JPS62232650A - Color photographic sensitive material improved in stability of cyan image against light - Google Patents

Abstract

PURPOSE:To obtain a color photographic sensitive material containing a cyan couple superior in color forming performance by incorporating one of specified phenol type cyan dye image forming couplers and one of specified compounds in at least one of silver halide emulsion layers. CONSTITUTION:The color photographic sensitive material has on a support at least one of the silver halide emulsion layers containing at least one of the phenol type cyan dye image forming couplers represented by formulae I and II, and at least one of the compounds represented by formula III, and in these formulae, each of R1, R2, and R4 is an aliphatic, aromatic, or heterocyclic group, each of R3 and R6 H, halogen, acylamino, or the like; R5 is alkyl; each of Z1 and Z2 is H or a group to be released by coupling reaction; n is 0 or 1; R7 is alkyl, cycloakyl, or the like; R8 is halogen, hydroxy, sulfamoyl, or the like; and l is 0 or an integer of 1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color photographic material containing a 7-el cyan coupler, and more specifically, it has excellent color development properties and improves the cyan dye image formed. The present invention relates to a color photographic material with improved stability against stress.

[Prior art]

As is well known, in subtractive color photography, an aromatic primary amine color developing agent is produced by reducing exposed halogenated kite particles, and the oxidation products of the color developing agent are combined with yellow, cyan, and magenta dyes. By oxidatively coupling the coupler to be formed in the silver halide emulsion layer,
Form a dye image. As the yellow coupler that forms the YA-dye, a compound having an open chain methylene group is generally used, and as the magenta coupler that forms the magenta dye, compounds such as pyrazolone type, pyrazoli/bencyimiguzole type, and imidacylone type are used. used. As a cyan coupler that forms a cyan dye, a compound having a phenol or naphtholic hydroxyl group is used.

Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent or in combination with an auxiliary solvent if necessary, and added to the silver halide emulsion, or dissolved in an alkaline aqueous solution and reduced to 7 L. added inside. The latter is the oil droplet dispersion method, and the latter is the alkali number method, but both methods are generally superior to the latter in terms of light resistance, heat resistance, moisture resistance, granularity, and color sharpness. It is said that there are.

The most important basic properties required for each coupler are excellent color development, high crystallization, high solubility in solvents or alkaline aqueous solutions, and silver halide photography. It is desirable to have various 111 characteristics such as good dispersibility and stability in emulsions, good spectral absorption characteristics, and good color reproducibility and fastness of the resulting dye image. It is rare.

In the color photographic light-sensitive materials to be used for printing, it is strictly required that the dye images obtained from each coupler have good fastness.

Numerous attempts have been made to improve the fastness of dye images obtained from each coupler.

For example, US Patent No. 1.432,300, US Patent No. 3,57
4. [No. +27, No. 3,573.05Q, Special Publication No. 1973
-47245, 4B-3272111, 51-
No. 30462, Machi 1-cho No. 48-26133, No. 49-
1344 (No. 20, No. 50-6338, No. 50-23
No. 822, 5+-12:1 (i42, 51-12
No. 4926, No. 52-35033, No. 52-1474
No. 33, No. 52-152224, No. 53-120,
No. 53-20327, No. 53-53321, No. 53
-70822 No. 1145: ]-7775213 No. 5
No. 3-77527, No. 54-48538, No. 54-6
No. 2826, No. 54-822: No. J4, No. 54-823
No. 85, No. 54-147038, No. 54-15434
No. 5, No. 5545954, No. 55424141, No. 56-39541, No. 56-159644, No. 50
-167138, 57-204037, 58-
No. 105147, No. 59-34'+3, No. 59-12
No. 5732, No. H-211455, No. 60-2831
49, No. 01-2151, No. 01-4041, No. 81-4045, etc., a method for improving the fastness of dye images was disclosed on January 1, and among these, the x-multiplexing technique There are also quite a few.

Most of the techniques described above are aimed at improving the light fastness of magenta dye images, and there are few techniques aimed at improving the fastness of yellow and cyan dye images. The number of technologies is limited.

However, techniques aimed at improving the fastness of cyan dye images have recently been increasingly developed.

For example, JP-A No. 59-343:1, No. 59-42541
No. 59-87456, No. 59-124340,
No. 00-222853 and others discloses a technique for improving the fastness of a cyan dye image by using a fer7-based compound of 1, d, in combination with a cyan coupler.

However, although these techniques have improved the fastness of cyan dye images to some extent, they are still not at their peak, and in addition, the phenolic compounds have the serious drawback of greatly reducing the coloring properties of cyan couplers. It was recognized that the In particular, the color development time [JIi! or reduce the pH of the color developer, or remove development-promoting components in the color developer (e.g., organic solvents such as benol alcohol and 7-enethyl alcohol, and alkaline non-isolate salts such as sodium hydroxide and potassium carbonate). ), the deterioration in the color development of the cyan coupler due to the coexistence of the above-mentioned 7-ol compound was more markedly observed.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a color photographic material containing a cyan coupler with excellent color development.

A second object of the present invention is to provide a color photographic material in which the stability of cyan dye images, particularly the fastness to light, is improved.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a color photosensitive material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the following general formula [1]. This is achieved by containing at least one coupler selected from the phenolic cyan dye image-forming couplers represented by and [11] and at least one compound represented by the following general formula C[l].

In the formula, R,, R2 and R1 each represent an aliphatic group, a 7-aryl group or a heterocyclic group, and R2 and R6 each represent,
represents a hydrogen atom, a halogen atom, an alkyl group or a 7-sylamine group, R5 represents a furkyl group, R2 and R
2 may be bonded to each other to form a 5-G nitrogen-containing heterocycle. zl and z2 each represent a hydrogen atom or a force gamma bling leaving group, n is O or 1.

In the SK formula, R represents an alkyl group, an alkenyl group, a 7-aryl group, or a dichlorofurkyl group, and R@ represents a halogen atom, a hydroxyl group, or a Schiff/2! i, a furkyl group, an alkenyl group, an aryl group, a dichlorofurkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloquine carbonyl group, an acyl group, an acylamide group, a carbamoyl group, a sulfonamide group, or a sulfonomyl group; , l represents 0 or an integer of 1 to 4.

The present invention will be explained in more detail below.

First, the cyan coupler represented by the general formula [1] and zo(r[] according to the present invention will be explained in more detail.

In the present invention, the term "aliphatic group" may be linear, branched, or cyclic, and includes saturated and unsaturated groups such as alkyl groups, dichlorofurkyl groups, alkenyl groups, and alkynyl groups. It may also be replaced.

+tif general formula [1] and zo [1j],
12 and R1 are aliphatic groups having 1 to 31 carbon atoms (for example,
methyl group, butyl group, octyl group, tridecyl group, hexenyl group, i-hexadecyl group, cyclohexyl group, etc.), aryl j5 (e.g., phenyl group, r7 thyl group, etc.), heterocyclic group (e.g., 2-bilinol group, 2-thiazolyl group, 2-imidazolyl group, 2-7lyl group, 6-
quinolyl group, etc.), and these represent an alkyl group, a 7-aryl group, a polycyclic group, an alkoxy group (e.g., a methoxy group, a 2-7 toxyethoxy group, a tetradecyloxy group, etc.), a 7-aryloxy group (e.g. , 2,4-no-7mil7eth/oxy group, 2-chlorophenoxy group, 4-thia7
7eth/oxy group, 4-butanesulfone 7midoffyo7oxy group, etc.), acyl group (e.g., acetyl, ni, benzoyl, etc.), ester group (e.g., ethoxycarbonyl group,
2.4-NoL-7mil7e/quinecarbonyl group, acetoxy group, benzoyloxy group, butkinsulfonyl group, toluenesulfonyloximi7 group, butanesulfonamide group, dodecylbenzenesulfonamide group, noprobylsul7 amoyl7 carbamoyl group (e.g., dimethylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group:
j (for example, butylsulfamoyl group, etc.), imide group (
For example, succinimide group, higantonyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), sulfonyl group (e.g., methanesulfonyl group, (carboquine methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic group or aromatic thio group (e.g., butylthio group, phenylthio group, etc.), hydroquine group, cyano group, carboxyne group, nitro group, sulfo group,
It may be substituted with a group selected from halogen atoms and the like. When there are 2 or more substituents and 6 substituents, they may be the same or different.

In addition, in the general formula CI], 1<, is a hydrogen atom,
A nonmetal group that forms a nitrogen-containing 5- to Gli ring together with a halogen atom, an alkyl group, an aryl group, a 7-syl-7-mino group, or 1<2.

In addition, in the general formula [11], 1(, represents an alkyl group), and may have a substituent, preferably an alkyl group having carbon rlt1 to 24. As a steric substituent, an Illi aliphatic group, Examples include an aryl group, a heterocyclic group, an aliphatic oxy group, an aliphatic thio group, an aryloxy group, an arylthio group, and an acylamide group. More preferably, 1(,
is an alkyl group having 1 to 14 carbon atoms; 4. ) is preferably a lower alkyl group having 1 to 4 carbon atoms.

1111 In the general formula [[1], 1<6 represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a lower furkyl group (for example, an ethyl group).

represents an aryl group (e.g., phenyl group, naphthyl group) or an acylamide group (e.g., acetylamino group, benzamide group, etc.).

Zl in the general formula (1) and general formula (II)
Z2 represents a hydrogen atom or a coupling-off group, such as a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), a flukoxy group (e.g., nidoxy group, dodecyloxy group, methoxyethyl group, etc.). Carbamoylmethoxy group, carboquine pro and ruoxy group,
methylsulfonylethoquine group, etc.), aryloxy group (e.g., 4-chlorophenoxy group, 4-7 toxyphenoxy group, 4-carboxyphenoxy group, etc.), 7-syloxy group (e.g., acetoquine group, tetrazochallyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., methanesulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., nochloroacetylamine group, heptafluorobutyrylamine group, seven methanesulfonyl group), 7 groups, toluenesulfonylamine 7 groups, etc.), alkyloxycarbonyloxy groups (e.g., nidoxycarbonyloxy groups, benoloxycarbonyloxy groups, etc.), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy groups, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, 7enylthio group, tetrazolylthio group, etc.), imide group (e.g.,
succinimide group, hyguntoynyl group, etc.), aromatic azo groups (eg, phenyl 7zo group, etc.), and the like. These leaving groups may include photographically useful groups.

Furthermore, the general formula [! ] or [■] Preferred examples of cyan couplers are as follows.

In general formula [1), RI is preferably an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, a flukoxy group, an aryloxy group, an acylamide group; an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group,
Sulfonyl group, sulfamide group, oxycarbonyl group,
More preferably, it is an aryl group substituted with a cyano group. In general formula []], when 12 and R1 do not form a ring, R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R7 is preferably It is a hydrogen atom.

In the general formula (11), 1 and 2 are preferably substituted or unsubstituted alkyl groups, and 1 and 2 are preferably substituted aryl-one-substituted alkyl groups.

In the general formula (II), the preferred 1(,) is an alkyl group having 1 to 4 carbon atoms, as described above.

In the general formula [11], R5 is preferably a hydrogen atom or a halogen atom r-, with salt lf, an atom, and a fluorine atom being particularly preferred.

In general formula (11), it is particularly preferable that 1(6 is a chlorine atom and R5 is lower alkyl J! having 1 to 4 carbon atoms).

Preferred Z in general formula [1] Ogori [1].

and Z2 are each hydrogen h; (Ryo・, halogen atom,
An alkoxy group which may have a substituent, an aryloquine group, and a sulfonamide group.

In the general formula (11), 72 is preferably a halogen atom, and chlorine and fluorine atoms are particularly preferred.

In general formula (1), when 11=0, Z1 is more preferably a halogen atom, and particularly preferably a chlorine atom and a fluorine atom.

In the present invention, the most preferred cyan coupler is a coupler represented by the following general formula (Ia).

R, , R2 and VZ in general formula [1a] have the same meanings as R, , R2 and zl in the above general formula (1), respectively, and specific examples of preferred groups are as shown in +iQ. .

Specific examples of the cyan coupler compounds represented by the general formulas [1] and [Il] are listed below.
It is not limited to these.

Below is the remainder.

(+-2) (1~4) tUzlh)2N off 2N11 (+-6) ([-8) (+-10) Ul (+-12) (+-14) II (+-18) rθ (+ -23) (+ -29) LJlv(t) (II-1) Shi! (■-2) (n-3) C! (II-5) Bi! I CII-7> 1. (II-9) l (II-10) C! (II-12) (■-13) l ([1-14) (II-15) C! (fl-16) (II-17) Shi! (II-18) Shi! (II-19) OO11 (II-21) Cl (n-22) f (It-24) These cyan couplers represented by the general formulas (1) and (II) of the present invention (hereinafter referred to as the couplers of the present invention) ) is U.S. Patent No. 2,369.929, U.S. Patent No. 2,772,16
No. 2, No. 2,895.826, No. 3,311,476
No. 3,446,622, No. 3,758.308,
3,880,661, 3,996,253, JP 49-11572, 56-65134, JP 55-163537, 56-29235, 5
No. 6-80045, No. 56-104333, No. 56-
No. 116030, No. 57-136650, No. 57-1
No. 57246, No. 57-204543, No. 57-20
No. 4544, No. 57-204545, No. 58-105
No. 229, No. 59-31953, No. 59-31954
No. 59-69755, No. 59-166956, etc., and can be synthesized according to the synthetic method described therein.

In order to incorporate the coupler of the present invention into a silver halide emulsion, conventionally known methods may be followed. For example, the coupler of the present invention is dissolved in a mixture of a known high-boiling point solvent and a low-boiling point solvent such as butyl acetate or butyl propionate, and then mixed with an aqueous gelatin solution containing a surfactant, and then mixed with a high-speed rotary mixer or a floid mill. Alternatively, a silver halide emulsion can be prepared after emulsifying with ultrasonic waves. Known high-boiling point solvents include 7-tar acid-engineered tils (e.g. dibutyl 7-talate, etc.), uAa ester*
(e.g., tricresyl phosphate, etc.), N-substituted acid amide M (e.g., N,N-noethyl laurylamide, etc.), 7E/-L M (e.g., 2°5-no-L-7milphenol, etc.) ), etc.

The couplers of the invention are usually 1) IX per mole of silver halide.
IO-co-5X 10-' mol, preferably H1x10-
It can be used in a range of 2 to 5 x 10-' moles.

The coupler of the present invention can also be used in combination with other types of cyan couplers.

Furthermore, when the color photographic material according to the present invention is used as a multicolor photographic material, in addition to the coupler of the present invention, yellow couplers and magenta couplers commonly used in the industry may be used in a normal manner. can. Also,
A colored coupler having a color correction effect may be used if necessary.

Two or more couplers can be used together in the same layer in order to satisfy the characteristics required for photosensitive materials.
The same compound can also be added in different amounts of 2M or more.

The compound used in conjunction with the cyan coupler of the present invention, which improves the coloring properties of the cyan coupler and also improves the light fastness of the resulting cyan dye image, has the general formula [
III] is a p-hydroxyphenylthioether compound.

S.R.

In the general formula [III], the alkyl group represented by R7 may be linear or branched, and is preferably a furkyl group having 1 to 24 carbon atoms (e.g., methyl group, 1-propyl group, butyl group, t-butyl group). , octyl group, di-octyl group, decyl group, dodecyl group, octadecyl group, etc.). Flukenyl group represented by R7, propenyl group, pentenyl group, hexenyl group, etc.; aryl group includes phenyl group, 7-tyl group, etc.; cycloalkyl group includes cyclopentyl group, cyclohexyl group, etc. can.

Each of the groups listed above may be further substituted with other substituents, such as halogen atoms,
Hydroxyl group, alkyl group, 7-aryl group, alkenyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, 7-aryloxycarbonyl group, alkyl 7-mi-7 group, arylami-7 group, 7-syl-7-mino group, carbamoyl group, carbonyl group Examples include an amide group, a sulfamoyl group, a sulfone 7-mido group, and the like.

In the general formula ([[l), the furkyl group, alkenyl group, 7-aryl group or cycloalkyl group represented by rho can include the groups explained for R7 above.

In addition, R6 is a halogen atom (for example, a chlorine atom, J2
hydroxyl group, cyano group, alkoxy group (e.g., methoxy group, 2-7toxyethkyne group, tetradenyloxy group, etc.), aryloxy group (e.g., 2-chloroa7e/quine group, 4- alkoxycarbonyl groups (e.g., ethquine carbonyl group, butoxycarbonyl group, Tetradecyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., 71-dicarbonyl group, 2.4-)-1-7mil7e/oxycarbonyl group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.) ), 7-syl amino group (e.g., acetamido group, tetradecanamide group, 4-chlorobenx7 mido group, etc.)
, carbamoyl group (e.g. dimethylcarbamoyl group,
ethylcarbamoyl group, etc.), sulfone 7-mido groups (e.g., butanesulfone-7-mido group, dodecylbenzenesulfone-7-mido group, etc.), and sulfamoyl groups (e.g., butylsulfamoyl group, phenylsulfamoyl group, etc.)
Table tF.

Each of the above-mentioned groups may be further substituted with other substituents as necessary, and examples of this substituent include a group that can be substituted with the alkyl group, alkenyl group, heptadyl group, and dichlorofurkyl group represented by R7. Examples include the groups mentioned above. 1 represents O or an integer from 1 to 4, but n
is 2 to 4, multiple 11. may be the same or different.

In the general formula ([1), it is preferable that R2 is a furkyl group or an aryl group, and ■1 is O or 1 (when n=1, R is preferably a furkyl group), and n is 0. is most preferable. Therefore, a preferred embodiment of the general formula CIII) is represented by the general formula ([[a], and a most preferred embodiment is represented by the general formula (llIl+3).

In the formula, R1 represents a furkyl group or an aryl group, and R5
° represents an alkyl group. The alkyl group and 7-aryl group represented by R3 have the same meaning as the furkyl group and 7-aryl group of R7 in the general formula (I[[), and 11
．． The furkyl method represented by is synonymous with the furkyl group of R6. In the general formula ([1la), Lt; and nlG
It is more preferable that the total number of carbon atoms is 6 to 24.

In the formula, R9 has the same meaning as R9 in the above general formula ([[la)]. In the general formula (tIrb), it is particularly preferable that R9 has 6 to 24 carbon atoms.

``Representative examples of these compounds are shown below, but the compounds used in the present invention are not limited thereto.

Margin below.

(Ill-1) (II
I-2) (III-7)
(1-8) (I[l-91(1-10) ([[l-15) (If
f-16) (fil-171(III-18) (llll-23) (I
ll -24) hL, -1IJv
δU1□11□.

(III-25) (I
II-26) (llll-31)
Cl11-32) The compound represented by the general formula (lit) of the present invention (hereinafter referred to as the compound of the present invention) is described in the Journal of the American Chemical Society (J, Δ鵠.

CI+eu+,Soc,), vol.51, 1526-1
536E'T (1929), Chemische Berichte (Cbem, Ber, ), vol. 87, 947~
955 pages (1954), Croat force, hemi force, acta (Croat, CItes, ^eta,),
Volume 29, 277-285TX (1957), Japanese Patent Publication No. 5
It includes the compounds described in No. 0-6339, No. 52-72225, etc., and can be synthesized according to the synthetic method described.

The amount of the compound of the present invention used is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the cyan coupler according to the present invention.
It is always used in the same layer as the cyan coupler of the invention.

The compound represented by the general formula (ill) of the present invention includes some of the compounds described in JP-A-50-6339 and JP-A-52-72225. The compound contained in the general formula [III] is 3
It has been described that the cyan coupler represented by the general formulas (1 and (U) of the present invention has the property of improving the fastness to light of a magenta dye image formed from a -7nilino5-pyrazolone magenta coupler. There is no suggestion at all about the effect of improving the color-forming property of the cyan coupler and the fastness of the cyan dye image obtained from the coupler.

As a result of intensive studies, the present inventors have determined that the general formula [fl
A person who cannot expect that the compound represented by l) will improve the coloring properties of the cyan coupler represented by the general formula CI3 and [■] of the present invention, and the fastness of the cyan dye image obtained from the cyan coupler. They discovered that it has a unique effect.

The color photographic light-sensitive material of the present invention can be, for example, a color negative or Bott film, or a color photographic paper, but the method of the present invention is especially effective when using a color photographic paper intended for direct viewing. is effectively demonstrated.

The color photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor color photographic materials, in order to perform subtractive color reproduction, silver halide emulsions containing magenta, yellow and cyan couplers are usually used as couplers for copying 1. ) and a non-photosensitive layer on the support with an appropriate layer.
Although it has a structure in which layers are laminated in number and J4 order, the number and layer order may be changed as appropriate depending on the important performance and usage.

Hac7 used in the halogenated photographic material of the present invention
For the silver halide emulsion, any of the halogen compounds used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, can be used. be able to.

The silver halide emulsion used in the silver halide 7L agent of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. Even if the method of collecting and growing the seed particles is the same, )°4
It's okay to be.

In the silver halide 7L agent, halide ions and silver ions may be mixed at the same time, or one of them may be present and the other Jj may be mixed therein. Alternatively, while taking into consideration the critical member rate of silver halide crystals, halide ions and silver ions may be added simultaneously and sequentially while controlling the pl-(+++Ag in the mixing vessel) to perform t&k. The silver halide composition of the grains may be changed later using a component method.

When producing the silver halide of the present invention, the grain size, grain shape, grain-r-size distribution, and grain membership rate of silver halide grains can be controlled by using silver halide tolerance as necessary.

The silver halide grains used in the silver halide 7L agent of the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, ilinium salt or complex salt, rhodium salt, Salts or complex salts, iron salts or complex salts can be used to add metal ions and incorporate them into the interior of the particles and/or on the particle surfaces, and also in a suitable reducing atmosphere (possibly within the particles and/or on the particle surfaces). Reduction-sensitizing nuclei can be attached to the surface.

The silver halide emulsion of the present invention may contain all IIfm salts after the growth of silver halide grains, or may contain them as they are. When removing salts, use the method described in Research Disclosure 1704: No. 3]
This can be done based on the j method.

The silver halide grains used in the silver halide emulsion of the present invention may have a uniform layer inside and on the surface, or may be composed of different particles.9 Silver halide emulsion of the present invention The silver halide grains used may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape, or may have an irregular crystal shape such as a spherical or plate shape. In these particles I:, any ratio of the 1lo01 plane and the (1111 plane) can be used.Also, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more silver halide emulsions that have been separately formed.

The silver halide emulsion of the present invention is sensitized by a conventional method. In other words, sulfur sensitization using a compound containing sulfur that can react with silver ions or activated gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and sensitization using gold or other metal compounds. Metal sensitization methods and the like can be used alone or in combination.

The silver halide 7L polishing of the present invention can be optically sensitized to a desired waveform region using a dye known in the photographic industry as a sensitizing dye. The sensitizing dye may be used alone or in combination of two or more. A dye that does not itself have a spectral sensitizing effect together with a sensitizing dye, or a compound that does not substantially absorb IIF visual potential,
A supersensitizer that enhances the sensitizing effect of the sensitizing dye may be included in the 7L cut.

The silver halide emulsion of the present invention can be used to prevent fogging during the first stage of manufacturing, storage, or photographic processing of light-sensitive materials, and/or
or during the chemical ripening with the aim of keeping the photographic performance stable, and/or at the end of the chemical ripening, and/or before the silver halide emulsion is coated after the chemical ripening. °
Compounds known in the industry as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as the binding agent (or protective colloid) for the silver halide 7L agent of the present invention, but other methods include gelatin derivatives, graft polymers of gelatin and polymers, proteins, sugar derivatives, and cellulose. Hydrophilic colloids such as synthetic hydrophilic polymer-materials such as derivatives, single or copolymers may also be used.

For photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion of the present invention, a hardening agent may be used alone or in combination to crosslink bainggu (or protective colloid) molecules and increase film strength. It is hardened by. The hardening agent is
Although it is desirable to add a hardening agent to the photosensitive material to the extent that it is not necessary to add a hardening agent to the processing solution, it is also possible to add a hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer 14 of the photosensitive material using the silver halide 7L agent of the present invention.

A photograph of a photosensitive material that has been subjected to the high C7'1' silver perforation of the present invention. , water insoluble or what,
A mixture containing a soluble intermediate and a polymer component plus a "fi" material (latex) is produced.

The emulsion layer of the silver halide color photographic light-sensitive material of the present invention contains a coupling reaction with an oxidized form of y7 valley group No. 111 & amine (for example, 9-7 enylene noamine derivatives, aminophenol derivatives, etc.) during color development treatment. A dye-forming coupler is used that forms a 9t dye. The dye-forming couplers are preferably selected such that a dye is formed which absorbs the likelihood spectrum of the emulsion layer for each 7L agent M1;
A yellow dye-forming Kapfu is used in the scraping layer, a magenta dye-forming coupler is used in the edge-color sensitive scraping layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, the silver halide color photographic material may be used in a manner different from the above combination.

Yellow dye-forming couplers include 7-7cetamide couplers (e.g., benzoylacetanilides, pivaloylaceto-7nilides); magenta dye-forming couplers include 5-pyrazolone couplers, pyrazo abenzimigzole couplers, pyrazolotriazoles; , open chain 7
Examples include cylacetonitrile couplers, and cyan dye-forming couplers include naphthol couplers and phenol couplers other than those of the present invention.

These dye-synthesizing couplers preferably have a group called a pallast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms.Also, these dye-forming couplers have 4 molecules in order to form one molecule of dye. It may be either 4-equivalence, in which 100 silver ions need to be reduced, or 2-equivalence, in which only 2 molecules of silver ions need to be reduced.

Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the surface of silver halide crystals can be prepared using the solid dispersion method, latex dispersion method, oil-in-water droplet N:! Various methods can be used, such as a 2L dispersion method, which can be appropriately selected depending on the chemical proximity of the hydrophobic compound such as the coupler. Oil in water 1 type? For the L-dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 15
For high boiling point organic solvents of 0℃ or higher, low boiling point, I,
70-
Using a dispersion means such as a jet mixer or an ultrasonic device,
? After dispersing the L component, a step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion, which may be added to the desired hydrophilic colloid layer.

High boiling, ", 1. As an oil agent, 7 er/-l, which does not react with the oxidized form of the developing agent, J lead fL 7 talic acid ester, phosphoric acid ester, citric acid ester, anthyl Q fi a ester, 7 alkylic 7 A solvent having a boiling point of 150° C. or higher, such as midonic acid ester, is used.

As a dispersion aid when a hydrophobic compound is dissolved in a low-boiling A-I: jar medium or a high-boiling R' solvent in combination with a solvent and dispersed in water using a machine or ultra-α waves, A 7-ionic surfactant, a 7-ionic surfactant, or a kanionic surfactant can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (color sensitivity difference and/or color sensitivity of 4 degrees) C4 1fl
l) A color antifogging agent is used to prevent color turbidity, deterioration of sharpness, and conspicuous graininess due to migration of the oxidized product of the developing agent or the P-transfer agent.

Color capri anti-shaving can be used for emulsion) T4 itself,
An intermediate layer may be provided between adjacent emulsions and used for the intermediate layer (4).

Protection of the photosensitive material of the present invention. Hydrophilic colloids such as aR4, intermediate M, etc. may contain ultraviolet absorbers to prevent capri due to discharge caused by charging of photosensitive materials due to friction, etc., and to prevent image deterioration due to UV radiation. good.

The color light-sensitive material using the silver halide 7L agent of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and a V/or yanoacetic acid 3 antilayer. These layers and/or the emulsion may contain dyes which are washed out or bleached from the color light-sensitive material during the development process.

Using the silver halide 7L shavings of the present invention), the halogenated mIL shavings of a 10-densified material and/or the hydrophilic colloid layer of the photosensitive material are improved to reduce the σ〈 of the photosensitive material. A matting agent can be added to prevent photosensitive materials from sticking to each other.

Slippage f of a light-sensitive material using the silver halide emulsion of the present invention?
, a lubricant can be added to reduce chafing.

An antistatic agent for the purpose of IL during charging can be added to a photographic material using the silver halide emulsion of the present invention.

':r/electronic protection+I-shaving is sometimes used when charging the side of the support on which the emulsion is not laminated. C) It may be used in protective colloid layers other than '7L and 711M on the side where it is applied.

Example 7 of a photosensitive material using the silver halide emulsion of the present invention
(Hydrophilic colloid of L layer and/or pond) C4 has improved applicability, ); stain prevention, improved slipperiness, ? Various m-surface active agents are used for improving photographic properties such as L dispersion, adhesive pasting IL, and V (development acceleration, contrast enhancement, sensitization, etc.).

'li of a photosensitive material using the silver halide 7L agent of the present invention
,true? No L agent, other layers are paper laminated with Baryta 84 or α-olefin polymer, flexible reflective support such as synthetic paper, cellulose acetate, cellulose nitrate,
It can be applied to films made of semi-synthetic or synthetic polymers such as polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc., as well as to rigid bodies such as hollows, metals, and ceramics.

The silver halide photosensitive material of the present invention is prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. depending on the change of heart.
Adhesion directly or on the surface of the support, band i1 prevention, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties,
and/or 1 or 2 to improve the properties of the pond.
It may be applied through the above undercoat layer.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. As for the coating method, EX1 Luno Yon Coating and Curtain Coating, which can apply two or more layers at the same time, are 4! It is useful.

The photosensitive material of the present invention has the structure δ of the photosensitive material of the present invention.
Exposure can be performed using electromagnetic waves in a spectral region to which L cut/l'f has sensitivity. Light sources include natural light ([''尤), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, shade 4 year old I
Any known light source can be used, such as a Q-tube flying tube, various lasers, light emitting diodes, or those emitting phosphors excited by electric gamma rays, Xm11 rays, C1m, etc.

The exposure time ranges from 1 millisecond to 1 second, which is normally used in cameras.11. Of course, it is possible to use an exposure shorter than 1 microsecond, for example, an exposure of 100 microseconds to 1 microsecond using a shadow tube or a xenon flash lamp, or it is possible to use an exposure shorter than 1 second. be. The exposure may be performed continuously or intermittently.

The silver halide photographic light-sensitive material of the present invention can be used for color development known in the art. By doing so, an image can be formed.

The aromatic flXIt class amine color developing main mulberry used in the color developing solution in the present invention includes known ones that are widely used in various color photographic processes. /- and II-phenylenenoamine derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, such as hydrochloride or sulfur 1'l'ffi salts. In addition, these compounds generally have a color developer IQ of about 0.1
．． A concentration of about 30 g to about 30 g is used, preferably about 1 B to about 1.5 g for color developer IQ.

Examples of amino 7 enol-based developers include -ami/phenol, u7minophenol, 5-ami/-2-
Oxytoluene, 2-7mi/-3-oxytoluene, 2
-Oxy-3-7-7-1°4-methylbenzene and the like are included.

Particularly useful primary aromatic amino color developers are N, N
-Dialkyl-+1-phenylenenoamine type compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, an example of a particularly useful compound is N,N-noethyl-p-phenylenenoamine W.
[I,N-methyl-p-phenylene-7-amine acid [,N
, N-tumethyl-p-7enylennoamine hydrochloride,
2-7 minnow 5-(N-ethyl-N-dodecyl 7 minnow)
-Toluene, N-ethyl-N-β-notanesulfonamidoethyl-3-methyl-4-7-7aniline sulfate, N
-ethyl-N-β-hydroxyethylamino-7niline,
Examples include 4-amino/-3-/chi-N, N-noethylaniline, 4-7minor N-(2-nodoxyethyl)-N-ethyl-3-methylaniline-1]-toluenesulfonate, and the like.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, and when the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed on its development. The bleaching agent used in the bleaching process is a metal complex salt of an organic acid, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time causing the uncolored areas of the coloring agent to develop color. The Mt composition is one in which metal ions such as iron, cobalt, and copper are coordinated with ami-7 polycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenenoamine thitraacetic acid [2] Nitrirotriacetic acid [3] Imi-7-acetic acid [4] Ethylenenoamine thitraacetic acid II! ! Disodium salt [5] Ethylenenoamine titraacetic acid tetra(trimethylammonium) salt [6] Ethylenenoamine titraacetic acid tetranatrium salt [7] Nitrilotriacetic acid sodium salt The bleaching agents used are as mentioned above. In addition to containing a metal complex salt of an acid as a bleaching agent, various additives can be included. As additives, it is desirable to include rehalogenating agents such as flukalihalide or ammonium halide, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide, metal salts, and chelating agents.

Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Those known to be added to ordinary bleaching solutions, such as 4L cutting, furkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, the fixing solution and bleaching chamber; rIa is ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, heptammonium metabisulfite, potassium metabisulfite, metabisulfite) 17
From various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. The following pH-class buffers may be used alone or may contain two or more types.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air may be blown or oxygen may be blown into the bleach-fix bath (7) in the bleach-fix replenisher storage tank, or a suitable method may be used. Oxidizing agents such as hydrogen peroxide, bromates, persulfates, etc. may be added as appropriate.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Cyan coupler 1-18 of the present invention (4,8 g7100
cm2) and 2,5-no-1-octylhydroquine (
0.4mg7100cw2) to Butyl 7 Talate (
Dissolved in 4,0H/100cmJ, gelatin (14,0
After emulsifying and dispersing with an aqueous solution of mg/100100e, the mixture was mixed with a silver chlorobromide emulsion (containing 80 mol% silver oxide) and coated to give a silver amount of 3.5 mg 7100 cm2, and dried to obtain a monochromatic color photographic material. This was designated as Sample 1.

Compound 111-2 of the present invention, I[l-3
Samples 2, 3, 4, 5, 6 and 7 were obtained in which 172 moles of cyan coupler were added to each of , ■-10, [[-17, ■-24 and ■-25. Similarly, samples 8.9 and Vlo were also prepared in which 172 moles of cyan coupler were added to each of compounds a, b and C outside the present invention.

Comparative Compounds B, l++ c (both compounds described in JP-A No. 59-3433) The following are the margins: The sample obtained in step 1 was exposed to light through an optical wedge according to a conventional method, and then processed in a rough process. .

[Processing process [Processing temperature Processing time Color development 33°C 3 minutes 30 seconds Bleach fixing 33'0 1 minute 30 seconds Washing with water
Dry for 3 minutes at 33℃
50-80°C for 2 minutes The components of each treatment are as follows. .

[Color developer 1 Benzyl alcohol 1211 diethylene glycol 10zl Potassium carbonate
25゜Sodium Bromide
0.6g anhydrous sodium sulfite
2.0g Hydroxylamine sulfate 2.5
2N-ethyl-N-β-7thanesulfonamidoethyl-3-methyl-4-ami/aniline sulfate Add 4.5g of water and prepare 1! and adjusted to 1+1110,2 with sodium hydroxide.

[Bleach-fix solution l Ammonium thiosulfate 120° Sodium metabisulfite 15g Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to bring the pH to 11, and adjust the pH to 6.7~
Adjusted to 6.8.

For Samples 1 to 10 treated above, the sensitivity and maximum reflection density were measured using a charged densitometer (Konishiroku Photo Industry Co., Ltd. P
D^-60 type). The results are shown in Table 1, provided that the sensitivity is expressed as a relative sensitivity when the sensitivity of sample 1 is taken as 100.

In addition, each treated sample was placed in a xenon fade meter for 15 minutes.
The dye image was irradiated for one day and the light fastness of the dye image was examined.

The results are also shown in Table 1. However, the evaluation of the light fastness of the dye image is as follows.

〔Survival rate〕

Percent dye remaining after likelihood test at initial concentration 1.0.

As is clear from the results in Table Pt51 in Table 1 below, the samples (2 to 7) according to the present invention all have increased maximum reflection density and dye residual rate, and the coloring properties of cyan coupler 5 and 5 have increased. The lightfastness of cyan dye images is excellent.

In contrast, samples to which the comparison compound was added (8-10
) somewhat improves the light fastness of the cyan dye, but reduces the color development of the cyan coupler.

Example 2 Each sample was processed in exactly the same manner as in Example 1, except that benol alcohol was removed from the color developer composition during the processing step. The results are shown in Table 2.

Below is a margin of Pt% 2 Table (Presence or absence of benol alcohol indicates the presence or absence of henol alcohol in the color developing solution.The results for the presence of benol alcohol refer to the results of Example 1.The SI+ degree is sample 1. (It is expressed as relative sensitivity when the sensitivity in the presence of benol alcohol is taken as 100.) From Section 2'y2, the color development rate of the sample added with the comparative compound decreases when treated without benol alcohol. It can be seen that in the case of the samples of the present invention, the deterioration in color development was very small even when treated with benol alcohol charcoal. Therefore, when processing samples of the present invention, there is no need to add benzyl alcohol to the color developer. This is very advantageous from the standpoint of pollution control.

Margin Example 3 Samples 11 to 30 were prepared by combining couplers and additive compounds as shown in Table 3 and coating them in the same manner as in Example 1.

Each sample was treated under the same conditions as in Example 2. Furthermore, the treated sample was subjected to a light resistance test under the same conditions as in Example 1. The results are also shown in the ill'$3 table. Note that the sensitivities in the table are relative sensitivities when the sensitivity of sample 11 is set as 100.

Comparative compounds d and e are both compounds described in W Kaimei No. 59-87456)
(d) From the results shown in Table 3;), it can be seen that by combining the coupler of the present invention and the compound of the present invention, the color-forming properties of the cyan coupler and the light fastness of the color-forming dye are improved.

Example 4 On a paper support laminated on both sides with polyethylene, each of the following materials was coated sequentially from the support side to prepare a multicolor silver halide photographic light-sensitive material, and Sample 31 was obtained.

No. 184: +T-sensitive silver halide emulsion [1] α-pivaloyl-α-(2+'t-
Nooxo 1-pencylimigzolinon-3-yl)-
2-chloro-5-[γ-(2,4-noL-7mil7e7quine)butyramide 1 acetanilide [j,8+B
/ ] 0Ocl12, blue feel and salt odor comparison emulsion (silver bromide 8
5 mol%) in terms of silver, 3.21 layers g/1OOC
II12, butyl 7 tallate 3.5uH/100
cm2 and gelatin: 1.5+abi/'100c+
It was applied so that the coating amount was O2.

2nd layer: Middle 84 2.5-not-t-octylhydroquinone 0.5I g/100c+a2, Noval 7 tallate 0.511
1g/100 C theory 2 and gelatin 9.0 mackerel/100
It was coated so that it was cm2.

3rd M: Green-sensitive silver halide emulsion layer Magenta coupler:゜5Ing/
locm', green-sensitive silver chlorobromide milk waste (containing 80 mol% silver bromide) converted to silver: 2. Olbi/1ooca+7,
Nobutyl phthalate 3, O+a g/100
c +n 2 and gelatin 12. (hg/ lo
ocm".

Pt54 layer: Intermediate 84 Ultraviolet absorber 2-(2-hydroxy-3-see-butyl-5-L-butylphenyl)benzotriazole at 5.0 tng/100 cm2, butyl 7-talate at 4.0 g/100 cm2. 2,5-not-t-octylhydroquinone at 0,5 +o H/100 c
+a 2 and gelatin at 12.0II/100cI
It was painted so that it became 112.

5th) I4: Red-sensitive silver halide emulsion 14 cyan coupler ■-18 5.0+aH/100c+++2
, red-sensitive silver chlorobromide 7L shaved (containing 80 mol% silver bromide) converted to silver is 3.0+al/100c+n2, trifrenorphosphate-1 is 3.5 III 11/l O
Oc III' and gelatin at 11.5+oH/1
．． The coating was applied so that the area was 0.00 cm2.

The 6th Jη is composed of exactly the same M[structure as the 1st intermediate R and the 111'l.

'5 7 M: (Dam + 'lt M gelatin was coated at 8.0 + 6 bi/100 cm2.

The compound of the present invention was added to the above sample 31 at step 5) t4 in the proportions shown in the table, and multilayer sample 32-
40 was prepared, exposed and processed in the same manner as in Example 1,
- (The test (irradiated on a 7-meter fade meter for 160 hours) was done. The results are also shown in Section 4.

As is clear from the results of Table 4 below with margin fjS4, the general formula [I
The compound represented by [II] is effective in stabilizing the dye image obtained from the cyan coupler of the present invention, and its effect becomes greater as the amount added increases.

〔Effect of the invention〕

According to the color photographic material containing the cyan coupler of the present invention and the compound represented by the general formula (Iff) in the same silver halide emulsion layer, the coloring properties of the cyan coupler are improved and a cyan dye image is formed. The stability (fastness) against light can be improved. Moreover, even if benzyl alcohol, which is an environmentally harmful substance, is removed from the color developing solution in the color processing step, the color development of the coupler is hardly reduced, which is a great advantage in terms of pollution control.

Claims (1)

[Scope of Claims] In a color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formulas [I] and [II].
1. A color photographic material comprising at least one coupler selected from the phenolic cyan dye image-forming couplers represented by the following formula [III] and at least one compound represented by the following general formula [III]. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, R_2 and R_4 are each an aliphatic group, an aryl group, or a complex Represents a ring group, R_3 and R_
6 each represents a hydrogen atom, a halogen atom, an alkyl group or an acylamino group, and R_5 represents an alkyl group. Further, R_2 and R_3 may be combined with each other to form a 5- to 6-membered nitrogen-containing heterocycle. Z_1 and Z_2 each represent a hydrogen atom or a coupling-off group. n is 0 or 1. ] General formula [III] ▲ Contains mathematical formulas, chemical formulas, tables, etc. , alkenyl group, aryl group, cycloalkyl group, alkoxy group,
Represents an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acylamino group, a carbamoyl group, a sulfonamide group, or a sulfamoyl group. l represents 0 or an integer of 1 to 4. ]