JPH03221942A - Color image forming method - Google Patents

Abstract

PURPOSE:To shorten processing time by specifying the amt. of silver chloride contained in a silver halide photographic emulsion and forming a hydrophobic resin layer having a specified titanium oxide content on one side of a reflective substrate coated with a photographic sensitive layer when a color image is formed with a silver halide color photographic sensitive material. CONSTITUTION:An image having a uniform white ground and sufficiently low min. density is obtd. even with anti-irradiation coating having high reflection density by increasing the concn. of a white pigment in the waterproof layer of waterproof paper. In order to obtain such an image, when an exposed color photographic sensitive material is color-developed, bleach-fixed and washed and/or fixed within 20-70sec total time, the emulsion layer is made of a singly dispersed silver halide emulsion contg. >=95mol% silver chloride and a hydrophobic resin layer contg. >=14wt.% titanium oxide is formed on one side of the substrate coated with the photosensitive layer. The reflection density of the sensitive material on the photosensitive layer side at 680nm wavelength is regulated to >=0.7 and the ratio of the reflection density at 550nm to that at 680nm is regulated to <=1.0.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color image forming method using a silver halide color photographic material. Specifically, the present invention relates to a color image forming method that can provide a high quality color image with extremely short development processing time.

(Prior art) Silver halide grains exposed to light are developed using an aromatic primary amine compound as a developing agent, and a color image is formed by coupling the oxidized product of the developing agent thus produced with a color coupler. Thereafter, the methods of bleaching, fixing, washing with water and/or stabilizing and drying are conventionally well-known techniques and are widely used in so-called silver salt photography.

In the photographic industry, developing photographic materials as quickly as possible has always been an important issue due to the need to improve the productivity of photo labs and shorten customer waiting times.

The easiest way to process photographic materials quickly is to increase the processing temperature to activate the reaction.
This method has already been used to significantly reduce processing time.

On the other hand, in recent years, a number of patents have been published that use high-silver chloride silver halide grains to perform rapid development processing (for example, JP-A-58-95345, JP-A-59-232342, and JP-A-6O-19140). By using these high-silver chloride silver halide grains, the color development processing time, which conventionally required more than 3 minutes, was shortened to less than 1 minute.However, in order to effectively shorten the total processing time, the color development process It was also necessary to shorten the time required for the steps after bleach-fixing.

In addition, a patent has been published for a rapid processing method that uses a silver halide emulsion with a high silver chloride content and performs color development in 25 seconds or less, and the entire processing time is within 2 minutes in total. (Unexamined Japanese Patent Publication No. 1-1999)
6044). This specification shows that this method provides white background and dye storage stability despite extremely short processing times. However, according to the inventor's own research, if the total processing time is significantly shortened, the process of washing out substances from the photosensitive layer may become rate-limiting, leading to a decrease in the finished quality of color images. I understand. In particular, in order to increase the sharpness of images, a hydrophobic resin layer containing 14% by weight or more of titanium oxide is provided on at least one side of the reflective support coated with a photographic photosensitive layer, and the irradiation of the photosensitive layer is reduced. If a relatively large amount of anti-irradiation dye is used to increase the reflection density of the photosensitive layer, the minimum density of the image will not be lowered sufficiently, resulting in insufficient whiteness and loss of image sharpness. This causes the problem that it is easily damaged.

In order to improve the image quality of color printing materials such as those of the present invention, there are two methods: using an irradiation prevention dye to reduce scattering of incident light in the photosensitive layer during exposure, and also supporting the incident light during exposure. In order to reduce the degree of scattering on the body surface and to reduce image smearing due to scattering of incident light when observing images after processing, there is a known method of increasing the filling rate of white pigment in a water-resistant layer installed on the surface of the support. ing.

Regarding the former, improvements have been made to anti-irradiation dyes (for example, Japanese Patent Application Laid-open No. 145125/1983;
No. 52-20830, No. 50-147712, No. 5
No. 9-111641, No. 61-148448, No. 61
-151538, 61-151649, same 6],
-151650, 61-151651, 61
-170742, 61-175638, 61-
No. 235837, No. 61-248044, No. 62-1
No. 64043, No. 62-253145, No. 62-25
No. 3146, No. 62-253142, No. 62-275
No. 262, specification No. 62-283336 and research
Disclosure RD-17643 (1978
(February 22, p.), RD-18716 (November 1979)
647 pages)).

Regarding the latter, for example, Japanese Patent Publication Nos. 5843734, 17433/1980, 14830/1983, and 6
1-259246, and a method of providing a water-resistant layer containing a high-density white pigment on the surface of a support by an electron beam curing method is described, for example, in JP-A No. 1-259246.
No. 27257, No. 57-49946, No. 61-262
No. 738, No. 62-61049, etc.

As one of the latter methods, examples using specular reflective or type 2 diffuse reflective supports have been reported (for example,
JP-A No. 63-24251 or No. 24253).

As mentioned above, these two methods have different effects, so it is preferable to use them together. Therefore, if the above-mentioned problem of increase in minimum density can be solved, it will be possible to obtain significantly superior color images in an extremely short processing time. I had high hopes that I could do it.

(Problems to be Solved by the Present Invention) When attempting to perform photographic development processing in an extremely short time as in the present invention, unnecessary components in the photosensitive layer, especially coloring components, are removed from the photosensitive layer. Washing out is delayed and the minimum concentration tends to increase.

On the other hand, improvements in image quality and reduction in photographic processing time are both urgent demands from the market, and a method that simultaneously achieves these has been strongly desired.

Therefore, it is an object of the present invention to have a high density white pigment in the water-resistant layer of water-resistant paper, and to prevent unevenness on the white background even when an irradiation-preventing dye with a relatively high reflection density as described in the claims is used. It is an object of the present invention to provide a color image forming method capable of obtaining an image with a sufficiently low minimum density.

(Means for Solving the Problem) As a result of repeated research to achieve the above object, the present inventor has found that
The following color image forming method was invented.

(1) At least one diffusion-resistant oil-soluble coupler that forms a dye by coupling with an oxidized product of an aromatic primary amine color developing agent and at least one high-boiling organic solvent are placed on a reflective support. A monodisperse silver halide emulsion comprising at least one silver halide photographic emulsion layer containing an emulsified dispersion of lipophilic fine particles containing one type of silver halide, and the silver halide photographic emulsion layer contains 95 mol % or more of silver chloride. In the color image forming method, the total time of the steps of color development, bleach-fixing, water washing and/or stabilization treatment after exposure of a color photographic light-sensitive material is 20 seconds or more and 70 seconds or less. At least one side of the support on which the photographic photosensitive layer is coated is free from a hydrophobic resin layer containing 14% by weight or more of titanium oxide, and the reflection density on the photosensitive layer side of the unexposed and untreated photosensitive material is The value at 680 nm is 0.7 or more, and the same (the ratio of the value at 550 nm divided by the value at 680 nm is 1.0 or less, and further, in the color development, bleach-fixing, water washing and/or stabilization steps, 1. A method for forming a color image, comprising processing the photosensitive material while colliding a jet of a processing solution with the surface of the photosensitive layer in at least a processing bath for bleach-fixing, washing and/or stabilization.

(2) In the processing step of the color photographic light-sensitive material in (1) above, after exposure, color development is performed for 5 seconds to 20 seconds, followed by bleaching and fixing for 5 seconds to 20 seconds, and then 30 seconds for 10 seconds to 30 seconds. 1. A color image forming method, characterized in that washing with water and/or stabilizing treatment is carried out in seconds or less.

(3) The reflection density on the photosensitive layer side of the photosensitive paulownia material in (1) above is
A color image forming method further characterized in that the wavelength is 0.2 or more at 470 nm.

(4) In the processing step of the color photographic material in (1) above, after exposure, color development is performed for 5 seconds to 20 seconds, followed by bleach-fixing for 5 seconds to 20 seconds, and then 10 seconds to 30 seconds. A method for forming a color image, which comprises washing with water and/or stabilizing the image, and finally removing water and drying for 10 seconds or more and 30 seconds or less.

(5) The washing and/or stabilizing process of the photographic light-sensitive material in (1) above is a so-called multi-stage process with three or more stages, and the degree of contamination of each processing bath gradually increases from the first bath to the final bath. A color image forming method characterized in that washing water and/or a stabilizing solution are replenished so that the water level becomes lower.

(6) A color image forming method according to the above (1), characterized in that the color development processing time is 5 seconds or more and 15 seconds or less, and the bleach-fixing processing time is 5 seconds or more and 15 seconds or less.

The present invention will be explained in detail below.

The feature of the support in the present invention is that the content of titanium oxide fine particles is more than 14% by weight, preferably 15% by weight or more.
The purpose is to inject it into the water-resistant resin layer so that the density is about 11% or less.

The surface of the fine particles of titanium oxide pigment may be coated with 2 to 4 inorganic oxides such as silica or aluminum oxide together or separately.
It is preferable that the surface be treated with a dihydric alcohol such as 2,4-dihydroxy-2-methylpentane or trimethylolethane described in JP-A-58-17151.

Water-resistant resin containing titanium oxide fine particles is 2 to 20
0 μm, preferably between 5 and 80 μm. In this case, the original! ] The water-resistant resin layer containing titanium oxide fine particles can be stacked with multiple water-resistant resin layers, for example, having different content rates, or containing other white pigments, or containing no white pigment. ξ may be overwritten.

In such a case, it is preferable to place the water-resistant resin layer of the present invention containing titanium oxide fine particles at a position farther from the support (closer to the silver halide emulsion layer).

In the present invention, the coefficient of variation of the occupied area ratio (%) of fine white pigment particles in the water-resistant resin layer is preferably 0.20 or less, more preferably 0.15 or less, particularly 0.10 or less.

The dispersibility of the white pigment fine particles in the resin layer is preferably about 0.1 μm from the surface of the resin, preferably 5oo.X.

The resin on the surface is scattered by the ion sputtering method using glow discharge, and the exposed fine particles of pigment are observed using an electron microscope.The photographed occupied area is determined and evaluated by the variation coefficient of the occupied area ratio (%). can.

The ion sputtering method was developed by Hiroshi Murayama-1 Kunihiro Aiki, "Surface treatment technology using plasma J, Research on Il! Machinery 3.
It is described in detail in Volume 3, No. 6 (1981).

In order to control the coefficient of variation of white pigment particles to 0.20 or less, it is best to sufficiently knead the white pigment in the presence of a surfactant, and also to adjust the surface of the pigment particles to 2 to 4 as described above. It is preferable to use one treated with a dihydric alcohol.

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

It is also possible for the water-resistant resin to contain a white pigment other than titanium oxide. For example, rutile titanium oxide, anatase titanium oxide, barium sulfate, calcium sulfate,
Silicon oxide, zinc oxide, titanium phosphate and aluminum oxide are preferably used as white pigments.

The white support used in the silver halide photographic light-sensitive material according to the present invention is provided by coating a water-resistant resin layer on a substrate, and the substrate may be obtained from natural pulp, synthetic pulp, or a mixture thereof. Base paper, polyester films such as polyethylene terephthalate and polybutylene ethylene phthalate, plastic films such as cellulose triacetate films, polystyrene films, polypropylene films, and polyolefin films can be used.

The base paper used in the present invention is selected from materials commonly used for photographic paper. In other words, the main raw material is natural pulp selected from conifers, hardwoods, etc., and if necessary, fillers such as clay, talc, calcium carbonate, urea resin fine particles, rosin, alkyl ketene dimer, higher fatty acids, paraffin wax, and alkenyl succinic acid. A paper to which a sizing agent such as, a paper strength agent such as polyacrylamide, a fixing agent such as sulfuric acid, a cationic polymer, etc. are added is used. Especially epoxidized fatty acid alkyl, alkyl ketene dimer,
p using a reactive sizing agent such as alkenylsuccinic acid.
H5-7 (for electrodes, flatness G manufactured by Toa Denpa Kogyo Co., Ltd.
It is preferable to use neutral paper (measured with a pH meter using ST-5313F). Furthermore, a synthetic pulp may be used in place of the above-mentioned natural pulp, or a mixture of natural bulb and base pulp in any ratio may be used.

The surface of the pulp can also be subjected to surface size treatment with a film-forming polymer such as gelatin, starch, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, or a modified product of polyvinyl alcohol. Examples of polyvinyl alcohol modified products in this case include carboxyl group modified products, silanol modified products, and copolymers with acrylamide. In addition, when the film-forming polymer is subjected to surface size treatment using
．． The film-forming polymer at this time may contain an antistatic agent, a fluorescent whitening agent, a pigment, an antifoaming agent, etc., if necessary.

In addition, the base paper is made by making a pulp slurry containing the above-mentioned pulp and additives such as a filler, a sizing agent, a paper strength reinforcing agent, and a fixing agent as necessary using a paper machine such as a Fourdrinier paper machine.
It is manufactured by drying and rolling. The surface size treatment is performed either before or after this drying, and calendering is performed after drying or between winding. If this calendering is performed after the surface size treatment is dried,
This can be carried out either before or after surface sizing.

Whether or not the base paper used for the support substrate of the present invention is neutral paper can be determined by using, for example, flat paper GST-5313F manufactured by Toa Denpa Kogyo ■ for electrodes.
This can be determined by measuring the pH value using a . The neutral paper has a pH value of 5 or more, preferably 6 or 5 to 9.

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

The water-resistant resin used in the present invention has a water absorption rate (weight%)
is 0. 5, preferably a resin of less than O,1, such as polyalkylene (polyethylene, polypropylene, or a copolymer thereof), vinyl polymer or a copolymer thereof (
These include polystyrene, polyacrylate, and their copolymers), polyester, and their copolymers. Preferably, the polyalkylene resin used is low density polyethylene, high density polyethylene, polypropylene, or blends thereof. A fluorescent brightener, antioxidant, antistatic agent, release agent, etc. are added as necessary.

For example, JP-A-57-27257, JP-A-57-49
As described in JP-A No. 946 and JP-A 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 Sho 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. Titanium oxide and other white pigments etc. 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 is described, for example, in the complete processing technology research "New Umonate Processing Handbook".
For example, dry lamination, solvent-free dry lamination, etc. are used, and coating methods include gravure roll type, wire bar type, doctor blade type, reverse roll type, dip type, air knife type, calendar type, and kiss type. , Squeeze-type coating, Fanchin-type coating, and other methods.

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

The support has a total thickness of 30 to 350 g/nf (approximately 3
0 to 400 μm), more preferably about 5
0 to 200 g/n (.

The optical reflection density in the present invention is measured by a reflection densitometer commonly used in the art, and is defined as follows.

However, during measurement, it is necessary to install a standard reflector on the back side of the sample to prevent measurement errors caused by striped light that passes through the sample.

Optical reflection density = 108 to (Fo/F) Fo: Reflected light flux of standard white plate F: Reflected light flux of sample The optical reflection density required in the present invention is 0.70 or more at the measurement wavelength of 680 nm, and is preferably 0
．． 7 or more and 2.0 or less, more preferably 0.8 or more and 1.9
Below, it is most preferably 1°0 or more and 1.8 or less. Further, the ratio of the optical reflection density at 550 nm to that at 680 nm is preferably 1 or less, more preferably O08 or less, even more preferably 0.6 or less, and most preferably 0.5 or less and 0.2 or more. Further, the optical reflection density at 470 nm is preferably 0.2 or more, and more preferably 0.3 or more.

In order to obtain the optical reflection density of the present invention, the amount of the dye added below may be adjusted. These dyes may be used alone or in combination. There are no particular restrictions on the layer to which these dyes are added, such as the layer between the bottom photosensitive layer and the support, the photosensitive layer, the intermediate layer, the protective layer, the layer between the protective layer and the top photosensitive layer, etc. Can be added.

Dyes to accomplish this purpose are selected from those that do not substantially spectral sensitize the silver halide.

Conventional methods can be used to add these dyes; for example, they can be added after being dissolved in water or an alcohol such as methanol.

The following coating amount can be used as a guideline for the amount of the dye added.

Cyan dye: 20mg/m~l OOw/n ((most preferred amount) Magenta dye: 0~50■/d (preferred amount) 0~10
mg/m (most preferred amount) 0 Yellow dye 20-30 ■/d (preferred amount) 5-20
■/rd (Jt is also a preferred amount) It is better to have the dye added to the layer in the form of diffusion throughout the entire layer between coating and drying of the photosensitive material than to fix it in a specific layer. This is preferable from the viewpoint of making the effects of the invention more noticeable and also from the viewpoint of preventing an increase in manufacturing costs due to the provision of a specific layer.

Dyes that can be used in the present invention include, for example, British Patent No. 506.
No. 385, No. 1,177.429, No. 1.311.8
No. 84, No. 1,338.799, No. 1,385.37
No. 1, No. 1,467.214, No. 1,433,102
No. 1,553,516, Japanese Unexamined Patent Publication No. 1985-85.13
No. 0, No. 49-114.420, No. 52-117.1
No. 23, No. 55-161, 233, No. 59-111.
No. 640, Special Publication No. 39-22,069, No. 43-13
．． No. 168, No. 62-273527, U.S. Patent No. 3,
247.127, 3,469,985, 4',
Oxonol dyes having a pyrazolone nucleus or a barbylic acid nucleus described in US Pat.
No. 533.472, No. 3,379,533, British Patent No. 1. Other oxonol dyes described in British Patent No. 575.691, British Patent No. 680, etc.
No. 631, No. 599,623, No. 786.907,
No. 907,125, No. 1,045,609, U.S. Patent No. 4,255,326, JP 59211.043
Azo dye described in No. 1, etc., JP-A-50-100.11
No. 6, No. 54-118,247, British Patent No. 2.01
Azomethine dyes described in US Pat. No. 4,598 and US Pat. No. 750.031, anthraquinone dyes described in US Pat. No. 2,865,752, US Pat. No. 2,538,00
No. 9, No. 2,688.541, No. 2,538°008
British Patent No. 584,609, 1°210.25
No. 2, JP-A No. 50-40,625, JP-A No. 51-3, 62
No. 3, No. 51-10,927, No. 54-418.24
No. 7, Special Publication No. 48-3,286, No. 59-37, 30
Arylidene dye described in No. 3 etc., Special Publication No. 28-3
, No. 082, No. 44-16.594, No. 59-28.
Styryl dye described in No. 898 etc., British Patent No. 44
No. 6.583, No. 1,335,422, JP-A-59-
228,250 etc., British Patent No. 1,075,653, British Patent No. 1,153,
No. 341, 1.284. No. 730, 1,475.
Merocyanine dyes described in U.S. Pat. No. 228, U.S. Pat.
, 294,539, and the like.

Among these, dyes that can be particularly preferably used in the present invention have the following general formulas (1), (II), (I[[),
It is a dye represented by (IV), (V) or (Vl).

General formula (1) In the formula, Zl and Zx may each be the same or different and represent a group of nonmetallic atoms necessary to form a heterocycle, and L+
, Lm, L3. La, Ls represent a methine group, nl+
n2 represents 0 or 1, and MΦ represents hydrogen or other monovalent cation.

General formula (I[) 1 42 In general formula (II), X and Y may be the same or different, represent an electron-withdrawing group, and X and Y may be linked to form a ring.

Ro and R42 may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, a substituted amino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or a sulfo group.

R43 and R44 may be the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, or a sulfonyl group, and R43 and Ras are linked to form a 5- to 6-membered ring. You can.

Further, R41 and R4ff, and R42 and R44 may be connected to each other to form a 5- to 6-membered ring.

Among the above XSY, R4,, R4□, R43, R44,
At least one has a sulfo group or a carboxyl group as a substituent.

Ll, L, □, Ll3 each represent a methine group, is 0
Or represents 1.

General formula (III) Ar+ N-N Arm In the formula, Ar, , Ar, may be the same or different,
Represents an aryl group or a heterocyclic group.

General formula (IV) In the formula, Rs+, Rsa, R5S, and Ris may be the same or different from each other, and hydrogen atoms, hydroxy groups, alkoxy groups, aryloxy groups, and R'' may be the same or different from each other. It often represents a hydrogen atom and an alkyl or aryl group containing at least one sulfonic acid group or carboxyl group.

R82, R53, R'' and R5'Lt may be the same or different from each other (representing a hydrogen atom, a sulfonic acid group, a carboxyl group, or an alkyl group or aryl group having at least one sulfonic acid group or carboxyl group) represent

General Formula (V) In the formula, L and L' represent a substituted or unsubstituted methine group or a nitrogen atom, and m represents 0.1, 2 or 3.

Z is pyrazolone nucleus, hydroxypyridone nucleus, barbyl nucleus, thiobarbyl nucleus, dimedone nucleus, indan-1,3-dione nucleus, rhodanine nucleus, thiohydantoin nucleus, oxazolidin-4-one 2-thione nucleus, homophthalide nucleus , bilimodine-2,4-dione nucleus, or 1,
2.3.Represents a group of nonmetallic atoms necessary to form a 4-tetrahydroquinoline-2,4-dione nucleus.

Y is an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphI thiazole nucleus, a benzoselenazole nucleus, a pyridine nucleus, a quinoline nucleus, a benzimidazole nucleus, a naphthimidazole nucleus, an iξdashiquinoxaline nucleus , indolenine nucleus,
It represents a group of nonmetallic atoms necessary to form an isoxazole nucleus, benzisoxazole nucleus, naphthoisoxazole nucleus, or acridine nucleus, and Z and Y may further have a substituent.

In the general formula (Vl) 7 or the formula, R and R' may be the same or different from each other and represent a substituted or unsubstituted alkyl group.

L+ and Lt 1Lz may be the same or different from each other and represent a substituted or unsubstituted methine group, m is 0,
1.2 or 3.

Z, , Z may be the same or different from each other and represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted 5-membered or 6-membered hetero ring, and E and n are each 0 or 1. It is.

) (e represents an anion. p represents 1 or 2,
p is 1 when the compound forms an inner salt.

Among the dyes represented by the general formula (1), particularly preferred are the dyes represented by the following general formula (I-a).

8 General formula (1-a) In the formula, R,, R, represents an aliphatic group, aromatic group, or heterocyclic group, R,, R4 is an aliphatic group, an aromatic group, -〇Rs
, -COORs, -NRs Ra, -CON R
s Rb , N Rs CON Rs Rb, -3on
RT, -COR? , NRh C0Rt, NRb
302 RT, cyano group (herein, R%sR6 represents a hydrogen atom, an aliphatic group or an aromatic group, R9 represents an aliphatic group or an aromatic group, R3 and R, or Rh and R7 are connected 5 or 6j! may form a ring), and represents L,,L,,L,.

L4. L% and "l+nt", M are general formula (1)
It is synonymous with the definition in .

Examples of dyes represented by the general formula (Ia>) are shown below, but the present invention is not limited thereto.

The dyes represented by the general formulas (I) to (Vl) used in the present invention include the dyes described in Japanese Patent Application No. 1999-1999. -297213 Specification No. 2
Those described on pages 7 to 103 can be used.

The dye used in the present invention is either eluted from the silver halide photographic material during any process from development to washing with water, or is decolorized by sulfite as described in British Patent System No. 506.385. .

3- The color photographic light-sensitive material of the present invention may be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. can. In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order. Furthermore, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the sensitizing light - yellow for blue, magenta for green, and cyan for red.
By containing a so-called color coupler that forms a color, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

As the silver halide emulsion used in the present invention, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide can be preferably used. 4 Here, "substantially no silver iodide" means that the silver iodide content is 1
It means mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (shell) [-
Particles with a so-called laminated structure in which the halogen composition differs between layers (layer or multiple layers), or structures with different halogen compositions in a non-layered manner inside or on the particle surface (if on the particle surface, on the edge, corner, or surface of the particle) Particles having a structure in which parts of different compositions are joined to each other can be appropriately selected and used. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to actively have continuous structural changes.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used. Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used.

Furthermore, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the localized silver bromide layer is provided inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen content of the localized layer is preferably at least 10 mol %, more preferably more than 20 mol %, in terms of silver bromide content. These localized layers can be located inside the grains or on the edges, corners, or surfaces of the grain surfaces, and one preferred example is one in which they are epitaxially grown on a part of the corner of the grains.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In such cases, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1μ to 2μ.

Further, the particle size distribution thereof is preferably so-called monodisperse with a coefficient of variation (standard deviation of particle size distribution divided by 1° by the average particle size) of 20% or less, preferably 15% or less. At this time, in order to obtain a wide latitude, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating.

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these particles, it is preferable to contain particles having the above-mentioned regular crystal shape in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

8 The silver chlorobromide emulsion used in the present invention is P, Glafkic
Chimie et Ph1sique Ph
otographique (Pau1Monte1, 1967), G, j? , Duffin, Ph.
oto-graphic Bmulsion Chem
istry (FocaIPress, 1966), V, L, Zelikman at al M
akingandCoatingPhotograp
hic Bmuldion (Focal Press
It can be prepared using the method described in, for example, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof. May be used. A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or monomer complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is preferably 10-I'-10-2 moles relative to silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding the compounds used for chemical sensitization, please refer to the lower right page of page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, F, M, ) Heter by Farmer.
ocyclic compoundsCyanine
dies and related compound
ds (John Wiley & 5ons CNew
York, London, 1964). Examples of specific compounds and spectral sensitization methods are described in the above-mentioned Japanese Patent Application Laid-open No. 62-21.
Those described in the upper right column of page 22 to page 38 of the specification of Japanese Patent No. 5272 are preferably used.

The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good.

When the present invention is applied to a color photosensitive material, the color photosensitive material includes a yellow coupler, a magenta coupler, and a cyan coupler that form yellow, magenta, and cyan colors respectively by coupling with an oxidized product of an aromatic amine color developer. is usually used.

Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention have the following general formulas (C-I), ((, -II), (M-I), <M-II
) and (Y).

General formula (C-I) []H General formula (C-II) H 2 General formula (M ■) a General formula (M-n) General formula () General formula (C-I) and (C-II) In, R1,
R2 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R3, R3 and R6 represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group, and R3 together with R2 It may also represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring. Yl
, Y2 represents a hydrogen atom or a group that leaves during the coupling reaction with the oxidized product of the developing agent. n represents 0 or 1.

R1 in general formula (C-11) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-methyl 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 ((, II) are as follows.

In the general formula ((, I), preferable RI is an aryl 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 cyan group.

In general formula (C-1), when R3 and R2 do not form a ring, R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R3 is Preferably it is a hydrogen atom.

In general formula (C-n), R2 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In general 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 the general formula (C-n), R5 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 ((, -n), preferred R6 is a hydrogen atom,
A halogen atom, with chlorine and fluorine atoms being particularly preferred. Preferred Yl and Y2 in the general formulas ((, -I) and (CT[)) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula <M-I), R7 and R3 represent an aryl group, R11 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y3 represents a hydrogen atom or a leaving group. represents.

Aryl group (preferably phenyl group) for R1 and R9
The substituents allowed for are the same as the substituents allowed for substituent R1, and when there are two or more substituents, they may be the same or different. R8 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom.

Preferred Y3 is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in US Pat. No. 4.3.
Particularly preferred are sulfur atom dissociative types such as those described in No. 51.897 and International Publication No. WO88104795.

In general formula (M-II), R1 represents a hydrogen atom or a substituent. Y represents a hydrogen atom or a leaving group, and particularly preferably a halogen atom or an arylthio group. ZaSZb
and 2c represents methine, substituted methine, N- or -total-, one of the Za-Zb bond and the Zb-2c bond is a double bond, and the other is a single bond.

The case where the Zb-1c bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. RID or Y.

When a dimer or more multimer is formed with Za.

When zb or 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 (M-TI), imidazo [1,2 -b] Pyrazoles are preferred, including pyrazolo [
:1,5-b] [1,2,411-riazole is 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 pyrazolo l-U azole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-147254, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent (Publication) No. It is preferred to use pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position, such as those described in No. 226.849 and No. 294.785.

In general formula (Y), R11 represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, and R4 represents a hydrogen atom, a halogen atom, or an alkoxy group. A is -NflCOR,3, -N11SO2-R3
3, -3D2NIIR,, -COOR,, -3O2
Represents N-R, □R8. However, RI3 and R8 are each an alkyl group,
Represents an aryl group or an acyl group. Y represents a leaving group. The substituents for R12, R13, and R14 are the same as those allowed for R1, and the leaving group Y is preferably one that leaves at either an oxygen atom or a nitrogen atom; Particularly preferred is the atomic dissociation type.

The cyan coupler, magenta coupler and yellow coupler that can be used in the color photographic light-sensitive material used in the present invention, and the method of incorporating them into the hydrophilic colloid layer of the light-sensitive material, are described in Japanese Patent Application No. 1116835 No. 1.
It is described in the publications listed or cited on pages 5 to 47.

In addition, regarding color anti-fogging agents, anti-fading agents, ultraviolet absorbers, dyes, binders, and protective colloids, patent application No. 1-116
It is described in the publications described or cited on pages 47 to 55 of the specification of No. 835.

0 The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, but p-phinidine diamine 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-1-luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer is pHllf?, such as an alkali metal carbonate or phosphate. Agents, bromide salts, iodide salts, development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are typically included. Hydroxylamine, diethylhydroxylamine, sulfite, N
, hydrazines such as N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, various preservatives such as catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, and quaternary ammonium salts. , development accelerators such as amines, dye-forming couplers, auxiliary developing agents such as the competing coupler 1-phenyl-3-pyrazolidone, tackifying agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphono Various calcinants such as carboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-11-diphosphonic acid, nitrilo- N,
Typical examples include N,N-1-rimethyl-phosphonic acid, ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid), and salts thereof. .

Further, when performing reversal processing, color development is usually performed after black and white development and reversal processing. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or amine phenols such as N-methyl-p-aminophenol, alone or Can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally less than 32 per square meter of photosensitive material processing, and by reducing the bromide ion concentration in the replenisher, it can be reduced to less than 500. It can also be done. 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. The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio=contact area between processing liquid and air (cm2)/capacity of processing liquid (cm3)
) The aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05.

Methods for reducing the aperture ratio in this way include, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, a method using a movable lid as described in Japanese Patent Application No. 62-241342; Examples include the slit development method described in JP-A No. 63-216050.

It is preferable to reduce the aperture ratio not only in both color development and black-and-white development, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization.

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

The time for color development processing is usually set between 2 and 5 minutes, but it is possible to further shorten the processing time by using high temperature, high pH, and high concentration of color development agents. can.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, depending on the purpose, treatment may be carried out in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (In) is used. A typical bleaching agent is iron (
Organic complex salts of II[), such as ethylenediaminetetraacetic acid,
Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid, etc. can be used. . Among these, aminopolycarboxylic acid iron(II) complex salts including ethylenediaminenishiacetate iron(III) complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(I[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(II[) complex salts is usually 4.0 to 8.0, but in order to speed up the processing, the pH is lowered. You can also do that.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3.893.858, German Pat.
．． No. 290.812, JP-A-53-95630, Research Disclosure No. 17.129 (197
Compounds having a mercapto group or disulfide bond as described in J.P. 1987); thiazolidine derivatives as described in JP-A-50-140129; U.S. Patent No. 3.706.5
Thiourea derivatives described in No. 61; JP-A-58-1623
Iodide salt described in No. 5; West German Patent No. 2.748.430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836: bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and in particular, compounds described in U.S. Pat. Compounds are preferred. Additionally, U.S. Patent No. 4.552.
Compounds described in No. 834 are also preferred. These bleach accelerators may be added to the light-sensitive 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, with ammonium thiosulfate being the most widely used. Can be used for Preservatives for bleach-fix solutions include sulfites, bisulfites, and p-
) Sulfinic acids such as luenesulfinic acid or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive paulownia material (for example, depending on the materials used such as couplers), the purpose, 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 flushing tanks and the amount of water in the multistage countercurrent method is described in Journal of the 5ociet.
y of Motion Picture and T
e1evision 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. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-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 isocyanurate,
8 Other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal J (1986), Sankyo Publishing, Complete hygiene technology "Sterilization of microorganisms, sterilization, antifungal technology J (1982) Society of Industrial Technology, Japan Antibacterial and antifungal “Encyclopedia of antibacterial and antifungal agents” edited by Hui Gakkai <198
The fungicides described in 6) can also be used.

9H of the washing water in the processing of the photosensitive material of the present invention is 4 to
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 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 resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3.342.59
Indoaniline compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
．． Metal complex described in No. 719.492, JP-A-53-13
Examples include urethane compounds described in No. 5628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated. Typical compounds are described in JP-A Nos. 56-64339, 57-144547, and 58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to.

In addition, West German Patent No. 2.226.7 was developed to save silver on photosensitive materials.
70 or U.S. Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

The color photographic material of the present invention is preferably subjected to color development, bleach-fixing, and water washing treatment (or stabilization treatment). Bleaching and fixing may be carried out separately instead of in one bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotriene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-[N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl N-( β−
(methanesulfonamide)ethyltwoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N- Ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-Cβ-(
methanesulfonamido)ethyltoaniline (exemplified compound D-6).

Further, salts of these p-phenylenediamine derivatives such as sulfates, hydrochlorides, sulfite salts, and 11)-) luenesulfonates may be used. The amount of aromatic secondary amine developing agent used is preferably about 0.1 g to about 2 g per 12 developer solution.
0 g, more preferably from about 0.5 g to about 10 g.

In practicing the present invention, it is preferred to use a developer solution that is substantially free of benzyl alcohol. Here, "substantially not containing" preferably means 2Tn1/!
! More preferably, the benzyl alcohol concentration is 1,5+d/ffl or less, and most preferably, the benzyl alcohol is completely contained.

It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency.

Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" preferably means a sulfite ion concentration of 3.0 x 10 -' mol/l or less, and most preferably no sulfite ion at all.

However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

The term "substantially free of hydroxylamine" as used herein preferably means a hydroxylamine concentration of 5.0.times.10@-3 morph 1 or less, and most preferably no hydroxylamine at all.

It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion.

The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for color photographic materials. That is, organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-Hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, di-waxy radicals, alcohols, oximes, diamide compounds, fused cyclic amines, etc. It is a particularly effective organic preservative. These are JP-A Nos. 63-4235, 63-30845, 63-21647, 63-44655, 6
No. 3-53551, No. 63-43140, No. 63-5
No. 6654, No. 63-58346, No. 63-4313
No. 8, No. 63-146041, No. 63-44657, No. 63-44656, U.S. Patent No. 3.615.50
No. 3, No. 2494.903, JP-A-52-14302
No. 0, Japanese Patent Publication No. 48-30496, etc.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 18056-88, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, US Pat. No. 3,746.
The aromatic polyhydroxy compounds described in No. 544 and the like may be contained as necessary. In particular, it is preferable to add alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, hydrazine derivatives, or aromatic polyhydroxy compounds.

Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
It is described in No. 5270, No. 63-9713, No. 63-9714, No. 63-11300, etc.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.

Examples of the above-mentioned amines include cyclic amines as described in JP-A-63-239447 and JP-A-63-128.
Amines such as those described in No. 340 and other patent applications filed in 1983
Examples include amines such as those described in No. 3-9713 and No. 63-11300.

In the present invention, 3.5% of chloride ions are added to the color developer.
It is preferable to contain Xl0-' to 1.5 Xl0-' mol/l. Particularly preferably, it contains 4
-'mol/l. Chlorine ion concentration is 1.5X10-
If the amount is more than 10-1 mol/fl, it has the disadvantage of delaying development, which is not preferable in achieving the object of the present invention of rapid development and high maximum density. Also, 3.5X 1
If it is less than 0-2 mol/1, it is not preferable in terms of preventing fog.

In the present invention, 3.0% bromine ion is added to the color developer.
It is preferable to contain X10-5 mol/l-1 and OX 10-' mol/l. More preferably 5.0×10−
'~5X10-' mol/l. Bromine ion concentration is l
If it is more than Xl0-' mol/l, development will be delayed and maximum density and sensitivity will be reduced; 3. OX 10-'mol/1
If it is less than that, fog cannot be sufficiently prevented.

Here, the chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the photosensitive material into the developer during the development process.

When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride.

Alternatively, it may be supplied from an optical brightener added to the developer.

As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among these, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development process, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to retain the above-mentioned pu, it is preferable to use various buffering agents. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3゜4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1°3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are soluble, PI(9,
These buffering agents have the advantage of having excellent buffering capacity in the high pif range of 0 or more, having no adverse effects on photographic performance (fogging, etc.) even when added to color developing solutions, and being inexpensive. is particularly preferred.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferably at least 0.1 mol/l-0, particularly 0.1 mol/l-0,
Particularly preferred is 4 mol/l.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid fi, N, N, N-)rimethylenephosphonic acid, ethylenediamine-N, N, N', N'
-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid L 1.2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,
2,4-)licarboxylic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, N.

Examples include N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
Hit 0. ．． It is about 1 g-Log.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3.813
．． 247, p-phenylenediamine compounds as shown in JP-A-52-49829 and JP-A-50-15554, JP-A-52-1989-
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
Quaternary ammonium salts shown in No. 6-156826 and No. 52-43429, etc., U.S. Patent No. 2゜494,
No. 903, No. 3.128.182, No. 4.230.7
No. 96, No. 3.253.919, Special Publication No. 41-114
No. 31, U.S. Pat. No. 2,482.546, U.S. Pat.
Amine compounds described in 6.926 and 3.582.346, etc., Japanese Patent Publication No. 37-16088, 42-2
5201, U.S. Patent No. 3.128.183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3.532゜501, and other 1-phenyl-3-pyrazolidones. etc., imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzo l-IJ asol, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains an optical brightener. As an optical brightener, 4.4'
-Diamino-22'-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/l, preferably 0.1 g to 4
/1.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the vine color phenomenon liquid applied to the present invention is 20~
The temperature is 50°C, preferably 30 to 40°C. Processing time is 20
The time is from seconds to 5 minutes, preferably from 30 seconds to 2 minutes. It is preferable that the amount of replenishment is small, but it is 20 to 600 m per 1 d of photosensitive material.
jl! is suitable, preferably from 50 to 300. More preferably 60-200-1, most preferably 6
0- to 150-.

Next, a desilvering process that can be applied to the present invention will be explained.

The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step.

The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below.

As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but especially iron (
Organic complex salts of I[[) (e.g. ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and malic acid: persulfates: hydrogen peroxide, etc. .

Among these, organic complex salts of iron (II [>) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution.
Aminopolyphosphonic acids, organic phosphonic acids, or their salts are listed, such as ethylenediaminetetraacetic acid, diethylenetriamine 5-section LL, 3-diaminopropanetetraacetic acid, propylnondiaminetetraacetic acid, nitrilotriacetic acid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Examples include iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like. These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, iron(I) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1.3 diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. In addition, a chelating agent can be used as a second
It may be used in excess to form an iron ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/A, preferably 0.05 to 0.50 mol/l.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, U.S. Pat.
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds having a mercapto group or disulfide bond, and Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
Thiourea compounds described in No. 5 and US Pat. No. 3,706,561, or halides such as iodine and bromide ions are preferred because they have excellent bleaching properties.

In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention contains bromides (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. If necessary, one or more inorganic acids having a pif buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution is a known fixing agent, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid. , 3,6-sithia-1,8-octanediol, and other water-soluble silver halide solubilizers such as thioureas, and these can be used alone or in combination of two or more.

It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per 11 is
Preferably 0.3 to 2 mol, more preferably 0.5 to 1 mol
．． It is in the range of 0 mol. pH of bleach-fix solution or fix solution,
The range is preferably 3 to 10, and particularly preferably 5 to 9.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.).

These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
The content is preferably 0.05 mol/l, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as necessary.

After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, 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. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers Uourn.
alof the 5ociety of Motio
n Picture and Television
Engineers) Volume 64, p. 248-253
(May 1955 issue).

Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multistage countercurrent method, the amount of washing water can be greatly reduced, for example, from 0.5 ffl to 11 or less per 1 m' of photosensitive material, and the effect of the present invention is remarkable. The increase in residence time causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. As a solution to this problem, Japanese Patent Application Laid-Open No. 62-288838
The method for reducing calcium and magnesium described in this issue can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds and cyabendazole described in JP-A-57-8542, chlorinated isocyanuric acid 1 sl-U rum described in JP-A-61-120145, JP-A-61-2677
Benzotriazole, copper ion, etc. described in No. 61, Hiroshi Horiguchi, "Chemistry of antibacterial and anti-mildew J (1986), Sankyo Publishing, complete hygiene technology "Sterilization, sterilization, and anti-mildew technology of microorganisms" (1)
It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents J (1986)," edited by the Society of Industrial Technology and the Japan Society of Antibacterial and Antifungal Research.

Further, in the washing water, a surfactant may be used as a draining agent, and a cooling agent such as EDTA may be used as a water softener.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound such as formalin, or a film suitable for stabilizing the dye.
Examples include buffers for preparing H and ammonium compounds. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without passing through a water washing step, Japanese Patent Application Laid-open Nos. 57-8543, 58-14834, and 60-
All known methods described in No. 220345 and the like can be used.

In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

A so-called rinsing solution is also used as a washing solution or stabilizing solution used after desilvering treatment.

Preferred p++ in the water washing step or stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but generally it is between 15 and 45
The temperature is preferably 20 to 40°C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time.

Preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to
It is 1 minute and 30 seconds. Regarding the amount of replenishment, it is preferable not to walk from the viewpoint of running costs, reduction in emissions, ease of handling, etc.

A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. Or, it is 1β or less, preferably 500 or less, per 1 m' of photosensitive material. Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to reduce the amount of waste liquid by using a multi-stage counter-current system to allow the overflow of the wash water to flow into the bleach-fix bath, which is a pre-bath, and to replenish the bleach-fix bath with concentrated liquid.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 (Preparation of support) LBKP for photographic paper (bleached hardwood, sulfate pulp)
100% (weighing i 75 g/rrr, thickness approx. 180μ
); A white pigment-containing resin layer made of water-resistant titanium oxide having the composition shown below was provided on the surface of a white base paper to obtain supports (1), (2) and (2).

Support ■: Polyethylene composition (density 0.920 g/cc.

Melt index (MI) 5.0g/l 0min) of 9
To 0 parts by weight, 10 parts by weight of a titanium oxide white pigment surface-treated with silicon oxide and aluminum oxide was added, and after further adding a bluish dye (ulmarine blue) and kneading, a 30 μm water-resistant resin layer was formed by melt extrusion coating. Obtained. On the other hand, another polyethylene composition (density 0.95
0 g/cc, MI 8.0 g/10 min) to obtain a 20μ water-resistant resin layer.

Support ■: 86 parts by weight of the polyethylene composition used in Support A,
After adding 14 parts by weight of the following surface-treated anatase titanium oxide white pigment and kneading in the same manner, a 30 μm water-resistant resin layer was obtained by melt extrusion coating.

The same titanium oxide powder used in support A was mixed with 2.4-
A surface-treated titanium oxide white pigment was obtained by immersing it in an ethanol solution of dihydroxy-2-methylpentane and heating it to evaporate the ethanol.

The alcohol was coated on the particle surface in an amount equivalent to about 1% by weight based on titanium oxide. On the back side of the blank base paper, a water-resistant resin layer was provided using a polyethylene composition in the same manner as Support A.

Sample (2) was obtained in the same manner except for changing the composition shown in Table 1.

Table 1 Support sample ■ A composition of 50 parts by weight of hexaacrylate ester of an adduct equivalent to 12 moles of dipentaerythritol propylene oxide and 50 parts by weight of rutile titanium oxide was mixed and dispersed in a ball mill for over 20 hours, and then dried. It was coated and dried on the following base paper so that the film thickness was 10 μm. The base paper used was a 20 μm thick layer of a polyethylene composition on the white base paper used in Support A, and a polyethylene composition (density 0.960 g/cc, MI 25 g/10
This was obtained by providing a 20 μm layer of 20 μm.

The coated layer was irradiated with an electron beam under a nitrogen atmosphere at an accelerating voltage of 200 kV and an absorbed dose equivalent to 5 megarads to obtain a support sample (2).

The dispersibility of the white pigment particles in the surface part of the water-resistant resin layer of the support according to the present invention was determined by etching the resin approximately 0.05 μm from the surface by ion sputtering method, observing the white pigment particles with an electron microscope, and continuously 6μm×6
Projected area ratio Ri of each particle for 6 unit areas of μm
was determined, and its standard deviation and average particle occupied area ratio (%) were determined.

The results are shown in Table 1-a.

Compared to support sample ① in Table 1-a, support samples H to ① are superior in the dispersibility of the white pigment.

Support V As a plastic film, a 26 μm polyethylene terephthalate film filled with 2% silica with an average particle size of 3 μm was coated with vinylidene chloride copolymer (vinylidene chloride/vinyl chloride/vinyl acetate/maleic anhydride-16/70/
10/4) An anchor coating agent having a composition of 80% by weight and 20% by weight of trimethylolpropane adduct of tolylene diisocyanate is dissolved in ethyl acetate, and after drying, it becomes 0.1 μm.
It was applied and dried in an oven at 100°C for 2 minutes. Vacuum deposition was performed on this substrate at 105 torr to form an aluminum thin film layer with a thickness of 800 angstroms on the anchor coat layer. The period of the surface irregularities is 0. Approximately 40 to 10 at 1 μm or more
It was 0 pieces/mm. The average roughness of the surface measured with a three-dimensional roughness meter was approximately 0.6 μm.

On the surface of this vapor-deposited thin film layer, vinylidene chloride/vinyl chloride/vinyl acetate/maleic anhydride copolymer (weight ratio: 1
0/70/17/3) A copolymer for the adhesive layer with a composition of 95 parts and 5 parts of hexamethylene diisocyanate and trimethylolpropane adduct is diluted with ethyl acetate to give 0.2 g/m after drying. It was coated in the same manner as above and dried in an oven at 100°C for 2 minutes to form an adhesive layer.

Next, wood pulp from 20 parts of LBSP and 80 parts of LBKP was refined to 300 cc of Canadian freeness using a disc refiner, and 1.
0 parts of anionic polyacrylamide, 0.5 parts of anionic polyacrylamide, 1.5 parts of aluminum sulfate, 0.5 parts of polyamide polyamine epichlorohydrin, and 0.5 parts of alkyl ketene dimer, all in absolute dry weight ratio to the wood pulp. A paper having a basis weight of 160 g/m was made using a Fourdrinier paper machine.

The density was set to 1.0 g/ci using a machine calender. After corona discharge treatment of this base paper, low density polyethylene (MI=7 g/l, 0 minutes, density 0.923 g/cc
) was extrusion coated to form a polyethylene resin layer with a thickness of 30 μm. Next, after corona discharge treatment was applied to the other surface (back surface) of the substrate, high-density polyethylene (MI=8 g/l, 0 minutes, density 0.9
50 g/CC) was extrusion coated to make a double-sided polyethylene laminate.

Next, a two-component polyurethane adhesive having the following composition was applied to the back side of the aluminum vapor-deposited film (the side opposite to the vapor-deposited surface) so that it would be 3 g/r& after drying, and it was heated at 100°C to After drying for minutes, this coated surface was combined with the low-density polyethylene surface of the double-sided polyethylene laminate paper, and heat and pressure bonding was performed at 80° C. and a pressure of 10 kg/cm.

Next, on the adhesive layer, a gelatin undercoat layer of about 0.1 μm was provided, and on the polyethylene laminate on the back side, an antistatic layer made of colloidal alumina and polyvinylidene chloride was provided.

Silver Halide Emulsion A-1 Preparation 1 20 g of lime-treated gelatin was added to 800+nA' of distilled water and dissolved at 40°C, and the p I-f was adjusted to 3.8 with sulfuric acid. Aqueous solution (I) was prepared by dissolving 2,0g of sodium chloride and 0.01 g of N,N'-dimethylethylenethiourea in this aqueous solution. Next, 125g of silver nitrate
500 mjl of distilled water! An aqueous solution (n)
And so. Additionally, 43g of thorium chloride and 0.25n of yellow blood salt.
+g and iridium hexachloride dipotassium salt 0.001
mg dissolved in distilled water 500mA to make an aqueous solution (I)
And so.

Aqueous solution (n) and aqueous solution (III) were simultaneously added and mixed over 55 minutes into aqueous solution (I) kept at 55°C. After removing excess salts from the dispersion of silver halide grains obtained by the above procedure by a coagulation sedimentation method, 40 g of lime-treated gelatin was added and dispersed again. This dispersion was spectrally sensitized by adding the following spectral sensitizing dye (V-1) in an amount of 4.2 x 101 mol per mol of silver halide, and then added to the silver chloride grains already formed by the halogen conversion method. Sulfur sensitization was carried out using N, N, N'-1-ethyl 2-thiourea to avoid the formation of silver bromide.

(V1) In the manner described above, a cubic silver chlorobromide emulsion 1-1 having an average grain size of 0.63 μm and a coefficient of variation of 0.09 and a silver chloride content of 99.3 mol % was prepared.

Preparation of Halogen Silver Emulsion B-1 Spectral sensitizing dye (
In place of V-1), the following spectral sensitizing dyes (V-2) and (V-3) were used at 3.0% per mol of silver halide, respectively.
8X10-' mol, and 7.0XlO-5 mol were used in the same manner as in Emulsion 1-1, except that the aqueous solutions (1), (II), and (II[) were added and mixed in the preparation method of Emulsion A-1. By adjusting the time, temperature, and stirring method, a cubic silver halide emulsion Bl having an average grain size of 0.59 μm, a coefficient of variation of 0.09, and a silver chloride content of 99.1 mol % was prepared (V2) (V-3). ) Spectral sensitizing dye used in the preparation of silver halide emulsion A-1 manufactured by
Emulsion A-1 was prepared in the same manner as in Emulsion A-1 except that 7.4 x 10 -5 mol of the following spectral sensitizing dye (V-4) was used per mol of silver halide in place of Emulsion A-1). By adjusting the addition and mixing time, temperature, and stirring method of the aqueous solutions (I), (n), and (III) in the preparation method, the average particle size was 0.54 μm, the coefficient of variation was 0.07, and the silver chloride content was 99.
A 5 mol % cubic silver chlorobromide emulsion C-1 was prepared.

(V-4) 5- Preparation of photosensitive material (sample number '''10) Using the support I prepared in the above method, a multilayer color photographic paper having the layer structure shown below was prepared.The coating liquid was as follows. It was prepared as follows.

19.1 g of yellow coupler (ExY), 4.5 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-7)
), 27.2 cc of ethyl acetate and solvent (So
lv-3) 2.7 g and solvent (Solv-1) 5.5
g was added and dissolved, and the Kono solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.

This emulsified dispersion and the emulsion (A-1) are mixed and dissolved,
A first coating liquid was prepared to have the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. l-oxy-3,5-dichloro-8-to6 lyazine sodium salt was used as the gelatin hardening agent for each layer.

For the red-sensitive emulsion layer, the following compounds were added at 2.6 x 10' moles per mole of silver halide.

For the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, 1-(5-methylureidophenyl)5-mercaptotetrazole was added at 8.0% per mole of silver halide, respectively.
5X10-'mol, 7.7XIO-'mol, 2.5X1
0-''mol was added.

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

Yellow dye SO+Na, magenta dye, and cyan dye ■ 9 (The number is the coating amount) (25°0■/ml': (50°0■/m') 00 (Layer composition) The composition of each layer is shown below.The numbers are Coating amount (g/rr1'
) represents. The silver halide emulsion represents the coated amount in terms of silver.

Support: Support I th layer (blue sensitive layer) Emulsion (A-1) 0125 Gelatin 0.98 Yellow coupler (ExY) 0.72 Color image stabilizer (Cpd-
1) 0. 17 Solvent (Solv-3)
0.10 solvent (Solv-1)
0.21 color image stabilizer (Cpd-7)
0.05 Second layer (color mixing prevention layer) Gelatin 0.75 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv
-1) 0.16 solvent (Solv-4)
0.08 Third layer (green sensitive layer) Emulsion (B-1) 0.13-1
01- Gelatin magenta coupler (ExM) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-9) Solvent (Solv-2) Fourth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) Solvent (Solv-5) Fifth layer (red sensitive layer) Emulsion (C-1) Gelatin cyan coupler (E x C) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-7) Color image stabilizer (Cpd-8) Solvent (Solv-6) 102- Sixth layer (ultraviolet absorbing layer) Gelatin 0.38 Ultraviolet absorber (UV-1) 0.16 Color mixture prevention agent (Cp
d-5) 0.02 solvent (Solv-5)
0.08 Seventh layer (protective layer) Gelatin 1.06 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%)
O,OS liquid paraffin
0.0203 (ExY) 1:1 mixture (molar ratio) with yellow coupler Ha 104- (Ex mixture of 2:11:4t (cpct-/) color image stabilizer (cp'a-,2) color image stabilizer 06 (Cpd-r) color image stabilizer H (cpct-F2 color image stabilizer (Uv −/ UV absorber CsH11(t) C4Hs(t) C4Hg (t) Nobi2=4t-Mixture (gold ratio) (Solv-t) Solvent (Solv-x) Solvent 09 2:l mixture ( Capacity ratio) (Solv-3) Solvent (Solv 4') Solvent (801Y-!) Solvent COOC8H17 (CH2)8 C00C8H1y 10 (Solv 6) Solvent A photosensitive material (10) was prepared in the manner described above.

Subsequently, in the method for preparing the photosensitive material (10), the method is exactly the same as that for the photosensitive material (10), except that instead of using the support I, the supports ■, ■ and the supports ■, ■ shown in Table 1 are used. Photosensitive materials (11) to (14) shown in Table 2 were prepared.

The above-mentioned irradiation prevention method is applied so that the reflection density on the photosensitive layer side of the unexposed and unprocessed photosensitive materials shown in Table 2 and above is 1°00 at 550 nm and 0.75.680 nm for all photosensitive materials. The amounts of magenta dye, cyan dye ①, and H added were adjusted.

A rectangular chart for measuring sharpness was printed on the photosensitive materials (lO) to (14) produced by Toyokosha in a manner better than Shisho value using a bow stretching machine, and the exposed sample was subjected to the following development process ( I)
It was processed using the following steps.

Processing process “Riojosori” top and color developer
38°C 5 seconds rinse ■ 38°C 5 seconds rinse ■ 38°C 5 seconds rinse ■ 38°C 5 seconds rinse ■ 38°C 5 seconds dry 65°014 seconds (rinse ■ [phase ) 1
12 The composition of each treatment liquid is as follows.

color developer Tank fluid replenishment fluid Water 800- Same as left Ethylenediamine-N, N.

N',N'-tetramethylenephosphonic acid 2.1g Triethanolamine 8.1g Potassium chloride 8.2g Potassium bromide 0.01g Sodium sulfite 0.14g Potassium carbonate 1
8.7g 4-Amino-3-methyl N-ethyl-N-(3 hydroxypropyl)aniline 2-p-1-luenesulfonic acid 12.8g Diethylhydroxylamine (80%) 6.3g Optical brightener (4 , 4-Sia 13 Same as left Same as left Same as left 37.0 g Same as left Same as left Same as left Same as left Same as left 37.0 g Same as left Same as left Same as left Same as left Same as left 37.0 g Same as left Add water 1.0007 nl Same as left pH (25 ° C) 10.05 ],
0.95 The replenishment amount of the above replenisher is 30 per meter of photosensitive material.
It was set as m1.

Naiwako Koyo Nitan Tank Liquid Replenishment Water 400 d 4
00 d Ammonium thiosulfate 100 d
250 d (70%) Ethylenediaminetetraacetic acid 3.4g 8.5g
Ethylenediamine tetratetradic acid iron I [I) ammonium dihydrate salt 73.0 g 183 g
Ammonium sulfite 40 g 100 g
Ammonium bromide 20.0g 50.0
g Nitric acid (67%) 9.6g Add 24g water
1000 d 1000 dpH (25
°C) 5.80 5.10 The replenishment amount of the above replenisher was 3014 ml per liter of light-sensitive material.

Yuno Tamao: Ion-exchanged water was used for both the tank liquid and the replenisher, and the replenishment amount was 55 mfl/rrr.

The development process in this example was carried out using an automatic developing machine. The features of the automatic developing machine in this case are: (1) Each processing bath has a liquid circulation mechanism that sprays tank liquid at a rate of 21 or more per minute toward the photosensitive layer surface of the photosensitive material; (2) The ratio of the surface area of the color developing bath where the developer is in contact with air to the total capacity of the developing bath is 0. 05c+yf/
mf! It must have the following structure: - During the process in which the photosensitive material enters the color developing bath and bleach-fixing bath, passes through the air, and enters the next bath, the air time and in-solution time of each bath are It must have a structure such that the ratio is 0.7 or less; ■ A plurality of liquid removal rollers are arranged between the final rinsing bath and the drying section to wipe off the liquid adhering to the surface of the photosensitive material. (1) Blowing dry air at a wind speed of 3 m/sec or more onto the photosensitive layer surface of the photosensitive material through a perforated plate or slit, and quickly blowing moisture-containing so-called screen air from the surface of the photosensitive material. Examples include having a drying section with a circulation mechanism for removing air.

The CTF value (0,
51i when the density difference at 21ine/mm is l
Table 3 shows the relative value of the density difference between thin lines (ne/mm).

Furthermore, using the same photosensitive materials (10) to (14), A3
Fifty sheets of the same size were prepared and developed (I) without being exposed to light. In this case, the photosensitive material exhibits the lowest density (that is, a white background), but if the photosensitive material or development processing is not appropriate, density unevenness often occurs on this white background. The degree of occurrence of this white background unevenness is also shown in Table 3. However, the degree of occurrence of uneven white background can be determined visually with the naked eye.
A sample with no unevenness on the white background was rated as ○, a sample with a slight amount of unevenness on the white background but no problem in practical use was rated as △, and a sample with obvious unevenness on the white background and unacceptable was rated as ×.

16 From the results shown in Table 3 and above, it can be seen that the image forming method of the present invention can provide a good image with excellent sharpness and no uneven white background in an extremely short development process.

An essential aspect of the present invention shown in this example is that a support is provided on at least one side with a hydrophobic resin layer containing 14% by weight or more of a titanium oxide pigment, and an irradiation preventing dye is used on the photosensitive layer side of the photosensitive material. The value of reflection density at 680 nm is 0. 7 or more, and the development process is performed while colliding a jet of the processing liquid against the surface of the photosensitive layer of the photosensitive material (hereinafter referred to as jet agitation).

117- If the CTF value shown in Table 3 is 0.03 or more, the difference can be identified under practical conditions, and if it is 0.05 or more, the difference can be easily recognized. Therefore, the inventive examples shown in Table 3 have clearly superior sharpness to the comparative examples.

The white background unevenness shown in Table 3 was good for all samples, but this was because in Example 1, jet stirring was performed in all treatment baths.

When carrying out the same development process as in Example 1 using the photosensitive material (11) of Example 1, a bleach-fix bath and a rinse bath
The evaluation of white background unevenness was carried out in the same manner as in Example 1 except that the stirring method (2) was changed as shown in Table 4 below, and the results are shown in Table 5.

118 Atsudou Omote 1 From the above results, in order to obtain the effects of the present invention, it is important to process the processing liquids of the bleach-fixing bath and the rinsing bath while colliding with the surface of the photosensitive layer of the photosensitive material as a jet stream. is clear. Here, method (2) is superior to method (4) and is therefore included in the present invention, but its effect is not sufficient, and the flow rate of the treatment liquid is preferably 21 or more per minute, preferably 51 or more. Although it depends on the shape of the processing apparatus, an excessive flow rate is undesirable from the viewpoints of transportability of the photosensitive material, scattering of the processing liquid, and stability over time.

The photosensitive materials (30) to 20 shown in Table 6 were prepared in the same manner as the photosensitive material (11) of Example 1 by changing only the amount of the anti-irradiation dye used.
(32) was created. In other words, for 470 nm, yellow dye, for 550 nm, magenta dye, 6
Regarding 80 nm, the amounts of cyan dyes (1) and (2) added were changed to obtain a predetermined reflection density.

The photosensitive materials shown in Table 7 and above were printed with rectangular charts for measuring sharpness using an enlarger in the same manner as in the evaluation in Example 1, and were processed in accordance with development process (I). However, in this case, the spatial frequency of the image for sharpness measurement obtained by processing is 0.
The color correction filter of the enlarger during exposure was adjusted so that the color at the 21ine/mm portion was gray.

21 Spatial frequency of the image for sharpness measurement obtained in this way: 5~] When observing the high frequency part of 61 in/mm with the naked eye, a bias in color tone may be seen in the blurred part of the image. This bias occurs when there is a large difference in sharpness between cyan, magenta, and yellow images, and appears as color blurring, which is not desirable in practice. Photosensitive material (
Evaluation of this color bleeding and Example 1 for 30) to (32)
Table 7 also shows the evaluation results for white background unevenness.

From the results shown in Table 7 and above, all of the photosensitive materials (30) to (32) show no white background unevenness, but there is a difference in color bleeding, and in order to obtain the effects of the present invention, it is necessary to The reflection density at 680 nm is 0°7 or more and the ratio of the value at 550 nm divided by the value at 680 nm is 1.0.
Below, the value at 4722 Onm is 0. It is preferable that it is 2 or more.

In addition, when the photosensitive materials (30) to (32) were developed by the process (4) in Table 4 of Example 2, uneven white background was observed in all of the photosensitive materials, making them unsuitable for practical use. I understand. Therefore, in order to obtain the effects of the present invention, it is necessary to direct the jet of the processing liquid onto the photosensitive material in at least the bleach-fixing, washing, and/or stabilizing processing baths of color development, bleach-fixing, water washing, and/or stabilizing processing. It can be seen that it is necessary to process the photosensitive layer while colliding it with the surface of the photosensitive layer.

The evaluations in the table above are as follows.

○ → No color bleeding is observed △ Li Some color bleeding is observed, but it is not a practical problem. ! In the same way as E4(1)),
=123 By changing only the amount of the anti-irradiation dye used, the photosensitive materials (40) to (43) shown in Table 8 were prepared.
)It was created.

Note that the amount of each dye added was adjusted in the same manner as in Example 3 so that a predetermined reflection density was obtained.

The above light-sensitive materials were evaluated for sharpness and white background unevenness in the same manner as in Example 1, and color bleeding was evaluated in the same manner as in Example 3. The results are shown in Table 9. Regarding the evaluation of white background unevenness, the results are shown in which the treatment bath was stirred in two ways, Table 4 of Example 2, treatments (1) and (4). For sharpness and color blur, use the above processing (
Since the same results were obtained for 1) and (4), only one type is shown.

24 From the results in Table 9 and above, first of all, the effect of improving sharpness (CTF) in the photosensitive material (40) is large, and this effect increases the reflection density on the photosensitive layer side of the photosensitive material to 1.0 or more at 680 nm. You can see that this can be achieved by doing. What is important here is that, like the photosensitive material (11) of Example 1, the photosensitive materials (40) to (42) are supported by the support (1) in Table 1.
The reason is as described in Example 1. Next, from the results of white background unevenness, it was found that in the case of photosensitive materials with inferior sharpness compared to the photosensitive material of the present invention, that is, in the case of photosensitive materials (41) to (43), white background unevenness was reduced even in processing (4). Therefore, there is no need to carry out processing while colliding a jet of processing liquid with the photosensitive material as in processing (1). Regarding color bleeding, there was no problem with any of the photosensitive materials (40) to (42), but this is because the reflection density on the photosensitive layer side of these photosensitive materials was 550nm from the value at 470nm.
This is because the value was set to gradually increase from the value at m to the value at 680 nm. Therefore, the photosensitive material (4
No. 0) to (43) do not have the problem of color bleeding in terms of practical sharpness, but the photosensitive materials (41) to (43) still have the drawback that the degree of sharpness itself is low, that is, the CTF value is low. The effect of the jet agitation of the present invention is that C
It is clear that this is remarkable for photosensitive materials with a high TF value and no brownish bleeding.

How to use the silver halide emulsion and how to use the water-soluble synthetic polymer (simply referred to as polymer in the following examples) in the method for preparing the photosensitive material (11) of Example 1 is described in Section 1 below.
A photosensitive material (20) was prepared in the same manner as the photosensitive material (11) except that the amounts listed in Table 0 were used. In this example, polyacrylamide (average molecular weight 100,000 to 100,000
200,000) was used. The amount of emulsion used is the silver equivalent coating amount (g/n
i').

Table 10 Photosensitive materials (11), (20) 27 Photosensitive materials (11), (20,) prepared as above
When the white background unevenness was evaluated in exactly the same manner as in Example 1, no white background unevenness was observed in any of the light-sensitive materials. Further, the same sharpness evaluation results as in Example 1 also showed that the performance was equivalent to that of the photosensitive material (11). The light-sensitive material (20) in this example has faster color development than the light-sensitive material (11), which is particularly preferable for extremely short-time development processing as in the present invention.
It is clear that the effects of the present invention can be reliably obtained even in such a photosensitive material.

Amount 1 A photosensitive material (11) was prepared in the same manner as in Example 1, except that the same automatic processor as in Example 1 was used and the following development treatments (II) and (I) were performed instead of development treatment (I). As a result of evaluation, it was confirmed that the image forming method of the present invention provides a clear image with no white background unevenness, similar to the result of the development process (1) in Example 1.

(For rinsing) A 3-tank AC type was adopted. ) The composition of each treatment liquid is as follows.

Water 800 Ethylenediaminetetraacetic acid-5゜6-cyhydroxybenzene 1, 2. 4-trisulfonic acid 0.3g Same as left Same as left 29 Triethanolamine 8.0g Thorium chloride 2.5g Sodium sulfite 0
．． 3g potassium carbonate 25.0gN-ethyl-N
-(β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline 0.5 g Diethylhydroxyl Amine 4.2g Fluorescent brightener (4,4-diaminostilbene type) 2.0 0.0g 12.0g Same as left Add water and pH (25°C) 000 d 10,10 Same as left Same as left

Claims (2)

[Claims] (1) At least one diffusion-resistant oil-soluble coupler that forms a dye by coupling with an oxidized product of an aromatic primary amine color developing agent and at least one high-boiling organic solvent are placed on a reflective support. After exposure, a color photographic material comprising at least one silver halide photographic emulsion layer containing an emulsified dispersion of lipophilic fine particles containing one type of oleophilic particles is subjected to color development, bleach-fixing, water washing and/or stabilization treatment. In a color image forming method in which the total step time is 20 seconds or more and 70 seconds or less, the silver halide photographic emulsion layer of the color photographic light-sensitive material is composed of a monodisperse silver halide emulsion containing 95 mol % or more of silver chloride. , and at least one side of the reflective support on the side on which the photographic photosensitive layer is coated is composed of a hydrophobic resin layer containing 14% by weight or more of titanium oxide, and the reflection density on the photosensitive layer side of the photosensitive material is 680n.
m is 0.7 or more, and the ratio of the value at 550 nm divided by the value at 680 nm is 1.0 or less, and the color development, bleach-fixing, washing and/or
Alternatively, in the stabilization process, at least in the bleach-fixing and water washing and/or stabilization process baths, a color image forming method is characterized in that processing is performed while a jet of a processing liquid is made to collide with the surface of the photosensitive layer of the photosensitive material. . (2) The processing step of the color photographic light-sensitive material is carried out after exposure.
Color development is carried out for at least 5 seconds and at most 20 seconds, followed by bleach fixing for at least 5 seconds and at most 20 seconds, followed by color development for at least 10 seconds and at most 30 seconds.
The color image forming method according to claim 1, wherein washing with water and/or stabilizing treatment is performed for less than a second.