JPH05173306A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance processing stability and to reduce disturbance of color balance by incorporating a specified dye stuff forming coupler in an emulsion layer and setting the content by weight of organic solvent high in a boiling point contained in this layer in specified range. CONSTITUTION:The silver halide emulsion layer contains the organic solvent high in the boiling point in an amount of 40-300weight% of the dye stuff forming coupler, and one of the dye stuff forming couplers represented by formulae I and II in which R1 is alkyl or aryl; R2 is alkyl, cycloalkyl, aryl, or a hetero-cyclic group; R3 is H, halogen, alkyl, or alkoxy; each of Z1 and Z2 is H or a group to be released by coupling with the oxidation product of a color developing agent; R11 is 2-6C alkyl; and R12 is a ballasting group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having an excellent color balance.

[0002]

BACKGROUND OF THE INVENTION Silver halide color photographic light-sensitive materials (hereinafter referred to as "color light-sensitive materials") are coupled with an oxidant of an aromatic primary amine type color developing agent to form yellow, magenta and cyan dyes, respectively. It is common to include the three dye-forming couplers provided.

Among them, as a cyan coupler, from the viewpoint of color reproduction, improvements have been continued in terms of the maximum absorption wavelength of the color forming dye and the sharpness of the absorption peak.

On the other hand, the color light-sensitive material (color negative film) photographed by the customer is collected at a developing station, developed and printed on color paper, and then returned to the customer as a color photograph. Recently, the proportion of "minilabs" as a photo lab has increased, maintaining the development level (that is, maintaining print quality).
In many cases, the stability of quality is strongly desired.

[0005]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a color light-sensitive material excellent in development processing stability.
A second object is to provide a color light-sensitive material which is less likely to lose color balance.

[0006]

As a result of intensive studies, the present inventors have found that the above object can be achieved by the following structure.

In a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one light-sensitive silver halide emulsion layer is provided.
The layer contains at least one dye-forming coupler represented by the following general formulas [I] and [II], and the weight ratio of the high-boiling organic solvent contained in the layer to the dye-forming coupler is 0.4 to A silver halide color photographic light-sensitive material characterized by being 3.0.

[0008]

[Chemical 3]

In the formula, R ₁ represents an alkyl group or an aryl group, and R ₂ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Also, R ₃ is R ₁
May form a ring together with. Z ₁ represents a hydrogen atom or an atom or group capable of splitting off upon reaction with an oxidized product of a color developing agent.

[0010]

[Chemical 4]

In the formula, R ₁₁ represents an alkyl group having 2 to 6 carbon atoms, and R ₁₂ represents a ballast group. Z ₂ represents a hydrogen atom or an atom or group capable of splitting off upon reaction with an oxidized product of a color developing agent.

The present invention will be described in more detail below.

In the cyan coupler represented by the general formula [I], the alkyl group represented by R ₁ is preferably one having 1 to 32 carbon atoms, which may be linear or branched and may have a substituent. Including those that have.

The aryl group represented by R ₁ is preferably a phenyl group, including those having a substituent.

The alkyl group represented by R ₂ is preferably an alkyl group having 1 to 32 carbon atoms, and these alkyl groups may be linear or branched and include those having a substituent.

The cycloalkyl group represented by R ₂ preferably has 3 to 12 carbon atoms, and these cycloalkyl groups include those having a substituent.

The aryl group represented by R ₂ is preferably a phenyl group, including those having a substituent.

The heterocyclic group represented by R ₂ is preferably a 5- to 7-membered heterocyclic group, which may have a substituent or may be condensed.

R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, but R ₃ is preferably a hydrogen atom.

The ring formed by R ₁ and R _{3 in combination} is preferably a 5- or 6-membered ring, and examples thereof include:

[0021]

[Chemical 5]

And the like.

The atom or group represented by Z which can be released by the reaction with the oxidized product of the color developing agent is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group or a sulfonylamino group. , An alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an imide group and the like (including those each having a substituent) are preferable, and a halogen atom, an aryloxy group and an alkoxy group are preferable.

Of the above-mentioned cyan couplers, those particularly preferable are those represented by the following general formula [IA].

[0025]

[Chemical 6]

In the formula, R ₄ represents a phenyl group substituted with at least one halogen atom, and these phenyl groups further include those having a substituent other than a halogen atom.

R ₅ has the same meaning as R _{1 in the} above general formula [I].

Z ₃ represents a halogen atom, an aryloxy group or an alkoxy group, and includes those having a substituent.

Typical examples of the cyan coupler represented by the general formula [I] are shown below.

[0030]

[Chemical 7]

[0031]

[Chemical 8]

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

Specific examples of the above cyan coupler include:
Further, Japanese Patent Application No. 61-21853, pages 26 to 35, JP-A No. 60-225155, page 7, lower left column, page 10, lower right column, JP 60-222853, page 6, upper left column, page 8 lower right column, and JP-A-59-185335, page 6, lower left column to 9
It includes the 2,5-diacylamino cyan couplers described in the upper left column of the page, and can be synthesized according to the methods described therein.

The cyan dye type coupler represented by the above general formula [I] of the present invention is usually 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-2 to 8 × 10 ^-1 per mol of silver halide. It can be used in the molar range.

Next, the cyan coupler represented by the general formula [II] will be described.

The alkyl group represented by R ₁₁ may be linear or branched and includes those having a substituent. The ballast group represented by R ₁₂ is an organic group having a size and shape that imparts sufficient bulk to the coupler molecule so that the coupler cannot substantially diffuse from the layer to which the coupler is applied to other layers. Is. The preferred ballast group is represented by the following general formula. —CH (R ₁₃ ) —O—Ar R ₁₃ represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and the aryl group includes those having a substituent. Next, specific examples of the cyan coupler represented by the general formula [II] are shown, but the cyan coupler is not limited thereto.

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

Specific examples of cyan couplers that can be used in the present invention, including these, are described in JP-B-49-11572.
No. 6, JP-A-61-3142, No. 61-9652, No. 61-9653, No. 6
1-39045, 61-50136, 61-99141, 61-105545
No. etc. The cyan coupler represented by the above general formula [II] of the present invention is usually 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ per mol of silver halide.
It can be used in the molar range. At least one of the couplers represented by the general formula [I] and the coupler represented by the general formula [II] is preferably 10% or more by weight.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate [DBP], dicyclohexyl phthalate, di-2-ethylhexyl). Phthalate [DEHP], decyl phthalate, bis (2,4-di-t
-Amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl) Phosphate [TCP], 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
Tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl)
-p-hydroxybenzoate, etc., amides (N, N-diethyldodecaneamide, N, N-diethyllaurylamide,
N-tetradecylpyrrolidone), alcohols or phenols (i-stearyl alcohol, 2,4-di-t-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate) , Glycerol tributyrate, i-stearyl lactate, trioctyl citrate, etc., aniline derivatives (N, N-dibutyl-2-butoxy-5-t-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, dioctyl citrate)
-i-propylnaphthalene).

As the support of the light-sensitive material of the present invention, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or used in combination with a reflector, or a glass plate, cellulose acetate or cellulose nitrite. There are transparent supports such as polyester film such as rate or polyethylene terephthalate, polyamide film, polycarbonate film, polystyrene film and the like, and these supports are appropriately selected according to the purpose of use of the light-sensitive material.

The colloidal silver-containing non-photosensitive layer preferably used in the present invention is preferably a hydrophilic colloid layer, and more preferably a gelatin layer. Among gelatins, it is preferable to use low-calcium gelatin having a calcium content of 800 ppm or less because the effect of the present invention is large.

The gelatin coating amount is from 0.05 to 1 layer.
5.0 g / m ^2, in particular in the range of 0.2 to 2.0 g / m ² is preferred.

In the present invention, as the colloidal silver added to the non-photosensitive layer when the non-photosensitive layer is one layer, and to at least one layer when the non-photosensitive layer is two or more layers, Various types can be used.

The color light-sensitive material of the present invention comprises a red light-sensitive layer,
At least one layer of each of the green photosensitive layer and the blue photosensitive layer is provided. For example, each of the photosensitive silver halide emulsions of the red photosensitive layer, the green photosensitive layer and the blue photosensitive layer is sequentially coated from the support side. It can be installed and formed. Each photosensitive layer may have a single-layer structure, but it is more preferable that it has a multi-layer structure, for example, a two-layer structure of a high-sensitivity layer and a low-sensitivity layer. or,
An intermediate layer may be provided in the middle of each layer.

As the silver halide emulsion used in the light-sensitive material of the present invention, any ordinary silver halide emulsion can be used. The effect is remarkable especially in the case of silver iodobromide emulsion.

The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

Dye-forming couplers can be appropriately used in the red, green and blue light-sensitive layers of the light-sensitive material of the present invention. Further, by coupling with a competing coupler having an effect of color correction and an oxidized product of a developing agent, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, and a fog. Compounds that release photographically useful fragments such as inhibitors, chemical sensitizers, spectral sensitizers and desensitizers can be used.

Further, the light-sensitive material of the present invention may be provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer and an irradiation prevention layer.

Further, a formalin scavenger, a fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, an antifoggant, a development accelerator, a development retarder or a bleaching accelerator can be added to the light-sensitive material. ..

[0060]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Example 1 A color reversal light-sensitive material (comparative sample 10) was prepared by providing the following first to eleventh layers on a paper support coated on both sides with polyethylene.
1) was created. The coating amount of each component is shown in g / m ² . However, for silver halide, the coating amount converted to silver is shown.

First layer (antihalation layer) Black colloidal silver 0.10 High boiling point solvent (DEHP) 0.90 Gelatin 1.5 Second layer (first red-sensitive layer) Cyan coupler (C-1) 0.20 Cyan coupler (C-2) 0.10 Anti-fading agent (A-1) 0.15 Anti-fading agent (A-2) 0.075 Anti-fading agent (AN-1) 0.0060 High boiling point solvent (DEHP) 0.22 Spectral sensitization with red sensitizing dye (S-1, S-2) Sensitized AgBrl (Agl 4.0 mol%, average particle size 0.42 μm) 0.16 Spectral-sensitized AgBrl (Agl 4.0 mol%, average particle size 0.90 μm) 0.07 with red sensitizing dye (S-1, S-2) 0.07 Polyvinylpyrrolidone 0.035 Gelatin 0.79 Third layer (second red-sensitive layer) Cyan coupler (C-1) 0.11 Cyan coupler (C-2) 0.056 Anti-fading agent (A-1) 0.085 Anti-fading agent (A-2) 0.043 Mixed color Inhibitor (AN-1) 0.0034 High boiling point solvent (DEHP) 0.13 Red AgBrl (Agl 4.0 mol%, average particle size 0.90 μm) 0.12 Polyvinylpyrrolidone 0.016 Gelatin 0.90 Fourth layer (first intermediate layer) Gelatin 0.90 Color mixture prevention spectrally sensitized with sensitizing dyes (S-1, S-2) Agent (AN-1) 0.020 Color mixing inhibitor (AN-2) 0.060 High boiling point solvent (DIDP) 0.13 Fifth layer (first green sensitive layer) Magenta coupler (M-1) 0.12 Anti-fading agent (A-3) 0.034 Anti-fading agent (A-4) 0.0056 Anti-fading agent (A-6) 0.070 Anti-fading agent (AN-1) 0.0046 High boiling point solvent (DIDP) 0.092 AgBrl spectrally sensitized with a green sensitizing dye (S-3) (Agl 4.0 mol%, average particle size 0.42 μm) 0.15 AgBrl spectrally sensitized with a green sensitizing dye (S-3) (Agl 2.0 mol%, average particle size 0.27 μm) 0.020 Polyvinylpyrrolidone 0.022 Gelatin 0.93 6th layer (Second green sensitive layer) Magenta coupler (M-1) 0.18 Anti-fading agent (A- ) 0.052 Antifading agent (A-6) 0.11 Antifading agent (A-4) 0.0085 Anticolor mixing agent (AN-1) 0.0070 High boiling point solvent (DIDP) 0.14 Spectral sensitized with green sensitizing dye (S-3) AgBrl (Agl 4.0 mol%, average particle size 0.90 μm) 0.24 Polyvinylpyrrolidone 0.031 Gelatin 0.83 7th layer (2nd intermediate layer) Yellow colloidal silver 0.15 Color mixing inhibitor (AN-1) 0.011 Color mixing inhibitor (AN-2) 0.034 High boiling point solvent (DEHP) 0.070 Gelatin 0.90 Eighth layer (first blue-sensitive layer) Yellow coupler (Y-1) 0.28 Anti-fading agent (A-1) 0.11 Anti-fading agent (A-5) 0.057 Anti-color mixing agent ( AN-1) 0.0085 High boiling point solvent (DNP) 0.055 Spectral sensitized with blue sensitizing dye (S-4) AgBrl (Agl 4.0 mol%, average particle size 0.42 μm) 0.12 Blue sensitizing dye (S-4) Spectrally sensitized AgBrl (Agl 2.0 mol%, average particle size 0.90 μm) 0.030 Gelatin 0. 95 9th layer (2nd blue sensitive layer) Yellow coupler (Y-1) 0.53 Anti-fading agent (A-1) 0.21 Anti-fading agent (A-5) 0.11 Anti-color mixing agent (AN-1) 0.016 High boiling point solvent ( DNP) 0.10 AgBrl spectrally sensitized with a blue sensitizing dye (S-4) (Agl 2.0 mol%, average particle size 0.90 μm) 0.23 Gelatin 1.1 10th layer (ultraviolet absorbing layer) Ultraviolet absorbing agent (U-1) 0.15 UV absorber (U-2) 0.45 Color mixture inhibitor (AN-1) 0.033 High boiling point solvent (DNP) 0.036 Gelatin 1.7 11th layer (protective layer) Gelatin 0.50 However, in addition to the above, surfactants and hardeners Agent, anti-irradiation dye, thickener, antifungal agent.

The additives used in each layer are as follows.

DEHP di-2-ethylhexyl phthalate DIDP di-i-decyl phthalate DNP dinonyl phthalate AN-1 2,5-di-t-octyl hydroquinone AN-2 2-hexadecyl-5-methyl hydroquinone A-2 4- (p-Dodecylphenyl) sulfamoyltoluene A-4 1,4-dioctyloxy-2,5-di-t-pentylbenzene A-6 1,4-dibutoxy-2,5-di-t-butylbenzene

[0065]

[Chemical 17]

[0066]

[Chemical 18]

[0067]

[Chemical 19]

The silver halide emulsion used for each photosensitive layer was prepared by referring to the method of Example-1 of JP-A-59-178447. All were monodisperse emulsions having a distribution of 20% or less. Each emulsion is desalted and washed with water, then sodium thiosulfate,
Optimum chemical ripening in the presence of chloroauric acid and ammonium thiocyanate, sensitizing dyes, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercapto Tetrazole was added. The gelatin used for Sample 101 was low calcium gelatin having a calcium content of about 50 ppm.

Next, samples 102 to 112 were prepared in the same manner as sample 101 except that the cyan couplers and high boiling point solvents of the second and third layers of comparative sample 101 were changed as shown in Table 1.

[0070]

[Table 1]

Samples 101 to 112 were exposed to white light through a sensitometric step wedge, and were subjected to the following development processing.

(Development process) First development (black and white development) 1 minute 15 seconds (38 ° C) Water washing 1 minute 30 seconds Light fog 100lux or more 1 second or more Second development (color development) 2 minutes 15 seconds (38 ° C) ) Washing with water 45 seconds Bleach-fixing 2 minutes (38 ° C) Washing with water 2 minutes 15 seconds However, the pH of the second development (color development) was changed as follows. The pH was adjusted with sulfuric acid or potassium hydroxide.

A condition pH = 10.45 B condition pH = 10.30 C condition pH = 10.15 First developer potassium sulfite 30.0 g sodium thiocyanate 1.0 g sodium bromide 2.4 g potassium iodide 8.0 mg potassium hydroxide (48%) 6.2 ml Potassium carbonate 14 g Sodium hydrogencarbonate 12 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Hydroquinone monosulfonate 23.3 g Water is added to make 1000 ml. (PH = 9.65) Color developer Benzyl alcohol 14.6ml Ethylene glycol 12.6ml Potassium carbonate (anhydrous) 26g Potassium hydroxide 1.4g Sodium sulfite 1.6g 3,6-Dithiaoctane-1,8-diol 0.24g Hydroxylamine sulfate 2.6g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Add water to make 1000 ml. (PH = 10.45,10.30,10.15) Bleach-fixing solution 1.56 molar solution of ferric ammonium ethylenediaminetetraacetate solution 115ml Sodium metabisulfite 15.4g Ammonium thiosulfate (58% aqueous solution) 126ml 3-Mercapto-1,2,4-triazole Add 0.4 g water to make 1000 ml. (PH = 6.5) The processed sample was measured for yellow, magenta and cyan densities with a Macbeth color densitometer and the magenta densities were measured.
The density ratio change with respect to the cyan density at the same exposure point of 0.50 and 2.00 was set to 1.0 under the condition A, and the ratio (rate of change) under the condition change was determined. The results are shown in Table 2.

[0074]

[Table 2]

As is clear from the results of Table 2, the sample of the present invention shows a small change in density at each exposure point (that is, a small color balance loss).

Also in the prints produced from the slides photographed by the camera under the respective developing conditions of A, B and C, the one according to the present invention has a small density change, and the density and color balance are not significantly disturbed. , The improvement effect was recognized.

[0077]

According to the present invention, it is possible to obtain a color photographic light-sensitive material in which the color balance is hardly disturbed.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one light-sensitive silver halide emulsion layer has the following general formula [I ] And [II] each of at least one dye-forming coupler, and the weight ratio of the high boiling point organic solvent contained in the layer to the dye-forming coupler is 0.4 to 3.0. Silver halide color photographic light-sensitive material. [Chemical 1] [In the formula, R ₁ represents an alkyl group or an aryl group, and R ₂ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ₃ may form a ring together with R ₁ . Z ₁ represents a hydrogen atom or an atom or group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] [Chemical 2] [In the formula, R ₁₁ represents an alkyl group having 2 to 6 carbon atoms,
R ₁₂ represents a ballast group. Z ₂ represents a hydrogen atom or an atom or group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]