JPH03156444A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide excellent sharpness, surface glossiness and mildew resistance by incorporating titanium oxide particles at >=14wt.% density into the water resistant resin layer on the side coated with silver halide photosensitive layers, specifying the optical reflection density at 680nm of the photosensitive material to >=0.70, using acid treated gelatin as the hydrophilic colloid of the uppermost nonphotosensitive layer and incorporating specific compds. into this layer. CONSTITUTION:The titanium oxide particles are incorporated at >=14wt.% density into the water resistant resin layer on the side coated with the silver halide photosensitive layers and the optical reflection density at 680nm of the photosensitive material is >=0.70. The acid treated gelatin is used as the hydrophilic colloid layer of the uppermost nonphotosensitive layer and at least >=1 kinds of the compds. selected from the compds. expressed by formulas I, II, etc., are incorporated into this layer. In the formulas, R<2> to R<7> denote a hydrogen atom, etc.; Y denotes a halogen atom; Z<1> denotes the nonmetal atom group necessary for constituting a thiazoryl group; n denotes 0 or 1. The photosensitive material having the excellent sharpness, surface glossiness and mildew resistance is obtd. in this way.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material using a reflective support with excellent image sharpness and non-image area whiteness. This invention relates to a color photographic paper that has excellent film quality and image storage stability, and is also suitable for rapid processing.

(Prior art) In recent years, with the spread of silver halide photosensitive materials, there has been an increase in the demand for silver halide color photosensitive materials that can be developed more quickly and easily and have superior finish quality compared to other image forming systems. Strong demands.

Regarding color print photosensitive materials, improvements have been made to dyes for color reproducibility, tone reproducibility, speeding up of processing, and prevention of irradiation.
145125, Kaimei 52-20830, Kaimei 50-
No. 147712, Kaimei No. 59-111641, Kaimei No. 61
-148448, Kaimei 61-151538, Kaimei 6
1-151649, Kaimei 61-151650, Kaimei 61-151651, Kaimei 61-170742, Kaimei 61-175638, Kaimei 61-235837,
Kaimei 61-248044, Kaimei 62-164043, Kaimei 62-253145, Kaimei 62-253146, Kaimei 62-253142, Kaimei 62-275262
No. 62-283336, Research Disclosure No. RD-17643 (December 1978, p. 22), and RD-18716 (No. 64, Nov. 1979).
There is a description of improvement of dyes in U.S. Pat.
Same No. 2882156, Same No. 2839401, Same No. 3
No. 706563, JP-A No. 55-33172, Kaimei No. 59
-193447, Kaimei 62-32448 Mei'tTI
It is described in A harm etc.

Color print photosensitive materials originally used baryta paper as a support. Recently, in order to speed up the development process, a water-resistant support in which ethylene is laminated on both sides of a base paper has been used. In order to maintain the whiteness of baryta paper plates, titanium oxide or titanium oxide whose particle surface has been treated with aluminum oxide or silicon oxide is used in the polyethylene layer, but the effect on image sharpness is not as good as that of baryta paper. Regarding the improvement of polyethylene layers containing titanium, for example, Japanese Patent Publication No. 58-43734, Japanese Patent Application Laid-Open No. 17433-1982, Japanese Patent Application Publication No. 58-14830, Japanese Patent Application Publication No. 6-6
1-259246, etc.

The upper water-resistant resin layer of the base paper has one or more 2! A method of applying a coating solution containing a bonded unsaturated organic compound and a white pigment to a base paper and curing it by heating and electron beam irradiation is disclosed, for example, in JP-A-57-27257 and JP-A-57. -49946,
It is described in JP-A No. 61-262738 and JP-A No. 62-61049.

Silver halide photosensitive materials using specular reflective or diffuse reflective supports are also known.
3-24251 to 24253, Kaikai 63-2
It is described in No. 4255, etc.

JP-A-63-63036 discloses that conventional photographic paper and high-sensitivity reflective color photographic paper have a transmittance density of less than 0.8! It has been shown that the deterioration of oxidation can be suppressed by providing an antihalation layer using colloidal silver. Furthermore, JP-A-63-63040 discloses that contact fog caused by colloidal silver that occurs during rapid development using a silver chloride-containing emulsion layer and a colloidal silver layer in a direct positive photosensitive material or a negative photosensitive material is avoided by preventing contact. It is stated that this can be prevented by providing an auxiliary layer.

In addition, color photographic materials are exposed to various environmental conditions during the manufacturing process, during and after the development process after exposure, and therefore the gelatin-based film that forms the photosensitive material may be optically damaged. It may not be possible to maintain a uniform film, resulting in minute irregularities on the surface or a decrease in the light transmittance of the film.

When such a phenomenon occurs, the beauty of an image is significantly impaired after the photograph is completed, and the designed performance cannot be fully demonstrated.

Furthermore, the color photosensitive material after processing can be used by putting it in a paper bag, pasting it on a paper mount, pasting it on a paper album, or sandwiching it in a paper mount.
Saved. In this case, mold may adhere to the surface of the treated color photosensitive material from the pasting side or paper fibers.
Under storage conditions such as high humidity, mold grows significantly, resulting in deterioration of the gelatin film on the surface of the color photographic light-sensitive material, resulting in image deterioration or discoloration of mold-adhered areas. In order to eliminate these drawbacks, techniques for adding benzoic acid formalin, citric acid, etc. to photographic light-sensitive material processing solutions have been known, but these have not been sufficient for practical use.

(Problems to be Solved by the Invention) Regarding silver halide photosensitive materials using a reflective support, especially color photographic papers using a first-class diffuse reflective white support, image sharpness and high resolution can be improved without deteriorating whiteness. The simple use of conventional anti-irradiation dyes or conventional colloidal silver anti-halation methods requires special efforts to visually improve the tonality reproduction of light details. There were problems such as the occurrence of fog, an increase in staining, residual color, and a decrease in sensitivity, and there was a limit to the ability to improve sharpness sufficiently.

The object of the present invention is to solve these problems, and the first object is to provide a photographic material using a white reflective material that has excellent image sharpness while maintaining the whiteness of non-image areas. The primary purpose of this is to provide color photographic paper that maintains beautiful gloss after processing and prevents mold from attaching and growing during storage.

(Next Means for Solving the Problem) The inventors have discovered that the above object can be effectively achieved by improving the white support used and the colloid layer provided thereon, and by improving the processing method.

That is, the object of the present invention is to compound a support substrate with a water-resistant resin layer, and then apply a layer on a reflective support.
At least one silver halide W & light layer and one non-photosensitive top layer... In Rogge/silver oxide color photographic light-sensitive materials, oxidation occurs in the water-resistant resin layer on the side coated with the silver halide light-sensitive layer. titanium particles are contained at a density of 1 cm weight or more, the optical reflection density of the photosensitive material at 4rOnrn is 0°70 or more and 69, and the non-photosensitive top layer uses acid-treated gelatin as a hydrophilic colloid, A halogen containing at least one compound selected from the compounds represented by the following general formulas (II) to (X):
The following was achieved using silver oxide color photographic materials.

General formula (II) General formula 11) General formula (fV) General formula (V) General formula (X) General formula (■) General formula (X) General formula (■) General formula (■) (wherein, B2. H, 3, 几 I R51 6. 几8 and R represent a hydrogen atom, an alkyl group, or an aryl group; group, sulfamoyl group, hydroxyl group, halogen atom, alkoxy group, and thiazolyl group. R is alkylene/group t7t is aryle/group), and R is halogen atom, or Referring to an alkyl group, 几14 and R represent a hydrogen atom, an alkyl group, an aryl group, or a nitrogen-containing heterocyclic residue. R16 and R are hydrogen atoms,
Alkyl group′! Alternatively, the aryl group may be truncated and R and R may be combined to form a benzene ring. R represents a hydrogen atom or an alkyl group.R represents an alkyl group or an aryl group.

Y represents a halogen atom, zl represents a nonmetallic atom group necessary to form a thiazolyl ring, and Z2 represents a nonmetallic atom group necessary to form a six-membered ring. n stands for 0 or l, and m stands for /1. ) (2) In the silver halide color photographic light-sensitive material,
(3) The above-mentioned silver halide color photograph, wherein the optical reflection a# at jJOnm is less than or equal to the optical reflection mw at Ar0r>m. In photosensitive materials,
The halog according to claim 1, characterized in that the optical reflection density at 70 nm is 0.20 or more.
Silver chemical color photographic material.

The present invention will be explained in more detail below.

The support in the present invention is characterized by containing fine particles of titanium oxide in a large amount, preferably /! Heavy weight 60 or more
It is to be dispersed in the water-resistant resin layer so that it is less than the weight of the powder.

The surface of the fine particles of titanium oxide is treated with an inorganic oxide such as aluminum oxide or aluminum oxide, and separately with a co- or μ-valent alcohol, such as JP-A No. 7/7/J-/. It is preferable to use the above-mentioned surface treatment with ≠-dihydroxy-co-methyl tan, trimethylolethane, or the like. The water-resistant resin layer containing titanium oxide fine particles is used in a range of 1 to 200 μm, preferably 1 to 200 μm. In this case, the next water-resistant resin layer containing the titanium oxide fine particles of the present invention may have different content rates, for example.
Alternatively, it may be laminated with a plurality of water-resistant resin layers containing other white pigments or containing no white pigment. In such a case, the water-resistant resin layer of the present invention containing titanium oxide fine particles should be placed in a layer far from the support (
It is preferable to install it on the side closer to the silver halide emulsion layer.

In the present invention, the occupied area ratio (phantom coefficient of variation) of fine particles of white pigment in the water-resistant resin layer is preferably O.io or less, more preferably O1/! or less, especially Q.

io or less is preferable.

The dispersibility of the white pigment fine particles in the resin layer is determined by scattering the resin on the surface of the resin to a thickness of approximately O6/μm, preferably about zooh, using glow discharge and scattering the exposed pigment fine particles. can be observed using an electron microscope, the area occupied by the image taken is determined, and evaluated by the coefficient of variation of the occupied area ratio (%). The ion sputtering method is described in Hiroshi Murayama-1 Kunihiro Aiki [Surface treatment technology using plasma], Machinery Research Vol. 33, No. 6 (/1/
(2013), etc., for details.

In order to control the coefficient of variation of white pigment particles to be less than O0λO, it is best to sufficiently knead the white pigment '#+ in order to make the surface active agent present, and the surface of the primary pigment particles should be ~
It is preferable to use a compound treated with dihydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area can be calculated by dividing the observed area into adjacent unit areas of 6 μm x 6 μm and projecting onto that unit area. It can be determined by measuring the occupied area ratio (%) (Ri) of the fine particles. The variation coefficient of the occupied area ratio (%) can be determined by the ratio s/12'' of the standard deviation S of Ri to the average value of Ri (tile).The number of target unit areas (n) is 6. The above is preferable.

Therefore, the coefficient of variation s/12″ is It can be found by

The water-resistant resin may contain white pigments other than titanium oxide. For example, barium sulfate, calcium sulfate, silicon oxide, zinc oxide, titanium phosphate, and aluminum oxide are preferably used as white pigments.

The inlaid support used in the silver halide photographic light-sensitive material of 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 film such as polyethylene terephthalate or polybutylene terephthalate, plastic film such as cellulose triacetate film, polystyrene film, polypropylene film, or polyolefin film can be used.

The base paper used in the present invention is selected from materials commonly used for photographic paper. That is, needle 51! The main raw material is natural pulp selected from trees, hardwoods, etc., and fillers such as clay, talc, calcium carbonate, urea resin fine particles, etc., as necessary.
Those to which rosin, alkyl ketene dimer, higher fatty acids, paraffin wax, sizing agents such as alkenyl succinic acid, paper strength agents such as polyacrylamide, fixing agents such as sulfuric acid, cationic polymers, etc. are added are used. In particular, using reactive sizing agents such as alkyl ketene dimer and alkenyl succinic acid, pH 5 to 7 (neutral paper measured with a pH meter using flat GST-5311F manufactured by Toa Denpa Kogyo Co., Ltd. as an electrode). Furthermore, a synthetic pulp may be used in place of the above-mentioned natural pulp, or a mixture of natural pulp and synthetic 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, carboxymethyl cellulose, polyacrylamide, modified polyvinyl alcohol, or the like.

Examples of polyvinyl alcohol modified products in this case include carboxyl group modified products, silanol modified products, and copolymers with acrylamide.

In addition, when surface size treatment is performed using a film-forming polymer, the coating amount of the film-forming polymer is 0.1 to 5.0 g/m
', preferably adjusted to 0.5 to 2.0 g/m'. Furthermore, an antistatic agent, a fluorescent whitening agent, a pigment, an antifoaming agent, etc. can be added to the film-forming polymer at this time, 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 the surface size treatment is performed after drying, this calender treatment can be performed either before or after the surface size treatment.

Whether the base paper used for the support substrate of the present invention is neutral paper or not, for example, the flat paper GST-5313F manufactured by Toa Denpa Kogyo @
This can be determined by measuring the pH value using a . Neutral paper is p
The H value is 5 or more, preferably 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 0.1 or less, such as polyalkylene resins (polyethylene, polypropylene, and copolymers thereof), vinyl polymers and copolymers thereof (polystyrene, polyacrylates, copolymers thereof, polyesters and copolymers thereof, etc.). .Preferably,
Low-density polyethylene, high-density polyethylene, polypropylene, and blends thereof are used as polyalkylene resins. A fluorescent brightener, antioxidant, antistatic agent, release agent, etc. are added as necessary.

For example, JP-A No. 57-27257, No. 57-49 of the same town.
As described in No. 946 and No. 1-262738, unsaturated organic compounds having one or more polymerizable carbon-carbon divalent polymers in one molecule, such as mekuacrylic acid ester compounds, Zintry or tetra-acrylic acid esters represented by the general formula in No. 61-262738 can be used. In this case, after being applied onto a substrate, it is cured by electron beam irradiation to form a water-resistant resin layer. Titanium oxide and other white pigments etc. are dispersed in this unsaturated organic compound. It is also possible to mix and disperse other resins.

6. The method of coating the water-resistant resin layer of the present invention is, for example, the laminator method described in the Processing Technology Research Section "New Laminating Processing Handbook", such as dry lamination, solvent-free dry lamination. Application methods include gravure roll type, wire perper type, doctor blade type, reverse roll type, day hook type, air knife type, calendar type, kiss type, squeeze type, fantine type, and coating type. Can be selected from and used.

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 a s o g/cd.
(about 30 to 400 μm), more preferably about 50 to 200 g/d.

The optical reflection degree in the present invention is measured by a reflection meter 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 allow the light to pass through the sample to prevent measurement errors due to 15 degrees.

Optical reflection density = log1° (FO/F) Fo: Reflected light flux of standard white plate F Reflected light flux of two samples The optical reflection density required in the present invention is 610 of the photosensitive material.
0.70 or more is required at the measurement wavelength of nm, preferably 0.7 or more, θ or less, and more preferably o, r
Above 1. less than or equal to 1, most preferably /, 0 or more 1. is below. Optical reflection density and el at 2j0nm
The ratio of Onm to that is preferably l or less, more preferably o, r or less, and even more preferably IL< is 0.6 or less,
Most preferably, Q is less than or equal to O1j, and is more than or equal to 2. 4 more
The degree of optical reflection at 170 nm is preferably 082 or more and 1.1 or less, and more preferably 013 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. t7tThere 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 for achieving 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 by dissolving them in water or alcohols such as methanol.

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

Shea/Dyeing Ri 0~ioo~/m (Most preferred noble) Magenta dye; 0-j 01Ni/m" (Preferable 1st amount) 0-/Om
g/m'' (most preferred amount) Yellow dye; The effect of the present invention is more pronounced by having it diffused over all floors during the period from application to drying 1 than by fixing it to a specific layer, and manufacturing costs increase due to providing a specific layer. It is also preferable from the viewpoint of preventing.

Such dyes include, for example, British patent no. 06.3
No. 11, same/, /77,! J5' issue, same/.

3ti, grit issue, same/, 331,7? No., same/,
Jlj, No. 37, same/, 4c67,. 2/44 issue,
Same/, No. 4433.102, Same/, jj3. ! lt issue, JP-A-Shosan t-rj, iJo issue, same≠2-//μ, Hiroλ
θ No., same jλ-//7. /Ko No. 3, same as j-iti, 2
No. 33, same ter iii, 6p.

No., Special Public Show 3 Turco λ, No. 06, Same Gu J-/J.

No./6, Core No. 62-273j, U.S. Patent No. 3, Co4c7. / Core issue, same J, 1749.911, same ≠
, No. 071,233, etc., oxonol dyes having pyrazolo/nucleoyaharbituric acid groups, US Patent g-
2,! 33, $7-No. 3.37P, No. 133,
British Patent No. 1. Core T, 6 Co No. 1, etc. 9 Other oxonol dyes, UK Percent No. J7J, 4F/No. 4, Same 4
! 10.63/issue, Touj Tata, 6λ3 issue, 716. Ri No. 07, same 07.1λ! No., lWJ/, 0 Hiroz,
toy No., US Patent No. ≠, -2! J, J2 issue, Tokukai Sho! Azo dyes described in Tar 2/i, Oko No. 3, etc., JP-A-Sho! o-1oo, lit issue, same! Dar IIT, AP No. 7, British Patent No. 1 2,0/4T,! Riwo issue, same fujQ.

031, etc., anthraquinone dyes as described in U.S. Pat.
First US patent! Jlf, 00'? No., IWI Co., tr
y, z g No. 1, same, JJI, No. 001f, British Patent No. 5t da, No. 602, pfJ/, 210° coj co, Japanese Patent Application Publication No. 10-4AO, No. 621, same! l-3,6 J No.,
Same pi-1o, P27 issue, same! 41-//I, Koμ7, Tokuko Akihiro l-3. λJ'4, same jter 37. J.O.J.
Ally IJ De/Dye, Tokko Akiko, r-
J, C# Ko No., same g44-/A, j9'1 No., same! ? -Jr., 1911, etc., styryl dye, British Patent No. 1.

No. 113, same/! ! ! , Hiroko 2, Tokukai Akira! tar2λ
g-ko! Triaryl meta/dye described in No. 0 etc.,
British Patent No. 1.07! , 4!3, 1kawal, Ar3.
, iai issue, same/, Jra, 730 issue, same/, ≠7, 2 pieces! No., same/, o-,? Specific merocyanine dye described in No. 07 etc., U.S. Patent No. 7,! ≠31 Hirot 6, 3
,2ri≠,! Examples include 7ani/dye described in No. 3.

Among these, dyes that can be particularly preferably used in the present invention have the following general formulas (X), (XI), (X[1),
(Xlll), (XIV) or ti(XV)teffl dyes, most preferably general formulas (X-a), (
X-b) or a dye represented by the general formula (XI[).

General formula (X) In the formula, 2.22 may be the same or different, and each represents a nonmetallic atomic group necessary to form the complex flA, and L
l, L2. L3. L, ,L, represents a methine group, 0□
+ n 2 represents O or /, and M■ represents hydrogen or other monovalent cation /.

General formula (XI) In general formula (M), X and Y may be the same or different, and contain an electron-withdrawing group, and X and Y are connected to each other.
It may form a ring.

几, R4□ may be different if they are the same, hydrogen atom, hydrogen atom, alkyl group, alkoxy group, droxy group, carboxyl group, substituted amine group, carbamoyl group, nulphamoyl group, alkoxycarbonyl group, Sulfo group tiwasu.

几 , 几 and 4 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 %kL43 and R44 are connected! ~ may form a member ring.

'! 7(,)t and , R4□ and '44 may be respectively connected to form a j~ membered ring.

The above X, Y, R%B,)1. , l(,
At least 7 of 4 have a sulfo group or a carboxyl group as a substituent.

L%, L, and 3 each represent a methine group.

k is O or / to kimono.

General formula (Xll) Ar 1-N=N-Ar 2 In the formula, Ar Ar2 may be the same or different,
Refers to an aryl group or a heterocyclic group.

General formula (XIn) General formula (XIV) In the formula, 几51 R54B, 55 and B58 may be the same or different from each other, and a hydrogen atom, 几/, l
(// and -It may be different from each other, and each represents a hydrogen atom and at least -3 nurphonic acid [7j is a carboxyl group, a qualkyl group, or an aryl group].

R52, 几53, B56 and B, 57 may be the same or different from each other, and represent a hydrogen atom, a nurphonic acid group,
An alkyl or aryl group having a carboxyl group or at least one sulfo group or a carboxyl group.

In the formula, L and L' are substituted or unsubstituted methine groups, and the primary nitrogen atom is 0. /, , to wear 2 or 3.

Z is pyrazolone nucleus, hydroxypyrido/nucleus, barbituric acid group, thiobarbital acid nucleus, dimed/nucleus, I/da/
-/, j-geo/nucleus, rhodanine nucleus, thiohida/toi/nucleus, oxazolidine-μm-o/-λ-thio/nucleus, homophthalimide nucleus, pyrimidi/2. l-dione nucleus%'lλl
J l Hiro-Tetrahydroquinoli/-2, Hiro-Geo/Nuclear,
The group of nonmetallic atoms necessary to form .

Y is oxazole nucleus, be/dioxazole nucleus, naphthoxazole nucleus, thiazole nucleus, be/dithiazole nucleus, naphthothiazole nucleus, be/zoselenazole nucleus, pyridi/nucleus, quinoline nucleus, be/siimidazole nucleus, naphthoimidazole nucleus, imidazo A group of nonmetallic atoms necessary to form a quinoxaline nucleus, a di/doreni/nucleus, an inoxazole nucleus, a be/diinoxazole nucleus, a naphthoisoxazole nucleus, an acridi/nucleus, and Z and Y further have a substituent. You may do so.

General formula (XV) In the formula, 7t and 9' are the same and 1fc may be different, and represents a substituted or unsubstituted alkyl group.

Ll, B2, L3t- may be the same or different from each other, substituted or unsubstituted methyl/groups are excluded, and m is 0.
1%λ or t measures 3.

z, z' may be the same as each other and may be different, substituted or unsubstituted complex! Member ring 19 excludes the nonmetallic atomic group necessary to form a 6-membered hetero ring, and l and n are 019 and /
It is.

Xe causes anion to thorn. p stands for/and when the compound forms an inner salt, p is/.

Each dye will be explained in detail below.

In general formula (X), the heterocycle formed by the nonmetallic atom group that is affected by zl and Z2 is! Alternatively, a 6-membered ring is preferred, and may be a single ring or a fused ring, such as pyrazolo/, 6-hydroxypyridone, pyran (j, $-
b) Pyridi/-j, 6-dione, barbylic acid, pyrazolidinedio/, thiobarbital acid, rhodani/, imidazopyridi/, pyrazolopyrimid/, pyrrolidone, pyrazoloimidazole, and the like.

The methine group represented by L
sulfoethyl, carboxyethyl, dimethylamino, cyano), or the substituents may be linked together or form a t-membered ring (for example, cyclohexe/, cyclopentene, !, j-dimethylcyclohexene). good.

Heptavalent cations other than hydrogen that are stimulated by Me are ff1
Jt#fNa", 'f' 1-tNe (c2H5)
3 Among the dyes represented by the general formula (X), the most preferred ones are the following general formulas (X-a), (X-b), and (X-C).
, (X-d) or (X-e).

General formula (X-a) In the formula, R and R3 represent an aliphatic group, an aromatic group, or a heterocyclic group, and R2 and R4 represent an aliphatic group, an aromatic group, and -(JR
-cuukL5, -NkL5, -C(JNR,R-
NRC(JNR5几6.5 6S 5 -8(J2 7, -cuh7, -NI(,6C(JR7
, -NR802R7, cyano group (herein, R5, R6 are water, aliphatic group or aromatic group, R7 is aliphatic group or aromatic group, 几, and R6 or R6 and R7
Connect! Or even if it forms a 6-membered ring. ], Ll, R2, R3, R4, R5 and nl, R2,
Me has the same meaning as defined in general formula (X).

General formula (X-b) In the formula, l(, R14 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -NR17R18, -NRCUNRB,
, -NRCUR□0.17 17
18 1g or -NR18S02R19, "12, RIs are each hydrogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, sulfonic acid group, -NR17
R18, -NRCUR-) 118802R 0.18
19% -NRCONR17E□8, -CUOR□7, -CON
RR-CUR-802R.

17 18% l'1 or -8 (J
2NR17R18 represents ・”13・几□6 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -okLl,
-C(J(JR1□, -C(JR□0,'''''C0NR
1, R18・-NfL17 R18・-NR,8COI
-L engineering, or -NR□88O□R19, -N)l,
C(JNRR-8O2R, 8,171718% -80NR), -(JR7 or cyano group) (herein, □7 and kL18 each represent a hydrogen atom, an aliphatic group, or an aromatic group, R1, may carbonate an aliphatic group or an aromatic group, and R and R may be connected to each other to form a 6-membered ring.) Lll L2
% R3・R4・R5, nl, R2, MIa) Fi Same as the definition in general formula (X).

General formula (X-C) In the formula, 几 and 1t24 each represent an aliphatic group, an aromatic group, or a heterocyclic group, and 25 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, respectively. group, C0) t29 or SO2
3 and '26 are hydrogen atoms, cyano groups, alkyl groups, aryl groups, -CIJ (JR%-
0R27, N R27R2s, -N(R28)C(JR
20, -N (R28) S, (J2几28, -CUN
R. 7R28, or -N(R27)CON 27R28
CR29 represents an aliphatic group or an aromatic group, approximately 27
, '28 each represent a hydrogen atom, an aliphatic group, or an aromatic group f, ), Z is an oxygen atom or NR, Z is an oxygen atom or NR (R,, R3□ is connected to 几 and R24, respectively) The nonmetallic atomic groups necessary to form a membered ring are destroyed, and Ll, R2, R3, R4, R5, nl
, R2, Mea have the same meaning as the definition in general formula (X). However, “21, 几, R 几 R, RL 22 23% 24% 25
26 S 1 %L2, R3, R4 or R
At least one of 5 is a group carrying at least 7 carbo/acid groups or sulfo/acid groups.

General formula (X-d) In the formula, R, R, R 313233/fL34 each represent 4 hydrogen atoms, an aliphatic group, an aromatic group, or a polycyclic group, and L
1, R2, R3, R4, R5, nl, 2, and Me have the same meanings as defined in general formula (X).

General formula (X-e) In the formula, R and R% 几 are respectively fatty 35 36 37 嘱 38 aliphatic group, aromatic group, t7t is a heterocyclic residue, R41, L4
□, R43 are methi/groups, respectively.

n4□ is 7% 21st order is 3. However, 几, 5, '36
, kL37% 几, carboxyl group t7 in either of 8
t has a nulpho group, and the total number is at least two or more.

Next, general formula (X-a) will be explained in detail.

The aliphatic group to be moxibusted with R3, B4, R5, H6 and R7 may be any straight chain, branched or cyclic alkyl group, aralkyl group, or alkenyl group, such as methyl, ethyl, etc. , n-butyl, be/zyl, cornulfoethyl, darnulphobutyl, -monosulfobenzyl, cocarboxyethyl, carboxymethyl, trifluoromethyl, dimethylaminoethyl, cohydroxyethyl, and the like.

Examples of the aromatic group represented by 几l, 几2, R3, R4, R5, R6, and R7 include phenyl, naphthyl, ≠-
Sulfo7enil, 3-Nurho7enil, λ,! Examples include -disulfophenyl, ≠-carboquinphenyl, z,y-disulfo-3-naphthyl, and the like.

Among them, if □ = / or - and n = 0,
Preferably, each of the phenyl groups of 几1 and R2 has two or more nulfonic acid groups.

Multi-ring groups affected by 几□ and 83 should be j or 6-membered nitrogen-containing heterocyclic groups (including fused rings), PJ, t[-sulfopyridin-2-yl,! -sulfobenzothiazole-λ-yl and the like.

It is formed by connecting 几, and R,, R, and R7! or 6
Examples of the membered ring include a pyrrolidine ring, a pyrrolidine ring, a pyrrolido/ring, and a morpholine ring.

Examples of dyes represented by general formula (X-8) are shown below, but the present invention is not limited thereto.

These dyes are described in British Patent No. J04.311, ibid.
No. 177.722, same/, J! r, 7 Tata No., same/,
31j, 37j No. 1, ≠67, λ/≠ No. 1, 4
c3! , No. 102, same/ , jjtJ.

sit issue, Tokukai Sho≠r-rriJo issue, same jj-/4/
No. 233, same! It can be synthesized by the method described in λ-20330, 1/27J127.

Next, the dye represented by the general formula (X-b) will be explained in detail.

R, R%R% 几 R1K 11 12 13 14%
The aliphatic group represented by 15 or 19 is, for example, methyl, ethyl, isopropyl, λ-chloroethyl, trifluoromethyl, be/zyl,
Cosulfobenzyl, ≠-sulfo7enethyl, carboxymethyl, -monocarboxyethyl, cosulfoethyl,
Examples include groups such as λ-hydroxyethyl, dimethylaminoethyl, and cyclointhyl.

R11%R12・R13・R14・”15・”16
・The aromatic group contained in R 几 or '19 is 17%
18 PI, t[phenyl, naphthyl, 3-sulfophenyl,
≠-sulfophenyl, i, r-synulfophenyl, ≠-
Examples include groups such as (3-nulfopropyloxy)phenyl, 3-carboxymphenyl, and λ-carboxyphenyl.

Ordinary□l・Ordinary 1□、R 3・"14・"15 or kL
Examples of the heterocyclic group represented by 16 include copyridyl, morpholino, j-sulfobe/shiimidazol-λ-yl, and the like.

It is formed by connecting R□7 and ordinary□8 or R-work, 几, and 9! Alternatively, examples of the 6-membered ring include a piperidine ring, a pyrrolidine ring, a morpholine ring, a pyrrolido ring, and the like.

Specific examples of the dye represented by the general formula (X-b) are shown below, but the present invention is not limited thereto.

b-/) (b-1/-) b-2) (b-t) (b-6) C) i2CH28u3Na CH2CH2SO3Na (b-7) (b-10) CH2CH2SO3Na Cf”12CH2SO3Na (b-r (b- ii Ct-i2cH2ut-t CH2C1-42(J)1 CH2CH2SO3Na CH3CH2Exi 3 Na (b-/ko) (b-F) (b-/J (b-/, A) (b-/≠) (b- / 7) (b-/j) (b-tr) UF1□L: 1-12 mountain 2Utt U) i2C) f2L'H2 (JH (b-/ri) b-20) S (δ to J3 (to J3 The dye represented by the general formula (X-b) is a British patent/2.
71, j, 2/issue, same/,! /2.163, same/
,! It can be synthesized by the method described in 7.

The arrow says, ``The general formula (X-C) will be explained in detail.

21, 2□, R23, '%'25, '26, I(
lIL24 About 27% of aliphatic groups covered by R and R2,
28 may be a straight chain, branched or cyclic alkyl group, aralkyl group, or alkenyl group, such as methyl, echya, n
-Methyl, be/zyl, cosulfoethyl, ≠-nurfobutyl, λ-sulfobe/zyl, 2゜≠-disulpobe/zyl, λ-carboxyethyl, carboxinmethyl, -monohydroxy/ethyl, dimethylaminoethyl, trifluoro Examples include methyl and the like.

几・几22・kL23・'24・'25・'26
・The aromatic group represented by R, R and '29 is tehaphenyl, naphthyl, Hiro-sulfophenyl, J,! -Disulfophenyl, glucarboxyphenyl,! , 7-dinurpho-3-naphthyl, ≠-methoxyphenyl, 1)-)dyl, and the like.

The multicyclic group represented by R1, R%RJ25 is j
Or a t-membered nitrogen-containing heterocyclic group (including fused rings), a full sulfopyridi/-coyl,! Examples include groups such as -sulfobenzothiazole-coyl.

When Z is NR, Z or R3□, the j-membered ring formed by linking 几 and R, R31 and ``24'' includes, for example, an imidazole ring, a benzimidazole ring, a triazole ring, etc. Substituents [e.g. carmenic acid group, sulfo/acid group, hydroxyl group, halogen/atom (e.g. F,
α, Br, etc.), alkyl groups (eg, methyl group, ethyl group, etc.), alkoxy groups (eg, methoxy group, ≠-nurhobutoxy group, etc.), etc.).

Specific examples of the dye represented by the general formula (X-C) used in the present invention are shown below, but the present invention is not limited thereto.

Dyes that are affected by the general formula (X-C) are, for example, the Tokuko Sho 3F
-2Joty, Dohiroj-JjOHiro, jJ-JJ'O
J4 issue, 7414-3112 issue, same! Yo-100 issue, Tokukai Show μ Tata yt JO issue, same! No. 1tr3 or U.S. Patent No. μ.

/II, No. 221, etc. can be used for synthesis.

Next, general formula (X-d) will be explained in detail.

The aliphatic groups represented by R3□, R3□, ``33, and kL34 have the same meaning as the aliphatic groups defined in 4, R2, R3, and R4 of general formula (X-a).

The aromatic groups represented by 3□, 32, '33, and 34 are R1, 2, 3, and 3 of the general formula (X-a). 21 which is synonymous with the aromatic group defined in ! Subtract c by six.

The heterocyclic group represented by R, R, 2, and R34 has the same meaning as the heterocyclic group defined for R1, 2, and 3 and R4 in the general formula (X-a).

Specific examples of the dye represented by the general formula (X-d) are shown below, but the present invention is not limited thereto.

These dyes are described in U.S. Patent No. 3. λ≠7. /-7, f
elJJ, 444P, No. 911, same J, l,! !
.

It can be synthesized by the method described in No. 03, No. 071,233, etc.

Next, general formula (Xe) will be explained in detail.

Substituent of dye represented by general formula (X-e) 35 3
6, R37・38 is an alkyl group (Example 1-L, R, methyl, ethyl, carboxymethyl, co-carboxyethyl, co-hydroxyethyl, methoxyethyl,
Cochloroethyl, be/zyl, λ-sulfobe/zyl, Hiro-sulfo7enethyl), aryl group (phenyl, ≠-sulfophenyl, 3-sulfophenyl, λ-sulfophenyl, ≠-carboxyphenyl, 3-carboxyne) phenyl, hydroxyphenyl) or heterocyclic residues (eg, cobiridyl, coimidazodyl).

L %L, L43 represents a methi/group, and these methine groups independently represent methyl, ethyl, phenyl, chlorine atom,
It may be substituted with sulfoethyl, carboquinethyl, etc.

'41 is 11, 3 people.

However, is at least one primary carboxyl group in any of R35, "36,"37, and R38 a nulpho group? ! death,
The total is at least two or more. These primary carboxyl groups and nurpho groups may form not only free acids but also salts (eg, Na salts, K salts, ammonium salts).

Next, specific examples of the dye general formula (X-e) used in the present invention will be shown, but the present invention is not limited thereto.

(, e-/) (e-λ) (e-J) 803f'11a (e-4) (e-r) δU3Na (e-da) (e-7) (e-2) (e-70) (e-/I) Next, the dye represented by the general formula (l) will be explained in detail.

The electron-withdrawing groups represented by X and Y include cyano group,
Carboxyl group, alkylcarbonyl group [preferably 7 or less carbon atoms, for example acetyl or propionyl, which may have a substituent (for example, a halogen atom such as chlorine)]
, arylcarbonyl group [The aryl group is preferably a phenyl group or a naphthyl group, and all substituents may be present. Examples of substituents include sulfo groups, carboxyl groups, hydroxy groups, halogen atoms (e.g., chlorine, bromine), cyano groups, alkyl groups (e.g., methyl, ethyl), alkoxy groups (e.g., methoxy, ethoxy), carbamoyl groups. (e.g. Eva, methylcarbamoyl), sulfamoyl group (
ethylsulfamoyl), nitro groups, alkylsulfonyl groups (e.g. meta/sulfonyl), arylsulfonyl groups (e.g. echabe/ze/sulfonyl), amino groups (e.g. dimethylamino), acylamino groups (e.g. acetyl amino, trichloroacetylamine), nurphonamide IN (for example, methanesulfonamide)], alkoxycarbonyl group (optionally substituted alkoxycarbonyl group, preferably having 7 or less carbon atoms, for example , ethoxycarbonyl, methoxyethoxycarbonyl), aryloxycarbonyl group (aryl group is preferably phenyl group or naphthyl group, all of the substituents explained in the section of arylcarbonyl group may be present), carbamoyl group (substituted IH is a carbamoyl group which may have a carbon number of 7 or less.
J, t, methylcarbamoyl, phenylcarbamoyl, 3-nulphophenylcarpamoyl), alkylsulfonyl group (optionally substituted alkylsulfonyl group, for example, meta/sulfonyl), arylsulfonyl group (substituted an arylsulfonyl group which may be filmed, such as phenylsulfonyl, sulfamoyl (an optionally filmed arylsulfonyl group, such as ethylsulfamoyl, ≠-chlorophenylsulfamoyl), Can be mentioned.

17+H1x%Y are connected to form a ring (e.g., pyrazolone ring, pyrazolotriazole ring, oxindole ring, isoxacilone ring, barbital acid ring, thiobarbital acid ring, i/da/dio/ring, pyridone ring) t'' A preferred ring is pyrazolo/ring.

R41%'4□ is a hydrogen atom, a halogen atom (for example,
chlorine, bromine), alkyl groups (optionally substituted alkyl groups preferably having carbon numbers of j or less, for example methyl, ethyl), alkoxy groups (optionally substituted alkoxy groups preferably having carbon numbers of j or less) , for example methoxy, ethoxy, cochloroethoxy), hydroxy group, carboxyl group, substituted amino group (for example acetylamino, methylamine, diethylamino, meta/sulfonylamino), carbamoyl group (optionally substituted carbamoyl group) , for example methylcarbamoyl), sulfamoyl group (optionally substituted sulfamoyl group, for example ethyls/L-7 amoyl), alkoxycarbonyl group (for example methoxycarbonyl)1. Represents a sulfo group.

R43% R44 is one hydrate atom one alkyl group (optionally substituted alkyl group, preferably the number of carbon atoms is as follows, such as methyl, ethyl, propyl, butyl,
Examples of substituents include sulfo group, carboxyl group, halogen atom, hydroxy group, cyan group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, acyloxy group, acylamino group, carbamoyl group, sulfamoyl group, alkylamino group, and dialkylamino group. , an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a nulfonamino group, a ureido group, an aryl group, and the like. ), alkenyl group (an optionally substituted alkenyl group, for example, 3-hexenyl), aryl group (the aryl group is preferably phenyl group, and in the section of carbonyl group for X and Y) may have the mentioned substituents),
Acyl group (acetyl, benzoyl), sulfonyl group Cf
1lJjr-1d, ) evening/sulfonyl, phenylsulfonyl) is a disaster, '43, R44! ~6-membered heterocycle (eg, piperidi/ring, morpholine ring, etc.) may be formed.

Also, R and ordinary, R and R are respectively Connected! ~ may form a heterocyclic ring.

Above X, Y,) LS 几 , R 几 Nou 41 4
2 43% 44 At least one of them has a sulfo group or a carboxyl crystal. Sulfo groups and carboxyl groups can be used in free form or in salt form (e.g. Na salt, K salt, (
C2H5)3NH salt, pyridinium salt, ammonium salt].

The methy/group represented by L1□, L12, L□3 does not matter even if it has all substituents (eg, methyl, ethyl, cyan, phenyl, chlorine atom, sulfoethyl). k represents ol or l.

Specific examples of dyes represented by general formula (M) used in unexploded BAVc are shown below.

XI-/ X-ko XI-J X-da Ha XI-7 XI-r XI-6 XI-7 l-10 b Oa Na X-2!
It can be easily synthesized by the method described in No. 23 and the like.

Next, the dye represented by the general formula (Xl[) will be explained in detail.

Ar The aryl i represented by Ar2 is preferably a phenyl group or a naphthyl group [e.g., a nulphonic acid group, a carbo/acid group, a hydroxyl group, an alkyl group with a carbon number of 1 to 2 (e.g., methyl, ethyl, n- (propyl, inpropyl), carbon T, alkoxy groups (e.g., methoxy, ethyne, butoxy), carbamoyl groups, nulfamoyl groups, hydrogen atoms (e.g., F1a, Br),
Cyano group, nitro group, etc.] may be included in 1.

The heterocyclic group represented by A r A r 2 is! Also, 1% is preferably a 6-membered @nitrogen heterocycle, for example, /-(≠
-sulfophenyl)-3-car〆* -, y -! -Hydroxy-Kuhirazolyl, /-(4(-sulfophenyl)-3-methyl-!-Hydroxy-Kuhirazolyl,
'(Co,j-disulfophenyl)-3-carboxy-yo-hydroxy-hiro-pyrazolyl, l-carboxymethyl-3-carbamoyl-/, -1-dihydro-3-hydroxy-hiro-methyl-λ-oxopyridine, i −<a
-sulfoethyl)-3-cyano-/,2-dihydro-6
-Hydroxy-≠-methyl--okinepyridine, etc. can be mentioned.

Specific examples of the dye represented by the general formula (XI[) are shown below.

Kari-7 Kari-2 b (J a Na Kari-lko■-14! U3Na 5 Us Na (J)i ■-2 Kari-/ Kari-is Kari-77 ■-/1 α Kari-/P Kari-ichi 3 Kari-λQ C) 12C) 12S (J3 ni■-Kohiro C) i□ C00N a Kari-Ko Yo Kari-λK103Na S (J a Na is expressed by the general formula (Xll) The dye has British patent No.XI
[I-j 7 6-7, same 07゜l-5, same/! It can be synthesized by the method described in No. 3121.

Next, specific examples of dyes represented by the general formula CXm) will be shown.

Xm-Hiroshi x■2/ Xm-λ ■−Otsu XII[-7 Next, specific examples of dyes represented by the general formula 0GV) will be shown.

XfV −/m−r X■−ta(CH2)3SO3Na .

X■−≠ to SO3a ■-ta to 803a XIV-/　0 XIV-/ X■-12 (C)12) 3 8 () a N a XM-/7 (CH2)20C)i3 ■-/r XIV-/J XIV-/4L S　U　a　N　a XIV-IP s　u　3　N　a XV-Coco XV-ko≠ SO2N3 XV-ko Next, specific examples of dyes destroyed by general formula (XV) will be shown.

(C)12)3SO3” (CH2)3803Na IV-Jj XV-27 C) 12C) 12S (73K XV-j XV-μ XV-Z (C)12), 8(J3” (Ut-i2) 3 people playing 4 games XV-6 W-ta (C)12)3S(J3e (C)12)3803K XV-i.

XV"-7 (CH2)3SO3K XV-it v -r (C)1□) 4803K XV-/λ The acid-treated gelatin used will be explained.

The acid-treated gelatin used in the present invention is gelatin produced by treatment with hydrochloric acid or the like in the production process from ko2-ge, and is treated with lime or the like which is commonly used in the photographic industry. ! -It is different from the accompanying alkali-treated gelatin. For details on the production and properties of these gelatins, please refer to Arthe
r Veis person “The Macromolecule
r Chemistry of Geratin J
Academic Press/r, pages 7 to 17 (published in 1996), the biggest difference is that the isoelectric point (PI) of acid-treated gelatin is
I=4, 0~ri,! In contrast, for alkali-treated gelatin, PI=≠, jxt.

This is the third point.

Isoelectric lighting of acid-treated gelatin used in the present invention: 6°Q~
ri, j, and good IL< is 7.0~ri.

! It is. The molecular weight of the acid-treated gelatin used in the present invention is not particularly limited, but the preferred IL< is 10,000 to λO
Ten thousand.

Next, compounds represented by formulas (n) to (IX) will be explained.

Among the compounds represented by general formulas (f[) to (K), preferred are general formulas (In), (■) and (Vl), and more preferred are general formulas (I) and (■). It should be expressed as.

Specific examples of the compounds represented by the general formulas (rl) to (K) that can be used in two layers in the present invention C are shown below.
Therefore, it is not limited.

(A-/) (A-1) (Person-J) (A-7) (Person-10) TA-r) (λ-//) (Person-'') (Person-?) (A-/J ) (person-/j) (A-74t) (A-/J) (A-/bu) (person-/7) (A-13) (person--4t) (A--J) (A- 1) (person-/1) N)! )IzsCtz-NH-C-NH2 (^-/de) (A-10) (A-ko/) (person-17) (A-ko♂) (A-Jo) (person-37) (A- JJ) (A-37) (A-JJ) (A-Jl) (A-J4t) (A-3P) (Person-34) In the present invention, general formulas (n) to (X) are used. The compound is contained in the non-photosensitive top layer of the acid-treated gelatin, but may also be contained in the silver halide emulsion layer, gelatin intermediate layer, etc. In the present invention, the compounds represented by the general formulas (n) to (X) may be added directly to the non-photosensitive uppermost layer, or may be added to the processing solution in the 2-current processing. It may also be included in the non-photosensitive top layer.

When added to a photosensitive material, it is preferably added to a non-photosensitive layer such as a non-photosensitive uppermost layer or an ultraviolet absorbing layer. When the compounds of general formulas (II) to (X) are added directly to the photosensitive material, the amount of the compound added is zxio
P-xxio -e Lua m2 is preferred, more preferably JXlo ~j×io'(mol/l'n
). When incorporated into a photosensitive material, it is added by dissolving it in an organic solvent such as methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, benzyl alcohol, ethanolamine, jetanolamine, triethanolamine, etc. ,
It is preferable to add it in the form of an emulsion.

When used by adding it to the processing solution, color developing solution, fixing solution, bleaching solution, bleach-fixing solution, stop solution, water wash, stabilizing solution,
It can be used for all kinds of processing solutions such as neutralizing solution, pre-hardening solution, post-development hardening solution, etc. However, considering the adhesion efficiency to the photosensitive material, the final bath such as stabilizing solution and washing solution should be used near the end. It is preferable to use the treatment liquid used or the treatment liquid for mold prevention after the conventional treatment process is completed. The amount of the compounds of general formulas (It) to (X) to be added to these treatment liquids is determined by
1) JXlo 〜, 2×10 mol is preferable 1
and more preferably zxio-6 to 1 xio'' moles.

Methanol, ethanol,
Ethylene glycol, ethylene glycol, Torie f
It is preferable to add the compound by dissolving it in an organic solvent such as glycol, benzyl alcohol, ethanolamine, jetanolamine, or triethanolamine.

The compounds of the present invention represented by general formulas (n) to (X) are:
Although it is effective against any mold traps that occur in silver halide photographic images, it is particularly effective against the following mold strains.

In other words, Anu is Aspergillus niger, Aspergillus grac
ilis), Anu is Aspergillus penicilloides (Aspergillus penicillo4d)
es), Plularia pullulans (Pu1lulari
apul-1ulans), Chaetomium globosum, Cladosporium r.
esinae), Asd A/Gilles Frazo, K (
Aspergillus flavus), Aspergillus oryz
ac), Penicillium citrinum (Penicil)
lium citrinum), Penicillium luteum A, Trichoderma uiri
de ), 7 Subergine restrift; x (As
pergillus restrictus), Aspergillus g.
laucus), Chrysosporita A (Chrysosp
orium), as
Aspergillus versirollor), Eu rotium rub A
run), Elarothilum tonophyllum (Euro
tiumtonophilum), Arthrium bestalotia 7
) etc.

The color photographic light-sensitive material of the present invention can 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. 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 light-sensitive emulsion layers contain silver halide emulsions that are sensitive to each wavelength range, and dyes that are complementary colors to the light to which they are exposed - 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. Here, "substantially free of silver iodide" means that the silver iodide content is 1 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. Furthermore, regarding the i-10-gen composition distribution inside the 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 grains, and cores inside the silver halide grains.
and the shell that surrounds it [-layer or multiple layers]
Particles with a so-called laminated structure in which the halogen composition differs between the grains, or structures with parts with different halogen compositions in a non-layered manner inside or on the surface of the grain (if there is a back surface of the particle, there are particles with different compositions on the edges, corners, or surfaces of the particle). Particles having a structure in which parts are joined 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 products with different halogen compositions are clear, the boundaries may become unclear due to the formation of mixed crystals due to compositional differences. Alternatively, the structure may be actively made to 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 1. 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 silver bromide localization layer is present inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and more preferably exceeds 20 mol%. These localized phases can be located inside the grain, or on the edge, corner, or surface of the grain surface, but one preferred example is one in which it is epitaxially grown on a part of the corner of the grain.

On the other hand, in order to minimize the decrease in sensitivity when a 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.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%.
Hereinafter, a so-called monodisperse material having a content of 15% or less is preferable. 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), irregular crystal shapes such as spherical or plate-like, or a combination thereof. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these, 50% or more of the particles have Kamikita regular crystal shape,
The content is preferably 70% or more, 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.

The silver chlorobromide emulsion used in the present invention is P, Glafkide.
Written by Chimia et Ph1sique Photo
ographique (Published by Piu1Mante1,
(1967), Photo by G. F. Duffin
-graphic [1mulsion Chemises]
try (Focal Press, 1966)
, V. L., Zelikman at al.
King and Coating Photogra
phic Bmuldion (Focal P
It can be prepared using the method described in (Published by Res Inc., 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 amount of P in the liquid phase in which silver halide is produced is 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 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-'' to 10-'' mol based on the 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 compounds used for chemical sensitization, see the lower right column on 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 dye-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, Het.
erocyclic compounds-Cyani
na dies and related compo
unds (John Wiley & 5ons (N
ew York, London), 1964)
Examples include those listed in . Specific examples of compounds and spectral sensitization methods are described in the above-mentioned JP-A-62-
Those described in the upper right column of page 22 to page 38 of the specification of JP 215272 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-1), (C-11), (M-1), and (M-II).
and (Y).

General formula (C-I) General formula (C-II) H H General formula (Y) In general formula (C-1) and (C-ff), R,,
R, and R1 represent a substituted or unsubstituted aliphatic, aromatic, or heterocyclic group, R3, R, and R6 represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group, and Rs is It may also represent a group of nonmetallic atoms forming a nitrogen-containing five-membered or six-membered structure together with R3. Y,
, Y represents a hydrogen atom or a vine group that is released during a coupling reaction with an oxidized product of a developing agent. n represents O or l.

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

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

In general formula (C-I), preferable R3 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 cyano group.

In general formula (C-I), when R1 and R2 do not form a ring, R3 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-11), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-n), R3 preferably has 2 to 1 carbon atoms.
It is a methyl group having an alkyl group of 5 and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In general formula (C-m), 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 general formula (C-11), preferable R1 is a hydrogen atom,
A halogen atom, with chlorine and fluorine atoms being particularly preferred. In the general formulas (C-In and (C-11)), Y+ and Y2 are preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, or a sulfonamide group, respectively.

In general formula (M-1), R1 and R1 represent an aryl group, R6 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a leaving group.

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

Preferred Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in 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 (Mn), R+a 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. ZalZb
k and Zc are methine, substituted methine, =N- or -NH-
, one of the Za-Zb bond and the Zb-1c bond is a double bond, and the other is a single bond.

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

When 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-11), imidazo (1,2 -b] pyrazoles are preferred;
Pyrazolo (1
, 5-b) [1,' 2.4)) 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 pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226. It is preferable to use pyrazolotriazole couplers having an alkoxy, ary or roxy group at the 6-position as described in No. 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 R11 represents a hydrogen atom, a halogen atom, or an alkoxy group. A represents -NHCOR13. However, R1
3 and R14 each represent an alkyl group, an aryl group or an acyl group. Y represents a leaving group. R12 and R13,
The substituents for R14 are the same as those allowed for R1, and the leaving group Y is preferably of the type that leaves off at either an oxygen atom or a nitrogen atom; Particularly preferred.

General formula (C-I), (C-n), (M-I), (M-I
Specific examples of couplers represented by I) and (Y) are listed below.

(C-1) (C-5) I (C-6) I (C-7) I (C-4) (C-8) I (C-17) (C-18) (C-19) I (C-14) (C-15) (C-20) (C-21) (C-22) UjiH5 (M-1) (M-2) (M-3) (M-7) (M-8) I I I CH5 (M-4) (M-6) I CH.

(Y-1) (Y-2) (Y-3) Ul'I (Y-4) (Y-5) (Y-6) (Y-9) (Y-7) (Y-8) The above general Couplers represented by formulas (C-1) to (Y) are
The silver halide emulsion layer constituting the photosensitive layer usually contains 0.1 to 1.0 mol per mol of silver halide, preferably 0.
．． It is contained in an amount of 1 to 0.5 mol.

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

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

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

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

General formula (A) L L-0-P=0 stomach.

General formula (B) wt-coo-w.

General formula (E) w, -o-wt (where Wl, W, and W are each substituted or unsubstituted T-alkyl group, cycloalkyl group, alkenyl group,
represents an aryl group or a heterocyclic group, W represents L, curvature, or SW (in formula (E), 1, 1 and W may form a condensed ring).

The high boiling point organic solvent used in the present invention has a melting point of 100°C or less and a boiling point of 140°C, even if other than those of general formula (A) or E).
Any of the above water-immiscible compounds can be used as long as they are good solvents for couplers. The melting point of the high boiling point organic solvent is preferably 8
The temperature is below 0°C. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 100°C or higher.

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

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a water-insoluble but organic solvent-soluble polymer.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W088100723 are used, and acrylamide-based polymers are particularly preferred from the viewpoint of color image stabilization.

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

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

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

Hydroquinones are U.S. Patent No. 2.360.290,
2.418.613, 2.700.453, 2.701, 197, 2.728.659
No. 2.732.300, No. 2.735.76
No. 5, No. 3.982.944, No. 4.430, 4
25, British Patent No. 1.363.921, U.S. Pat. No. 2,710.801, U.S. Patent No. 2.816.028, etc. U.S. Patent No. 3.432.30
No. 0, No. 3.573.050, No. 3.574.6
No. 27, No. 3.69'8゜909, No. 3.764
．． No. 337, JP-A-52-152225, etc., and spiroindanes are described in U.S. Patent No. 4.360.589, p.
-Alkoxyphenols are U.S. Patent No. 2.735.7
No. 65, British Patent No. 2.066, 975, JP-A-59
-10539, Japanese Patent Publication No. 57-19765, etc., and hindered phenols are disclosed in U.S. Pat.
No. 52-72224, U.S. Pat. No. 4.228.
No. 235 and Japanese Patent Publication No. 52-6623, gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Pat.
．． No. 332.886, Japanese Patent Publication No. 56,21144, etc., and hindered amines are disclosed in U.S. Patent No. 3.336.135.
No. 4.268.593, British Patent No. 1.326
．． No. 889, No. 1.354.313, No. 1, 41
No. 0.846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 1983-
No. 114036, No. 59-53846, No. 59-
No. 78344, etc., and metal complexes are disclosed in U.S. Patent No. 4.050.
．． No. 938, No. 4.241゜155, British Patent No. 2
．． 027.731 (A) etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with the respective color couplers in an amount of usually 5 to 100% by weight and adding them to the photosensitive layer. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As a UV absorber, an aryl group is used! IJ azole compounds (e.g. U.S. Pat. No. 3,53
3.794), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3.314.794, U.S. Pat. No. 3.3
52,681), penzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3.705°805, U.S. Pat. No. 3.707.395) (mentioned in the issue),
butadiene compounds (as described in U.S. Pat. No. 4.045.229), or benzoxidol compounds (e.g., U.S. Pat. No. 3.406.070;
72 and No. 4, 271.307) can be used. UV-absorbing couplers (e.g. α
- naphthol-based cyan dye-forming couplers), ultraviolet absorbing polymers, etc. may also be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, benzotriazole compounds substituted with an aryl group as described above are preferred.

In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds. Particularly preferred is the combination with a pyrazoloazole coupler.

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

A preferred compound (F) has a second-order reaction rate constant ki (in trioctyl phosphate at 80°C) with p-anisidine of 1. Of/mol-sea ~l xl
It is a compound that reacts in the range of o-' 1 /mol·sec.

Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

When R2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

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

General formula (FI) R, - (A), - General formula (FII) R2C=Y In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0.

A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group,
Y represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (Fn). Here, R, XSY, and R8 or B may be bonded to each other to form a cyclic structure.

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

For specific examples of compounds represented by general formulas (Fl) and (Fn), see JP-A-63-158545 and JP-A-62-2.
83338, European Patent Publication No. 298321, European Patent Publication No. 277
Those described in specifications such as No. 589 are preferred.

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

General Formula (Gl) In the formula, R represents an aliphatic group, an aromatic group, or a heterozygous group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. The compound represented by the general formula (Gl) has a nucleophilic CH11 value (
RlG, Pearson, et al., J.A.
m.

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

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

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 2T'11589.

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

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

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-phenyl diamine derivatives, and representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenyl diamine 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)amino]aniline D-64-amino-3-methyl-N- Ethyl-N-(β
τ(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenyl diamine 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-7 22-diamine derivatives, 4-amino-3-methyl-N-ethyl-N-(β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6).

Further, salts such as sulfates, hydrochlorides, sulfites, and p-)luenesulfonates may be used with these p-phenylenediamine derivatives. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g per developer solution 11.
1 and 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 free" means preferably 2m171 or less, more preferably 0.5mj! /1 or less, and most preferably no benzyl alcohol at all.

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"' mole/1 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.

Here, "substantially no hydroxylamine is contained" preferably means a hydroxylamine concentration of 5.0x10-' mol/l 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 a color photographic light-sensitive material. That is, organic compounds having the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same shall apply hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones,
Particularly effective organic preservatives include Fi@, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and wig-type amines. These are JP-A Nos. 63-4235, 53-30845, and 63-30845.
No. 21647, No. 63-44655, No. 63-535
No. 51, No. 63-43140, No. 63-56654, No. 63-58346, No. 63-43138, No. 6
No. 3-146041, No. 63-44657, No. 63-
44656, U.S. Patent No. 3.615.503, U.S. Patent No. 2
, No. 494.903, Japanese Unexamined Patent Application Publication No. 143020/1982, and Japanese Patent Publication No. 30496/1983.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
No. 349, the polyethyleneimines described in U.S. Patent No. 3.
If necessary, aromatic polyhydroxy compounds described in No. 746.544 and the like may be contained. In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine,
Preferably, a hydrazine derivative or an aromatic polyhydroxy compound is added.

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 bulk 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.
Xl0-' ~1.5 XIG-'%le/j! It is preferable to contain. Particularly preferably 3.4 x 10-'
~ I X 10-' mol/1. If the chloride ion concentration is more than 1.5X10-'~1G-1 mol/i, the present invention has the disadvantage of slowing development, and has a rapid and high maximum concentration.

undesirable for achieving the purpose of Also, 3.5×1
01morph less than 1 is not preferable in terms of preventing fog.

In the present invention, 3. bromine ions are added to the color developer.
OX 10-'MoJb/It ~1. OX 10-
It is preferable to contain 3-11-ru/1. More preferably, 5. oxlo-s~5X10-'mol/1. If the bromide ion concentration is greater than 1X10-'' mole/1, development will be delayed, maximum density and sensitivity will be reduced, and 3.0X
If it is less than 10-'morph, fogging 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 development processing, 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 is preferably p)1
9 to 12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, 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. Especially carbonates, phosphates, tetraborates, hydroxybenzoates are soluble, p) 19.
These buffers have the advantage of having excellent buffering ability in the high pH range of 0 or more, having no adverse effects on photographic performance (fogging, etc.) even when added to color developers, and being inexpensive. is particularly preferred.

these! Specific examples of tf agents include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraboron Potassium acid, 0-hydroxybenzoic acid potassium (sodium salicylate), 0-hydroxybenzoic acid potassium, 5-
Examples include sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 2.5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention
It is not limited to these compounds.

Applicable! The amount of agent II added to the color developer is 0.1 mol/
It is preferably 1 or more, especially 0.1 morph 1 to 0
．． Particularly preferred is 4 mol/1.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N, N, N-)limethylenephosphonic acid, ethylenediamine-N, N, N',
N'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid,
Glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-
1,2,4-)licarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N+N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, and the like.

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
It is about 0.1g to 10g per serving.

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
．． thioether compounds shown in JP-A No. 247, p-phinidine diamine compounds shown in JP-A-52-49829 and JP-A-50-15554;
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 No. 6.926 and No. 3.582.346, etc., Japanese Patent Publication No. 37-16088, No. 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 as 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-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterogroove compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The bright color developer used in the present invention preferably contains an optical brightener. As an optical brightener, 4.4'
-Diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/l, preferably 0.1 g to 1 liter.
It is 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 color phenomenon liquid that can be applied to the present invention is 20
-50°C, preferably 30-40°C. Processing time is 2
The time is 0 seconds to 5 minutes, preferably 30 seconds to 2 minutes. It is preferable that the amount of replenishment is small, but it is 20 to 600 per photosensitive material ego.
i is suitable, preferably 50 to 300 m1.

More preferably 60mj! ~200mj! , most preferably 60m1! ~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.

Below are bleaching solutions and bleach-fixing solutions that are applied to the present invention.

The liquid and fixer will be explained.

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,
Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, etc. preferable.

Among these, organic complex salts of iron (I[[) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids useful for forming organic complex salts of iron (Iff),
Aminopolyphosphonic acids, organic phosphonic acids, or salts thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic 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, 1) thium or ammonium salts. Among these compounds, iron(III) 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/1, preferably 0.05 to 0.50 mol/1.

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.

Other invention 1! : The applied bleach or bleach-fix solution contains bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. A rehalogenating agent such as ammonium iodide) may be included. If necessary, use borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. with pH-lowering ability.
More than one type of inorganic acid, organic acid, alkali metal or ammonium salt thereof, or a corrosion inhibitor such as ammonium nitrate or 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. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more 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/1, more preferably 0.04 to 0.40 mol/1.

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, JltI agents, optical brighteners, chelating agents, antifoaming agents,
A fungicide or the like 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.
nalof the 5ociety of Moti
on Pictura and Ta1evi-sio
n Bngineers) Volume 64, p, 248-25
3 (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 multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, to 0.51 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, the method of reducing calcium and magnesium described in JP-A No. 62-288838 is
It can be used very effectively. Also, JP-A-57-
Chlorine disinfectants such as isothiazolone compounds and thiapendazoles described in No. 8542, salt-accumulated sodium incyanurate described in No. 61-120145, JP-A-61
- Benzotriazole, copper ion, etc. described in No. 267761, Hiroshi Horiguchi, "Chemistry of antibacterial and anti-mildew J" (1986), Sankyo Publishing, Hygiene technology complete volume "Sterilization of microorganisms, sterilization, anti-mildew technology" (1982) Industrial technology It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents J (1986)," published by the Japan Antibacterial and Antifungal Society.

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

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,
No. 8543, No. 5B-14834, No. 60-2203
All known methods described in No. 45 and the like can be used.

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

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

The preferred pH of the water washing step or stabilization step is 4-10, more preferably 5-8. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is 15 to 45°C.
Preferably it is 20-40°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 1 minute
It is minute 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

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 11 or less per m' of photosensitive material,
Preferably 500mJ! It is as follows. 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 reducing the amount of waste liquid by using a multi-throw countercurrent system to allow the overflow of the washing water to flow into the bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.
The present invention is not limited to this.

Example 1゜LBKP for photographic paper (bleached hardwood, sulfate/hair lubricant)
ioo<<Basic weight/7.197 m, thickness ltoμ); A support A was obtained by providing a water-resistant resin layer having the following composition on the top surface of a white base paper.

Support A: Polyethylene/composition (density O1 aot/cc.

Meltoi/Detsukunu (MI), oyyio minute) 2O
To the N amount part, 70 parts by weight of anatase type titanium oxide white pigment surface-treated with trimethylolethane was added, and after kneading, a water-resistant resin layer with a thickness of 3 Q μm was obtained by melt extrusion coating. On the other hand, another polyethylene/composition (density 00/cc, MI I,
A water-resistant resin layer of 0 μm was obtained by coating only 0 minutes).

Supports with different densities of titanium oxide were prepared in the same manner by changing the addition t of the titanium oxide white pigment.

Plot a layer of multilayer color photographic paper with the layer structure shown below on top of the support. The coating solution was prepared as follows.

Preparation of coating solution for the first layer Yellow coupler (BxY) /2, color image stabilizer (Cpd-/) 4t, 4Af and color image stabilizer (C:p
d-7) 0.79 ethyl acetate, 27.2 cc and solvent (Solv-/) 1.2? Add and dissolve this solution f
100% dodecylbe/ze/sodium sulfonate rcc
It was emulsified and dispersed in k containing/θ steamed gelatin/aqueous g/Ijcc. On the other hand, chlorobromide button emulsion (cubic, average particle size o, r
A 3-near mixture (silver molar ratio) of a 0.70 μm dog size emulsion and a 0.70 μm small size emulsion. The coefficient of variation of the grain size distribution is o, or, and 00IO1. Each size emulsion contains 0.2 mol of silver bromide locally on the grain surface). For emulsions, add λ and 0×io' moles, respectively, and for primary small size emulsions, add 2. ! It was prepared by adding 10 mol of sulfur and sulfur sensitization.

Mixing and dissolving the emulsified dispersion and this silver chlorobromide emulsion,
Prepare the first coating solution to have the composition shown below.

The coating liquids for the second to seventh layer phases were also prepared in the same manner as the coating liquid for the first layer. As the gelatin/hardening agent for each layer, l-oxy-3,j-dichloro-5-)diazide/sodium salt was used.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each layer.

Spectral sensitizing dye for blue-sensitive layer (Halog/per mole of silveride, 0x10 mole each for large emulsions, and 0xIO-' mole each for small emulsions) Green sensitivity Spectral sensitizing dye for layer (halogen/silver oxide 1 mol 90%, 0x10 mol for large size emulsion, s for small size emulsion,
txio-' mole) and (per mole of halogen/silveride, f for dog-sized emulsion)
17.0 x 10 mol, 1.0 x lO-5 mol for primary small size emulsions) Spectral sensitizing dye for red-sensitive layer (Halog/per 1 mol of silver oxide, Q for large size emulsions, RiX/ For the red-sensitive emulsion layer, the following compounds were added per mole of silver halide, AX/(7 moles added). For the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1 mol of silver halide was added to each of /-(j-methyl9-laydophenyl)-!-mercaptotetrazole, and !x10-5 mol, 7.7×70 mol, co, j×10 mol were added.

17? , For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 1 mol i of silver halide or /X10
-' moles and 2X10' moles were added.

(Layer structure) The composition of each layer is shown below. The numbers are painted ffi (97m
2) is thorny. The silver halide emulsion has a silver equivalent coating weight of t-6.

Support polyethylene/laminated paper: Support A [White pigment ('I Io 2
) and Yoi-mi dye (including Group-Ikuin) 1st layer (Yoi-kan/1ll) The above-mentioned silver chlorobromide emulsion 0.30 gelatin:
y/, It yellow coupler (BxY) 0, J'λ color image stabilizer (
Cpd-1) 0.19 solvent (S
olv-1) 0.35 Color image stabilizer (Cpd-7) 0.0
6 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.
16 solvent (Solv-4)
0.08 Fifth layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1=3 mixture (Ag molar ratio) of one with an average grain size of 0.55 m and one with an average grain size of 0.391! m. Grain size The coefficient of variation of the distribution is 0, lO and 0.0
8. Each emulsion contained 0.8 mol% of Ag8r locally on the grain surface) 0.12 Gelatin
1.24 magenta coupler ([
lxM) 0.20 color image stabilizer (Cp
d-2) 0.03 color image stabilizer (
Cpd~3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02
Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (tlV-1) 0.16 Color mixing prevention agent (Cpd-5) 0.0
2 solvent (Soly-5)
0.08 Seventh layer (protective layer) Gelatin (pi-5 lime treatment) 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 1
7%) 0.17 liquid paraffin 0.03 (uxY) 1:1 mixture with yellow coupler (molar ratio Solv-2) 0
= 40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (Cpd-5) 0.05
Anti-irradiation dye (a-12) 0.005 Anti-irradiation dye (a-18) 0.017 Solvent (Soly-5) 0.2
4 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture (Ag molar ratio) of average grain sizes of 0.58- and 0.45-. Grain size distribution The coefficient of variation is 0.09 and 0.11,
Each emulsion contained 6 mol% of 0.23 gelatin locally on a part of the grain surface.
1.34 cyan coupler (OxC)
0.32 color image stabilizer (Cpd-6)
0.17 color image stabilizer (Cpd-
7) 0.40 color image stabilizer (CP
d-8>0.04 Solvent (Sal
t-6) 0.15(BX
M) 1:1 mixture (molar ratio) of magenta coupler ([1xC) Cyan coupler R = 2::4 mixture by weight of CJs and C4H8 and l (Cpd-1) Color image stabilizer (Cpd-6) 2::4 mixture of color image stabilizers (weight ratio) (Cpd-7) Color image stabilizer 7CH, -CH) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixing inhibitor (Cpd-9) Color image stabilizer (tlV-1) Ultraviolet absorber 4:2:4 Mixture (weight ratio) 2:1 mixture (volume ratio) of (Solv-1) solution (Solv-2) solution (Solv-4) solution (Solv-1) solvent Co0C8H1° (''2) 8 CL) UC8H□ 7 (Solv-A) Solvent The multilayer color photographic paper thus prepared was sample 7N1.
/. Next, the density of titanium oxide in the polyethylene on the first layer side, the type and amount of the dye next to the optical reflection I1 degree adjustment, the concentration of gelatin in the seventh layer, and the concentration of the compound of the present invention for the sample &/; Sample &
I created the λ-ki/Yuu.

The amount of addition of the compound of the present invention is JX/0 mol/m2, and when two or three types are used in combination, each is added in equal amounts.

The optical reflection density of the thus prepared sample 1fa/-/j was measured by the method described above. 3 for sensitometry using a sensitometer (manufactured by Fuji Photo Film Co., Ltd., FWH type, light source color temperature J200”K).
Next, give the gradation aX of the color separation filter. The exposure at this time was performed with an exposure time of o and i seconds and an exposure amount of KozoCM8.

Primary, shear/concentration is 7. Exposure is given through the sharp edge so that it becomes negative. Similarly, maze/yellow and yellow are also exposed and circled.

After the exposure, the nine samples are refilled twice the color development capacity using a K-par processing machine in the following steps.
After continuous processing, development processing was performed.

Color development Jj'C≠j seconds 7411114 Bleach fixing 30~3!0C≠! Sho Col! dsu/nu ■ 30~
ij"c 20 seconds/s■ 30^JJ"C20 seconds/s■ 30~3!0C20 seconds 3!0l drying 70~to'c to second tank supplementary light amount is photosensitive material/m Abiji (The rinsing method was 3/3 countercurrent from ■ to ■.

The composition of each treatment liquid is as follows.

0I water Echire/Jiami/-N.

N,N,N-tetrametele/phosphonic acid potassium bromide triethanolamine/sodium chloride potassium carbonate N-ethyl-N-(β- 00yJ/, It o, oizy r, or l, ≠V cotr 00tt1 2.0f 12.0? λ!V Methanesulfo/amidoethyl)-3-methyl Kazuhiro-aminoaniline sulfate N,N-bis(carboxymethyl)hydrazine fluorescent brightener (W)l I T EX j, Of !,!? 7 ,Of 7.0? Add water 10001L11000yd
p) + (27'C) io, oz io, at
Bleach-fix solution (tank solution and refill solution are the same) water
Da00 Ammonium Gothiosulfate/Monicum (70%) 100ml Sodium Sulfite/7p Ethylene/Diami/Iron(IIl) Ammonium! ! ? Ethylene/diamine acetic acid disodium acetate j? pH(λ-
t”c) t,,.

Water/Nu liquid (tank liquid and replenishment liquid are the same) Ion exchange water (calcium and magnesium are each
Table λ shows the measurement results of the optical character reflection m degree, the sharpness, and the reflection density of the unexposed area (white background area) of the processed ethyl.

Sharpness evaluation is e at a spatial frequency of 6 lines/mm.
The higher the TF value, the better the sharpness. The reflection @ degree of the unexposed area (white background area) of the 1st processed ethyl was evaluated at 6J Onm.

Add water to 1ooo Mr.-2, sample m/-, r is a sample wash in the comparative example ~
/j is the present invention.

From the results of Mr.-2, it was found that it is not sufficient to improve sharpness by increasing the optical reflection density at 61 Onm to 0.70 or more, and that the density of titanium oxide in the water-resistant resin layer of the present invention is It can be seen that this can be achieved extremely effectively when used in combination with a white support that has a brightness above a whisper.

At this time, it is also clear that the sharpness is improved without any blemishes impairing the whiteness of the non-image areas.

Next, the dried sample was left at room temperature for λ days under JJ attack H, and then left in 10% R)i for 3 minutes to observe the unevenness of the surface.

In addition, we conducted a mold resistance test on gray-exposed/pull. The mold that grows on color photographic paper is cultured on a potato textulose agar medium, and the spores are collected and the size is approximately /X104.
Next, prepare a spore suspension with a concentration of spores/d. Drop this spore suspension 0,1yJ onto the sample, and
% and observe the state of mold growth.

friend.

Sample black ratio s Compare 2 examples 1j Comparative example Comparative example Comparative example ratio S! Example Comparison Example Comparison; It is clear from the results that the gloss increased in the order of -3 to ++ that the samples with the structure of the present invention were excellent in human face gloss and also excellent in mold resistance. In other words, the sample of the present invention was shown to be a color photographic paper that was excellent in both whiteness and sharpness, maintained beautiful gloss, and had excellent mold resistance.

(Effects of the Invention) According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material that is excellent in sharpness, hexagonal glossiness, and mold resistance without completely impairing the whiteness of non-image areas.

Display of incidents 1999 Patent Application No. 7220 name of invention Silver halide color photographic material person who makes corrections Relationship with the incident

Claims (3)

[Claims] (1) A silver halide color photographic material having at least one silver halide photosensitive layer and a non-photosensitive uppermost layer on a reflective support whose support substrate is coated with a water-resistant resin layer. Titanium oxide particles are contained in the water-resistant resin layer on the side coated with the photosensitive layer at a density of 14% by weight or more, the optical reflection density at 680 nm of the photosensitive material is 0.70 or more, and the non-photosensitive material is Silver halide color photographic photosensitive material, characterized in that the top layer uses acid-treated gelatin as a hydrophilic colloid and contains at least one compound selected from the compounds represented by the following general formulas (II) to (X). material. General formula (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (III) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IV) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (V) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (VI) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (VII) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (VIII) ▲ Numerical formulas, chemical formulas, There are tables, etc. ▼ General formula (IX) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (X) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^2, R^3, R^4 , R^5, R^6, R
^8 and R^9 represent a hydrogen atom, an alkyl group, or an aryl group, and R^7 represents a hydrogen atom, an alkyl group,
Represents an aryl group, nitro group, carboxy group, sulfo group, sulfamoyl group, hydroxy group, halogen atom, alkoxy group, or thiazolyl group. R^1^0 represents an alkylene group or an arylene group. R^1^1,
R^1^2 and R^1^3 represent a halogen atom or an alkyl group, and R^1^4 and R^1^5 represent a hydrogen atom, an alkyl group, an aryl group, or a nitrogen-containing heterocycle. Represents a residue. R^1^6 and R^1^7 represent a hydrogen atom, an alkyl group, or an aryl group, and R^1
^6 and R^1^7 may be combined to form a benzene ring. R^1^8 represents a hydrogen atom or an alkyl group. R^1^9 represents an alkyl group or an aryl group. Y represents a halogen atom, Z^1 represents a nonmetallic atomic group necessary to form a thiazolyl ring, and Z^2 represents a nonmetallic atomic group necessary to form a six-membered ring. n represents 0 or 1, and m represents 1 or 2. ) (2) 550n of the silver halide color photographic light-sensitive material
The silver halide color photographic light-sensitive material according to claim 1, wherein the optical reflection density at m is less than or equal to the optical reflection density at 680 nm. (3) 470n of the silver halide color photographic light-sensitive material
The silver halide color photographic light-sensitive material according to claim 1, characterized in that the optical reflection density at m is 0.20 or more.