JPS58209734A - Color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance light-resistance of a magneta dye image and to improve the color balance among the magenta and the other dye images in the course of color fading, by forming a non-photosensitive layer contg. no UV absorber on the uppermost non-photosensitive layer contg. the UV absorber. CONSTITUTION:The magenta coupler to be used is at least one of 3-anilino-5- pyrazolone type coupler represented by the shown formula. At least 2 non-photosensitive layer made of a hydrophilic binder contg. a UV absorber are formed on a layer located farther than a magneta-contg. layer from a support. It is desirable that the UV absorber is a benzotriazole compound. A non-photosensitive layer contg. no UV absorber, and consisting substantially of a binder component is formed on the reverse side of the support as the uppermost layer. The presence of this layer enhances light fastness of the magenta dye image to an extremely high grade.

Description

[Detailed description of the invention] l Background of the invention Technical field The present invention relates to color photographic materials.

More particularly, the present invention relates to a color photographic material for printing in which the light fastness of magenta dye images is improved.

Prior art and its problems In color photosensitive materials for printing, 3-anilino-5-bilane' is used as a magenta coupler for forming magenta dyes because of its excellent color reproducibility and high light fastness. Ron type couplers are used.

However, the dye formed from this 3-anilino-5-pyrazolone thread Kagura has poor light fastness compared to the yellow dye f cyan dye, and the disadvantage is that the light fastness of the magenta dye image is low. Conventionally, in color photographic materials for printing, a non-photosensitive layer is provided adjacent to and above a silver halide emulsion layer containing a magenta coupler, and this non-photosensitive layer is coated with an ultraviolet absorber. Contains.

1-Also in this case the lightfastness of the magenta dye image is low. Furthermore, the light fastness of the emulsion usually located above the magenta coupler-containing layer, the cyan dye image formed in hot weather, and the yellow dye image formed in the emulsion layer usually located below the layer is still low, and The residual rate of pigment varies widely, and there is the disadvantage that the color fades due to light (lance is poor).

In order to eliminate all such inconveniences (2. A non-g-based layer is provided on the uppermost emulsion layer containing normal/anchor gray,
It is conceivable to further include an ultraviolet absorber in this non-photosensitive layer.

And like this: To do jiFt・□・Koyo,
The lightfastness of each dye image is improved. 7+A L, the light fastness of the agenta dye image was insufficient;
The disadvantage is that the color balance of fading is poor compared to other dye images.

■ Purpose of the Invention The present invention has been made in view of the above-mentioned circumstances, and is an object of the present invention to improve the light resistance of magenta dye images in color photographic materials containing a 3-anilino-5-pyrazolone magenta coupler. , its primary purpose is to improve fading color balance with other dye images.

As a result of various studies for this purpose, the inventors of the present invention have decided to provide a non-photosensitive layer that does not contain an ultraviolet absorber on top of the uppermost non-photosensitive layer that contains an ultraviolet absorber.
When the present invention was carried out, the inventors obtained the unexpected finding that such an object could be achieved, and came to form the present invention.

That is, the present invention has 21 or more silver halide emulsion layers on a reflective support, and at least one of the silver halide emulsion layers is represented by the following general formula [I]. 3
- Contains an anilino-5-pyrazolone magenta coupler, and two non-photosensitive layers containing an ultraviolet absorber are located on the side farther from the magenta coupler-containing layer when viewed from the support.
It is characterized by having a non-photosensitive layer containing no ultraviolet absorber, adjacent to the non-photosensitive layer farthest from the support and on the opposite side from the support. This is a color photographic material.

General formula [I] In the above general formula [I], Xl represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an arylox/group, an amide group, a droxy group, a cyano group, or a nitro group, Y, , Y2 and ¥3 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a carbonyl group, an alkoxycarbonyl group, a nitro group, an aryloxy group, a cyano group or an acylamino group, Wl represents a hydrogen atom, a halogen atom, or a monovalent organic residue; Z represents an atom or group that is separated upon coupling; ) ■Specific structure of the invention The color photographic light-sensitive material (hereinafter referred to as "light-sensitive material") of the present invention has two or more silver halide emulsion layers, but in a normal embodiment, three types of light-sensitive materials having different spectral sensitivities are used. Characteristic: It has a silver halide emulsion layer, and each emulsion layer contains one of three types of diffusion-resistant couplers: yellow, magenta, and cyan.

Sensitivity ratio in such a case: The combination of the silver halide emulsion layer and the coupler is usually such that the red-sensitive silver halide emulsion layer contains a cyan coupler, and the green-sensitive silver halide emulsion layer contains a cyan coupler, and the green-sensitive silver halide emulsion layer contains a cyan coupler. A magenta coupler is combined in layer V, and a yellow coupler is further combined in seven light-sensitive silver halide emulsion layers.

In this case, there is no restriction on the order in which the emulsion layers are stacked.

However, normally, from the reflective support side, the yellow coupler-containing emulsion layer, the magenta coupler-containing emulsion layer, and the cyan coupler-containing emulsion layer are coated in this order. Alternatively, the cyan coupler-containing emulsion layer, the magenta coupler-containing emulsion layer, and the yellow coupler-containing emulsion layer may be coated in this order from the reflective support side.

In terms of non-invention, it is preferable that the magenta coupler-containing layer be located on the support side or in the middle.

The magenta coupler used in the invention is at least one type of magenta coupler represented by the above general formula [Ij].

To explain the above general formula '■] in more detail, W represents a hydrogen atom, a location atom, or a monovalent organic group. group, alkyl group, alkokino group, azurua, 7 group, sultinamide group, each of which may contain a substituent, alkylcarbamoyl group, alkylcarbamoyl group, alkylsulfamoyl group, 7 IJ -rusulfamoyl group, arsulfamoyl group, phosphoric acid imide
Suitable examples include a 7-alkylamino group, a 7-carboalkylamino-so-lamino group, an alkylamino-carboal-so-lamino group, an arylaminocarbo-alkylamino group, an aralkylaminoalza-alkylamino group, and Z is a known ridge. The atom that separates during coupling must be one group.Next, a typical example of a magenta coupler represented by the general formula [IJ] will be given.

-1 t t -2 M-3 ρI -5 ρI t -6 -70t -9 t -11 t C't M12 ct -13ct t -14ct t M-isct Ct Ct -18 z Ct -19 Ct Ct - 21 t M-=25 -26 -27 1 t M-29a (3 t C't M32 oqH3 t XN/ t -3707 H3 t M-42 -43 (I -44 -45) These magenta couplers For example, U.S. Patent No. 46
No. 8-514, U.S. Patent No. L183515, Special Publication No. 6031-1973, Special Publication No. 40-6031, Special Publication No. 40-6031
No. 0-6035, Special Publication No. 15754, Special Publication No. 15754, Special Publication No. 4
5-40757, JP 46-19032, JP 50-13041, JP 53-129035, JP 51-37646, JP 55-62454,
It can be synthesized according to the method described in et al.

In addition to such magenta couplers, there are 3-acylamino-5-pyrazoloy-based, a-ureido-5-dolazolone-based, and lazolo? Other magenta couplers such as limassol, virazolobenzimidazole, and anoacetyl may be used in combination.

The yellow coupler used in the present invention is not particularly limited, but is preferably an α-vivaloylucetanilide coupler. Among these, one or more compounds represented by the following general formula (i'+I 1) are particularly preferred.

General formula CII[] In the above general formula CI), R6 represents a hydrogen atom, a halogen atom, or an alkyl group, R7L'X, -NHCOR71, -NHSO2几, 1,
-Co.

1'72 R7 each represents an alkyl group which may be substituted. ), and Z2 represents an atom or group that is separated upon coupling.

To explain the general formula CI[I] in more detail, R7 is a group -NHCOR,1, -NH8O2, but R71 and R? 2 may each be an unsubstituted alkyl group, or a substituted aryloxy group,
It may be an alkyl group substituted with an alkoxycarbonyl group, an alkylcolphonyl group, a sulfonic acid group, an aryl group, a substituted alkylamide group, or the like.

Further, as z2, representative examples of various known couplers are listed. \/ -16 -18 -19 -21 ¥-22 C't 1 O-C-CH3 CH3 1 -CH 噸CH,.

1+ -27 t -28 0□S C=O 1 02C-CH2 -29 -3-O -31 -32 Shit Shit Y-33 The yellow sword 7'ra of this q is described in, for example, West German Published Patent No. 2. No. 05'4941, West German Published Patent No. 2.163,
No. 812, JP-A-47-26133, JP-A-48-2
No. 9432, JP-A-50-65231, @ JP-A-51-
No. 3631, JP-A-51-50734, JP-A-51-
No. 102636, Japanese Patent Publication No. 51-33410, Japanese Patent Publication No. 4
It can be synthesized according to the methods described in JP-A No. 8-66835, JP-A-48-94432, JP-A-49-1229, JP-A-49-10736, JP-B-Sho 52-25733, and the like.

In addition, there are no particular restrictions on the cyan coupler, but it is preferable to use a phenolic coupler. It is preferable that there be more than one species.

General formula [■] In the above general formula (In, R8, Ro and Rto are each a hydrogen atom,...
Rogge/atom represents an alkyl group, aryl group or alkoxy group, Rol and R1 respectively represent a hydrogen atom, an alkyl group or an alkoxy group, R13 represents a hydrogen atom or 7 represents an alkyl group, Z, , Atoms or foundations that break away in a coupling.

In this case, Z may be an atom that undergoes one elimination in various known couplings or an .'I'i group.
List.

-1 -2 -3 -4 t -5 -6- 7 Su-9 09 -10 -11 -12 -13 -14 -15 -16 -17 -18 -19 -20 -21 C existence -22 fl -23 e -24 C-25 a -26 -27 -28 -29 Su -30 KuJ -31 -32 (U -33 ■ Cβ Cβ Shi3 (Tsukuda -38 -39 -40 Side C-42 C -43 - 45 These cyancafurades 1, such as U.S. Pat.
423.730, US Patent No. 2.801,171, and the like.

Each of these couplers is contained in the silver halide emulsion layer in an amount of about 0.05 to 1 mole per mole of silver halide.

On the other hand, two or more non-photosensitive layers are provided in a layer farther from the magenta coupler-containing layer when viewed from the support side.

The two or more non-photosensitive layers are made of a hydrophilic binder, such as gelatin, and contain an ultraviolet absorber.

The ultraviolet absorber to be used may be a compound that absorbs ultraviolet rays of about 400 mμ or less, but in particular, compounds of the following general formula [■
] Preferably, it is a benzotriazole compound represented by the following.

- In the general formula [11], R,, R2 and R3 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, or a nitro group. It represents a hydroxyl group.Next, typical examples of the ultraviolet absorbent represented by the above general formula (n) will be shown.

V-1 H3 V-3 V-4 V-5 H3 UV-6 UV-7 UV, -8 UV-9 UV-10 UV-11 JV-12 UV-13 〇4H9(see) '[JV-14 UV -15 UV-16 UV-17 r4v-1 product UV-19 These benzotriazole compounds are
No. 10466, No. 42-26187, No. 48-549
No. 6, No. 48-41572, U.S. Patent No. 3754919
No. 4220711, etc.

Such a UV absorber is used as binder 1 of the non-photosensitive layer.
It is contained in an amount of about 0.01 to 2 per part by weight.

In such a case, two or more layers are present on the far side (upper layer 1) when viewed from the support containing the ultraviolet absorber.

That is, in a preferred embodiment, when the light-sensitive material is composed of 39 silver halide emulsion layers, when the magenta coupler-containing layer is located in the middle of the silver halide emulsion layers, the uppermost emulsion layer is A light-insensitive layer is provided between the intermediate emulsion layers and on the top emulsion layer (and preferably also below the middle emulsion layer), and the two light-insensitive layers located on the magenta coupler-containing layer are coated with ultraviolet light. When an absorber is added or when the magenta coupler-containing layer is an emulsion layer located on the support side, a non-photosensitive layer is provided between each emulsion layer and on the topmost emulsion layer, and these three layers are non-photosensitive. Two of the sexual layers are: (Adds ultraviolet absorbers to the skin.

The amount of binder applied in each non-photosensitive layer is 1 to 30'.
%/dm" or so.

The content ratio of the ultraviolet absorber in each non-photosensitive layer can be changed in various ways, but Torihama has When the content is 1, the content 1 in the non-photosensitive layer above it is about 0.01 to 1O.

It should be noted that each of these non-photosensitive layers may contain, if necessary, a color mixing inhibitor such as dictylhydroquinone or dibutylhydroquinone, a whiteness regulator, a coating aid, and the like.

Among such non-photosensitive layers, adjacent to and above the non-photosensitive layer VC, which is farthest from the support, that is, on the opposite side from the support, a layer consisting essentially only of a binder component and containing an ultraviolet absorber is added. A non-photosensitive layer containing no light is applied as the top layer.

In this case, the non-photosensitive layer located at the top layer generally has a binder coating amount of about 1 to 30 mfldd, and the presence of this layer makes the light fastness of the magenta dye image extremely high. . 1, the decrease in surface gloss over time due to light, called perspiration, is also reduced.

On this premise, various methods can be used to disperse the diffusion-resistant coupler in the photosensitive material of the present invention, such as the so-called alkaline aqueous dispersion method, solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. This can be appropriately selected depending on the chemical preparation of the diffusion-resistant coupler.

In the present invention, the latex dispersion method and the oil-in-water emulsion dispersion method are particularly effective.These dispersion methods are well known, and the latex dispersion method and its effects are described in JP-A-49-74538. , No. 51-59943, No. 54-32552 and Research Disclosure.
), August 1976, pp. 14850177-79.

Suitable latexes include, for example, methane, engineered acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate,
2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)furopane-1-sulfonic acid sodium salt, N-inflovir acrylamide, N-[2,-(2-methyl-4
-oxopentyl)] homopolymers, copolymers, and terpolymers of monomers such as acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, and the like. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, such as N-n-butylacetanilide, diethyl lauramide,
Dibutyl phthalate, tricresyl phosphate-1-, N
- The diffusion-resistant coupler can be dissolved in a high-boiling solvent such as dodecylpyrrolidone and finely dispersed in a hydrophilic colloid such as gelatin.

Examples of the silver halide used in the silver halide emulsion layer of the sensitive material of the present invention include silver chloride, silver bromide, silver iodide,
Any of those used in conventional silver halide photographic emulsions, such as silver chlorobromide, silver iodobromide, and silver chloroiodobromide, are included.

These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide.

Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of the 1001 plane to the (111) plane can be used.Furthermore, the crystal structure of these silver halide grains is The silver halide may be uniform from the inside to the outside, or it may have a layered structure with different internal and external layers.Also, these silver halides may be of a type that mainly forms a latent image on the surface. , or a type formed inside the particle.

These silver halide grains can be prepared by known methods commonly used in the art.

It is preferable to remove soluble salts from the silver halide emulsions used in the photosensitive materials of the present invention, or those without removal can also be used.

It is also possible to use a mixture of two or more silver halide emulsions prepared separately.

As the binder for the silver halide emulsion layer or the non-photosensitive layer, conventionally known binders are used, and examples of suitable binders include gelatin, phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin. These binders can be used as a compatible mixture of two or more if necessary.

A silver halide photographic emulsion in which halide steel particles are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in combination in the present invention are roughly classified into four types: noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers.

As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used.

In addition, when using a gold compound, ammonium thiocyanate and sodium thiocyanate can also be used together.

As the sulfur sensitizer, activated gelatin powder and sulfur compounds can be used.

As selenium sensitizers, active and inactive selenium compounds can be used.

Examples of reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives.

On the other hand, in order to contain an ultraviolet absorber in the non-photosensitive layer,
Any conventional boiling method may be used. SunaVchi,
Usually, it is dissolved in a high boiling point organic solvent with a boiling point of about 175°C or higher, if necessary in combination with a low boiling point solvent, and then finely dispersed in a hydrophilic binder such as gelatin water using a surfactant. It may be added to hydrophilic colloid waste for the purpose of dispersion.4 To explain more specifically, as a high boiling point solvent, M
Organic amides, carbamates, esters, ketones, urea conductors, etc.

In particular, dimethyl phthalate, diethyl/I/7 talate,
Phthalate esters such as dipropyl tsthalate and sibutyl phthalate; phosphoric acid esters such as trimethyl phosphate, tothethyl 7-osphate, tripropyl phosphate, and tributyl phosphate; dioctyl sebacate, di(2-ethylhexyl) sebacate, diisodecyl sebacate Sepacylate esters such as cate.

Glycerin esters such as glycerol tripropionate and glycerol dotributyrate, others, azopic acid esters, geltal esters,
Nisuccinic acid ester, maleic ester, 7-mall version ester, citric acid ester, etc. are used.

Then, at the same time, add ultraviolet absorbers to these high boiling point solvents as necessary, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, clohexanetetrahydrofuran, and methyl alcohol. , ethyl alcohol, acetonitrile, dimethylformamide, diochibne, methylethylketone, methylinoptylgtone, diethylketone, diethylene glycol, monoacetate, acetylacetone, nitromethane, nitroethane, carbon tetrachloride, chloroform, etc. The high boiling point solvent and the low boiling point solvent may be used alone or in combination. ), anionic surfactants such as alkylbenzene sulfonic acids and alkylnaphthalene sulfonic acids, and/or hydrophilic binders such as serratin, etc., and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate. Mix with water containing J solution,
It may be emulsified in a high-speed indicator mixer, colloid mill, ultra-fine filtration device, etc., and then added to the hydrophilic colloid A.

In addition to the above-mentioned additives, the light-sensitive material of the present invention further contains stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, lubricants, DIR substances, fireflies, photosensitizer mordants, Alternatively, other additives useful for photographic materials may be added.

Further, in addition to the silver halide emulsion layer and the non-photosensitive layer, the sensitive material of the present invention may be provided with a non-photosensitive layer adjacent to the lower side of the magenta coupler-containing layer, a back layer, etc. as appropriate.

As the reflective support for the photosensitive material of the present invention, conventionally known supports such as plastic laminated paper, baryta paper, synthetic paper, etc. can be selected as appropriate depending on the purpose of use, and these supports are generally made of photographic emulsion. Various treatments are applied to strengthen the adhesion to the material.

(2) Specific Effects of the Invention The light-sensitive material of the present invention is exposed to light through a negative light-sensitive material having an image formed of a coupling product, and then subjected to color development processing.

The color development process is performed by a normal color development method.

That is, first, it is processed with a color developing solution containing a color developing agent. Alternatively, a color developing agent or its precursor is contained in a sensitive material, and this is treated with a so-called activator liquid.

Thereafter, a bleaching process and a fixing process are usually performed as usual.

In this case, the color development process using a color developer or activator liquid, the bleaching process, and the fixing process may be performed independently, but instead of performing two or more processes independently, a process that has these functions is used. Once with liquid (
It is also possible to carry out the process using one bath). For example, a one-bath processing method in which the color development retention solution or activator solution contains both a bleaching agent and a fixing agent as described below, and a bleaching and fixing method in which bleaching and fixing are carried out after the color development step. Methods include using a bath.

Furthermore, after processing with a color developer or activator solution, desilvering can be carried out by immediately processing with a bleach-fixing bath, etc., but an acidic stop step may be provided between the color development step and the bleaching and fixing steps. You can also do it. For such an acidic stop bath, an aqueous solution of acetic acid, citric acid, etc. can be used. Furthermore, if necessary, the anterior dura mater, its neutralization,
Processes such as water washing and stabilization may also be provided.

Through such color development processing, a dye image is formed on the print sensitive material by a coupling reaction.

A typical color developing agent for the photosensitive material of the present invention is an aromatic primary amine color developing agent.

Aromatic primary amine color developing agents include aminophenol and P-phenylenediamine derivatives, and these compounds are particularly preferred, in the a-state, or as their hydrochlorides, sulfur salts, and P-toluenesulfone. It can be used as an organic void salt such as Ie salt, tetraphenylboron tR salt, and P-(t-octyl)benzenesulfonate.

Specific aromatic primary amine color developing agents include 0
-aminophenol, P-aminephenol, 5-amino-2-oxytoluene, 2-amino-,1-yrxytoluene, 2-oxy-3-amino-1,4-dimethylbenzene, N.

N-diethyl-P-phenyl diamine hydrochloride, N-)
Chi-P-phenylenediamine hydrochloride, NUN-dimethyl-P-1 enylenediamine salt [4, N-ethyl-N-
β-methanesulfonaminoethyl-3-methyl-4-aminoaniline oyohi its sulfate, N-ethyl-N-β-
Hydroxyenalaminoaniline, N,N-diethyl-
3-(μm methanesulfonamidoethyl)-4-aminoaniline salt, R salt, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-P-toluenesulfone 17N-ethyl -N-β-Methanesulponamidoethyl-3-methyl-4-aminoaniline tetraphenylborate, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline tetraphenyl Borate, P-morpholinoaniline, P-piperidinoaniline, 4-amino-N,N-diethyl-3
-Chloroaniline etc. can be mentioned as a typical example.

In some cases, the light-sensitive material of the present invention may contain a color developing agent precursor. The color developing agent precursor is a compound that can produce a color developing agent under alkaline conditions, and includes, for example, a Schiff 6-s type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, and a phthalic acid imide derivative precursor. Examples include acid amide derivative precursors, sugar amine reactant precursors, and urethane type precursors.

Precursors for these aromatic primary amine color developing agents are described, for example, in U.S. Pat.
, 507,114, 2,695,234, 3,719,492, British Patent No. 803,783, JP-A-53-135,628, JP-A-54-7
9.035, Research Disclosure Magazine No. 15159, Research Disclosure No. 12146, and Research Disclosure No. 13924.

These aromatic primary amine color developing agents are usually contained in the color developing solution in an amount of about 1 to 20 to 'p. Further, when it is contained as a precursor in a sensitive material, it is contained in an amount of about 0.5 to 3 moles per mole of silver halide.

The color developing solution or activator solution used for the photosensitive material of the present invention includes potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate,
These include alkaline agents such as tribasic potassium phosphate, bibrite salts such as sodium sulfite and potassium sulfite, and bromide salts such as sodium bromide, potassium bromide, and ammonium bromide. Furthermore, if necessary, known development inhibitors, thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, chloride salts such as ammonium chloride, potassium chloride, and sodium chloride, ethylene glycol, diethylene glycol , organic bath media such as methanol, ethanol, n-butanol, benzyl alcohol, acetone, dimethylformamide, amines such as hydroxylamine, ethanolamine, ethylenediamine, jetanolamine, sodium hexametaphosphate, sodium tripolyphosphate, ethylenediaminetetraacetic acid, It may also contain a water softener such as diethylenetriaminepentaacetic acid, a water bath fluorescent brightener, and the like.

The color developing solution or activator solution used in the present invention may contain an auxiliary developer.

The auxiliary developer is preferably a 1-aryl-3-virazolidone derivative, and is used in an amount of (1) r11f to 1y-1, preferably 10 drops to 500 drops, per 1 B of color developer or activator solution. Typical auxiliary developers include 1-phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-virasoliton, 4
゜4-dimethyl-1-phenyl-3-pyrazolidone, 4
-Methyl-4-hydroxymethyl-1-phenyl-3-
Pyrazolidone, 4-methyl-4-hydroxymethyl-1
-(P-tolyl)-3-pyrazolidone and the like.

The color developing solution or activator solution used in the present invention is kept alkaline according to a conventional method, and its hydroxyl ion concentration is adjusted to
The pH may be appropriately selected depending on the type, composition, purpose, and use of the photosensitive material, but the pH is generally 9.5 to 13.5.

Color developing solution or activator solution used in the present invention (
is generally used within a certain temperature range. The temperature range can be appropriately selected depending on the print according to the present invention to be processed, the neo species 1, composition, use, purpose, etc., but preferably 15°C to 7()°C, and 30°C to 5°C.
0°C is more preferred.

As the bleaching agent used in the bleaching or whitening fixing bath, known compounds can be used, including aminopolycarboxylic acids such as ethylenediamine, sodium ferric acetate, and ferric ammonium in ethylenediamine. Persulfates such as ferric complex salts, ammonium persulfate, and sodium persulfate can be used. Further, as the fixing agent used in the fixing or bleach-fixing bath, known compounds can be used, such as thiosulfates such as sodium thiosulfate and ammonium thiosulfate, 3,6-cythyl, s-octanediol, etc. , 3, 6, 9, 12-tetrathia-1,14-tetratecanyl, ethylene-bis-thiol glycol, cholic acid, nitylene-histio-glycol, etc. Water-bathable sulfur-containing dibasic substances such as chytrium salts, etc., inside the potatoes,! l: Gadesaru.

③ Practical Effects of the Invention According to the present invention, the luminosity of the marker dye image is extremely high.

Furthermore, the fading color balance with other dye images is also very good.

Furthermore, capri caused by static during transportation in the chamber or during transportation within the Zlinta is also reduced.

In addition, since it has a non-containing layer consisting essentially of a binder as the uppermost layer, there is very little decrease in surface gloss over time (so-called sweating phenomenon).

~1 Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown to explain the present invention in further detail. 'Example Sample 1 was prepared under the beak formation conditions shown in Table 1 below.1. Ta,
.

Formation of Layer 4 and Layer 6 In this case, the above-mentioned UV-7 was used as the ultraviolet absorber, and in this case, the above-mentioned UV-7 was used as the ultraviolet absorber, and the amount of Zoptylphukunt tube 1 (weight ratio 1:l) was used as the ultraviolet absorber. , Mazenko coupler, yellow coupler and shear coupler, the above M-22, Y-7 and C-9 were used.

Next, as a comparison sample, a sample obtained by removing layer 6 from sample 1,
A sample was prepared with layer 7 removed, and then sample 2
, and sample 3. In addition, up to the ridge of ONg in Table 1 above, replace the magenta coupler with the comparative magenta coupler M below.
' was prepared and designated as sample 4 (see Table 2 below).

Comparative magenta coupler M' Table 2 The four samples (1 to 4) prepared as described above were tested using a sensitometer (model KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.) for magenta light and green light. , and red light through the light beam, and then processed according to the following processing steps to obtain a three-color separation sample (yellow, magenta, cyan).

Processing process> Processing time Processing temperature Color development 3.5 minutes 33℃ Bleach fixing 1.5 minutes 33℃ Washing with water 3 minutes Drying at 33℃
Drying 80℃ Color developer composition Pure water 70
0mb benzyl alcohol 15-diethylene glycol 15-hydroxylamine sulfate 2f potassium carbonate
30y-potassium bromide 0.4
y- Potassium chloride 0.51 Add pure water to make it 14 (PH = 10.2) Bleach-fix solution composition Ammonium periosulfate 125ψ Sodium metabisulfite 13y Photofading tests using light 2 and sunlight were conducted to evaluate light fastness. Measures of light fastness and 1-
Now, using the dye residual rate, the percentage of the reflection density after sunlight with respect to the reflection yield before exposure of 1.0 was calculated. In this case, if the exposure of the white background causes yellowing (especially yellow colored samples), that amount will be subtracted and the result will be the 4 qualities after punishment. For example, if the white background density is adjusted to 0.00 and the yellow pigment density is 1.00 before the 4th exposure, then the white background density after the 4th exposure is 0.1.
8. Yellow pigment a degree is 0.78, pigment remains - J
, j ma, (0,78-+11.18)/1.00X10
0=60 inches.

The heirs are shown in Table 3K.

From the results shown in Table 3, it is evident that Sample 1 used in the present invention has extremely high light fastness. On the other hand, in Sample 4, which uses magenta color 27, which is not of the present invention, the light resistance of the magenta dye is extremely low even though the layer structure is the same as Sample 1. f. Sample 2, which has only one non-photosensitive ultraviolet absorber layer on the side far from the magenta coupler-containing layer as viewed from the support, has low light fastness for all yellow, magenta, and cyan dyes. All I get is sex. Furthermore, layer 7
When comparing Sample 3 without M and Sample 1 of the present invention,
It can be seen that the light fastness of all yellow, magenta, and cyan coloring dyes is improved, and the magenta dye in particular shows a remarkable improvement effect.

Example 2 A coupler with the same layer structure as Sample 1 of Example 1 was prepared in Table 4 below.
Samples with the following changes were prepared and designated as Samples 5, 6, and 7. In addition, the sample prepared by removing layer 7 from sample 5, (i, 7) was designated sample 8.9.10. In this case, the ultraviolet absorber 1dUV-4t-
Using.

These 61iJ samples were subjected to the same exposure and treatment as in Example 1, and a halophotobleaching test was conducted. The results are shown in Table 5.
Shown below.

From the setting speed shown in Table 5, sample 5.6,' according to the present invention
1 has higher light fastness than the corresponding comparative sample 8.9.10, clearly showing a remarkable effect on improving the light fastness of the magenta dye.

Note that such an effect can be achieved by using other 3-afrino-5-pyrazolone magenta couplers represented by the general formula CI3 and other ultraviolet absorbers, especially those represented by the general formula [1], as well as other yellow and cyan couplers. It has been confirmed that the same result can be achieved even if the method is used.

Applicant Konishi Roku Photo Industry Co., Ltd. Agent Patent Attorney Akira Ishii - Procedural Amendment (2008) December 31, 1932 Commissioner of the Japan Patent Office Kazuo Wakasugi 1. Indication of the case 1982 Patent application No. 92616 2, Name of the invention Color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant's office
1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Konishiroku Photo Industry Co., Ltd. Representative: Nobuhiko Yomoto 4, Agent 171 Address: 5-17-11 Nishiikebukuro, Toshima-ku, Tokyo
No. Yabe Building, 1st floor Telephone: 98B-1680 Detailed Description of the Invention column 6 of the Specification, Contents of Amendment Clear Answer, - in "3. Detailed Description of the Invention" is amended as follows, l) No. On page 9, lines 10 to 11, the words "aryl albamoyl group" and "aryl albamoyl group" are corrected.

2) 49 pages ax 2? In T, correct "alkylsuccinimide group" to [alkylsuccinimide group]. 3) On page 9, g, lines 17 to 18, "aralkylaminoalboalkylamino acid" should be corrected. 4) The structural formula of M-30 written in the l'h bud on page 20 is corrected as follows.

-30cL 5) In lines 12 to 13 of the 65th page, the word "compatibility" is corrected to "compatibility."

6) In lines 9 and 10 of page 467, correct the text "thioethyl phosphate" (: ) to "I".

7) On page 68, lines 11 to 12, [Jiechi'L
// Glycol, monoacetate", correct it to "diethylene glycol monoacetate".

8) On page 75, line 7, it says “chloride salt”.
Correct to "salts".

9) In Table 4 on page 88, there are two M'L33J couplers used for layer 3.

Both of these are corrected as "M-17J010". In the 7th line of page 91, the word "Anlino" is changed to 1 Anniversary.
1 no,” he corrected.

Claims (1)

[Claims] Two or more silver halide emulsion layers on a reflective support? and at least one of the halogenated emulsion layers contains a 3-anilino-5-pyrazolone magenta coupler represented by the following general formula [I], and when viewed from the support, it contains this magenta coupler. Two or more non-photosensitive layers containing an ultraviolet absorber are provided on the side farthest from the support. Contains ultraviolet absorber on the opposite side 1
A color photographic material characterized by having no non-photosensitive layer. General formula C1'l (In the above general formula [■], X□ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amide group, a hydroxyl group, a cyano group, or a nitro group) , Yl, Y, and Y3 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a carboxy group,
represents an alkoxycarbonyl group, nitro group, aryloxy group, cyano group or acylamino group, W represents a hydrogen atom, a halogen atom or a +t monovalent organic residue, and Zl represents an atom or group that leaves during cambling. represents. ;