JPS62232649A - 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 coupler 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 formula 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 is 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; and each of R7-R9 is H, alkyl, alkenyl, aryl, or cycloalkyl.

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. This invention relates to a color photographic material with improved stability against light.

[Prior art]

As is well known, subtractive color photography uses oxidation products of a color developing agent, which are produced when an aromatic primary amine color developing agent reduces exposed halogenated root particles, and yellow, cyan, and magenta dyes. By oxidative coupling in the silver halide emulsion layer of couplers forming
Forms a pigmented image. As a yellow coupler that forms a yellow dye, a compound having an open chain methylene group is generally used, and as a magenta coupler that forms a magenta dye, compounds such as pyrazolone, pyrazoli/bencyimigzole, and imigzolone are used. Ru. As a cyan coupler for forming a cyan dye, a compound having a 7 er/- or 7 thol hydroxyl group is used.

Each coupler can be dissolved in a water-insoluble high-boiling organic solvent or in combination with an auxiliary solvent if necessary, and added during milking after halogenation, or dissolved in an alkaline aqueous solution. Added to emulsion. The former is an oil drop dispersion method, and the latter is an alkali dispersion method, but the former is generally considered to be superior to the latter in terms of light resistance, heat resistance, moisture resistance, granularity, and color sharpness. .

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

In particular, in color photographic materials 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 Pat. No. 3,432.300, US Pat. No. 3,574
, No. 627, same: No. J1573.050, Special Publication No. 1973-
No. 47245, No. 48-32728, No. 51-304
No. 62, JP-A-48-28133, JP-A No. 49-1:14
J26, Ii'150-6338, Ii'150-238
No. 22, No. 51-123642, No. 51-12492
No. 6, No. 52-35633, No. 52-147433, No. 52-152224, No. 53-126, No. 53
- z O327, 53-53'J21, 53
-70822, 53-77526, 53-77
No. 527, No. 5418538, No. 54-62826, No. 54-822 (No. 4, No. 54-82385, No. 54-147038, No. 54-154345, No. 5)
No. 5-65954, No. 55-124141, No. 5G-
No. 39541, No. 56-159644, No. 56-16
No. 7138, No. 57-204037, No. 58-105
No. 147, No. 59-34: No. J3, No. 59-12573
No. 2, No. 60-211455, tio-2631
No. 49, No. 61-2151, No. 61-4041, No. 61-4045, etc. disclose methods for improving the fastness of dye images, and many of these techniques have been put into practical use.

Most of the above-mentioned techniques are aimed at improving the fastness of magenta dye images, and few techniques are aimed at improving the fastness of yellow and cyan dye images. are limited in number.

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

For example, in JP-A-59-3433, JP-A-59-42541, JP-A-59-87456, JP-A-59-124340, and JP-A-60.222853, specific 7E/-l compounds are used in combination with cyan couplers. A filtration technique is disclosed to improve the fastness of cyan dye images.

However, although the fastness of cyan dye images has been improved to some extent by these techniques, it is still not sufficient, and in addition, the 7-el compound has the serious problem of significantly reducing the coloring properties of cyan couplers. Missing, −′! , was recognized as having the following. 1,! In addition, it is possible to shorten the color development time, lower the I+11 of the color developer by 1 degree, or reduce the development accelerating components in the color developer (for example, benzyl alcohol,
When the concentration of an organic solvent such as 7-ethyl alcohol or an alkaline salt-free salt (M) such as sodium hydroxide or potassium carbonate is reduced, the color development of the cyan coupler due to the coexistence of the 7-ethyl-based compound occurs. Is sexual decline more pronounced?
It was recognized by J.

[Purpose of the invention]

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

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

[hη formation of invention]

The second object of the present invention is to provide at least one/fi
In a color photographic light-sensitive material having a silver halodenide 7L layer, at least one of the silver halo-Ynide emulsion layers contains an image-forming 7-7-l cyan dye represented by the following general formula CI3 and ([3). This is achieved by containing at least 61 types of couplers selected from couplers and at least one type of compound represented by the following general formula (III).

In the formula, R1, R2 and R4 each represent an aliphatic group, a 7-aryl group or a Fl ring group, and Lts and R6 each represent
Represents a hydrogen atom, a halogen atom, a furkyl group or an acyl group, and R1 represents a furkyl group. In addition, 1(, and It) may be bonded to each other to form a 5 to 6 nitrogen-containing elementary ring. Z and 1z2 each represent a hydrogen atom or a coupling-off group, r, nl Sat 0 again (Sat 1.

Below margin 01<8 In the formula, R2, 11, t, ; and R5 are each a hydrogen atom,
represents an alkyl group, alkenyl group, aryl group or cycloalkyl group, provided that It t ! ; Therefore, one of R11 represents a hydrogen atom, and R7 and R8 do not represent a hydrogen atom at the same time.

The present invention will be explained in more detail below.

First, the cyan couplers represented by general formulas [I] and (II) according to the present invention will be explained in more detail.

In the present invention, the "aliphatic group" may be linear, branched, or cyclic ifT, and includes saturated and unsaturated groups such as alkyl groups, cycloalkyl 7y, alkenyl groups, and furkynyl groups. It may also be replaced.

In general formula [I] and (H), R3
, 112 and R4 are aliphatic groups having 1 to 31 carbon atoms (e.g., methyl group, butyl group, octyl group, tridecyl group,
hexenyl group, i-hexadecyl group, cyclohexyl group, etc.), aryl group (e.g., phenyl group, naphthyl group, etc.), heterocyclic group (e.g., 2-bilinol group, 2-thiazolyl group, 2-imidazolyl group, 2-furyl group), group, 6-kyl/lyl group, etc.);
2-methoxyethoxy group, tetradecyloxy group, etc.)
, 7-aryloxy group (e.g., 2.4-not-7 milphenoxy group, 2-chloro 7-ethyl/oxy group, 4-cya/phenoxy group, 4-butanesulfonamide 7-ethyl/cydo group, etc.), acyl groups (e.g. acetyl group, benzoyl group, etc.) ester groups (e.g. ethoxycarbonyl group, 2.4
-N-L-amylphenoxycarbonyl group, 7cetoxy group, benzoyloxy! , b)oxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g. 7
cetylamine 7 group, butanesulfone 7mide group, totylbenzenesulfone 7mide group, nobropyrsul 7ammoyl 7mide group, etc.), carbamoyl group (e.g. trimethylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (e.g. butyl sulfone 7mide group), famoyl group, etc.), imide 7I! i (e.g., succinimide group, higntonyl group, etc.), ureido group (e.g., phenylureido group, trimethylureido group, etc.), sulfonyl group (e.g., methanesulfonyl group, carboxymethanesulfonyl group, phenylsulfonyl group, etc.), IJli aliphatic Alternatively, it may be substituted with a group selected from aromatic thio groups (eg, butylthio group, phenylthio group, etc.), hydroxyl group, cyano group, carboxy group, nitro group, sulfo group, halogen atom, etc. (where two or more substituents are present) may be the same or different.

Furthermore, in the general formula [I], R5 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group, or together with R2 '9! A nonmetallic group that forms 5 or 6 shell rings of a cord (represents a child group).

In addition, in the general formula [ll], R1 represents an alkyl group.
However, six substituents may be used, preferably an alkyl group having 1 to 24 carbon atoms. Specific substituents include fatty h5:, group,
Examples include aryl group, heterocyclic group, aliphatic oxy J, (aliphatic thio group, 7-aryloxy) 1, arylthio group, acylami/j118'''c. More preferably, R9 has 1 carbon number. -14 alkyl group, particularly preferably a lower alkyl group having 1 to 4 carbon atoms.

In the general formula [■], R6 is a hydrogen atom, a halogen atom (e.g., 弗'J/, Hara Ryo, chlorine atom, bromine Fy, T-, etc.), a lower furkyl group (e.g., a methyl group). , ethyl group, i-propyl group, butyl group, etc.) represents an aryl group (e.g., phenyl group, naphthyl group, (,), or acylamide/group (e.g., acetylamide group, benzamide group, etc.).

Z in the general formula (1) and z2 in the general formula (IT) represent a hydrogen atom or a Campling leaving group. bromine atom, etc.), alkoxy groups (e.g., nidoquin group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carpoquinprobyluoquine group, methylsulfonylethoxy group, etc.), aryloxy group (
For example, t-chlorophenoxy group, t-methoxyphenoxy 7, r, 4-carboquine 7ヱ/xy group, etc.),
Acyloxy J& (e.g., 7-cetoxy group, tetradeca/yloxy group, benzoyloxy group, etc.), Su JL
, t, niroquine 1 (, (for example, methanesulfonyl oximide group (for example, nochloro 7cetyl 7 group, heptafluorobutnaryl 7 group, methanesulfonyl 7 group,
toluenesulfonylamine 7 groups, etc.), alfkidicarbonyloxy 71I8 (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy J,9, etc.),
Aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), 1j-aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, tetrazolylthio JIr., etc.), imide group (e.g., succinimide group, higntoynyl group, etc.) , aromatic Azob. 5 (for example, a phenylazo group), and the like. These leaving groups may include photographically useful groups.

Furthermore, preferred examples of the cyan coupler represented by the general formula [I] or [■] are as follows.

In the general formula [I], preferably R1 is an aryl group, a heterocyclic group; C), a halogen MC group, an alkyl group, an alkoxy group, a 7-aryloxy group, an acylamide group; an acyl group, a carbamoyl group, a sulfonamide group; More preferably, it is an aryl group substituted with a sul77moyl group, a sulfonyl group, a sul77mido group, an oxycarbonyl group, or a cyano group. In general formula (1), when R2 and R do not form a ring, 1 (2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted furkyl group, 1 (Preferably a hydrogen atom.

In the general formula [lf], 1(, , is preferably a substituted or Xtt-substituted alkyl group, and 1 and r are preferably an alkyl group substituted with substituted aryloxy.

In the general formula [I1], preferred 1(, is an alkyl group having 1 to 8 carbon atoms as described above.

R6 in general formula [■] is preferably a hydrogen atom or a halogen IC<7-, and a chlorine atom or a fluorine atom is particularly preferred.

In the general formula [■], it is most preferable that 1<, is a chlorine element f, and [(, is a lower alkyl group having 1 to 4 carbon atoms).

In general formulas (1) and [■], preferably ν1Z + and Z2 are an alkoxy group, an aryloxy group, or a sulfonamide group, each of which may have a substituent. .

In the general formula [II)i, 7□ is preferably a denene atom, and a chlorine atom and a fluorine atom are particularly preferred.

In general formula [I], when +1=0, Z1 is /N C7
It is more preferable that it is densine r-, and particularly preferable are chlorine≦( and fluorine IIλ).

In the present invention, the most preferred cyan coupler is a coupler represented by the following general formula []a].

R1, R2 and Z] in general formula [1u] have the same meanings as R1, R2 and zl in general formula (1), respectively, and specific examples of preferred groups are as described above.

Specific examples of the cyan coupler compounds represented by the general formulas (r) and [IT] are listed below, but the present invention is not limited thereto.

Below margin (+-4) 511□ (1-:12) (L)Csl11+ L;4fly+t) (II-1) I C11-2) Shi! (II-3) Shil (II-4) (n-5) C! C! ( [1-7) 1. (II-8) (II-9) C! (II-In) C! (II-11) (fl-13) (■-15) Shil (Row 10) Ji! ( II-18) (II-19) OOII (IT-211 C1 C11-22) C! (II-23) CI! (tl-24) These cyanogens represented by the general formulas [I] and (II) of the present invention Coupler (hereinafter referred to as the coupler of the present invention)
No. 2,369,929, 772
, No. 162, No. 2, 895, No. 826, No. 3, 31
No. 1.476, No. 3,446.622, 3, 758
, :'108, No. 3,880,661, No. 3,
No. 996.253, Machiko No. 49-11572, No. 56
-65134, Special Ill It? (55-16353
7117, lm56-292359, lm58-8004
No. 5, No. 56-104333, No. 56-116030
No. 57-136650, No. 57-157246, No. 57-204543, No. 57-204544,
No. 57-204545, No. 58-105229, 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, a conventionally known method may be followed. For example, after dissolving the coupler of the present invention in a mixture of a known high-boiling solvent and a low-boiling solvent such as butyl acetate or butyl propionate, the coupler is mixed with an aqueous gelatin solution containing a surfactant, and then a high-speed rotary mixer or After emulsifying with a colloid mill or ultrasonic dispersion machine, the silver halide emulsion is Ma! can do.

Known high-boiling, α-solvents include heptataric acid esters (e.g., dibutyl heptatarate, etc.), phosphoric acid ester M (
(e.g., trifrenol phosphate, etc.), N-substituted acid amide M (e.g., N,N-noethyl laturylamide, etc.), phenol M (e.g., 2°5-sheet t~amyl7
1 nor, etc.).

The couplers of the invention typically have IX per mole of silver halide.
10-'-5X 10-' moles, preferably 1. t
It can be used in the range of I X 10-2 to 5X10-' moles.

The coupler of the present invention can also be used with other types of Cyankabu 2- and O
You can also tm.

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 of the above couplers can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers.

The compound which is used in conjunction with the cyan coupler of the present invention and which improves the coloring properties of the cyan coupler and also improves the fastness of the resulting cyan dye image, is of the general formula (
This is a hydroquinone monoether compound represented by III).

υH.

In general formula (1111), the alkyl groups represented by R7, Raj, and R may be linear or branched, and are preferably alkyl groups having 1 to 24 carbon atoms (for example, methyl group, i
-propyl group, butyl group, butyl group, octyl group,
(L-octyl group, denyl group, dodecyl group, octadecyl group, etc.). The alkenyl group represented by R7, R, and R5 includes a propenyl group, a pentenyl group,
Hexenyl 7, r:y; examples of the aryl group include phenyl group, naphthyl group, etc.; examples of the cycloalkyl group include ncrobentyl group, cyclohexyl group, etc.

Each of the groups listed above may be further substituted with other substituents. Examples of this substituent include a halogen atom,
Hydroxyl group, furkyl group, aryl group, alkenyl group, flukoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, 7 alkylamino groups, 7 arylamino groups, 7-syl amino group, carbamoyl group, carbonamide group, sulfamoyl group, Examples include sulfonamide groups.

In the general formula ([11), the total number of carbon atoms in R7, R1 and Rs is preferably 6 to 24.

In the general formula (In), R9 is most preferably a hydrogen atom, and therefore is represented by the general formula (the most preferred embodiment of Ill is the general formula Cl1la).

01<.

In the formula, 1(, is synonymous with 1(, in general formula (III), but preferably an alkyl group having 6 to 24 carbon atoms,
It is an alkenyl group, a 7-aryl group, or a cycloalkyl group.

Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

Below margin (III-1) (I[
l-2) (III-71 (III-8) (III-9) ([1
l-10) (Ill-15)
(III-16) (Ill-2:11
(l1l-24) The following margin is next a compound represented by the general formula [[[) of the present invention (hereinafter,
A typical synthesis example of the compound of the present invention is shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound 1'1l-1) 1 g of hydroquinone I was dissolved in a mixed solution of 7.0 g of potassium hydroxide and 100 ml of alcohol, and after adding 10 ml of hexyl when cold, it was heated to reflux. Boiled for 3 hours. After cooling and filtering off the generated potassium bromide, the alcohol was distilled off under reduced pressure. Ether 100+1 and 5 in the residue
% aqueous sodium hydroxide solution was added and shaken, the aqueous layer was separated, acidified with hydrochloric acid, and re-extracted with 100+ liters of ether. 11 of the ethers were combined, dried over anhydrous sodium sulfate, the ether was distilled off, and the remaining solid was recrystallized from an 80% furfur aqueous solution to give 13.51
White scaly crystals were obtained. Melting point: 40-41.5°C Nuclear magnetic resonance spectrum and mass spectrum confirmed that it was hytroquinone monohexyl ether.

Synthesis Example 2 (Synthesis of Exemplified Compound 1ff-3) Octylbromide 19 was substituted for hexyl 10mide in Synthesis Example 1.
A similar reaction was carried out using g.

The residue obtained by distilling off the alcohol under reduced pressure was purified by column chromatography, and then crystallized from methanol to give white flaky crystals 12. I got it. Melting point 60-61℃'fk
Supported the formation of hydroquinone mo/octyl ether (la 'x (A sound spectrum, mass spectrum)).

The amount of the compound represented by the general formula [1111 of the present invention] is 5 to 3% relative to the cyan coupler of the present invention.
00 mol% is preferable, more preferably 10·-200
It is mole%. The compounds of the invention are always used in -JC4 with the cyan couplers of the invention.

The compound represented by the general formula (III) of the present invention includes 1.
1 Kai No. 49-134327 marked II+! The above 1, i Kaimei 49-t:r4
zz1s; and the general formula (Ill) of the present invention.
) has the property of increasing the hardness of the magenta dye image formed from the anionic/-5 pyrazolone 7 pinta coupler. , :
Although it is not mentioned above, it is possible to improve the color development of the uncoupler represented by the general formulas [l) and [l] of the present invention, and to improve the light fastness of the cyan dye image obtained from the coupler. There is no suggestion that it has any effect.

As a result of intensive studies, the present inventors have determined that the general formula (l[
It is completely unexpected that the compound represented by [] improves the coloring properties of the cyan couplers represented by the general formulas (1) and (ff) of the present invention, and the light fastness of the cyan dye image obtained from the cyan couplers. They discovered that it has a distinct effect.

The color photographic light-sensitive material of the present invention can be, for example, a color photographic film, a color photographic paper, etc., but in particular, a color photographic paper used for direct viewing can be used. In such cases, the effects of the method of the present invention are effectively exhibited.

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 a-, and cyan couplers as photographic couplers and non-photosensitive silver halide emulsions are usually used. It has a structure in which the functional layers are laminated on a support in an appropriate number and order of layers, but the number and order of layers may be changed as appropriate depending on the performance and purpose of use. Good too.

The silver halide 7L agent used in the silver halide photographic light-sensitive material of the present invention includes conventional halides such as silver chloride, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any one used in silver oxide emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The method for producing and growing particles may be the same or different.

Does a silver halide emulsion contain halide ions and silver ions at the same time? Either one may be mixed with the other in the presence of JL. In addition, while considering the critical growth rate of silver halide crystals, we sequentially added halide ions and silver ions to the same 11L reactor while transporting 9Hel)AH in the 11L pot.
4? It may be grown by adding 2 to 2. Nari L (
The silver halide composition of the grains may then be changed using a component process.

During the production of the silver halide of the present invention, a silver halide solvent may be used as necessary. , particle size of silver particles, particle shape, particle size distribution, particle-r
-Can control growth rate.

The silver halide grains used in the silver halide emulsion of the present invention are produced by cadmium salt, zinc salt, lead salt, thallium salt, ilinium salt or complex salt, anoium 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 surface of the particles.
By placing the particles in the atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains.C may be added, or C may be left as is. When removing the salts, the method described in Research Disclosure No. 17643 can be used.

The silver halide grains used in the silver halide emulsion of the present invention may consist of grains whose interior and surface are uniform, or may be formed from different grains.

The silver halide grains used in the silver halide emulsion of the present invention 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). good.

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, any ratio of 1001 planes to 11111 planes can be used. Also, they may have a composite form of these crystal forms, or grains E 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 chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination. .

The silver halide emulsion of the present invention can be optically sensitized to a desired range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. In the emulsion, together with the sensitizing dye, a dye that does not itself have spectral sensitization of 11 mm, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye, is added. may be included.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, and/or at the end of chemical ripening, and/or chemical ripening for the purpose of preventing capri during preservation (f) or during photographic τ processing, and/or to keep photographic performance stable. After completion of the process and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as the pineapple (or protective colloid) in the silver halide 7L agent of the present invention, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, and cellulose may also be used. Woodophilic colloids such as synthetic hydrophilic polymeric substances such as derivatives, monopolymers, or copolymers can also be used.

Photographic breast wound layer and other hydrophilic colloids of photosensitive materials using the silver halide emulsion of the present invention) C4 is 5B! The film is hardened by using alone or in combination with a hardening agent that increases film strength. The hardener is used to the extent that it is not necessary to add a hardener to the processing solution.
It is desirable to add a compound that can harden the light-sensitive material, but the ! It is also possible to add a hardener to the solution.

7% C of the light-sensitive material using the silver halide emulsion of the present invention
Plasticizers can be added to increase the flexibility of the F silver denide emulsion layer and/or other hydrophilic colloid layers.

Photographic emulsions JC/J and other hydrophilic colloid layers of photosensitive materials using the silver halide emulsion of the present invention are coated with water-insoluble or sparingly soluble synthetic polymers for the purpose of improving dimensional stability.
t)-can contain latex.

Emulsion 1 of halogen ft, silver color photographic light-sensitive material of the present invention
In step 14, in the color development process, a cambling reaction is carried out with an oxidized product of a primary amine developer (for example, p-phenylenenoamine derivative, amino/7 ether conductor, etc.). Pigment-forming turnip 2 - month 1
I can stay. 1. The dye-forming coupler is preferably selected such that a dye absorbing in the sensitivity spectrum of -C,7L agent is formed for the 7L agent layer of 7'r,
A yellow dye-forming coupler is present in the blue light-sensitive emulsion layer.
The green light-sensitive emulsion layer contains a magenta dye-forming coupler.
A cyan dye-forming coupler is used in the red light sensitive emulsion/M. However, depending on the purpose, silver halide color photographic materials can be used in different ways than the above combinations.
You may create [.

Yellow dye-forming couplers include acyl 7-ceto-7 mido couplers (e.g., benzoylacetanilides, pivaloyl-7-ceto-7 nilide M); magenta dye-forming couplers include 5-pyrazolone couplers, virazolobenlimigzole couplers, virazoloto, lyazole; , I.J.
Examples include IIrn acyl 7cetonitrile couplers, and cyan dye-forming couplers include naphthol couplers and phenol couplers other than those of the present invention.

It is desirable that these dye-synthesizing couplers have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has a carbon number of 1 or more. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either C) is fine.

Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface can be prepared using various methods such as solid dispersion, latex dispersion, and oil-in-water type 7L dispersion.
The method can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water type emulsification dispersion method can be applied to the well-known Noj method of dispersing hydrophobic additives such as couplers. Usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is used, and if necessary, a low boiling point, and/or water-soluble right t”121; medium (Jllll
7L by using a surfactant in a hydrophilic binder such as an aqueous gelatin solution and using a dispersion means such as a stirrer, homonizer, colloid mill, 70-NoeF mixer, Mr'f wave device, etc. After being dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point solvent may be included simultaneously with the molecular i5c liquid or dispersion.

Examples of high boiling point oils include 7㎯/-l conductors, 7talates, phosphoric esters, citric esters, benzoic esters, alkylamides, which do not react with the oxidized form of the developing agent.
lff1 An organic solution μ having a boiling point of 150° C. or higher, such as flocic acid ester or trimenoic acid ester, is used for C7.

When a hydrophobic compound is dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using a machine or MA waves, anionic activators, nonionic field 1fii activators, cations can be used as dispersion aids. A surfactant can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the color photographic light-sensitive material of the present invention (between layers of the same color sensitivity and/or between layers of different color sensitivity), causing color turbidity, A color antifoggant is used to prevent deterioration of sharpness and graininess of 1'l-J.

The various pre-inhibitors may be used in the emulsion layer itself or in an intermediate layer provided between adjacent 7LJ'11 layers.

Prevents fogging due to discharge caused by electrostatic charging of the photosensitive material in the hydrophilic colloid layer such as 1st layer and intermediate J (4) by rubbing etc. of the photosensitive material of the present invention, and prevents deterioration of the image due to UV exposure.
- It may contain an ultraviolet absorber in order to

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiylanoeicin layer.

These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material during development or are bleached.

silver halide emulsion layer of a silver halide photosensitive material using the silver halide emulsion of the present invention, and/or parentness of the pond)
A matting agent can be added to the aid LC4 for the purpose of increasing the desire to reduce the gloss of the photosensitive material, preventing the photosensitive materials from sticking together, etc.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

・: i7 antistatic agent is sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or when emulsion 71'J is laminated on the emulsion layer and/or the support. It may be used in a protective colloid layer other than the emulsion layer on the side where
.

Is the photosensitive material using the silver halide emulsion of the present invention true? The L-shaving layer and/or other hydrophilic colloids 711 have properties such as improving coating properties, preventing static electricity, improving slipperiness, emulsifying and dispersing, preventing adhesion, and copying properties (such as development acceleration, high contrast, and sensitization). Various surfactants are used for the purpose of improvement.

The photographic WL agent layer of a photosensitive material using the silver halide 7L layer of the present invention is laminated with a baryta layer or an α-olefin polymer, etc. to produce R-paper, paper, etc.
(m-reflective support, cellulose 1 acid, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene tele7
It can be applied to films made of semi-synthetic or synthetic polymers such as Talay 1, polycarbonate, and polyamide, and rigid bodies such as glass, metal, and ceramics.

The uninvented silver halide photosensitive material is prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
Adhesiveness directly or on the support surface, antistatic property, dimensional stability, 17 rub resistance, hardness, anti-roon tan property, J9. It may also be applied through one or more base coats to improve the hospitality and/or properties of the pond.

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 a coating method, extra coating, coating, and curtain coating, which can simultaneously coat two or more types of t4, are useful.

The photosensitive material of the present invention has 7L constituting the photosensitive material of the present invention.
Exposure can be performed using electromagnetic radiation in the spectral region to which the agent is sensitive. As a light source, natural light (11 Yen),
Tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lamps, light emitting diode lamps,
It is possible to use any known iL, such as those emitted from a phosphor excited by electron beams, XIQ, γ rays, α rays, etc.

Exposure times range from 1 millisecond to 1 second exposure11,7, which is normally used in cameras, as well as exposures shorter than 1 microsecond, such as ++:100 using a polar FA tube or xenon flash lamp.
Exposures of microseconds to 1 microseconds can be used, and it is possible to use more than one microsecond of exposure.The exposure can be done continuously or intermittently. Good too.

Images can be formed using the halogenated photographic material of the present invention by color development as known in the art.

Color developing solution in the present invention; aromatic r51 used in this
The g-amine color developing agents include those known and widely used in various color photographic processes.

These developers include ami/phenolic and zo1]-phenylenenoamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds generally have a yield of about 0.1 Bi to about 30 Bi for 10 Llu of color development.
about 1 g of dark J branch, preferably color developer ill
Use at a concentration of ~1.5 g.

Examples of the 7mi/phenol-based developer include -7minophenol, p-amino71nol, 5-7mi/-2-oxytoluene, 2-7mi/-3-oxytoluene, and 2-7mi/-3-oxytoluene.
Includes oxy-3-7mi/-1°4-no/thylbenzene.

In particular, the primary aromatic, There may be 61 among them! Examples of useful compounds include N,N-noethyl-V-phenylenedi7minem[! , N-methyl-phenylenenoamine hydrochloride, N,N-tumethyl-p-7znylennoamine hydrochloride, 2-7 minnow 5()J-ethyl-N-
dodecyl 7mi/)-toluene, N-ethyl-N-β-methanesulfonamidoethyl 12(-methyl-・I-゛?
Mi/7 diline sulfate, N-ethyl-N-β-hydroquinethylaminoaniline, 4-7 mi/-3-methyl-N,
N-nonalaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-; (-nonalaniline-
Examples include p-toluenesulfonate.

In the present invention, after color development processing, the fixing ability is determined by J'11! However, if the processing solution that destroys the constant X+ ability is a fixing solution, a bleaching treatment is performed before that. A' A metal complex salt of R acid is used as the whitening agent used in the bleaching process, and the metal complex salt is the same as the metal silver produced by development when it is converted into N2 and converted into silver halide.
, 7 is a coloring agent that controls the action of coloring the uncolored area, and its properties include amino/polycarboxylic acids, oxalic acid, citric acid, etc. The most preferred organic acids used to form the metal t11 salts of these 8! acids include polycarboxylic acids or 7-polycarboxylic acids. These polycarboxylic or amine/polycarboxylic acids may be alkali metal salts, aqueous or water-soluble amine salts.

Specific representative examples of these include the following.

[I] Ethylenenoamine titraacetic acid [2] Nitrirotri 1 acid [3] Iminonoacetic acid [4] Ethylenenoamine titraacetic acid monosodium salt [5] Ethylenenoamine titraacetic acid tetra(trimethylammonium) ,) 4 [for] Ethylenenoamine triacetic acid tetrasodium salt (7) 2) The whitening agent used in ethylenenoamine triacetic acid tetrasodium salt is used to bleach metal complex salts of organic acids such as those mentioned above. In addition, a wide variety of additives can be included.Additives include, in particular, alkali halides or ammonium halides, such as rehalogenated hexachlorides such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, etc. It is desirable to include metal salts and chelates.

In addition, 1111 acid salts, oxalates, acetates, carbonates, phosphates, etc., which are known to be added to ordinary bleaching solutions such as II [buffers, alkylamines, polyethylene oxide M, etc.] may be added as appropriate. r can.

Furthermore, in the fixing solution and bleach-fixing bath, ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, metani IIj Q M
Sulfites such as ammonium, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, etc.
cum, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate (sodium sulfate, sodium bicarbonate, potassium bicarbonate, 1Iil acid, sodium acetate, ammonium hydroxide, etc.). Alternatively, two or more types may be included.

When carrying out the process of the present invention while supplementing a bleach-fixing bath) with a bleach-fixing supplement, the white fixing bath may contain thiosulfate, thiocyanate or! (2) Sulfur 1l12 salts or the like may be included, or these salts may be included to supplement the light in the processing bath for 11-wave bleach-fixing replenishment.

In the present invention, in order to increase the activity of the bleach constant 'rI solution, 'IZ' or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank as desired, or an appropriate 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 Paper support laminated on both sides with polyethylene-I:
l: , the present invention cyan coupler r-18 (4.8m
g/100era”) and 2.5-octylhydroquinone (0,411111/+00 (!162> dibutyl 7 thale) (4,0mH/100c+n”)
) dissolved in gelatin (14, OmH/100cm”
) After dispersing with an aqueous solution to form 7L, silver chlorobromide? Cutting (Bromide [
80 mol A containing rr) with silver amount of 3,
It was coated to a concentration of 5 mg/100c+a2 and dried to form a monochromatic color photographic material, which was designated as Sample 1.

Compounds m-2, I■-3, and ■-1 of the present invention were added to Sample 1.
Sample 2.3 to which 0, ■-17, I-23 and ■-24 were added, each with 172 moles of cyan coupler.
．． 4.5.6 3 and V7. Similarly, samples 8.9 and 1 were added with compounds a, bt, and C, which are not of the present invention, each in an amount of 1/2 mole of the cyan coupler.

Created by

Comparative Compounds ur b, C (both compounds described in Machi No. 1311, No. 59-3433) The sample was exposed to light through an optical wedge according to a conventional method, and then treated in the next step (1114).

[Processing process J Processing temperature Processing time Color development
Bleach and fix at 33°C for 3 minutes and 30 seconds 3
:)"C1930 seconds water washing 33℃
Dry for 3 minutes 50-80℃
The components of each 2-minute treatment plj are as follows.

One color development Zr! i, J benzyl alfurzenerengelicol 1011jk potassium acid 25y sodium bromide z
．． 0. (ig anhydrous!ll(storium sulfate 2.OJ chlorohenruamine sulfate 2.52N-ethyl-N-β-7
Tansulfonamide enal-3-methyl-4-aminoaniline sulfate 4.5g Water was added to bring the solution to 11, and pHio. 2, ν
4 arrangements.

[Bleach-fix solution 1 Ammonium thiosulfate 120g Sodium metabisulfite 15.

Black water sodium sulfite 3JL: I)
'1'' Δ Ferric ammonium 1. Salt 652 Add water to 1! and adjust pH to 6.7-6.8 H<6 Densitometer charging maximum reflection density (Roku Konishi photo) - Manufactured by Gyo Co., Ltd. +
10^-bOQ). The results are shown in Table 1. However, 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 1 hour and the light fastness of the dye image was examined.

These results are also shown in table rjS1. However, the evaluation of the light fastness of the dye image is as follows.

〔Survival rate〕

Percentage of dye remaining after light fastness test at initial density 1.0.

As is clear from the results of Table ii1 in the margin below, the sample according to the present invention (
Examples 2 to 7) all have increased maximum reflection density and dye residual rate, and are excellent in the color development of the cyan coupler and the light fastness of the cyan dye image.

In contrast, samples to which the comparison compound was added (8-10
) improves the light fastness of the cyan dye by some C, 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 benzyl alcohol was removed from the color developer composition during the processing step. The results are shown in Table 2.

Below is a table with a margin of m2.
) Indicates the presence or absence of le furfur. In addition, the results of Example 1 were cited for the results with benol alcohol. The sensitivity was expressed as a relative sensitivity when the sensitivity of sample 1 with benol alcohol was set as 100. ) From Table 2, it can be seen that in the sample to which the comparative compound was added, the color development rate decreased significantly when treated with benzyl alcohol group, but in the case of the sample of the present invention, the color development rate decreased significantly even when treated with benzyl alcohol group. It turns out it's small. Therefore, when processing samples of the present invention, there is no need to include benol alcohol in the color developer. This is very advantageous in terms of pollution control.

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

Each sample was treated under the same conditions as in Example 2. Further treatment PI
The light resistance test was performed on the finished sample under the same conditions as in Example 1.

The results are also shown in Table 3. Note that the sensitivities in the table are relative sensitivities when the sensitivity of sample 11 is taken as 100.

Below margin 1 Comparative compound d (Compound described in JP-A-59-42541) n1 rich OCI+.

Comparative compound e (compound described in JP-A-59-87456) Table 3 below (margin) The results in Table 3 also show that the coupler of the present invention and the compound of the present invention were combined by 8It, and the color development of the cyan coupler was Also, the light resistance of the coloring dye is improved.

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

1st) IIJ: a-pivaloyl-α-(2,4-) as l'i-sensitive silver halide emulsion layer yellow coupler
Oxo-1-pennolimidazolinon-3-yl)-2
-Chloro-5-[γ-(2,4-amyl7e7
xy)butyramide 1 acetanilide at 6.8 Ing/
100cn2, blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide (T) converted to silver: 1, 2 InN,
/ IOOc m”, butyl 7 tallate 3.5
Plow vinyl/100cu' and gelatin at 13.5+obi/1
One coat was applied so that the coating amount was 0.00 cm2.

2nd Jl! : Intermediate layer 2.5-not-t-octylhydroquinone at 0.5mF
17100cm2, butyl 7 tallate 0.5mg/
100 cm2 and 1 gelatin at 9,0 mg/
It was coated to give 100 c vb 2.

3rd M: Green-sensitive silver halide emulsion layer 1-(2,4,(3-)lichlorophenyl)-3-(2-chloro-5-tetrathecanamidoanilino)-5-pyrazolone was used as a magenta coupler at 4°5Inw
/ 100c+a', green sensitive silver chlorobromide milk resistant (silver bromide 80
(containing mol%) converted to silver is 2,0 +a 8/1
00 c-', Nobuchiru 7 tally 1.3. OmH/
10oc+n2 and gelatin 12. OsH/IO
It was painted so that Oc + a'.

Fourth scrap: Intermediate layer T: External radiation absorber 2-(2-hydroxy-3-5ee-
7f-5-1-butylphenyl)penztriazole at 5.0 + u H/I 00 c In'', butyl 7-thalet at 4, OmH/I (loc'', 2.
5-No one ocnal hydroquine 7 0.5111
) (/l OOc 10' and gelatin 12.0m
The coating was applied so that g/IOOc +o'.

:jS5 layer: Red-sensitive silver halide emulsion layer 5.0 ml of l-18 as a cyan coupler (7100 cm2, red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver: J, Omg / 100cm2, tricrenorphos 7
E.

- 3.5mg/1ooc of cormorant 2 and gelatin 11
．． A was set so that it was 5 Ing/100 cm2.

61st-Second Intermediate Layer ' A layer composed of exactly the same composition as No. 4 JrA.

7th layer: Protective layer gelatin was applied by hand to give 8.0 mK/100 cm2.

Sample No. 2: (In 1, the chemical compound of the present invention was added to the f:Is 5 layer in the proportions shown in the table, and !R layer samples: 2 to 40 were prepared. After exposure and processing to the same 4.r+ as 1, a 1-likelihood test (irradiated for 1611 hours on a xenon 7 ademeter) was performed.The results are shown in Table 4 in 01.

As is clear from the results in Table 4&, the general formula [[
The compound represented by 1r) 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 [1[ This also improves the stability (fastness) of the cyan dye image produced.Moreover,
6 at the Environment Department from the color developer at Color Shop 711
;I,: Even if the substance benol alcohol is removed, the color development of the coupler is hardly reduced, and it is a 7.
'J ノ) or big.

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. [In the formula, R_7, R_8 and R_9 each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a cycloalkyl group.] General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are included. However, either one of R_7 and R_8 represents a hydrogen atom, and R_7 and R_8 do not represent a hydrogen atom at the same time. ]