressed by formula I, formula II, etc., are further incorporated into the photosensitive material having photosen sitive layers contg. microcapsuls in which a silver halide, reducing agent, image forming material, polymerizable compd., and basic precursor are housed on a base. In the formula I, Z denotes a hydrogen atom, alkyl group, etc., when n=1 and denotes Zn or Ni when n=2; R<1> to R<5> denote a hydrogen atom, substit uent or chemical bond. In the formula II, X denotes an oxygen atom, sulfur atom, substd. imino group, etc.; R<6> to R<9> denote a hydrogen atom, substituent or chemical bond. An excellent green preservable property is obtd. in this way and the images having the high image densities and low stains are obtd. in a short period of time.

Description

[Detailed description of the invention] <Industrial application field> The present invention uses silver halide and a reducing agent on a support.

The present invention relates to a photosensitive material having a photosensitive layer containing microcapsules containing a color image-forming substance, a polymerizable compound, and a base precursor.

<Prior Art> A photosensitive material in which a silver halide, a reducing agent, a one-color image forming substance, and a polymerizable compound are housed in microcapsules (photosensitive microcapsules) has been disclosed in Japanese Patent Application Laid-Open No.
, No. 2 and J/-271#μri Publication.

Regarding an image forming method using a photosensitive material having the above structure, a recording material (photosensitive material) having a photosensitive layer having the above-mentioned photosensitive microcapsules supported on a support is imagewise exposed to form a latent image, and then a latent image is formed. By heat-developing this, a polymerizable compound is polymerized in the area where the latent image has been formed, and the photosensitive material is superimposed on an image-receiving material having an image-receiving layer, and pressure is applied in this state to remove the unpolymerized polymerizable compound. A commonly used method is to transfer the image to an image-receiving material to obtain a transferred image on the image-receiving material.

On the other hand, methods for polymerizing the polymerizable compound in areas where no latent image is formed are described in JP-A No. 7013, No. 12-T/13J, and JP-A No. 41/7! It is described in various publications and specifications, such as No. 1 and Coda No. 717.

On the other hand, the development or polymerization reaction in the development process of the above image forming method proceeds smoothly under alkaline conditions. For this reason, it is preferable to include a base or a base precursor as an image formation accelerator in the photosensitive layer of the photosensitive material. Regarding a photosensitive material characterized in that the photosensitive layer contains a base or a base precursor, Japanese Patent Application Laid-open No. 6
There is a description in Publication No. 2-Jtaoat.

When a base or base precursor is added to a photosensitive material using the photosensitive microcapsules described above, accommodating the base or base precursor in the photosensitive microcapsules improves the image formation promoting function of the base or base sinker. It is preferable in that respect.

% containing base precursors within microcapsules
Regarding the photosensitive material with this characteristic, please refer to Japanese Patent Application Laid-open No. 4-322! r
No. 1, Japanese Patent Publication No. 1/-2t3ttl, Japanese Patent Application No. 1/-/12
It is described in various publications such as No. 21j, Japanese Patent Application No. 1999/-/1,01at, and Mei I1fB Homare, in which a solid base precursor is housed in a microcapsule.

In this way, image formation is promoted by accommodating the base or base precursor under the internal pressure of the microcapsule, but
On the other hand, it has become a serious problem that this type of photosensitive material deteriorates over time and its responsiveness to light is impaired.

In the specification of the patent application No. 1999/-/jucoco/, Fi, a base precursor is embedded in a water-insoluble heat-fusible substance and housed in a photosensitive capsule, and the aging of the photosensitive material is disclosed. Although methods for suppressing deterioration have been described, they are not necessarily sufficient and further improvements have been sought.

<Problems to be Solved by the Invention> The purpose of the present invention is to provide a photosensitive material with excellent raw storage stability.The first purpose of the present invention is to provide a photosensitive material with high image durability in a short period of time. The object of the present invention is to provide a photosensitive material from which images with low stain can be obtained.

<Means for Solving the Problems> An object of the present invention is to provide silver halide, a reducing agent,
A photosensitive material having a photosensitive layer containing microcapsules containing a color image-forming substance, a polymerizable compound, and a base precursor further contains at least one compound represented by Noshiro CI) to []V) below. I was able to achieve it.

-Noshiro CI) In the formula, when Zken = /, a hydrogen atom, an alkyl group or -C
OY (Yld represents an alkyl group, aryl group, cycloalkyl group, alkoxy group, substituted amino group), n
-2 represents Zn or Ni.

R~1 also represents a hydrogen atom, a substituent, or a chemical bond.

However, this chemical bond is one that is bonded directly or via a λ to μ-valent residue to the compound represented by the general formula CI), the number of which corresponds to the valence of the residue.

Furthermore, adjacent substituents of R1-R5 are still R1-R5
and the above divalent to monovalent residues are linked to each other to form j-
An IQ ring may be formed.

-Noshiro [I[) R~R#-1t Represents a hydrogen atom, a substituent, or a chemical bond. However, this chemical bond is one that is bonded directly or via a λ to η valent residue to the compound represented by the general formula CII), the number of which corresponds to the valence of the residue.

Furthermore, ■(any substituents of 6 to R9 or any of R6 to 9 and the above 2 to μ-valent residues are connected to each other and a
, may form a 7-membered ring.

- Noshiro (1) %formula% During the ceremony.

W represents Ag, -8R'' or R11 when n=/, and represents Zn or N1 when n=ko.

R, R) i alkyl group, heterocyclic residue, -C8Y (Y is the same as defined in general formula [■]) or in the formula.

X represents an oxygen atom, a sulfur atom, or a substituted imino group (-N-).

(12 to B14 each represent an alkyl group or an aryl group).

-Noshiro [■] H R15N R16 In the formula, R, Is, and B16 each represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and these may be linked to each other to form a j-J membered ring. .

The compounds of the present invention will be explained in more detail.

In addition, in the following, an alkyl group, an aryl group, a heterocyclic group,
Cycloalkyl groups, alkenyl groups, alkoxy groups, and other substituents include those substituted with other substituents.

The compound represented by the general formula CI) will be explained.

In the formula, when Z ij n = /, hydrogen atom, alkyl group (e.g. methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, 5ee-butyl group, ter
t-butyl group, n- is methyl group, 5ee-1 methyl group%
tert-pentyl group, neopentyl group.

n-hexyl group, cyclohexyl group, n-octyl group (e.g. methyl group, tcrt-butyl group, etc.),
represents an aryl group (eg, phenyl group, etc.), a cycloalkyl group (eg, cyclohexyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, etc.), a substituted amino group (eg, dimethylamino group, anilino group, etc.).

Also, when n=-, Z represents Zn or Ni. Bl
~R5 represents a hydrogen atom, a substituent or a chemical bond. Examples of substituents include hydroxyl group, norogen atom, and alkyl group (
For example, tert-butyl group, n-butyl group, 1s
o-propyl group, neo is methyl group, tert-amyl group, methyl group, ethyl group, dimethylaminemethyl group, hydroxymethyl group, benzyl group, ethoxycarmenylmethyl group, diethylphosphorylmethyl group, carboxyethyl group, allyl group , 1so-butyl group, 5ee-hexyl group, n-octyl group, n-undecyl group, n-octadecyl group, etc.), cycloalkyl group (e.g., cyclo means methyl group, cyclohexyl group, etc.), aryl & (e.g., phenyl group) , naphthyl group, 3-hydroxyphenyl group, 3-chlorophenyl group, μ acetylaminophenyl group, 2-furyl group, 2-pyridyl group, etc.), alkoxy group (
(e.g., methoxy group, ethoxy group, etc.), aryloxy group (e.g., phenoxy group, 3-methoxyphenoxy group, etc.), alkylthio group (e.g., n-butylthio group, n-octylthio group, etc.), arylthio group (e.g., phenylthio group, etc.) group), heterocyclic amino group (e.g. -
-(2,4t,l,-)riazyl group (eg, methyl group, tert-butyl group, etc.), aryl group (eg, phenyl group, etc.), cycloalkyl group (eg, cyclohexyl group, etc.).

Alkoxy group (e.g. methoxy group, ethoxy group, etc.),
Substituted amine groups (e.g. dimethylamino groups).

Examples include (representing anilino group)).

When R1-R5 represents a chemical bond, the substitution position and 2
- R1-R5 of a compound of the general formula CI) of a number depending on its valency, either via monovalent residues or directly
Concatenate at any one substitution position.

At this time, the divalent to monovalent residues include, for example, (1) -CH
2-(2) -C-(3)-Open-CH3C3H7-n (6) +CH2O-CH2CH2)C(-CH2CH
2C-0SCH2)6 αO +CI(2CH2C-OCH2)C (-CH2O(2C-0CH2CH2-')7 S is R
Any one of -R and the above-described 2- to .mu.-valent residues may be bonded to each other to form a j-membered ring (such as a cyclohexene ring, a spirochroman ring, a chroman ring, or a coumaran ring).

Among the compounds represented by the general formula [■], preferred from the viewpoint of the effects of the present invention are the compounds represented by the general formula [I'].

General formula [1'] αQ a<　　　-5- a-　-　- αB-c- C[no CH2S-Chochu 2 Examples include.

Furthermore, one adjacent group of R1-R5 is also here,
B is -s --s-s --o--CH2-8-CH2
-1-so2- -s.

R, R, R, and R are each preferably a hydrogen atom or an alkyl group with a carbon number of 1 to 0, an aryl group, an aralkyl group, an alkylthio group, a halogen, an alkoxy group, an arylthio group, an aralcoquine group, an allyloxy group, -COR29 -NHCOR”9-NH8O2R
29, -8021"9 indicates +CH2-1A. B
25 represents a hydrogen atom, an alkyl group, or an aryl group, and R
, R each represents a hydrogen atom, an alkyl group, an aryl group, or a substituted j-membered or t-negative ring bonded to each other.

R represents a hydrogen atom or an alkyl group.

R29 represents an alkyl group or an aryl group, B50B,
31 is a hydrogen atom, an alkyl group, and an aryl group, respectively.

A heterocyclic group, an aralkyl group, or bonded to each other and having any of the above-mentioned substituents! A is a negative or ha negative heterocycle, and A is an ester group.Next, general formula [n] will be explained. In the formula, X is represented.

R6-R9 represent a hydrogen atom, a substituent or a chemical bond.

Examples of substituents include alkyl groups (e.g., cochloroethyl group, n-hexyl group, n-octyl group, 1so-decyl group, methyl group, dodecyl group, octadecyl group, etc.), cycloalkyl groups (e.g., cyclohexyl group, etc.), Done-
(eg, phenyl group, tolyl group, 3-methoxyphenyl group, n-nonylphenyl group, etc.).

When R6-R9 represents a chemical bond, the substitution position and
Directly or via F'iλ~μ-valent residues, B'6 of a number of other compounds of the general formula CI) depending on their valences.
~R9 is connected at any seven substitution positions).

Furthermore, any two of R6-R9 may be mutually or the above two.
- May be linked with a tetravalent residue to form a,4 negative ring.

Next, general formula CII[) will be explained. In the formula, W is n
When = /, it represents -8RII, R11, and when n = J, it represents Zn%Ni. RIOlRll is an alkyl group (
(e.g., dodecyloxycarbonylethyl group, octadecyloxycarbonylethyl group, etc.), heterocyclic residues (e.g., benzimidazolyl group, optionally substituted alkyl groups (e.g., methyl group, n-butyl group, etc.), aryl represents a group (such as a phenyl group).

Next, the general formula (■) will be explained. During the ceremony.

R, RFi alkyl group (e.g. methyl group, ethyl group, etc.), cycloalkyl group (e.g. cyclohexyl group, etc.)
, represents an alkenyl group (e.g. propenyl group, etc.), an aryl group (e.g. phenyl group, naphthyl group, etc.),
These may be linked to each other to form a j-1 negative ring.

The above-mentioned compounds - Noshiro CI) to []V) are conventionally known compounds as antioxidants, such as those described in "Organic Oxidation Reaction" by Yoshio Kamiya (Gihodo/Li 73).

Detailed information can be found in ``Antioxidant Handbook'' by Saruwatari, Nishino, and Tabata (Taiseisha/Ri7J) and ``Theory and Practice of Antioxidants'' by Kajimoto et al. (Sankabo/Riru).

Specific examples of compounds represented by general formulas [1) to (fV) are listed below.

Example of general formula [1] Shi4Mg-n 1O1 /7 Q(3 3t 33° 4A 3 ma t z H H JJ7 J. tt μ7 t2 t44 jQ.

! l ! Hiroshi jJ: ! 6゜ IA (n-Cl2H250YP-OH tt.

P+α? xsH37)3 61r.

P(-8Ct2H2s)a t Example of general formula (II) L 0℃4H9)3 z P+0C6H17-n)3 to.

P+0c12H25)3 A/.

P(-OCH2CHCH2Q!)3 α j t Example of general formula [■] 7 and 75! (Et2N-c-s\Ni tri S+a(2cH2cO2c18H37)2riO 8+Cf'(2a'(2CO2C13H27)2ri/2 H3 S+CH-a (2C02C18H37) 2 solutions tyu G! f7゜ 8% CH2CH2C02C12H25)2IrIr.

S+c) (2cH2C02C14H29)2ri6° ri7 S+CH2CI(2CO2H)2 Example of general formula CIV) begging 100° IO3゜ 101° 0IA IOA.

／　／　／.

//2 The amount of the above compound added is 0.0 of the reducing agent in 1 molar ratio.
It is preferably about 0/-100 times, and more preferably about 0.0/-/D times.

Also, for polymerizable compounds, the molar ratio is 0.000/-/
About twice as much is preferable, and 0.00j to O0! More preferably, it is about double that.

It is desirable that the compound of the present invention has a lower silver halide reducing power than the reducing agent used in combination.

These compounds are known and can be obtained as commercially available products, or can be synthesized and used by known methods.

The above compounds can be accommodated in microcapsules, and a photosensitive layer and an intermediate layer outside the microcapsules.

It may be added to any layer other than the protective layer. As for its addition method, it may be used by dissolving it in an organic solvent such as a polymerizable compound, or it may be used as a fine particle dispersion using the solid dispersion method described in JP-A No. 74NJO. .

<Detailed Description of the Invention> Below, silver halide used in the photosensitive material of the present invention,
The reducing agent, color image forming substance, polymerizable compound, base precursor, microcapsule, and support will be explained in detail.

The light-sensitive material of the present invention includes silver chloride, silver chloride,
Any grains of silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide can be used.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and dodecahedrons, those with irregular crystal systems such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.01 micron or less, or large grains with a projected area diameter of up to about 10 microns, and may be used in polydisperse emulsions or in U.S. Pat.
Monodisperse emulsions such as those described in British Patent No. 574,628, British Patent No. 3.655.394 and British Patent No. 1,413.748 may also be used.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
, 434°226, 4,414,310, 4,
433.048, 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. Furthermore, two or more types of silver halide grains having different halogen compositions, crystal habits, grain sizes, etc. can also be used together.

Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) No.

17643 (December 1978), pp. 22-23,
1. Emulsion preparation
on and types)”, and k18716
(November 1979), p. 648, etc.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Nα1
7643 and Nα18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Additive type RD 17643 RD 187
16 Chemical sensitizers Page 23 Page 648 Right column Sensitivity enhancers Dotan photosensitizers
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 Right column Antifoggant 24~
Page 25, page 649, right column ~ and stabilizer The above-mentioned silver halide grains include Japanese Patent Application Laid-Open No. 63-6
It is preferable to use silver halide grains having a relatively low fog value, such as the light-sensitive material described in Japanese Patent No. 8830.

In order to uniformly contain silver halide in the microcapsules, it is preferable that a copolymer consisting of a hydrophilic repeating unit and a hydrophobic repeating unit be dissolved in the polymerizable compound. For details, please refer to JP-A-62-20
There are descriptions in Japanese Patent Application No. 9450, No. 63-287844, and Japanese Patent Application No. 1-37782.

The reducing agent that can be used in the light-sensitive material of the present invention 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 above reducing agents include hydroquinones, catechols, p
-Aminophenols, p-phinidine diamines, 3
-Vyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4゜5
-dihydroxy-6-aminopyrimidines, reductones, amyl reductones, 0- or p-sulfonamidophenols, 0- or p-sulfonamidonaphthols, 2,4-disulfonamidophenols, 2,
4-disulfonamide naphthols, 0- or p-acylaminophenols, 2-sulfonamide indanones, 4-sulfonamide-5-pyrazolones, 3-sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, Examples include sulfonamide pyrazolotriazoles, α-sulfonamide ketones, and hydrazines. 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, 1-phenyl-3-pyrazolidones, hydroquinones, and sulfonamidophenols are particularly preferred as reducing agents.

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.
Publications No. 1-228441 and JP-A-62-7
No. 0836, No. 62-86354, No. 62-8635
No. 5, No. 62-206540, No. 62-264041
No. 62-109437, No. 63-254442, Japanese Patent Application No. 63-97379, No. 63-296774, No. 63-296775, Japanese Patent Application No. 1-27175,
1-54101, 1-91162, 1-90
It is described in publications such as No. 087 and specifications. (Including those described as developing agents or hydrazine derivatives) Also, regarding the above-mentioned reducing agents, see "Th
e Theory of the Photography
hicProcess” 4th edition, pp. 291-334 (1
977) Research Disclosure Magazine Vat,
170° No. 17029 (pages 9-15) of June 1978, and No. 17643 (pages 22-31) of the same magazine Vol. 1.176. December 1978. Also,
As in the photosensitive material described in JP-A-62-210446, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base may be used in place of the reducing agent. The reducing agents and reducing agent precursors described in each of the above-mentioned publications, specifications, and literature can also be effectively used in the photosensitive material used in this specification. Therefore, "reducing agent 1" in this specification includes the reducing agents and reducing agent precursors described in each of the above-mentioned publications and literature.

Among these reducing agents, those having basicity that form salts with acids can also be used in the form of salts with appropriate acids.

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 (
The oxidized form of the first reducing agent produced by the reduction of the first reducing agent (and/or organic silver salt) causes the polymerization of the polymerizable compound (or suppresses the polymerization) through a redox reaction with other reducing agents coexisting. ), etc. can be considered. 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 above reducing agent are shown below.

C 6H53 He(t) CH.

2H5 C H33 1-t3(.

C) 1B The amount of the reducing agent added can vary widely, but is generally 0.1 to 1500 mol%, preferably 10 to 1500 mol%, based on the silver salt.
It is 300 mol%.

There are no particular limitations on the color image-forming substance that can be used in the light-sensitive material of the present invention (although materials with various types of layers can be used).

i.e. substances that are themselves colored (dyes and pigments)
Also, substances (color formers) that are colorless or pale in themselves but develop color when exposed to external energy (heating, pressure, light irradiation, etc.) or when they come into contact with another component (color developer) are also color image forming substances. include.

As the color image forming substance of the present invention, JP-A-62-187
As described in Japanese Patent Application No. 346, dyes and pigments that have excellent image stability and are colored themselves are preferred.

As the pigment used in the present invention, in addition to commercially available pigments, known pigments described in various literatures can be used. Regarding literature, see Color Index (C1,) Handbook, ``
Latest Raw Materials Handbook” edited by Japan Pigment Technology Association (published in 1977),
"Latest Pigment Application Technology JCMC Publishing (published in 1986),"
Examples include Printing Ink Technology J (CMC Publishing, published in 1984).

By color, the types of pigments include white pigments, black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple raw materials, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and others.
Included are polymer-bound dyes.

Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, and isoindolinone pigments. For dyeing, lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic raw materials, etc. can be used.

The pigment that can be used in the present invention may be the above-mentioned naked pigment, or may be a pigment that has been subjected to a surface treatment. Surface treatment methods include surface coating with resin or wax;
Possible methods include attaching a surfactant and bonding a reactive substance (for example, a silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, which are described in the following documents.

Properties and Applications of Metallic Soaps (Terashobo) Printing Ink Technology (CMC Publishing, 1984) Latest Pigment Application Technology (CMC Publishing, 1986) The particle size of the pigment that can be used in the present invention is determined by the following after being dispersed in a polymerizable compound: 0.01μ～
It is preferably in the lOμ range, and more preferably in the 0.05 to 1μ range.

The amount of pigment is 10 to 60 parts by weight per 100 parts by weight of the polymerizable compound.
It is preferable to use parts by weight.

As a method for dispersing the pigment into the polymerizable compound, known dispersion techniques used in ink production, toner production, etc. can be used.

Examples of the dispersing machine include a sand mill, an attriter pearl mill, a super mill, a ball mill, an impeller, a desparzer-1KD mill, a colloid mill, a ditetron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

The polymerizable compound used in the photosensitive material is generally a compound having addition polymerizability or ring-opening polymerizability, and the solubility of the base precursor used is preferably 0.01% or less at room temperature. Compounds with addition polymerizability include compounds with ethylenically unsaturated groups, compounds with ring-opening polymerizability include compounds with epoxy groups, etc.
Particularly preferred are compounds having ethylenically unsaturated groups.

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, and ethoxynidoxy. Ethyl acrylate, tricyclodecanyloxyacrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, trimethylolpropane triacrylate,
Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylated bisphenol A diacrylate, 2-(2-hydroxy-
1,1-dimethylethyl)-5-hydroxymethyl-5
-ethyl-1,3-dioxane diacrylate, 2-(
2-hydroxy-1,1-dimethylethyl)-5,5-
Dihydroxymethyl-1,3-dioxane triacrylate, doria acrylate of propylene oxide adduct of trimethylolpropane, hexaacrylate of caprolactone adduct of dipentaerythritol, polyacrylate of hydroxy polyether, polynistyl acrylate and polyurethane acrylate, etc. can be mentioned.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentanyrythritol trimethacrylate, Examples include erythritol tetramethacrylate and polyoxyalkylenated bisphenol A dimethacrylate.

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-62-210445. 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 can also be used as a polymerizable compound.

The base precursors that can be used in the photosensitive material of the present invention include base precursors of inorganic bases and organic bases (
(decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) can be used.

Preferred base precursors include JP-A-59-18
No. 0549, No. 59-180537, No. 59 (952
No. 37, No. 61-32844, No. 61-36743, No. 61-51140, No. 61-52638, No. 6
No. 1-52639, No. 61-53631, No. 61-5
No. 3634, No. 61-53635, No. 61-5363
No. 6, No. 61-53637, No. 61-53638,
No. 61-53639, No. 61-53640, No. 61
-55644, 61-55645, 61-55
No. 646, No. 61-84640, No. 61-10724
No. 0, No. 61-219950, No. 61-251840
No. 61-252544, No. 61-313431, No. 63-316740, No. 64-68746, and Japanese Patent Application No. 62-209138, which describe organic acids and bases that are decarboxylated by heating. Salt, also JP-A-59-157637, JP-A-59-166943, JP-A No. 6
Examples include compounds that eliminate bases upon heating as described in Publication No. 3-96159.

As the base precursor used in the photosensitive material of the present invention, the following base precursor consisting of a salt of a carboxylic acid and an organic base, which has a solubility in water at 25°C of 1% or less, is used to accommodate it in microcapsules. preferable.

(a) The base precursor consists of a salt of a carboxylic acid and an organic base, and the organic base has a partial structure corresponding to an atomic group obtained by removing one or two hydrogen atoms from an amidine represented by the following formula (1). It is a diacid to tetradisperse base consisting of from four to four structural groups and the structural group of the partial structure.

[In the above formula (1), Rl, R'', RI + and R'' 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. each group may have one or more substituents), and Rl l, Rlt, Rl
(b) The base precursor is a salt of a carboxylic acid and an organic base. The organic base 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 (2), and a diamic acid base consisting of a linking group of the partial structures. It is an acid or a tetrabasic.

R” / [In the above formula (2), R”% R”, R”R” and R” each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group and Represents a monovalent group selected from the group consisting of heterocyclic residues (each group may have one or more substituents), Sosite, R", R"SR", R"O, J:
and R” may be bonded to each other to form a three- or six-membered nitrogen-containing heterocycle.]For the base precursors (a) and (b) above, , JP-A-63-31670 and JP-A-64, respectively.
It is described in detail in JP-A-68746.

Specific examples of these base precursors are shown below, but are not limited thereto.

2 2 z = = z z \/ Hibiki Somura δ /\ = = z z There are no particular restrictions on the microcapsules of the present invention, and various known techniques can be applied.

Examples include U.S. Pat.
No. 800458 Method using coacervation of hydrophilic wall-forming material described in each specification: US Patent No. 32871
54 and British Patent No. 990443, and the interfacial polymerization method described in Japanese Patent Publication Nos. 38-19574, 42-446, and 42-771; U.S. Patent Nos. 3418250 and 3660304. 1
Method by precipitation of the described polymer; US Pat. No. 3,796
Methods using isocyanate-polyol wall materials described in '669; Methods using isocyanate wall materials described in U.S. Pat. No. 3,914,511; U.S. Pat.
No. 001140, No. 4087376, No. 4089
No. 802 and No. 4025455, JP-A-62-2
No. 09439, JP-A-64-91131, JP-A-1-
There is a method using an amine/aldehyde resin described in No. 154140 and Japanese Patent Application No. 63-241635.

Examples of amino aldehyde resins include urea-formaldehyde resin, urea-formaldehyde-resorcinol resin, melamine-formaldehyde resin, acetoguanamine-formaldehyde resin, benzoguanamine-formaldehyde resin, and the like.

Also, Japanese Patent Publication No. 36-9168 and Japanese Patent Publication No. 51-90
In 5it by polymerization of monomers described in each revolution in No. 79
u method; British Patent No. 927807 and British Patent No. 965
No. 074 Polymerization dispersion cooling method described in each specification: US Patent No. 3
Examples include the spray drying method described in No. 111407 and British Patent No. 930422. Although the method of microcapsulating oil droplets of a polymerizable compound is not limited to the above, a method of emulsifying a core substance and then forming a polymer film as a microcapsule wall is preferable. Regarding photosensitive materials using microcapsules with outer shells made of polyamide resin and/or polyester resin, Japanese Patent Application Laid-Open No. 62-209437 describes microcapsules with outer shells made of polyurea resin and/or polyurethane resin. The photosensitive material used is described in JP-A-62-209438, and the photo-sensitive material using microcapsules having an outer shell made of gelatin is described in JP-A-62-209440. Regarding photosensitive materials using microcapsules, see JP-A No. 62-209441, and regarding photosensitive materials using microcapsules having a composite resin outer shell containing polyamide resin and polyurea resin, see JP-A No. 62-209447. For photosensitive materials using microcapsules having a composite resin outer shell containing polyurethane resin and polyester resin, JP-A-62-
Each of these is described in JP-A No. 209442.

In the present invention, it is particularly preferable to use a melamine formaldehyde resin, since it is possible to obtain highly dense capsules.

In addition, Japanese Patent Application No. 1-37782 discloses that in order to obtain capsules with particularly excellent wall density, a reaction product of a water-soluble polymer having a sulfinic acid group and a polymerizable compound having an ethylenically unsaturated group is used. A microcapsule is disclosed in which a polymer wall of a high molecular compound is provided around a membrane.
Preferred for the present invention.

In addition, when using aminoaldehyde-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.

The average particle diameter of the microcapsules is preferably 3 to 20 μm. 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 microcapsule is
As in the photosensitive material described in Publication No. 6, it is preferable that the particle diameter is within a certain range.

In addition, when storing silver halide in microcapsules, it is preferable that the average particle size of the silver halide particles mentioned above is set to 1/5 or less, and preferably 1/10 or less, of the average size of the microcapsules. 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.

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.

In the present invention, in order to accommodate the base precursor in microcapsules, a photosensitive composition in which the base precursor is directly solid-dispersed in a polymerizable compound may be used (JP-A-64-32251, JP-A-1 -263641
It is particularly preferable to use a photosensitive composition described in each publication, in which a base precursor is dispersed in water and emulsified in a polymerizable compound. (Japanese Patent Application Laid-open No. 63-218964, Japanese Patent Application No. 1-182245, Japanese Patent Application No. 1-160148
(References in each publication and specification) Here, when dispersing the base precursor in water, it is preferable to use a nonionic or amphoteric water-soluble polymer.

Examples of nonionic water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-coacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, and methylcellulose. etc. can be mentioned.

Moreover, as an amphoteric water-soluble polymer, seratin can be mentioned.

The above water-soluble polymer has 0
．． It is preferably contained in a proportion of 1 to 100% by weight, and more preferably contained in a proportion of 1 to 50% by weight. Further, the base precursor is preferably contained in an amount of 5 to 60% by weight, and 10 to 5% by weight based on the dispersion.
More preferably, it is contained in an amount of 0% by weight. Also,
The base precursor is preferably contained in a proportion of 2 to 50% by weight, more preferably 5 to 30% by weight, based on the polymerizable compound.

In producing the photosensitive microcapsules of the present invention, an oily liquid consisting of a polymerizable compound containing silver halide, a reducing agent, a color image-forming substance, and a base precursor is dispersed in an aqueous medium to form the outer shell of the capsule. Preferably, the aqueous medium contains a nonionic water-soluble polymer.

In this case, the oily liquid containing the polymerizable compound is preferably 10 to 120% by weight, more preferably 20 to 90% by weight, based on the aqueous medium.

Examples of nonionic water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-coacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, and methylcellulose. etc. can be mentioned.

In addition, in order to efficiently disperse a hydrophobic core substance containing an oily liquid into microdroplets in an aqueous medium, it is necessary to use an anionic water-soluble polymer in combination with the above-mentioned nonionic water-soluble polymer. preferable.

In this case, the concentration of the anionic water-soluble polymer in the aqueous medium is preferably in the range of 0.01 to 5% by weight, more preferably in the range of 0.1 to 2% by weight.

Examples of anionic water-soluble polymers include polystyrene sulfinic acid, styrene sulfinate copolymers,
Examples include polystyrene sulfonate, styrene sulfonic acid copolymer, polyvinyl sulfate ester salt, polyvinyl sulfonate, maleic anhydride/styrene copolymer, maleic anhydride/isobutylene copolymer, and the like.

In the above case, it is particularly preferable to use a nonionic water-soluble polymer and a water-soluble polymer having a small amount of sulfinic acid groups together.

In addition, in order to reduce the solubility of the base precursor in the polymerizable compound, polymerizable compounds such as polyethylene glycol, polypropylene glycol, benzoic acid amide, cyclohexyl urea, octyl alcohol, dodecyl alcohol, stearyl alcohol, stearamide, etc. and 10H1-Sot N
It is also possible to add compounds having hydrophilic groups such as H,, CONH, and -NHCONH.

Although there are no particular limitations on the support for the photosensitive material of the present invention,
It is preferable to use a material that can withstand the processing temperature during development.

Materials that can be used for the support include glass, paper, high quality paper, baryta paper, coated paper, cast coated paper,
Synthetic paper, metals and their analogs, polyester, polyethylene, polypropylene, cellulose acetate, cellulose ester, polyvinyl acetal, polystyrene,
Examples include films such as polycarbonate, polyethylene terephthalate, and polyimide, and papers laminated with resin materials and polymers such as polyethylene. When a polymer film is used as a support, it is preferable to provide an undercoat layer as described in JP-A-61-113058.

In addition, when using a porous support such as paper, Japanese Patent Application Laid-Open No. 62
-209529, 63-38934, 63-8
No. 1339, No. 63-81340, No. 63-9794
Supports described in publications such as No. 1, No. 64-88543, and No. 64-88544 can be used.

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. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc. synthetic polymeric materials such as water-soluble polyvinyl compounds.

Other synthetic polymeric substances include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photographic materials, among others. Incidentally, a photosensitive material using a binder is described in JP-A-61-6906.2. Furthermore, a photosensitive material using a binder together with microcapsules is described in JP-A-62-2095.25.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide.

Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the organic silver salt oxidizing agent described above include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in columns 53 and the like. Furthermore, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235, and JP-A-61-24904
Acetylene silver described in the publications No. 4 and No. 64-57256 is also useful. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 1■ to Log/rr in terms of silver.
r is appropriate.

The anti-smudge agent used in the photosensitive material is preferably a particulate material that is solid at room temperature. As a specific example, British Patent No. 1
Starch particles described in the specification of No. 232347, fine polymer powders described in the specification of US Pat. No. 3,625,736, etc., microcapsule particles containing no color former as described in the specification of British Patent No. 1,235,991, etc., and US Pat. No. 2,711,375. Examples include inorganic particles such as cellulose fine powder, talc, kaolin, bentonite, waxite, zinc oxide, titanium oxide, and alumina. The average particle size of the particles is preferably in the range of 3 to 50 μm, more preferably in the range of 5 to 40 μm in volume average diameter. As mentioned above, when the oil droplets of the polymerizable compound are in the form of microcapsules, it is more effective if the particles are larger than the microcapsules.

Various image formation accelerators can be used in the photosensitive material.

Image formation accelerators have functions such as ■ promoting the movement of bases or base precursors, promoting the reaction between reducing agents and silver salts, and promoting immobilization of dye-donating substances through polymerization. are classified into the aforementioned bases or base precursors, nucleophilic compounds, oils, heat solvents, surfactants, compounds that interact with silver or silver salts, compounds that have an oxygen scavenging function, and the like. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. For more information on these, see U.S. Pat.
, No. 678, 739, columns 38-40, JP-A-62-20
It is described in publications such as No. 9443 and specifications.

In photosensitive materials, in systems that polymerize polymerizable compounds in areas where latent images of silver halide are not formed, the purpose is to initiate polymerization or to polymerize unpolymerized polymerizable compounds after image transfer. A thermal or photopolymerization initiator can be used.

Examples of thermal polymerization initiators include azo compounds, organic peroxides,
Examples include inorganic peroxides and sulfinic acids. Details of these are described in pages 6 to 18 of "Addition Polymerization/Ring-Opening Polymerization J" (Imori Publishing, 1983) edited by the Society of Polymer Science and the Editorial Committee of Polymer Experimental Science.

Examples of photopolymerization initiators include benzophenones, acetophenones, benzoins, thioxansones, and the like. For details on these, see “Ultraviolet curing system J (1989, General Technology Center), Vol.
It is described on pages 3 to 147, etc.

Various surfactants can be used in photosensitive materials for the purposes of coating aids, improving peelability, improving slipperiness, preventing electrification, accelerating development, and the like. Specific examples of surfactants are given in JP-A-62-1
It is described in No. 73463, No. 62-183457, etc.

An antistatic agent can be used in the photosensitive material for the purpose of preventing static electricity.

Research Disclosure Magazine 1978 as an antistatic agent
It is described in No. 17643 (page 27) of November 2013.

A dye or pigment may be added to the photosensitive layer of the photosensitive material for the purpose of preventing halation or irradiation. JP-A-63-29748 describes a photosensitive material in which a white pigment is added to the photosensitive layer.

When the photosensitive layer of the photosensitive material uses the above-mentioned microcapsules, the microcapsules may contain a dye that can be decolored by heating or light irradiation. The dye having the property of being decolored by heating or light irradiation can function as a yellow filter in conventional silver salt photography.

Regarding photosensitive materials using dyes having the property of decolorizing by heating or light irradiation as mentioned above, Japanese Patent Application Laid-Open No. 63-9
There is a description in Publication No. 74940.

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. 24. A water-soluble vinyl polymer may be adsorbed onto the silver halide grains described above. A photosensitive material using a water-soluble vinyl polymer as described above is described in JP-A-62-91652.

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 for 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 anti-curl layer, a peeling layer,
Examples include a cover sheet, a protective layer, an antihalation layer (colored layer), and the like.

Instead of using an image-receiving material as a method of using the photosensitive material, the above image-receiving layer may be provided on the photosensitive material and an image may be formed on this layer. The image-receiving layer provided on the photosensitive material can have the same structure as the image-receiving layer provided on the image-receiving material.

Regarding photosensitive materials using a heat generating layer, Japanese Patent Application Laid-open No. 1983
-294434, for photosensitive materials provided with a cover sheet or protective layer, see JP-A-62-210447, and for photosensitive materials provided with a colored layer as an antihalation layer, JP-A-63-101842. , respectively. Furthermore, examples of other auxiliary layers and their usage are also described in the applications relating to the above-mentioned series of light-sensitive materials.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD176
43 (1978) pages 24-25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and phosphoric acids described in JP-A-59-111636. Metal salts thereof, acetylene compounds described in JP-A No. 62-87957, and the like can be used.

For photosensitive materials, there are various processing temperatures and processing times during development.
Various development stoppers can be used for the purpose of always obtaining a constant image.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds that undergo a substitution reaction with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and precursors thereof.

For more details, see JP-A No. 62-253159 (31) - (
32), Japanese Patent Application No. 1-72479, Japanese Patent Application No. 1-3471, etc.

The photosensitive material of the present invention is used to form an image according to the usage method described below, and an image-receiving material is generally used.

The image receiving material will be explained below.

The image-receiving material may be a support only, or an image-receiving layer may be provided on the support.

There are no particular restrictions on the support for the image-receiving material, and like the supports for photosensitive materials, glass, paper, high-quality paper, baryta paper, coated paper, cast coated paper, synthetic paper, metals and their analogues, and polyester can be used. , polyethylene, polypropylene, acetyl cellulose, cellulose ester, polyvinyl acecool, polystyrene, polycarbonate,
Examples include films such as polyethylene terephthalate, and papers laminated with resin materials and polymers such as polyethylene.

Note that when a porous material such as paper is used as the support for the image-receiving material, it is preferable that the support has a certain level of smoothness as in the image-receiving material described in JP-A-62-209530. Further, an image receiving material using a transparent support is described in JP-A-62-209531.

The image-receiving layer of the image-receiving material is composed of a white pigment, a binder, and other additives, and the white pigment itself or the voids between the particles of the white pigment increase the receptivity of the polymerizable compound.

Examples of white pigments used in the image-receiving layer include inorganic white pigments such as oxides such as silicon oxide, titanium oxide, zinc oxide, magnesium oxide, and aluminum oxide, magnesium sulfate, barium sulfate, calcium sulfate, magnesium carbonate, and barium carbonate. , alkaline earth metal salts such as calcium carbonate, calcium silicate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, etc., as well as aluminum silicate, aluminum hydroxide, zinc sulfide, various clays, talc, kaolin, zeolite, Examples include acid clay, activated clay, and glass.

As organic white pigments, polyethylene, polystyrene,
Examples include benzoguanamine resin, urea-formalin resin, melamine-formalin resin, and polyamide resin.

These white pigments may be used alone or in combination, but those with high oil absorption for polymerizable compounds are preferred.

Further, as the binder used in the image-receiving layer of the present invention, water-soluble polymers, polymer latexes, polymers soluble in organic solvents, and the like can be used. As a water-soluble polymer,
For example, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, and methyl cellulose, proteins such as gelatin, phthalated gelatin, casein, and ovalbumin, starches such as dextrin and etherified starch, polyvinyl alcohol, polyvinyl alcohol partial acetal, and poly-N- vinylpyrrolidone,
Polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole,
Examples include synthetic polymers such as polystyrene sulfonic acid, locust bean gum, pullulan, gum arabic, and sodium alginate.

Examples of the polymer latex include styrene-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, acrylic ester and/or
Alternatively, methacrylic acid ester polymers or copolymer latexes, ethylene/vinyl acetate copolymer latexes, etc. may be mentioned.

Examples of polymers soluble in organic solvents include polyester resins, polyurethane resins, polyvinyl chloride resins, polyacrylonitrile resins, and the like.

The above-mentioned binders can be used in combination of two or more types, and can also be used in combination in such a ratio that the two types of binders cause phase separation. An example of such usage is described in Japanese Patent Application Laid-open No. 1-154789.

The average particle size of the white pigment is 0.1 to 20μ, preferably 0.1 to 10μ, and the coating amount is 0.1 to 60g.
1 Preferably, it is in the range of 0.5 g to 30 g. The weight ratio of white pigment to binder is 1 part pigment to 0 part binder.
．． The range is preferably from 0.01 to 0.4, and more preferably from 0.03 to 0.3.

In addition to the binder and the white pigment, the image-receiving layer can contain various additives as described below.

For example, when using a coloring system consisting of a color former and a color developer, the image receiving layer can contain the color developer. Typical color developers include phenols, organic acids or their salts, or esters, but when a leuco dye is used as a color image forming substance, zinc salts of salicylic acid derivatives are preferred; Among them, 3,5-di-α-
Zinc methylbenzylsalicylate is preferred.

The above color developer is applied to the image-receiving layer at a concentration of 0. Preferably, the coating amount is in the range of 1 to 50 g/rrf.

More preferably, it is in the range of 0.5 to 20 g/m.

The image-receiving layer may contain a thermoplastic compound. When the image-receiving layer contains a thermoplastic compound, it is preferable that the image-receiving layer itself is constituted as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above structure has the advantage that it is easy to form a transferred image, and that a glossy image can be obtained by heating after image formation. The above thermoplastic compound is not particularly limited and can be arbitrarily selected from known plastic resins (plastics), waxes, and the like. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 20G00 or less. An image receiving material having an image receiving layer containing thermoplastic compound fine particles as described above is disclosed in Japanese Patent Application Laid-Open No. 62-2800.
No. 71 and No. 62-280739.

The image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In image formation using an image receiving material,
The color image-forming material is transferred along with the unpolymerized polymerizable compound. Therefore, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of smoothly proceeding with the curing process (fixing process) of the unpolymerized polymerizable compound. In addition,
For an image receiving material having an image receiving layer containing a photopolymerization initiator, see JP-A-62-161149, and for an image-receiving material having an image-receiving layer containing a thermal polymerization initiator, see JP-A-62-21.
Each is described in the No. 0444 publication.

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 latter method is particularly excellent for developing the photosensitive material of the present invention.

As the heating method in the above heat development treatment, various conventionally known methods can be used. In addition, like the photosensitive material described in JP-A 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, heat development may be performed while suppressing the amount of oxygen present in the photosensitive layer. The heating temperature is generally 50°C to 200°C, preferably 60°C to 16°C.
It is 0°C. The heating time is generally 1 second or more, preferably 1 second to 5 minutes, and more preferably 1 second to 1 minute.

The photosensitive material can be thermally developed as described above to polymerize the polymerizable compound in the areas where the silver halide latent image is formed or the areas where the silver halide latent image is not formed. In addition, if a polymerization inhibitor is generated in the area where the silver halide latent image is formed by reaction with a reducing agent, it may be added in advance to the photosensitive layer, preferably in microcapsules, to initiate thermal or photopolymerization. It is also possible to decompose the agent with heat or light to generate radicals in the same manner as - to polymerize the polymerizable compound in the area where the latent image of silver halide is not formed.

In this way, by pressing the photosensitive material and the image-receiving material, which have obtained a polymer image on the photosensitive layer, in a superimposed state,
The unpolymerized polymerizable compound can be transferred to an image-receiving material to obtain a color image on the image-receiving material.

As the above-mentioned pressurizing method, a conventionally known method can be used.

For example, the photosensitive material and the image-receiving material may be sandwiched between press plates such as a presser, or pressure may be applied while conveying them using a pressure roller such as a nip roll. Pressure may be applied intermittently using a dot impact device or the like.

Alternatively, highly pressurized air can be blown with an air gun or the like, or pressurized with an ultrasonic generator, piezoelectric element, or the like.

Photosensitive materials have many uses, such as color photographing and printing photosensitive materials, printing photosensitive materials, computer graphics/photocopying photosensitive materials, and copying machine photosensitive materials.

Example / Preparation of silver halide emulsion (ER-/) Aqueous gelatin solution (20 g of gelatin in 1 AOOtul of water)
and sodium chloride 0. Add Ig and pH 3 with /N sulfuric acid.
, z and kept warm at 4tz"c), 200 ml of an aqueous solution containing potassium bromide Ajg and a silver nitrate aqueous solution (100 g of silver nitrate dissolved in -00 ml of water).
were simultaneously added at equal flow rates over 30 minutes. This addition is finished! From the particle diameter, add sensitizing dye (SR-/), and after addition of nuclear sensitizing dye, add potassium iodide 2゜.
100 ml of an aqueous solution containing 0 g and a silver nitrate aqueous solution (water 1
0.00ml of silver nitrate. OJ, 2 g dissolved) was added at an equal flow rate over 5 minutes.

To this emulsion, 1,000 g of poly(isobutylene-monosodium co-maleate) was added and allowed to settle.

After washing with water and desalting, 3.4 g of gelatin was added and dissolved, and further 0.45 mg of sodium thiosulfate was added.
Chemical sensitization was performed for 2θ minutes at oc, and the average particle size was 0.
A monodisperse/tetrahedral silver iodobromide emulsion (ER-/) with a coefficient of variation of 24% (ER-/) a<tog was prepared.

Sensitizing dye (SR-/) Base cursor (BG-/) of lime-processed gelatin in a 100 ml dispersion container! Aqueous solution jug, ring group precursor (BG-/
) 3 j g, 10 ml of 1% aqueous solution of polyethylene glycol λ000 and diameter 0°, t ~ 0.77 m
100 ml of glass beads of m are added and dispersed for 30 minutes at 3000 revolutions per minute using a Dyno Mill to obtain particle sizes of i, o.
A solid dispersion (KB-/) of less than μm was obtained.

In 170 g of a polymerizable compound (MN-, 2) having the following structure, 3.0 g of Tsurusperse Rooo (trade name, manufactured by ICI) was dissolved, and 30 g of copper phthalocyania (manufactured by Tokyo Kasei ■) was dissolved.
were mixed and stirred for an hour using an Eiger motor mill (manufactured by Eiger Engineering Co., Ltd.) at ooo rotation for each molecule to obtain a dispersion (GC-/).

Polymerizable compound (N-r) Copolymer (/P-/) CH3C)]3 Pigment dispersion (GC-/) 4trg, copolymer with lower B pi structure (/P-/)/(SV-/ ), 20% by weight solution g was dissolved. Add (RD-/)2 to this solution.
3 g, stearyl alcohol jg, and 0.3 g of the following mercapto compound (FF-J). jt% methanol solution/, Og,
was added to obtain an oily liquid.

Silver halide emulsion (ER-/)j was added to this solution.

Add rg and solid dispersion (KB-/), add jo'
While keeping warm at C, use a homogenizer every minute/! 0
The mixture was stirred at 00 rpm for 5 minutes to obtain a W10 emulsion photosensitive composition (PR-/).

(SV-i) o+3-CH-C)120cH3H (RD-/) (FF-3) A /j% aqueous solution of the polymer (CoP-/) It, Og was added with 2% polymer (JP- r) 70g aqueous solution
The pH of the mixed solution was adjusted to 0. The above-mentioned photosensitive composition (PR-/) was added to this liquid mixture, and the mixture was stirred for 20 minutes at RO 0C and jooo rotations per minute using a Daysilver to obtain an emulsion in the form of a W10/Ai emulsion.

Separately, melamine/IA, formaldehyde 37 to #g
Add 20.0 g of % aqueous solution and 3 g of distilled water 7A to
The mixture was heated to a temperature of 100 m and stirred for a period of 50 m to obtain a transparent aqueous solution of a melamine/formaldehyde precondensate.

7.jg of the above W10/W emulsion/It t giC distilled water and 37.7g of this aqueous solution of melamine/formaldehyde initial condensate were added, and while keeping the temperature at λr 0C, the pH was adjusted to j, θ using 2N sulfuric acid. . This was then heated to Ao 0C over 30 minutes, and continued to be heated and stirred at tO 0 C for an additional 30 minutes. Then urea Ilo
Add 10.3 g of an aqueous solution of
．． ! Adjust rKp54, continue heating and stirring at Ao 0C for 10 minutes, cool to room temperature, and 1.2N hydroxide) IJ
A photosensitive microcapsule dispersion (CR-7) using a melamine-formaldehyde resin as a capsule wall material was prepared by adjusting the pH to x and jKgm using diluted sodium chloride.

Polymer (,2P-/) Potassium polyvinylbenzenesulfinate polymer (,
2P-, 2) +cH2-CH-) One taO (OAFg) photosensitive material in polyvinylpyrrolidone (
1) Creation of the photosensitive microcapsule dispersion (CR-/) 13
g, 5% aqueous solution of surfactant (WW-/)7. jg,
2.2 g of (WW-co)/CH aqueous solution, and PVA co-O
Add 20% aqueous solution of J (manufactured by Kuraray@), and add μO
Stirred at 0C for 30 minutes.

Add 3μ of this solution to polyvinylpyrrolidone-vinyl acetate.
Coated on a thickly coated polyethylene terephthalate film with a coating MAO ml/m2, to 0
The photosensitive material (1) of the present invention was prepared by drying at c.

(WW-/) (~VW-2) 2H5 CH2αJ2CH2CH-c4H9 Na03S-C”HCO2CH2CHC4Hg2H5 Preparation of photosensitive materials (2) to 01 Compound of the present invention (O) in photosensitive composition (P) L-/)
, (//), (tt), (3'0), (4J'), (&
Light-sensitive materials (2) to 01 were prepared in exactly the same manner except that 10 mmol of each of j), (J', ?), (r), and (106) were added.

Preparation of image receiving material Calcium carbonate (PC7oo, manufactured by Shiraishi Kogyo □□□3) r
Og, surfactant (Poise! 20. manufactured by Kao ■) /, Ag
, and water co/, uml were mixed and dispersed for 20 minutes at 2000 revolutions per minute using a Polytron disperser (PT10/3jt type, manufactured by Kinematica). This dispersion! -g, a 70% polyvinyl alcohol (PVA-//7, manufactured by Kuraray) aqueous solution jg, and a 10% aqueous solution 4<g of the surfactant (WW-/) were mixed, and further 22g of water was added. A coating solution for forming an image-receiving layer was prepared.

Weigh this coating solution and apply it to a paper support (jlI Og/m2).
Paper using a base paper having a fiber length distribution defined by JIS-P-4207 such that the sum of the weight % of the Kokumesh residue and the weight % of the μ-comesh residue is 30 to tO%. Support [JP-A-43-/rj23
(See Publication No. P)]) was coated evenly on the film to give jOml/m2, and then dried to 'C to prepare an image-receiving material.

Evaluation of transferred images Light-sensitive material (1) ~ α1 was transferred using a tungsten light bulb, and θ ~
Passed through a gray filter with a transmission density of 3.0 and a color temperature of 11. After exposure at 20,000 Iux for 7 seconds, the photosensitive material was placed on a hot plate heated to /zr0c, the support surface was brought into close contact with the photosensitive material, and heat development was performed for 2 seconds. Next, the light-sensitive material is stacked so that the image-receiving material and the q cloth surface are in contact with each other, and in this state, a weight of / 000 kg/m2
was passed through a pressure roller.

The image-receiving material was then peeled off from the photosensitive material to obtain a positive image on the image-receiving material. The cyan density of the obtained image was measured using a Macbeth reflection densitometer.

In addition, the photosensitive materials (11 to α1) were stored at to 0c for 3 days and after 7 days, the same evaluation was performed.

The results are shown in Table-/.

As is clear from Table 7, the photosensitive materials to which the compounds of the present invention were added produced images with high density and low stain, and were also found to have excellent shelf life.

Example 2 A silver halide emulsion (EB-/) was added to an aqueous solution of vM gelatin (gelatin/Jg and 0.1 g of sodium chloride in 7,500 ml of water, and the pH was adjusted to λ with sulfuric acid to jOoC. 300 ml of an aqueous solution containing potassium bromide/g and a silver nitrate aqueous solution (3 oom of water)
(silver nitrate/θOg dissolved in l) was simultaneously jCOD
Added at equal flow rate over minutes. Seven minutes after this addition was completed, 30 mg of a sensitizing dye (SB-7ea) was added, and from 75 minutes after the addition, 100 rrJ of an aqueous solution containing 2.2 g of potassium iodide and an aqueous solution of silver nitrate (water ioo
3 g of silver nitrate dissolved in ml) was added at equal Kik over j minutes.

To this emulsion, 7.2 g of poly(imbutynone-monosodium comaleate) was added to precipitate it, washed with water to desalt it, μg of gelatin was added and dissolved, and 0.1 mg of sodium thiosulfate was added. ,! l at 0°C! Monodisperse/μ-hedral silver iodobromide emulsion (EB-/) with an average grain size of 0.2-μm and a coefficient of variation of -0% after chemical sensitization for minutes.
460g was prepared.

Preparation of silver halide emulsion (EG-/) Gelatin aqueous solution (0 g of gelatin and 0.1 g of sodium chloride were added to 1600 ml of water, and the mixture was purified with IN sulfuric acid.
(adjusted to H3.2 and kept warm at ur 0c) was heated with equal wave sound for 30 minutes simultaneously with Oθml of an aqueous solution containing 7/g of potassium bromide and an aqueous silver nitrate solution (100g of silver nitrate dissolved in 200ml of water). Added with. One minute after this addition was completed, sensitizing dye (8G-/')a
g.

70 minutes after the addition of the sensitizing dye, 100 ml of an aqueous solution containing potassium iodide λ, g and a silver nitrate aqueous solution (nitric acid @3 g dissolved in 100 ml of water) were simultaneously added over j minutes. Add poly(isobutylene-monosodium co-maleate) to this emulsion.
g, sedimented, washed with water and desalted, gelatin μ
, add Mag and dissolve, and then add 0.7 ml of sodium thiosulfate.
Add mg, to oc is 7! Chemically sensitized for 1 minute, average particle size 0.72 μm coefficient of variation, 2% monodisperse/
A dihedral silver iodobromide emulsion (EG −/)μ&Og was prepared.

Sensitizing dye (SB-/) Sensitizing dye (so-y) Preparation example/described polymerizable compound (λ4N-, 2) of pigment dispersion (GY-/) Cojjg
45 g of Microlith Yellow gOA (trade name, manufactured by Ciba Geigy) was mixed with the mixture, and the mixture was heated and stirred at RO 0C for 20 minutes to obtain a dispersion (OY-/).

Mix 45 g of Microrethread JRA (trade name, manufactured by Ciba Geigy) with jjjg of polymerizable compound (MN-2), heat and stir at RO 0C for 0 minutes to obtain a dispersion (G
M-/) was obtained.

Copolymer (/P-/) to 45g of pigment dispersion (GY-/)
Pg, (R
D-/ ) 2.3g, stearyl alcohol jg, (F
A 0.3 g/methanol solution of F-J) was added and dissolved to prepare an oily solution.

Add 3, ♂g of silver halide emulsion (EG-/) to this solution,
Add zμg of solid dispersion (KB-/).

The mixture was stirred for 5 minutes using a homogenizer at a rotational speed of i/min and rooo while keeping the temperature at 0°C to obtain a photosensitive composition (PB-/) of 10 emulsion.

Preparation of photosensitive composition (PG-/) Pigment dispersion (GM-/) 4t j g copolymer=
(/P-/) (SV-i) % (mat) solution g, (RD-/) 2,3 g, (FF-3
) of methanol 01. tti solution/Og was added and dissolved to prepare an oily solution.

Add silver halide emulsion (EG-/) to this solution. .

, rg and 2 μg of solid dispersion (KB-i) were added.

The mixture was stirred for 5 minutes at 3000 revolutions per minute using a homogenizer while keeping the temperature at 0°C to obtain a W10 emulsion photosensitive composition (PG-/).

The photosensitive composition (PB −/ ) (PG-i) was converted into (P
The photosensitive microcapsule dispersion (CB-/), (C
G-/) was prepared.

Preparation of photosensitive material 01) The above photosensitive microcapsules! [(CB-/), (
CG-/) was mixed with each /, Og, and the photosensitive microcapsule dispersion (CR-/) used to create the photosensitive material (1) was mixed with Ag, and the surfactant used in Example / (W)～-1) /CH aqueous solution 0, tg, Surflon S
/// (piece name, made by Asahi Glass Suspension 3) 3-chi aqueous solution o,
7g of PVA, 2os (manufactured by Kuraray ■), 1μg of 20ti aqueous solution O, and 0.6g of distilled water were added, and αo 0C
The mixture was stirred for 30 minutes.

This solution was mixed with polyvinylpyrrolidone-co-vinyl acetate for 3
The photosensitive material α) of the present invention was prepared by coating a polyethylene terephthalate film with a thickness of 2 μ and having a thickness of 1-7 o ml/m 2 and drying at Ao 0C.

No photosensitive material! Preparation of J and 0(Photosensitive microcapsule dispersion used in photosensitive material 0υ)
CB-i), (C()-i) and (CI'L-
A photosensitive microcapsule dispersion (CB2) in which / OS l) mol of the compound (7) of the present invention was added in / ),
Photosensitive material 1 negative z was prepared in exactly the same manner as Fi photosensitive material 0]) except that (CG-λ) and (CR-, 2) were used. Furthermore, a photosensitive material 0Q was similarly prepared using capsule dispersion liquids each containing 10 mmol of the compound of the present invention (coj).

Transcription li! Evaluation of images The Dmax and Dmin of the photosensitive materials 09 to 0 were measured by processing in the same manner as in Example 1.

The results are shown in Table 1.

Heisei year//month 24? Day

Claims (2)

[Claims] (1) A photosensitive material having a photosensitive layer containing microcapsules containing silver halide, a reducing agent, a color image forming substance, a polymerizable compound, and a base precursor on a support, further comprising the following general formulas [I] to A photosensitive material containing at least one compound represented by [IV]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z is a hydrogen atom, an alkyl group, or -COY when n=1
(Y represents an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, or a substituted amino group), and when n=2 represents Zn or Ni. R^1 to R^5 represent a hydrogen atom, a substituent, or a chemical bond. However, this chemical bond is one that is bonded directly or via a divalent to tetravalent residue to the compound represented by the general formula [I], the number of which corresponds to the valence of the residue. Furthermore, two adjacent groups of R^1 to R^5 or R^
Any one of 1 to R^5 and the above divalent to tetravalent residue may be linked to each other to form a 5- to 6-membered ring. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ X represents an oxygen atom, a sulfur atom, a substituted imino group ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R^6 to R^9 represent a hydrogen atom, a substituent, or a chemical bond. However, this chemical bond is one that is bonded directly or via a divalent to tetravalent residue to the compound represented by the general formula [II], the number of which corresponds to the valence of the residue. Furthermore, any substituents of R^6 to R^9 or R^6
-R^9 and the above divalent to tetravalent residue may be linked to each other to form a 4- to 6-membered ring. General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, W is Ag, -SR^1^1 or R^1 when n=1
^1, and when n=2, it represents Zn or Ni. R^1^0, R^1^1 are alkyl groups, heterocyclic residues, -
CSY (Y is the same as defined in general formula [I]) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^1^2 to R^1^4 each represent an alkyl group or an aryl group) represent. General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1^5 and R^1^6 each represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and these are linked to each other. A 5- to 6-membered ring may be formed. (2) The color photosensitive material according to claim (1), wherein the compound represented by the general formula [I] is further represented by the following general formula [I']. General formula [I'] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, B is -S-, -S-S-, -O-, -CH_2-S-CH_2-, -SO_2-, -SO-
, -CH_2-O-CH_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, which is R^2^
1 to R^2^4 represent a hydrogen atom or a substituent, R^2^5 is a hydrogen atom,
Indicates an alkyl group or an aryl group, R^2^6, R^2
^7 represents a hydrogen atom, an alkyl group, an aryl group, or a substituted 5- or 6-membered ring bonded to each other, and R^2
^8 represents a hydrogen atom or an alkyl group. m represents an integer of 1 to 3.