JP2533367B2 - Reflective color photosensitive material and its color image forming method. - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a reflective color light-sensitive material having excellent image sharpness and capable of quickly and easily obtaining a color image. The present invention relates to a reflection type color light-sensitive material capable of quickly and easily obtaining a CG image, line drawing or character image having excellent sharpness and edge contrast together with a photograph.

(Prior Art) Usually, a color print is obtained by printing an original obtained from a color photographic material for photographing (for example, a color negative film, a color positive film or a reversal color film) on a color photographic paper and performing color development. Recently, by improving the performance of color photographic materials for photography, the image quality of color photographic paper has been improved, especially microscopic images such as image sharpness and line drawing without sacrificing conventional performance such as sensitivity, gradation and whiteness. The need for improved contrast has increased. In addition to the widespread use of color prints, color photographic paper is often used to print CG (Computor Graphics) images, line drawings or character images in addition to ordinary photographic images for printing. For example, in order to print various cards, postcards, sticker prints, etc., to print line drawings and character images from color photographic paper, conventionally, the same enlarger and printer as those for obtaining photographs were used, and a separate lith film was used. A method has been used in which an original film for printing a line drawing or a character image is created and used as an original. With this method, line drawings and character images with excellent image quality can be obtained, but it is artificial and time consuming. Although it is possible to print on a semitransparent base paper using a word processor instead of the above block film, the image quality is inferior. In addition, a CG image or a character image can be input from a storage means that has been previously input using a digitizer to a CRT (Cathode Ray Tube) or FOT (Fiber Op
tics Tube) is also known to print with the image output and displayed. Printers having a so-called "CRT exposure system" are disclosed, for example, in JP-A-62-43281 and JP-A-62-184.
446, 62-295037, 62-295038 and 62
No. 62-89965 and No. 6 of JP-A-6-89965 are described in many specifications such as JP-A-295039.
2-89965. However, the use of ordinary color photographic paper was insufficient in terms of image quality, sensitivity and speed of processing. A printer using a laser beam controlled from a similar storage means is also known, but it is insufficient in price and compactness.

JP-A-63-63036 discloses that a thin transmission density is 0.8
It is described that, in a light-sensitive material using an inversion type silver halide emulsion, a sharpness deterioration due to a thin support is provided on a reflective support by providing an anti-halation layer. However, it does not suggest the improvement of the surface latent image type silver halide emulsion used for general-purpose color photographic paper, the support, and the scanning exposure, in particular, the reproducibility of characters.

(Problems to be solved by the present invention) The image quality of ordinary photographic prints has improved due to improvements in color photosensitive materials for photography and color photographic paper. (Or FOT) exposure method results in insufficient printing image quality, and particularly in an image having a line image or a character image printed along with a photographic image, the image quality of the line image or the character image is easily noticeable. In particular, Japanese characters are more difficult to reproduce than Alf Abet characters, and the thick lines and blurring of thin lines are more noticeable.

In order to facilitate color development processing of color photographic paper rapidly, when a silver halide emulsion having a high silver chloride content (for example, 80 mol% or more of total silver halide) is used in at least one layer of the color light-sensitive material of the present invention. In comparison with conventional silver chlorobromide emulsions (for example, silver halide emulsions having a silver chloride content of less than 20 mol%), it is difficult to increase the sensitivity, and the sensitivity and stability of the latent image are poor. When a large amount of dye is used for prevention of irradiation and halation, the effective sensitivity is further lowered and especially the spectral sensitivity is apt to be lowered due to the anti-color sensitizing effect and desorption of the sensitizing dye used. This problem of spectral sensitivity is particularly important because silver halide emulsions having a high silver chloride content have almost no light absorption in the visible region (400 to 700 nm) and sensitivity is obtained by spectral sensitization.

For the scanning exposure method, laser light having a light intensity in at least three different wavelength ranges, phosphor light emission, LED light emission, liquid crystal light emission, and the like are used, and if necessary, used in combination with a color separation filter. Especially in the scanning exposure method using fluorescent light emission, such as CRT or FOT exposure method, it is necessary to adapt the emission intensity and efficiency of the fluorescent material and the spectral sensitivity of each photosensitive layer of color photographic paper to speed up and simplify the exposure process. And needed for stabilization. Normally, stable tungsten light,
A halogen lamp or a xenon lamp light is used, and the sensitivity of each photosensitive layer of color printing paper is determined by adapting to this. The sensitivity ratio of each photosensitive layer of ordinary color photographic paper is CR
Not suitable for T or FOT exposure method. Many are relatively lacking in sensitivity to longer-wave light, especially red sensitivity.

The object of the invention is to remedy these deficiencies. That is, a first object of the present invention is to provide a color light-sensitive material which is excellent in image quality of CG images, line images or character images without lowering effective sensitivity. Secondly, color sensitization for photographic images, CG images, line drawings and character images with high image sharpness and edge contrast, can be performed quickly and easily, especially by shortening the exposure time by the three light sources in the exposure process and the color development processing time. Materials and color imaging methods. Third, the reflective support is 200 μm
It is to provide a color photographic paper that can be used to make various cards or postcards by using the thinner color photographic paper.

(Means for Solving the Problem) The inventors of the present invention have examined the factors such as the exposure means to be used, the sensitivity of color printing paper and the adaptation of the exposure means, and as a result, the object of the present invention has been achieved as follows. I found that I could do it.

(1) A color light-sensitive material comprising at least one silver halide light-sensitive layer containing a color coupler on a reflective support, wherein the silver halide light-sensitive layer has an average silver chloride content of 50 mol%. Above, and having a silver bromide-containing localized phase inside or on the surface of the grain, the surface of the grain contains a gold sensitized silver chlorobromide emulsion, and a color layer is formed between the photosensitive layer and the reflective support. A reflection type color light-sensitive material, which is provided with a colored layer capable of being decolorized by a developing process.

(2) The above-mentioned reflective support contains 12% by weight or more of white pigment particles in a water-resistant resin, and the dispersity of the white pigment particles is a prescribed projected area ratio (%) per unit area. Variation coefficient S / (for example, white pigment particles are contained at a density of 10% by weight or more, and the variation coefficient S / of the occupied area ratio of the white pigment particles per 6 μm × 6 μm (unit area) is S /
Of 0.20 or less, and further having a colored layer which can be decolorized by photographic processing between the support and the silver halide photosensitive layer.

(4) The colored layer that can be decolorized by photographic processing contains a solid fine particle dispersion of a dye that is substantially insoluble in water having a pH of 7.0 and is soluble in water having a pH of more than 9.0. The silver halide photographic light-sensitive material according to item (1), (2) or (3).

(5) A solid of a dye selected from the compounds represented by the following general colors (X), (XI), (XII), (XIII) and (XIV) in a colored layer which can be decolorized by photographic processing. A fine particle dispersion is contained, Claims (1)-which are characterized by the above-mentioned.
The silver halide photographic light-sensitive material as described in any of (4).

General formula (X) General formula (XI) General formula (XII) A ₂ = L ₁ − (L ₂ = L _{3 n} A ₂ General formula (XIII) General formula (XIV) (In the formula, A ₂ is an acidic nucleus having at least one substituent selected from a carboxyphenyl group, a sulfamoylphenyl group, a sulfonamidephenyl group, a carboxyalkyl group and a hydroxyphenyl group (as a substituent, May have in addition to the above groups), the acidic nucleus, 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione,
It is selected from the group consisting of isoxazolidinone, barbituric acid, thiobarbituric acid, indandione and hydroxypyridone. B ₂ represents a basic nucleus having at least one substituent selected from a carboxyl group, a sulfamoyl group and a sulfonamide group (the substituent may have other than the above groups), and the basic nucleus is , Pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole, and pyrrole. R ₄₀ represents a hydrogen atom or an alkyl group, R ₄₁ and R ₄₂ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an acyl group or a sulfonyl group, and R ₄₁ and R ₄₂ are linked to each other. To form a 5- or 6-membered ring. R ₄₃ and R ₄₆ each represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an alkoxy group or a halogen atom, and R ₄₄ and R ₄₅ each represent a hydrogen atom or R _41.
And R ₄₄ or R ₄₂ and R ₄₅ are connected to each other to represent a nonmetallic atom group necessary for forming a 5- or 6-membered ring. L ₁ , L ₂ and L ₃ each represent a substituted or unsubstituted methine group, X ₃ and Y ₃ each represent an electron-withdrawing group, and at least one carboxy group is present in either X ₃ or Y _3. It has an enyl group, a sulfamoylphenyl group, a sulfonamidephenyl group, a carboxyalkyl group or a hydroxyphenyl group. m represents 0 or 1, and n represents 0, 1 or 2. p represents 0 or 1, but when p is 0, R ₄₃ represents a hydroxy group or a carboxy group and R ₄₄ and R ₄₅ represent a hydrogen atom. (6) A color image forming method, which comprises subjecting the reflective color light-sensitive material according to any one of the items (1) to (5) to printing by a scanning exposure method, and then performing color development processing.

The scanning exposure method according to the present invention means image exposure by the scanning method. The scanning method is a method in which an image to be reproduced on a plane is decomposed according to a certain rule and pixels are assembled in time series according to the certain rule. Further details are described in, for example, Basic Handbook, Chapter 3, pages 45 to 55 of Image Electronics Handbook (edited by The Institute of Image Electronics Engineers). For image exposure, laser light, CRT, LED (Luminescence Emittin
g Diode) is used.

In the present invention, the scanning exposure system by CRT is preferable.
Also preferred color photographic papers according to the invention are at least 3
A kind of silver halide photosensitive layer is provided on a support, the maximum wavelength of these silver halides having different spectral sensitivities and the emission of CRT,
The wavelengths of maximum intensity are adapted to each other. In the case of laser light, at least three types of laser light, such as He-
Cd laser, Ar-gas laser, He-Ne gas laser,
It is preferable to use laser light selected from a semiconductor laser such as GaAs, GaAsxPrx, or InP. In scanning exposure, since the light emission of each pixel is repeated light emission of several milliseconds to several microseconds, a sufficiently high light amount can be obtained by using a CRT having a relatively low output. The device is also compact and inexpensive. In the present invention, a color CRT, a black-and-white CRT, particularly a high-performance tube, which has a high resolution, is free from distortion, can obtain an image on the entire fluorescent surface, and has a small number of spot halos is used. A particularly preferred CRT exposure method according to the present invention uses a black-and-white CRT using a fluorescent substance that emits light in the blue, green, and red wavelength regions in order to increase the density of pixels, and a storage means for input digital information, for example, A photo or CG image, or a line drawing or character image is displayed on a black and white CRT by directly inputting it from a floppy disk, etc., and a photosensitive layer of color photographic paper with an optical lens and a shutter through blue, green and red filters. This is a method in which images are sequentially formed on the surface of and exposed. The exposure time of each blue image, green image, and red image obtained through the blue, green, and red filters is taken in inverse proportion to the spectral sensitivity of each light-sensitive layer of color photographic paper by high-intensity short-time multiple exposure. The CRT used in the present invention has a pixel number of about 500 to 1000 × 500 to 1500, and the emission time of one pixel is about 1 × 10 ⁻³ to 1 × 10 ⁻⁷ seconds. Lights 10 to 100 times for each exposure. The boom diameter of the light emission of one pixel is about 20 to 100μ.

It is also possible to perform exposure using the above-mentioned FOTCRT.
In this case, for example, special device for blue, green and red color separation,
For example, contact exposure can be performed using a liquid crystal filter or the like.

FIG. 1 exemplifies the print making process by the CRT exposure method according to the present invention.

The character image input unit 12 is composed of a console including a CRT and a keyboard, and inputs character information by operating the keyboard while watching the CRT. It is also possible to store the character information that has already been input in a storage medium (for example, a floppy disk).

The start of CRT exposure can be instructed. The graphic image input section 13 is composed of a digitizer, and can input line drawings and computer graphic (CG) images.
The input data of the graphic image can be stored in the floppy disk. The start of CRT exposure can be instructed. The person image input unit 10 can be separately exposed by a photographic image exposure system, but can also be input by a digitalizer, for example, information or a photographic image input by an electronic still camera.

The image synthesizing unit 11 is composed of a micro computer, and reads out data from the person image input unit 10, the character image input unit 12 or the graphic image input unit 13 in a predetermined order as necessary, and lays them out at predetermined positions. Can be input to the CRT controller 14. The CRT controller 14 controls the color monitor 15 and the exposure black / white CRT 16. The composite image data is output only to the color monitor 15 before the exposure is started, and a positive image is displayed on the display surface. During exposure, the composite image is inverted into a negative image, and black and white CRT1
It is output to 6, and the electron beam is deflected in the direction opposite to the normal direction, and the composite image is also reversed left and right.

Through the optical lens 18, the optical filters B, G and R are synchronized with the light emission of the black and white CRT display surface to insert the black and white CRT image,
In synchronization with the shutter 17, the color photographic paper 19 is printed by the three-color sequential exposure method for each predetermined time. Thereafter, a predetermined color developing process can be carried out through the photographic processor 20.

The fluorescent material used for the black and white CRT is 3 of the color printing paper used.
It is preferred to use the phosphor with the wavelength of highest brightness that is compatible with the dominant wavelength of the spectral sensitivity of the photosensitive layer of the species. It is preferable that the afterimage time is short, there is no afterimage, and the flare on the display surface is small.

Further, because of the need for short-time exposure, a phosphor is used that emits intense light at high voltage and high current density and has excellent current saturation characteristics and temperature stability. The phosphor can be selected from among those for a projection tube. As fluorescent materials that can be obtained industrially stably, Y ₂ O ₃ : Eu, Y ₂ O ₂ S: Eu for red and Zn ₂ Si for green are available.
O ₄ : Mn, Gd ₂ O ₂ S: Tb, and among them Y ₂ SiGeO ₅ : Tb and Y ₃ Al ₅ O ₁₂ : Tb for blue, there are ZnS: Ag, Cl or ZnS: Ag, Al.

The balance of red sensitivity (S _R ), green sensitivity (S _G ), and blue sensitivity (S _B ) in ordinary color photographic paper is low in the order of S _B , S _G, and S _R. Especially the emission wavelength of the red phosphor is 600
To 630 nm and 700 nm, the compatibility with the red sensitivity wavelength of color photographic paper is poor. In the present invention, it is particularly important to increase the spectral sensitivity of the color light-sensitive material and to optimize the wavelength distribution.

The feature of the color light-sensitive material of the present invention is that, firstly, a silver chlorobromide emulsion having a high silver chloride content is used in order to obtain a rapid processing property. Secondly, in order to obtain sufficient spectral sensitivity to compensate for the decrease in sensitivity due to the dye used for effectively suppressing the spread of the exposure light flux, a silver halide multi-grain structure (halogen composition distribution), a chemical sensitization method and It is in the spectral sensitization method. Thirdly, a newly devised support is coated with an anti-halation layer.

The silver chlorobromide emulsion having a high silver chloride content used in the present invention is
A type in which a latent image is mainly formed on the surface of the silver chlorobromide grains is preferable.

The silver chlorobromide emulsion according to the present invention is substantially a silver chloride or silver chlorobromide emulsion having a silver iodide content of 2 mol% or less, preferably 1 mol% or less, particularly preferably 0.1 mol% or less. It is a thing. The silver chlorobromide emulsion according to the present invention has a silver chloride content of at least 50 mol%, preferably 80 mol%.
The above content is 90 mol% or more, particularly preferably 95 mol% or more. The remaining components are silver bromide, silver iodide, silver rhodan and the like. These halogen components are preferably different in layers or discontinuously isolated inside or on the surface of the silver halide grain. Particularly preferably, a localized phase having a higher silver bromide content than the surrounding phase is present in the vicinity of the surface of the grain in a layered or discontinuous manner. The silver bromide content of the localized phase is 5 mol% or more, preferably 10 mol% or more, particularly preferably 20 mol% to 70 mol%.

The silver halide grains contained in the silver halide emulsion according to the present invention may be grains of any crystal habit, but regular grains such as cubic, tetradecahedral and octahedral grains and tabular grains are more preferable than spherical grains and polymorphic grains. Particles are preferred. The silver halide grains are
A multi-structured particle having different crystal structures inside or near the surface is preferable. Layered structure grains having different halogen compositions and grains having a localized phase different from the phase around the silver bromide content in the vicinity of the grain surface are preferred. In the case of core-shell type grains, the silver chloride content in the core part is preferably higher than that in the shell part.

The silver halide grains having a high silver chloride content (hereinafter referred to as “high silver chloride grains”) according to the present invention are generally (100)
Only cubic grains consisting of planes can be obtained, but by devising it, grains such as octahedrons having (111) faces and tabular grains can be obtained. A method for producing octahedral grains having (111) faces is described in Japanese Patent Application No. 62-47225, Japanese Patent Application No. 55-26589, Claes' et al., “Journal of Photographic Scienc”.
e) ", Vol. 21, 39 (1973) and Wyrsh" International Congress of Photographic Scienc.
e), III-13, 122 (1978) and the like.
The method described in the above-mentioned Japanese Patent Application No. 62-47225 is preferred.

The normal crystal grains having a (111) plane are described in the above-mentioned Japanese Patent Application No. 62-47225.
Compounds represented by the general formula (I) or the general formula (II) described in JP-A No. 63-25643, pages 2 to 6: (Z ¹ is a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and together with the sulfur atom represents a 3- to 8-membered heterocyclic ring forming atom group) or (N is an integer of 1 to 3, Z ² represents a group of atoms forming a 3- to 8-membered ring together with an oxygen atom or a thiocarbonyl group), etc., during the grain formation, preferably after forming the core grain. It is preferably used in the grain growth process to limit the crystal habit. The tabular grains according to the present invention include the compounds having a sulfur-containing heterocycle described above and the compounds described in JP-A-63-41845: R ₁ -S- (X) _m -Y-R ₂ (X is 2 A valent organic group,
Alkylene, arylene, alkenylene, -SO ₂ -, - S
O-, -O-, -S-, , R ₁ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, R ₂ is a hydroxyl group, an alkyl group, an aryl group, a heterocyclic residue, an amino group, an alkoxy group, an aryloxy group, etc. CO -, - SO ₂ - represents an, m is 0
Or 1. R ₃ represents a hydrogen atom, an alkyl group, an aryl group or the like. Substituents may be introduced into each group) and the like are preferably used in the process of grain formation for controlling the crystal habit. Particularly for the formation of high silver chloride tabular grains, it is advantageous that the concentration of chloride in the aqueous gelatin solution added at the time of forming the core grains is as low as about 0.15 mol / l or less.
The chloride concentration for grain growth is preferably 5 mol / l or less, more preferably 3 to 0.07 mol / l.

The silver chlorobromide grains of the present invention can be grown by adding silver ions and chloride or bromide or a mixture thereof after the core grains are formed, preferably in the presence of the above-mentioned compound for controlling crystal habit. it can. Preferably, silver chloride, silver bromide or silver chlorobromide emulsion is mixed with fine grain silver halide grains such as silver bromide, silver chloride or a mixed silver halide thereof,
Particle formation can be performed. A layered or isolated localized phase can be provided on the grain surface by recrystallization of silver halide or halogen convergence. Particle formation is preferably carried out at 10 to 95 ° C, especially 40 ° to 90 ° C.

Examples of the silver halide solvent that can be used during grain formation include thiocyanates, thioethers, and thioureas, and ammonia can also be used together in a range that does not have a bad effect.

For example, thiocyanates (US Pat. Nos. 2,222,264, 2,448,534, 3,320,069, etc.), thioether compounds (for example, US Pat. Nos. 3,271,157, 3,574,628).
No. 3, No. 3,704, 130, No. 4,297, 439, No. 4,276, 34
No. 7, etc.), thione compounds (for example, JP-A-53-144319).
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A No. 54-100717, etc.) and the like can be used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an indium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together. Particularly, it is preferable to use an iridium salt, a rhodium salt, an iron salt, or a complex salt thereof.

During the production of the silver halide grains of the present invention, the addition rate, the amount and the concentration of addition of the silver salt solution (for example, AgNO ₃ aqueous solution) and the halide solution (for example, NaCl aqueous solution), which are added to accelerate the grain growth, are increased. The method is preferably used.

For these methods see, for example, British Patent No. 1,335,925.
U.S. Pat.Nos. 3,672,900, 3,650,757, and 4,
242,445, JP-A-55-142329, 55-158124,
58-113927, 58-113928, 58-111934, and
Reference can be made to the description in No. 58-111936 and the like.

The structure of the surface and the vicinity of the high silver chloride grains according to the present invention is particularly important for the sensitivity and the stability thereof, the reciprocity law property and the stability of the latent image according to the present invention. At the final stage of grain formation, for example, when 85 mol% or more of all silver halide grains are grown, Japanese Patent Application No. 62-86252 and Japanese Patent Application No. 62-32926.
The grain forming method and the CR-compound (halogen convergence and chemical sensitization inhibitor) described in JP-A No. 5 and No. 62-152330 are preferably used.

When a halide is added after the CR-compound is adsorbed on the silver halide grains, a halogen donor capable of controlling the supply rate or supply amount of chlorine ion or bromine ion is desirable as the halide. . A localized phase having a silver bromide content different from the surrounding phase can be formed on or near the surface of the silver halide grain, which is suitable for this method.

The localized phase or other substrate of the silver halide grain of the present invention may contain a metal ion selected from Group 8 metal ions or a complex salt thereof. For example, a metal ion or its complex ion mainly selected from iridium ions in the localized phase and osmium ions, iridium ions, rhodium ions, ruthenium ions, palladium ions, iron ions, cobalt ions, nickel ions, etc. mainly in the substrate. It is preferable to use different types and concentrations of metal ions in the localized phase and the substrate, such as in combination.
Also, metal ions such as cadmium ion, zinc ion, lead ion, mercury ion and thallium ion can be used. The addition amount of these metal ions or complex ions thereof is about 10 ^-8 to 10 ^-5 mol with respect to silver halide.

The presence of the localized phase and its silver bromide content in the present invention are described by an X-ray diffraction method (for example, described in “New Experimental Chemistry Constituency” 6, edited by Chemical Society of Japan, published by Maruzen in Structural Analysis, etc.) or XPS. Methods (eg surface analysis; “IMA, Auger Electronics,
Application of photoelectron spectroscopy "published by Koyomisha). In addition, the silver bromide content of the localized phase, which is nonuniform or isolated on the surface of the silver halide grains, especially on the edges and corners, can be measured by the EDX method (Energy Dispersive X-ra
y analysis) (for example, described in “Electron Beam Micro-Analysis” by Hiroyoshi Soejima, published in Nikkan Kogyo Shimbun, 1087, etc.) using an EDX spectrometer equipped with a transmission electron microscope. It can be measured with an aperture of an accuracy of about 5 mol%.

In the high silver chloride emulsion used in the present invention, 50% or more of all grains in terms of the projected area have a circle equivalent diameter of the projected area of the grains of about 0.1 to 3 μm. And the particle thickness ratio (called aspect ratio) is 2 or more, preferably 3 to 10, and particularly preferably 5 to 8. The high silver chloride emulsion is preferably a monodisperse emulsion, and one having a dispersion coefficient of equivalent circle diameter (ratio of standard deviation of equivalent circle diameter to average grain diameter) of 0.15 or less is preferred.

Another feature of the present invention lies in the method of chemical sensitization. The chemical sensitization according to the present invention is preferably carried out by combining an emulsion containing high silver chloride grains having a localized phase with gold sensitization, particularly sulfur sensitization and gold sensitization in the presence of a compound controlling the chemical sensitization. There is something to do.

The high silver chloride emulsion for gold sensitization is, among others, a green-sensitive emulsion or a red-sensitive emulsion, and it is particularly preferable to subject the red-sensitive emulsion to gold sensitization.

The conditions (pH, pAg, temperature, time) for gold sensitization are not particularly limited, but for example, the pH value is 3.0 to 8.5, especially 5.0.
~ 7.5 is preferred, and pAg value is 5.0-9.0, especially 5.5-
7.5 is preferable, and the temperature is 40 to 85 ° C, particularly 45 to 75 ° C.
Is preferred, and the time is preferably 10 to 200 minutes, particularly preferably 30 to 120 minutes.

Preferred gold sensitizers include US Pat.
No. 540085, No. 25400086, No. 2597856, and the like. Specific examples of the compound include chloroauric acid and salts thereof, potassium aurate cyanide, potassium aurothiocyanide, and gold sulfide. It is also useful to use thiocyanate in combination to enhance gold sensitization, and to use a tetra-substituted thiourea compound in combination as described in JP-B-59-11892.

Examples of sulfur sensitizers that can be used in the present invention include thiosulfates, sulphonates, thioureas, thiazoles, rhodanins, and the like described in U.S. Patents 1574944, 2410689, 2728668, 3656955. Compounds of In addition, U.S. Patent Nos. 3857711, 4266018 and
The sulfur-containing compounds described in 4054457 can also be used.

The amount of total sensitizer used is selected from the order of 10 ^-8 mol to 10 ^-5 mol to enhance the sensitivity / fog ratio. By using a chemical sensitization suppressor in combination, it is possible to obtain high sensitivity with less fogging by using a relatively small amount. It is preferable to use a relatively small amount depending on the target sensitivity.

The amount of sulfur sensitizer that can be used in combination with this is as follows:
The optimum amount can be selected depending on the conditions such as the temperature of chemical sensitization, pAg and pH. 10 ^-7 ~ per silver halide / mole
The amount used is 10 ^-3 mol, preferably 5 × 10 ^-7 to 10 ^-4, more preferably 5 × 10 ^-7 to 10 ^-5 mol. When both gold and sulfur sensitizers are used together, the sulfur sensitizer and 250 mol% of this
It is preferable to carry out chemical sensitization by coexistence with the above gold sensitizer.

The silver halide emulsion of the present invention can be treated with an oxidizing agent after grain formation. This method is disclosed in JP-A-60-1367.
No. 36, for example, hydrogen peroxide is used.

By adding at least one compound represented by any one of the following general formulas [I] to [III] to the high silver chloride emulsion used in the present invention, the fog is increased, and in particular, the fog at the time of using a gold sensitizer is increased. It is remarkably effective in preventing the increase. It may be added at the particle forming step, the desalting step, the chemical ripening step, or immediately before the application, but the particle forming,
It is preferably added in the desalting and chemical ripening steps, especially before the addition of the gold sensitizer. General formula [I], [II] or [II
The compound having a thiosulfonyl group represented by I] will be described.

General formula [I] Z-SO ₂ S-M General formula [II] General formula (III) In the formula, Z represents an alkyl group, an aryl group, or a heterocyclic group, which may be further substituted. Y represents an atomic group necessary for forming an aromatic ring or a hetero ring, and these rings may be further substituted. M represents a metal atom or an organic cation. n represents an integer of 2 to 10.

Examples of the above-mentioned alkyl group, aryl group, and substituent capable of substituting on an aromatic ring or a heterocycle include a lower alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group, an alkoxyl group having 1 to 8 carbon atoms, Examples thereof include a halogen atom such as chlorine, a nitro group, an amino group and a carboxyl group.

The alkyl group represented by Z has 1 to 18 carbon atoms,
The aryl group and aromatic ring represented by Z and Y have 6 carbon atoms.
~ 18.

Examples of the heterocycle represented by Z and Y include a thiazole, benzthiazole, imidazole, benzimidazole and oxazole ring.

Examples of the metal cation represented by M include an alkali metal cation such as a sodium ion and a potassium ion.
As the organic cation, an ammonium ion, a guanidinium ion and the like are preferable.

Specific examples of the compound represented by the general formula [I], [II], or [III] are shown below.

e H ₃ C ・ SO ₂・ SNa k L-cystine-disulfooside 1 H ₅ C ₂ · SO ₂ · S · K m H ₁₇ C ₈ · SO ₂ · SNa The compounds represented by the general formulas [I], [II] and [III] are sulfites. , Alkylsulfinate, arylsulfinate, heterocyclic sulphonate and the like.

For the spectral sensitization in the present invention, methine dyes that are commonly used are used. In the present invention, in particular, JP-A-62-1
86252, No. 62-152330 and No. 62-329265, specific monomethine, trimethine and pentamethine dyes, and merocyanine dyes as a chemical sensitization control agent, high silver chloride grain growth It is advisable to adsorb it on the silver halide grains during the above process or the process of chemical sensitization.

When the silver chlorobromide emulsion used in the present invention is a high silver chloride tabular grain, the selection of the dye addition timing is extremely important, and it is necessary to perform it before the completion of silver halide precipitation. The addition methods described below can also be used together.
Most commonly after the completion of chemical sensitization, but before application, U.S. Pat.Nos. 3,628,969 and 4,225,6
It is also possible to add spectral sensitization at the same time as the chemical sensitizer, as described in JP-A-66, and to simultaneously perform the chemical sensitization.
It can also be carried out prior to the chemical sensitization as described in −113,928. Furthermore, as taught in U.S. Pat.No. 4,225,666, it is possible to add these said compounds separately, i.e. to add some of these compounds prior to chemical sensitization and the balance after chemical sensitization. It can be added at any time during the formation of the silver halide grains, including the method taught in US Pat. No. 4,183,756.

Dyes used for spectrally sensitizing the silver chlorobromide emulsion used in the present invention include cyanine dyes, merocyanine dyes,
It includes complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, that is, an indolenine nucleus,
Benzindolenin nucleus, indole nucleus, benzoxadol nucleus, naphthoxadol nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2, as a nucleus having a ketomethylene structure.
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied. Examples of these spectral sensitizing dyes include those represented by the general formulas [IIIa] and [IIa] described in Japanese Patent Application No. 62-227338.
Examples thereof include compounds represented by Ib] and [IIIc].

The addition amount is 1 × 10 ⁻⁶ to 8 × per mol of silver halide.
It can be used in an amount of 10 ^-3 mol, but in the case of a more preferred silver halide grain size of 0.2 to 1.2 μm, it is about 5 × 10 ^-5 to 2
× 10 ^-3 mol is more effective.

The tabular silver halide emulsion is preferably spectrally sensitized in the blue region and used in the blue-sensitive emulsion layer. Here, spectrally sensitized in the blue region means that when it is adsorbed on the emulsion grains of the present invention, it is from 400 to 500 nm, more preferably from 430 nm to 490 nm.
More preferably, a spectral sensitizing dye having at least one absorption peak at 445 nm to 490 nm is used. As specific examples of the blue spectral sensitizing dye, compounds having a structure of n ₃₁ = 0 in the general formula (IIIa) and the general formula (IIIc) of the above-mentioned application can be used. Specific examples of the compounds include the compounds III-1 to III-8 and III-29 to III-32 described in the above-mentioned application, and the plate-shaped plate formed into grains in the presence of these dyes can be used. Silver chloride grains can be preferably used.

It can be judged from the spectral sensitivity distribution that the high silver chloride tabular grains are formed in the presence of the dye. That is, it is generally difficult to form a sharp spectral sensitivity distribution in a high silver chloride emulsion. When particle formation is carried out in the presence of a dye as in the present invention, a sharp J-band is formed in the case of the methine dyes represented by the general formulas (IIIa) and (IIIb), which is represented by the general formula (IIIc). In the case of the merocyanine dye described above, a sharp monomer band (M-band) is formed, and in any case, a sharp spectral sensitivity distribution is given.

Therefore, it is possible to determine that the particle formation is performed in the presence of the dye, by identifying the peak wavelength, the spectral sensitivity distribution, and the dye species. For the J-band and M-band, see T.
M. James, Theory of Photographic Process, Chapter 8, Macmillan, Inc. (1
977) is explained.

The spectral sensitizing dyes can be used alone or in combination. It is preferable to use it together with a supersensitizer. For example, amino-stilbene compounds (for example, US Pat. No. 2,933,390
No. 3635721, No. 3615,613, No. 3615,641
No. 3,617,295, No. 3635721, Japanese Patent Application No. 61-306030
It is preferable to use an aromatic ring or heterocyclic mercapto compound as a supersensitizer in a high silver chloride emulsion.

Especially for red spectral sensitization, that is, for sensitization in the wavelength range of 580 to 750 nm, a sensitizing dye having a reduction potential of -1.27 (V.vs SCE) or less is excellent in sensitivity and sensitivity and latent Excellent image stability. As a chemical structure, a pentamethine cyanine dye having a condensed structure having one or two methine chains conjugated between N atoms, a trimethine cyanine dye having a 4-quinoline nucleus, and a tetramethine merocyanine dye. Alternatively, a dimethine merocyanine dye having a 4-quinoline nucleus is preferable. The reduction potential can be measured by phase discrimination type second harmonic alternating current polarography. A mercury dropping electrode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, and platinum is used as a counter electrode. It is preferable to use these sensitizing dyes in combination with hydroquinone, catechol, aminophenol, a formylhydrazine compound adsorbing to silver halide, or a derivative thereof. Details of the formylhydrazine compound are described in Japanese Patent Application No. 63-97905.

The high silver chloride emulsion used in the present invention has an intrinsic sensitivity in the visible wavelength region lower than that of a high silver bromide content, and when the silver chloride content is 80 mol% or more, the sensitivity is substantially increased by spectral sensitization. Will be On the other hand, since the spectral sensitivity in the blue wavelength region of the silver halide emulsion according to the present invention is not mixed with the green spectral sensitivity or the red spectral sensitivity, the inherent sensitivity of the silver halide emulsion is increased to substantially increase the spectral sensitivity. It is easy to take a way to increase

Therefore, in order to increase the intrinsic sensitivity of the silver halide emulsion in addition to the above-mentioned spectral sensitization technique, it is necessary to balance the spectral sensitivities of the B, G and R photosensitive layers. This is extremely effective because it can be done.

By adding a compound having a mercapto group to the silver halide emulsion used in the present invention, the fog of the light-sensitive material is reduced, the raw storage stability is improved, and the stability of the emulsion coating solution with time before the production of the light-sensitive material is improved. Can be improved.

Usually, tetrazaindenes are commonly used for these purposes, and mercapto-containing compounds must be used in extremely small amounts (limited amounts) for these purposes. It was thought that the negative effects such as feeling were great. Unexpectedly, it is preferable to add a mercapto compound, which is considered to have a strong inhibitory effect, to the emulsion of the present invention for the above-mentioned purpose, and there are few adverse effects such as desensitization and development inhibition. In the case of a high silver chloride emulsion, it may be used together with a sensitizing dye to exhibit a supersensitizing effect.

The mercapto-containing compound preferably used in the present invention can be represented by the following general formula (S).

General formula (S) In the formula, M ₁ represents a hydrogen atom, a cation or a protecting group for a mercapto group which is cleaved by an alkali, and Z ₁ represents an atomic group necessary for forming a 5-membered to 6-membered heterocycle. This heterocycle may have a substituent or may be condensed. More specifically, M ₁ is a hydrogen atom, a cation (eg, sodium ion, potassium ion, ammonium ion, etc.) or an alkali-cleavable mercapto group protecting group (eg, —COR ′, —COOH ′, —CH ₂ CH _2). CO
R ′ etc. However, R'represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or the like).

Z ₁ represents an atomic group necessary for forming a 5- to 6-membered heterocycle. This heterocycle contains a sulfur atom, a selenium atom, a nitrogen atom, an oxygen atom, etc. as a hetero atom,
It may be condensed, or may have a substituent on the heterocycle or the condensed ring.

Examples of Z ₁ are tetrazole, triazole, imidazole, oxazole, thiadiazole, pyridine,
Pyrimidine, triazine, azabenzimidazole, burin, tetraazaindene, triazaindene, pentaazaindene, benztriazole, benzimidazole, benzoxazole, benzothiazole, benzselenazole, naphthimidazole and the like. The substituents on these rings include an alkyl group (eg, methyl, ethyl, n-hexyl, hydroxyethyl, carboxyethyl), an alkenyl group (eg, allyl), an aralkyl group (eg, benzyl, phenethyl), an aryl group (eg, Phenyl, naphthyl, p-acetamidophenyl, p-carboxyphenyl, m-hydroxyphenyl, p-sulfamoylphenyl, p-acetylphenyl, o-methoxyphenyl, 2,4-diethylaminophenyl, 2,4-dichlorophenyl), alkylthio groups (eg methylthio, ethylthio, n-butylthio), arylthio groups (eg phenylthio, naphthylthio),
It may be substituted with an aralkylthio group, (eg, benzylthio), a mercapto group and the like. In addition to the above substituents, a nitro group, an amino group, a halogen atom, a carboxyl group, a sulfo group and the like may be substituted on the condensed ring.

The use amount of these mercapto-containing compounds is preferably 10 ^-3 mol or less per 1 mol of silver halide.

Specific examples of the nitrogen-containing heterocyclic compound having a mercapto group include compounds A-374 to A-827 described on pages 51 to 68 of JP-A No. 62-215272.

The color coupler used in the present invention will be described. In addition to general requirements such as its color development phase and its high extinction coefficient, since the development of the emulsion used in the present invention is particularly fast, a coupling color reaction with an oxidation product of a color developing agent such as a paraphenylenediamine derivative is performed. A highly active color coupler is required so that it does not become the rate-controlling factor. From this viewpoint, the following formulas [IV], [V], [VI], [VII] or [VIII]
The use of couplers represented by

Formula (IV) Formula [V] Formula [VI] Formula (VII) [VIII] In the formula, R ₁ , R ₄ and R ₅ each represent an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, R ₂ represents an aliphatic group, and R ₃ and R ₆ represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group, R ₇ and R ₉ represent a substituted or unsubstituted phenyl group, and R ₈ represents a hydrogen atom, an aliphatic or an Represents an aromatic acyl group, an aliphatic or aromatic sulfonyl group, R ₁₀ represents a hydrogen atom or a substituent, Q represents a substituted or unsubstituted N-phenylcarbamoyl group, Za and Zb represent methine, A substituted methine, or ═N-, Y ₁ , Y ₂ and Y _{4 each} represent a halogen atom or a group capable of splitting off during a coupling reaction with a developing agent with an oxidant (hereinafter abbreviated as splitting group); ₃ represents a hydrogen atom or a leaving group Y ₅ represents a leaving group, and R ₂ and R ₃ in the general formula [IV] and Formula [V]
R ₅ and R ₆ may combine to form a 5-, 6- or 7-membered ring, respectively.

Furthermore, R ₁ , R ₂ , R ₃ or Y ₁ ; R ₄ , R ₅ , R ₆ or Y ₂ ; R ₇ ,
R ₈ , R ₉ or Y ₃ ; R ₁₀ , Za, Zb or Y ₄ ; Q or Y ₅ may form a dimer or higher multimer. R ₅ and R ₆ combine to form 5
Form a member ring and form an oxindole or indazoline-
It is preferable to form a 2-one type cyan coupler.

The above general formulas [IV], [V], [VI], [VII] and [V]
III) in R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ ,
For details of Za, Zb, Q ₁ , Y ₁ , Y ₂ , Y ₃ and Y ₄ , the general formula (I) described on pages 4 to 24 of JP-A-63-11939, It is the same as that of (II), (III), (IV) and (V).

Specific examples of these color couplers include (C-1) to (C-40) and (M-1) to (C-1) described on pages 11 to 24 of JP-A-63-11939. (M-42),
(Y-1) to (Y-46) can be mentioned.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide,
Preferably 0.01 to 0.5 moles for yellow couplers,
It is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

In the light-sensitive material using the color coupler represented by the above general formula [IV], [V], [VI], [VII] or [VIII], the preferable silver halide coating amount is 1.5 g / m 2.
^{2 to} 0.1 g / m ² .

These couplers can be contained in the dispersed emulsion layer in the presence of at least one high boiling point organic solvent. Preferably, high boiling organic solvents represented by the following formulas (A) to (E) are used.

Formula (A) Formula (B) W ₁ -COO-W ₂ Formula (C) Formula (D) Formula (E) W ₁ -O-W ₂ (In the formula, W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, and ₄ is W ₁ , OW ₁ or S
Represents -W ₁ , n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different, and in the general formula (E), W ₁ and W ₂ are condensed. May form a ring).

The light-sensitive material produced by using the present invention, as a color antifoggant or color mixing inhibitor, is a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a non-absorption coupler, a sulfonamide phenol. You may contain a derivative etc.

A known anti-fading agent can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, and methylene dioxyquinone. Representative examples include benzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

The compound having both the hindered amine and the hindered phenol partial structure in the same molecule as described in U.S. Pat. No. 4,268,593 gives good results for preventing the deterioration of the yellow dye image by heat, humidity and light. In order to prevent deterioration of the magenta dye image, especially deterioration due to light,
The spiroindanes described in JP-A-56-159644 and the hydroquinone diether- or monoether-substituted chromanes described in JP-A-55-89835 give preferable results.

Further, the image stabilizer described in JP-A-59-125732 is particularly advantageous for stabilizing a magenta image formed by using a pyrazolotriazole type magenta coupler.

In order to improve the storability of cyan images, particularly the light fastness, it is preferable to use a benzotriazole-based ultraviolet absorber in combination. This UV absorber may be coemulsified with a cyan coupler.

The coating amount of the ultraviolet absorber may be an amount sufficient to impart light stability to the cyan dye image, but if used in an excessively large amount, it may cause yellowing in the unexposed portion (white background portion) of the color photographic light-sensitive material. Therefore, it is usually preferably 1 × 10 ^-4 mol /
m ^{2 to} 2 × 10 ⁻³ mol / m ² , especially 5 × 10 ⁻⁴ mol / m ^{2 to} 1.5 × 1
It is set in the range of 0 ^-3 mol / m ² .

In the light-sensitive material layer structure of a normal color paper, either one of both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer,
Preferably, the layers on both sides contain an ultraviolet absorber.
When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When an ultraviolet absorber is added to the protective layer, another protective layer may be further applied as the outermost layer. The protective layer may contain a matting agent having an arbitrary particle diameter or a latex having a different particle diameter.

In the light-sensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

In the photosensitive material of the present invention, in addition to the above-mentioned additives, various stabilizers, antifouling agents, developers or precursors thereof, development accelerators or precursors thereof, lubricants, mordants,
A matting agent, an antistatic agent, a plasticizer, or other various additives useful for photographic light-sensitive materials may be added. A representative example of these additives is Research Disclosure 1764
3 (December 1978) and 18716 (November 1979).

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain a stilbene-based, triazine-based, oxazole-based or coumarin-based brightening agent. Water-soluble ones may be used, and water-insoluble whitening agents may be used in the form of dispersion.

The reflective support used in the silver halide photographic light-sensitive material according to the present invention can be provided by coating a substrate with a water-resistant resin layer. As the substrate, a raw paper obtained from natural pulp, synthetic pulp or a mixture thereof, or a polyester film such as polyethylene terephthalate or polypropylene terephthalate, a cellulose triacetate film, a polystyrene film, a polypropylene film, or a plastic film such as a polyolefin film is used. be able to.

The base paper used in the present invention is selected from materials generally used for photographic printing paper. That is, the main raw material is a natural pulp selected from softwood, hardwood, etc., if necessary, clay,
Salts such as talc, calcium carbonate, urea resin particles, rosins, alkyl ketene dimers, higher fatty acids, paraffin wax, sizing agents such as alkenyl succinic acid, paper strengthening agents such as polyacrylamide, sulfuric acid bands, cationic polymers, etc. A fixing agent or the like is added.
In particular, use neutral paper with a reactive size agent such as alkyl ketene dimer or alkenyl succinic acid, pH 5 to 7 (measured with a pH meter using planar GST-5313F manufactured by Toa Denpa Kogyo Co., Ltd. as an electrode). The one used is preferred. Further, synthetic pulp may be used in place of the above natural pulp, or natural pulp and synthetic pulp may be mixed in an arbitrary ratio.

The surface of the pulp may be surface-sized with a film-forming polymer such as gelatin, starch, carboxymethyl cellulose, polyacrylamide, polyvinyl alcohol, or a modified product of polyvinyl alcohol.
Examples of the modified polyvinyl alcohol in this case include a modified carboxyl group, a modified silanol, and a copolymer with acrylamide. Further, the coating amount of the film-forming polymer when the surface size is treated with the film-forming polymer is adjusted to 0.1 to 5.9 g / m ² , preferably 0.5 to 2.0 g / m ² . Further, an antistatic agent, a fluorescent whitening agent, a pigment, a defoaming agent, etc. can be added to the film-forming polymer at this time, if necessary.

Further, the base paper is a pulp slurry containing the above-mentioned pulp and, if necessary, an additive such as a salt, a sizing agent, a paper-strengthening agent, and a fixing agent by a paper machine such as a Fourdrinier paper machine, and dried. It is then rolled and manufactured. The surface size treatment is performed before or after the drying, and the calender treatment is performed between the drying and the winding. When the surface sizing treatment is performed after drying, this calendering treatment can be performed either before or after the surface sizing treatment.

Whether or not the base paper used as the support substrate of the present invention is a neutral paper can be determined by, for example, measuring the pH value using GST-5313F for flat surface manufactured by Toa Denpa Kogyo KK as an electrode. Neutral paper has a pH value of 5 or more, preferably 5 to 9.

Further, the water resistant resin layer according to the present invention may itself constitute a support, such as a vinyl chloride resin.

The water-resistant resin used in the present invention is a resin having a water absorption rate (% by weight) of 0.5, preferably 0.1 or less. For example, polyalkylene (polyethylene, polypropylene, or copolymer thereof), vinyl polymer or copolymer thereof (polystyrene, Polyacrylate and its copolymer) and polyester and its copolymer. Preferably, the polyalkylene resin is low density polyethylene, high density polyethylene, polypropylene or a blend thereof. If necessary, a fluorescent whitening agent, an antioxidant, an antistatic agent, a release agent, etc. are added. In this case, the resin layer has a thickness of about 5 to 200 μm, particularly preferably 10 to 40 μm.
In general, a white pigment is kneaded by a melt mixing method or the like, and the pigment is passed through a melt extruder and melt-extruded for lamination.

Further, as described in, for example, JP-A-57-27257, JP-A-57-49946 and JP-A-61-262738, there is no polymer having one or more polymerizable carbon-carbon double bonds in one molecule. Saturated organic compounds such as methacrylic acid ester compounds,
The gintry or tetra-acrylic acid ester represented by the general formula in the specification of 61-262738 can be used. In this case, after being applied on a substrate, it is cured by electron beam irradiation to form a waterproof resin layer. White pigments and the like are dispersed in the unsaturated organic compound. It is also possible to mix and disperse other resins.

The method of coating the water-resistant resin layer of the present invention, for example, the lamination method described in, for example, Processing Technology Research Council "New Laminating Handbook", such as dry lamination, solventless dry lamination, etc. are used, For coating, a gravure roll type, a wire bar type, a doctor blade type, a reverse roll type, a dipped type, an air knife type, a calender type, a kiss type, a squeezing type, a fantin type coating or the like is used.

White pigments are contained in the waterproof resin, for example, rutile type, titanium oxide, anatase type titanium oxide, barium sulfate, calcium sulfate, silicon oxide, zinc oxide, titanium phosphate, aluminum oxide, etc. are used. The surface of the fine particles of the pigment is combined with or separately from an inorganic oxide such as silica or aluminum oxide, or a divalent or tetravalent alcohol, for example, 2,4-dihydroxy-2-methyl described in JP-A-58-17151. It is preferable to use it after surface-treating it with pentane or trimethylolethane.

The surface of the support is preferably subjected to a corona discharge treatment, a glow discharge treatment, a flame treatment or the like to provide a protective colloid layer group of the silver halide photosensitive material.

The support has a total thickness of 30 to 350 g / m ² (about 30 to 4
00 μm) is preferred, more preferably about 50 to 200 g / m
² of which the waterproof resin layer is about 5 to 200 μm
Is preferable, and more preferably about 10 to 40 μm.

The feature of the support in the present invention is that the fine particles of a white pigment (particularly preferably titanium oxide) are contained in the water-resistant resin layer so that the density thereof is preferably 12% by weight or more, more preferably 15% by weight or more and 60% by weight or less. It is to disperse in. In particular, the fine particles of the white pigment are preferably densely and uniformly dispersed (so that there is no rough portion) on the surface of the waterproof resin layer or at a thickness of about 10 μm from the surface.

The dispersibility of the white pigment particles in the resin layer is such that the resin on the surface or about 0.1 μm, preferably about 500 Å of thickness is scattered by the ion-sputtering method by glow discharge to expose the exposed pigment particles to the electronic state. Observe with a microscope, find the area occupied by the image, and occupy area ratio (%)
It can be evaluated by the coefficient of variation of. The ion-sputtering method is described in detail in Yoichi Murayama, Kunihiro Kashiwagi “Surface Treatment Technology Using Plasma”, Mechanical Research Vol. 33, No. 6 (1981), etc.

In order to control the coefficient of variation of the fine particles of white pigment to 0.15 or less, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and the surface of the pigment particles should be 2 to 4 as described above.
It is preferable to use a product treated with a dihydric alcohol.

The occupying area ratio (%) of the white pigment fine particles per defined unit area is most typically projected by dividing the observed area into adjacent 6 μm × 6 μm unit areas. It can be determined by measuring the occupied area ratio (%) (R _i ) of the fine particles. The coefficient of variation of the occupied area ratio (%) is the ratio of the standard deviation s of R _{i to} the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore, the coefficient of variation s / is Can be obtained by

In the present invention, the occupied area ratio (%) of the fine particles of the pigment
The coefficient of variation of 0.15 or less is particularly preferably 0.12 or less. 0.
When it is 08 or less, the dispersibility of the particles is substantially “uniform”.
Can be said.

In general, when such a white pigment is contained in the support of a silver halide light-sensitive material, it gives a white background (white background) and at the same time deteriorates the sharpness of an image when viewing a photograph. On the other hand, if the conditions of the density and dispersibility of the white pigment in the present invention are satisfied, the intensity of the first-class diffuse reflected light with respect to the incident light can be increased, and the spread of the diffused light can be reduced. This improvement effect of the support is remarkable not only in the incident light at the time of exposure but also in the incident light when viewing a photograph.

Another feature of the silver halide photographic light-sensitive material of the present invention is that it can be decolorized between the support and the silver halide light-sensitive layer after photographic processing (development, bleaching / fixing / washing or stabilization processing). It is to provide a layer.

By fixing the light absorber to the colored layer, the antihalation effect on the silver halide photosensitive layer can be effectively exhibited while avoiding the inhibition of spectral sensitivity and the occurrence of fog. Colloidal silver (black to yellow) or dye is used as the light absorber. By providing this colored layer, it is possible to more effectively prevent deterioration of image sharpness due to diffusion of diffused light from the support side.

It is preferable to use a colloidal silver emulsion as a light absorber in the colored layer of the present invention. As the colloidal silver emulsion, those used for color photographic materials for photographing can be used.

Colloidal silver is disclosed, for example, in U.S. Pat.
It can be produced according to the method described in 63 or Belgian Patent No. 62695. The colloidal silver used in the present invention is preferably desalted to a conductivity of 1800 μs cm ⁻¹ or less after preparation. The amount of the colloidal silver-containing layer used is 0.01 to 0.5 g, preferably 0.05 to 0.2 g per m ² as silver.
Is preferred.

Further, a dye may be used together for other purposes such as prevention of irradiation, stabilization of sensitivity, improvement of safelight safety, and improvement of spectral sensitivity distribution.

As another preferable embodiment, a dye and a cationic polymer for mordant thereof can be used in the colored layer of the present invention.

The cationic polymer which can be preferably used in the present invention is a non-color forming polymer having an ammonium salt group having at least one hydrogen atom at the cation site which functions as an anion exchange polymer.

General formula (IX) In the formula, A represents a monomer unit obtained by copolymerizing a copolymerizable monomer having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain.
B represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer. R ₄₁ represents a hydrogen atom, a lower alkyl group or an aralkyl group. Q is a single bond or an alkylene group, an arylene group, an aralkylene group, Represents a group represented by. Here, L represents an alkylene group, an arylene group or an aralkylene group, and R represents an alkyl group.

OrRepresents R₁₂, R₁₃, R₁₄, R_Fifteen, R₁₆, R₁₇, R₁₈, R₁₉Is
Hydrogen atom, alkyl group, aryl group, or aralkyl group
Which may be the same or different from each other
Yes. Also, any of the above-mentioned groups include substituted ones.
Mu. X Represents an anion.

Also, Q, R ₁₂ , R ₁₃ , R ₁₄ or Q, R ₁₅ , R ₁₆ , R ₁₇ , R
Any two or more groups of ₁₈ and R ₁₉ may be bonded to each other to form a ring structure together with the nitrogen atom.

However, In, at least one of R ₁₂ , R ₁₃ and R ₁₄ is a hydrogen atom.

x, y, and z represent mole percentages, x represents a value of 0 to 60, y represents a value of 0 to 60, and z represents a value of 0 to 60.

Explaining the general formula (IX) in more detail, examples of the monomer in A include divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol dimethacrylate, tetramethylene dimethacrylate and the like, among which divinylbenzene and ethylene glycol dimethacrylate are particularly preferable.

Examples of ethylenically unsaturated monomers in B are ethylene, propylene, 1-butene, isobutene, styrene,
α-methylstyrene, vinyl ketone, monoethylenically unsaturated ester of aliphatic acid (eg vinyl acetate, allyl acetate), ester of ethylenically unsaturated monocarboxylic acid or dicarboxylic acid (eg methyl methacrylate, ethyl methacrylate, n-butyl) Methacrylate, n-
Hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate) monoethylenically unsaturated compounds (eg acrylonitrile) or dienes (eg butadiene, isoprene) and the like, of which styrene , N-butyl methacrylate, cyclohexyl methacrylate and the like are particularly preferable. B may contain two or more of the above monomer units.

R ₁₁ is preferably a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (eg methyl, ethyl, n-propyl, n-butyl, n-amyl, n-hexyl) aralkyl group (eg benzyl), and among these, hydrogen Atoms or methyl groups are especially preferred.

Q is preferably a divalent optionally substituted alkylene group having 1 to 12 carbon atoms (for example, a methylene group or-(C
H ₂ ) _6- ), an optionally substituted phenylene group or an optionally substituted aralkylene group having 7 to 12 carbon atoms (for example, Is also preferable, and a group represented by the following formula is also preferable.

Here, L is preferably an optionally substituted alkylene group having 1 to 6 carbon atoms, an optionally substituted arylene group or an optionally substituted aralkylene group having 7 to 12 carbon atoms, and preferably has 1 to 6 carbon atoms. Is more preferably an alkylene group which may be substituted. R is preferably an alkyl group having 1 to 6 carbon atoms.

G is Or Represents R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R
₁₉ is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, each of which may be the same. It may be different. The alkyl group aryl group and aralkyl group include a substituted alkyl group, a substituted aryl group, and a substituted aralkyl group.

The alkyl group is an unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, cyclohexyl, n-heptyl, n
-Octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl); the alkyl group preferably has 1 to 12 carbon atoms. More preferably, the carbon atom is 4-10.
Individual. As the substituted alkyl group, for example, an alkoxyalkyl group (eg, methoxymethyl, methoxyethyl,
Methoxybutyl, ethoxybutyl, ethoxypropyl,
Methoxybutyl, butoxyethyl, butoxypropyl,
Butoxybutyl, vinyloxyethyl), cyanoalkyl group (for example, 2-cyanoethyl, 3-cyanopropyl,
4-cyanobutyl), a halogenated alkyl group (for example, 2
-Fluoroethyl, 2-chloroethyl, 3-fluoropropyl), an alkoxycarbonylalkyl group (for example, ethoxycarbonylmethyl), an allyl group, a 2-butenyl group, a propargyl group and the like.

The aryl group is an unsubstituted aryl group (eg, phenyl, naphthyl), and the substituted aryl group is, for example, an alkylaryl group (eg, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4). -Tert-butylphenyl), an alkoxyaryl group (for example, 4-methoxyphenyl, 3-methoxyphenyl, 4-ethoxyphenyl), an aryloxyaryl group (for example, 4-phenoxyphenyl) and the like. The aryl group has preferably 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Particularly preferred is a phenyl group.

As the aralkyl group, an unsubstituted aralkyl group (eg, benzyl, phenethyl, diphenylmethyl, naphthylmethyl); a substituted aralkyl group, eg, an alkylaralkyl group, (eg, 4-methylbenzyl, 2,5-dimethylbenzyl, 4-isopropylbenzyl) ), Alkoxyaralkyl groups (eg, 4-methoxybenzyl, 4-ethoxybenzyl), cyanoaralkyl groups, (eg, 4-cyanobenzyl), perfluoroalkoxyaralkyl groups,
(For example, 4-pentafluoropropoxybenzyl group, 4
-Undecafluorohexyloxybenzyl group, etc.), a halogenated aralkyl group, (eg, 4-chlorobenzyl group, 4-bromobenzyl group, 3-chlorobenzyl group, etc.). The carbon number of the aralkyl group is preferably 7 to 15, and preferably 7 to 11. Of these, a benzyl group and a phenethyl group are particularly preferable.

 X Represents an anion, such as a halogen ion (eg
For example, chlorine ion, bromine ion), alkyl or ant
Sulfonic acid ion (eg methanesulfonic acid, ethanol
Sulfonic acid, benzene sulfonic acid, p-toluene sulphate
(Phosphoric acid), acetate ion, sulfate ion, nitrate ion, etc.
Yes, chlorine ion, acetate ion, and sulfate ion are particularly preferred.
New

It is also preferable that any two or more groups of Q, R ₁₂ , R ₁₃ and R ₁₄ are bonded to each other to form a cyclic structure together with the nitrogen atom. The cyclic structure formed is preferably a pyrrolidine ring, piperidine ring, morpholine ring, pyridine ring, imidazole ring, quinuclidine ring or the like. Particularly preferred are pyrrolidine ring, morpholine ring, piperidine ring, imidazole ring and pyridine ring.

Further, any two or more groups of Q, R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ may be bonded to each other to form a ring structure together with the nitrogen atom. Particularly preferred is a 6-membered ring or a 5-membered ring.

x is 0 to 60 mol%, preferably 0 to 40 mol%, and more preferably 0 to 30 mol%. y is 0 to 60 mol%, preferably 0 to 60 mol%.
To 40 mol%, more preferably 0 to 30 mol%. z is 30 to 100 mol%, preferably 40 to 95 mol%, and more preferably 50 to 85 mol%.

G in the general formula (IX) has a pKa value of 4.5 in an aqueous solution.
Above all, especially 7 or more basic residues are preferable.

Among the cationic polymers of the general formula (IX), polymer latex is particularly preferable in terms of film quality.

Specific examples of the compound represented by the general formula [IX] are listed below.

When a fine particle dispersion of a cationic polymer is prepared, a crosslinkable monomer such as divinylbenzene is generally used as a monomer, but the use of the crosslinkable monomer is not essential depending on the monomer used.

Among the compounds represented by the general formula (IX) of the present invention, G
But A method for synthesizing the compound represented by will be described below.

The polymer represented by the general formula (IX) of the present invention is generally a copolymerizable monomer containing at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer, and a general formula (However, R ₁₁ , R ₁₂ , R ₁₃ , and Q are the same as those shown above) (for example, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N- (N, N-dimethylaminopropyl) acrylamide, N- (N, N-dihexylaminomethyl) acrylamide, 3- (4-pyridyl) propyl acrylate , N,
N-dimethylaminomethylstyrene, N, N-diethylaminomethylstyrene, N, N-dihexylaminomethylstyrene, 2-vinylpyridine, 4-vinylpyridine or the like, particularly preferably N, N-diethylaminoethyl methacrylate, or N, After polymerization with N-dimethylaminomethylstyrene, N, N-diethylaminomethylstyrene), a compound having the structure of R ₁₄ —X (wherein R ₁₄ and X are the same as those shown above) (for example, Hydrochloric acid, nitric acid, sulfuric acid, acetic acid, p-toluenesulfonic acid, etc.) to form an ammonium salt.

The polymer represented by the general formula (IX) of the present invention includes a copolymerizable monomer having at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer, and a general formula (Provided that R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , X and Q are the same as those shown above) (for example, N,
N-dimethylaminoethyl methacrylate hydrochloride, N, N-
Diethylaminoethyl methacrylate sulfate, N, N-dimethylaminoethyl acrylate hydrochloride ring, N, N-diethylaminoethyl acrylate acetate, N, N-dimethylaminostyrene hydrochloride, N, N-diethylaminomethylstyrene sulfate, 2-vinyl It can be obtained by polymerizing with pyridine hydrochloride or 4-vinylpyridine hydrochloride.

Further, the polymer represented by the general formula (IX) of the present invention is a copolymerizable monomer having at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer, and a general formula (Provided that X represents a halogen atom (eg chlorine atom, bromine atom), sulfonic acid ester (eg p-toluenesulfonyloxy group), and R ₁₁ and Q are the same as those shown above) After polymerization with a monomer (eg β-chloroethyl methacrylate, β-p-toluenesulfonyloxyethyl methacrylate, chloromethylstyrene) To an amine having the structure of (wherein R ₁₂ , R ₁₃ and R ₁₄ are the same as those shown above) (eg, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, morpholine, piperidine, etc.) It can also be obtained by using an ammonium salt.

In the compound represented by the general formula (IX) of the present invention, G is A method for synthesizing the compound represented by will be described below.

The polymer represented by the general formula of the present invention includes a polymerizable monomer containing at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer, and a general formula (However, R ₁₁ , R ₁₅ , and Q are the same as those shown above) (for example, methyl vinyl ketone, methyl- (1-methyl vinyl) ketone, ethyl vinyl ketone, ethyl- ( 1-methyl vinyl) ketone, n-propyl vinyl ketone, diacetone acrylamide, diacetone acrylate, etc., particularly preferably methyl vinyl ketone, ethyl vinyl ketone, diacetone acrylamide, diacetone acrylate), and then the general formula (However, R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ are the same as those shown above) (for example, aminoguanidine bicarbonate, N-amino-N′-methylguanidine bicarbonate, Bicarbonate N-amino-N'-methylguanidine, etc.,
Particularly preferably, aminoguanidine bicarbonate) is reacted,
Further, it can be obtained by forming a guanidinium salt with a compound represented by H-X (H-X is the same as those shown above) (for example, hydrogen chloride, hydrogen bromide, sulfuric acid, acetic acid, nitric acid). You can

The above-mentioned polymerization reaction may have any of generally known methods of solution polymerization, emulsion polymerization, suspension polymerization, precipitation polymerization and dispersion polymerization. Solution polymerization and emulsion polymerization are preferred.

Among the above-mentioned polymerization reactions, for example, emulsion polymerization is generally performed by using anionic surfactants (for example, sodium dodecyl sulfate, Triton 770 (commercially available from Rohm & House), cationic surfactants (for example, octadecyltrimethylammonium chloride), nonionic surfactants. Agent (for example, Emarex NP-20 (commercially available from Nippon Emulsion)), gelatin, at least one emulsifier selected from polyvinyl alcohol and the like and a radical polymerization initiator (for example, a combination of potassium persulfate and sodium bisulfite, (Commercially available under the name V-50 from Wako Pure Chemical Industries, Ltd.)
It is carried out at a temperature of 30 ° to about 100 ° C, preferably 40 ° C to about 80 ° C.

The above-mentioned reaction with ammonium salt is generally carried out at a temperature of -10 ° C to about 40 ° C, with 0 ° C to 30 ° C being particularly preferred.

The polymer of the present invention can be manufactured very easily because the whole manufacturing process can be carried out in one container.

Examples of the hydrophilic protective colloid used for dispersing the cationic polymer according to the present invention include gelatin, modified gelatin, gelatin derivatives and graft polymers of gelatin and other polymers, and proteins such as albumin and casein; Hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates; saccharide derivatives such as dextran, sodium alginate and starch derivatives; polyvinyl alcohol, partially acetalized polyvinyl alcohol,
Homopolymers and copolymers such as poly-N-vinylpyrrolidone, polyacrylamide, acrylic acid or methacrylic acid copolymer, and polyvinylpyrazole can be used in combination. Particularly preferably, gelatin is used as the hydrophilic colloid, and so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin and the like are used. It is particularly preferable for rapid processing that it has a narrow molecular weight distribution.

The molecular weight distribution of gelatin can be measured by the GPC method (gel permeation chromatography). Gelatin containing 12% by weight or more, preferably 14% by weight or more of the high molecular weight component is preferable. The GPC method is described in the text of JP-A-62-87952 and Example-1.

The cationic polymer dispersion layer or other hydrophilic colloid layer used in the present invention is hardened with an inorganic or organic hardener. Examples of hardening agents include chromium salts, aldehydes (formaldehyde, glitalaldehyde, etc.), N-methylol compounds (dimethylolurea, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, Bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β
-Vinylsulfonyl) propionamide], etc.), for example, active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine) described in US Pat. No. 3,325,287, mucohalogen acids (such as mucochloric acid), N
-Carbamoylpyridinium salts (1-morpholinocarbonyl-3-pyridinio) methanesulfonate, etc.,
Haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium, 2-naphthalene sulfonate, etc.) can be used alone or in combination.
In the present invention, a hardening agent having two or more vinylsulfonyl groups (for example, compounds described in the specifications of JP-B-47-24259, JP-B-49-13563 and JP-B-57-24902), active vinyl groups Hardener having two or more (for example, JP-A-53-4122).
0, Dosho 53-57257, Dosho 59-162546, Dosho 60-80
Compounds described in the specification such as 846), and others, JP-A-6
The compounds described in the specifications such as 2-222242, 62-245261, 62-109050, and Japanese Patent Application No. 61-139713 stably damage the cation site of the polymer used in the present invention. It can be used without doing.

The acid dye used with the cationic polymer according to the present invention has a light absorption selected in the spectral sensitivity wavelength range of the light-sensitive layer of the color light-sensitive material of the present invention, and particularly has a molar extinction coefficient of 10 ² l · mol · cm ⁻¹ or more. The ones are good. In a color light-sensitive material using a reflective support, a dye that does not leave a residual color by being decolorized or eluted after development is particularly preferable.

As such a dye, it is preferable to use a dye having a pH of 7.0 or less and being substantially insoluble in water, together with a dispersion aid, in the form of solid fine particles dispersed in a colloid. "Solid fine particles" means that the average particle size (projection, circle approximation) is 1μ
m or less, preferably 0.5 μm to 0.01 μm, is substantially diffusion resistant to other adjacent layers in the colloid layer, and is 3 μm or more in a state in which it is not aggregated and dispersed.

Examples of the dispersion aid include ordinary nonionic surfactants, anionic surfactants and amphoteric surfactants such as those disclosed in JP-A-62-2152.
No. 72, pages 649 to 668, and the compounds represented by the specific compounds W-1 to W-99, Japanese Patent Publication Nos. 56-36415, 59-31688 and 59-31688. General formulas [VII] and [VII] of Japanese Patent Application No. 62-118519
It can be used by selecting from the surfactants represented by the formulas I] and [IX]. For example The dispersion aid, a water-soluble organic solvent, such as dimethylformamide, methyl alcohol, ethyl alcohol,
Dimethylsulfonylamide or the like can be used.
In addition, hydrophilic colloids such as gelatin, casein, hydroxyl ethyl cellulose, poly-N-vinylpyrrolidone, polyacrylic acid and gelatin derivatives are used as the dispersion medium.
Also, alkaline water can be used.

Solid fine particle dispersion is a method in which a dye solid is dissolved in a water-soluble organic solvent and dispersed in an aqueous colloidal solution having a neutral or acidic pH, particularly preferably, the dye solid is wetted with water or an insoluble liquid and kneaded with a dispersion aid. Then, a method of forming fine particles in a mill and dispersing in a colloidal aqueous solution, a method of making a dye solid into a fine powder by using ultrasonic waves, and then dispersing in a colloidal aqueous solution by using a surfactant as a dispersion aid, or the like, It can be produced by a method such as dissolving a dye in alkaline water and dispersing it in an acidic colloidal aqueous solution.

An organic layer, for example, citric acid, oxalic acid, acetic acid, tartaric acid, etc. may be used together with the dye or colloid aqueous solution.

The solid fine particles used in the present invention may be fine crystals of a dye, fine particles having a micelle structure, or fine agglomerated particles. The particle size of the solid fine particles can be measured by observing the cross section of the section of the colloid layer containing them using a transmission electron microscope.

The solid fine particle dispersion method is substantially insoluble in water having a pH of 7 or less, and in the molecule, a hydroxyl group, a carboxyl group, an amino group, a sulfomoyl group and the like, which does not substantially dissociate at pH 7 and dissociates at pH 9 or more, is hydrophilic. Dyes containing functional groups are preferred. The term "substantially insoluble in water" means that the fine particle dispersion state is insoluble to the extent that it can be retained in a hydrophilic colloid having a pH of 7 or less, for example, an aqueous gelatin solution.

Dyes having a solubility in water of pH 7 at room temperature (24 ° C.) of 10% by weight or less, more preferably 5% by weight or less are preferable.

Such dyes are generally known dyes such as arylidene dyes, styryl dyes, butadiene dyes, oxonol dyes, cyanine dyes, merocyanine dyes, hexianine dyes, diarylmethane dyes, triaryl dyes. , Azomethine dyes, azo dyes, metal chelate dyes, anthraquinone dyes, katylben dyes, chalcone dyes, and indophenol dyes. Also, for example, U.S. Pat.
880,658, 3,931,144, 3,932,380, 3,932,3
No. 81, No. 3,942,987 J. Fabian, H. Hartmann, "Light Absorption-Organic Colorants" (Li)
ght Absorption of Organic Colorants), (published by Springer-Verlag) (or a diffusion-resistant analogue).

The dyes used in the present invention include the functional dyes described in Japanese Patent Application No. 62-106892, Japanese Patent Application No. 62-21527, Japanese Patent Application No. 6-21527.
2-293243 (pages 109 to 117) and Japanese Patent Application No. 62
-43704 and Japanese Patent Application No. 62-153132, the general formula [I]
Among the dyes represented by formula (II) and the dye represented by formula (II) of the specification of JP-A-62-226131, those which have spectral absorption characteristics and have no residual color after development are selected. You can In order to prevent halation, a dye that absorbs light in the spectral sensitivity wavelength range of the photosensitive layer provided on the cationic polymer dispersion layer is used, and in order to correct the spectral sensitivity distribution, it is adjusted to the sensitivity wavelength range to be corrected. A dye having light absorption is used. It is preferable that 80% or more of the dye used in the photographic emulsion layer or other layers of the light-sensitive material is contained in the cationic polymer-containing layer. In addition, the amount of dye added is 0 compared to the number of cation sites.
Advantageously, it is 01 to 10, preferably 0.2 to 1.

Preferred dyes used in the present invention include Japanese Patent Application Nos. 61-287295, 61-314428, and 61-314428 for preventing halation.
62-79483, 62-110333, 62-226131, 62
No. 277669, No. 62-284448, etc., and Japanese Patent Application Nos. 62-34264 and 62-239 for modifying spectral sensitivity.
032, 62-264396, 62-261052, 62-24747
Examples include dyes described in No. 7 and the like.

Particularly preferred dyes are Japanese Patent Application Nos. 61-287295 and 62-62.
-79483, 62-153132, 62-226131, 62-2
The dyes described in JP-A-84448 and JP-A-62-123454 can be mentioned.

Next, specific examples of the dye used in the present invention are shown. However, it is not limited.

Among these dyes, dyes -18, -37 and -43
Is suitable for solid fine particle dispersion, and Dye-45 can also be used for solid fine particle dispersion.

General formulas (X), (XI), (XII), (XII
The dyes represented by I) and (XIV) are particularly suitable for solid fine particle dispersion. In particular, when used in a colored layer (compared to, for example, a method using colloidal silver or a method using a cationic polymer that provides a cation site as a mordant), the following features are exhibited.

(1) Appropriate spectral absorption characteristics can be easily selected according to the purpose of use, such as a filter layer or an anti-halation layer.

(2) Photochemically inactive. It does not chemically desensitize, fog, or degrade latent images in adjacent silver halide light sensitive layers.

(3) Elution and decolorization are easy during the development process. Leaves no residual color or stain.

(4) Solid fine particles do not diffuse into other layers. It also has good stability over time and does not discolor or fade.

These features are especially true for color photosensitive materials for printing that use a reflective support, specifically color photographic paper, direct positive
It is useful as an anti-halation layer for color printing paper and color reversal printing paper, a filter layer for correcting spectral sensitivity distribution, and the like. When used as a filter layer, it is preferable to appropriately provide a filter layer by changing the layer structure of the light-sensitive layer constituting the color light-sensitive material, for example, the blue-sensitive layer (BL), the green-sensitive layer (GL) or the red-sensitive layer (RL). . It is also possible to form a filter layer by incorporating fine dye solid particles in a usual intermediate layer. It is preferable to use a combination of dye solid fine particles and the above-mentioned acid dye.

Formulas (X), (XI), (XII), (XIII) and (XI
Each group in V) is explained in detail.

The carboxyphenyl group possessed by the acidic nucleus represented by A ₂ and the electron-withdrawing group represented by X ₃ or Y ₃ includes not only one but also two or three carboxyphenyl groups. Similarly, a sulfamoylphenyl group, a sulfonamidophenyl group and a hydroxyphenyl group also include a sulfamoyl group, a sulfonamide group and a hydroxy group each having not only one but also two or three phenyl groups, Substituents other than carboxy group, sulfamoyl group, sulfonamide group, and hydroxy group (As a substituent, a dissociable substituent having a pKa (acid dissociation constant) of 4 or more in a solution having a volume ratio of water to ethanol of 1: 1 or more. Alternatively, it is not particularly limited as long as it is a non-dissociative substituent). Specifically, 4-carboxyphenyl, 3,5-
Dicarboxyphenyl, 2,4-dicarboxyphenyl,
3-carboxyphenyl, 2-methyl-3-carboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl, 2,5-dicarbonoxyphenyl, 2 , 4,6-trihydroxyphenyl, 3-benzenesulfonamidophenyl,
4- (p-cyanobenzenesulfonamide) phenyl,
3-hydroxyphenyl, 2-hydroxyphenyl, 4
-Hydroxyphenyl, 2,4-dihydroxyphenyl,
3,4,5-Trihydroxyphenyl, 2-hydroxy-4
-Carboxyphenyl, 3-methoxy-4-carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl and the like groups can be mentioned, and these groups are not only directly in the acidic nucleus but also in the methylene group. It may be bonded via an ethylene group or a propylene group.

The carboxyalkyl group contained in the acidic nucleus represented by A ₂ and the electron-withdrawing group represented by X ₃ or Y ₃ preferably has 1 to 10 carbon atoms, and examples thereof include carboxymethyl, 2-carboxyethyl and 3-carboxy. Propyl,
2-carboxypropyl, 4-carboxybutyl, 8-
Examples include groups such as carboxyoctyl.

The alkyl group represented by R ₄₀ , R ₄₃ or R ₄₆ has 1 carbon atom.
Alkyl groups of 10 are preferred, such as methyl, ethyl,
Examples thereof include groups such as n-propyl, isoamyl and n-octyl.

The alkyl group represented by R ₄₁ and R ₄₂ is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl, n
-Butyl, n-octyl, n-octadecyl, isobutyl, isopropyl) are preferable, and substituents [for example, halogen atom such as chlorine bromine, nitro group, cyano group, hydroxy group, carboxy group, alkoxy group (for example, methoxy, ethoxy). ), An alkoxycarbonyl group (for example, methoxycarbonyl, i-propoxycarbonyl), an aryloxy group (for example, a phenoxy group), a phenyl group,
It may have an amide group (eg, acetylamino, methanesulfonamide), a carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl), a sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].

The aryl group represented by R ₄₁ and R ₄₂ is preferably a phenyl group or a naphthyl group, and has a substituent (the above-mentioned R ₄₁
And the groups mentioned as the substituents of the alkyl group represented by R ₄₂ and the alkyl groups (for example, methyl and ethyl). ] May be included.

The acyl group represented by R ₄₁ and R ₄₂ is preferably an acyl group having 2 to 10 carbon atoms, for example, acetyl, propionyl, n
Examples thereof include groups such as -octanoyl, n-decanoyl, isobutanoyl and benzoyl. As the alkyl or arylsulfonyl group represented by R ₄ and R ₄ ,
Examples thereof include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl and o-carboxybenzenesulfonyl groups.

The alkoxy group represented by R ₄₃ and R ₄₆ is preferably an alkoxy group having 1 to 10 carbon atoms, for example, methoxy, ethoxy, n
Examples thereof include groups such as -butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy and isopropoxy. Examples of the halogen atom represented by R ₄₃ and R ₄₆ include chlorine, bromine and fluorine.

The ring formed by linking R ₄₁ and R ₄₄ or R ₄₂ ,
For example, a diurolidine ring can be mentioned.

Examples of the 5- or 6-membered ring which can be formed by connecting R ₄₁ and R ₄₂ include a piperidine ring, a morpholine ring and a pyrrolidine ring.

The methine group represented by L ₁ , L ₂ and L ₃ may have a substituent (eg methyl, ethyl, cyano, phenyl, chlorine atom, hydroxypropyl).

The electron-withdrawing groups represented by X ₃ and Y ₃ may be the same or different, and are a cyano group, a carboxy group, an alkylcarbonyl group (an optionally substituted alkylcarbonyl group, for example, acetyl, propionyl, heptanoyl, Dodecanoyl, hexadecanoyl, 1-oxo-7-chloroheptyl group, etc., arylcarbonyl group (which may be substituted arylcarbonyl group, for example, benzoyl,
4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl group and the like), alkoxycarbonyl group (which may be substituted alkoxycarbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl,
t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, Two
-Cyanoethoxycarbonyl, 2- (2-chloroethoxy) ethoxycarbonyl, 2- [2- (2-chloroethoxy) ethoxy] ethoxycarbonyl group, etc., aryloxycarbonyl group (which may be substituted aryloxycarbonyl group) , For example, phenyoxycarbonyl,
3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4-fluorophenyloxycarbonyl, 4-
Nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl, 2,4-di- (t-amyl) phenoxycarbonyl group and the like), carbamoyl group (which may be substituted, for example, carbamoyl group, Ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl, 4
-Propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4
-Di- (t-amyl) phenylcarbamoyl, 2-chloro-3- (dodecyloxycarbonyl) phenylcarbamoyl, 3- (hexyloxycarbonyl) phenylcarbamoyl group, etc., a sulfonyl group (for example, methylsulfonyl, phenyl, etc.) And an sulfamoyl group (which may be substituted, for example, sulfamoyl and methylsulfamoyl groups).

Next, specific examples of the dyes used in the present invention, which are particularly suitable for solid fine particle dispersion, will be given, but the present invention is not limited thereto.

The dyes used in the present invention include international patents WO88 / 04794, European patent EP0274723A1, JP-A-52-92716, and JP-A-55.
-155350, 55-155351, 61-205934, 48-
68623, U.S. Pat.Nos. 2,527,583, 3,486,897, and
3,746,539, 3,933,798, 4,130,429, 4,04
It can be easily synthesized according to the method described in No. 0841 and the like.

Examples of the hydrophilic protective colloid used in the colored layer in the present invention include gelatin, modified gelatin, derivatives of gelatin, graft polymers of these with other polymers, proteins such as albumin and casein; hydroxycellulose, carboxymethylcellulose and cellulose sulfate. Cellulose derivatives such as esters; sugar derivatives such as dextran, sodium alginate and starch derivatives; polyvinyl alcohol, partially acetalized polyvinyl alcohol,
Homopolymers and copolymers such as poly-N-vinylpyrrolidone, polyacrylimide, acrylic acid or methacrylic acid copolymer, and polyvinylpyrazole can be used in combination. Particularly preferably, gelatin is used as the hydrophilic colloid, and so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin are used. It is particularly preferable for rapid processing that it has a narrow molecular weight distribution.

The molecular weight distribution of gelatin can be measured by the GPC method (gel permeation chromatography). Gelatin containing 12% by weight or more, preferably 14% by weight or more of the high molecular weight component is preferable. The GPC method is described in the text of JP-A-62-87952 and Example-1.

The cationic polymer used in the present invention is dispersed in the hydrophilic colloid as water-soluble or latex. In the case of a water-soluble cationic polymer, a dye may be further added to prepare a coating solution for a colored layer. In the case of a cationic latex, it is preferable to dilute and disperse a master coating solution to which a dye is added in advance in a hydrophilic colloid to obtain a coating solution. The dispersion of the water-soluble cationic polymer is relatively easy to collect, and a relatively small amount of dye is used for the cationic polymer. The cationic polymer according to the present invention varies depending on the use conditions, but it is a hydrophilic protective colloid.
It is preferable to use 1 to 100 g per 0 g, more preferably 1 to 50 g, and further preferably 1 to 120 g. In addition, for example, for each anion group of the anionic compound such as a dye, 0.1 or more cation sites of the cationic polymer are used, preferably 0.3 to 50.
In particular, quantities corresponding to 1 to 30 are used. The water-soluble cationic polymer is preferably 1 to 20 g per 100 g of the hydrophilic protective colloid, and the anionic group of the acid dye is 1
An amount corresponding to 5 to 30 cation sites is preferable for each.

Furthermore, a nonionic, amphoteric or anionic surfactant is used in the coating liquid for the colored layer, and it is particularly preferable to use a cationic surfactant. In the case of a water-soluble cationic polymer, a polymer latex dispersion is preferably used together, and particularly preferably used in combination with a cationic polymer latex dispersion.

The colored layer or other hydrophilic colloid layer used in the present invention is hardened with an inorganic or organic hardener.
Examples of hardening agents include chromium salts, aldehydes (formaldehyde, glitalaldehyde, etc.), N-methylol compounds (dimethylolurea, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-).
Triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β-vinylsulfonyl)
Propionamide], etc.), eg US Pat. No. 3,325,28
No. 7, etc., active halogen compounds (2,4-dichloro-
6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid etc.), N-carbamoylpyridinium salts (1-morpholinocarbonyl-3-pyridinio) methanesulfonate etc.), haloamidinium salts (1- (1-chloro- 1-pyridinomethylene) pyrrolidinium, 2-naphthalene sulfonate, etc.) can be used alone or in combination. In the present invention, a hardening agent having two or more vinylsulfonyl groups (for example, Japanese Patent Publication No. 47)
No. -24259, No. 49-13563, No. 57-240902, etc.), a hardener having two or more active vinyl groups (for example, JP-A Nos. 53-41220 and 53-41220). 53-57257
Nos. 59-162546 and 60-80846, and other compounds described in the specification, and JP-A-62-222242 and
The compounds described in the specifications such as 62-245261, 62-109050, and Japanese Patent Application No. 61-139713 can be stably used without damaging the cation site of the polymer used in the present invention. .

The average particle diameter of the cationic polymer latex fine particles used in the present invention is 1 μm or less, preferably 1 to
0.001 μm, particularly 0.2 to 0.01 μm is preferable, and a narrow particle size distribution is preferable. Further, in the photographic constituent layer, other polymer latexes described in US Pat. Nos. 3,411,911 and 3,411,912 and Japanese Patent Publication No. 45-5331 can be used in combination. For example, when an anionic compound such as an acid dye is adsorbed and dispersed, it is preferable that the anionic compound be adsorbed on the cation site of the polymer in advance. By using this dispersion method, it is possible to prevent desorption due to the anionic surfactant coexisting in the hydrophilic colloid layer, the anionic group of the hydrophilic colloid itself, and the like.

The colored layer according to the present invention can be directly applied and dried on the water resistant resin layer containing a white pigment. It can also be provided directly on the support side of the silver halide photosensitive layer.
Further, it is preferable to provide the front two intermediate layers. Further, another silver halide light-sensitive layer can be inserted. The colored layer is preferably provided so that the spectral sensitivity distribution of the silver halide photosensitive layer provided on the support side of the colored layer is modified.

The colored layer of the present invention has a membrane layer of 0.1 to 10 μm, preferably 0.2.
To 5 μm is preferable. The maximum spectral reflection density is preferably 0.2 or more, and particularly preferably 0.3 to 1.5.

The color light-sensitive material according to the present invention comprises, on a support, a blue-sensitive silver halide light-sensitive layer containing a yellow coupler,
It is preferable to provide a green-sensitive silver halide photosensitive layer containing a magenta coupler and a red-sensitive silver halide photosensitive layer containing a cyan coupler, but the order of the layers can be changed according to the purpose. In particular, high silver chloride silver halide has a small intrinsic sensitivity in the blue-sensitive wavelength range (400 to 500 nm), so that the order of layers can be easily changed. For example, from the support side, the order of red-sensitive, green-sensitive, and blue-sensitive photosensitive layers, or blue-sensitive, green-sensitive, and green-sensitive photosensitive layers is in order.

The color sensitivity of each light-sensitive layer of the color light-sensitive material according to the present invention is
It is preferable to select according to the scanning exposure light source to be used and also to use in combination with a color separation filter. For example, a combination of blue-sensitive, green-sensitive and red-sensitive layers or a combination of green-sensitive, red-sensitive and infrared-sensitive layers.

Next, the color development processing applied to the coupler light-sensitive material of the present invention will be described. The color light-sensitive material of the present invention is preferably subjected to color development processing subsequent to scanning exposure.

The color developer used for the development processing of the light-sensitive material of the present invention,
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent, but p-
A phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-4-N-ethyl-N-β-hydroxyethyl. Aniline, 3-methyl-4
-Amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonic acid Examples include salt. 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, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, hydrazides, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,
It is preferable to add various preservatives such as 2,2] octane). Among them, hydrazines and hydrazides are preferably used, and these compounds correspond to the compounds represented by the general formula (II) in Japanese Patent Application No. 63-11295, and specific examples thereof are the above-mentioned application. The compounds listed on pages 27-47. The amount of these compounds added is per developer.
The amount is preferably 0.01 to 50 g, more preferably 0.1 to 30 g.
Also, the amount of hydroxylamines added per developer
0g to 10g is preferable, and 0g to 5g is more preferable. If the stability of the color developer is maintained, it is preferable that the addition amount be small.

Other additives to the color developing solution include organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers and sodium. As represented by fogging agents such as boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids. Various chelating agents,
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 salts thereof can be mentioned as representative examples.

The processing temperature of the color developer in the present invention is from 30 ° C to 50 ° C.
C is preferably, and more preferably 33 to 42 ° C. The replenishing amount is 2000 ml or less, preferably 1500 ml or less per 1 m ² of the light-sensitive material. From the viewpoint of reducing the amount of waste liquid, it is preferable that these replenishing amounts are small.

In the color developing solution of the present invention, it is preferable to use a color developing solution substantially free of benzyl alcohol, which is disadvantageous due to environmental pollution, preservation of a color image, generation of stain, etc. It is preferable to constitute a color developing system in which a reconstituting agent for the oxidized form of the color developing agent described in 259799 and a capturing agent for the oxidized form of the reconstituting agent are used together.

Further, it is preferable that the color developing solution in the present invention does not substantially contain iodide ions. Here, the term "substantially free of iodide ions" means that iodide ions of less than 1 mg / l are included. Further, the color developing solution in the present invention preferably contains substantially no sulfite ion, and the phrase "substantially free of sulfite ion" means that the sulfite ion content is 0.02 mol / l or less.

The photographic emulsion layer after color development 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, iron (III) aminodicarboxylate iron (III) complexes and other aminopolycarboxylic acid iron (II)
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

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-
95630, 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 above; 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-45-8836; silver bromide ion, etc. Can be used. 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 effective when bleach-fixing a color photographic 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 the preservative of the bleach-fixing solution, sulfite, bisulfite, sulfinic acid 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. In addition, isothiazolone compounds and siabendols described in JP-A-57-8542, chlorinated fungicides such as chlorinated sodium isocyanurate, and benzotriazole, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide" ,
Sanitizing agents described in "Sterilization, disinfection and fungicide technology of microorganisms" edited by the Sanitary Technology Society, and "Encyclopedia of antibacterial and antifungal agents" edited by the Japan Society of Antifungals and Fungi can also be used.

The pH of the milky water in the processing of the light-sensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but in general, at 15-45 ° C for 20 seconds-10 minutes, preferably at 25-40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the aqueous solution. In such a stabilizing process, the method disclosed in
All known methods described in 57-8,543, 58-14,834, 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. Examples include a stabilizing bath containing formalin and a surfactant. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the 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, indoaniline compounds described in U.S. Pat.Nos. 3,342,597, 3,342,599, Schiff base type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, and U.S. Pat. And urethane compounds described in JP-A-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 to improve 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.

In this development processing step, from color development to desilvering, washing and drying can be performed within 120 seconds.

(Preferred embodiment of the present invention) (1) The reflective support contains 15% by weight or more of white pigment particles in a water resistant resin, and the degree of dispersion of the white pigment particles is a coefficient of variation (s /). And 0.12 or less, and a light-sensitive layer containing a silver chlorobromide emulsion chemically sensitized in the presence of a CR-compound and an antihalation layer are provided on the support. Type color photosensitive material.

(2) In the above-mentioned embodiment item (1), the general formula [1],
Gold sensitized in the presence of a compound having a thiosulfonyl group represented by [II] or [III], having a silver bromide-containing localized phase on the grain surface with an average silver chloride content of 90 mol% or more. A reflective color light-sensitive material having a light-sensitive layer containing a silver chlorobromide emulsion.

(3) A color image forming method in which the color light-sensitive material of the present invention is printed using a printer having a CRT exposure system and then processed at present.

(4) A color image forming method as described in the above item (3), which uses a printer having a black and white CRT exposure system.

Example-1 Production of support LBKP (bleached hardwood, sulfate pulp) 100 for photographic printing paper
% (Weighing 175 g / m ² , thickness about 180 μ); A white pigment-containing resin layer made of water resistant titanium oxide having the following composition was provided on the surface of a white base paper to obtain a support I.

Support I: Add 90 parts by weight of polyethylene composition (density 0.920 g / cc, melt index (MI) 5.0 g / 10 min), 10 parts by weight of titanium oxide white pigment surface-treated with silicon oxide and aminium oxide Then, after kneading, a water-resistant resin layer having a thickness of 30 μm was obtained by melt extrusion coating. On the other hand, another polyethylene composition (density 0.950g / cc, MI8.0g / 10
Min) was coated to obtain a water resistant resin layer having a thickness of 20 μm.

Support II: 88 parts by weight of the polyethylene composition used in Support I,
12 parts by weight of the following surface-treated anatase-type titanium oxide white pigment was added, and after kneading in the same manner, a water-resistant resin layer of 30 μm was obtained by melt extrusion coating.

The same titanium oxide powder as that used for the support I was immersed in an ethanol solution of trimethylolethane, heated and evaporated to obtain a surface-treated titanium oxide white pigment. The alcohol is about 1% by weight with respect to titanium oxide.
The surface of the corresponding particles was coated. A water resistant resin layer was provided on the back surface of the blank base paper using the polyethylene composition as in the case of the support A.

Support III: The same as Support II, except that 15 parts by weight of titanium oxide containing 3% by weight of zinc oxide was used in the polyethylene composition instead of the anatase-type titanium oxide white pigment in Support II.

Support Sample IV: Composition of 50 parts by weight of hexaacrylate ester of dipentaerythritol propylene oxide 12 mol equivalent adduct and 50 parts by weight of rutile-type titanium oxide and 20 by ball mill.
After mixing and dispersing for more than an hour, the following base paper was coated and dried so that the dry film thickness was 20 μm. The base paper used was the white base paper used for the support A and the polyethylene composition having a thickness of 20%.
It is obtained by providing a 20 μm layer of a polyethylene composition (density 0.960 g / cc, MI 25 g / 10 min) on the back surface.

The coating layer was irradiated with an electron beam at an acceleration voltage of 200 kv and an absorbed dose of 5 megarads in a nitrogen atmosphere to obtain a support sample IV.
I got

Substrates I, II and III contained about 0.3% by weight of ultramarine blue, and Substrate IV contained about 0.15% by weight of ultramarine blue, based on the sum of the polyethylene and the white pigment particles.

The dispersibility of the white pigment particles on the surface portion of the water resistant resin layer of the support according to the present invention is determined by etching the resin of about 0.05 μm from the surface by an ion sputtering method, and observing the white pigment particles by an electron microscope. 6 μm x 6 μ
Calculate the projected area ratio Ri of each particle for 6 unit areas of m, and standard deviation The average particle occupation area ratio (%) was determined. The results are shown in Table 1.

In comparison with the support sample I, the support samples II to IV are excellent in dispersibility of the white pigment. In particular, Samples III and IV are substantially evenly dispersed.

Example-2 Silver halide milks-1 to 6 were produced as follows.

After heating (1st liquid) to 55 ° C and adding (2nd liquid),
Solution 4 and Solution 4 were added simultaneously after spending 10 minutes. 10 more
After 5 minutes, (5 solution) and (6 solution) were added simultaneously spending 35 minutes. Five minutes after the addition was completed, the temperature was lowered to desalt.

Monodisperse cubic silver chlorobromide emulsion (i) with water and gelatin for dispersion adjusted to pH 6.2 with an average grain size of 0.70μ and a coefficient of variation (standard deviation divided by the average grain size) of 0.13.
I got

Next, the emulsion (i) was mixed with Ex Dye B as a CR-compound at 58 ° C.
After adding 2.3 × 10 ⁻⁴ mol per mol of silver halide,
Sodium thiosulfate, silver gold chloride, and ammonium rhodanate were added and subjected to optimum chemical sensitization to obtain a surface latent image type emulsion, and then 4-hydroxy-6-methyl-1, as a stabilizer.
The emulsion to which 3,3a, 7-tetraadesignden was added was designated as emulsion (1).

As shown in Table 2, when the grain formation temperature and CR-compound were changed and silver bromide was contained, the amount of chloroauric acid was halved and optimum chemical sensitization was performed. To obtain emulsions 2 to 6.

Paper laminated on both sides with polyethylene (support sample
On top of II), a multi-layer color photographic paper having the following layer constitution was produced.

The coating solution is prepared by mixing and dissolving an emulsion, various chemicals, and an emulsified dispersion of a coupler. The respective preparation methods are described below.

Preparation of coupler emulsion Yellow coupler (Ex Y) 19.1 g and color image stabilizer (C
pd-1) 4.4 g of ethyl acetate (27.2 cc) and a solvent (Solv-
1) 7.7 cc was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.

Thereafter, each emulsion for magenta, cyan and intermediate layers was prepared in the same manner.

Stabilizer Ex-3d was added to the silver halide emulsion layer 1 in the blue-sensitive emulsion layer.
2.5 × 10 ⁻⁴ mol was added per mol.

As a gelatin hardening agent for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

Dye Ex-3 is added to the emulsion layer to prevent irradiation.
a, Ex-3b was added.

The compound Ex-3c was further added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

As shown in Table 3, samples 1 and 2 were applied in combination.
I got 3 and 4.

(Layer structure) The composition of each layer in Samples 1 to 4 is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper (Support sample II) [However, the first layer side polyethylene contains a white pigment (TiO ² ) and a bluish dye (ultraviolet)] First layer (colored layer) Sensitivity sample-1: ( A) Gelatin: 0.50〃 Sample-2, 3: (B) Gelatin: 0.80 Black colloidal silver: 0.20 Ex-3e: 0.002〃 Sample-4: (C) Gelatin: 0.80 Cationic polymer (1) …… 0.50 Dye (2) …… 8.5 (mg / m ² ) 〃 (3) …… 8.5 (mg / m ² ) 〃 (38) …… 5.0 (mg / m ² ) Second layer (blue sensitive layer) Silver halide emulsion 0.30 Gelatin 1.86 Yellow coupler (Ex Y) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Third layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-2) 0.08 Fourth layer (green-sensitive layer) Silver halide emulsion 0.36 Gelatin 1.24 Magenta coupler (Ex M1) 0.31 Color image stabilizer (Cpd-3) 0.25 Color image stabilizer Cpd-4) 0.12 Solvent (Solv-2) 0.42 Fifth layer (UV absorbing layer) Gelatin 1.58 UV absorber (UV-1) 0.62 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-3) 0.24 Sixth layer (Red sensitive layer) Silver halide emulsion 0.23 Gelatin 1.34 Cyan coupler (blend of Ex C1 and EX C2, 1: 1) 0.34 Color image stabilizer (Cpd-6) 0.17 Polymer (Cpd-7) 0.40 Solvent (Solv-4) ) 0.23 7th layer (UV absorbing layer) Gelatin 0.53 UV absorber (UV-1) 0.21 Solvent (Solv-3) 0.08 Eighth layer (protecting layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification 17% ) 0.17 Flowing paraffin 0.03 The following experiments were conducted to investigate the photographic characteristics of these coated samples.

First, a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was used for the coated sample, and gradation exposure for sensitometry was given through blue-green and red filters. . The exposure at this time was performed so that the exposure amount was 250 CMS in the exposure time of 1/10 second.

 Then, the following color development processing was performed.

(Processing step) (Temperature) (Time) Color development 35 ° C 45 seconds Bleach fixing 35 ° C 45 seconds Water wash 28-35 ° C 90 seconds Color development solution Triethanolamine 8.12g N, N-diethylhydroxylamine 4.93g Fluorescent bleach ( Ciba-Geigy UVITEX CK) 2.80 g 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -p-phenylenediamine sulfate 4.96 g sodium sulfite 0.13 g potassium carbonate 18.40 g Potassium hydrogencarbonate 4.85g EDTA 2Na ・ 2H ₂ O 2.20g Sodium chloride 1.36g Water is added 1000ml pH 10.05 Bleach-fix solution Water 400ml Ammonium thiosulfate (70%) 150ml Sodium sulfite 18g Ammonium iron (III) tetraacetate 55g Ethylenediamine tetra Disodium acetate 5 g Water was added to 1000 ml pH (25 ° C) 6.70 For the light-sensitive material samples 1 to 4 thus treated, red light, green light or blue And density measurement using light was determined relative sensitivity and fog of the photosensitive layer. Table 4 shows the results.

As is clear from the results in Table 4, the relative sensitivity of Sample 2 was lower than that of Sample-1 by providing the anti-halation coloring layer on the support. In particular, the B and G sensitivities were significantly reduced. Sample 3
The sensitivity of the emulsion used was increased, and by suppressing fog, it was possible to match the sensitivity to the same level as Sample-1 and suppress fog.

It can be seen that Sample 4 has higher levels of blue, green, and red sensitivities than Sample 1, and the fog is more strongly suppressed.

In addition, a rectangular wave pattern for CTF measurement was brought into close contact with each sample surface for resolution measurement, and exposure was performed using the sensitometer. Subsequently, the color development treatment described above was performed, and the density was measured with a micro densitometer, and the results shown in Table 5 were obtained.

As is clear from the results in Table 5, Samples 3 and 4 are superior to Sample 1 in resolution.

In Samples 3 and 4, the couplers used were EXM2, ExM3, and ExM4 instead of ExM1 used in the fourth layer, and ExC3, ExC4, and ExC5 were used instead of the mixture of ExC1 and ExC2 used in the sixth layer. However, similar performance can be obtained.

Also, in the above emulsion 6, Ex Dye R was replaced by Ex D
Similar performance is obtained with YER-1.

Yellow coupler Magenta coupler Cyan coupler Example 3 A color photographic paper sample 5 was prepared in the same manner as the photosensitive material sample 3 obtained in Example 2 except that the supports I, III and IV were used instead of the support sample II obtained in Example-1. , 6
And 7 were obtained. Sensitometry was performed as was done in Example-2. Further, as in Example 2, the rectangular wave pattern for CTF measurement was contact-exposed to the sample surface to measure the resolution, and the results shown in Table 6 were obtained.

As is clear from the results in Table 6, the color photographic papers (Samples 6 and 7) using Samples III and IV had higher sensitivity and resolution than the support Sample I.

Example 4 Emulsions 8 and 9 were prepared as follows. An emulsion (i) of Example 2 was prepared in the same manner, and the above-mentioned Ex Dye R-1 as a CR compound was added at 1.5 × 10 ⁻⁴ mol / mol Ag at 42 ° C.,
Fine grain silver halide was added and heated in the same manner as in Emulsion 6 of Example 2, and then sodium thiosulfate, chloroauric acid and ammonium rhodanate were added, and further 10 mg / mol Ag of compound g having a thiosulfonyl group or Compound i is 15 mg / mol
After chemical sensitization was optimally performed by adding Ag to obtain a surface latent image type emulsion, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene and further Example 3
The compound Ex-3f described in 1 above was added to obtain Emulsions 7 and 8.

Emulsion 7 or Emulsion-8 was used in place of Emulsion-6 in Sample 4 of Example 2 to obtain Samples 8 and 9, respectively.

In the same manner as in Example 2, samples 8 and 9 were subjected to sensitometry, and the results shown in Table 7 were obtained.

The resolution of each of the light-sensitive material samples 8 and 9 was the same as that of the sample 4. As is clear from the results shown in Table 7, both emulsions 7 and 8 (RL) using the compound having a thiosulfonyl group can remarkably increase the sensitivity and further reduce fog at any time.

Example 5 With respect to the light-sensitive material samples 1 to 4 obtained in Example 2 and the samples 8 and 9 obtained in Example 4, practical tests were conducted as follows.

Each of the above 6 kinds of samples was loaded into a video printer FVP600 manufactured by Fuji Photo Film Co., Ltd. to prepare a color business card consisting of a human image, a CG image and a character image. FVP600 is the first
It incorporates the mechanism shown in the figure. The portrait image is used as digital information, and the CG image and the character image are combined by the image combining unit and displayed on the color monitor and the black and white CRT through the CRT controller. In synchronism with the yellow, green and red images displayed on this black and white CRT, three types of color filters with the spectral transmittance shown in Fig. 2 are applied: B + Y filters, G filters and R filters, and lenses The sample was baked through the system. For the black and white CRT, a phosphor (P-22R and P-45 system) which gives a spectral emission intensity as shown in FIG. 3 was mixed and used. The time to bake with each of the blue, green and red lights depends on the BL, GL and RL of the sample.
It is set in advance in conformity with the spectral sensitivity of. The baking time is shown in Table 8.

The photosensitive material samples 8 and 9 can reduce the baking time to 0.3 to 0.7 times that of the samples 1 to 4.

In particular, the character image quality obtained from Samples 1 to 4 and 8 and 9 was excellent as compared with that of Sample 1 because the edge contrast was high in sharpness.

Samples 3 and 4 were cut into rolls of 102 mm width and loaded into a printer incorporating a CRT exposure system and photographic image exposure as described in JP-A-62-184446. The portrait image was printed by the photographic image exposure method, and the character image was printed by the CRT exposure method.

Subsequently, the color development processing shown in Example 2 was performed through a photographic processor to obtain a photographic print in which characters were written. This was cut into 98 mm x 148 mm, and a postcard print could be obtained. The quality of the character image was equivalent to that obtained by normal lithographic printing.

As described in Japanese Patent Application Laid-Open No. 63-70858, a postcard could be obtained by laminating a postcard with a lottery number.

Example-6 <Method of dispersing solid fine particles of dye><Dispersion method A> Dye crystals having the following composition were kneaded and finely divided by a sand mill.

Dye-45 ... 0.3g-37 ... 0.7g-43 ... 0.8g 5% aqueous solution of the above-mentioned surfactant (5) ... 5ml Further, it was dispersed in 25ml of 10% lime-treated gelatin aqueous solution prepared by dissolving 1g of citric acid. Then, the used sand was removed using a glass filter. Rinse the dye adsorbed on the sand on the glass filter with hot water and add it to 100m of 7% gelatin solution.
l (solid fine particle dispersion of dye) was obtained.

Corona discharge treatment was carried out using Support Sample II to provide a gelatin undercoat layer, and then a colored layer was provided according to the first layer of Example-2. 2,4-dichloro-5-hydroxy-
Sodium 1,3,4-triazine was used.

First layer Observation with a transmission electron microscope revealed that the solid fine particles of the dye had an average particle size of about 0.25 μm, and no aggregates larger than 3 μm were observed.

When this sample was immersed in the color developing solution shown in Example-2, it was decolorized in about 15 seconds. Similarly, a considerable amount of decolorization was observed even when immersed in the bleach-fix solution.

Further, according to Example-2, the second to eighth layers were provided to obtain Sample-10. In Example-2, the same sensitometry and CTF measurement as in Samples 1 to 4 were performed, and the results shown in Table 9 were obtained.

In comparison with the results shown in Tables 4 and 5, it can be seen that higher resolution and lower fog can be obtained by applying the solid fine particle dispersion method.

Example-7 According to the dispersion method A shown in Example-6, the dye crystals shown in Table 10 and the dispersion aid were kneaded and pulverized with a ball mill.
Furthermore, disperse in 25 ml of 10% lime-treated bone gelatin aqueous solution in which 1 g of citric acid was dissolved, remove the beads from the filter, wash away the dye adsorbed on the filter and the beads with hot water, and add 100 ml of 7% gelatin solution ( A solid fine particle dispersion) was obtained.

Support Samples III and IV were used, with a solid fine particle (microcrystalline) dispersion of the dye in the first layer. Furthermore, an example-
Samples 11 to 15 were obtained by applying the second layer and the eighth layer shown in Example-2 in the same manner as in Samples 6 and 7 of 3.

Sensitometry similar to that shown in Example-2 was performed on these samples. Also, CTF measurement was performed in the same manner. The results obtained are shown in Table 10.

As is clear from the comparison between the results in Table 10 and the results in Tables 4 and 5 of Example 2, the sample using the solid fine particle dispersion of the dye has a coloring layer using black colloidal silver. It can be seen that the desensitization is less than that of the samples (Samples 2 and 3) and that a sufficiently high resolution is given. In particular, Sample 15 was found to improve the color separation between the green-sensitive layer and the red-sensitive layer and improve the resistance to safelight light.

The sections of Samples 11 to 15 were taken, and the cross section was observed with a transmission electron microscope (200 KV). The fine crystal dispersion of the dye contained in the colored layer (first layer) or the eighth layer was not diffused to the adjacent other layer, and no aggregate of 3 μm or more was observed.

Example-8 The support III and the first layer (colored layer) used for the sample 11 in the example-7 were used, and the sample 9 was used in the example-4.
Sample 16 was obtained by providing the second to eighth layers used for obtaining.

This sample 16 was subjected to the same sensitometry as that performed using sample 9 in Examples 4 and 5, and a blue light, a green light and a red light were emitted using a video printer FVP-600. The baking time was measured.
The results are shown in Table 11.

From the results shown in Table 11, it can be seen that Sample 16 can be baked as fast as or faster than Sample 9.

Further, the fog of Sample 16 was 0.08 in all of BL, GL, and RL, which was small.

(Effects of the Invention) By using the color light-sensitive material of the present invention, not only a photographic image excellent in image sharpness but also a color print having a high edge contrast of a line drawing or a character image can be obtained quickly and easily. In particular, using a so-called minilab system that has a CRT exposure printer and photo processing device, not only photographic images but also image
You can easily obtain a print that combines CG images, line drawings and character images with excellent sharpness in a short time of about 4 minutes or less. It is especially convenient for creating postcards.

[Brief description of drawings]

FIG. 1 shows a print production process by the CRT exposure method. FIG. 2 shows the spectral transmission curves for B, G, R and Y filters. The vertical axis represents transmittance and the horizontal axis represents wavelength (nm). FIG. 3 shows a relative emission intensity analysis of P-22R and P-45 based phosphor mixture. The vertical axis represents relative light intensity, and the horizontal axis represents wavelength (nm).

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location G03C 7/26 G03C 7/26 (72) Inventor Kazunori Hasebe 210 Nakanuma, Minamiashigara-shi, Kanagawa Fujisha Shin Film Co., Ltd. Internal Examiner Toshiyasu Kimura (56) Reference JP-A-2-28640 (JP, A)

Claims (3)

(57) [Claims] 1. A color light-sensitive material comprising a reflective support and at least one silver halide light-sensitive layer containing a color coupler, wherein the silver halide light-sensitive layer has an average silver chloride content of 50. Mol% or more and having a silver bromide-containing localized phase inside or on the surface of the grain, and the surface of the grain contains a gold sensitized silver chlorobromide emulsion, and is provided between the photosensitive layer and the reflective support. Providing a colored layer that fixedly contains a light absorber capable of being decolorized by color development processing, and the reflective support contains 12% by weight or more of white pigment particles in a water-resistant resin, and the white pigment particles. The coefficient of variation of the projected occupation area ratio (%) per unit area, where the degree of dispersion is specified, is S / (however, it is the average occupation area ratio per unit area, and S is the standard deviation of the occupation area ratio). A reflective color light-sensitive material characterized by the following. 2. The reflection type color photosensitive material according to claim 1, wherein a compound having a thiosulfonyl group is added to the silver chlorobromide emulsion before, during or after the gold sensitization. material. 3. A color image forming method, which comprises subjecting the reflective color light-sensitive material according to claim 1 or 2 to printing by a scanning exposure method and then performing color development processing.