JP2533338B2 - Color image forming method - Google Patents

Description

TECHNICAL FIELD The present invention relates to an image forming method using a silver halide color print light-sensitive material, and in particular, it has excellent color forming properties, little color mixing, excellent color reproducibility, and stable stability. Another object of the present invention is to provide a color image forming method.

(Prior Art) In a color image forming method using a silver halide color print light-sensitive material, it is important to reduce the cost and increase the cost of the print light-sensitive material in order to perform a process that is excellent in color development and color mixing and color reproducibility. This is an essential technology for quality improvement. In particular, performing color processing with excellent color development makes it possible to reduce the amount of couplers and silver used in print photosensitive materials, and is a very effective means for reducing the cost of print photosensitive materials. Is.

Further, as a technique for preventing color mixture of a multi-layer color print light-sensitive material, a hydroquinone derivative, an aminophenol derivative, an amino compound, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a sulfonamide in an intermediate layer and a part of a light-sensitive layer are used. There is a method of incorporating a reducing compound such as a phenol derivative. Especially US Patent No. 2,
728,659, 2,732,300 and JP-A-50-156438, 60-
55339 and the like, dialkyl, substituted hydroquinones and the like, for example, U.S. Patent Nos. 2,360,290 and 3700453, JP-A-49-
Monoalkyl-substituted hydroquinones are used in 106329 and 51-156438. Further, methods using competitive couplers can be mentioned, but these methods are not always sufficient.

As described above, an appropriate method has not yet been found for a stable color image forming method that is excellent in color developability, little color mixing, and excellent color reproducibility.

Furthermore, in recent years, in addition to the conventional silver salt color photographic technology, many other technologies have been developed and spread, such as the commercialization of high-definition televisions, the introduction of electronic cameras in the market, and the progress of electrophotographic color image copying technology. is there. On the other hand, a silver halide multilayer color light-sensitive material is used as a light-sensitive material for photography to realize high sensitivity and high image quality, especially faithful color reproducibility, and as a print light-sensitive material, a copy from a color photograph or color printed matter or digital color image information. Increasingly diverse demands such as hard copy and reproduction of photographs from the company are being created. In addition to the conventional large-scale development method for color development processing, minilab systems are also widely used.

In this trend, demands for high sensitivity, high image quality, especially faithful color reproducibility and stabilization of finish quality, which are the characteristics of silver halide color multi-layered light-sensitive materials, are increasing more and more.

Regarding the multi-layer color light-sensitive material for photographing, the color material, the masking method, the method of using the DIR-compound, and the method for forming the layer, and the print light-sensitive material, the color material, silver halide grains, spectral sensitization and Improvements have been proposed regarding the layer construction method or the color development method.

(Problems to be Solved by the Invention) However, there is no proposal for an improved method as a total system such as a color print original, a color print photosensitive material or a printing method thereof and a color development processing method, and various technical advances have been made. The more I do so, the more the flaws of this total system become serious. At the time of shooting, the color print obtained by exposing the subject with the same visual characteristics as the human naked eye is obtained.
It is important to have spectral characteristics that match the impression obtained by capturing the subject with the naked human eye, and it can be said that the various processes during that time are only one type of carrier. The present invention is an unprecedented comprehensive improvement of the carrier, which has excellent color forming properties, low pollution, and high image quality, without lowering the productivity of forming an image from a color print original. It is in the process of improving color fidelity and reproducibility.

An object of the present invention is to improve the color developing property by increasing the color developing processing method including the first color developing solution at a low cost without increasing the amount of silver halide or a color coupler to be used, and to provide a rapid and stable color developing process. In order to reduce the pollution load caused by the processing liquid, various color development processes are performed. Secondly, the photographic color light-sensitive material and print light-sensitive material used for color print originals, in particular, the improvement of the printing process overcomes the difficulties of the improved color development processing and improves the color mixture synergistically to improve the color reproducibility. To improve. Other purposes will be apparent from the description of the specification.

(Means for Solving Problems) As a result of various investigations, the present inventors have found that the object of the present invention can be achieved by the following method.

(1) In a color image forming method in which an original for color printing is printed on a photosensitive material for color printing by a subtractive exposure method and then color development processing is performed, the photosensitive material for color printing is at least on a support. 1
The layer is provided with a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, and in the wavelength range excluding the wavelength range of the maximum wavelength ± 20 nm of the effective spectral photosensitive light amount distribution of each photosensitive layer of the color print photosensitive material when printing, Approximate at half maximum width (W _1/2 ) of spectral transmittance curve
Color image formation characterized by using a band stop filter having a spectral absorption band of 10 to 60 nm, and using a color developer containing substantially no sulfite ion during color development processing of a color print photosensitive material. Method.

(2) Color print photosensitive material has a silver chloride content of 80 mol%
The color image forming method according to claim 1, which has a layer using the above silver chlorobromide or silver chloride emulsion.

(3) The color image forming method according to claim (1) or (2), wherein a color developing solution containing substantially no benzyl alcohol is used in the color developing treatment.

(4) The ratio ((W _1/4 / W _3/4 )) of the 1/4 value width (W _1/4 ) to the 3/4 value width (W _3/4 ) of the spectral transmittance curve is 0.35 or more. Claims using a band stop filter (1st
Item) to the color image forming method according to item (3).

The original for color printing of the present invention includes a color photosensitive material for photographing, for example, a color negative photosensitive material, a color reversal photosensitive material, an instant photographic photosensitive material, a dupe, a negative film obtained from the color photosensitive material, a transparent positive film or a transparent film. It may be a printed matter such as a color photograph using an opposite support. These usually have an image composed of at least three primary colors of a yellow color material (Y), a magenta color material (M) and a cyan color material (C) on a support.

The color print photosensitive material of the present invention is a color photographic paper,
Direct color light-sensitive materials, reversal color light-sensitive materials, etc., which are composed of a yellow color developing layer, a magenta color developing layer and a cyan color developing layer, are generally spectrally dispersed on the support in the wavelength range of 380 to 520 nm. Sensitive blue-sensitive silver halide photosensitive layer (blue-sensitive layer: BL), virtually 480 nm or
Green-sensitive silver halide photosensitive layer (green sensitive layer: GL) having spectral sensitivity in the wavelength range of 600 nm and red-sensitive silver halide photosensitive layer (red sensitive layer: RL) having substantially spectral sensitivity in the wavelength range of 570 nm to 740 nm. Has at least three photosensitive layers.

In the present invention, the main role of the color print light-sensitive material is to provide image information of the three primary color materials of the color print original, that is, the yellow color material (Y), the magenta color material (M) and the cyan color material (C). It has the spectral sensitivity of the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer of the color print light-sensitive material corresponding to its spectral transmission characteristics, and is independently incorporated into the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer. It is to faithfully reproduce with coloring materials.

The color development processing method used in the present invention will be described.

The first feature of the present invention is that sulfite ion in the color developing solution is reduced or substantially not contained.

When the amount of sulfite ion is reduced, the color developability can be enhanced without increasing the amount of silver halide or color coupler used. On the other hand, however, the problem can be solved by using the above-described image forming method of the present invention, which was found to increase the color mixture and deteriorate the color reproducibility.

The sulfite ion also acts as a solvent for a silver halide emulsion having a high chlorine content (high silver chloride emulsion), which may cause a remarkable decrease in concentration. When the concentration of sulfite ion in the color developing solution changes due to the above-mentioned action, it is shown as a change in photographic characteristics, and especially in the case of a print photosensitive material, printer conditions are constantly changed.

More preferably, the amount of benzyl alcohol is not reduced or substantially contained in order to reduce the pollution load caused by the color development processing solution and to reduce the occurrence of color mixing and stain.

When benzyl alcohol is used, its solubility in water is low, so that diethyl glycol, triethylene glycol or the like is required as a solvent. However, these compounds, including benzyl alcohol, have a
Because of high D and COD, it is preferable to remove benzyl alcohol for the purpose of reducing pollution load.

Further, even if the solvent is used, it takes time to dissolve the benzyl alcohol, so it is preferable not to use benzyl alcohol for the purpose of reducing the preparation work.

Further, when benzyl alcohol is brought into a bleaching bath or a bleach-fixing bath which is a post-bath, it causes the formation of a leuco dye which is a cyan dye, which causes a decrease in color density. Further, since the washing-out speed of the developer component is delayed, the image storability of the processed light-sensitive material may be adversely affected. Therefore, it is preferable not to use benzyl alcohol for the above reasons.

In the present invention, sulfite ion may be added to the extent that it does not substantially affect the photographic property as it does not substantially contain, specifically 0 to 0.005 mol / l, preferably 0 to 0.002 m.
ol / l. Further, the phrase "substantially free of benzyl alcohol" means that the color developer is not more than 5.0 ml, preferably not more than 2 ml, and more preferably not contained at all.

In the present invention, instead of containing no sulfite ion, it is preferable to contain the following organic preservatives.

That is, it is possible to stabilize the color developing solution and improve the color mixture without deteriorating the color developability.

The organic preservative described in the present invention refers to all organic compounds that reduce the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, it is an organic compound having a function of preventing the oxidation of the color developing agent by the air, among them, hydroxylamines, hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-
Aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds,
Fused amines and the like are particularly effective organic preservatives. These are Japanese Patent Application Nos. 61-147823, 61-173595, and
61-165621, 61-188619, 61-197760, 61
-186561, 61-198987, 61-201861, 61-
186559, 61-170756, 61-188742, 61-1887
41, U.S. Pat.Nos. 3,615,503 and 2,494903, JP-A-52-14
3020, Japanese Examined Patent Publication No. 48-30496, and the like.

With respect to the preferred organic preservatives, general formulas and specific compounds are shown below, but the present invention is not limited thereto.

In addition, as a technology using the following organic preservatives,
Examples thereof include a technique using an alkanolamine described in 60-57586, and a technique using a polyalkyleneimine described in JP-A-56-94349.

The amount of the following compounds added to the color developer is 0.005
Mol / l to 0.5 mol / l, preferably 0.03 mol / l to 0.1 mol
It is desirable to add it so that the concentration becomes / l.

The following are preferred as the hydroxyamines.

In the formula, R ¹¹ and R ¹² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group.
R ¹¹ and R ¹² do not become hydrogen atoms at the same time, and may be linked to each other to form a heterocycle with the nitrogen atom.

It is preferable that R ¹¹ and R ¹² are an alkyl group or an alkenyl group, and the carbon number is preferably 1 to 10, and particularly preferably 1 to 5. Examples of the nitrogen-containing hetero ring formed by linking R ¹¹ and R ¹² include a piperidyl group, a pyrrolidyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benzotriazole group.

Preferred substituents of R ¹¹ and R ¹² are hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amido group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

The following are preferable hydroxamic acids.

In the formula, A ²¹ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted Alternatively, it represents an unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an acyl group, a carboxy group, a hydroxyamino group or a hydroxyaminocarbonyl group. Examples of the substituent include a halogen atom, an aryl group, an alkyl group, an alkoxy group, and the like.

Details of the general formula (II) are described on pages 13 to 14 of Japanese Patent Application No. 62-65115, and specific examples are described on page 15 of the specification.

The following are preferred as hydrazines and hydrazides.

In the formula, R ³¹ , R ³² , and R ³³ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R ³⁴ is a hydroxy group, a hydroxyamino group, a substituted or unsubstituted group, Represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group. X ³¹ is -CO-, -SO _2- , or Represents a divalent group selected from, and n is 0 or 1. In particular, when n = 0, R ³⁴ represents a group selected from an alkyl group, an aryl group and a heterocyclic group, and R ³³ and R ³⁴ may form a heterocyclic ring together.

In the general formula (III), R ³¹ , R ³² , and R ³³ are preferably hydrogen atoms or alkyl groups, and most preferably R ³¹ and R ³² are hydrogen atoms.

In formula (III), R ³⁴ is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group or an amino group. X ³¹ is preferably —CO— or —SO ₂ —, and most preferably —CO—.

(III-2) NH ₂ NHCH _{2 4} SO ₃ H (III-3) NH ₂ NHCH _{2 2} OH (III-6) NH ₂ NHCOCH ₃ (III-7) NH ₂ NHCOOC ₂ H ₅ (III-12) NH ₂ NHSO ₃ H (III-10) NH ₂ NHCONH ₂ (III-14) NH ₂ NHCOCONHNH ₂ (III-15) NH ₂ HNCH ₂ CH ₂ CH ₂ SO ₃ H (III-18) NH ₂ NHCH ₂ CH ₂ COOH The following are preferred as phenols.

In the formula, R ⁴¹ is hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, carboxyl group, sulfo group, carbamoyl group, sulfamoyl group, amide group, sulfonamide group, ureido group, alkylthio group, It represents an arylthio group, a nitro group, a cyano group, an amino group, a formyl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxysulfonyl group, and an aryloxysulfonyl group. When R ⁴¹ is further substituted, examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxy group, an alkoxy group and the like. When two or more R ⁴¹ are present, they may be the same or different, and when they are adjacent to each other, they may be bonded to each other to form a ring.

R ⁴² represents a hydrogen atom or a hydrolyzable group. Further, m and n are integers from 1 to 5, respectively.

Details of the general formula (IV) are described on pages 19 to 20 of the specification of Japanese Patent Application No. 62-65115, and specific examples thereof are described on pages 21 to 2 of the specification.

The following are preferred as α-hydroxyketones and α-aminoketones.

In the formula, R ⁵¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group, and R ⁵² represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. Represents a group, and R ⁵¹ and R ⁵² may together form a carbocycle or a chlorine ring. X ⁵¹ represents a hydroxyl group or a substituted or unsubstituted amino group.

In general formula (V), R ⁵¹ is preferably a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, and R ⁵²
Is preferably a hydrogen atom or an alkyl group.

Specific examples of the general formula (V) include Japanese Patent Application No. 62-65.
No. 115, pages 24 to 25.

 Sugars are also preferred organic preservatives.

Sugars (also called carbohydrates) consist of monosaccharides and polysaccharides,
Many have the general formula C _n H _2m O _m . Monosaccharides are generally aldehydes or ketones of polyhydric alcohols (called aldose and ketose, respectively) and their reduced derivatives,
It is a generic term for oxidized derivatives, dehydrated derivatives, and a wider range of derivatives such as amino sugars and thio sugars. The polysaccharide refers to a product obtained by dehydrating and condensing two or more of the aforementioned monosaccharides.

Among these sugars, more preferable ones are aldoses having a reducing aldehyde group, and derivatives thereof, and particularly preferable ones are those corresponding to monosaccharides.

Specific examples of saccharides are described in Japanese Patent Application No. 62-65115, pages 27 to 28.

Examples of the monoamines include the following.

In the formula, R ⁷¹ , R ⁷² and R ⁷³ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. Where R ⁷¹ and R ⁷² , R ⁷¹ and R ⁷³ or R ₇₂ and R
₇₃ may be linked to form a nitrogen-containing heterocyclic ring.

Here, R ⁷¹ , R ⁷² and R ⁷³ may have a substituent. As R ⁷¹ , R ⁷² and R ⁷³ , a hydrogen atom and an alkyl group are particularly preferable.

VII-1 NCH ₂ CH ₂ OH) ₃ VII-2 H ₂ NCH ₂ CH ₂ OH VII-3 HNCH ₂ CH ₂ OH) ₂ VII-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ VII-11 HNCH ₂ COOH) ₂ VII-13 H ₂ NCH ₂ CH ₂ SO ₂ NH ₂ VII-14 H ₂ N-CCH ₂ OH) ₂ The following diamines are preferred.

In the formula, R ⁸¹ , R ⁸² , R ⁸³ , and R ⁸⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group.

R ⁸⁵ represents a divalent organic group, specifically an alkylene group, an arylene group, an aralkylene group, an alkenylene group or a heterocyclic group.

R ⁸¹ , R ⁸² , R ⁸³ , and R ⁸⁴ are particularly preferably a hydrogen atom or an alkyl group, and R ⁸⁵ is particularly preferably an alkylene group.

VIII-2 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ VIII-4 H ₂ NCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ Specific examples of the general formula (VIII) include Japanese Patent Application No. 62-
No. 65115, pages 34 to 35.

The following are preferable polyamines.

In the formula, R ⁹¹ , R ⁹² , and R ⁹³ and R ⁹⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group.

R ⁹⁵ , R ⁹⁶ , and R ⁹⁷ represent a divalent organic group, and specifically have the same meaning as R ^{85 in the} general formula (VIII).

X ⁹¹ and X ⁹² R represents a linking group composed of —O—, —S—, —CO—, —SO ₂ —, —SO— or a combination of these linking groups;
⁹⁸ has the same ^meaning as R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ . m represents 0 or an integer of 1 or more.

(The upper limit of m is not particularly limited and may be a high molecular weight as long as the compound is water-soluble, but usually m is preferably in the range of 1 to 3) IX-2 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ OCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ Specific examples of the general formula (IX) include Japanese Patent Application No. 62-65.
115, pages 36-37.

 The following are preferred as quaternary ammonium salts.

 Where R¹⁰¹Represents an n-valent organic group, R¹⁰², R¹⁰³And R
¹⁰⁴Quaternary ammo by combining at least two groups of
It may form a heterocycle containing a nitrogen atom. n is 1
Is an integer greater than or equal to X Represents a counter anion.

Details of the general formula (X) are described in Japanese Patent Application No. 62-65115, page 38, and specific examples are described on pages 38 to 40 of the same.

The following are preferred as the nitroxy radicals.

R ¹¹¹ and R ¹¹² each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Further, these alkyl group, aryl group or heterocyclic group may have a substituent.
Examples of such a substituent include a hydroxy group, an oxo group, a carbamoyl group, an alkoxy group, a sulfamoyl group, a carboxy group and a sulfo group. Examples of the heterocyclic group include a pyridyl group and a piperidyl group.

(Compound example) Details of general formula (XI) are described on page 40 of the specification of Japanese Patent Application No. 62-65115, and specific examples thereof are described on pages 41 to 42 of the specification.

Wherein R ¹²¹ represents a hydroxy-substituted alkyl group;
¹²² represents an unsubstituted alkyl group or the same group as ^R121 . R
¹²³ represents a hydrogen atom or a group similar to ^R122 . X ¹²¹ is a hydroxy group, a carboxyl group, a sulfo group, a nitro group,
It represents an unsubstituted or hydroxy-substituted alkyl group, an unsubstituted or substituted amide group, and a sulfonamide group.

In the general formula (XII), X ¹²¹ is preferably a hydroxy group, a carboxyl group or a hydroxyalkyl group.

Specific examples of the general formula (XII) include Japanese Patent Application No. 62-6.
No. 5115, pp. 43-44.

The following alcohols are preferable.

In the formula, R ¹³¹ , R ¹³² and R ¹³³ each represent a hydrogen atom or an alkyl group, and n represents a positive integer up to 500.

XIII-1 HOCH ₂ CH ₂ O ₄ OH XIII-2 CH ₃ OCH ₂ CH ₂ O ₃ OH XIII-8 HOCH ₂ CH ₂ O _n H 〃 About 800 For more information on the general formula (XIII), see Japanese Patent Application No. 62-65115. It is described on page 45 of the specification, and as a specific example, it is described on page 45 of the same specification.
Pp. 47-47.

 The following oximes are preferred.

In the formula, R ¹⁴¹ and R ¹⁴² represent a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group, respectively. R ¹⁴¹ and R ¹⁴² may be the same or different, and these groups may be linked together.

Details of the general formula (XIV) are described in Japanese Patent Application No. 62-65115, page 48, and specific examples are described on pages 48 to 49 of the specification.

 The following are preferable polyamines.

In the formula, X ¹⁵¹ , X ¹⁵² represent —CO—, or —SO ₂ —, R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ and R ¹⁵⁶ represent a hydrogen atom, an unsubstituted or substituted alkyl group, R ¹⁵⁷ represents an unsubstituted or substituted alkylene group, an unsubstituted group or a substituted arylene group, and an unsubstituted or substituted aralkylene group.

m ¹ , m ² and n represent 0 or 1.

XV-6 H ₂ NSO ₂ NHSO ₂ NH ₂ A specific example of the general formula (XV) is Japanese Patent Application No. 62-65.
No. 115, page 1 to page.

 The following compounds are preferable as the condensed ring amines.

In the formula, X represents a trivalent atom group necessary for completing a condensed ring, and R ¹ and R ² represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

Here, R ¹ and R ² may be the same or different.

Among the general formula (XVI), the particularly preferable one is the general formula (1
-A) and compounds represented by (1-b).

In the formula, X ¹ represents N or CH.

R ¹ and R ² are defined as in the general formula (XVI), and R ³
Is a group similar to R ¹ and R ² , or Represents

In the general formula (1-a), X ¹ is preferably N. The carbon number of R ¹ , R ² , and R ³ is preferably 6 or less, more preferably 3 or less, and most preferably 2.

R ¹ , R ² and R ³ are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R ¹ and R ² are defined as in the general formula (XVI).

In the general formula (1-b), it is preferable that R ¹ and R ² have 6 or less carbon atoms. R ¹ and R ² are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds of the general formulas (1-a) and (1-b), the compound represented by the general formula (1-a) is particularly preferable.

The compound of general formula (XVI) according to the present invention can be easily obtained from many commercial products.

The amount of the organic preservative represented by the general formulas (I) to (XVI) is 1 × 10 ^{-4 to} 5.0 to 10 ^-1 per color developing solution.
The molar amount is preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol.

From the viewpoint of preservative performance, it is preferable to use the compounds of the general formulas (I) to (VI) and the compounds of the general formulas (VII) to (XVI) in combination,
Particularly, it is preferable to use one kind selected from the general formulas (I) and (III) and one kind selected from the general formulas (VII) and (XVI) in combination.

The color developing solution used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3 -Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
Examples include -β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, organic solvents such as ethylene glycol and diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, 1 -Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid , Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and them Can be mentioned as a representative example.

When the reversal process is performed, black and white development is usually performed before color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When reducing the amount of replenishment, it is preferable to reduce the contact area with the air in the processing tank to prevent evaporation of liquid and air oxidation. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer of the color developing solution is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salt (III) The complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution containing these aminocarboxylic acid iron (III) complex salts is usually
5.5 to 8, but lower p for faster processing
H can also be processed.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-
95,630, Research Disclosure No. 17,129 (July 1978) and the like, compounds having a mercapto group or a disulfide bond; thiazolidine derivatives described in JP-A-50-140,129; US Pat. No. 3,706,561 Thiourea derivatives described therein; iodide salts described in JP-A-58-16235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B-4-8836; bromide ion and the like are used. it can. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly preferred are compounds described in U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95,630. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly useful when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the purpose, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, calcium ions described in Japanese Patent Application No. 61-131,632,
The method of reducing magnesium ions can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isoannurate, other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide",
It is also possible to use the bactericides described in "Microbial Sterilization, Sterilization, and Antifungal Agents" edited by the Sanitary Technology Association and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Society for Antibacterial and Antifungal Society of Japan.

The pH of the washing water in the treatment of the present invention is 4-9,
Preferably it is 5-8. Washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, application, etc.
A range of 20 seconds to 10 minutes at -45 ° C, preferably 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8,54
All known methods described in Nos. 3, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and as an example, it is used as a final bath of a color light-sensitive material for photographing. Mention may be made of a stabilizing bath in which formalin and a surfactant are derived. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanied by the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

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 the processing.
For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosures 14,850 and 15,159, aldol compounds described in No. 13,924, U.S. Patent No. 3,719,492. Examples thereof include metal salt complexes described in JP-A No. 53-135,628 and urethane compounds described in JP-A No. 53-135,628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-type light-sensitive materials for the purpose of promoting color development, if necessary.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A Nos. 56-64,339, 57-14,4547, and 58.
-115,438 etc. are described.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality and the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The second feature of the present invention resides in the step of printing an original for color printing onto the color print photosensitive material of the present invention and the spectral sensitivity distribution of the print photosensitive material used.

As a method of printing a color print original on a color print photosensitive material, there are usually an additive color exposure method and a subtractive color exposure method.
The present invention is particularly a color image forming method including a printing process by an automatic printer including a subtractive color exposure system, particularly a white light color sensitive exposure system, that is, a white light exposure by a white light source.

When printing (exposure) in a so-called printer using the color filter used in the present invention, the exposure time is not particularly limited, but preferably 1 second to 1/100 second.

The color print photosensitive material needs to receive image information such as hue and gradation independently of each other due to the spectral absorption characteristics of the images of the color materials of the color print original, such as yellow, magenta and cyan. For this reason, the present invention most preferably receives information only in the vicinity of the maximum sensitivity wavelengths λ _{bs max} , λ _{gs max} and λ _{rs max} of the yellow, magenta and cyan color developing layers of the color print photosensitive material.

The blue-sensitive layer of a color print photosensitive material is practically 400 to 4
85nm, the green sensitive layer is practically 485 to 570nm, or the red sensitive layer is practically 570 to _750nm , the spectral sensitivity is set in the wavelength range, and the maximum sensitive wavelength length (λ _smax ) of the blue sensitive layer is 400 to _485nm , the green sensitive layer. The maximum sensitivity wavelength can be set to 520 to 570 nm, or the maximum sensitivity wavelength of the red-sensitive layer can be set to 600 nm to 740 nm.

The effective spectral light amount distribution used in the color print photosensitive material according to the present invention will be described. The spectral transmittance distribution of a color material of a color print original, for example, a color negative film is T _(λ) , and the spectral sensitivity distribution of a photosensitive layer of a color print photosensitive material, for example, a green photosensitive layer is S _(λ). When the distribution is P _(λ) , the effective spectral photosensitive light amount distribution E _(λ) received by the photosensitive layer is expressed by the following equation (1) E _(λ) = S _(λ) · T _(λ) · P _(λ) ( 1), and the effective photosensitive light amount, for example, the effective photosensitive light amount of the green sensitive layer is expressed by the following formula (2). Given in. Here, normally, T _{m (λ)} can be obtained from the spectral transmittance of the color material of the original of the color print obtained by photographing a gray subject, for example, Macbeth's color chart gray (i = 22).

Effective spectral photosensitivity energy distribution E given by equation (1)
_{(Λ) is referred} to as the effective spectral photosensitive light amount distribution.

Thus, the effective spectral sensitized light quantity distribution (hereinafter referred to as Eb) of the blue sensitive layer (BL) of the color print photosensitive material according to the present invention
_(Λ) ), in the same manner, the effective spectral sensitized light amount distribution (Eg _(λ) ) for the green sensitive layer (GL) and the effective spectral sensitized light amount distribution (Er _(λ) ) for the red sensitive layer (RL) are given. To be In the present invention, at least Eg _(λ) and Er _(λ) or Eg _(λ)
(Λ) and Eb _(λ) are preferably Eb _(λ) , E
Each of g _(λ) and Er _(λ) is substantially independent. Here, (1) 10% or less of the effective spectrophotometric amount (Eb, Eg, or Er) of a certain photosensitive layer obtained by printing a gray object of a color print light-sensitive material on a color negative film obtained by photographing it so as to be gray. In the presence or absence of that of the other layer, or preferably 7% or less, or (2) the effective spectral light intensity distribution (Eb _(λ) , Eg of a certain photosensitive layer ₎ .
_(Λ) , or Er _(λ) ) is present in less than about 15% of the maximum value of the other photosensitive layers, the effect of color mixing is substantially not clearly observed and can be substantially independent. Can be said.

For example, regarding the green-sensitive layer (GL) of a color print light-sensitive material (1) Eg _(λ) × 0.
When Er _(λ) and Ed _(λ) are suppressed below the value of 15 or when Er _(λ) and Eg _(λ) do not exist, or (2) In the wavelength range of 485 to 570 nm, below Eg × 0.10 When Er and Eb are suppressed, or when Er and Eb are not present, the effective spectral sensitized light intensity distribution (Eg _(λ) ) of the green sensitive layer
Can be said to be "substantially independent" of the other photosensitive layers.

In order to realize the effect of faithful color reproducibility in the present invention, the color material used for the color print light-sensitive material is particularly improved, and the color development processing causes residual color, generation of stain, defective desilvering, etc. It is necessary that there is no contamination of the color image, preferably the spectral sensitivity of the color light-sensitive material for photographing is set as described in, for example, Japanese Patent Application No. 61-234518, and more preferably a yellow coupler or a magenta coupler. That is, the coloring material according to (1) is improved so as to have a block type spectral transmittance.

Next, a method of making the effective spectral photosensitive light amount distribution independent will be described.

The color print light-sensitive material of the present invention, particularly the silver halide emulsion used for GL and RL, preferably has no strong intrinsic sensitivity in the wavelength range of BL and longer wavelength range.

Silver halide light-sensitive materials are usually practically used in the wavelength range shorter than about 540 nm for silver iodobromide emulsions, shorter than about 500 nm for silver bromide, and shorter than about 420 nm for silver chloride. It absorbs light and gives a latent image. In other words, it has photosensitivity. For example, TH James edited The Theory of the Photographic Pr
It is shown in the description on pages 39 to 44 of ocess (1977, 4th edition). Therefore, the halogen composition of silver halide grains and the method of crystal formation are extremely important for the present invention.

The silver halide emulsions used in the present invention, especially in color print light-sensitive materials, are disclosed in Japanese Patent Application Nos. 62-39825 and 61-311.
A silver chlorobromide emulsion essentially free of silver iodide, which remains from silver chloride, silver bromide, or a mixed crystal thereof surrounded by (100) faces as described in 131, is preferred. Further, as described in Japanese Patent Application No. 62-47225 and Japanese Patent Application No. 62-150320, it contains substantially silver iodide mainly composed of silver chloride having a (111) face, silver bromide or a mixed crystal thereof. Preferred is a silver chlorobromide emulsion.

Substantially free of silver iodide means that the content of silver iodide is 2 mol% or less, preferably 1 mol% or less, based on the total silver halide amount. More preferably 0.
It is 5 mol% or less, and most preferably contains no silver iodide. Including silver iodide has many useful points such as increasing the light absorption amount in terms of photosensitivity, enhancing the adsorption of the spectral sensitizing dye, or weakening the desensitization by the spectral sensitizing dye. In the case where rapid development is carried out for a short time in the system using the present invention, the slow development speed leads to a delay in the development speed of the entire silver halide grains, and also in terms of improving the average color mixing degree of the present invention, Bring disadvantages. 0.4
Although it may be advantageous to contain silver iodide in an amount of not more than mol% in terms of adsorption of the spectral sensitizing dye and the like, in the present invention, it is basically preferable to use a silver halide emulsion containing no silver iodide. preferable.

In the present invention, various silver bromide, silver chlorobromide, and silver chloride can be used in combination with the effects of an optical filter or a filter layer described later. However, in order to improve the color reproducibility according to the present invention, silver chlorobromide having a silver bromide content of 30 mol% or less or further silver iodide of 0.4 mol% or less and a silver bromide content of 10
Silver chlorobromide or silver chloride emulsions up to mol% are especially preferred.

Reducing the silver bromide content not only improves the speed of development, but also increases the equilibrium accumulation amount in the developing solution, which is determined by the relationship with the replenishment rate, when the photosensitive material containing it is run in the processing solution. Since the bromine ion is present at a low concentration, the rapid developing property of the developer itself can be set high, which is preferable.

The halogen composition of the silver halide emulsion used in the present invention is
Further, it is also related to the residual color of the dye and the desilvering property in the color development process, and it is disadvantageous especially when the silver iodide content is large. The characteristics related to the halogen composition are not determined only by the halogen composition of the whole grain, but also by the kind of halogen distribution in the grain. Therefore, in the present invention, the silver halide emulsion can have a distribution or a structure with respect to the halogen composition within the grain.

Next, the spectral sensitivity distribution of the silver halide emulsion used in the color print light-sensitive material is extremely important for the present invention, and therefore, the shape habit of the silver halide grains, the method of making them and the method of using the sensitizing dye are important. is there.

In the present invention, cubic or tetradecahedral grains and, moreover, junction type grains having a shape close to those of the grains are preferably used.
Cubic particles are particularly preferably used. The shape of silver chlorobromide is preferably an octahedron having a (111) plane, tabular grains, and particularly tabular grains having an aspect ratio of about 2 to 10 and having a thickness.

Emulsions containing silver halide grains having controlled development starting points as described in Japanese Patent Application No. 61-311131, Japanese Patent Application No. 62-86163 or Japanese Patent Application No. 62-150320 are particularly preferable. It is also preferred that the CR-compound (defined above) is a sensitizing dye.

The average grain size (average diameter of equivalent spheres in terms of volume) of the silver halide emulsion used in the present invention is 2 μm or less, preferably 0.1 μm or more. Particularly preferred is 1.4 μ or less and 0.15 μ or more. A narrower grain size distribution is better, and a monodisperse emulsion is preferred. Particularly, a monodisperse emulsion having a regular shape is preferable in the present invention. Emulsions containing 85% or more of all the grains within ± 20% of the average grain size in terms of the number or weight of grains, and particularly those containing 90% or more, are preferred. Even in the case of such a monodisperse emulsion, an emulsion comprising silver halide grains having any structure as described above is particularly preferable. And even such monodisperse emulsions, especially cubes,
It is preferable to use two or more kinds of tetradecahedral monodisperse emulsions in a mixed or multi-layered coating to obtain preferable results. When two or more kinds of monodisperse emulsions are mixed and used, it is preferable to mix and use each in a silver conversion mixing ratio of 5% or more and 95% or less.

In the process of grain formation or physical ripening of silver halide, a cadmium salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof may be present together. In particular, the iridium salt or its complex salt is particularly useful for obtaining rapid developability and stability when exposure is carried out at a high illuminance or a low illuminance outside the appropriate exposure illuminance range.

A silver halide emulsion used for a direct positive color print light-sensitive material is, for example, a halogenated silver halide emulsion having the above-mentioned halogen composition composed of internal latent image type silver halide grains having a large amount of structure described in Japanese Patent Application No. 62-25737. Silver emulsions are preferred.

Silver halide emulsions used in color reversal and print light-sensitive materials are described in, for example, EP No. 0217353A-2 and JP-A No. 61-39.
The emulsions described in JP-A No. 043 and JP-A No. 61-61156 are preferable.

The color print light-sensitive material used in the present invention is prepared by using the silver halide as described above and Eb _(λ) , E of each light-sensitive layer.
Spectral sensitization is performed so that g _(λ) or Er _(λ) becomes substantially independent.

Regarding the blue-sensitive layer (BL), only the intrinsic sensitivity of silver halide may be used, but the maximum intrinsic sensitivity wavelength is preferably 460 nm or less for speeding color development and preventing contamination.
It is provided below the wavelength range for spectral sensitization. Preferably, the wavelength λ _smax of the maximum S _(λ) of BL is selected from sensitizing dyes represented by the following general formula (VII) so that it is caused by J-type spectral sensitization.

In the formula, Z ₁₇₁ and Z ₁₇₂ are respectively a benzothiazole nucleus,
Naphthothiazole nucleus, benzazelenazole nucleus, naphthoselenazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, naphthoicidazole nucleus, indolenine nucleus, benzoindrenine nucleus, indole nucleus, or quinoline nucleus Represent. Each nucleus may be substituted.

R ₁₇₁ and R ₁₇₂ are each an alkyl group, an alkenyl group, an alkynyl or aralkyl group, R ₁₇₁ and R
One or both of ₁₇₂ has at least one sulfonic acid group, carboxyl group or hydroxyl group. j ₁ and k ₁
Represents an integer of 0 or 1, n ₁ represents 0 or 1, and represents n or 0 or forming an intramolecular salt.

X ₁ ^- represents an acid anion.

In the general formula (XVII), the hetero ring formed by Z ₁₇₁ and Z ₁₇₂ has a halogen atom such as F, Cl and Br,
Lower alkyl group such as methyl, ethyl, trifluoromethyl, benzyl group, phenethyl group, hydroxyl group, alkoxy group, acetyl group such as phenyl, chlorophenyl group, carboxyl group and its esterified carboxyl group, carbamoyl group, sulfamoyl group, etc. May be introduced. In particular, a group that strongly forms a J band, a halogen atom, a trifluoromethyl group, an aryl group, an esterified carboxyl group and the like are preferable.

R ₁₇₁ and R ₁₇₂ are each a lower alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group, an acetoxyalkyl group, an alkylureidoalkyl group, a hydroxyalkyl group, a chloroalkyl group, a sulfoalkyl group, a carboxyalkyl group, an allyl group, and benzyl. Group, phenethyl group and the like can be used for ordinary cyanine dyes.

Next, specific examples of the compound represented by the general formula (XVII) are shown. However, the present invention is not limited to this.

For the green layer (GL), its Eg _(λ) is Eb _(λ)
The maximum S _(λ) is J so that it is independent of Er and Er _(λ) .
It is advisable to select the sensitizing dye represented by the general formula (XVIII) due to the type spectral sensitization for spectral sensitization. In particular, spectral sensitization that reduces the contribution of M-type spectral sensitization is preferable. For this purpose, the use as a CR compound described in Japanese Patent Application No. 61-311131 and Japanese Patent Application No. 62-47225 is particularly preferable.

In the formula, Z ₁₈₁ represents a benzimidazole nucleus, a henzoxazole nucleus, a naphthimidazole nucleus or a naphthoxazole nucleus, and a Z ₁₈₂ represents a benzimidazole nucleus, a naphthimidazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus or a benzizerena. Represents a sol nucleus. Each nucleus may be replaced. R ₁₈₁ and R ₁₈₂ are respectively synonymous with R _D1 and R _D2 in the general formula (XVII). R ₁₈₃ represents a hydrogen atom, a lower alkyl group or an aralkyl group. j ₃ and k ₃ are the same as j _{1 in} formula (XVII), and n ₃ is the same as n _{1 in} formula (XVII). X ₃ ⁻ represents an acid anion.

Preferred substituents for the hetero ring formed by Z ₁₈₁ and Z ₁₈₂ in formula (XVIII) are described as preferred in the hetero ring formed by Z ₁₇₁ and Z ₁₇₂ in formula (XVII). The substituents mentioned can be mentioned.

Specific examples of the compound represented by formula (XIII) are shown below, but the invention is not limited thereto.

The amount of the compound of the general formula (XVIII) to be contained in the green-sensitive layer is not particularly limited, but is usually 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, preferably 5 ×, per mol of silver halide. 10 ^-5 ~
It is 2 × 10 ⁻³ mol. Two kinds of sensitizing dyes of formula (XVIII) may be used in combination in the green-sensitive layer.

Regarding the red-sensitive layer (RL), unlike the blue-sensitive layer and the green-sensitive layer,
It is easy to provide a wide wavelength range longer than the wavelength of the green-sensitive layer in correspondence with the color material T _(λ) of the color print original. So Er
_(Lambda) as is independent of the other effective spectral sensitive energy distribution, the maximum S _(lambda) so that due to J-type or M type spectral sensitization, the general formula (XIX), (XX), and The sensitizing dye represented by (XXI) can be selected and used. That according to general formula (XIX) may be used to provide J type spectral sensitivity, and that according to general formulas (XX) and (XXI) may be used to provide M type spectral sensitivity.

In the formula, Z ₁₉₁ and Z ₁₉₂ are a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a zenerazole nucleus, a benzozelenazole nucleus, a naphthoselenazole nucleus, an oxazole nucleus,
Benzoxazole nucleus, naphthoxazole nucleus, imidazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tetrazole nucleus, benzoterula Zol nucleus,
It represents a 5- or 6-membered heterocyclic nucleus such as a naphthotellurazole nucleus, and R ₁₉₁ and R ₁₉₂ are each an alkyl group, an alkenyl group, an alkynyl group or an araalkyl group, and the alkyl group may be substituted. The substituent is, for example, a halogen atom, a cyano group, an alloxy group, a substituted or unsubstituted amino group,
Examples thereof include a carboxylic acid group, a sulfonic acid group, and a hydroxyl group. m ₁₉₁
Is a positive number of 1, 2, or 3 and when m ₁₉₁ is 1, R ₁₉₃ represents a hydrogen atom, a lower alkyl group, an aralkyl group or an aryl group, and R ₁₉₄ represents a hydrogen atom. When m ₁₉₁ is 2 or 3
R ₁₉₃ represents a hydrogen atom, R ₁₉₄ represents a hydrogen atom, a lower alkyl group or an aralkyl group, and R ₁₉₄ may _combine with another R ₁₉₃ to form a hydrocarbon ring or a heterocycle. j ₄ and k ₄
Represents 0 or 1. X ₄ represents an acid anion and n ₄ represents 0 or 1.

In the formula, Z ₂₀₁ and Z ₂₀₂ have the same meaning as Z ₁₉₁ or Z ₁₉₂ described above. R ₂₀₁ and R ₂₀₂ have the same meaning as R ₁₉₁ or R ₁₉₂ and R ₂₀₃ represents an alkyl, alkenyl, alkynyl or aryl group (such as a substituted or unsubstituted phenyl group), m ₂₀₁ is 0, 1
Or represents 2. R ₂₀₄ is a hydrogen atom, a lower alkyl group,
In addition to the aryl group, when m ₂₀₁ represents 2, R ₂₀₄
And other R ₂₀₄ may combine to form a hydrocarbon ring or a heterocycle. These rings are preferably 5- or 6-membered rings.

 Q_FiveIs a sulfur atom, an oxygen atom, a selenium atom or is N-R
₂₀₅Represents R₂₀₅Is R₂₀₃Is synonymous with. j_Five, R₂₀₁, X_Five
And n_FiveEach j_Four, K_Four, X_Four And n_FourIs synonymous with
You.

In the formula, Z ₂₁₁ represents an atomic group necessary for forming a heterocycle. Examples of the heterocycle include those described with respect to Z ₁₉₁ and Z ₁₉₂ and specific examples thereof include thiazolidine, thiazoline, benzothiazoline, naphthothiazolin, selenazolidine, selenazoline, benzoselenazoline, naphthoselenazoline, benzoxazoline, naphthoxazoline, Cores such as dihydropyridine, dihydroquinoline, benzimidazoline and naphthimidazoline can be mentioned. Q ₆ is synonymous with Q ₅ . R ₂₁₁ is R ₂₀₁ or R ₂₀₂ ,
R ₂₁₂ is synonymous with R ₂₀₃ . m ₂₁₁ has the same _meaning as m ₂₀₁ .
R ₂₁₃ has the same _meaning as R _204, and when m ₂₁₁ represents 2 or 3, R ₂₁₃ and another R ₂₁₃ may combine to form a hydrocarbon ring or a heterocycle. j ₆ is synonymous with j ₅ .

Next, specific examples of preferable sensitizing dyes will be shown.

General formulas (XIX), (XX) and (X used in the present invention
The sensitizing dye represented by XI) is 1 × 10 ⁻⁶ mol to 5 × 10 ⁻³ mol, preferably 5 × 10 5 mol per mol of silver halide.
About ^10-6 mol to about ^1-10-3 mol may be used alone or in combination with another supersensitizer.

Spectral sensitization in the color print light-sensitive material according to the present invention is substantially characterized by J-type spectral sensitization or M-type spectral sensitization.

In the present invention, the effective spectral sensitized light amount distribution (Eg
_(Λ) ) is substantially J-type spectral sensitization, and the effective spectral sensitized light amount distribution (Er _(λ) ) of the red-sensitive layer is substantially M-type spectral sensitization or J-type spectral sensitization. Is preferred. J
Type spectral sensitization is the sensitization by spectral absorption obtained by adsorbing a sensitizing dye on a silver halide adsorption substrate with a J aggregate.
M-type spectral sensitization is sensitization by spectral absorption obtained by molecular adsorption of a sensitizing dye. For example TH James edition The Thery o
f The Photographic Process 4th edition (1977), pages 218 to 222.

Here, for example, that Eg _(λ) is J-type spectral sensitization means
Means that the Eg _(lambda) does not indicate a maximum of Eg _(lambda) corresponding to M type, the Eg _(lambda) is substantially J-type spectral sensitization in the wavelength range of the green-sensitive layer, J Eg _(λ) corresponding to the mold
It means that the maximum value of Eg _(λ) corresponding to M type is not shown above the value of Eg _(λ) of about 3/4 of the maximum value of.

As shown in the relationship between the effective spectral exposure light amount distribution E _(λ) and the spectral sensitivity distribution S _(λ) of the color print photosensitive material according to the equation (1), S _(λ) is generally the J-type spectral sensitization. Sometimes E _(λ) corresponding to that wavelength is J-type spectral sensitization. Those skilled in the art can easily discriminate whether the J-type spectral sensitization or the M-type spectral sensitization is based on the structure of the sensitizing dye used, the spectral absorption characteristics of the solution, and the spectral absorption characteristics when adsorbed on silver halide. . The sensitizing dyes used may be used alone or in combination. Particularly in the case of M-type spectral sensitization, for example, Japanese Patent Application No. 62-39825, US Pat. No. 2,933,390, and US Pat.
Aminostilbene compounds and mercaptoheterocyclic compounds described in No. 1 and the like may be used together.

The next feature of the present invention is to use a band stop filter in the baking process. As a result, even if the spectral sensitivity distribution of the silver halide emulsion does not substantially match, the effective spectral light amount distribution of each photosensitive layer of the color print photosensitive material can be made independent. By using the predetermined band stop filter of the present invention, the color mixing can be easily improved without extending the baking time. As a result, it is possible to remove the color-mixing defect caused by the color development process of the present invention.

The color print light-sensitive material according to the present invention is printed from a color print original, especially a color negative film or a color slide, by a subtractive color exposure system, especially the above-mentioned white light exposure system. At this time, a sharp band stop having a spectral absorption band in a wavelength range other than the wavelength range λ _smax ± 20 nm of the maximum E _(λ) of the photosensitive layer of the color print photosensitive material.
It is preferable to use a filter. In the color print light-sensitive material of the present invention, the wavelength of the maximum E _(λ) of each photosensitive layer substantially coincides with the wavelength of the maximum S _(λ) . The sharp band stop filter used in the present invention is preferably a band stop filter obtained by multi-layer vapor deposition of an organic dielectric, an inorganic oxide, a metal or a compound thereof on a filter substrate such as glass or plastic film. For example, it can be manufactured in accordance with a multilayer optical interference filter as described in JP-A-57-190908 and a multilayer optical filter using titanium oxide and magnesium fluoride as described in JP-A-54-53548. . Furthermore, the spectral transmittance is 70% or more, and the minimum transmittance of the spectral absorption band is 20%.
It is preferably 10% or less. The shape factor W _1/4 / W _3/4 (however, 3/4 of the spectral transmittance is W _3/4 and its 1/4 value is W 1/4) is 0.35 or more, preferably 0.5 or more. It is preferable. Furthermore, 430 nm or less, 490 to 53
A filter having a spectral absorption in the wavelength range of 0 nm or 570 to 630 nm is preferable.

 Next, the materials used in the present invention will be described.

In general, couplers described in Research Disclosure (RD) No. 17643, VII-C to G are used for color photographic materials for photographing.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
No. 1,476,760, etc. are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
619, 4,351,897, European Patent 73,636, U.S. Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355.
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630,
Those described in No. 4,540,654 and the like are particularly preferable.

Cyan couplers include phenol and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233 and 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308,
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,
329,729, European Patent 121365A, U.S. Patent 3,446,62
No. 2, No. 4,333,999, No. 4,451,559, No. 4,427,7
Those described in 67, European Patent No. 161,626A and the like are preferable.

Colored couplers to correct unwanted absorption of colored dyes are Research Disclosure No. 17643 VII.
-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57-39413,
U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No.
Those described in No. 1,146,368 are preferable.

As a coupler in which the coloring dye has an appropriate diffusibility,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,782.
No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that also release development inhibitors are RD17643, VII-F described above.
Patents described in paragraphs, JP-A-57-151944 and JP-A-57-1542
The compounds described in U.S. Pat. No. 34,60-184248 and U.S. Pat. No. 4,248,962 are preferable.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material used in the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,3.
Nos. 93 and 4,310,618, etc., multiequivalent couplers, DIR redox compound releasing couplers, such as those described in JP-A-60-185950, and couplers releasing a dye that recolors after separation as described in EP 173,302A. Etc.

T _(λ) of the color material of the color photosensitive material for photographing is reflected in E _(λ) . In the present invention, the magenta / color material and the yellow color material are particularly important, and the coupler represented by the general formula (XXIII) is particularly advantageous. Long-wave side mask color material of yellow color material, E of GL of color print photosensitive material
There is an advantage that it is easy to use a coloring material for a filter suitable for improving _(λ) . This also makes it possible to use a benzoylacetanilide type yellow coupler to reduce the thickness of the photosensitive layer and to improve image sharpness.

Color-printing light-sensitive materials in which the effect of the present invention is particularly exhibited include magenta couplers described in Japanese Patent Application No. 60264125, cyan couplers described in JP-A No. 58-105229, and Japanese Patent Application No. 62-39825. The specific color couplers shown are useful. In particular, general formulas (XXII-a) and (XXII-b)
And color couplers represented by (XXIII) are preferred.

In the formula, R ₂₂₁ , R ₂₂₄ and R ₂₂₅ each represent an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic amino group, an aromatic amino group or a heterocyclic amino group, and R ₂₂₂ represents an aliphatic group. Represent, R
₂₂₃ and R ₂₂₆ each represent a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group. Here, the aliphatic group represents a linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group.

Further, R ₂₂₂ and R ₂₂₃ or R ₂₂₅ and R ₂₂₆ may be linked to each other to form a 5-, 6- or 7-membered ring to form a condensed ring such as carbostyril or oxindole. R ₂₂₂ and R ₂₂₃ may be condensed to form a substituted naphthol ring.

Further, R ₂₂₁ , R ₂₂₂ , R ₂₂₃ or Y ₁ , or R ₂₂₄ ,
R ₂₂₅ , R ₂₂₆ or Y ₂ may form a dimer or higher multimer.

Y ₁ and Y ₂ represent a hydrogen atom or a group capable of splitting off after a coupling reaction with an oxidation product of a color developing agent.

In the formula, R ₂₃₁ represents a hydrogen atom or a substituent, and an alkyl group (eg, methyl group, ethyl group, butyl group, etc.), branched alkyl group (eg, isopropyl group, isobutyl group, tert-butyl group, etc.), substituted alkyl Group (including branch), alkoxy group (eg, methoxy group, ethoxy group,
Butoxy group, etc.), substituted alkoxy group (ethoxyethoxy group, phenoxyethoxy group), aryloxy group (eg phenoxy group, etc.), ureido group, etc. are preferable, and branched alkyl group and alkoxy group are particularly preferable. X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. Examples of such a group include a halogen atom (eg, chlorine atom, bromine atom, etc.), an arylthio group (eg, 2-butoxy-5-tertialoctylphenylthio group, 2-propoxy-5-).
Tert-hexylphenyl group, etc.), nitrogen-containing heterocyclic group (eg, imidazole group, 4-chloroimidazole group, etc.), aryloxy group (eg, p-methylphenoxy group, 2,4-dimethylphenoxy group, 2,4) -Dimethylcoushal phenoxy group etc.) and the like. Of these, a halogen atom and an arylthio group are particularly preferable. Za, Zb and Zc are methine, substituted methine, or =
It represents N- or -NH-, and one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond. When Za-Zb is a carbon-carbon double bond, it also includes the case where it is part of an aromatic ring. Further, it also includes the case where R ₂₃₁ or X forms a multimer or more multimers. Also, when Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or higher multimer is also included. When Za, Zb or Zc represents a substituted methine, the substituent is preferably a substituted alkyl group, particularly a branched substituted alkyl group (eg, substituted isopropyl group, substituted tert-butyl group, etc.) and the like.

In the formula, Y ₃ is a hydrogen atom or a leaving group, and R ₂₄₁ and R ₂₄₃
Represents a substituted or unsubstituted phenyl group, and R ₂₄₂ represents a hydrogen atom, an aliphatic or aromatic acyl group or a sulfonyl group.

In the formula, Q represents a substituted or unsubstituted N-phenylcarbamoyl group, and Y ₄ represents a halogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent (referred to as splitting group).

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The steps and effects of the latex dispersion method, and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Next, specific examples of the main coupler for forming a color-developed image which can be particularly used in the color light-sensitive material for photography or the color print light-sensitive material in the present invention will be shown.

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

Suitable supports that can be used in the present invention are, for example, those mentioned above.
RD.No. 17643, page 28, and RD.No. 18716, page 647 From the right column
See page 648, left column.

Example 1 Sample 101, which is a multilayer color light-sensitive material for photographing, was prepared by applying multiple layers of the following compositions on a cellulose triacetate film support having an undercoat layer.

Preparation of Color Photographic Material for Photographing (Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer; anti-halation layer Black colloidal silver ... Silver 0.18 gelatin ... 0.40 Second layer; Intermediate layer 2,5-di-t-pentadecylhydroquinone ... 0.18 EX-1 ... 0.07 EX- 3 ... 0.02 EX-12 ... 0.002 U-1 ... 0.06 U-2 ... 0.08 U-3 ... 0.10 HBS-1 ... 0.10 HBS-2 ... 0.02 Gelatin ... 1 . 04 Third layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size)
0.6μ Coefficient of variation for grain size 0.15) Silver 0.55 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II… 1.8 × 10 ^-5 Sensitizing dye III… 3.1 × 10 ^-4 Sensitizing dye IV… 4.0 × 10 ^-5 EX-2 ... 0.350 HBS-1 ... 0.005 EX-10 ... 0.020 Gelatin ... 1.20 Fourth layer (second red-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 10 mol%, Average particle size
0.7μ average aspect ratio 5.5, average thickness 0.2μ) ... Silver 1.
0 Sensitizing dye I ... 5.1 × 10 ^-5 Sensitizing dye II… 1.4 × 10 ^-5 Sensitizing dye III… 2.3 × 10 ^-4 Sensitizing dye IV… 3.0 × 10 ^-5 EX-2… 0.400 EX-3… 0.050 EX-10… 0.015 Gelatin… 1.30 Fifth layer (third red emulsion layer) Silver iodobromide emulsion (16 mol% silver iodide, average grain size 1.1μ)
… Silver 1.60 Sensitizing dye IX… 5.4 × 10 ^-5 Sensitizing dye II… 1.4 × 10 ^-5 Sensitizing dye III… 2.4 × 10 ^-4 Sensitizing dye IV… 3.1 × 10 ^-5 EX-3… 0.240 EX-4 0.120 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (interlayer) EX-5 0.040 HBS-1 0.020 EX-12 0.004 Gelatin 0. 80 7th layer (1st green emulsion layer) Tabular silver iodobromide emulsion (6 mol% silver iodide, average grain size)
0.6μ Average aspect ratio 6.0 Average thickness 0.15)… Silver 0.40 Sensitizing dye V… 3.0 × 10 ^-5 Sensitizing dye VI… 1.0 × 10 ^-4 Sensitizing dye VII… 3.8 × 10 ^-4 EX-6… 0.260 EX-1 ... 0.021 EX-7 ... 0.030 EX-8 ... 0.025 HBS-1 ... 0.100 HBS-4 ... 0.010 Gelatin ... 0.75 Eighth layer (second green emulsion layer) Monodisperse silver iodobromide emulsion (iodine Silver halide 9 mol%, average grain size
0.7μ Particle size variation coefficient 0.18)… Silver 0.80 Sensitizing dye V… 2.1 × 10 ^-5 Sensitizing dye VI… 7.0 × 10 ^-5 Sensitizing dye VII… 2.6 × 10 ^-4 EX-6… 0.180 EX -8 ... 0.010 EX-1 ... 0.008 EX-7 ... 0.012 HBS-1 ... 0.160 HBS-4 ... 0.008 Gelatin ... 0.10 Ninth layer (third green sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 12 Mol%, average particle size 1.0)
… Silver 1.2 Sensitizing dye V… 3.5 × 10 ^-5 Sensitizing dye VI… 8.0 × 10 ^-5 Sensitizing dye VII… 3.0 × 10 ^-4 EX-6… 0.065 EX-11… 0.030 EX-1… 0.025 HBS-1 ... 0.25 HBS-2 ... 0.10 Gelatin ... 1.74 10th layer (yellow filter layer) Yellow colloidal silver ... Silver 0.05 EX-5 ... 0.08 HBS-3 ... 0.03 Gelatin ... 0.95 11th layer ( First blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (6 mol% silver iodide, average grain size)
0.6μ Average aspect ratio 5.7, Average thickness 0.15) ... Silver 0.24 Sensitizing dye VIII ... 3.5 × 10 ^-4 EX-9 ... 0.85 EX-8 ... 0.12 HBS-1 ... 0.28 Gelatin ... 1.28 12th layer (second blue sensation) Emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 10 mol%, average grain size)
0.8μ Particle size variation coefficient 0.16)… Silver 0.45 Sensitizing dye VIII… 2.1 × 10 ^-4 EX-9… 0.20 EX-10… 0.015 HBS-1… 0.03 Gelatin… 0.46 13th layer ( Third blue-sensitive emulsion layer) Silver iodobromide emulsion (14 mol% silver iodide, average grain size 1.3μ)
Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 14th layer (first protective layer) Silver iodobromide emulsion (1 mol% silver iodide, average grain) (Diameter 0.07μ)
... silver 0.5 U-4 ... 0.11 U-5 ... 0.17 HBS-1 ... 0.90 gelatin ... 1.00 15th layer (second protective layer) polymethyl acrylate particles (diameter about 1.5 µm) ... 0.54 S-1 ... 0.15 S-2 ... 0.05 Gelatin ... 0.72 In addition to the above components, a gelatin hardening agent H-1 and a surfactant were added to each layer.

HBS-1 Tricresyl phosphate HBS-2 Dibutyl phthalate HBS-3 Bis (2-ethylexyl) phthalate In the method of producing the sample 101, E-6 was used instead of EX-6.
Samples 102 and 103 were obtained in the same manner as sample 101, except that part of X-13 was replaced with part of EX-9 and EX-14 was used as shown in Table 1.

Next, Macbeth's color chart Gray chart (No. 2
The subject with 2) and a fresh flower (for example, chrysanthemum flower, or a medicine for chrysanthemum) was used for photography using a light source with a color temperature of about 5400 ° K.

A color negative film (printed original) was obtained using the following color development processing.

 Color development processing method for color photographic materials for photography Processing method Processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching 1 minute 00 seconds 38 ℃ Bleaching fixing 3 minutes 15 seconds 38 ℃ Washing with water (1) 40 seconds 35 ℃ Washing with water (2) 1 minute 00 seconds 35 ° C Stability 40 seconds 38 ° C Drying 1 minute 15 seconds 55 ° C Next, the composition of the treatment liquid is described.

(Color developer) Unit (g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5 Add water 1.0l pH 10.05 (Bleaching solution) (unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching acceleration Agent 0.005mol Ammonia water (27%) 15.0 ml Add water 1.0 l pH 6.3 (bleach-fixing solution) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution ( 70%) 240.0 ml Ammonia water (27%) 6.0 ml Water is added to 1.0 ml pH 7.2 (Washing solution) Tap water is H type strong acid cation exchange resin (Amberlite IR-120B by Rohm and Haas) and OH Anion exchange resin (Amberlite IR-400) made of water is passed through a mixed bed column to reduce the concentration of calcium and magnesium ions to 3 mg / l or less, followed by 20 mg / l sodium diisocyanurate dichloride. Sodium sulfate 150 mg / l was added.

The pH of this solution is in the range 6.5-7.5.

(Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water is added to 1.0 l pH 5.0 to 8.0 Example 2 Preparation of multilayer color print photosensitive material A multilayer color photographic paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. A coating solution was prepared as described below to obtain Sample 201.

Preparation of 1st layer coating solution Yellow coupler (ExY) 19.1g and color image stabilizer (Cp
d-1) 27.2 cc of ethyl acetate and solution (Solv-
1) 7.7 cc was added and dissolved, and this solution was emulsified and dispersed in 18.5 cc of 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (silver chloride
A blue-sensitizing sensitizing dye shown below was added to 99.0 mol% and Ag70 g / kg) at 5.0 × 10 ⁻⁴ mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating liquid for the first layer having the composition shown below. The coating solutions for the second layer to the seventh layer were prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer, 1-oxy-
3,5-Dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizing dye for each layer.

Compound of blue-sensitive emulsion layer XVII- (1) (5.0 × 10 ^-4 mol per mol of silver halide) Compound of green-sensitive emulsion layer XVIII- (9) (4.0 × 10 ^-4 mol per mol of silver halide) And XVIII- (8) compound (7.0 × 10 ^-5 mol per mol of silver halide) Red-sensitive emulsion layer XVV- (8) compound (0.9 × 10 ^-4 mol per mol of silver halide) Red-sensitive emulsion Compound I- (9) was added to the layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
4.0 × 10 ⁻⁶ mol, 3.0 × 10 ⁻⁵ and 1.0 × 10 ⁻⁵ mol were added.

Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer at 1.2 × 10 ^-2 and 1.1 × 10 ² per mol of silver halide, respectively. ^-2
Mole was added.

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

(Layer composition) The composition of each layer is shown below. The numbers indicate the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white paper pigment (TiO ₂ ) and bluish dye (ultra-blue)] First layer (blue sensitive layer) Silver halide emulsion (Cl: 99%) 0.26 Gelatin 1.83 Yellow Coupler (ExY) 0.83 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-2) 0.08 Third layer (green sensitive layer) Halogen Silver halide emulsion (Cl: 99%) 0.16 Gelatin 1.79 Quezenta coupler (ExM) 0.32 Color image stabilizer (Cpd-3) 0.20 Color image stabilizer (Cpd-4) 0.01 Solvent (Solv-2) 0.65 Color image stabilizer (Cpd-8) 0.06 〃 (Cpd-9) 0.06 Dye D-1 0.10 Fourth layer (UV absorbing layer) Gelatin 1.58 UV absorbing agent (UV-1) 0.62 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-) 3) 0.24 Fifth layer (red sensitive layer) Silver halide emulsion (Cl: 93%) 0.23 Gelatin 1.34 Cyan coupler (ExC 0.34 Color image stabilizer (Cpd-6) 0.17 Polymer (Cpd-7) 0.40 Solvent (Solv-4) 0.23 Dye (D-2) 0.12 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorbing agent (UV-1) 0.21 Solvent (Solv-3) 0.08 Seventh layer (protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer (degree of modification
17%) 0.17 Liquid paraffin 0.03 (ExY) Yellow coupler: same as XXV- (2) (ExM) Magenta coupler: Same as (XXIII-6) (ExC) Cyan coupler: Same as XXII- (4) Preparation of Emulsion A Formation of silver chloride host grains (2 solutions) Sulfuric acid (1N) 24cc (3 solutions) The following compound A (1%) 3cc (5 liquid) 200cc including AgNO ₃ 5g H ₂ O (1 solution was heated to 76 ° C, (2 solution) and (3 solution) were added, and then (4 solution) and (5 solution) were added simultaneously spending 10 minutes. After 10 minutes, (6 solution) was added. ) And (7 solution) were added simultaneously spending 35 minutes. 5 minutes after the addition, the temperature was lowered and desalted. Water and dispersed gelatin were added to adjust the pH to 6.3, the average particle size was 1.1 μm, and the variation coefficient ( The value obtained by dividing the standard deviation by the average grain size: s / d) gave a monodisperse cubic silver chloride emulsion of 0.10.

Take 1/2 of this emulsion, and add 12.6 cc of a 0.6% solution of the blue-blue dispersion sensitizing dye XVII- (1), and add 0.0
5μ AgBr ultrafine grain emulsion was added to the host AgCl emulsion at 0.5
The mixture was added at a mol% ratio and mixed and aged at 58 ° C. for 10 minutes. After that, sodium thiosulfate was added, and optimal chemical sensitization was performed to add the following stabilizer B at 10 ⁻⁴ mol / mol Ag. This was designated as emulsion (A). (Stabilizer B) Preparation of silver halide emulsion (B) (9 solutions) Sulfuric acid (1N) 24 ml (10 solutions) Compound A of emulsion A (1%) 3 ml (8 liquid) was heated to 52 ° C., and (9 liquid) and (10 liquid) were added. After that, (11 solution) and (12 solution) were spent for 14 minutes and added simultaneously. After another 10 minutes, (solution 13) and (solution 14) were added simultaneously for 15 minutes. Five minutes after the addition, the temperature was lowered to desalt.

Water and dispersed gelatin were added and the pH was adjusted to 6.2 to obtain a monodisperse cubic silver chloride emulsion having an average grain size of 0.48 μm and a coefficient of variation (standard deviation divided by the average grain size: s / d) of 0.10. Sensitizing dye XVIII- (8) (4.0 × 10 ^-4 mol per mol of silver halide) was added, and a silver bromide ultrafine grain emulsion (grain size 0.05 μ) was added in an amount of 1 mol% based on the silver chloride emulsion. An amount containing silver bromide was added, and the mixture was aged at 58 ° C for 10 minutes.

Sodium thiosulfate was added to this emulsion at 58 ° C for optimal chemical sensitization, and sensitizing dye XVIII- (8) was added,
Spectral sensitization was carried out by adding 4 × 10 ⁻⁴ mol per mol of silver halide. Further, the compound B used in the emulsion A was added as a stabilizer in an amount of 5 × 10 ^-4 mol per mol of silver halide.

ExY, ExM or ExC used herein are preferred color couplers in the present invention. The sample 201 was exposed using a spectrograph corrected so that the spectral energy intensities of the light sources were equal, and the following color development processing A was performed.

Step Temperature Time Color development 35 ° C. 45 seconds blix 30 to 36 ° C. 45 seconds stable 30 to 37 ° C. 20 seconds stable 30 to 37 ° C. 20 seconds stable 30 to 37 ° C. 20 seconds stable 30 to 37 ° C. 30 seconds Drying 70 〜85 ℃ 60sec (Stabilized → tank countercurrent system) The composition of each processing solution is as follows. Color developer water 800 ml Ethylenediaminetetraacetic acid 2.0 g Triethanolamine 8.0 g Sodium ammonium chloride 1.4 g Disodium ethylenediaminetetraacetate 3 g Potassium carbonate 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline sulfate 5.0g N, N-diethylhydroxysylamine 4.2g 5,6-dihydroxybenzene 1,2,4-trisulfonic acid 0.3g Fluorescent brightener (4,4'-diaminostilbene type) 2.0g Add water to 1000 ml pH (25 ℃) 10.10 Bleach and fixer Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 18g Ethylenediaminetetraacetic acid (III) 55g Glacial acetic acid 8g Add water 1000ml pH (25 ℃) 5.5 Stabilizer Formalin (37%) 0.1g Formalin-sulfite adduct 0.7g 5-chloro-2-methyl-isothiazolin-3-one 0.02g 2-methyl-4-isothiazo The down-3 added on 0.01g copper sulfate 0.005g water 1000ml pH (25 ℃) 4.0 spectral sensitivity distribution of the photosensitive layer obtained is shown in Figure 1.

Curves 1 to 3 are curves obtained from the sample 201.

Example-3 Samples 101 and 102 obtained in Example-1 using the sample of Sample 201
The color negative films obtained from Nos. 103 and 103 were printed as originals using an auto printer FAP-35000 type manufactured by Fuji Film, and the color development processing A was performed.

Further, a sample 202 was similarly printed by using the band stop filter shown in FIG.

As shown in Table 3, by combining the color negative film and the color print photosensitive material used in this embodiment, a gray object (Macbeth color chart gray i = 22) is obtained.
Eb _(λ) , Eg
_(Λ) or Er _(λ) are shown in FIGS. 2 and 3. Second
Although the figures Er _(lambda) and Eg _(lambda) is independent indicates that Eb _(lambda) is not independent, further, FIG. 3 is Er _(λ), Eg
It shows that _(λ) and Eb _(λ) are all independent.

When the sample 102 or 103 was used instead of the sample 101 of No. 1, E _(λ) showed a distribution similar to that in FIG.

Example-4 In Example-1, the color photosensitive material sample 101 for photographing was used.
And a color negative film obtained from Sample 102,
Color print photosensitive material sample 20 in the same manner as in Example-2
Baked in 1. (Print A) Further, at the time of printing, a sharp cut off filter (cutting a wavelength range shorter than 440 nm) I which is one of the band stop filters of the present invention shown in FIG. 5 is shown in FIG. Sharp band stop filter (cuts the wavelength range of 490 to 530, W _1/4 /
W _3/4 was 0.70) II, respectively, and exposure was performed to obtain color prints in the same manner. (Prints B and C) Next, using the above print A, continuous processing (running test) was performed until the tank capacity of the color developing solution was doubled in the next processing step. However, the composition of the color developer was changed as shown in Table 4, and a running test was performed for each of them.

The composition of each processing solution is as follows.

Bleach-fix solution (tank solution and replenisher are the same) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetate disodium 5g Ammonium bromide 40g Glacial acetic acid 9g Add water 1000ml pH (25 ℃) 5.40 Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium and magnesium are each 3ppm or less) For each running solution, use color printing paper 201 exposed with prints A, B and C. After processing, the green leaf of the natural cycad of the subject was visually judged for density, saturation and lightness.

 The results are shown in Table 4.

When Sample 103 was used in place of 102, almost similar results were obtained, especially when printing conditions were B and C.

From Table 4, Treatments I, III, V containing sulfite ion
In I, the density is low, and the saturation and brightness are not sufficient. However, in prints B and C using the filter of the present invention, when the sulfite ion and benzyl alcohol were not substantially contained, remarkably excellent density, saturation and lightness were exhibited.

(Treatments IV, V, VII).

(Example 5) Compounds I-2, II-1, III-15, IV-5, V-1, and VI- were used instead of the compounds I-I in the treatment IV of Example 4.
When 5 was used, the same preferable result was obtained by using the filter of the present invention.

Further, in Example Treatment IV, instead of compound VII-1, VIII-5, VIII-8, IX-1, IX-3, X-1, X
-3, XI-1, XI-2, XII-3, XII-10, XIII-8,
When XIV-1, XV-1, XV-6, and XVI-1 were used, the same favorable results were obtained using the filter of the present invention.

(Example 6) In the treatment IV of Example 4, the CIE (L ^* a ^* b ^* ) surface pigment (for example, edited by the Japan Color Society) was used for the green leaves of natural cycads in the color prints at the start and end of running. Color Color Chemistry Handbook (Published in 5th edition, 1985)
, Page 140-141).

By using the filter of the present invention, the brightness, saturation and hue fidelity of green are improved. And, when the sulfite ion is not contained, the above performance is deteriorated in the running state, while (→) excellent performance is obtained in the constitution of the present invention.

[Brief description of drawings]

FIG. 1 shows the relative spectral sensitivity distributions (logarithmic display) of BL, GL, and RL obtained from sample 102. The vertical axis represents sensitivity and the horizontal axis represents wavelength. Curves 1, 2 and 3 represent BL, GL and RL respectively. FIG. 2 shows the effective spectral light amount distributions Eb _(λ) , Eg _(λ) , Er _(λ) obtained by the samples 101 and 201. FIG. 3 shows the effective spectral light amount distributions Eb _(λ) , Eg _(λ) , Er _(λ) obtained by the sample 102 and the sample 202. Here, the vertical axis in FIGS. 2 and 3 indicates the light amount (energy), and the horizontal axis indicates the wavelength. FIG. 4 is a chromaticity diagram of prints A, B, and C under the running conditions in Example 6 ,. Figure 5 shows the spectral transmittance distribution of the Sharp Cut Off Filter. FIG. 6 shows the spectral transmittance distribution of a sharp cut band stop filter, the vertical axis shows the transmittance, and the horizontal axis shows the wavelength.

Claims (3)

(57) [Claims] 1. A color image forming method in which an original for color printing is printed on a light-sensitive material for color printing by a subtractive exposure method and then color development processing is carried out.
A color print light-sensitive material is provided with at least one blue-sensitive layer, green-sensitive layer and red-sensitive layer on a support,
About 10 to 60 nm in half-width (W _1/2 ) of the spectral transmittance curve in the wavelength range excluding the maximum wavelength ± 20 nm wavelength range of the effective spectral exposure light amount distribution of each photosensitive layer of the color print photosensitive material when printing A color image formation using a band stop filter having a spectral absorption band and a color developing solution containing substantially no sulfite ion and benzyl alcohol during color development processing of a color print photosensitive material. Method. 2. A color print light-sensitive material having a silver chloride content of 80.
The method for forming a color image according to claim 1, which has a layer using a mol% or more of silver chlorobromide or silver chloride emulsion. 3. The ratio (W _1/4 / W _3/4 ) of the 1/4 width (W _1/4 ) to the 3/4 width (W _3/4 ) of the spectral transmittance curve is 0.35 or more. The color image forming method according to any one of claims (1) to (2), wherein a certain band stop filter is used.