JPH0237342A - Color picture forming method - Google Patents

Abstract

PURPOSE:To form a picture which does not generate the color unevenness and the density unevenness of the picture over the whole region of the picture by curing a photosensitive material with a specified compd. CONSTITUTION:The photosensitive material is cured with the compd. shown by formula I. In the formula, X<1> and X<2> are each -CH=CH2 or -CH2CH2Y group, X<1> and X<2> may be the same or the different with each other, Y is a group capable of subjecting a substituting reaction with a nucleophilic group such as amino group, etc. contd. in a gelatin or a group capable of being released a group HY by a basic group, L is a divalent linking group which may be substd. The compounding amount of a hardening agent to the photosensitive material is 0.01-20wt.%, further, preferably 0.1-10wt.% on the basis of a died gelatin. Thus, the generation of the color unevenness and the density unevenness at the starting and finishing parts of exposure which is liable to generate the scanning exposure of the photosensitive material, is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method of forming a color image by scanning and exposing a conventional silver halide color photographic light-sensitive material and then performing a conventional color development process. Specifically, the present invention relates to a color image forming method in which scanning exposure is performed using a visible light source.

(Prior Art) As a method of forming an image by scanning exposure, there is a so-called image forming method using a scanner. In this method,
Since the image information of the original image is once converted into an electrical signal and then extracted, this image information can be subjected to various types of image processing.

Examples include contrast correction, negative-positive conversion, or image transformation (not only can it be enlarged or reduced in any direction, but it is also possible to correct the distortion of an aerial photograph that shows a shadow from diagonally above). It will be done. Therefore, if this method is used, it is not only possible to simply obtain a copy of the original drawing, but also to create various variations from the original drawing. From this point of view, in recent years, various types of image forming systems using one type of scanner have been appearing.

There are various types of recording apparatuses that have put a scanner type into practical use, and glow lamps, xenon lamps, mercury lamps, tungsten lamps, light emitting diodes, and the like have conventionally been used as recording light sources for these scanner type recording apparatuses. However, all of these light sources have practical drawbacks of low output and short lifespan. To compensate for these shortcomings, Ne-He laser, argon laser, He-
There are scanners that use a coherent laser light source such as a gas laser such as a Cd laser or a semiconductor laser as a light source for the scanner method.

Although gas lasers can provide high output, they have disadvantages such as large size, high cost, and the need for a modulator.

On the other hand, semiconductor lasers have advantages such as being small, inexpensive, easy to modulate, and have a longer lifespan than gas lasers. The emission wavelength of these semiconductor lasers is mainly in the infrared region, and therefore a sensitive material having high photosensitivity in the infrared region is required.

However, infrared-sensitive materials have poor storage stability due to the instability of infrared sensitizing dyes, are not easy to manufacture, and are also very difficult to handle. Therefore, there has been a desire for a method of forming images by exposing a silver halide material that has been spectrally sensitized in the visible region using a spectral sensitizing dye with good storage stability while retaining the advantages of a semiconductor laser.

If this method is realized, for example, ordinary color photographic paper, which has good image quality and is easy to process, can be used for recording, making it possible to easily use a scanner-based image forming processing system. .

As one method, as disclosed in JP-A-63-113534 and JP-A-63-18345,
There is a method of using a second harmonic obtained by combining a laser and a wavelength conversion element made of a nonlinear optical material as a light source.

(Problem to be Solved by the Invention) However, when scanning exposure and color development processing was performed on commercially available color photographic paper based on the examples of JP-A No. 63-18345, etc., it was found that no visible color was observed during normal printer exposure. A big problem arose. The problem is that the color tone of a single print obtained by scanning exposure differs between the beginning and end of scanning exposure. For this reason, for example, the color balance of the neutral gray background changes depending on the location on the screen, resulting in so-called color unevenness, making it impractical.

Therefore, an object of the present invention is to expose a silver halide photographic light-sensitive material containing at least one type of coupler that forms a dye by coupling with an oxidized product of an aromatic primary amine developing agent on a support using a single scanner. The object of the present invention is to provide a method of forming a color image by performing color development processing and forming an image without color unevenness or density unevenness over the entire screen.

(Means for Solving the Problems) As a result of intensive research, the present inventors have found that the above-mentioned objective is to provide a coupler that forms a dye by coupling with an oxidized product of an aromatic primary amine developing agent on a support. In a method of forming an image on a silver halide photographic light-sensitive material containing at least one type of silver halide by exposing it to light using a scanner and further performing color development and desilvering treatment, the photographic light-sensitive material is represented by the following general formula (II). This was effectively achieved by an imaging method characterized by 17, which is hardened by a compound of

General 2[H] X'-5()z L Sol
Y, and Xl and X2 may be the same or different. Y represents a group that undergoes a substitution reaction with a nucleophilic group such as an amino group in gelatin, or a group that can be separated in the form of HY by a base. is a divalent linking group, which may be substituted.

The hardener represented by the general formula [H] will be explained in detail below.

Specific examples of Y include a halogen atom, a sulfonyloxy group, a sulfuric acid monoester group, a carboxylic acid ester group, and a trialkylammonium group.

Moreover, as specific examples of Xl and X2, the following can be mentioned, for example.

(X 1 ) CH= CHt (X-2> -cHt CIlz CI(X-3)
CHtC)lzBr(X-4)-CHI
CI (20SOz CHI Among these, (X-1, (X-2>, (X-4), (X-7),
(X-12) is preferred, and (X-1) is particularly preferred.

The divalent linking group is an alkylene group, an iri-lene group, or these groups and -0--N--CO-so--so□ -
S O3 -soz N (X-7) (X-8) (X-9> (X-10) (X-11) Ht -CH.

CH.

CH2 Hx Hz CH.

H2 CH.

CH.

0303 Na 03O,K OCOCH.

0COCF.

OCOCHCI z R' NCO is a divalent group formed by combining one or more bonds.

R1 represents a hydrogen atom, or an alkyl or aralkyl group having 1 to 15 carbon atoms. In addition, when two or more of these R1s are included, they may be bonded together to form a ring. Furthermore, [, may have a substituent, and examples of the substituent include a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group, an aryl group, and an amino group.

In addition, these substituents may be further substituted, and their chemical structure may contain one or more groups represented by x"-so□-
X3 has the same meaning as Xl and X2 described above.

Representative examples of L include the following.

(L-1) (CH,)-.

(L-2) (CHg)-b0(CHI)-
.

(Cllz )-a Co N (Cll□ )-8N
CO-(C1l, t.

(L-4) R'(CHI, N
ba CHz) -h (し(C11□ ト Ｇｕｒａｎｔ Ｃ０Ｎ－((Jl□)Jo -fcHffi)k NCO CH□ (L トL (L-7) (CHI)-qSow (CHI ト.

In the formula, a''-r is an integer from 1 to 6, and only 8 may be 0. Among these, a, eX j, and n are 1 to 3.
It is preferable that b, c, dXLg, h, t, I
, m, p, q, r are preferably 1 or 2. R1-R5
is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R1, R2 and R
4 and R8 may be combined to form a ring. R1 to R6 are preferably a hydrogen atom, a methyl group, or an ethyl group. Further, these groups may have a substituent.

Typical examples of cases where L has an In group and cases where the above R1 and R2 are combined include the following.

-(C11! )-, C0O -(CI+! 0C0 (C1h juice.

Chemical CH- (H-1) CH,=CH3O□CH, So□CH=CH! (H-2
) CHt = CH3Oz CHx CHI CHt 5O
tCH=CHt(H-3) CHz SO2CH=CH2 cHw so□CH=CHz -CH, -c-cHt CHl -CH5Ot CHx CCHz Sow C
H=CHzCHt SO2CHt CHl NHCHx
CHt SOs NaCHl Sow CHt CH
zNHCH! CHt SOs Na(L-10) (H-4) C1h =CH5Ot CHz 0CHI So□CH
=CHz(H CHz =CH3Ch CHHz CHz 0CHz C
H□SOz CH=CH2(H-6) Co-(CHz)-wSOx CH=CHtCHz
=CH3Ch CHz C0NHNHCOCH! so
w CH CH2 CHI cH.

During the ceremony, S -, = W means 1 or 2.

(H-7) Of these L, (L 1).

(L-2) (L (L-8) (L is preferable, (L 1).

(L-9) is particularly preferred.

C0NHCHt CHHz NH2O Next, specific examples of the hardening agent used in the present invention are listed. The present invention is not limited to this.

(H (H-12) CHz CHl CHI (H-9> (Hz H5 C0N-CH, CHI CHl NCOCOCH30□
CH2CHg C1 CH.

CH3 xHs (H (H CH,=CH3O□CHz CI(t CHz CHI SO2CH=CH2 CHz =CH3Oz CHz CHCHz SCh
CHCl□ cH COCHg CHI Sow CH-CHl(H-11
) CH.

CHl 5OzNa CONHCHz CHl NHC0 These methods for synthesizing the hardening agent used in the present invention include, for example, Japanese Patent Publication Nos. 47-2429, 50-35807, 49-24435, 53-41221, and 59 −
It is described in detail in publications such as No. 18944.

In the present invention, even if the hardening agent is added to the coating solution in advance,
It may be mixed with the coating liquid immediately before coating.

In the present invention, the amount of hardener added is 0.000000000000000000000000000,0000,0000,0000,0000,000,000,000,000,000, with respect to dry gelatin. The range is from 0.1 to 20% by weight, particularly preferably from 0.1 to 10% by weight.

The layer to which the hardener used in the present invention is added is not particularly limited as long as it is a gelatin-containing layer on the support, and it is not necessarily necessary to add it to the entire layer, for example, to only the top layer (protective layer) or the top layer. Even if it is added only to the lower layer, the object of the present invention can be achieved because the entire layer is hardened by diffusion.

The silver halide photographic material used in the present invention preferably has a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a reflective support, but if necessary, this layer arrangement may be changed. It may be changed as appropriate, and it is common that an intermediate layer is provided between these photosensitive layers, and a protective layer is further provided as the uppermost layer.

The pH of the film of the photosensitive material used in the present invention is preferably 5.5 or higher, more preferably 6.0 or higher. The pH of this film can be determined by dropping 0.05 cc of pure water onto the surface of the top layer of the photosensitive material, which is obtained by coating the coating solution once or several times on the support and drying it, and then leaving it for 3 minutes. Film pH measurement electrode (Toa Denpa type O3-165F
) means the value measured at

The halogen composition of the silver halide grains according to the present invention is 20 mol% of the total silver halide constituting the silver halide grains.
Preferably, at least 90% by mole (more preferably at least 90 mol %) of the silver chloride consists of silver chlorobromide or silver chloride, which is substantially free of silver iodide.

Here, "substantially free of silver iodide" means that the silver iodide content is 1.0 mol% or less. A particularly preferred halogen composition of the silver halide grains is silver chlorobromide containing substantially no silver iodide, in which 95 mol % or more of the total silver halide constituting the silver halide grains is silver chloride. .

Further, the silver halide grains according to the present invention preferably have a silver bromide content of at least 10 mol % and 70 mol %.
The grains have less than mol % of silver bromide localized phase.

The arrangement of such a localized silver bromide phase can be freely determined depending on the purpose, and it may be located inside the silver halide grain, on the surface or subsurface, or divided into the interior and the surface or subsurface. In addition, the localized phase may have a layered structure surrounding the halogenated root particles, or may have a discontinuously isolated structure inside or on the surface. One preferred example of the arrangement of localized silver bromide phases is a localized phase with a silver bromide content of at least 10 mol%, more preferably more than 20 mol%, on the surface of silver halide grains (particularly at the corners of the grains). The existing phase is locally epitaxially grown.

It is preferable that the silver bromide content of the localized phase exceeds 20 mol%; however, if the silver bromide content is too high, it may cause desensitization when pressure is applied to the photosensitive material, or the composition of the processing solution may be affected. Fluctuations may impart unfavorable characteristics to the photographic material, such as large changes in sensitivity and gradation.

Taking these points into consideration, the silver bromide content of the localized phase is determined by
The range is preferably 20 to 60 mol%, and 30 to 50 mol%
The other silver halide constituting the localized phase is preferably silver chloride. The silver bromide content of the localized phase can be determined by the X-ray diffraction method (for example, described in "New Experimental Chemistry Course 6, Structural Analysis," edited by the Chemical Society of Japan, published by Maruzen) or the XPS method (for example, described in "Surface Analysis, -1MA, Application of Auger Electron/Photoelectron Spectroscopy'' (published by Kodansha), etc. can be used for analysis. The localized phase accounts for 0.1 to 20% of the total silver amount constituting the silver halide grains of the present invention.
% silver, more preferably 0.5-7% silver.

The interface between the silver bromide localized phase and other phases may have a clear phase boundary, or may have a short transition region where the halogen composition gradually changes. The position of the silver oxide localized phase can be determined by observation using an electron microscope or other methods described in Japanese Patent Application No. 319741/1982.

In order to form such a localized silver bromide phase, various methods can be used.1 For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halide salt by a one-sided mixing method or a simultaneous mixing method. can be formed. Furthermore, the localized phase can also be formed using a so-called conversion method, which includes a process of converting already formed silver halide into silver halide having a smaller solubility product. Alternatively, a localized phase can also be formed by adding silver bromide fine particles and recrystallizing them on the surface of silver chloride particles.

Regarding these manufacturing methods, for example, the above-mentioned patent application 1986-3
It is described in the specification of No. 19741.

Preferably, the localized phase is deposited with at least 50% of the total iridium added during the preparation of the silver halide grains.

Here, depositing the localized phase together with iridium ions means supplying an iridium compound simultaneously with, immediately before, or immediately after supplying silver and/or halogen to form the localized phase. For example, an iridium compound may be contained in the halide fine grains in advance, this may be added to a desired silver halide emulsion, and the fine grain silver halide may be further dissolved to precipitate the localized phase together with the iridium.

The silver halide grains according to the present invention have (l O
Whether it has an O) plane, a (111) plane, or both,
Furthermore, even those containing higher order planes are preferably used.

The shape of the silver halide grains used in the present invention is cubic,
Those with regular crystal shapes such as tetradecahedrons and octahedrons, and those with irregular crystal shapes such as spherical and plate shapes, or these crystal shapes. There are some that have a compound form. It is also possible to use a mixture of particles with various crystal forms, but in particular, particles with the above-mentioned regular crystal forms account for 50% or more, preferably 70% or more, and more preferably 90% or more. It is better to include % or more.

The silver halide emulsion used in the present invention has an average aspect ratio (length/I! ratio) of 5 or more, particularly preferably 8.
The emulsion may be such that the tabular grains described above occupy 50% or more of the total projected area of the grains.

The size of the silver halide grains according to the present invention may be within the range commonly used, but the average grain size is 0.1. c+m
It is preferable that the loss is 1.5 μm.

The particle size distribution may be polydisperse or monodisperse, but
The particle size distribution representing the degree of RL dispersion, which is preferably monodisperse, is determined by the statistical coefficient of variation (standard deviation S when the projected area is approximated as a circle divided by the diameter d (a S /
d) is preferably 20% or less, more preferably 15% or less.

Further, two or more types of such tabular grain emulsions and monodisperse emulsions may be mixed. When the emulsions are mixed, it is preferable that at least one of them has the above-mentioned coefficient of variation, and the coefficient of variation of the mixed emulsion is the above-mentioned coefficient of variation. It is more preferable that the range of values is satisfied.

When the silver halide grains used in the present invention have a silver bromide localized phase, the so-called matrix portion other than the localized phase is composed of a uniform phase even if the interior and surface layers have different phases. Also good.

The photographic emulsion used in the present invention is B. gelafchides (
Chimie eL Ph.
ysiquePhotographiques (for Paul Montell, 1967), by G. F. Duffino, Photographic Emulsion Chemistry (Photogra
phic Emulsion Chea+1try(
Focal Press, 1966), V. L. Zelikman et al., Making and Coating Photographic Emulsions (Making and Coating Photographic Emulsions)
It can be prepared using the method described in Focal Press (Focal Press, 1964).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. No. 3,271,157,
Same No. 3,574,628, Same No. 3,704,130, Same No. 4,297.439, Same No. 4,276.374
), thione compounds (for example, JP-A-53-144
No. 319, No. 53-82408, No. 55-77737
), amine compounds (for example, Japanese Patent Application Laid-open No. 5410071)
No. 7) etc. can be used.

The silver halide grains used in the present invention are preferably of the surface latent image type, and are preferably chemically sensitized on the surface to some extent.The chemical sensitization includes active gelatin and sulfur that can react with silver. Sulfur sensitization using compounds (e.g. thioiaa salts, thioureas, mercapto compounds, rhodanines); reducing substances (e.g. stannous salts, amines,
Reduction sensitization method using hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal compounds (e.g.
In addition to gold complex salts, it is preferable to use a noble metal sensitization method using complex salts of metals in group 1 of the periodic table such as PL, Ir, Pb, Rh, and Fe, either alone or in combination.

For details on these methods, see Japanese Patent Application Laid-Open No. 62-21527.
Specification No. 2, page 12, lower left column, line 18 - lower right of the same page, line 1
1! It is written on line 116.

When the silver halide emulsion used in the present invention is a high silver chloride emulsion, the following - bottom ((1 to [[[l]
By adding at least one compound represented by any of the following, it is extremely effective to prevent an increase in fog, especially when a gold sensitizer is used.

The addition time may be the particle formation step, the desalting step, the chemical ripening step, or just before coating, but it is preferably added during the particle forming, desalting, and chemical ripening steps, especially before the addition of the gold sensitizer.

General formula [+1. A compound having a thiosulfonyl group represented by [■] or [I[[] will be explained.

General formula [1] Z-3o, SM - bottom [■] General formula [111 In the formula, 2 represents an alkyl group, an aryl group, or a heterocyclic group, which may be further substituted. Y represents an atomic group necessary to form an aromatic ring or a heterocycle, and these rings may be further substituted. 0M represents a metal atom or an organic cation; n represents an integer from 2 to 10. .

1 to the above alkyl group, aryl group, aromatic ring or hetero ring
Examples of the substituents include lower alkyl groups such as methyl and ethyl groups, aryl groups such as phenyl, alkoxyl groups having 1 to 8 carbon atoms, halogen atoms such as chlorine, nitro groups, amino groups, and carboxyl groups. etc. can be mentioned.

The alkyl group represented by Z has 1 to 18 carbon atoms,
The number of carbon atoms in the aryl group and aromatic ring represented by Z and Y is 6.
~18.

The heterocycle represented by Z and Y includes thiazole,
Examples include henzthiazole, imidazole, henzimidazole, and oxazonyl ring.

The metal cation represented by M is preferably an alkali metal cation such as a sodium ion or potassium ion, and the organic cation is preferably an ammonium ion or a guanidinium ion.

-Bottom [1], [■1. Specific examples of compounds represented by (Iff) are listed below.

kL-cystine-disulfoxide H, C-3o, ・5Na 1 1 (SOX ・ SO□ ・ S-Km
H1? CI ・ 30g ・ 5Na General 2 [1], The compounds represented by [nl and [+111] are sulfites, alkylsulfine MFM,
It can be used in combination with sulfinates such as arylsulfinates and heterocyclic sulfinates.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promohenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazole aminotriazoles, benzotriazoles, nitrohencitriazoles, mercaptotetrazoles (particularly l-phenyl-5-mercaptotetrasoles and those in which the m-position of the phenyl group is substituted with an N-methylureido group), Mercaptopyrimidines, mercaptopyrimidines, etc.:
thioketo compounds, such as oxadorinthione; azaindenes, such as triazaindenes, tetraazaindene R, especially 4-hydroxy substituted (1,3,3a
, 7) tetraazaindene), pentaazaindenes, etc.; many compounds known as anti-capri agents or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. .

Among them, the following general formula (T
It is preferable to add a mercaptoazole represented by V), (V) or (Vl), and the amount added is preferably IX 10-' to 5X10-'' mol per mol of silver halide, more preferably IX IO-'~lXl0-"
Moles are particularly preferred.

- Boatman (■) X In the formula, R represents an alkyl group, an alkenyl group, or an aryl group. X represents a hydrogen atom, an alkali metal atom, an ammonium group, or a precursor.

The alkali metal atom is, for example, a sodium atom, a potassium atom, etc., and the ammonium group is, for example, a tetramethylammonium group, a trimethylbenzylammonium group, etc. In addition, the precursor is X- under alkaline conditions.
A group that can be H or an alkali metal, such as an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.

Among the above R, the alkyl group and alkenyl group include unsubstituted and substituted groups, and also include alicyclic groups.

Substituents for substituted alkyl groups include halogen atoms, nitro groups, cyano groups, hydroxyl groups, alkoxy groups, aryl groups, acylamino groups, alkoxycarbonylamino groups, ureido groups, amide groups, heterocyclic groups, acyl groups, and sulfamoyl groups. group, sulfonamide group, thioureido group,
Examples include a carbamoyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, and further a carboxylic acid group, a sulfonic acid group, or salts thereof.

The above ureido group, thioureido group, sulfamoyl group, carbamoyl group, and amino group are each unsubstituted,
Examples of aryl groups, including those substituted with N-alkyl and those substituted with N-aryl, include phenyl and substituted phenyl; substituents include alkyl and the substituents for the alkyl groups listed above. can be mentioned.

-Bottom (V) It has the same meaning as (IV).

A specific example of the divalent linking group represented by the above is -CH-
, -C-, etc., and combinations thereof can be mentioned as R6R2.

n represents 0 or l, and R', R', and R2 each represent a hydrogen atom, an alkyl group, or an aralkyl group.

General formula (Vl) In the formula, Y represents an oxygen atom or a sulfur atom.

L represents a divalent linking group, R is a hydrogen atom, an alkyl group,
Represents an alkenyl group or an aryl group.

In the general formula, the alkyl group, alkenyl group and X of R are
R and X have the same meanings as in general formula (rV), and L has the same meaning as in general formula (V).

R1 has the same meaning as R, and may be the same or different.

Below are the general formula (rV), -4 formula (V) and -bottom (
Specific examples of the compound Vl) are listed below, but the invention is not limited thereto.

H H H CH3 NHCOCH.

Dyes are preferred.

General Formula (S) CH2 The sensitive material of the present invention has at least one blue-sensitive layer, at least one green-sensitive layer, and at least one red-sensitive layer, and a sensitizing dye is used for the purpose of imparting spectral sensitivity in a desired wavelength region.

As the spectral sensitizing dye, methine dyes such as cyanine dyes and merocyanine dyes commonly used for photography can be used. Specific examples of these sensitizing dyes include
2-215272, pages 22 to 34, and JP-A-63-
0 described in detail on pages 3 to 6 of No. 113534
Particularly useful for the present invention are 2161 and Z in the cyanine formula represented by the following general formula (S). 2 each represents an atomic group necessary to form a heterocyclic nucleus.

Examples of the heterocyclic nucleus include a 5- to 6-membered ring nucleus containing a nitrogen atom and other heteroatoms such as a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom (a fused ring may be further bonded to these rings). , or further substituents may be bonded)
is preferred.

Specific examples of the above-mentioned heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, imidazole nucleus, benz Imidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine Maki, benzindolenine nucleus, indole nucleus, tellurazole nucleus, penzotellazole Maki, naphthotellazole nucleus, etc. Can be done.

R1゜ and R2゜2 each represent an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group.These groups and the groups described below are each used in a meaning including their substituents.6For example, an alkyl group is used. This includes unsubstituted and substituted alkyl groups, and these groups may be linear, branched, or cyclic. The alkyl group preferably has 1 to 8 carbon atoms.

Specific examples of substituents for substituted alkyl groups include halogen atoms (chlorine, bromine, fluorine, etc.), cyano groups, alkoxy groups, substituted or unsubstituted amino groups, carboxylic acid groups, sulfonic acid groups, hydroxyl groups, etc. One or more of these may be substituted in combination.

A specific example of the alkenyl group is a vinylmethyl group.

Specific examples of the aralkyl group include benzyl group and phenethyl group.

ml, represents a positive number of 0 or l, 2 or 3, m
, , represents l, R2° represents a hydrogen atom, a lower alkyl group, an aralkyl group, or an aryl group.

Specific examples of the aryl group include substituted or unsubstituted phenyl groups.

R8°4 represents a hydrogen atom. When mlo represents 2 or 3, R1° represents a hydrogen atom, R1°4 represents a hydrogen atom, a lower alkyl group, an aralkyl group, and R
It can be linked with 1°2 to form a 5- to 6-membered ring. Also ml. When 1 represents 2 or 3 and R2゜represents a hydrogen atom, R103 may be linked with another R1゜ to form a hydrocarbon ring or a heterocycle, and these rings are 5- to 6-membered. Ring is preferred -J+. l, kllll is 0
Or represents 1, X. .

represents an acid anion, n and □ represent 0 or 1.

Among these, red sensitizing dyes in particular have a reduction potential of 1.23.
(v□SCF,) or a compound with a value more base than that is preferable, and among them, a compound with a reduction potential of 1.27 or a value less than that is preferable.As for the chemical structure, two of the methine groups of the pentamethine linking group are preferable. Benzothiadicarbocyanine dyes that are linked together to form a ring are preferred.

It is preferable that an electron-donating group such as an alkyl group or an alkoxy group is bonded to the benzene ring of the penzothiadurine nucleus of the dye.

The reduction potential can be measured by phase-discriminative second harmonic AC polarography using a mercury dropping electrode as the zero working electrode, a saturated calomel electrode as the reference electrode, and platinum as the counter-oscillator.

In addition, measurement of the reduction potential by phase-discriminative second harmonic AC voltasimetry using platinum as the working electrode is described in [Journal of Imaging Science J (Journal of Imaging Science J
al of Imaging 5science), Vol. 30, pp. 27-35 (1986).

Typical specific examples of blue sensitizing dyes that can be used in the present invention are listed below. (SB-1-3B-17> The timing of adding these sensitizing dyes is before the grain formation of the silver halide emulsion;
It can be selected from during grain formation, immediately after grain formation and before entering the water washing step, before chemical sensitization, during chemical sensitization, from immediately after chemical sensitization until the emulsion is cooled and solidified, and during preparation of the coating solution.

Among these, it is particularly preferable to use the method before the emulsion washing step or before chemical sensitization.

The amount of these spectral sensitizing dyes added varies over a wide range depending on the case, but is usually 1/mol of silver halide.

A range of 0XIO-r to 1.0XIO-'' is preferred.

More preferably, 1.0XIO-'-1.0XIO-
The range is 3.

These spectral sensitizing dyes can be added in the emulsion preparation process by following the usual method, that is, by dissolving the dye to be used in an appropriate organic solvent (methanol, ethanol, ethyl acetate, etc.) and adding it to an appropriate concentration. It can be added to the emulsion as a solution. Further, the dye used can be added as an aqueous dispersion by dispersing it in an aqueous solution using a surfactant or the like, or by dispersing it in an aqueous gelatin solution of an appropriate concentration.

The light-sensitive material used in the present invention is preferably a color light-sensitive material.

In color light-sensitive materials, yellow couplers, magenta couplers, and cyan couplers, which develop yellow magenta and cyan colors, respectively, by coupling with oxidized products of aromatic amine color developers are commonly used.

Among the yellow couplers that can be used in the present invention, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred.

Among them, yellow couplers have the following general formula (Y-
Those represented by 1) and (Y-2) are preferred.

(Y-1) at (Y-2) For details of the pivaloylacetanilide type yellow coupler, see US Pat. No. 4,622,287, No. 3.
It is described in column 15, line 15 to column 8, line 39, and column 14 @ line 50 to column 19, line 41 of the specification of 4623.616.

For details on benzoylacetanilide type yellow couplers, see U.S. Pat.
No. 3,501, 4. 046. No. 575, 4.1
It is described in No. 33,958, No. 4,401゜752, etc.

Specific examples of pivaloylacetanilide type yellow couplers include compound examples (Y-1) to (Y
-39), among which ('/-1'),
(Y-4), (Y-6).

(Y-7), (Y-15), (Y-21),
(Y22), (Y-j3), (Y-26),
(Y-35), (Y-36), (Y-37
), (Y-38), (Y-39), etc. are preferred.

Also, No. 1 of the above-mentioned U.S. Pat. No. 4,623,616
Compound examples (Y-1) to (Y-33) in columns 9 to 24 can be cited, among them (Y2), (Y-'?),
(Y-8), (Y-12), (Y-20), (
Y-21), (Y-23).

(Y-29) etc. are preferred.

Other preferred examples include US Pat. No. 3,408.
Typical example (3) described in No. 6fll of Specification No. 194
4) Compound examples (16) and (19) described in column 8 of the same specification No. 3,933,501, compound examples described in columns 7 to 8 of the same specification 4,046,575 ( 9), 4,1
Compound examples described in columns 5 and 6 of specification No. 33,958 (
1), Compound Example 1 described in Column 5 of 401.752, and the following compounds a) to h).

Among the above-mentioned couplers, those having a nitrogen atom as a leaving atom are particularly preferred.

Examples of the magenta coupler that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. Same second
, No. 343.703, No. 2. 600. No. 788,
2.908.573, 3.062.653, 3.152,896 and 3,936.0
It is written in No. 15 etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Pat.
No. 19 or the nitrogen atom leaving group described in U.S. Pat.
, 351.897 is preferred, and 5-pyrazolone couplers having a ballast group as described in European Patent No. 73,636 provide high color yield.

As a pyrazoloazole coupler, U.S. Patent No. 2,
369.879, preferably the pyrazolo(5,1-C)(1,2,4) lyazoles described in U.S. Pat. No. 3,725.067, Research Disclosure 24220
(June 1984) and Research Disclosure 24230 (1)
Examples include the virazolopyrazoles described in June 1984). Any of the couplers mentioned above may be polymeric couplers.

Specifically, these compounds have the following general formula (M-1)
, (M-2> or (M-3)).

R3-3g Among pyrazoloazole couplers, it is preferred in U.S. Pat.
The imidazo(1,2-b)pyrazoles described in U.S. Pat.
Triazoles are particularly preferred.

In addition, pyrazolotriazole couplers in which a branched alkyl group is directly connected to the 2,3 or 6 position of the pyrazolotriazole ring as described in JP-A No. 61-65245, and as described in JP-A-61-65246 Pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226,849. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an alkyloxy group at the 6-position as described in No.

Specific examples of these couplers are listed below.

Among the cyan couplers, phenolic cyan couplers and naphthol cyan couplers are most commonly used.

As a phenolic cyan coupler, US patents 2 and 3
No. 69.929, No. 4,518,687, No. 4,51
1.647 and 3. 772. There are compounds (including polymer couplers) that have an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position, such as those described in Canadian Patent No. 62.
Coupler of Example 2 described in No. 5,822, U.S. Pat.
, 772.002, No. 4,56
Compounds (1-4) and (1-5) described in No. 4゜590,
The compound fil, (2
), (3) and (24), and the compound (C-2) described in No. 62-70846.

As a phenolic cyan coupler, U.S. Patent 2
, No. 772,162, No. 2.895,926, No. 4.
No. 334,011, No. 4,500゜653 and JP-A-5
There are 2,5-diacylaminophenol couplers described in U.S. Pat.
, the compound αη described in 4.557.999, 4.557.999,
Compounds (2) and (b) described in No. 565.777, No. 4
Compound (4) described in , No. 124.396, No. 4,61
Examples include the compound (1-19) described in No. 3゜564.

As a phenolic cyan coupler, U.S. Pat.
, No. 372,173, No. 4,564,586, No. 4,
There are compounds in which a nitrogen-containing heterocycle is fused to a phenol nucleus, as described in U.S. Pat. Coupler + described in No. 173
No. 11 and (3), compound (3) and α-barrel described in No. 4,564,586, compound ill (3) described in No. 4,430,423, and the following compounds.

C,I(S CH.

Other examples of C,H-coh phenolic cyan couplers include U.S. Patent No. 4,333.999, U.S. Pat.
, 444.872, 4,427.767, 4,
No. 579,713, European Patent (BP) 067.689B
There are ureido couplers described in U.S. Pat. No. 1, etc., and representative examples thereof include coupler (7) described in U.S. Pat. , Coupler (3) described in No. 4,444.872, Coupler (3) described in No. 4,427,767, Coupler (6) described in No. 4,609,619.
) and (24), coupler fil and 0υ described in 4,579,813, European Patent No. (BP) 067.689B
Coupler (45) and (50) described in No. 1, JP-A-61
Coupler (3) described in No.-42658 can be mentioned.

Examples of naphthol-based cyan couplers include those having an N-alkyl-N-carhamoyl group at the 2-position of the naphthol nucleus (for example, U.S. Pat. No. 2,313,586);
those having an alkylcarbamoyl group at the 2-position (e.g., U.S. Pat. Nos. 2,474,293 and 4,282,31.2); those having an arylcarbamoyl group at the 2-position (e.g., Japanese Patent Publication No. 14523/1983); Those having a carbonamide or sulfonamide group at the 5-position (for example, JP-A-60-2
No. 37448, No. 61-145557, No. 61-15
No. 3640), those with aryloxy leaving groups (e.g., U.S. Pat. No. 3,476,563), and those with substituted alkoxy leaving groups (e.g., U.S. Pat. No. 4,296,199).
No.), those with a glycolic acid leaving group (e.g.
0-39217).

These couplers having a high boiling point can be contained in the dispersed emulsion layer in coexistence with at least one type of organic solvent. Preferably, a high boiling point organic solvent represented by the following formula (A) to E) is used.

2 Formula % Formula % Formula (E) w, -o-wz (wherein, Wl, Wz and W are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group,
Represents an aryl group or a heterocyclic group, W4 is W, , o
w, or S −W +, where n is a positive number from 1 to 5, and when n is 2 or more, W4 may be the same or different from each other. W! may form a fused ring).

These couplers can also be impregnated into rhodapulu latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling ml media described above.
Alternatively, a water-insoluble polymer can be dissolved in a solvent-soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 38100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminephenol derivative, a gallic acid derivative, an ascorbic acid derivative, or the like as a color antifoggant.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as organic antifading agents for cyan, magenta and/or yellow images, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Also, (bissalicylaldoximado)nickel complex and (bis-N,N dialkyldithiocarbamado)
Metal complexes such as nickel complexes can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are disclosed in U.S. Patent No. 2,360,290;
Same No. 2,418,613, Same No. 2,700.453, Same No. 2,701,197, Same No. 2,728.659
No. 2. 732. No. 300, No. 2.735,
No. 765, No. 3,982.944, No. 4,430
, 425, British Patent No. 1,363,921, U.S. Patent No. 2,710.801, U.S. Patent No. 2,816,028, etc., 6-hydroxychromans, 5-hydroxycoumarans, spirochromans is U.S. Patent No. 3°432.
No. 300, No. 3,573,050, No. 3,574
, No. 627, No. 3. 698. No. 909, same No. 3,
No. 764,337, Japanese Unexamined Patent Publication No. 52152225, etc.
Spiroindanes are described in U.S. Pat. No. 4,360.589, and p-alkoxyphenols are described in U.S. Pat. No. 2,735.
, 765, British Patent No. 2,066.975, JP-A-59-10539, JP-B-19765, etc.;
No. 55, JP-A No. 52-72224, U.S. Patent No. 4,2
No. 28,235 and Japanese Patent Publication No. 52-6623, and US Pat. No. 3,457,079 for gallic acid derivatives, methylenedioxybenzenes, and aminophenols, respectively.
No. 4,332.886, Japanese Patent Publication No. 56-21144, etc., hindered amines are disclosed in U.S. Patent No. 3.3361.
No. 35, No. 4.268,593, British Patent No. 132
, No. 889, No. 1,354,313, No. 1,41
No. 0.846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 1983-
No. 114036, No. 59-53846, No. 59-78
No. 344, etc., phenol external water f11 group ether,
Ester derivatives are disclosed in U.S. Patent Nos. 4,155,765, 4,174°220, 4,254,216,
No. 4゜264.720, JP 54-145530
No. 55-6321, No. 58-105147, No. 59-10539, Japanese Patent Publication No. 57-37856, US Pat. Patent No. 4゜050.938,
No. 4,241,155, British Patent No. 2,027,7
31 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with the couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the respective color couplers.

In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an external ray absorber into the layers on both sides adjacent to the cyan coloring layer.

Among the above antifading agents, spiroindanes, hindered amines, and the like are particularly preferred.

In the present invention, it is preferred to use the following compounds together with the couplers mentioned above, especially with the vilasoloazole couplers.

That is, a compound (A) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (B) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferred compound (A) has a second-order reaction rate constant with p-anisidine of 2 (in trioctyl phosphate at 80°C) and 1. Oj! /mol・s e c=l X
10-J'/moj! It is a compound that reacts within the range of -sec.

When k2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention.

A more preferable compound (A) can be represented by the following - bottom (AI) or (An).

-m formula (AI) R1-(A) l, -X General formula (An) R2-C=Y In the formula, R1R2 each represents an aliphatic group, an aromatic group, or a heterocyclic group, and n is 1 Or represents O. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes the addition of an aromatic amine developing agent to the compound of general formula (An). represents a group that

Here, R1, XSY, and R2 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (AI) and (An), see Japanese Patent Application No. 62-158342 and No. 62-15.
No. 8643, No. 62-212258, No. 62-214
No. 681, No. 62-228034 and No. 62-2798
It is described in No. 43, etc.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. ), 4-thiazolidone compounds (e.g. those described in U.S. Pat. Nos. 3,314,794 and 3,352°681), benzophenone compounds (e.g. those described in JP-A-46-2784)
, cinnamate ester compounds (e.g., U.S. Pat. No. 3,705
．． No. 805, those described in No. 3,707,375),
Butadiene compounds (e.g. U.S. Pat. No. 4,045,229)
Alternatively, benzo 4-sidole compounds (such as those described in US Pat. No. 3,700,455) can be used. UV-absorbing coupler (
For example, cyan dye-forming couplers of α-naphthol type), ultraviolet absorbing polymers, etc. may be used, and these ultraviolet absorbers may be mordanted in a specific layer.

The photosensitive material produced according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anionine dyes, and ab dyes, etc.
Dyes represented by M] are also preferably used.

-Bottom [M] In the formula, R and XR represent -COOR, -CON, respectively. R3 and R4 each represent a hydrogen atom or an alkyl group, Rs and Rh each represent a hydrogen atom, an alkyl group,
--Ql and Qz each represent an aryl group, Xl and X2 represent a bond or a divalent linking group, and Y, Y2 represent a sulfo group and a carboxyl group, respectively.

Ll, L! , L each represent a methine group.

m, , m2 is 1 or 2, n is 0, ■ or 4.
2, p+, pt are respectively O11, 2, 3 or s+, S
z represents 1 or 2, respectively.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrace film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention refers to one that enhances the reflectivity and makes the colored image formed in the silver halide emulsion layer clearer. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films, vinyl chloride resins, and the like, and these supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjoining unit areas of 6 μm x 6 μm and projecting onto that unit area. It can be determined by measuring the occupied area ratio (%) (Ri) of fine particles. The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/R of the standard deviation S of R1 to the average value (1'7) of R3. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation s/R can be determined.

In the present invention, the coefficient of variation of the occupied area ratio (%) of fine pigment particles is 0.15 or less, particularly 0.15 or less. 12 or less is preferable, and if it is 0.08 or less, the dispersibility of the particles is substantially "
It can be said that J is uniform.

Description of the light source for scanning exposure that can be used in the present invention Basically, any light source that can be used in the present invention can be used as long as it emits blue light, green light, or red light. From the viewpoint of ease of controlling the time required for scanning exposure and the amount of light, it is preferable to use laser light as the light source.Furthermore, from the viewpoint of device life and device size, wavelength conversion using a semiconductor laser and nonlinear optical material is preferable. A light source with a combination of elements is preferred.

A wavelength conversion element made of a nonlinear optical material used in the present invention will be explained. Nonlinear optical materials are materials that can exhibit nonlinearity between polarization and electric field (nonlinear optical effect), which occurs when a strong optical electric field such as that of a laser beam is applied. Inorganic compounds such as potassium dihydrogen (KDP), lithium iodate, BaB10n, etc., urea derivatives and nitroaniline derivatives (e.g. 2-methyl-4-nitroaniline (MNA))
, 2-N,N-dimethylamino-5-nitroacetanilide (DAN), metanitroaniline, L-N-(
(4-nitrophenyl) -2-(hydroxymethyl)pyrrolidine, and the compounds described in Japanese Patent Application No. 61-53462, Japanese Patent Application No. 61-53884, and Japanese Patent Application No. 61-29999, etc.) Nitropyridine- N-oxide derivatives (for example, 3-methyl-4-nitropyridine-1 oxide (POM), etc.), diacetylene derivatives (for example, the compounds described in JP-A-56-43220), and also JP-A-61-60638. , Japanese Patent Publication No. 61-78748,
JP-A-61-152647, JP-A-61-13713
No. 6, JP-A-61-147238, JP-A-61-14
No. 8433, the compound described in JP-A No. 61-1 (i7930), and 'Nonliner Optical P
properties or Organic andP
Olymeric Materials” AC5S
YMPO5UM 5ERIES2 3 3, 0av
id J, William*sli(Amer
icanChemical 5ociety +
Organic compounds such as those described in "Organic Nonlinear Optical Materials" edited by Masao Kato and Hebe Nakanishi (published by CMC Co., Ltd., 1985) are known.

Regarding the present invention, among these, those having high blue light transmittance, such as KDP, lithium iodate, lithium niobate, [3a Bz Oa, urea, POM, JP-A-62-210430 and JP-A-Sho 62-210430, 62-21043
Compounds described in No. 2 are preferred, and moreover, POM and JP-A-62-210430 and JP-A-62-21043 are preferred.
The organic compound described in No. 2 is particularly preferred.

Specifically, as an organic nonlinear optical material, the following - ship bottom (■
) or -bottom (■) is particularly preferred.

General formula (■) In the formula, 2+ represents an atomic group necessary to form a 5- to 6-membered aromatic ring having at least one nitro group as a substituent. 22 is pyrrole, which may be substituted or fused. Represents an atomic group necessary to form a ring, imidazole ring, pyrazole ring, triazole ring, or tetrazole ring.

-Bottom (■) N (J In the formula, Zl and ZX may be the same or different and represent an N atom or a CR'' group.

X is an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, an acylamino group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxysulfonyl group, an aryloxysulfonyl group, an alkylthio group , arylthio group, hydroxy group, thiol group,
Represents a carboxyl group, ureido group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group or nitro group. n
represents 0 or an integer from 1 to 3, R1 is a hydrogen atom,
represents an alkyl group, an aryl group or an acyl group, R2 represents a hydrogen atom, an alkyl group or an aryl group, where X
The alkyl group and aryl group contained in , R' and R'' may be !!A.

Nonlinear optical effects include second harmonic generation, optical mixing, parametric oscillation, optical rectification, Pockels effect, etc. as second order effects, and third harmonic generation, Kerr effect, optical bistability, etc. as third order effects. In the present invention, the purpose of using a nonlinear optical material is to convert the light of a semiconductor laser with an infrared wavelength into a wavelength in the visible range, and therefore, Among the above effects, second harmonic generation, optical mixing, parametric oscillation, and third harmonic generation, which are related to wavelength conversion, are important.

The wavelength conversion element using a semiconductor laser and a nonlinear optical material used in the present invention may have a single crystal optical waveguide type,
Fiber type etc. are known.

As for the leading waveguide type, JP-A-51-142,284, JP-A-52-108,779, JP-A-52-125,2
Flat waveguide type described in No. 86, JP-A-60-14
, No. 222, JP-A No. 60-57゜825, JP-A No. 60-Sho.
-Embedded waveguide-like thing described in No. 112,023,
Furthermore, there is a tapered waveguide described in JP-A No. 60-250.334. As a fiber type, JP-A-57
There is one that satisfies the phase matching condition of the incident laser wave and the converted laser wave described in No. 211.125.

In the development of the light-sensitive material of the present invention, a color developer is used. The zero color developer is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component.

As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a representative example thereof is 3-methyl-4-
Amino-N.

N-diethylaniline, 3-methyl-4-amino N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino -N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH 1 buffers such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds, or fogging agents. It generally contains an inhibitor. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), etc. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, auxiliary developing agents such as l-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. Various chelating agents such as acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, and ■-hydroxyethylidene- 1
．． 1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N'N'
-tetramethylenephosphonic acid, ethylene glycol (0
-hydroxyphenylacetic acid) and their salts are representative examples.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-virapriton, or amine phenols such as N-methyl-p-aminephenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but -a is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
It can also be less than ml. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment layer with the air.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is bleached.

Bleaching treatment may be carried out simultaneously with fixing treatment.'a
(white fixing process) may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment in two continuous bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■) and colloid (I).
[I), Chromium (Vl),! Compounds of polyvalent metals such as ji (n), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron, (■) or cobalt ([1), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3 - Aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. may be used. can. Among these, aminopolycarboxylic acid iron (III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (III) TFT salt, are preferable from the viewpoint of rapid processing and environmental pollution prevention. Complex salts are particularly useful in both bleach and bleach-fix solutions.

These aminopolycarboxylic acid iron(I[I)I! The pH of the bleach or bleach-fix solution using salt is usually 5.5 to 8, but it is also possible to process at a lower pH to speed up the process.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3.893.858, German Pat.
, No. 290.812, No. 2,059°988, JP-A No. 53-32,736, No. 53-57,831, No. 5
No. 3-37,418, No. 53-72,623, No. 53
-95,630, 53-95,631, 53-
No. 104,232, No. 53-124,424, No. 53
-141.623, 53-28,426, Research Disclosure Corps No. 17,129 (July 1978), etc. Compounds having a mercapto group or disulfide group; JP-A-50-140.129 Thiazolidine derivatives described in JP-B No. 45-8,506, JP-A No. 52-20,832, JP-A No. 53-32,735,
1,000 urea derivatives described in U.S. Pat. No. 3.706.561; West German Patent No. 1,127,715;
6゜235; West German Patent No. 996,41
Polyoxyethylene compounds described in No. 0 and No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication No. 49-42.434 and No. 49
-59,644, 53-94,927, 54-
No. 35.727, No. 55-26,506, No. 58-1
Compounds described in No. 63.940; bromide ions, etc. can be used.

Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in U.S. Pat.
The compounds described in JP-A-53-95,630 are preferred, and the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, and ammonium thiosulfates are the most commonly used. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of M
tion PjcLure andTelevisi
on Engineers Volume 64, P, 2482
53 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-13], No. 632 can be used very effectively. Also, JP-A-57-8.54
Chlorine-based disinfectants such as isothiazolone compounds and cyabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles described in No. 2, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, Sanitary technology complete volume "Microorganisms" It is also possible to use disinfectants described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-9. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5-40°C is selected. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-8,543, 58-14゜83
All known methods described in No. 4, No. 60-220,345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, and an example thereof is a stabilization bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for shadows. can.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
．． Metal salt complex described in No. 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35,628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain pyrazolidones are JP-A-56-64,339 and JP-A-57-144,547.
No. 58-115.438, etc.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. At a low temperature? It is possible to achieve improvements in i.e. quality and stability of the processing solution. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2 226.770 or US Pat. No. 3,674.499 may be carried out.

Although there are no particular restrictions on the uses of the present invention, typical examples of its use include: 1) Using a color analyzer together with print materials (color prints, instant photographs, posters, etc.)
Positive images such as slides, negative images such as negative film),
Process the image and reprint.

2) Printing of CRT output images such as computer graphics, video images, electronic still images, output images for medical diagnosis, etc.

3) Output of image information sent via communication line, etc.

etc. are possible.

Preferred embodiments of the present invention are listed below, but the present invention is not limited thereto.

(1) It has a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a reflective support, and is hardened with a compound represented by the above general formula [H]. A color image forming method in which a coated color photosensitive material is scanned and exposed and then subjected to color development processing.

(2) A color image forming method according to claim (11) or embodiments full, in which a laser is used as a scanning exposure light source.

(3) In claim (1) or implementation llLi+11, the scanning exposure light source is a semiconductor laser and S)! A color image forming method using second harmonics obtained using a device.

(4) A color image forming method using an organic nonlinear optical material as the second harmonic conversion element in embodiment (3).

(5) A color image forming method according to embodiment (4), characterized in that the compound represented by -bottom (■) or -bottom (■) is used as the organic nonlinear optical material.

(6) The color image forming method according to embodiment a (3), wherein the wavelength conversion element has a waveguide structure.

(7) The image forming method according to embodiment (3), wherein the wavelength conversion element has a fiber type structure.

(8) A color image forming method according to embodiment a (5), wherein the organic nonlinear optical material is PRA or TRI below.

PRA TRI [Examples] Next, the present invention will be described in more detail based on Examples. However, the present invention is not limited to these specific examples.

The exposure apparatus used in the examples is shown below.

(N-optical device-1) GaAs semiconductor laser (oscillation wavelength, approx. 900 nm)
nm), InGaAs (oscillation wavelength, approximately 11l100
n, InGaAs (oscillation wavelength, approximately 1309 nm), and second harmonics (450 nm, 550 nm, respectively) using fiber-type elements in which TRI (below), a nonlinear optical material, is crystallized in glass fiber.
, 650 nm) was taken out. Wavelength converted blue, green,
An apparatus was constructed in which the red and red laser beams could be sequentially scanned and exposed onto a color photographic paper that moved in a direction perpendicular to the scanning direction using a rotating polyhedron. The amount of exposure was electrically controlled by the amount of light from a semiconductor laser.

(Chemical structure of TRI) (Exposure device-2) An exposure device in which the green light source in exposure device-1 was replaced with an LD-excited YAG laser.

(Exposure equipment-3) GaAs semiconductor laser (oscillation wavelength, approx. 900 nm)
nm), InGaAs (oscillation wavelength, approximately 1300 nm)
), this is synthesized using a dichroic mirror, and this is incident on a fiber-type element in which TRI (below), a nonlinear optical material, is crystallized in a glass fiber, and the second harmonics of the two wavelengths (450 nm, 650 nm) are synthesized using a dichroic mirror. , and the sum frequency (532 nm) of the lid horn wavelength was extracted.

We constructed a device that can sequentially scan and expose the wavelength-converted blue, green, and red laser beams onto a color photographic paper that moves in a direction perpendicular to the scanning direction using a rotating polyhedron with a filter. The amount of exposure was electrically controlled by the amount of light from a semiconductor laser.

(Exposure device-4) GaAs semiconductor laser (oscillation wavelength, approx. 920 nm)
nm), InGaAs (oscillation wavelength, approximately 1300n
m), synthesized with a dichroic mirror, and synthesized with PRA3.5-dimethyl-1, which is a nonlinear optical material.
-(4-nitrophenyl)pyrazole> is incident on a fiber-type element crystallized in a glass fiber, and the second harmonics of the two wavelengths (460 nm, 650 nm, and the sum frequency of the two wavelengths (539 nm) are extracted. Ta.

We constructed a device that can sequentially scan and expose the wavelength-converted blue, green, and red laser beams onto a color photographic paper that moves in a direction perpendicular to the scanning direction using a rotating polyhedron with a filter.

Example 1 (Example of silver chlorobromide emulsion) A total of seven types of multilayer color photographic papers having the layer configurations shown below were prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

27.2 cc of ethyl acetate and 7.7 cc of solvent (Solv 1) were added to 19.1 g of yellow coupler (ExY) and 4.4 g of color image stabilizer (Cpd-1) and melted.
This solution is a 10% aqueous gelatin solution containing 10% sodium dodecylbenzenesulfonate. fl 185c
It was emulsified and dispersed in c. On the other hand, silver chlorobromide emulsion (silver bromide 80.
0 mol %, containing 70 g/kg of Ag), and the following blue-sensitive sensitizing dye was added in an amount of 5.0XlO-' mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

The coating liquids for the second to seventh layer phases were also prepared in the same manner as the coating liquid for the first layer.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer (CHz)a (CHI)4 SOz H-N (cz Hs)sSO
3 (5°0XIO-' mol per mol of silver halide) SOs H-N (C2H5)3 (7.0XIO-' mol per 1 mol of halogen (IJ)) Green-sensitive emulsion layer 5O1 (1 mol of silver halide per 4゜SOi H-N (Cz Hs: h OXIO” mole) CsHu de CtHs (halogenated 1
! For red-sensitive emulsion layers, the following compounds were added at a concentration of 2
．． 6X10-3 moles were added.

and for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, 1-(5-methylureidophenyl)5-mercaptotetrazole was added at a concentration of 4.0% per mole of silver halide, respectively.
0XlO-'mol, 3.0XI (1'mol, 1.0X1
0-'mol was added.

Furthermore, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4hydroxy-6-methyl-1,3,3a, ? - 1.2XIO- of tetrazaindene per mole of each halogenated i
"Mole, 1.1XIQ-" mole was added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (layer structure) The composition of each layer is shown below. The numbers refer to the coating amount (g/d). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [white pigment (TiOz) and bluish bundle f! 4 (ulmarine blue)] th layer (blue-sensitive layer) Silver halide emulsion (Br: 80%) 0.26 gelatin
1.83 yellow coupler (
ExY) 0.83 color image stabilizer (Cpd-1
) 0.19m capacity (Solv-1>
0. 35 second layer (
Color mixture prevention N) Gelatin 0.99 Color mixture prevention agent (Cpd-2) 0.08 Third Ji! (Green sensitive layer) Silver halide emulsion (Br: 80%) 0.16 gelatin
1.79 magenta coupler (
ExM) Color image stabilizer (Cpd-3> Color image stabilizer (Cp d-4) Solvent (SOIV-2) Fourth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd- 5) Solvent (3o1v-3) Fifth layer (red-sensitive layer) Silver halide emulsion (Br near gelatin cyan coupler (ExC,) Cyan coupler (ExCz) Color image stabilizer (Cpd-6) Polymer (Cpd-7) Solvent (Solv~4) Sixth layer (R external ray absorption layer) Gelatin ultraviolet absorber (UV-1) 0%) 0, 53 0, 21 Solvent (S.

1v-3) 0° (Cpd-1) color image stabilizer Seventh layer (protective layer) gelatin l.

Acrylic 0° modified copolymer of polyvinyl alcohol (degree of modification 17%) Liquid paraffin 0° (Cpd) Color mixture inhibitor I (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (cpa Poly(Cth-) CI1) 7 CONHC4Hq(t) Average molecular weight 80° (LjV Ultraviolet absorber (Cpd-5) Color mixture inhibitor H (Cpd 2:9;8 mixture (weight ratio) of color image stabilizer 51:9 mixture (weight ratio) ) (2:1 mixture (volume ratio) of SOIV (Solv-2)) (3o1v (ExC) cyan coupler (EXC,) cyan coupler Samples 1 to 7 were prepared by adding a hardener as shown in Table 1 () Ta.

(SOIV-4) Solvent (Ex Y) Yellow coupler (ExM) Magenta coupler In order to find out how much the difference in density will be between the beginning and end of exposure by scanning exposure, we used exposure device-3. The gray density is approximately 1. The amount of blue light, green light, and red light of the exposure device was adjusted so that the amount of light was 0, and uniform scanning exposure was performed using these amounts of exposure. The time required for scanning exposure was approximately F minutes and 30 seconds.

The exposed sample was immediately subjected to the following color development treatment (within 10 seconds after exposure).

Using the sample thus obtained, the reflection density (D, ) at the beginning of scanning exposure and the reflection density (D, ) at the end of scanning exposure were measured for yellow, magenta, and cyan, respectively, and ΔD = D s D t was calculated. The density change was defined as the change in density between the beginning and end of scanning exposure.

These results are summarized in Table 2.

Processing process Mu skin prisoner plate color development
33℃ 3 minutes 30 seconds bleach fixing 33℃
Wash with water for 1 minute and 30 seconds 24-34℃
Dry for 3 minutes at 70-80℃ 1
The composition of each treatment solution is as follows.

Sadate Niri 1 Kisui 800
mediethylenetriaminepentaacetic acid 1.0g nitrilotriacetic acid M 1.5g Hensyl alcohol 15ml diethylene glycol 10mff sodium sulfite
2.0g potassium bromide 0
．． 5g potassium carbonate 30gN
-Ethyl-N-(β-methanesulfonamidoethyl)-3 -3-methyl-4-aminoaniline sulfate 5.0g Hydroxylamine sulfate 4.0g Fluorescent brightener (WHITE)
X4B.

)1.0 1000mf 10.20 add water pH (25℃) Reconstruction Ushi” Tatsu water Ammonium thiosulfate (70%) Sulphite I/Rium Iron(III) ethylenediaminetetraacetate ammonium Ethylenediaminetetraacetic acid disodium Rium add water pH (25℃) 400m1 1 50m1 8g 5g 1000mj! 6, 70 Table 2 As is clear from Table 2, the effects of the present invention are remarkable.

That is, in the comparative example, the difference in density between the beginning and end of scanning exposure is large for yellow, magenta, and cyan, and the color balance is also disrupted because these density differences are not equal. On the other hand, when the hardener of the present invention is used, not only the difference in density is small but also the color balance is maintained.

Example 2 (Example of high silver chloride emulsion) A total of seven types of multilayer color photographic papers having the layer configurations shown below were prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of 1st layer coating solution Add 27.2 cc of ethyl acetate and 7.7 cc of T medium (So Iv-1) to 19.1 g of yellow coupler (ExY) and 4.4 g of color image stabilizer (Cpd-1) and dissolve. This solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 13 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a silver chlorobromide emulsion (containing 1.0 mol % of silver bromide, 70 g/kg of Ag) was prepared by adding the following blue-sensitive sensitizing dye in an amount of 5.0XIO-' mol per mol of root. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

The coating liquids for the second to seventh layer phases were also prepared in the same manner as the coating liquid for the first layer.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer 5O1 so, H (5.0 x 10" mol per 1 mol of halogenated i)S
Ol SOs H-N (Ct H5)3 (halogenated! 7.0X10-' mol per II mol)
For the green-sensitive emulsion layer (4.0XIO-' mole per mole of halide) and the red-sensitive emulsion layer (4.0XIO-' mole per mole of halide) and the red-sensitive emulsion layer, 2.6 x 10-'' moles per mole of silver halide were added.

In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl) = 5-mercaptotetradules was added at 8.5 x 10-' mol per mol of halogenated i, respectively. 7.7X I O-'mol, 2
．． 5 x 10-' moles were added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (Layer configuration) The composition of each layer is shown below, and the numbers represent coating N (g/M). The silver halide emulsion represents the coated amount in terms of silver.

Support Polyethylene laminate Fuito [The polyethylene on the first layer side contains a white pigment (TiOz) and a blue dye (ulmarine)] Layer-1 (blue sensitive layer) Halogenated 1FATL agent (B r 1 mol %) 0.30
Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (
cpa-1,) o, 19n capacity (So
lv-1) 0. 35
Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-2) 0.08 Third layer (green sensitive layer) A Cl Silver saponide emulsion (Br 1 mol%) 0.36
Gelatin 1.24 magenta coupler (ExM) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Solvent (3o1v-2) Fourth layer (UV absorption N) Gelatin UV absorber (UV-1) Color mixing inhibitor (Cpd~5) Solvent (3o1v-3) Fifth layer (red sensitive layer) Silver halide emulsion (Br1 mol%) Gelatin cyan coupler (EXCJ) Color image stabilizer (Cpd~6) Polymer (Cpd- 7) Solvent (3o1v 4) 6th layer (ultraviolet absorbing layer) Gelatin ultraviolet*W & absorbent (UV-1) medium (SOIV-3> 0, 21 0, 08 7th layer (protective layer) Gelatin polyvinyl alcohol Acrylic modified copolymer (degree of modification 17%) Liquid paraffin 1, 33 0, 17 (Ex Stabilizer (ExCz) Noan coupler (Cpd Color image stabilizer CII.

0 ( (Cpd Color mixing prevention agent H (Cpd color image stabilizer 5:8 9 mixture (weight ratio) (Solv l) melt medium (Solv medium (Solv melt medium C00CI1. CI ((CI Its) C4H.

(C11ri 1 COOCHz CH(CtH,)C,H.

(Cpd-7) Poly(CI-It CH)-r- CONHCg H*(t) Average molecular weight 80° (UV l) 2:9:8 mixture of ultraviolet absorber H @yJ (weight ratio) (Solv Solvent No. As shown in Table 3, in order to find out how much the difference in density will be between the beginning and end of exposure by hardening sample 8-1 (R1) hardening agent scanning exposure with the addition of a hardening agent, Using Exposure Device-3, the amounts of blue light, green light, and red light of the exposure device were adjusted so that the gray density was approximately 1.0, and uniform scanning exposure was performed using these exposure amounts. The time required was approximately 1 minute and 30 seconds.

Immediately after this exposure (within 10 seconds), the following color development process was performed.

Using the sample obtained in this way, what is the reflection density (D,) at the beginning of scanning exposure and the reflection at the end? m degrees (D t
) are measured for yellow, magenta, and cyan respectively, and ΔD=D, -D! is the density change between the beginning and end of scanning exposure.

These results are summarized in Table 4.

Processing process><Temperature> Processing time> Color development 35℃ 45 seconds Bleach fixing
35℃ 45 seconds water washing ■ 35℃
Wash with water for 30 seconds ■ 35℃ 30
Wash with water for seconds ■ Dry at 35°C 75°C 30 seconds 60 seconds 31 mEthylenediamine-N,N,N'N'-tetramethylenephosphonic acidtriethanolamineSodium chloridePotassium carbonateN-Ethyl-N-(β-methanesulfonamide Ethyl)-3-methyl 4-aminoaniline sulfate N,N-bis(carboxymethyl) hydrazine optical brightener (UVITEX CK manufactured by Ciba Geigy) Add water to pH (25°C) 1000ml Mother liquor 800ml 3.0g 8, Og 1.4g 5g 5.0g 5.0g 1.0g Kanye 1ji 1 straight water 700
m1 ammonium thiosulfate r volume 100ml (
700g/I) Ammonium sulfite 18g ferric ethylenediaminetetraacetate 55g ammonium dihydrate ethylenediaminetetraacetic acid flI2 sodium 3g lium ammonium chloride bromide, tog ice vinegar M
Add 8g water
1000mJp1000℃) 5.5 Washing liquid Use tap water treated with an ion exchange resin to reduce calcium and magnesium to 3 ppm or less. (The electrical conductivity at 25° C. was 5 μs/cII.) As is clear from Table 4, the effect of the present invention is remarkable in this example as well. That is, in the comparative example, the 4-degree difference between the beginning and end of scanning exposure is large for yellow, magenta, and cyan, and the density differences are not equal, resulting in color balance. On the other hand, when the hardener of the present invention is used, not only the difference in density is small but also the color balance is maintained.

Example 3 A similar test was conducted using coating samples 8 to 14 used in Example 2, but changing the development process and processing solution to those shown below.

Similar to Example 2, the results showed the remarkable effects of the present invention.

Processing process: Profitable and inexpensive Single-plate color development Bleach fixing at 35°C for 45 seconds
30~36℃ Stable for 45 seconds ■ 30~37℃
Stable for 20 seconds ■ Stable for 20 seconds at 30-37℃ ■ Stable for 20 seconds at 30-37℃ ■
Dry for 30 seconds at 30-37℃ 70-8
5℃ 60 seconds (4 tanks countercurrent direction to stable ■-■) N-Ethyl-N-(β-methanesulfonamidoethyl)-3 Methyl-4-aminoaniline sulfate N,N-diethyl Hydroxylamine 56-cyhydroxyhensen-1.2.4-trisulfonic acid fluorescent brightener (4,4'-diaminostilbene) Add water to pH 5,0g 4,2g 0,3g 2,0 1000ml 10.10 The composition of each treatment liquid is as follows.

Left side: "■1 European water ethylenediaminetetraacetic acid triethanolamine sodium chloride potassium carbonate 80 0r+1 2,0g 8,0g 1,4g 25.0g! Top 1 C1 Cinnamon Ammonium 1000 sulfate (70%) Sodium sulfite Iron ethylenediaminetetraacetate (I[[) Ammonium ethylenediaminetetraacetic acid disodium 40 0 ml! 00ml 8g 5g 3g Add water to pH 1000ml 5.5 λ plantar formalin (37%) 0.1g formalin-sulfite adduct 0.7g 5-chloro-
2-Methyl-4-isothiazolin-3-one 0.02 g2~Methyl-4-isothiapurin-3-one 0.01g0.00
5 Add water 1000ml1tpH4
, 0 (Effects of the Invention) According to the color image forming method of the present invention, color unevenness and density unevenness at the beginning and end of exposure, which tend to occur in scanning exposure, can be reduced to a minimum.

Claims (1)

[Scope of Claims] 1) Scanning exposure is performed on a silver halide photographic light-sensitive material containing on a support at least one coupler that forms a dye by coupling with an oxidized product of an aromatic primary amine developing agent. , a color image forming method further comprising color development and desilvering treatment, characterized in that the photographic light-sensitive material is hardened with a compound represented by the following general formula [H]. Formation method. General formula [H] X^1-SO_2-L-SO_2-X^2 [In the formula, X^1 and X^2 are -CH=CH_2 or -
Either CH_2CH_2Y, X^1 and X^
2 may be the same or different. Y represents a group that undergoes a substitution reaction with a nucleophilic group, or a group that can be eliminated in the form of HY with a base. L is a divalent linking group and may be substituted.