JPS60170852A - Color photosensitive material - Google Patents

Abstract

PURPOSE:To facilitate control of color balance after sensitization treatment by incorporating a combination of a photosensitive silver halide emulsion contg. internally fogged nuclei and a merocyanine dye in at least one of emulsion layers and/or its adjacent nonphotosensitive emulsion layer. CONSTITUTION:One of red, green, and blue sensitive emulsion layers contains a combination of photosensitive silver halide emulsion and/or its adjacent nonphotosensitive layer contains a silver halide emulsion having internally fogged nuclei and a merocyanine dye. Such a photosensitive material is used as a color reversal photosensitive material, and it is prepared by coating each of surface- fogged silver halide nuclei with a silver halide outer shell to form core-shell type silver halide grains, and using an emulsion contg. these grains. The use of a combination of such a merocyanine dye and the silver halide emulsion having the internally fogged nuclei permits color balance at the time of sensitization treatment to be controlled easily, and color balance to be adjusted by controlling an amt. of merocyanine dye to be combined without changing a ratio of silver halide emulsion to be used, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color photographic light-sensitive material, and particularly to a color photographic light-sensitive material with improved suitability for sensitization processing.

(Prior art) Color photosensitive material v! l+ usually has at least one each having a different color sensitivity (here, color sensitivity refers to the property of being sensitive to light in any of the three regions of the visible spectrum, namely red, green, and blue) on the support. Layer silver halide emulsion 1
-.

Color photographic JL photosensitive materials, especially in the field of color reversal photosensitive materials that are often used by photographers, are used for special purposes such as sports photography that requires a fast shutter speed or stage photography where the amount of light required for exposure is insufficient. Color photographic materials with high sensitivity are immersed in water in order to photograph scenes, but there are few color photographic materials that meet the requirements for extremely high sensitivity.

Under these circumstances, in order to compensate for the lack of exposure, sensitivity adjustment is carried out by processing f''17.Sensitivity adjustment by this processing is usually called "sensitization processing", and in the case of Cassie reversal photosensitive materials. This is implemented by extending 1'ol from the standard processing time when using JX/X/Genten Hakugentetsu.

However, conventional color reversal light-sensitive materials do not necessarily have adequate sensitization processing, and cannot be intensified unless the first development time is much longer than the standard processing. ■ In a photosensitive material that has a structure with a high-sensitivity layer and a low-sensitivity layer with an official seal on it, the effects of both layers can be properly processed. ■ If you try to increase the 8 degrees of sensitization by extending the time of the first phenomenon, a significant decrease in color development density will occur; ■ red-sensitive layer, green-sensitive layer, Due to the phenomenon between the blue-sensing layer and the improper processing, the color balance sometimes deteriorated when sensitized.

Therefore, it has been desired to develop a technique that can solve the above-mentioned drawbacks, can freely control the degree of sensitization, and does not cause any negative effects during standard processing.

The present inventors have previously developed a technology that does not cause a 1:1 change in color balance or deterioration of color balance even after sensitization treatment, and can relatively reduce the degree of decrease in surface density of color development. ,
Invented a technique in which a silver halide emulsion with internal fog nuclei is added to the silver halide emulsion layer or its adjacent layer, and the fog nuclei function during sensitization. Gansho! r-rt 3 issue). In this technology, sensitization is achieved by changing the ratio of the silver halide emulsion that covers the fog nuclei inside to the light-sensitive silver halide emulsion, and the thickness of the outer silver halide film that covers the fog nuclei. Color balance 'r'F after processing
It makes it possible to adjust A. However, it is quite difficult to determine the mtM value of the above usage ratio and the thickness of the outer film due to the power, and in some cases, good color balance cannot be obtained without increasing the total amount of coated silver. There was a drawback that there was no

(Object of the Invention) Therefore, the object of the present invention is the above-mentioned patent application! When improving the suitability of sensitization using the technique described in Section 3, it is easier to adjust the color balance between the red-sensitive layer, green-sensitive layer, and blue-sensitive layer after sensitization. An object of the present invention is to provide a color photographic material which can be achieved without increasing the coating silver density.

(Structure of the Invention) The object of the present invention is to provide a color photographic light-sensitive material having at least one red-sensitive, green-sensitive, and blue-sensitive light-sensitive silver halide emulsion layer, in which at least 1) of the emulsion layers are provided. ↓ and/or non-photosensitive 1Ili adjacent to it
This was achieved by using a color photographic material containing a combination of a silver halide emulsion with internal fogging nuclei and a merocyanine dye.

By using the merocyanine dye in combination with a silver halide emulsion having fog nuclei inside, the color balance can be easily adjusted during sensitization. That is, by adjusting the wrinkles of the above-mentioned combination of merocyanine pigments, can the nucleus be covered inside? Color balance can be adjusted without changing the ratio of silver halide emulsions used or the thickness of the outer film. The reason for this is not clear, but it is probably because the timing at which the sensitizing effect of this emulsion appears is controlled by increasing or decreasing the amount of adsorption of merocyanide 7 dye to the surface of silver halide emulsion grains that have internally fogged nuclei. be interpreted.

1. According to the present invention, the thickness of the outer film of a silver halide emulsion having internal fog nuclei is increased, and the timing (a) of the onset of the sensitizing effect by this emulsion is delayed. As a result, the color and ζ lance during the sensitization process can be freely adjusted without increasing the total coated silver.

As is clear from the above, the combination ratio of the merocyanine dye of the present invention and the arsenic emulsion is the same as that of the emulsion VC! : It can be changed as appropriate depending on the desired timing to omit the 3A sensitizing effect, but generally it is 10-5 to 10 per mole of silver halide having an internal fog nucleus. -1 mol, especially lo-4~/
Favorable results are obtained in the range of θ-2 moles.

In the present invention, the merocyanine dye and the silver halide emulsion having fog nuclei inside are contained in the same layer. When both are mixed, it is desirable that the dye be adsorbed exclusively to the surface of the silver halide emulsion grains. Therefore, when a silver halide emulsion with internal fog nuclei is contained in a red-sensitive, green-sensitive, or blue-sensitive light-sensitive silver halide emulsion +i, the silver halide emulsion with internal fog nuclei must be prepared before mixing the two emulsions. It is preferable to add a merocyanine dye to the emulsion in advance. In particular, US Patent No. 73j, 7At, 3,62g.

No. 760, JP-A-265-2, etc., the method of adding a dye before the physical ripening process of a silver halide emulsion is applied, and the silver halide emulsion has fog nuclei inside.
It is useful to add a merocyanine dye to the silver halide emulsion before the physical ripening is completed.

Merocyanine dyes suitable for use in the present invention are compounds represented by the following general formula (I).

General formula (I) Represents an acidic heterocycle-forming atomic group.Ll.

Even if L2 is substituted, the methine group is red, and n is 09l1
．． Represents 2 芊take and 3.

Examples of the basic carbocycle or basic heterocycle of Z are:
Oxazole ring, benzoxazole ring, oxazoline ring, naphthoxazole ring, thiazole ring, benzothiazole ring, thiazoline ring, natutothiazole ring, selenazole ring, benzoselenazole ring, selenazoline ring, naphthoselenazole ring, pyridine ring, quinoline ring, Examples include imidazole ring, benzimidazole ring, natuimidazole ring, indolenine ring, and indole ring.

Among these rings, benzoxazole ring, oxazoline ring, naphthoxazole ring, thiazole ring, benzothiazole ring, thiazoline ring, natutothiazole ring, selenazole ring, benzoselenazole ring, pyridine ring, quinoline ring, benzoimidazole ring, and indolenine ring. A ring is preferred.

The acidic carbocycle or acidic heterocycle of Y includes a thiohydantoin ring, a rhodanine ring, an oxazoline-linked one-corchion ring, a virazolodi ring, a barbital acid ring, a thiobarbital acid ring, a dimedone ring, an indan-/, 3- Examples include dione ring, cochioselenazolinco, and ≠-dione ring.

Among these rings, a thiohydantoin ring, a rhodanine ring, and an oxazoline-guone-λ-thione ring are preferred.

Various I substituents well known in the merocyanine dye art may be present in the Z and Y rings.

Substituents for the methine group of L and L include lower alkyl groups.

Specific examples of merocyanine dyes suitable for use in the present invention are listed below, but the present invention is not limited thereto.

(CH2) 'a C2H5 5O3H-N(C2Hs)3 (CH2)a C2i-Is SO3H-N(C2H5)a (,:2H5UzH5 1 03K SO3H・N(C2H5)a (1 side L"I(2) a QIzCH20CHaSO3 t21) CH3 I Shilia C205 03Na SO2 1 i49 Czns Shiyu5 C2H5 The silver halide emulsion having internally fogged nuclei of the present invention is
It is not developed at all in standard processing, and only after sensitization processing can it be developed uniformly regardless of whether it is unexposed or exposed.The following test method is used to determine whether or not it can be used. can be determined. That is, the emulsion to be tested was coated on a film support with a silver content of 0. jtl//rI
A sample prepared by applying L2 (without exposure) was processed for 2 minutes (without exposure) in JIoC using a developer with the following formulation.
Standard treatment) and 10 minutes (sensitization treatment) at the same temperature.

Developer formulation As a result of the above test, the emulsion used for the sample showed almost no increase in density after 2 minutes of processing, but an increase in density of more than 1 times the density after 2 minutes of processing after 10 minutes of processing. It is suitable for use as a silver halide emulsion having nuclei.

Preferably, the silver halide emulsion having a fogged core inside is a core-shell type emulsion consisting of a silver halide inner core with a fogged surface and a silver halide outer shell covering the surface. It is an emulsion consisting of silver particles.

In general, the core-shell type silver halide emulsion covered with the surface of the inner core is produced by chemically treating the surface of the silver halide grain with light after forming the silver halide grain in which the inner core is to be formed. It is produced by fogging and then depositing silver halogenide on the surface of an inner core silver halogenide grain to form an outer shell.

The above-mentioned fogging step can be carried out by adding a reducing agent or gold salt under suitable conditions of pH and I)Ag, or by adding a low I)
) The method can be carried out by heating under A g or by providing uniform exposure. reducing agent and (7
For example, stannous chloride, cetrazine compounds, ethanolamine, thiourea dioxide, etc. can be used.

It is advantageous to use the above-mentioned core-shell type silver halide grains because the timing at which the sensitization effect appears can be adjusted by changing the thickness of the outer shell. Therefore, the thickness of the outer shell should be determined depending on how much the sensitizing effect is produced when the first shell is extended. In the extension time range adopted in normal sensitization processing, the outer shell thickness fjO ~ 10
It is preferable to set it to 00k (Angstrom), and good results can be obtained by setting it in the range of 100 to 200A.

Even if the silver halide forming the inner core and the silver halide forming the outer shell of a core-shell type silver halide grain have the same halogen composition, they may have different halogen compositions. Good too.

Silver halides with internally fogged nuclei include silver chloride,
Any of silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used.

There is no particular limitation on the grain size of silver halide having internally fogged nuclei, but fine grains are preferable when it comes to ρ, and in particular, the average grain size is 0°0/, 0.71μ.
, further fokeo, oi~0. jμ is ugly.

In addition, there is no particular limitation on the grain shape of a silver halide emulsion having fog nuclei inside, and regular lregula
r) They may be particles or irregular particles.

The halogen-1 arsenic emulsion with internally fogged nuclei may be polydisperse, but monodisperse (especially the coefficient of variation of particle size distribution C) may be polydisperse.
It is preferable to use a material with V of 20% or less. Further, it is preferable that this emulsion has no photosensitivity.

In the present invention, the silver halide emulsion having fog nuclei inside is contained in a conventional light-sensitive silver halide emulsion layer and/or in a layer adjacent thereto. The silver norogenide emulsion having fog nuclei inside the present invention is applied.
The layers include one or more of the red-sensitive emulsion layer and/or its adjacent layer, the green-sensitive emulsion layer and/or its adjacent layer, the blue-sensitive emulsion layer and/or its adjacent layer, and the blue-sensitive emulsion layer and/or its adjacent layer. It is a layer. In addition, when the same color-sensitive layer is divided into a higher-sensitivity jii layer and a lower-sensitivity Y- layer, the technology of the present invention can be applied to both of them, but it is particularly important to add VC to the low-sensitivity layer. It is preferable.

In the present invention, a silver halide emulsion having fog nuclei inside can accelerate the development of adjacent light-sensitive silver halide by sensitization treatment.
If there is a difference in sensitization processing characteristics between -, it is possible to prevent deterioration of gradation compared to standard processing by adding it to 1-, where development progresses slowly through sensitization. In addition, deterioration of color balance (deterioration during sensitization) due to differences in sensitization processing characteristics existing between different color-sensitive layers can also be prevented in the same way.

In the present invention, the degree of sensitization when the first development is extended for a certain period of time can be changed by completely changing the ratio of the silver halide emulsion having internal fog nuclei and the photosensitive silver halide emulsion. can. Therefore, this usage ratio should be determined depending on the desired II# sensitivity, but it is usually 0.0r-j for the light-sensitive silver halide emulsion.
θ mol %, especially 0. /, 21 mol%, further Bo, zNi
A preferable sensitizing effect can be achieved by using a silver halide emulsion having internal r(fogging nuclei) in the range of 0 mol %.

The light-sensitive silver halide emulsion used in the present invention has fog nuclei inside the grains, and has a dark I# color when exposed to -I# light. It may be any of koji bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, and silver chloride that can form .

The average grain size of the silver halide grains in the above photographic emulsion (expressed as the grain diameter for spherical or approximately spherical grains, and principal grain size for cubic grains, expressed as an average based on projected area) is Although it does not matter, it is preferably 3μ or less. The particle size distribution may be narrow or wide.

Silver halide grains in photographic emulsions may have regular crystal trees such as cubic or octahedral, or irregular crystal trees such as spherical or plate-like.
It may have a crystalline form (egular) or a complex of these crystalline forms. It may also consist of a mixture of particles of various crystalline forms.

These photographic emulsions include P, Chi by Glafkjdes.
mie et Physique Photograp
hique (published by Paul Monte 1, 1967), G, F.

Photographic Emuls by Duffin
ion Chemistry (The Focal Pr.
(Published by ess, 1994), V, L, Zelikman
et al@Makingand Coating P
Photographic Emulsion (The
It can be prepared using the method described in Focal Press, 6≠Year).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and as a rare method for reacting a soluble silver salt and a soluble norogen salt, any of the one-sided mixing method, simultaneous mixing method, and a combination thereof may be used. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method of keeping the pAg in the liquid phase produced in the no-rogen formation constant, ie, 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.

Silver halide emulsions of different types or higher may be formed separately and used in combination.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

Although the silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, the Glafkides i or (Akademi
sche VerlahsgeselJschaft.

The method described in (1) can be used.

That is, a sulfur sensitization method using a sulfur-containing compound or activated gelatin that can react with silver ions, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other precious metal compounds, etc. are used alone or in combination. Can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
, 4C/Ni 1,41rF No. 1.2.271r, μ7 No. 1.2,721,661, 3. Art, No. m. As reduction sensitizers, stannous salts, amines,
Hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof can be found in US Patent No. 1117. J'jO issue, 2. ≠lri, ri7hiro, co, 111) 2r, 2, yr3. to2, J
,! It is fully described in PfJ, A/θ No., λ, 6ri II, No. 637.

For noble metal sensitization, in addition to total complex salts, complex salts of gold scraps in group ■■ of the periodic table, such as platinum, iridium, and palladium, can be used; specific examples thereof are given in the US patent.

3 Tata, or3, λ, ≠≠r, o4o, British patent 4
It is described in the it, oti issues, etc.

Each light-sensitive photographic emulsion layer of the light-sensitive material of the present invention contains a color-forming coupler, that is, a color is formed by oxidative coupling with an aromatic primary amine developer (e.g., phenylene diamine derivative, amine phenol derivative, etc.) during color development processing. Contains compounds that can For example, as a magenta coupler used in a green-sensitive emulsion layer! - There are pyrazolone couplers, pyrazolone benzimidazole couplers, cyanacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc.Acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides) are used as yellow couplers used in the blue-sensitive emulsion layer. , etc., and cyan couplers used in the red-sensitive emulsion layer include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a pallast group in the molecule. The coupler may be either g-equivalent or co-equivalent to the silver ion.

A specific series of magenta coloring couplers is disclosed in a US patent.

No. 600.711, same x, ye3. toy number, same 3.0
42. l, No. 33, 3. /+27. +2t issue, same!
, 3//, Hiroshi No. 76, same 3. μl, No. 39, 3.
! /ri, No. 112, J, 111', No. Jl, No. 3. jl', No. 2,322, 3. T/! .

, tot issue, same 3. t3p, yor issue, same 3. trill
, ≠IIj, West German patent/, I10,4tt Hiro, West German patent application (OL'S>29μor, ttr, same 2.≠
/7. Kago] No., Same Ko, Gu/I, Rijri No., No. 2,112
1A, No. 1147, Special Publication Showao-4゜31, Special Publication Showa K
1-2Ot2 No., same jO-/30g No. 1, same jλ-r
rri 2λ, ≠ 2-121631, t turf 11
O27, same 5o-l! No. 2336, same! No≠2/2
/ issue, Doko Turf 11.021, jcTl j OA
(7-2J J issue, same j/-2t5≠/ issue, same 33-
No. 11122, etc.

A specific example of a yellow coupler is given in US Patent λ, f7, 01
No. 7, same J, 261, JOt No., same 3゜g O♂, l
No. 3,111,116, J, 1!2.3
．． No. 22, 3.71t, No. 07.2, No. 3,1/
, No. J, West German Patent/, No. 7゜rtg, West German Application Publication Co., Ltd. No. 77, 2. ．． 21r/, 31.
/ issue, same, z, pie, oot issue, British patent l, ≠λ!
, No. 0.20, Tokko Akira! No. l-10713, Japanese Patent Publication No. 7
−． 27/Jj issue, same lAl-73/177, same! /
-10, ZAJt No., same jO-t31A/No. 10-
/233'l+2, same jtO-/30≠day λ, same j
/-2/127 issue, same jλ-tVtrO issue, same! no g
1 μ issue, same, t no / /! , No. 2/R, etc.

A specific example of a cyan coupler is U.S. Patent No. 36? .

riλri No., same λ, ≠3≠, 272, same, ≠7pi, 2
No. 23, 2.62/, No. 10g', λ.

191.121s, 3,03u, 192, J,
J//, Hiroshi 76, 3rd, 1st, 3/j, 3rd. ≠7
A, jtJ No. 3, I11'3, Ri No. 71,
Same J, jri/, 31fJ issue, same J, 7t7. Hiroshi No. 1,
Dohiro, 00Hiro, Ri2ri No., West German patent application (OLS) 2.
'I/! I, No. 130, No. 2.4't44゜322, JP-A Show≠? -j7131 issue, same, 1/-kot03≠ issue, same≠zaichi 1orz issue,, same! /-7←Eg issue, same j
No. 49Aλ≠ and J2-Ta No. 0732 VC.

The photographic emulsions of this invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine color X,
Merocyanine colors include X, +X combined cyanine dyes, ventralized merocyanine dyes, holopolar cyanine dyes, hexyanine dyes, styryl dyes, and hemioxonol dyes. % (, This useful dye is a cyanine dye, a merocyanine dye and a complex merocyanine dye [belonging to the dyes belonging to these dyes. can also be applied, i.e., pyrroline nucleus, oxazinone nucleus,
Thiazoline group, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; an alicyclic hydrocarbon ring is fused to these nuclei, and the following nucleus; and an aromatic hydrocarbon to these nuclei Nuclei in which rings are fused, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, nandooxazole nucleus, be/dithiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus,
Quinoline nuclei etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes contain pyrazoline-! -one nucleus, thiohydantoin nucleus, cochoxazoline, l-dione nucleus, thiazolidine-2μm dione nucleus,'
Rhodanine nuclei, thiobarbic acid nuclei, etc.! ~tH heteroartic ring nuclei can be applied.

Among these, sensitizing dyes having at least a water bathing group are particularly useful. Such dyes are described in the applicant's '4 application No. RR-IOO, yi.

The sensitizing dyes C) may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Its representative columns are US patent λ, try, tμ! No. λ.

P77,. No. 2 Kota, No. 3,327, No. OtO, No. j
, 122.0! λ No. 3. ! λ7,641/No. J, t/7,293, No. 3, 421, 9444, No. 3, 444, ≠tro, No. 3,67, j2
No. I, 3. t7ri, ≠2, same J, 703.

No. 377, same'*7 AP, Jo1, same 3. lr/p,
Totar 吋, same! , No. 137, 162, Ibid.

No. 026.707, British Patent/, 31AI! ,
2Ir1 issue, same/! 07. Io3, patent 1+3 a
No. J-II 3, No. 13-/2371, JP-A-Sho! No. 110611, same jJ-t o y 92.
Nt is written in the number.

Along with the sensitizing dye, it is a dye that itself has no spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Each of the valley photosensitive emulsion layers of the present invention may be separated into two or more layers. In this case, it is preferable to arrange a layer with higher sensitivity on top of a layer with lower sensitivity having the same color sensitivity.

Gelatin is advantageously used as the binder in each light-sensitive photographic emulsion layer and in the intermediate or other groove layers of the invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxydimethylcellulose, cellulose sulfate esters, sodium alginate, starch derivatives, etc. Sugar derivative, =W IJ vinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinylimidazole, polyvinylpyrazole, and the like.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Phot, and Japan.
.

Enzyme-treated gelatin such as those described in NO, tt, 3θ1 (IL?AA) may be used, and hydrolyzed gelatin and enzymatically decomposed products of gelatin may also be used.

For the purpose of increasing sensitivity, increasing contrast, or promoting phenomena, the light-sensitive material of the present invention may contain, for example, polyalkylene oxasode or its ether, derivatives such as ester amines, thioether compounds, thiomorpholines, and quaternary ammonium salt compounds. , urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, U.S. Patent No. 0.13λ, same, ≠23
．． ! μri issue, same number, 7/A, 042 issue, same number 3. Bu/7゜λto issue, same! , 77.2, No. 0a1, 3. t.

n7t described in No. R, OOS, etc. can be used.

The light-sensitive material of the present invention can contain various compounds as antifoggants or stabilizers.

Namely, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially di-o- or halogen substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles. , mercaptobenzimidazoles, mercaptothiadiazoles, mercaptothiazoles (especially l-phenyl-mercaptotetrazole), mercaptopyridines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; Thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes; especially dihydroxy-substituted (/, J, 3a).

7) Many compounds known as antifoggants or stabilizers can be added, such as tetraazaindenes); benzenethiosulfonic acid; benzenesulfinic acid;

More detailed examples of these and how to use them can be found in, for example, U.S. Pat. rij II, ≠ No. 7, No. 3
, 112. No. 4L7, No. μ, No. 0.2i, No.

The description in the tto publication can be referred to.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other constituent layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glycidol, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (J, J-dihydroxy dioxane, etc.), active vinyl compounds (/, J, j-) lyacryloyl-hexahydro-3-) riazine, 1,3-vinylsulfonyl-coprono-nornato), active halogen compounds (co-,
≠-dichloro-4-hydroxy-3-)riazine)
, mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), etc. may be used alone or in combination.

The photographic emulsion layer or other constituent layers of the light-sensitive material of the present invention include coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (yc, for example, development acceleration, high contrast, and sensitization). Various surfactants may be included for various purposes such as.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycolalkylamine ta is amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylconophosphate polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Nonionic surfactants; alkyl carboxylates, alkyl sulfonates, argylbenzenesulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurine acid, sulfosuccinic acid esters, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphoric esters, etc.Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphoric ester groups, etc. Containing anionic surfactants; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates, amphoteric surfactants such as phosphoric acid esters, alkyl betaines, amine oxides; alkylaquine salts, aliphatic or aromatic Cationic surfactants such as ammonium salts, heterocyclic primary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The light-sensitive material of the present invention may contain a developing agent. As current herbal medicines, those listed in Research Disclosure, Vol. 174, P. Kota, section ``Developing agents J'' can be used.

The photographic material produced according to the present invention may contain a dye in the photographic emulsion layer or other constituent layers as a filter dye or for various purposes such as preventing irradiation. As such dyes, [Absoring a
nd filter dies described in the section J.

The photosensitive material of the present invention may also contain an antistatic agent, a plasticizer, a matting agent, a lubricant, an ultraviolet absorber, a fluorescent whitening agent, an air antifoggant, and the like.

The silver halide emulsion layer and/or other constituent layers are coated on a support. The coating method is described in Research Disclosure, Vol. 77A, P27-2t.
The method described in rocedures J may be used.

For photographic processing of the light-sensitive material of the present invention, any of the known color image forming methods, such as those described in the above-mentioned NoriSearch Disclosure, Vol. 174, pages JJ-30, can be used. Processing temperature is normal/r0c
It is preferable to set the value between 6 and 6(:).

In the processing of the color reversal light-sensitive material which is a preferred embodiment of the present invention, the following steps are usually carried out: black and white phenomenon (first development) → stop → water washing → reversal → water washing → color development → stop → water washing → adjustment bath → water washing → Bleaching → Water washing → Fixation → Water washing → Stabilization → Drying steps are used. This step may further include a pre-bath, pre-hardening bath, middle shade, etc. Washing with water after the adjustment bath or bleaching may be omitted. Reversal may be performed in a fogging bath or re-exposure. Also, a fogging agent is added to the color development bath. Furthermore, the adjustment tower can also be omitted.

As the first chemical solution used in the present invention, any known chemical compound can be used. Current active drugs include dihydroxybenzenes (fC and hydroquinone), 3-pyrazolidones (e.g. l-phenyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p-
amine phenol), l-phenyl-3-pyrazolines, ascorbic acid, and / as described in U.S. Pat. No. 7.272, 2. ．． 3. A heterocyclic compound such as 1c in which an II-tetrahydroquinoline ring and an intrene ring are condensed can be used alone or in combination.

In addition, the black and white developer used in the present invention may include preservatives (e.g., sulfites, bisulfites, etc.), buffers (e.g., carbonates, boric acid, borates, alkanolamines),
alkaline agents (e.g. hydroxides, carbonates), d-depolymerizers (
For example, polyethylene glycols, esters thereof), pH adjusters (e.g., organic acids such as acetic acid), sensitizers (e.g., quaternary ammonium salts), development accelerators, surfactants, color toners, antifoaming agents. A hardening agent, a viscosity-imparting agent, etc. can be included.

The first iron solution used in the present invention must contain a compound that acts as a silver halide solvent, and the sulfite added as a preservative as described above usually plays this role.

The sulfite and other usable silver halide solvents include KSCN%Na5CN, 2SO3,
Na2SO3, K2S 205%Na2S
205s K 2 S 2035Na2S203 and the like.

If the amount of these silver halide solvents used is too small, the development progress will be slowed down, and if it is too large, the silver halide emulsion will be fogged, so there is a preferable amount to use. Determination of amounts can be readily made by those skilled in the art.

For example, the binding using 5CN-2 is 0.0 per liter of developer solution.
06 to 0.02 mol, particularly preferably o, oi to 00 oir mol, and when using 5032-, 0,
It is preferably 0jt-1 mol, especially 0.1 to 0.11 mol.

In addition, antifoggants (for example, halides such as potassium bromide and sodium bromide, benzimidazoles, benzotriazoles, benzothiazoles, tetrazoles, thiazoles, etc.), chelating agents (if kept, ethylenediaminetetravinegar), These alkali metal salts, polyphosphates, nitriloacetates) can be included.

The pH value of the developer solution adjusted in this way is selected to be within a reasonable range to provide the desired concentration and contrast, but it is preferably in the range of about t,j to about //,2. .

In order to carry out sensitization treatment using such a first incubation solution, usually,
It is sufficient to extend the time up to about three times the standard processing time.

If the treatment temperature is raised at this time, the extension time for the sensitization treatment can be shortened.

The fogging bath used in the present invention can contain a known fogging agent. That is, stannous ion-organophosphate complex salt (U.S. Patent No. 3.t17゜2t-2),
Stannous ion organic phosphonocarbon enemy complex salt (% disclosure j
4-J2t/A) stannous ion complex salt borohydride compounds such as stannous ion-aminopolycarboxylic acid complexes (British Patent No. 7.020) II, TT No. 7 Specification'wt), Heterocyclic Amine Iran Compound (British Patent No. 1.0/L, 000
boron compounds, such as those in the patent specification). The pH of this fogging bath (reversal bath) ranges over a wide range from the acidic side to the alkaline side, and is preferably in the range of %DH' to /λ, preferably 3 to 3. .

The color developer used in the present invention has the composition of a general color developer containing an aromatic primary amine developer and a drug. Preferred examples of aromatic primary amine color developing agents are p-phenylenediamine derivatives as shown below. N,N-diethyl-p-phenylenediamine, no amino! -diethylaminotoluene, no-amino-(N-ethyl-N-laurylamino)toluene%"(N-ethyl-N
-(β-hydroxyethyl)aminocoaniline, no methyl-[N-ethyl-N-(β-hydroxyethyl)aminecoaniline, N-ethyl-N-(β-methanesulfamidoethyl)-J-methyl- ≠-aminoaniline, N-(j-amino-!-diethylaminophenylethyl)methanesulfonamide, N,N-dimethyl-p-phenylenediamine, U.S. Pat. ≠-Amino-3-methyl-N-enal-N-methoxyethylaniline, ≠-amino-3-methyl-N-ethyl-he-β-ethoxyethylaniline and Hiro-amino-3-methyl-N described in the specification etc.
Preferred representative examples include -ethyl-N-β-butoxyethylaniline and salts thereof (eg, sulfur salts, hydrochlorides, sulfites, p-toluenesulfonates, etc.).

The color developing solution can also contain other known color developing solution component compounds. For feeding, caustic soda, caustic potash, soda carbonate, potassium acid, tribasic sodium phosphate or potash, potassium metaphosate, horax, etc. are used alone or in combination as alkali, detergent, buffering agent, etc. It will be done.

Color developing solutions usually contain sulfites, which are used as preservatives.
For example, sodium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite) or hydroxylamine can be added.

If necessary, any development accelerator can be added to the color developing solution. For example, US Pat. Cationic dyes, neutral salts such as thallium nitrate and potassium nitrate, Japanese Patent Publication No. Akihirohiro-yJ'ohiro, US Pat. No. 26332
Specification No. 20, U.S. Patent No. 2/3/131, same Kota! Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in No. 0170 Specification, No. λ677/27-Specification, Tokko Sho≠μm9! O
Organic solvents and organic amines, ethanolamine, ethylenediamine, jetanolamine, etc. described in Publication No. 6Jrλrt2 of Belgium; o>L, F
, A. Mason Photography
Processing Chemistry P4!0
-03 (Focal Press-London-z
The accelerator sounds described in P+a) can be used.

Furthermore, the color developing solution may contain an aminopolycarboxylic acid represented by ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriamine, and ntaacetic acid as a water softener. can.

Competing couplers and compensating developers can also be added to the color development solution.

Citrazic acid, J acid, H acid, etc. are useful as competitive couplers.

As the compensation compound *i, p-aminophenol, N-benzyl-p-aminephenol, /-phenyl-3-pyrazolidone, etc. can be used.

The pl-1 of the color developing @ solution is approximately 1. /J range is preferred.

The temperature of the color developing solution is selected within the range of λO0C to 70'C, preferably 300C to 60'C.

After color development, the photographic emulsion layer is usually subjected to a white printing process. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As bleaching agents, polyvalent metal compounds such as iron (III), cobalt (tIV), chromium (■), and copper (n), peracids, quinones, and nitrone compounds are used. For example, 7 eryzonide, dichromate, M complex salts of iron (nl) or cobalt (l[I), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /I3-diamino-λ-propatol tetra Aminopolycarboxylic acids such as vinegar or complex salts of citric acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; and nitrosophenols can be used. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (1) sodium worm and iron ethylenediaminetetraacetate (1)
1) Ammonium is particularly useful. Aminobolic mono-ill N salts are useful in both stand-alone bleach solutions and -bath bleach formulations.

For bleaching or bleach-fixing solutions, US Patent No. 30 Hiroko! -0 specification, same 3co$/P44 specification, special public show as-tj
It is also possible to add various additives, including the bleaching accelerators described in Japanese Patent Publication No. OT, Japanese Patent Publication No. SHOAJ-RRST, and the like.

The fixing bath of the present invention contains 309/I ammonium salt, sodium salt, and potassium salt of thiosulfate as a fixing agent.
In addition, stabilizers such as sulfites and isomeric bisulfites, hardeners such as potash alum, acetates, borates, phosphates, and carbonates are used at a concentration of 00 g/l. , etc. may be included. The pH of the fixer is 3~
io, more preferably r and y.

The present invention will be described in detail with reference to Examples below.

Implementation row 1 Average particle size 0. A cubic silver bromide emulsion of /jμ was prepared and overlaid with hydrazine and a total complex salt under low pAg.A silver bromide shell was then formed on the surface of the emulsion to a thickness of 210 μm. This emulsion was coated on a film support with a silver content of 0. The nine samples were designated as sample number 10/, and this will be used as a comparative control sample from now on.

Next, the table-
Samples 102 to 34L were prepared by adding the merocyanine dye shown in I and adsorbing it to the surface of the emulsion grains, and then coating the same amount of silver as Sample 10/.

These samples were processed (without exposure to light) at 3.10C using a developer having the following formulation and varying the processing time as shown in Table 2.

Developed iron solution formulation The optical density of the developed silver of the obtained sample was measured and the results are shown in Table 7.

From Table 7, it can be seen that the sample obtained by adding a mononocyanine dye to a silver halide emulsion having fog nuclei inside was found to be defective.

For example, in the sample to which no merocyanif dye was added (sample number 101), almost no development occurred until the development time was 2 minutes.
The optical density of silver is rapidly increasing.
A significant increase will occur. On the other hand, in the sample to which dye (3) was added (sample number 10λ, lθ3°1on), the concentration increased by the same degree as the sample without the additive, unless the current time was further increased to 11 hours. It turns out that there isn't. It is also known that the increase in the degree of a is slowed down when the amount of dye added is increased.

This result is similar for other dyes, and despite the addition of all merocyanine dyes, it is possible to control the timing at which silver halide emulsions with internally diffused nuclei are developed. It shows.

EXAMPLE On the cotriacetate film base, first
- Coating the 72nd layer to produce a color reversal photographic material.

First layer; antihalation layer (gelatin layer containing black colloidal silver).

1st layer; gelatin middle j-0 2,! - Total di-t-octyl-hydroquinone, dibutyl phthalate 10 OCL and 6 ul ethyl 100 Ω were dissolved in 10% gelatin aqueous solution with high speed stirring with J9. #1 grain emulsion (grain size o, otμ, 1 mol% silver iodobromide emulsion) / J' with io% gelatin /,,tkg
It was mixed with silver and coated to give a dry film thickness of
．． Ifl/m2).

3rd layer: Low-speed red-sensitive emulsion layer cyan coupler λ-(heptafluorobutyramide)-(,2/ (,2// ,g//-di-t)
-aminophenoxy)butyramide)-pheno-k10
0/l was dissolved in 100 CC of tricresylphos 7A) and ethyl acetate, and stirred at high speed with a 10% aqueous solution of sectetine (fI), resulting in an emulsion of 9 emulsion Z o 01 k
was mixed with 1 kg of red-sensitive silver iodobromide emulsion (containing 70 g of silver, tOg of gelatin, and iodine content of t mol %) and coated to a dry film thickness/μ. (Wife 0.JJ/y
L2) At the same time, an emulsion having internal fog nuclei prepared in the same manner as in Example 1 was also mixed, so that the amount of coated silver was 0.
．． It was coated at a coating density of 0/79/m2.

4th A layer: MJ red-sensitive emulsion layer containing =-(heptafluorobutyramide)-1-()'-(λ〃,4t"-di-t-aminoneenoxy)butyramide)-phenol 1009, which is a cyan coupler. , tricresyl phosphate i.

oct, and an emulsion obtained by dissolving in 100 cc of ethyl acetate and stirring at high speed with a 70% gelatin aqueous solution lkI.
oog5, red-sensitive silver iodobromide emulsion 1 kg (silver 70/i,
Contains 60 g of gelatin, iodine content is t mol %), and the dry film thickness is... It was applied so that it was μ. (Silver@o
, tfi/m2) 1st layer; Middle layer: An emulsion obtained by dissolving j-t-octylhydroquinone in 100 cc of dibutyl phthalate and 700 cc of ethyl acetate, and stirring at high speed with 1 kg of an aqueous solution in 10% gelatin. 9f, mixed with 10% gelatin/kg,
The coating was applied to a dry film thickness of lμ.

Layer 1; low green sensitivity emulsion layer with magenta coupler instead of cyan coupler /-(
,2,da,6-dolychlorophenyl)-3-(J-(J
Emulsion 3oo11k, green-sensitive silver iodobromide emulsion 1kII (silver 70g, contains gelatin AOfi, iodine content is 7 mol%) K mixed, dry film thickness /,
It was applied so that it became Jμ. (Amount of silver/-/I/m") At the same time, an emulsion having internal K-shaped cores prepared in the same manner as in Example 1 was also mixed, and the amount of coated silver was 0.
It was applied so that it was 0 koi/trL.

7th layer: Highly sensitive green-sensitive emulsion layer with magenta coupler instead of cyan coupler /-(
λ, μ, trichlorophenyl)-3-(J-(ko,
≠-G-t-amylphenoxyacetamide)benzamide)-! - A green-sensitive silver iodobromide emulsion/1c9 (containing silver 70y1 gelatin toIi),
Iodine content #'it mol%) and dry film thickness 3. j
Apply it so that it becomes μ. (Amount of silver /, /,!i'/m"
) First layer: Yellow filter layer An emulsion containing yellow colloidal silver was coated to a dry film thickness of lμ.

yr@H low-sensitivity blue-sensitive emulsion layer α-(
hivaloyl)-α-(/-benzyl-!-ethoxy 3
-Hydantoinyl) -Korroro! -1000 g of an emulsion obtained in the same manner as the emulsion of the seventh layer except that dodecyloxycarbonylacetanilide was used was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (contains silver 7077, gelatin top, and has an iodine content of 7 mol%), dry film thickness/, j
It was applied so that it was μ. (Amount of silver O0≠g/rIL2)
- 7th θ layer; Highly sensitive blue-sensitive emulsion layer α-(
pivaloyl)-α-(/-benzyl-!-ethoxy3
-hydantoinyl)-1-chloro-! 1 kg of a blue-sensitive silver iodobromide emulsion (containing 70 g of silver and gelatin TOG) was added to the emulsion iooog obtained in the same manner as the emulsion of the first layer using -dodecyloxycarbonylacetanilide.
The iodine content was 6 mol %) and coated to a dry film thickness of 3 μm. (Amount of silver o, r9/m2) 1st/layer;
Emulsion used in the 1st protective layer and 3rd layer/kif, 10% gelatin 1kg
was mixed and applied to a dry film thickness of λμ.

1st layer: Cover the surface of the 1st protective layer with a fine-grain emulsion (grain size 0° 0tμ,
A 10% gelatin aqueous solution containing 1 mol % silver iodobromide emulsion) was coated to give a silver coating amount of 0.1117 m'' and a dry film thickness of O6jμ.

The sample prepared as described above will be designated as sample number λO/ and will be used as a comparative sample from now on.

Next, an emulsion prepared in the same manner as in Example 1 and having fog nuclei inside was added to the P-th layer; low-sensitivity blue-sensitivity emulsion layer,
Sample-02 was prepared by coating so that the amount of silver coated was 7'm2.

Next, Sample 203 was prepared in the same manner as Sample 02, except that the amount of dye (6) shown in Table C was added together with the emulsion to the second layer (low-sensitivity blue-sensitive emulsion layer). did.

The obtained sample was exposed to a light source of μroo0, and the illuminance of the exposed surface was
It was exposed to white light through a sensitometric wedge under θ00 lux, and then subjected to inversion standard processing and inversion sensitization processing described later to obtain a color image.

The treatment steps and treatment liquid used here are as follows.

Standard processing process Process time temperature First development 6 minutes 3rOc Wash with water for 2 minutes Reversal 2 minutes Color development 6 minutes Adjustment 2 minutes Bleaching 6 minutes Fixed arrival time: 4 minutes Wash with water 4 minutes Stability 7 minutes at room temperature drying Sensitization process Process time temperature The current time is io minutes JIr0C Wash with water for 2 minutes Reversal 2 minutes Color development 6 minutes Adjustment 2 minutes bleach Fixed arrival μ minute Jt OC Water washing participation Stable for 1 minute at room temperature drying The composition of the treatment liquid used is as follows.

Back: 1111 Water 7001d Sodium tetrapolyphosphate 2g Sodium sulfite CooII Hydroquinone monosulfonate 30g Sodium carbonate (l hydrate) JO9 l-Phenyl methyl chloride 1 μm Hydroxymethyl-3-pyrazolidone Co9 Potassium bromide 1.3g Thiocyanine Potassium acid 1.2g Potassium iodide (o, i% solution) -2d Add water
1000al Hawk (plooO,/) Reverse liquid water 700ml Nitro-he-N-N-trimethyleneoschinic acid @tNa salt 3g Stannous chloride (l hydrate) ig P-aminophenol o, ig Sodium hydroxide rl Ice Acetic acid /! Add water and add 1000ml Color developer water 700ml Sodium tetrapolyphosphate All Sodium sulfite 7g Sodium tertiary phosphate (11 hydrate) 36g Potassium bromide /fi Potassium iodide (O, i% solution) Yotxt Sodium hydroxide 3g Citrazic acid i-rg OK Ethyl-N-(β-methanesulfonamidoethyl)-3 Methyl-Hiro-aminoaniline ///i Sulfate 3g Ethylenediamine 10100O Add water and ti Water 700tnl Sodium sulfite l koy Ethylenediamine, sodium tetraacetate (l hydrate) rg Thioglycerin O0 1 Glacial acetic acid 3M Add water 1000rrdj l 1 water roog Sodium ethylenediaminetetraacetate (l hydrate) s, og Ethylenediaminetetraacetate iron (III ) Ammonium (dihydrate salt) /20. Og Onii I/-hII J, / /) /) -130 Add water 1000Fd Fixer water 100ml Ammonium thiosulfate to, og Sodium sulfite z, og Sodium bisulfite j, 0g Add water 1000al Takam Water 100 Formalin (37% by weight), ONT Fuji Drywell J, 0ml Water was added and the optical density of the yellow image of the obtained sample was measured through a blue filter to evaluate the sensitization developability. .

From the characteristic curve, constant density<D=i.

The sensitivity was expressed as the reciprocal of the exposure amount required to obtain the yellow density t- of O).

The results obtained are shown in Table C.

From Table 1, an emulsion with internal fog nuclei was added to the low-sensitivity blue-sensitive emulsion layer. It can be seen that the increase in sensitivity increases when the development process is performed.Also, an emulsion with internal K-shaped nuclei and dye (6) were added to the low-sensitivity blue-sensitivity emulsion layer. )teeth,
It can be seen that the range of increase in sensitivity due to the sensitization development process becomes smaller depending on the amount of dye (6) added compared to the paper stock λO.

.

The above results show that by using a combination of an emulsion having internal fog nuclei and the merocyanine dye of the present invention, it is possible to control the extent of increase in sensitivity due to sensitization development. Furthermore, it can be seen that the decrease in maximum density when sensitized and developed is also reduced by adding the merocyanine dye.

Next, the sensitization rate (specific sensitivity in sensitized development/ratio W&wL in standard development) for each sample is shown in Table 3.

The sensitization rates of the red-sensitive layer and the green-sensitive layer were determined by setting the specific sensitivity in standard development to 100, respectively. From Table 3, it can be seen that the sensitization rate of sample 203 is the same as that of the red-sensitive layer and the green-sensitive layer, and it shows good colorpa and lance even during the sensitization process.

Table-3 Procedural amendment dated Z/9/1952 2 Title of the invention Color photographic light-sensitive material 3 Relationship to the case of the person making the amendment Person of the patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. \(- 4. Subject of amendment We will submit a revised version of the specification 5, details of the amendment (no changes to the content).

Procedural amendment '4'5/Administrator's Palace 1, Indication of the case Showa J. R. Patent Application No. λt73/No. 2,
Title of the invention Color photographic light-sensitive material 3, Relationship to the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. 4, Subject of amendment Column 5, "Detailed Description of the Invention" of the specification, Contents of the amendment (11 Change "1 mol%" in line 12 of page 57 of the present specification to "containing iodine") 1 mol% of the amount of mol%.

(2) "t-aminophenoxy" on page 57, line 18 and page 58, line 13 of the same book are respectively corrected to "t-amylphenoxy."

(3) Page 60, line 20 and page 61, line 10 of the same book. “The 1st JWJ "Third layer" and correct it.

(4) Same book, page 65, line 4 "Oskin wij" "Phosphonic acid" and correct it.

that's all

Claims (1)

[Scope of Claims] (1) In a color photographic material comprising at least one red-sensitive, one green-sensitive and one blue-sensitive emulsion layer, at least seven of the emulsion layers are formed and/or adjacent thereto. A color photographic light-sensitive material that contains a combination of a silver halide emulsion having internal fog nuclei and a merocyanine dye in a non-photosensitive emulsion. (21Th1l) The color photographic light-sensitive material according to claim 1, characterized in that the color photographic light-sensitive material is a color reversal light-sensitive material. (3) The silver halide emulsion having fog nuclei inside the surface Gakaburasa f'L7' (with silver halide inner core,
3. A color photographic light-sensitive material according to claim 1 or 2, which is an emulsion comprising core-shell type silver halide grains having a silver halide outer shell covering the surface thereof.