JPH036554A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow a rapid color development processing with high image quality by forming three photosensitive layers which respectively have spectral sensitivity peaks in 3 kinds of different photosensitive wavelength regions and confining the total amt. of the silver halide to be applied to <=0.78g/m<2> in terms of silver. CONSTITUTION:This silver halide color photographic sensitive material is constituted by forming the base of the reflecting base which is incorporated with a synthetic polymer by an impregnation treatment from the surface of raw paper and is further coated with a water resistant resin layer contg. a white pigment, by forming the three photosensitive layers which respectively have the spectral sensitivity peaks at 3 kinds of the different photosensitive wavelength regions; 650 to 690nm, 720 to 790nm and 770 to 850nm, and by confining the total amt. of the silver halide to be applied to <=0.78g/m<2> in terms of silver. The silver halide color photographic sensitive material which is thin but is relatively stiff, is easy to handle and rapidly and easily forms color photographs is obtd. in this way.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a color photographic material that has spectral sensitivity suitable for scanning exposure and rapid developability, and in particular has excellent surface smoothness or optical uniformity. , relates to a color photographic material that has improved transportability and suppresses the occurrence of edge stains.

(Prior Art) Recently, with advances in information processing, storage and image processing technology, and the use of communication circuits, technology for making hard copies from soft information has become widely used. On the other hand, with advances in silver halide photosensitive materials and compact rapid development systems (such as the Mini-Lab System), extremely high-quality printed photographs can be provided relatively easily and at low cost. Therefore, there is a high demand from software information sources to easily and inexpensively make hard copies of these printed photographs with high image quality.

Traditionally, the means of making a hard copy from a soft information source is
There are methods that do not use photosensitive recording materials, such as methods that use electricity or electromagnetic signals, and inkjet methods, and methods that use photosensitive materials (for example, silver halide photosensitive materials and electrophotographic materials). In addition, color copying technologies include copiers and laser printers that use electrophotography, silver halide heat development dye diffusion methods, and Pictrography (manufactured by Fuji Photo Film ■, product name) that uses LEDs. .

The means using photosensitive materials is a means of recording with an optical system that emits light under control according to image information, and is advantageous in obtaining high image quality as it is capable of not only high resolution and binary recording but also multi-gradation recording. It is.

In particular, compared to a method using an electrophotographic material, a method using a silver halide color light-sensitive material is advantageous because image formation is carried out chemically.

JP-A-55-13505 discloses that the color of a color photographic material can be improved by controlling the development of yellow, magenta, and cyan using three types of light beams each having a different wavelength, such as green, red, and infrared light beams. It discloses an image recording method.

JP-A-61-137149 discloses that at least three silver halide emulsion layers using conventional color couplers are provided on a substrate, and at least two layers are exposed to red light rather than exposed to visible light. A color photographic material sensitized to external laser light and its basic conditions are disclosed.

JP-A No. 63-197947 discloses that a photosensitive layer unit containing a color coupler is provided on a support, at least one of which has a maximum spectral sensitivity wavelength of about 670n+*. A full-color recording material that is spectrally sensitized to longer wavelengths and is designed to be exposed to LED or semiconductor laser light, and that produces a color image through optical scanning exposure and subsequent color development processing, especially one that is highly sensitive and stable. Spectral enhancement methods and methods of using dyes are disclosed.

In addition, using a semiconductor laser for scanning exposure is advantageous because the space between exposure bags is compact and inexpensive;
Baek et al., 4th Non-Impact Printing (
NIP) International Conference! l (SPSR) Proceedings 245-24
On page 7, the basic conditions of a semiconductor laser output control mechanism for continuous scanning printers are announced.

(Problem to be Solved by the Invention) As mentioned above, the means of using silver halide color photosensitive materials to make hard copies from soft information sources is superior to the means of using non-photosensitive recording means or electrophotographic materials. It is advantageous in that it is easy to stably obtain high image quality, but color development processing can be performed quickly and easily in accordance with the speed of scanning exposure (
The problem is that

In accordance with the speed of writing in an output device using a semiconductor laser beam, color development processing of a full-color recording material requires speed of 90 seconds or less.

Silver halide emulsions used in silver halide photosensitive materials written by laser beams include silver iodobromide emulsions,
Although silver bromide emulsions and silver chlorobromide emulsions are known, silver halide emulsions with a high silver chloride content are useful in order to achieve the above-mentioned rapidity. However, in the case of silver chlorobromide emulsions or silver chloride emulsions with a high silver chloride content, especially a silver chloride content of 96 mol% or more, the above-mentioned prior art does not contain any specific description, and there is no specific description in these technologies. It has been found that rapid processing as described above cannot be achieved with the color light-sensitive materials described in . Furthermore, it has been found that simply using a silver halide emulsion with a high silver chloride content of 96 mol % or more cannot achieve the above-mentioned rapid color development process.

Therefore, it is desired to develop a silver halide color photographic light-sensitive material that has high image quality and is compatible with the scanning exposure speed and allows rapid and simple continuous color development processing.

Furthermore, in order to achieve the above-mentioned quick and simple color development processing, in order to improve the transportability of the photosensitive material, it is required to be thin and strong enough to easily pass through the processing machine. In particular, when a scanning exposure method using a laser beam as a light source is used, the surface of the photosensitive material is required to have smoothness and uniform light reflection characteristics. It is also necessary to reduce production costs.

Generally, supports for photographic paper are made of base paper coated on both sides with polyethylene, and in order to obtain a support with a smooth surface, for example,
No. 0 specification states that the base paper constituting the support has a void volume of 0.4- or less in diameter, which is 0.04! The average fiber length is 0.4 to 0.9 mm, and the average fiber length is 13.5 mm.
As mentioned above, JP-A-61-275752 describes the use of wood pulp with an average fiber thickness of 4 mm or less, and JP-A-61-275752 describes the use of natural bulbs mixed with 5 to 60% hydrophobic fibers, and JP-A-61-275752. No. 284762 proposes limiting dehydration conditions when obtaining wet paper from pulp slurry using a two-wire paper machine.

It has also been done to increase the density of the base paper used as a support for photographic paper by calendering the base paper between metal rolls and increasing the pressure at this time, that is, the pressure of the machine calender. There is.

On the other hand, for coating polyolefin such as polyethylene, -
Extrusion coating method, that is, coating the surface of base paper by casting polyolefin melted at high temperature, has been adopted as the first method. Countermeasures have been taken such as increasing the thickness of the polyolefin layer and increasing the pressing pressure when coating the polyolefin.

However, with the above-mentioned measures regarding the water-resistant resin layer provided on the surface of the support, its smoothness cannot be said to be sufficient in the above-mentioned rapid processing, especially in the scanning exposure method using a laser beam, and the production cost is low. It is also disadvantageous in this respect. Furthermore, if the above-mentioned measures such as increasing the density of the base paper are applied to a thin support, blanking and smudges are likely to occur, and edge stains are even more likely to occur during the rapid color development process. Defects occur.

The first object of the present invention is to provide a silver halide color photographic photosensitive material that has spectral sensitivity that matches the scanning exposure speed, provides high image quality, and enables quick color development processing, and is strong and easy to handle despite its thinness. To provide the materials. The second object is to provide a color photographic material with less occurrence of edge stains and exposure unevenness in a quick and simple color development process.

(Means for Solving the Problems) The above objects of the present invention are as follows: (1) Silver chloride or salt having an average silver chloride content of 96 mol% or more and substantially free of silver iodide is coated on a support. A silver halide color photographic material comprising at least three silver halide photosensitive layers containing a silver bromide emulsion, each photosensitive layer containing at least one of a cyan coupler, a magenta coupler, or a yellow coupler,
The support is a reflective support in which a synthetic polymer is contained in the surface of base paper by impregnation treatment, and is further coated with a water-resistant resin layer containing a white pigment, and each of the three photosensitive layers has three different types. Sensitive wavelength range 650 to 69
A silver halide color photographic material having spectral sensitivity peaks at 0ns+, 720 to 790nm and 770 to 850n11, and a total halide vA coating amount of 0.78 g/v or less in terms of silver.

(2) The support has 30% of the synthetic polymer in the base paper.
This is a reflective support in which a white pigment of 12% to 641% by weight is substantially uniformly dispersed in the water-resistant resin layer.
) Silver halide color photographic light-sensitive material.

(3) The synthetic polymer contained by the impregnation treatment is at least one compound selected from the group of anionic polyacrylamide, cationic polyacrylamide, amphoteric polyacrylamide, carboxy-modified polyvinyl alcohol, polyvinyl alcohol, and silica-modified polyvinyl alcohol. The silver halide color photographic material according to (1) or (2).

(4) Total silver halide coating amount is 0.64 g in terms of silver
/M or less, the silver halide color photographic material according to any one of (1) to (3).

It was found that this can be achieved by

First characteristic of the silver halide color photographic material of the present invention
The support used in the photosensitive material of the present invention is a reflective support in which a synthetic polymer is impregnated into the base paper from the surface of the base paper, and is further coated with a water-resistant resin layer containing a white pigment. be.

The base paper is obtained by paper-making a paper stock that uses natural pulp selected from softwood, hardwood, etc. as the main raw material and adds chemicals to be described later.

60% by weight of hardwood pulp, which is a short fiber, may be made by using synthetic pulp instead of the above natural pulp, or may be a mixture of natural pulp and synthetic pulp in any ratio.
It is preferable to use the above.

Additive chemicals are usually fillers such as clay, talc, calcium carbonate, urea resin fine particles, etc., sizing agents such as rosin, alkyl ketene dimer, higher fatty acid salts, paraffin wax, alkenyl succinic acid, etc., and paper strength agents such as polyacrylamide. Those to which a fixing agent such as a reinforcing agent, sulfuric acid, etc. are added are used.

In addition, dyes, fluorescent dyes, slime control agents, antifoaming agents, etc. may be added as necessary. Moreover, the following softeners can be added as necessary. Regarding softeners, for example, see the New Paper Processing Handbook (Shigyo Times Co., Ltd. [) 55
Described in pages 4 to 555, published in 1980. In particular, those with a molecular weight of 200 or more are preferable, that is, those with a carbon number of 1
It has zero or more hydrophobic groups, and also has an amine salt or quaternary ammonium salt that self-fixes with cellulose. Specifically, reaction products of maleic anhydride copolymer and polyalkylene polyamine, reaction products of higher fatty acid and polyalkylene polyamine, reaction products of urethane alcohol and alkylating agent, quaternary ammonium salts of higher fatty acids, etc. Among them, a reaction product of a maleic anhydride copolymer and a polyalkylene polyamine, and a reaction product of a urethane alcohol and an alkylating agent are particularly preferred.

In the present invention, among the above additives, paper strength enhancers are particularly important. Synthetic polymers, generally called paper strength agents, are used as additives in base paper to increase stiffness and to suppress peeling failures within the base paper layer during polyolefin coating. However, in the present invention, the internal addition amount of such synthetic polymer is suppressed as much as possible, and instead, after a web is once formed by papermaking, the synthetic polymer is impregnated from the surface of the base paper, thereby achieving rapid processing, which is an object of the present invention, especially in scanning. It has been found that even in rapid processing compatible with the exposure method, it has excellent transportability and smoothness, and can also achieve high image quality (high density, high sensitivity, prevention of processing streaks, etc.).

When the above-mentioned paper strength enhancers are internally added to base paper, it is estimated that their agglomeration effect causes uneven mass distribution within the base paper and ultimately deteriorates the flatness. By impregnating it from the surface instead of suppressing it,
It seems possible to achieve smoothness, stiffness, and suppression of peeling failures at the same time. In particular, in the case of thin photographic paper, if it is attempted to incorporate a paper strength enhancer into the base paper only by internal addition, a large amount of addition is required, so the support of the present invention is particularly effective for thin photographic paper.

The synthetic polymer of the present invention is a polymer that has the property of imparting hydrogen bonds to pulp fibers and coagulating itself, and preferably has an amide group, a carboxyl group, or a hydroxyl group. In particular, it is effective to impregnate the surface of the base paper with a synthetic polymer that is a paper strength enhancer selected from the group of anionic polyacrylamide, cationic polyacrylamide, polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, and silica-modified polyvinyl alcohol. Examples of anionic polyacrylamide include Gi and Fiber Processing Resin and its Test Method, p. 283 (Shokodo 1968).
These include a partially hydrolyzed product of polyacrylamide or a copolymer of acrylamide and acrylic acid, as disclosed in . Note that methacrylic acid or maleic anhydride can be used instead of acrylic acid, and a terpolymer in which a part of acrylamide is replaced with acrylonitrile, acrylic ester, etc. can also be used as the third monomer. Among these anionic polyacrylamides, molecular weight 1
00,000-2,000,000 is preferable, and the molecular weight is 500,000-100,000.
00,000 is more preferable.

The cationic polyacrylamide that can be used in the present invention is generally used as a paper strength agent, and for example, Kobunshi Ronshu Vol. 33, No. 6, pp. 309 to 316 (1
970), Special Publication No. 52-47043, Special Publication No. 53-
Preferred are those disclosed in No. 45411 and JP-A-55-6556, etc., specifically, Mannich-modified polyacrylamide, Hofmann decomposition product of polyacrylamide, reaction product of polyacrylamide and polyethyleneimine, Alternatively, a copolymer of acrylamide and a cationic monomer typified by dimethylaminoethyl methacrylate may be used. Among these cationic polyacrylamides, those with a molecular weight of 100,000 to 2,000,000 are preferred, and those with a molecular weight of 200,000 to 500,000 are more preferred.As polyvinyl alcohol, in addition to normal polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, Silica-modified polyvinyl alcohol is effective, and carboxyl-modified polyvinyl alcohol is particularly desirable.

The carboxyl-modified polyvinyl alcohol that can be used in the present invention preferably has a degree of saponification of 80 to 98%, a carboxyl group unit of 1 to 20 mol%, and a viscosity of about 5 to 100 cps in a 5% aqueous solution. and
The degree of polymerization is preferably about 1000 to 3000,
In particular, those having a degree of polymerization of about 1600 to 1800 are preferred.
Carboxyl-modified polyvinyl alcohol is usually obtained by (1) saponification of a vinyl ester copolymer and (2) modification of polyvinyl alcohol.

There are the following methods for producing carboxyl-modified polyvinyl alcohol that can be used in the present invention, and any of them can be used.

(1) Method by saponification of vinyl ethyl copolymer Vinyl esters such as vinyl acetate, vinyl formate, vinyl propionate, acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, acrylic ester, methacrylic acid It is produced by saponification of ethylenically unsaturated carboxylic acids such as acid esters, crotonic esters, and maleic esters, or copolymers of ethylenically unsaturated carboxylic esters. Copolymer components containing vinyl monomers such as acrylamide, methacrylamide, and methylol acrylamide can also be used.

(2) Modification of polyvinyl alcohol Polyvinyl alcohol is produced by esterification with a dibasic acid such as maleic acid or its anhydride, carboxylation with a halogenoalkyl carboxylic acid such as monochloroacetic acid, or acetalization with glyoxylic acid. Produced by introducing a carboxyl group into alcohol. In addition, ethylene-based products such as acrylic acid in the presence of polyvinyl alcohol,
Although there is a method of obtaining a graft polymer by polymerizing an unsaturated carboxylic acid, in particular, carboxyl-modified polyvinyl obtained by saponifying a copolymer of vinyl acetate and an ethylenically unsaturated carboxylic acid, especially maleic acid or itaconic acid. Alcohol is preferred.

When using these as surface treatment agents, for example, antistatic agents (inorganic salts such as sodium sulfate and calcium chloride, or surfactants), fluorescent dyes, antifoaming agents, etc. may be mixed and used in combination with a carboxyl-modified polyvinyl alcohol aqueous solution. Alternatively, these may be applied or impregnated onto paper separately. The surface treatment method is preferably an on-machine size press or an on-machine tab size method, but it may also be applied off-machine with a bar, gravure air knife, or the like.

The amount of the above-mentioned synthetic polymer as a paper strength enhancer that is impregnated from the paper surface is related to the amount of internal addition.
Preferably 0.5 to 2 weight percent based on pulp, 1.0
-1.5 weight percent is particularly preferred.

Further, the addition of the above-mentioned internal paper strength agent should be as small as possible from the point of view of flatness, but it is preferably 0. 1 to 1.0 weight percent, particularly preferably 0
．． It is desirable to add 2 to 0.5 weight percent.

The base paper subjected to the above-mentioned impregnation treatment is dried to a moisture content of 7 to 9%, and then controlled to a desired thickness using a machine calender and/or a supercalender before use. The basis paper used for the support of the present invention has a basis weight of 300
g/nl or less, but is particularly effective for thin base paper of 50 to 150 g/nf. The density of the base paper is preferably adjusted to 1.0 to 1.2 g/ai using the above-mentioned calendar.

The base paper used in the present invention is particularly preferably neutral paper. Neutral paper is defined by pouring water onto the surface or the center of the broken thickness of the base paper used and measuring its pH using a flat glass electrode GS↑-5313F manufactured by Toa Denpa Kogyo Co., Ltd., and the pH value is 5. Above, preferably 5 to 9.

The water-resistant resin used for the support of the present invention has a water absorption rate (weight%).
) is 0.5, preferably 0.1 or less, such as polyalkylene (polyethylene, polypropylene, and copolymers thereof), vinyl polymers and copolymers thereof (polystyrene, polyacrylate, and copolymers thereof), polyester and copolymers thereof, etc. Can be mentioned. Preferably, the polyalkylene resin used is low density polyethylene, high density polyethylene, polypropylene, or blends thereof. Optical brighteners, antioxidants, antistatic agents, release agents, etc. are added as necessary. In this case, the thickness of the resin layer is preferably about 5 to 50 ts, particularly preferably 10 to 40 ts, and the white pigment is usually kneaded by a melt mixing method or the like, and the pigment is passed through a melt extruder and then melt extruded and laminated onto the substrate. .

For example, JP-A-57-27257 and JP-A-57-499.
As described in No. 46 and No. 61-262738, unsaturated organic compounds having one or more polymerizable carbon-carbon double bonds in one molecule, such as methacrylic acid ester compounds, Zintry or tetra-acrylic acid esters represented by the general formula in No. 61-262738 can be used. In this case, after being applied onto a substrate, it is cured by electron beam irradiation to form a water-resistant resin layer. White pigments and the like are dispersed in this 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 includes, for example, the lamination method described in "New Lamination Processing Handbook" edited by the Processing Technology Study Group, such as dry lamination, solvent-free dry lamination, etc. Coating methods can be selected from gravure roll type, wire bar type, doctor blade type, reverse roll type, dip type, air knife type, calendar type, kiss type, squeeze type, and fantine type coating.

The water-resistant resin contains a white pigment substantially uniformly, preferably in an amount of 12% by weight or more and 60% by weight or less. For example, rutile type, titanium oxide, anatase type titanium oxide, barium sulfate, calcium sulfate, oxidized silicon, zinc oxide,
Titanium phosphate, aluminum oxide, etc. are used, and the surface of the fine particles of titanium oxide pigment is coated with a di- or tetrahydric alcohol, for example, JP-A No. 58-17151, together with or separately from an inorganic oxide such as silica or aluminum oxide. It is preferable to use it after surface treatment with 2,4-dihydroxy-2-methylpentane, trimethylolethane, etc. described in .

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

The support has a total thickness of 30 to 350 g/rd (approximately 3
0 to 400, x), more preferably about 5
0 to 200 g/m2 (approximately 50 to 220 um)
The thickness of the water-resistant resin layer is preferably about 5 to 50 ρ, more preferably about 10 to 40 us.

The photographic paper support of the present invention is coated with a photographic emulsion on its glossy side and dried to become a photographic paper. Various embodiments are possible, such as the possibility of providing layers.

The feature of using such a support in the present invention is that firstly, the surface of the base paper is impregnated with a specific synthetic polymer to fix natural bulb fibers densely from the surface and sparsely from the inside, preferably further smoothing the surface. The base paper is smoothed by a chemical treatment (e.g., mechanical smoothing treatment, e.g., machine calendering) to obtain a base paper with excellent stiffness for one hand (e.g., 200 to 50 degrees), and is further protected by a water-resistant resin layer. It is a support with excellent flatness and rigidity, so it has good transportability.Secondly, it suppresses the occurrence of edge stains that tend to occur in the rapid color development process (especially if the base paper is By using synthetic paper, it is possible to particularly suppress the occurrence of fibrous hairs on the cut surface of the support.

Thirdly, 12% to 60% by weight, preferably 15% to 541% of white pigment particles (preferably a diameter of 0.1 to 0.31) are applied to the smooth surface of the base paper substantially uniformly and Since it is relatively thin (for example, 5 to 20p), it is possible to reduce the fluctuation of the light beam for scanning exposure and improve the sharpness of the image. Here, the fluctuation of the light flux for scanning exposure refers to fluctuations in the intensity of reflected light on the surface of the support and the spread of the reflected light.

The second feature of the color photosensitive material according to the present invention is the halogen composition of the silver halide grains contained in the silver halide window optical layer. The halogen composition of the silver halide grains is such that 96 mol % or more of the total silver halide constituting the silver halide grains is silver chloride. Preferably, it does not substantially contain silver iodide.

Here, "substantially no silver iodide" means that the silver iodide content is 1.0 mol % or less. 0.9 mol% or less for salt-forming anions of sensitizing dyes, adsorption promoters for sensitizing dyes, etc.
In particular, it may be adsorbed to the particle surface. Further, inorganic silver salts other than silver halide, such as silver rhodan, may be contained. A preferred halogen composition is silver chlorobromide or pure silver chloride with a silver chloride content of 96 mol % to 99.9 mol % of the total silver halide constituting the silver halide grains.

In the present invention, it is preferable that the structure of the silver halide grains has the following localized phase. When the silver halide grains of the present invention are silver chlorobromide grains, it is preferable that the grains have localized phases with different silver bromide contents in at least either the interior or the surface of the grains. When the particles are pure silver chloride particles, it is preferable that the particles have localized phases having different contents of metal ions such as Ir ions, )lh ions, Fe ions, etc., than silver ions.

When the silver halide grains of the present invention are silver chlorobromide, it is preferred that the silver bromide content has a localized phase exceeding at least 15 mol %. The arrangement of such localized phases with a higher silver bromide content than the surroundings can be freely arranged depending on the purpose.
It may be located inside the silver halide grain, on the surface or subsurface, or may be divided into the interior and the surface or subsurface.

In addition, the localized phase may have a layered structure surrounding the silver halide grains or a discontinuously isolated structure inside or on the surface, and the silver bromide content may be higher than the surroundings. One preferred example of a localized phase arrangement having a high bromide content is one in which a localized phase with a silver bromide content of at least 15 mol % is epitaxially grown on the surface of a silver halide grain.

It is preferable that the silver bromide content of the localized phase exceeds 15 mol%; however, if the silver bromide content is too high, it may cause desensitization when pressure is applied to the photosensitive material, or the composition of the processing solution may be affected. Fluctuations may impart unfavorable characteristics to the photographic material, such as large changes in sensitivity and gradation.

Taking these points into consideration, the silver bromide content of the localized phase is determined by
In particular, the silver bromide content of the localized phase, which is preferably in the range of 20 to 60 mol%, and most preferably the remaining silver chloride in the range of 30 to 50 mol%, can be determined by X-ray diffraction method (for example, Chemical Gold Wire, New Experimental Chemistry Course 6, Structural Analysis'' Maruzen) or XPS method (for example, ``Surface Analysis, -
4M^, Application of Auger electron and photoelectron spectroscopy,” Kodansha,
), etc. can be used for analysis.

The localized phase consists of all S constituting the silver halide grains of the present invention.
Preferably, the MI consists of 0.1-20% silver, more preferably 0.5-7% silver.

The interface between such a localized phase with a high silver bromide content and other phases may have a clear phase boundary, or may have a region where the halogen composition gradually changes. .

Various methods can be used to form such a localized phase with a high silver bromide content.

For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-sided mixing method or a simultaneous mixing method. Furthermore, it includes a process of converting already formed silver halide to silver halide with a smaller solubility product,
A localized phase can also be formed using the so-called convergecon method. Alternatively, a localized phase can also be formed by recrystallizing the surface of silver chloride particles by adding silver bromide fine particles.

In the case of silver halide grains with a discontinuous, isolated localized phase on the surface, the grain matrix and the localized phase are essentially on the same surface of the grain, so they function simultaneously in the exposure and development processes. In the present invention, high silver chloride with red sensitivity to infrared sensitization is advantageous for high sensitivity, latent image formation, rapid processing, especially gradation balance, and efficient use of silver halide. By providing a localized phase, the problems of emulsions such as high sensitivity, stabilization of sensitivity, and stability of latent images are comprehensively and significantly improved, and the characteristics of high silver chloride emulsions related to rapid processing are secured. can do.

Further, it is possible to adsorb an antifoggant, a sensitizing dye, etc. so as to functionally separate the particle matrix and the local phase, and to chemically sensitize the particles to suppress the occurrence of fog and facilitate rapid development.

The silver halide grains contained in the silver halide emulsion according to the present invention are hexahedrons or tetradecahedrons with (100) faces, and the localized phase is located at or near one corner of the hexahedrons, and on the (111) faces. Discontinuously isolated localized phases on the surface of such silver halide grains, often located at surface sites, impart p/Ig, pH 1 to the emulsion containing the substrate grains.
It can be formed by halogen conversion by supplying bromide ions while controlling temperature and time. It is preferable to supply the halogen ion at a particularly low concentration, and for example, an organic halogen compound or a halogen compound whose capsule membrane is covered with a semi-permeable film can be used. In addition, silver ions and halide ions are supplied to an emulsion containing substrate grains while controlling 9A8, etc., to grow silver halide in localized areas, or depending on the substrate, fine grains of silver halide such as silver iodobromide, silver bromide, etc. A "localized phase" can also be formed by recrystallization by mixing fine particles of silver, silver chlorobromide, or silver iodochlorobromide. In this case, a small amount of silver halide melting may also be used if necessary. Also, European Patent No. 273430, European Patent No. 273429, Patent Application No. 1986-86
No. 163, No. 62-86165, No. 62-86252
The OCR-compounds described in the specification of No. 62-152330 can also be used in combination.

The end point of the formation of the localized phase can be easily determined by observing the morphology of the silver halide during the ripening process while comparing it with the morphology of the silver halide grains of the substrate. The composition of silver halide in such a localized phase can be determined by XPS (X-ray Photoele).
For example, ESCA manufactured by Shimadzu-Dupont is
It can be measured using a 750-type spectrometer. More specifically, it is described in "Surface Analysis" by Someno and Yasumoi, published by Kodansha (1977). Of course, the silver halide composition of the localized phase on the surface of the silver halide according to the present invention, such as the silver bromide content, can be determined by calculation from the manufacturing recipe.
X (Energy Dispersive X-ray
analysis) method, it can be measured with an accuracy of about 5 mol % at an aperture of about 0.1 to 0.2 p diameter using an EDX spectrometer equipped with a transmission electron microscope. More specifically, it is described in "Electron Beam Microanalysis" by Hiroyoshi Soejima, published by Nikkan Kogyo Shimbunsha (1987).

Average grain size of the silver halide emulsion used in the present invention (
The average diameter of the volume equivalent method) is preferably 2p or less and 0.1p or more, particularly preferably 1.4- or less 0.15-
That's all.

The narrower the particle size distribution, the better, and monodisperse emulsions are preferred. In particular, a monodispersed emulsion with a regular shape is preferred. Emulsions in which 85% or more of the total grains are within ±20% of the average grain size in terms of grain number or weight, and especially 90%.
Emulsions containing the above are preferred.

The silver chlorobromide emulsion used in the present invention is P, Glafkides.
Written by 'Chimie et Physique Photo
ographique J (Pau1Monte1, 1967), 'Pho' by G, F, Dufftn.
togr-apic Emulsion Chemi
"Stry" (Focal Press, 1966), by V.L., Zelikman et al. rMa
King and Coating Photograp
hic Emulsion J (Fcal Pres.
It can be prepared using the method described in J.S. Publishing Co., Ltd., 1964). That is, any of the acid method, neutral method, ammonia method, etc. may be used, but the acid method is particularly preferred. In addition, as a method for reacting the soluble root salt and the soluble silver halide salt, any of the one-sided mixing method, the simultaneous mixing method, a combination thereof, etc. may be used. In the present invention, the simultaneous mixing method is preferred in order to obtain monodisperse particles. It is also possible to use a method (so-called back mixing method) in which preferable zero particles are formed under conditions of excess silver ions. One type of simultaneous mixing method is the method of keeping the silver ion concentration constant in the liquid phase in which silver halide is produced, that is, the so-called Chondrold double method.
A jet method can also be used. According to this method,
A monodisperse silver halide emulsion suitable for the present invention with a regular crystal shape and narrow grain size distribution can be obtained. The above-mentioned grains preferably used in the present invention are prepared based on the simultaneous mixing method. This is desirable.

Known silver halide solvents (e.g. ammonia, potassium thiocyanate, or US Pat. No. 3,271,157)
No., JP-A-51-12360, JP-A-53-8240
No. 8, JP-A-53-144319, JP-A-54-10
When physical ripening is performed in the presence of thioethers and thione compounds described in No. 0717 or JP-A-54-155828, a monodisperse silver halide emulsion with a regular crystal shape and a narrow grain size distribution is produced. is obtained, which is preferable.

In order to remove soluble root salts from the emulsion after physical ripening, Nudel water washing, flocculation sedimentation method, ultrafiltration method, etc. can be used.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. That is, sulfur sensitization methods using activated gelatin, sulfur-containing compounds that can react with silver ions (for example, thiosulfates, thiourea compounds, mercapto compounds, rhodanine compounds, etc.), and reducing substances (
For example, reduction enhancement methods using stannous salts, amine salts, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc.), and metal compounds (such as total complex salts, Pt,
fr, Pd, I? Noble metal sensitization using complex salts of metals in group (1) of the periodic table such as h, Fe, etc.) can be used alone or in combination. Also, Tr, Rh,
It is preferable to use a complex salt of a metal in Group 1 of the periodic table, such as Fe, by separating or distributing it into a substrate and a localized phase.

In the monodisperse silver chlorobromide emulsion that can be used in the present invention, sulfur sensitization or selenium sensitization is particularly preferably used, and it is also preferable to have a hydroxyazaindene compound present during this sensitization.

The color photosensitive material of the present invention has less high-intensity reciprocity law failure characteristics, that is, 1o-4 to 1o-8 seconds, especially 104
It is preferable that the sensitivity is high and the obtained latent image is stable in exposure for 1 to 10-8 seconds.For this improvement, silver halide grains according to the present invention contain Ir, Rh, P.
It is preferable to use metal ions of Group 1 of the periodic table, such as a, or complex salts thereof.0 When the silver halide grains according to the present invention have a localized phase, the content of Ir ions or complex salts thereof may be changed, Furthermore, by incorporating other metal ions, such as Rh ions or complex salts thereof, into the matrix or localized phase of silver halide grains, it is possible to achieve both high sensitivity and stabilization of the obtained latent image. ■ Used
The content of group metal ions is 10-1 mole of silver halide.
About 9 mol to 10-1 mol, preferably 10-'' mol to 101 mol. For example, Japanese Patent Application No. 63-78
It can be incorporated into silver halide grains as described in No. 61 specification.

On the other hand, in the color light-sensitive material according to the present invention, the average silver chloride content of silver halide grains must be 96 mol % or more, or the silver chloride grains must be spectrally sensitized to match the wavelength distribution of the scanning exposure light flux. In particular, it is preferable to infrared sensitize silver halide grains having an average silver chloride content of 96 mol % or more to achieve high sensitivity and good storage stability.

In the present invention, the use of spectral sensitizing dyes is important. As the spectral sensitizing dye used in the present invention, cyanine dyes, merocyanine dyes, composite merocyanine dyes, etc. are used.

In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used. As cyanine dyes, simple cyanine dyes, carbocyanine dyes, and dicarboxyanine dyes are used. In particular, for red sensitivity or infrared sensitization, the following general formulas (T), (II) and (I[I
) can be selected and used from among the sensitizing dyes represented by. These sensitizing dyes are characterized by being relatively chemically stable, relatively strongly adsorbed onto the surface of silver halide grains, and resistant to desorption by coexisting dispersions such as couplers.

In the silver halide photosensitive layer of the present invention, preferably at least one photosensitive layer out of at least three types of photosensitive layers, more preferably at least two photosensitive layers have the following general formula (1).
, CI+) and (III) using at least one sensitizing dye selected from the group of compounds represented by 65
0~690rv, 720~790nm and 770~
It is preferable that the spectral sensitization is selectively performed in accordance with the wavelength of the semiconductor laser beam in any wavelength range of 850 nm.

In the present invention, '660~690r+m, 720~
790n11 and 770 to 850 nm" means that the dominant wavelength of one laser beam is in any one of the above wavelength ranges. Compared to the sensitivity of the main photosensitive layer at the main wavelength of the laser beam, which is spectrally sensitized in accordance with the main wavelength of the laser beam, the sensitivity of the other photosensitive layers at the main wavelength is practically at least This refers to spectral sensitization with a low value of 0.5 (in logarithmic terms).For this purpose, it is recommended to set the main sensitivity wavelength of each photosensitive layer to at least 30n*lII, corresponding to the main wavelength of the semiconductor laser beam used. Preferably, the sensitizing dye used is one that provides high sensitivity at the dominant wavelength and provides a sharp spectral sensitivity distribution. Also, the term dominant wavelength is used here because
Laser light is originally coherent light, but in reality there is incoherency, so it is necessary to consider this with a certain degree of latitude.

The sensitizing dyes represented by formula (1), [■] and ([[[]) will be described in detail below.

General formula (1) % formula %) In the formula, Zll and Zlffi each represent an atomic group necessary to form a heterocyclic nucleus.

The heterocyclic nucleus includes a 5- to 6-membered ring nucleus containing a nitrogen atom and optionally a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom as a heteroatom (a fused ring is further bonded to these rings). (or a substituent may be further bonded) is preferred.

Specific examples of the above-mentioned heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, imidazole nucleus, benz Examples include imidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, lysine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tellurazole nucleus, penzotelllazole nucleus, naphthotellazole nucleus, etc. be able to.

R11 and R78 each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group.

These groups and the groups described below are used to include their respective substituents.For example, taking an alkyl group as an example, it includes unsubstituted and substituted alkyl groups, and these groups may be linear or branched. Alternatively, the alkyl group, which may be cyclic, preferably has 1 to 8 carbon atoms.

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

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

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

11111 represents a positive number l, 2 or 3.

RI3 represents a hydrogen atom, and R14 represents a hydrogen atom, a lower alkyl group, or an aralkyl group, and can also be linked to Lx to form a 5- to 6-membered ring.

Also, RI4 represents a hydrogen atom, R13 is another RI
may be linked with 3 to form a hydrocarbon ring or a heterocycle, these rings are preferably 5- to 6-membered rings, j, 1, kll
represents O or 1, X11 represents an acid anion, and n11 represents 0 or 1.

General formula [I[) ○ (Xt□), l□.

In the formula, Z□ and ZXt have the same meanings as Z or II2 described above; e L+ and RlZ have the same meanings as R11 or RlZ; 1hff is an alkyl, alkenyl, alkynyl, or aryl group (for example, a substituted or unsubstituted phenyl group)
represents. 1111 represents 1.2 or 3. Fh
In addition to 4 representing a hydrogen atom, a lower alkyl group, or an aryl group, R14 and another Ih4 may be linked to form a hydrocarbon ring or a heterocycle, and these rings are preferably 5- or 6-membered rings.

Q□ is a sulfur atom, oxygen atom, selenium atom or >N-R
x5, and Ls is synonymous with Ro.

j*+ , kll , Xt+ and l+ are respectively L+
, kll, X11 and n11.

General formula (II) In the formula, Z31 represents an atomic group necessary to form a heterocycle. Examples of this heterocycle include those mentioned regarding Zll and z+i, and other specific examples thereof, such as thiazolidine,
Nuclei such as thiazoline, benzothiazoline, naphthothiazoline, selenazolidine, selenazoline, benzoselenazoline, naphthoselenazoline, benzoxazoline, naphthoxazoline, dihydropyridine, dihydroquinoline, benzimidacilline, and naphthimidacillin may be mentioned.

To+ is mouth 2. a synonymous with a R31 is Ro or L
x and R3! are synonymous with Ro. Warm, 1 is 2
Or represents 3. Rj3 has the same meaning as Ln, and R32
and another R33 may be linked to form a hydrocarbon ring or a heterocycle. j 31 is synonymous with j z.

In general formula (1), 2. and/or 2+2 heterocyclic nucleus, especially naphthothiazole nucleus, naphthoselenazole nucleus, naphthoxazole nucleus, naphthoimidazole nucleus, 4
- Sensitizing dyes with a quinoline nucleus are preferred, general formula (II
The same applies to L+ and/or 2□ in ) and general formula (DI).

Also preferred are sensitizing dyes in which the methine chain forms a hydrocarbon ring or a heterocycle.

Since infrared sensitization uses sensitization using the M band of a sensitizing dye, the spectral sensitivity distribution is generally broader than sensitization using the J band. For this reason, it is preferable to correct the spectral sensitivity distribution by providing a colored layer containing a dye in the colloid layer on the photosensitive surface side of the predetermined photosensitive layer.This colored layer has a filter effect that prevents color mixing. It is valid.

As the sensitizing dye for red sensitivity or infrared sensitization, compounds having a reduction potential of -1.00 (VvsSCE) or less than that are preferred, and in particular compounds with a reduction potential of -1.
A sensitizing dye having this characteristic, preferably a compound having a value of .

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

In addition, reduction potential can be measured by phase-discriminating second-harmonic AC portammetry using platinum as a working electrode.
"Op Imaging Science" (Journal
of Imaging 5science), Volume 30,
27-35 (1986).

Furthermore, compounds selected from the group of compounds represented by shell formulas (TV), (V), (V[) and [■] shown in Japanese Patent Application No. 63-310211, or the general formula [ It is preferable to use it in combination with a compound selected from formaldehyde condensates of compounds represented by (■-a), (■-b) and (■-C).

Further, as specific examples of the sensitizing dyes of general formulas (1), (II) and (DI), (V-1) to (V -45) can be mentioned.

The sensitizing dye used in the present invention is 5 per 111 moles of halogen.
Xl0-'mol-5X10-''mol, preferably I
It is contained in the silver halide photographic emulsion in a proportion of Xl0-' mol - lXl0-3 mol, particularly preferably 2XIO-' mol to 5X10-' mol.

The sensitizing dye used in the present invention can be directly dispersed into the emulsion. In addition, these can be prepared using a suitable solvent, such as evaporated methyl alcohol, ethyl alcohol, methyl cellosolve,
It can also be dissolved in acetone, water, pyridine or a mixed solvent thereof and added to the emulsion in the form of a solution. Ultrasonic waves can also be used for dissolution. Also, as a method of adding this infrared sensitizing dye, US Pat.
A method of dissolving a dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 469.987, etc.
A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion, as described in U.S. Pat. No. 3,822,135, etc. A method of dissolving a dye in a surfactant and adding the solution to an emulsion, as described in JP-A-51-74624, a method of dissolving a dye using a red-shifting compound and adding the solution to an emulsion. Method of
A method such as that described in No. 826, in which a dye is dissolved in a substantially water-free acid and the solution is added to an emulsion, is used. Other additions to emulsions include U.S. Patent No. 2.912,
No. 343, No. 3,342,605, No. 2,996,2
The methods described in No. 87, No. 3,429.835, etc. can also be used. Furthermore, the above infrared sensitizing dyes may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, or may be added before chemical sensitization or may be added prior to the formation of silver halide grains. It is best to add it in the latter half of the season.

In the silver halide color light-sensitive material according to the present invention, in order to be compatible with rapid color development processing, it is preferable to use a coupler having a high molar ratio of color-forming coupler to developed silver halide. The amount of silver used can be reduced. In particular, so-called 2-equivalent couplers are preferably used. Furthermore, it is also possible to use a so-called 1-equivalent coupler, in which the quinone/diimine form of the aromatic amine of the color developing agent and the color coupler undergo a coupling reaction and the subsequent 1-electron oxidation color development process is carried out using an oxidizing agent other than silver halide. good.

Usually, color photosensitive materials use a color coupler so that the maximum color density is 3 or more in transmission density and 2 or more in reflection density. Since color gradation conversion processing is performed in conjunction with color correction processing, the maximum colored reflection density is approximately 1.2,
An excellent color image can be obtained preferably at a ratio of about 1.6 to 2.0. Therefore, the amount of color coupler and photosensitive silver halide used can be reduced.

The amount of each yellow coupler, magenta coupler and cyan coupler used in the color photosensitive material used in the present invention, especially the reflective color photosensitive material, is 2.5 to 1 oxio-
', 1.5-8X10-' and 1.5-7xio-'
Mol/m2.

A coupler suitable for the color photosensitive material according to the present invention will be explained.

The cyan coupler, magenta coupler and yellow coupler preferably used in the present invention have the following general formulas (C-1), (C-I[), (M-■), (M-11)
and (Y).

General formula (Ci) 0 ■ General formula (M-n) General formula (Y) General formula (C-n) H t General formula (M-1) In general formula (C-1) and (C-It), R3,
R1 and R4 represent a substituted or unsubstituted aliphatic, aromatic, or heterocyclic group, R1, R6, and R4 represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group; eYl may represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring
, Y8 represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent, and n represents 0 or 1.

R2 in general formula (C-It) is preferably an aliphatic group, such as methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenyl group. Examples include thiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-1) or (C-11) are as follows.

In the general formula (C-1), preferable Pl is an ori-ru group,
A heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, it is an aryl group substituted with a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

-a When R1 and R2 do not form a ring in formula (C-I), R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R7 is preferably a hydrogen atom.

In the general formula (C-n), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

- In formula (C-II), R3 preferably has 2 to 2 carbon atoms.
It is a methyl group having 15 alkyl groups and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In general formula (Cn), R3 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In the general formula (C-n), R & is preferably a hydrogen atom or a halogen atom, with chlorine and fluorine atoms being particularly preferred. In the general formulas (C-1) and (C-If), preferred Yl and Y2 are hydrogen atoms, respectively. atoms, halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, and sulfonamide groups.

In the general formula (M-■), R1 and R1 represent an aryl group, R6 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y3 represents a hydrogen atom or a leaving group.

Aryl group (preferably phenyl group) of R7 and R1
The substituents allowed for are the same as the substituents allowed for substituent R1, and when there are two or more zero substituents, they may be the same or different. R1 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom.

Preferred Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in U.S. Pat.
Particularly preferred are the sulfur atom separation types as described in No. 51,897 and International Publication No. W088104795.

In general formula (M-11), R1° represents a hydrogen atom or a substituent, Y4 represents a hydrogen atom or a leaving group,
Particularly preferred are halogen atoms and arylthio groups. Za,
Zb and ZC are methine, substituted methine, 1- or -N
It represents H-, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. R1° or Y.

When forming a dimer or more multimer, Za, zb
Alternatively, when Zc is a substituted methine, this includes the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (MU), imidazo (1,2 -b) Pyrazoles are preferred, pyrazolo (1,
5-b)(1,2,4) triazoles are particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, European Patent Publication No. 226, It is preferred to use pyrazolotriazole couplers having an alkoxy or aryloxy group at the 6-position, such as those described in No. 849 and No. 294,785.

In the general formula (Y), R11 represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, Lx represents a hydrogen atom, a halogen atom, or an alkoxy group, A is -NICOR+ 3, -NIISO□-R1
ff, -8O□NHR+s, -COOR+3, -3o
□Represents N-RI31ta, however, R13 and R14 each represent an alkyl group, an aryl group, or an acyl group, Y represents a leaving group, Lx and R13, and the substituents for R)4 are The leaving group Y, which is the same as the permissible substituents, is preferably of the type leaving off at either an oxygen atom or a nitrogen atom, with the leaving type leaving a nitrogen atom being particularly preferred.

Furthermore, general formulas (C-1), (C-11), (M-I)
, (M-1) and (Y), as described in Japanese Patent Application No. 1-84013 No. 63-8.
(C-1) to (C-22), (M-1) described on page 3
) to (M-30) and (Y-1) to (Y-9) can be mentioned.

The couplers represented by the above-mentioned formulas (C-1) to (Y) are:
The silver halide emulsion layer constituting the photosensitive layer usually contains 0.1 to 1.0 mol per mol of silver halide, preferably 0.
．． It is contained in an amount of 1 to 0.5 mol.

In the present invention, in order to add the coupler to the photosensitive layer, various known techniques can be applied.Usually, the coupler can be added by an oil-in-water dispersion method known as an oil protection method. After dissolving, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such couplers, the dielectric constant (25°C
) 2 to 20 and a high boiling point organic solvent and/or a water-insoluble polymer compound having a refractive index (25° C.) of 1.5 to 1.7.

As the high boiling point organic solvent, preferably the following general formula (A) ~
A high boiling point organic solvent represented by (E) is used.

General formula (A) Buttocks W, -0-P TomiO 3 General formula (B) 41-(:0O-W.

General formula (D) 111! vinegar ~ General formula (E) W, -0-w.

(In the formula, -1, h and i each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, and 匈 is -1, OWI
or represents S-1, n is an integer from 1 to 5, and when n is 2 or more, may be the same or different from each other, and in the general formula (E), 1 and - are a fused ring may be formed. ) High boiling point organic solvents that can be used in the present invention are:
Compounds other than general formula (A) or E) that are immiscible with water and have a melting point of 100°C or lower and a boiling point of 140°C or higher,
Any good solvent for the coupler can be used. The melting point of the high boiling point organic solvent is preferably 80°C or lower. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher.

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4.

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a polymer (for example, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 88100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

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

Various line color inhibitors can be used in the light-sensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

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

Hydroquinones are disclosed in U.S. Patent No. 2,360,290;
No. 2,418,613, No. 2,700,453, No. 2.701.197, No. 2,728.659
No. 2,732,300, No. 2,735.76
No. 5, No. 3,982,944, No. 4,430.4
25, British Patent No. 1,363,921, U.S. Patent No. 2,710,801, U.S. Patent No. 2,816,028, etc., 6-hydroxychromans, 5-hydroxycoumarans, spirochromans are U.S. Patent No. 3,432,30
No. 0, No. 3,573,050, No. 3,574,6
No. 27, No. 3,698°909, No. 3,764,
No. 337, JP-A-52-152225, etc., and spiroindanes are described in U.S. Pat. No. 4,360,589, p-
Alkoxyphenols are covered by U.S. Patent No. 2,735.76.
No. 5, British Patent No. 2.066.975, Japanese Unexamined Patent Publication No. 1983-
No. 10539, Japanese Patent Publication No. 57-19765, etc., and hindered phenols are disclosed in U.S. Pat.
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Pat. No. 3,457,079 and U.S. Pat.
332,886, Special Publication No. 56-21144, etc.
Hindered amines are disclosed in US Pat. No. 3,336,135, US Pat. No. 4,268,593, British Patent No.
No. 889, No. 1,354,313, No. 1.410
, No. 846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 58-1
No. 14036, No. 59-53846, No. 59-7
No. 8344, etc.; metal complexes are disclosed in U.S. Pat. No. 4,050,
No. 938, No. 4,241゜155, British Patent No. 2,
No. 027,731(A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with a coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352.
681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705°805)
No. 3,707,395), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxazole compounds (e.g., U.S. Pat. No. 3,406,070; Same No. 3,677.76
No. 2 and No. 4.271,307) can be used. UV-absorbing couplers (e.g. α-
Naphthol-based cyan dye-forming couplers), ultraviolet absorbing polymers, etc. may be used, and these ultraviolet absorbers may be mordanted in a specific layer.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition, it is particularly preferable to use the following compounds together with the couplers described above, particularly in combination with pyrazoloazole couplers.

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

A preferred compound (F) has a second-order reaction rate constant kg (in trioctyl phosphate at 80°C) with p-anisidine of 1. Oj! /mol-sec ~IX
10-J! /mol-sec.

The second-order reaction rate constant can be measured by the method described in JP-A No. 63-158545. If 1 kg is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. Sometimes it happens. On the other hand, k! If it is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent side effects of the remaining aromatic amine developing agent.

A more preferable compound (F) can be represented by the following general formula (Fl) or (FIG).

General formula (Fl) R+-(A), -x General formula (FII) RO C=Y In the formula, R1 and R1 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0.

A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group,
Y represents a group that promotes the addition of an aromatic amine developing agent to the compound of general formula (Fn), where R1 and X, Y and R2 or B are bonded to each other to form a cyclic structure. It's okay.

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

For specific examples of compounds represented by general formulas (Fl) and (Fn), see JP-A-63-158545 and JP-A-6228.
3338, European Patent Publication No. 298321, European Patent Publication No. 2775
Those described in specifications such as No. 89 are preferred.

On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound is the following general formula (CI ).

General formula (Gl) -Z In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and Z is a nucleophilic group or a nucleophilic group that is decomposed in a photosensitive material to release a nucleophilic group. In the compound represented by the general formula (C1), which represents a group, Z is Pearson's nucleophilic CH31 value (R
, G., Pearson+ et al., + J.A.
m.

Chew, Soc, 90.319 (196B)
) is preferably 5 or more, or a group derived therefrom.

For specific examples of compounds represented by the general formula (Gl), see European Patent Publication No. 255722, Japanese Patent Application Laid-Open No. 1430-1980
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-214681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589.

The photosensitive materials produced using the present invention may contain ultraviolet absorbers in the hydrophilic colloid layer.For example, benzotriazole compounds substituted with aryl groups (e.g. ), 4-thiazolidone compounds (e.g. those described in U.S. Pat. Acid ester compounds (e.g., U.S. Pat. No. 3.
No. 705.805, No. 3,707,375), butadiene compounds (e.g., U.S. Pat. No. 4,045)
, 229) or benzoxidol compounds (such as those described in US Pat. No. 3,700.455). An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used.

These ultraviolet absorbers may be mordanted in specific layers.

Colloidal silver and dyes are used in the full-color recording material of the present invention to prevent irradiation and halation, particularly to separate the spectral sensitivity distribution of each photosensitive layer and to ensure safety against safelight in the visible wavelength range. Such dyes include oxonol dyes, hemioxonol dyes,
Included are styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

Indolenine dyes are particularly useful.

Especially for dyes for red end or infrared, for example, JP-A-62-32
No. 50, No. 62-181381, No. 62-12345
4, No. 63-197947, etc., as well as dyes for back layers and JP-A-62-39682, JP-A-62-123192, JP-A-62-158779, JP-A-62-174741, etc. The dye described above or the same dye can be used by introducing a water-soluble group that can flow out during processing.The infrared dye of the present invention is colorless and has no substantial light absorption in the visible wavelength range. It's okay.

When the infrared dye of the present invention is mixed into a silver halide emulsion that has been spectrally sensitized in the end-red to infrared wavelength range, it causes desensitization, fogging, and in some cases, the dye itself is adsorbed to the silver halide grains and becomes weak. There are problems such as broad spectral sensitization. Preferably, it is substantially contained only in colloid layers other than the photosensitive layer. For this purpose, it is preferable to contain the dye in a predetermined colored layer in a diffusion-resistant state.
The first step is to add a ballast group to the dye to make it resistant to diffusion. However, residual color and processing stains may occur.Secondly, the anionic dye of the present invention must be mordanted with a polymer or polymer latex that provides cationic sites. The third method is to use a dye that is insoluble in water with a pH of 7 or less and is decolored and eluted during the treatment process in fine particle dispersion.

For this purpose, it is used by dissolving it in a low boiling point organic solvent or solubilizing it in a surfactant and dispersing it in an aqueous solution of a hydrophilic protective colloid such as gelatin. Preferably, the solid dye is kneaded with an aqueous surfactant solution and mechanically turned into fine particles using a mill, which is then dispersed in an aqueous solution of a hydrophilic colloid such as gelatin.

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

In the present invention, the gelatin may be either lime-treated or acid-treated; details of the gelatin manufacturing method can be found in "The Macromolecular Chemistry of Gelatin" by Arthur Vuis ( Published by Academic Press, 1964).

The color photosensitive material according to the present invention includes known photographic additives,
In particular, materials used in commercially available color papers using high silver chloride (particle average silver chloride content of 96 mol % or more) can be selected and used. You can select and use the additives and materials listed in Research Disclosure below.

Additive type 1 Chemical sensitizer 2 Sensitivity enhancer 4 Strong color enhancer 5 Brightener 7 Coupler 8 Solvent Ultraviolet absorber Stain inhibitor Dye Image stabilizer Hardener Binder Plasticizer, lubricant RD17643 Page 23 Same as above Same as above 24 pages 25 pages 25 pages same as above 25 pages Right column 25 pages Reserved 26 pages 27 pages RD1B716 648 pages Right column Same as above Same as above Same as above Same as above Same as above 650 pages Left to right column Same as above 651 pages Left column Same as above 650 pages Right column In the present invention A color photosensitive material consists of a photosensitive layer (YL) containing a yellow coupler, a photosensitive layer (ML) containing a magenta coupler, a photosensitive layer (CL) containing a cyan coupler, and a protective layer (PL) on a support. , middle layer (IL
), and if necessary, a colored layer, especially an antihalation layer (AH), which can be decolored during development processing, is provided. YL, ML, and CL each have a different dominant wavelength (all have spectral sensitivities suitable for three types of luminous flux. The main sensitivity wavelengths of YL, ML, and CL are each 30 rv or more, preferably 40 rv
and 80 rv apart, and at least 0.5 Log at the main sensitivity wavelength of one photosensitive layer from the other photosensitive layer,
[l (light amount), preferably there is a difference in anger level of 0.8 or more.

At least one of each photosensitive layer has sensitivity in a wavelength region longer than 660r++w, more preferably at least one
Preferably, the layer is sensitive to wavelengths longer than 750 nm.

For example, as shown in the following table, R means red sensitized, and IR-
1 and IR-2 indicate that they are spectrally sensitized to different infrared wavelength regions.

7 Static Inhibitor Page 27 Same as above In the present invention, the photosensitive layer having spectral sensitivity in the wavelength region longer than 6501- is imagewise exposed to a laser beam. Therefore, the spectral sensitivity distribution should be within the main sensitivity wavelength ±25nm, preferably within the main sensitivity wavelength ±15n−wavelength range, while the other 67
The spectral sensitivity of the present invention in wavelengths longer than 0rr++, particularly in the infrared wavelength region, tends to be relatively broad. Therefore, the spectral sensitivity distribution of the photosensitive layer is corrected by using a dye, preferably by fixing and containing the dye in a specific layer. It is better to do so. For this purpose, the dye is contained in the colloid layer in a diffusion-resistant state and is used so that it can be decolored during the development process. The first is to use a solid, particulate dispersion of a dye that is substantially insoluble in water at pH 7 and which decolorizes and elutes during processing.

The second is to use acid dyes with polymers or polymer latexes that provide cation sites. For the first and second methods, Japanese Patent Application Laid-Open No. 63-19794
Dyes represented by the general formulas (Vr) and (■) are useful.

In particular, dyes with carboxyl groups are useful for the first method.

The third feature of the color photosensitive material of the present invention is the coating amount of silver halide and the structure of each photosensitive layer. The total amount of silver halide used in each photosensitive layer of the color photosensitive material in the present invention is 0.78 g/rrf or less, more preferably 0.64 g/rrf or less, and more preferably 0.55 g/rrf or less, in terms of silver. , 42g/m2. The total consumption of conventional color paper is 1.2g10f to 0.78g/r
RF, and the continuous color development processing time (excluding drying) was 130 seconds at the fastest.

The total amount of silver halide used in each photosensitive layer, that is, the yellow coupler-containing photosensitive layer, the magenta coupler-containing photosensitive layer, and the cyan coupler-containing photosensitive layer, varies depending on the coupler used and the structure of the layer, but in terms of silver, the total amount of silver halide used is 0. 27 to 0
．． 18 g/I, 0.25 to 0.20 g/B, 0
．． 20 to 0.14 g/bo. Preferably,
The amount of silver halide used in the photosensitive layer located farthest from the support is smaller than the amount of silver halide used in the photosensitive layer located closest to the support, because the development progresses quickly and uniformly in each photosensitive layer. , is advantageous.

The silver halide grains used in the color light-sensitive material according to the present invention have a development ratio of high<9 when exposed to a sufficient amount of light to obtain the highest color density based on the amount used.
It will be 5 to 10 oz. In ordinary color photosensitive materials for printing, the amount is 80 to 95%, and in color photosensitive materials for photography using silver iodobromide emulsions, it is 20 to 35%. In particular, when using the silver halide grains according to the invention and also using a peterocyclic compound having a water-soluble group such as a carboxylic acid, sulfonic acid or sulfate group or a salt thereof, 4
By high-temperature development at 0°C or higher, sensitivity is increased without deterioration of fog or graininess, and the development ratio is increased to 95 to 100χ.In some cases, physical development effects are used to increase the development ratio to 100% or more.
It can also be set to 105z.

Regarding the color photosensitive material obtained by providing the photosensitive layer as described above, the total amount of silver halide used in the photosensitive layer is 0 as the silver equivalent amount.
．． When the treatment liquid temperature is set to 78 g/m2 or less, preferably 0.64 g/m2 or less, and further 0.55 to 0.42 g/m2, and the temperature of the treatment liquid is set to 40°C to 60°C,
The color development time can be shortened to 30 seconds or less, preferably 20 seconds or less, and even 9 seconds or less. Further, the desilvering time can be shortened to 20 seconds or less, and even to 9 seconds or less. Furthermore, the time for washing or stabilizing bath can be shortened to 60 seconds to 10 seconds. Therefore, the total processing time excluding drying can be shortened to 90 seconds or less, 50 seconds or less, or even 30 seconds or less.

For high-temperature color development processing, it is useful to use a copying machine having a processing section incorporating the above-mentioned slit-shaped processing tank.

The image processing device in the exposure section according to the present invention performs gradation conversion processing (lookup table method) to change the color gradation.
For example, 1 for magenta and cyan color images at each maximum color density.
．． When compressing and reproducing to about 2 to 2.0, the total amount of silver halide used in the color photosensitive material should be reduced to 0.2 to 2.0 in terms of silver.
55 to 0.3 g/rrf. In this case, the desilvering step can be substantially omitted.

The time for image reading, image processing, and exposure according to the present invention can be 30 seconds to 10 seconds for A-4 size, and even less than 10 seconds.

In the present invention, in order to speed up the entire process from color document insertion and exposure to color development processing, after exposure,
substantially following the exposure for as short a time as possible;
It is necessary to transport it to the development processing section. In the present invention, this time is 20 seconds or less, preferably 5 seconds or less.

According to the present invention, when the amount of silver halide used in each photosensitive layer and correspondingly the amount of color coupler used is reduced, the amount of hydrophilic colloid used in each photosensitive layer can also be reduced. In conventional color papers, the ratio of hydrophilic components to non-hydrophilic components in each photosensitive layer was about 2.0 to 1.3. In the present invention, it can be set to 0.8 to 1.1.

This makes it possible to reduce the drying time to 30 seconds or less, even 20 seconds or less, most preferably substantially 10 seconds or less. "Substantially" means that it can be treated as dry for practical purposes. For rapid color development of the color photosensitive material according to the present invention, it is advantageous for the non-photosensitive layer in contact with each photosensitive layer to have a larger amount of hydrophilic colloid component than the photosensitive layer. The ratio of the hydrophilic component in the non-photosensitive layer to the hydrophilic component in the entire photosensitive layer is preferably 0.5 to 1.2, and it is particularly advantageous to have a large amount of the hydrophilic component in the non-photosensitive layer near the support.

By using the copying apparatus according to the present invention and the color photosensitive material having the features of the present invention described above, it is possible to automatically supply the color photosensitive material, expose it, and print the original, regardless of whether it is a negative image or a positive image. Continuous color development processing, discharge and delivery of prints to a take-out tray can be performed substantially continuously and stably. "Substantially continuously" means that the transport speed during scanning exposure of the color photosensitive material of the present invention is 0.8 to 1.25 times the transport speed during color development processing, most preferably. is set so that the conveyance speed during scanning exposure, that is, the so-called sub-scanning speed, and the conveyance speed during color development processing are the same.

If the above value is 0.8 or less, 1.25
If it is more than double, it will cause waiting time in color development process,
This requires a complicated coping mechanism for the copying device, resulting in an increase in size and production cost. It also takes longer to print.

Components that can be added to the developer of the present invention will be explained below.

Here, the color developing solution is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a representative example thereof is 3-methyl-4
-amino-N,N-diethylaniline, 3-methyl-4
-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 3-methyl-4
-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. If necessary, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, and foggants such as sodium boron hydride may also be used. agent, auxiliary developing agent such as l-phenyl-3-pyrazolidone, viscosity imparting agent, various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, etc. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-
Representative examples include N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, ethylenediamine-di(O-hydroxyphenylacetic acid), and salts thereof. .

At high temperatures, mercapto compounds with water-soluble groups (JP-A No. 51-27935), 5
-Mercapto-1,3,4-thiadiazole
1-102639), mercaptohydrotriazine (
It has been disclosed that 3-mercaptobenzoic acid (Japanese Unexamined Patent Publication No. 55-79436) and 3-mercaptobenzoic acid (German Publication No. 3226231) are particularly effective; Generally, it can be used effectively even in the case of temperature development.

In addition, in order to adjust the balance between the development speed between the surface layer and the deep layer during high-temperature development, compounds with relatively high activity and strong selective action on the surface layer are added to the light-sensitive material, pre-bath solution, initial developer solution, etc. Alternatively, it may be appropriate to include it in the developer.

For this purpose, British patent no.
Mercapto-5-amide triazole derivatives, Special Publication 1977
Suitable examples include mercaptotriazoles disclosed in No. 6-19039, benzothiazoliums disclosed in U.S. Pat. No. 3,342,596, mercaptotetrazaindenes disclosed in U.S. Pat. be.

The pH of these color developing solutions is 9 to 12, but
It is preferable to change the pl+ between the initial developer and the latter developer.

In the present invention, if sulfite is used as a preservative, it has the disadvantage of reducing the density of color during development, so it is preferable not to use sulfite. The main agent is reduced and at the same time a tar component is generated, which causes stains to adhere to the photosensitive material being processed and an increase in staining.

Therefore, the amount of sulfite should be reduced as much as possible, for example, 0.0% in the developer.
04 mol/l or less, preferably 0.002 mol/l or less, more preferably 0.001 mol/l or less, hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, Phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused cyclic amines It is best to use a preservative such as These are JP-A Nos. 63-4235, 63-30845, 63-21647, 63-44655, 63-
535s1, 63-43140, 63-566
No. 54, No. 63-58346, No. 63-43138, No. 63-146041, No. 63-44657, No. 63-44656, U.S. Patent No. 3,615,503, No. 2,494,903 , Japanese Patent Publication No. 52-14302
No. 0, Japanese Patent Publication No. 48-30496, etc.

Regarding the preferred organic preservative, its general formula and specific compounds are listed below, but the invention is not limited thereto.

In addition, the amount of the following compounds added to the color developing solution is 0.00
5 mol/Il to 0.5 mol/l, preferably 0.03
Mol/! It is desirable to add it to a concentration of ~0.1 mol/l.

As the hydroxylamine derivative, the following are preferred.

General formula (P-1) where R61 and Rbz represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group; and R1 cannot be hydrogen atoms at the same time, and may be linked to each other to form a heterocycle together with a nitrogen atom. The ring structure of the heterocycle is a 5- to 6-membered ring composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.

It is preferable that R61 and Rhz are an alkyl group or an alkenyl group, and the number of carbon atoms is preferably 1 to 10, particularly 1 to 10.
5 is preferred. The nitrogen-containing heterocycle formed by linking R1 and R1 includes a piperidyl group, a pyrolisilyl group, and an N-
Examples include an alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benztriazole group.

Preferred substituents for R1 and R6m are a hydroxyl group, an alkoxy group, an alkyl or arylsulfonyl group, an amide group, a carboxyl group, a cyano group, a sulfo group, a nitro group and an amino group.

-8 stomach.

General formula (P-n) In the formula, Ay+ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted A substituent representing an unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an acyl group, a carboxy group, a hydroxyamino group, or a hydroxyaminocarbonyl group. Examples include halogen atoms, aryl groups, alkyl groups, and alkoxy groups.

Preferably A? l is a substituted or unsubstituted alkyl group, aryl group, amino group, alkoxy group, or aryloxy group. Particularly preferred examples include substituted or unsubstituted amino groups, alkoxy groups, and aryloxy groups.

The number of carbon atoms is preferably 1 to 10.

OS -5O-, preferably X? I is -C- and 1 Ru.

Rtl is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted aryl group.

In this case, A1.1 and R5 may be connected to form a ring structure, and the substituent is A1. This is the same as the substituent listed above. Preferably Rt is a hydrogen atom.

Y'11 represents a hydrogen atom or a group that can become a hydrogen atom through a hydrolysis reaction.

As the hydrazines and hydrazides, the following are preferred.

General formula (P-111) In the formula, R81% R1! , Res represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, R14 represents a hydroxyl group, a hydroxyamino group,
The heterocyclic group representing a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group or amino group is a 5- to 6-membered ring, C,H.

X6. represents a divalent group selected from -co-H 1 -SO, - or -C-, and n
ll is 0 or 1. In particular, when n□-0, R14 represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and Rss and RI4 may jointly form a heterocyclic group.

In the general formula (P-1[[), R1, R1! , Rm2 are preferably a hydrogen atom or a C3-C1. alkyl group, and most preferably R□ and R112 are hydrogen atoms.

In the general formula (PI[[), Re4 is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amino group. Particularly preferred are alkyl groups and substituted alkyl groups. Preferred substituents of the alkyl group here include carboxyl group, sulfo group, nitro group, amino group, phosphono group, etc. *XIl is preferably -C〇- or -5O2-, most preferably CO-. preferable.

Specific examples of the compounds represented by the above general formulas (P-1) to (P-111) include Japanese Patent Application No. 184023, respectively.
No. 1-1 to I-7 described on page 114 of the specification, No. 117 of the same
Compounds ni to If-6 described on pages 119 to 122 and I[[-1 to ■-22 described on pages 119 to 122 of the same may be mentioned.

The processing temperature of the color developer according to the invention is 30°C to 60'C, preferably 40°C to 50'C.
It is preferable that the amount of replenishment of the color developer is small. Generally, the amount of replenishment is 1 to 31 per 1M of color photosensitive material, but when the color photosensitive material according to the present invention is used, 1r
20 to 60M per rr, preferably 50 to 30
It can be set to 0d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

For the specific implementation of the above development processing, a special formulation for high temperature development may be designed, or existing processing may be modified for high temperature development such as time, temperature, use of antifoggants and development inhibitors, and development agents. It is recommended to perform 11w1 of each component concentration including .

In order to reduce the amount of replenishment, perform high-temperature development, prevent evaporation of the developer, and adjust the concentration and pH of each component in the development process, it is preferable to use a slit-shaped processing tank or a stream development process as described above.

After color development, it is usually bleached. The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. It is also possible to carry out processing in a continuous bleach-fixing bath or to carry out a fixing treatment after a bleach-fixing treatment depending on the purpose.

Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (■), cobalt (■), chromium (■), and copper (■), peracids, quinones, and nitro compounds.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I) or cobalt (ill), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, tyliminodiacetic acid, 1 .Aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates-permanganates; nitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron (III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (I [[) complex salts] are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, the aminopolycarboxylic acid iron(I[[) complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (I[[) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. You can also do it.

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

Useful bleach accelerators include, specifically, U.S. Pat.
No. 893,858, West German Patent No. 1,290.812,
JP-A No. 53-95630, Research Disclosure + -No.

17, No. 129 (July 1978), etc.; thiazolidine derivatives described in JP-A No. 140129/1983; thiourea described in U.S. Patent No. 3,706.561. Derivatives: 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 No. 45-8836; bromide ions, etc. It will be done. Among them, compounds having a mercapto group or a disulfide group are preferred because they have a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,85.
No. 8, West German Patent No. 1,290,812, Japanese Unexamined Patent Publication No. 1983-
The compounds described in No. 95630 are preferred. Further preferred are the compounds described in US Pat. No. 4,552,834.

These bleach accelerators may be added to the photosensitive material.

These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, and ammonium 100sulfate is the most common. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the above desilvering treatment, it is common to undergo a water washing and/or stabilization process. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range.

Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the 5ociet.
y of Motion Picture and Te
1evision Engineers Volume 64,
p, 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method of reducing calcium ions and magnesium ions described in Japanese Patent Application No. 62-288838 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate,
Others, such as benzotriazole, "Chemistry of antibacterial and antifungal agents" by Hiroshi Horiguchi, Hygiene Technology Kinsen "Sterilization of microorganisms, sterilization, and antifungal technology", Japan Antibacterial and Antifungal Science Kinsen "Encyclopedia of antibacterial and antifungal agents" It is also possible to use the fungicides described in .

The pH of the washing water used is 4 to 9, preferably 5.
~8. Washing water temperature and washing time also depend on the characteristics of the photosensitive material.
Although various settings can be made depending on the purpose, generally the temperature is 15 to 45°C for 20 seconds to 10 minutes, preferably 25 to 40°C for 30 seconds to 5 minutes.
A range of minutes is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-8
No. 543, No. 58-14834, No. 60-22034
The known method described in No. 5 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

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

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

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342.59
Indoaniline compound described in No. 7, No. 3,342,5
No. 99, Schiff base type compounds described in Research Disclosure No. 14,850 and Research Disclosure No. 15.159, Research Disclosure No. 1
No. 3,924, the aldol compounds described in U.S. Pat.
Metal salt complex described in No. 719.492, JP-A-53-13
The urethane compounds described in No. 5.628 will be mentioned.

The silver halide color light-sensitive material that can be used in the present invention may contain various 1-phenyl-3-pyrazolidones, if necessary, for the purpose of promoting color development. No. 56-64, 339, No. 57-14,
No. 4547 and No. 5B-115,438.

In addition, West German Patent No. 2,226゜7 was published to save silver on photosensitive materials.
70 or US Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Example-1 (Preparation of support) Support I LBSP (hardwood bleached sulfite bulb) 30 parts, LBKP
A wood valve consisting of 70 parts of C hardwood bleached sulfate pulp was refined to 300 cc of Canadian freeness using a disc refiner, and 1 part of sodium stearate was added.
．． 0 parts, anionic polyacrylamide (molecular weight 800,000)
0.5 parts of aluminum sulfate, 1.5 parts of aluminum sulfate, and 0.5 parts of alkyl ketene dimer were added in the absolute dry weight ratio to the wood pulp, and paper was made using a Fourdrinier paper machine. After completion of the primary drying, an impregnation treatment was carried out using a size bath to impregnate anionic polyacrylamide (molecular weight: 400,000) at an absolute dry weight ratio of 1.7% with respect to the wood pulp. Thereafter, it was re-dried and further subjected to machine calendering.

The weight was adjusted to 100 g/m2, the thickness was 95 μm, and the moisture content was adjusted to 8.0%.

pl+ was 4.3.

Titanium oxide particles (particle size 0.1 to 0.31 #) were added to 2.
A surface-treated white pigment was obtained by immersing it in an ethanol solution of 4-dihydroxy-2-methylpentane and heating it to evaporate the ethanol.

After adding 12 parts by weight of the titanium oxide white pigment to 88 parts of a polyethylene composition (density 0.920 g/cc, melt index (Ml) 5.0 g/10 minutes) and kneading, 28- A water-resistant resin layer was obtained. On the other hand, another polyethylene composition (density 0.950 g/cc, Ml B, Og/
10 minutes) to obtain a 20 m water-resistant resin layer. This was used as a support (■).

Support ■ Anionic polyacrylamide impregnated with support ■ is treated with carboxyl-modified polyvinyl alcohol (polymerization degree 1600).
) was obtained in the same manner as support (■) except that the support (2) was changed to (2). The amount of carboxy-modified polyvinyl alcohol added was 1.6% by weight based on the wood pulp.

Support ■ Support ■ The addition amount of polyacrylamide internally added to the wood pulp was 0.8% by weight, and the amount of carboxyl-modified polyvinyl alcohol added by impregnation treatment was 1.3% by weight based on the wood pulp. is the support ■
A support (2) was obtained in the same manner as described above.

Support ■ A polyethylene composition prepared by kneading 15 parts by weight of a titanium oxide white pigment surface-treated with zinc stearate was coated on the base paper of Support I, and Support ■ was obtained in the same manner as above. .

Support ■ 50 parts by weight of hexaacrylate ester of an adduct equivalent to 12 moles of dipentaerythritol propylene oxide, 50 parts by weight of rutile-type titanium oxide, and 50 parts by weight of rutile-type titanium oxide were placed on the base paper of support ■. After mixing and dispersing the composition in a ball mill for more than 20 hours, the dry film thickness was 20 nm.
It was applied and dried so that it looked like this. On the back side is a polyethylene composition (density 0.960g/cc, M 125g/
20 layers were applied (10 minutes).

The coated layer was irradiated with an electron beam under a nitrogen atmosphere at an acceleration voltage of 200 kV and an absorbed dose equivalent to 5 megarads to obtain a support sample V.

Support ■ (Support using neutral paper) Wood pulp consisting of 20 parts of LBSP and 80 parts of LBKP was beaten to a Canadian freeness of 300 cc using a disc refiner, and 0.5 x of pulp was added as a fixing agent.
Polyamide polyamine epichlorohydrin (manufactured by Dick Vercules Co., Ltd., trade name Kamain 557) (weight percentage based on bone-dry bulb, hereinafter the same) was then added to cationic polyacrylamide (manufactured by Arayo Kagaku Co., Ltd., trade name Polystron 705) and Each of onic polyacrylamide (manufactured by Hamano Kogyo Co., Ltd., trade name Boriaclone 5T-13) was added at 0.5x. Furthermore, 0.5% of alkyl ketene dimer (manufactured by Dick Bercules, trade name: ACO-BEL) was added, and carboxy-modified polyvinyl alcohol was impregnated to contain 1.0% by weight of the wood pulp. , Weighing 100g/rrf by Fourdrinier paper machine
paper was made. The density is 1 by machine calender.
．． It was set to 0 g/d. The pH value was 5.5.

A support (2) was obtained in the same manner as the support (2) in other respects.

Support ■ (Support using acidity) Wood pulp consisting of 20 parts of LBSP and 80 parts of LBKP was refined to a Canadian freeness of 300 cc using a disc refiner, and 1.0 part of sodium stearate, 1.0 part of anionic polyacrylamide, 1.5 parts of aluminum sulfate and 0.5 parts of polyamide polyamine epichlorohydrin were added in an absolute dry weight ratio to the wood pulp, and the wood pulp was impregnated with 1.0% by weight of carboxy-modified polyvinyl alcohol by impregnation treatment (
(Same as for support ①) Weighed 100g using a Fourdrinier paper machine.
/m of paper was made.

The density was set to 1.0 g/rrf using a machine calender.

The pH value was 4.3.

A support (2) was obtained in the same manner as the support (2) in other respects.

Support ■ Support ■ The addition amount of polyacrylamide internally added to the wood pulp was 1.5 percent by weight, and the amount of carboxyl-modified polyvinyl alcohol added by impregnation treatment was 0.6 percent by weight, based on the wood pulp. , support I
A support (2) was obtained in the same manner as described above.

Support ■ Support I The addition amount of internally added polyacrylamide was 2.0% by weight based on the wood pulp, and the amount of carboxyl-modified polyvinyl alcohol added by impregnation treatment was 0.3% by weight based on the wood pulp. Support (2) was obtained in the same manner as support (2).

Comparative Support A Support A was obtained in the same manner as Support I, except that the amount of carboxy-modified polyvinyl alcohol added during the impregnation treatment of Support I was reduced to zero. However, during the process of forming the water-resistant resin layer, peeling failures occurred frequently within the base paper layer.

Comparative Support B Support B was prepared in the same manner as Support ■, except that the amount of carboxyl-modified polyvinyl alcohol added during the impregnation treatment was O.

The dispersibility of the white pigment particles on the surface of the water-resistant resin layer of each of the above supports was determined by etching the resin for about 0.051 seconds from the surface using an ion sputtering method and observing the white pigment particles using an electron microscope. , W x 6
Projected area ratio R of each particle for 6 unit areas of ta
i was determined, and its standard deviation and average particle occupied area ratio (%) R were determined.

Visual evaluation of flatness, stiffness, and total reflectance at 550 nm were measured for Supports 1 to 1 according to the present invention and Supports A and B obtained from the above birch trees. The results are shown in Table 1, and the total reflectances were all in the range of 0.79 to 0.92.

Further, the stiffness was measured by converting the stiffness of the base paper in the paper making direction into the load amount g per width 11 according to the test method specified in JIS-P-8125.

Evaluation of flatness: The surface of the support was subjected to corona discharge treatment, then undercoated, and a normal gelatin silver halide emulsion was applied (
0.3g/m2 in terms of silver, approximately 1.3. x), then exposed to -like light and developed to blacken the surface. The surface was observed with the naked eye.

(Manufacture of photosensitive material) Silver halide color photographic light-sensitive materials as shown in Table 2 were prepared using the above Support I. This sample was designated as I-1.

The silver halide emulsions shown below were used in each layer.

Emulsion for cyan coupler-containing layer: lime-treated gelatin 30. g was added to 1000 d of distilled water, dissolved at 40°C, and the pH was adjusted to 3.8 with sulfuric acid.
Add 5.58 g of sodium chloride and 0.02 g of N,M'-dimethylimidazolidine 2-thione and bring the temperature to 52.5 g.
°C. 62.5g of silver nitrate in 750I of distilled water
The solution dissolved in R1 and a solution prepared by dissolving 21.5 g of sodium chloride in 500 d of distilled water were added to and mixed with the above solution for 40 minutes while maintaining the temperature at 52.5"C. Furthermore, 62.5 g of silver nitrate was added and mixed.
5 g dissolved in 500 d of distilled water and 2 ml of sodium chloride
1.5 g dissolved in 300 m of distilled water and 52.5
The mixture was added and mixed for 20 minutes at °C.

During this addition and mixing, l
Xl0-@mol 1 mol Ag of iridium dipotassium hexachloride was added.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 46 CI and a coefficient of variation of grain size distribution of 0.09.

After demineralizing and washing this emulsion with water, a monodisperse silver bromide emulsion containing 0.2 g of nucleic acid and an average grain size of 0.05 μm (containing 1.2 Xl0−' mol of iridium dipotassium hexachloride 1 mol Ag) was prepared.
to which 1.0 mol % of silver halide was added, chemically sensitized with about 2 x 10-' mol of triethylthiourea, 1 mol of Ag, Compound (1-1) is 7×10−′ mol 1 mol Ag, compound (F-1) is 5×10 4 mol 1 mol Ag
An emulsion was prepared.

Emulsion for magenta coupler-containing layer: Add 30 g of lime-treated gelatin to 10,001 dl of distilled water and dissolve at 40°C, then add 5.5 g of sodium chloride and N,
N'-dimethylimidazolidine-2-thione 0.02
The temperature was raised to 50"C by adding 1.6 g of nitric acid.
A solution in which 2.5 g of sodium chloride was dissolved in 750 ml of distilled water and a solution in which 21.5 g of sodium chloride was dissolved in 500 ml of distilled water were added to and mixed with the above solution over 40 minutes while maintaining the temperature at 50'C. Furthermore, 62.5 g of silver nitrate was dissolved in 500 m of distilled water, and 21.5 g of sodium chloride was dissolved in 300 m of distilled water.
and the solution dissolved in m were added and mixed under the condition of 50'C over 20 minutes.

During this addition and mixing, l
Xl0-'' mol A of iridium dipotassium hexachloride was added.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 44μ and a coefficient of variation of grain size distribution of 0.08.

After demineralizing and washing this emulsion with water, a monodisperse silver bromide emulsion (containing 2×10 −' mol of iridium dipotassium hexachloride 1 mol Ag) containing 0.2 g of nucleic acid and an average grain size of 0.05 μm was added with 0.5 g of silver halide. mol% of triethylthiourea was added, chemically sensitized with triethylthiourea about 2.5 Xl0-' mol 1 mol Ag, and further compound (V-5) was added at 1.1 x 10-' mol 1 mol 8 g1 compound (1 An emulsion was prepared by adding 8 g of compound (F-1) (1.1 x 10 -3 mol 1 mol) and 5 x 10 4 mol (1 mol A) of compound (F-1).

Emulsion for yellow coupler-containing layer: Compound (V-40) and compound (V-41) were added in place of compound (V-5) to an emulsion prepared in the same manner as the emulsion for magenta coupler-containing layer described above. 1.
2 Xl0-' mol 1 mol A, and 0.2 x 10-4
An emulsion was prepared with the only difference being that 1 mol of Ag was added and compound (F-1) was not added.

Solid fine particle dispersion of dye in antihalation layer: Dye crystals having the composition shown below were kneaded and ground into fine particles (average diameter of which was 0.151# or less) using a sand mill. Further, 0.1 g of citric acid was dispersed in 25 d of a 10% lime-treated gelatin aqueous solution, and the sand used was removed using a glass filter. The dye adsorbed on the sand on the glass filter was also washed away using hot water to obtain 100 ml of a 7% gelatin aqueous solution. The thus obtained solid fine particle dispersion of dye is used to prevent haleysilane.

Dispersion A Dye (D-7) ・−・−・−・0.
8g' (D-8) 1.5g Surfactant (W) 5% aqueous solution 5d Dye (D-7) Surfactant (W) These samples contain additives that improve safety against safelights and improve image quality. To improve sharpness, the compound (
D-1), (D-2), (D-3), (D-4), (D
-5) and (D-6) at 0.016g/n(,
0,006g/rrr, 0.008g/rrr,
0.013g/i, 0.018g/m2, 0.022g
/rrf.

Further, the following three types of compounds were used as hardening agents for gelatin at a molar ratio of 3:2:1.

QC) ItSOtCH-(Jlz Summer CH*SO*CH-CHg ■υutat, shi-N l;Hxl;HtNH5(h
to lh (D-1) (D 2) (D-3) (D-4) (D-5) (D-6) (CHz) asOxK ((:Hz)4sOs ([-1) (F-1 ) (S-1) (H-1) (H-2) (H-3) (S-3) (CHi)i Js COOCHgCHCJw (CHz)t CHCHCI)11? \/ (H-4) 1 (X-4) (C-4) 0■ (Y-3) (Y 9) (Y 10) (C-5) (M 5) (M-10) (V- 5) (V-15) (■ 19) (V-20) In contrast to this sample 1-1, samples 1-2 and I- were obtained by changing the coating amount of silver halide and the halogen composition of the emulsion as shown in Table 3.
3 was produced in the same manner.

Table 3 (V-40) (V-41) The upper row of the wooden table shows the halogen composition of each emulsion (mol% silver bromide content).
), and the lower row represents the amount of coated silver halide (silver equivalent g/m
).

Each of these samples had an emission wavelength of 670 nm and 750 nm.
, using an 810 nm laser diode, 400 dp+ through an optical wedge, average exposure time per pixel 2 x 1
After applying scanning exposure for 0-' seconds, the following color development treatment 1 was performed 3 seconds later.

1-degree color development 50°C Bleach-fixing 50°C Rinse 1 40°C Rinse 2 40"C Rinse 3 40°C Drying 90°C 1 ml normal liquid ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid N,N-di(carboxymethyl) hydrazine N,N-diethylhydroxylamine oxalate triethanolamine sodium sulfite potassium chloride potassium bromide potassium carbonate N-ethyl-N= (β- Methanesulfur period 9 seconds 9 seconds 4 seconds 4 seconds 4 seconds 14 seconds 3.0 g 4.5 g 2.0 g 8.5 g 0.14 g 1.6 g 0.01 g 25.0 g Honamidoethyl)-3-methyl -4-aminoaniline, sulfate 5.OgWHIT
EX-4 (manufactured by Sumitomo Chemical) Add 1.4 g water to 1000dpH10,
Ammonium thiosulfate (55imtχ) 100 Id Sodium sulfite 17.0 g Iron(III) ammonium ethylenediaminetetraacetate 55.0 g Disodium ethylenediaminetetraacetate 5.0 g Ammonium bromide 40.0 g Glacial acetic acid
Add 9.0g water
1000 dpH adjusted to 5.80 Yukuoka ion-exchanged water (calcium ion 3 ppm or less, magnesium ion 29 p# or less) Also, for each sample exposed to light in the same manner as above, the above treatment step 1 was carried out as follows. A modified treatment step 2 was applied.

Processing step 1, daytime, single-dish color development
Bleach and fix at 35°C for 45 seconds Rinse at 35°C for 45 seconds 1 Rinse at 25°C for 30 seconds 2 Rinse at 25°C for 30 seconds 3 Dry at 80°C for 90 seconds Cyan, magenta, and yellow densities of samples after these treatments was measured using a TCD densitometer manufactured by Fuji Photo Film Co., Ltd., and the obtained sensitivity and maximum density (Dmax) were measured using the fourth
Shown in the table. Sensitivity is expressed relative to the sensitivity of each coloring layer of sample 1 when processed in processing step 2 as 100, and the maximum density is expressed as the coloring density at an exposure amount that is 10 times the exposure amount that gives a density of 1.0. did.

Table 4: When sample 1-1 of the present invention was passed through processing step 1, which is a high-temperature rapid treatment, higher sensitivity was obtained than when it was passed through processing step 2, which is used for normal color paper processing. . Comparative samples 1-2 and I3 also showed higher sensitivity when passed through processing step 1 than when passed through processing step 2, but for these samples, sample I of the present invention was passed through processing step 2. When the highest density, which showed almost no difference from -1, was passed through processing step 1, there was clearly a decrease in magenta and yellow, and Sample 1 of the present invention showed almost no such decrease. It is inferior to -1.

Processing step 1 took 44 seconds including drying time, forming an image very quickly, but processing step 2 took 4 minutes and 3 minutes.
The photosensitive material of the present invention is excellent in rapid processing. It was also excellent in terms of edge staining and transportability.

Example 2 In Example 1, supports ■ to ■ and A and B were used instead of support ■ in photosensitive materials 1-1 and I-3, and the other conditions were the same, and photosensitive materials n-1, ■3, and I [[-1, I[
[-3, ■-1, IV-3, ■-1, VT-3, ■-1
, ■-3, ■-1, ■-3, ■1, [X-3, A-1,
A-3, B-1 and B3 were obtained.

Each sample was cut to a width of 12 cm and made into a roll. After rubbing the cut sections under the same conditions, printing was carried out by image exposure, color development processing 1 (however, the rinsing bath was 2 baths for 9 seconds each), and color development. 2.

For color development 1, a prototype automatic developing machine having a mechanism as shown in FIG. 1 and having a developing tank (1), a bleach-fixing tank, and a two-chamber rinsing tank was used. However, the rinsing bath was for 9 seconds.

Each color-developed sample was wound up into a roll without cutting into prints, and the rolled print sample was aged at 40°C for 5 days. were visually compared and observed. The results are shown in Table 5. The evaluation criteria are: ◎−・−・No stains are observed ○−・・・・−No stains Δ・・・−・・Stains are observed but acceptable ×・・−
・・・・Lots of dirt××・・・・−The dirt extends deeper than 0.2m1m from the cut surface.

The prototype treatment tank used in the present invention is disclosed in Japanese Patent Application No. 63450883.
The carried-in photosensitive material prepared by the method described in the specification is conveyed and processed by a guide (5) and a conveyance roller (4). A shortage of the processing liquid due to removal of the processing liquid is detected by the pressure detector OI and replenished by the reservoir (9). The processing liquid whose temperature is controlled by the sub-tank flows into the sub-tank chamber (7), is sent to the sub-tank chamber (8), and is stirred.

A similar bleach-fix tank was used, and two washing tanks were connected.

Regarding the fifth surface edge stain, the photosensitive material according to the present invention has less stain compared to comparative samples A-1 and A-3, especially photosensitive material sample 1.
-1, ll-1, ll-1, IV-1, V-1, Vl
-1, ■-1, and ■-1 treated with Invention Development 1 are as good as those treated with Color Development 2. In particular, photosensitive material samples IV-1, ■-1, and Vl-1 are It turns out to be excellent. Comparative samples A are all inferior in edge staining.

Concerning transportability, those that were able to be transported smoothly in conjunction with color development processing 1 and 2 - those that showed unevenness in the O1 transport speed - Δ, those that required re-testing to ensure smooth transport ...Rated as ×.

It will be appreciated that the sample according to the present invention has relatively good transportability.

Example 3 A sample in which the aggravating dyes used in the 3N, 5th, and 7th layers were changed as shown in Table 6 in Sample 1-1 of Example 1! -4 to I-9 were prepared, samples 1-4, I-6, I
Samples 1-5 and I-7 were subjected to laser diode scanning exposure of 670na+, 750nm, and 810n-.
, 670rv, 780nm for I-9.

A laser diode scanning exposure of 830n was applied, and for all samples, 670n+m, 750rv, 83
A laser diode scanning exposure of 0 nm was applied, and the same treatment as in Example 1 was performed.

Table 6 These samples were also subjected to treatment step 1 in the same manner as in Example 1.
When processed with 1), an image with excellent color density, sensitivity, and rapid processability could be formed, demonstrating the superiority of the present invention. As with sample Il in Example 2, the transportability in the prototype processing machine using color development processing 1 was also good.

Example 4 Using the silver halide emulsion shown below and the support I obtained in Example 1, the same halide i as shown in Table 2 was prepared.
A color photographic material was prepared.

Emulsion for cyan coupler-containing layer: Add 30 g of lime-treated gelatin to 1000 d of distilled water,
After dissolving at 40°C, adjust p)I to 3.8 with sulfuric acid,
Add 5.5 g of sodium chloride and 0.02 g of N,N-dimethylimidazolidine-2-thione and bring the temperature to 52°C.
It was raised to . A solution of 62.5 g of silver nitrate dissolved in 750 g of distilled water and 21.5 g of sodium chloride dissolved in 50 g of distilled water.
The solution dissolved in 0m was added to and mixed with the above solution for 40 minutes while maintaining the temperature at 52°C. Furthermore, a solution of 162.5 g of nitric acid dissolved in 500 d of distilled water and 21.5 g of sodium chloride were added.
A solution prepared by dissolving 300 g of distilled water was added and mixed at 52°C for 20 minutes.

In this addition and mixing, 1
．． 5×10-” moles of iridium dipotassium hexachloride were added.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 45 μm and a coefficient of variation of grain size distribution of 0.08.

After demineralizing and washing the emulsion with water, a monodisperse silver bromide emulsion containing 0.2 g of nucleic acid and an average grain size of 0.05 μm (containing 2.4 Xl0−' mol of iridium dipotassium hexachloride and 1 mol Ag) was prepared.
was added in an amount equivalent to 0.5 mol % with silver halide, and chemically sensitized with triethylthiourea about 1X10-6 mol 1 mol Ag and gold chloride #1X10-' mol 1 mol Ag, and further compound (V-20 ) of 7×10-” mol 1 mol Ag.

An emulsion was prepared in which compound (1-1) was added in an amount of 7×10-' mol 1 mol A, and compound (F-1) was added in an amount of 5×10-' mol 1 mol^g.

Emulsion for magenta coupler-containing layer: Add 30 g of lime-treated gelatin to distilled water LOOOrnl, dissolve at 40°C, and add 5.5 g of sodium chloride and N
, N'-dimethylimidazolidine-2-thousand 0.02
g was added and the temperature was raised to 52°C. silver nitrate 62
．． A solution obtained by dissolving 5 g of sodium chloride in 750 m of distilled water and a solution of 21.5 g of sodium chloride dissolved in 500 m of distilled water are combined into 52
．． The mixture was added to the above solution and mixed for 40 minutes while maintaining the temperature at 5°C. Furthermore, dissolve a solution of 62.5 g of silver nitrate in 500 m of distilled water and 21.5 g of sodium chloride in 300 m of distilled water.
The solution was added and mixed at 52°C for 20 minutes.

During this addition and mixing, 5% of the total silver halide amount is
X10-'' moles of iridium dipotassium hexachloride were added.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 45μ and a coefficient of variation of grain size distribution of 0.08.

After demineralizing and washing this emulsion with water, a monodisperse silver bromide emulsion (containing 2.4 x 10-S mol of iridium dipotassium hexachloride 1 mol Ag) containing 0.2 g of nucleic acid and an average grain size of 0.05 μm was added with silver halide. The compound (V-5) was chemically sensitized with 1.5XIO-' mol of triethylthiourea, 1 mol of Ag, and 1.5XIO-' of chloroauric acid, 1 mol of Ag. 1. I XIO 1 mol Ag, compound (T-1) 1. I
, an emulsion was prepared.

Emulsion for yellow coupler-containing layer; To an emulsion prepared in the same manner as the above-mentioned emulsion for magenta coupler-containing layer, compound (V-40) and compound (V-41) were added in place of compound (V-53) at 1 dose each. ．．
An emulsion was prepared that differed only in that 1 mol of Ag and 0.2 x 10 -4 mol of Ag were added, and compound (F-1) was not added.

These samples contained compounds (D-1), (D2), and (D
-, 3), (D-4), (D-5), and (D-6) at 0.016 g/rrf and 0.006 g/rrf, respectively.
A, 0.008 g/B, 0.009 g/I, 0
．． 0.012 g/I, 0.011 g/%.

In addition, the same three types of compounds as in Sample 1-1 were used as hardening agents for gelatin.

This sample was designated as 1-10, and samples 1-11 and 112 were prepared in the same manner by changing the amount of halogenated i1 applied in each layer as shown in Table 7.

Table 7 (g/bo) However, the fifth layer coupler (M
-5) and (M-10) were replaced with the following coupler (M-17) by 1.5 times the mole, and the compound (H-5) was added to the coupler (M-17) at 20 mole%. The added compound (H-3) was removed.

(M-17) Emission wavelengths of 670 ns and 750 nm were applied to each of these samples.
.

400dp using 810nm laser diode
i.

After applying gradation-modulated scanning exposure with an average exposure time of 2×10 −' seconds per pixel, the following color development treatment 3 was performed 3 seconds later.

Processing ■ Yu U Mutual - ■ Color development 45°C 14 seconds bleach fixing 45"C 14 seconds rinse 1 38°C 6 seconds rinse 2 38°C 6 seconds rinse 3 38°C 6 seconds drying 90°C 13 seconds Color developer, bleach fixing The composition of the liquid and the rinsing liquid are the same as those used in treatment step 1.

The cyan, magenta, and yellow densities of samples 1-10 to 1-12 that had passed through this processing step 3 and processing step 2 of Example 2 were measured using a TCD densitometer manufactured by Fuji Photo Film Co., Ltd., and the obtained sensitivities were and the maximum concentration (D-ax) are shown in Table 8. Sensitivity is for sample 1- treated in processing step 2.
The sensitivity of each of the 10 coloring layers is expressed relative to 100,
The maximum density was expressed as the color density at an exposure amount that is 10 times the exposure amount that gives a density of 1.0.

Table 8 When samples 1-10 and 1-11 of the present invention were passed through processing step 3, higher sensitivity was obtained than when they were passed through processing step 2. Even in comparative sample 1-12, higher sensitivity was obtained when it was passed through processing step 3 than when it was passed through processing step 2, but for this sample, the highest concentration obtained in processing step 2 was A clear decrease in yellow density appears in processing step 4, and samples 1-10 and l- of the present invention show almost no such decrease.
It is inferior to 11. Further, regarding comparative sample 1-12, some residual developed silver was observed, which was not preferable.

Furthermore, the processing time for processing step 3, including drying time, was 59%.
The image was formed very quickly, but the processing step 2
It takes 4 minutes and 30 seconds, and the combination of the sample of the present invention and high-temperature rapid processing such as processing step 3 is superior.

Using the supports 1, 2, and A obtained in Example 1, samples of the irradiated light materials were prepared in the same manner. The first one similar to that used in Example 2
The color developing tank and bleach-fixing tank shown in the figure, as well as the processing tank shown in Fig.
A developing processing machine was prepared which consisted of a processing tank in which a squeezing piece was provided at the tip of a separation plate so as to be in contact with a central conveyance roller.

By color development process 3 (however, the rinse bath is approximately 7 seconds, 7 seconds,
7 seconds, 7 seconds), and the samples obtained using supports r, IX and A were developed. The sample using Support I could be transported without any trouble, the sample using Support I could be transported with difficulty, and the sample using Support A suffered from jamming at the exit.

From the above, sample l-10 is the one that can achieve high intensity and clear images without compromising the maximum density, and can be processed quickly and safely without causing jamming! -11,
[X-10 and ■-11 preferably sample l-10 and sample l
-11.

(Preferred embodiments of the present invention) (1) The total thickness of the support is 50 to 220 - preferably 5
0 to 180- or the stiffness of the support is ICl
The silver halide color photographic light-sensitive material according to any one of claims (1) to (4), which uses a support having an amount of 4.0 g or more per silver halide.

(2. The silver halide color photographic light-sensitive material according to any one of claims (1) to (4) or the above (11) is produced in a color development time of 20 seconds or less, excluding drying time. A color image forming method that requires processing time of 90 seconds or less.

(Effects of the Invention) By using the silver halide color photographic light-sensitive material using the support according to the present invention, color photographs or color prints that are relatively thin, yet sturdy, and easy to handle can be quickly and easily obtained. . Moreover, the obtained color photographs have a quality appearance and no lη deviation is observed.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view for explaining a color developing tank used in the rapid development process (color development process 1) used in Examples. Color developing tank ------1 Photosensitive material loading row ---2 Outlet ----3 Conveyance roller ----4 Guide ------5 Squeegee --- 6 Sub-tank (temperature control stirring) low--7, 8 reservoir---9 Pressure detector--10 Control means--11 Step motor--12 Photosensitive Materials - 1111.-20 (3 idiots) Procedural Dispute Book September 1999

Claims (4)

[Claims] (1) At least three silver halide photosensitive layers containing silver chloride or silver chlorobromide emulsions having an average silver chloride content of 96 mol % or more and substantially free of silver iodide are provided on a support. A silver halide color photographic light-sensitive material in which each light-sensitive layer contains at least one of a cyan coupler, a magenta coupler, or a yellow coupler,
The support is a reflective support in which a synthetic polymer is impregnated from the surface of base paper and further coated with a water-resistant resin layer containing a white pigment. Wavelength range 650 to 690
nm, 720 to 790 nm and 770 to 85
A silver halide color photographic material having a spectral sensitivity peak at 0 nm and having a total silver halide coating amount of 0.78 g/m^2 or less in terms of silver. (2) The support contains 30 to 90% by weight of the synthetic polymer in the base paper through impregnation treatment, and furthermore, 12 to 60% by weight of the white pigment is substantially uniformly contained in the water-resistant resin layer. The silver halide color photographic material according to claim 1, which is a reflective support containing dispersed silver halide. (3) The synthetic polymer contained by the impregnation treatment is at least one compound selected from the group of anionic polyacrylamide, cationic polyacrylamide, amphoteric polyacrylamide, carboxy-modified polyvinyl alcohol, polyvinyl alcohol, and silica-modified polyvinyl alcohol. The silver halide color photographic material according to claim (1) or (2). (4) Total silver halide coating amount is 0.64 g/m in terms of silver
The silver halide color photographic material according to any one of claims (1) to (3), which has a silver halide color of ^2 or less.