JP2681658B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a silver halide color photographic light-sensitive material having a small post-curing property, and more specifically, a silver halide having a small post-curing property due to a rapid curing reaction. The present invention relates to a color photographic light-sensitive material.

Background of the Invention A silver halide color photographic light-sensitive material has an emulsion layer, a protective layer, an intermediate layer, an antihalation layer, a backing layer, an undercoat layer and the like. These layers contain gelatin as a binder. It is mainly used. Therefore, in order to prevent the gelatin binder from being eluted during the development process, the film is hardened with various hardeners from the past to enhance water resistance and mechanical strength.

Inorganic curing agents such as chrome alum, aldehyde compounds such as formaldehyde are used as curing agents, and US Pat.
Compounds having a reactive ethylenic unsaturated bond described in US Pat. No. 3,094,537, epoxy compounds as described in U.S. Pat. No. 3,094,537, and carboxyl groups of gelatin as described in JP-A-60-225148. There are hardeners that act by activating the groups, but the hardening effect is insufficient or the hardening reaction is slow, so the degree of hardening changes over time or the hardening reaction is fast but halogenated. Those that adversely affect the photographic performance of silver color photographic light-sensitive materials,
Has some drawbacks.

In particular, the change in hardness over time is called post-hardening.This not only changes the mechanical strength of the silver halide photographic light-sensitive material, but also changes the maximum color density with changes in hardness. This is not preferable because it affects photographic performance.

Examples of the hardener that does not adversely affect the photographic performance of the silver halide photographic light-sensitive material include, for example, Japanese Patent Publication No. Sho 49-13563.
53-47271, 53-1782, 55-38645, JP Sho
48-74832, 49-24435, 51-44164, 53-6
6960, 53-41221, 53-57257, 53-76026
Issue No. 59-18944, No. 63-53541, No. 62-4275, No.
61-1282 and the like.

These curing agents are less likely to adversely affect photographic performance and are preferable as curing agents for halogen photographic light-sensitive materials, but the curing reaction rate cannot be said to be sufficiently fast, and they were described above after the production of silver halide photographic light-sensitive materials. It has a problem that it must be left for a long period of time in order to prevent such a problem of post-curing.

As a result of examining from various angles, the inventors of the present invention have studied the use of a vinyl sulfone-based curing agent to accelerate the curing speed, and as a result, surprisingly, the particle size of the dispersion liquid of the coupler contained in the silver halide photographic light-sensitive material was investigated. It has been found that when the value is increased, the curing degree becomes constant quickly, and that a silver halide photographic light-sensitive material having a small post-curing property can be provided earlier. However, in this case, there is a drawback in that the ultimate level of the curing degree becomes low.

[Object of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material having a low post-curing property without lowering the ultimate curing degree.

[Configuration of the invention]

The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one hydrophilic binder layer containing gelatin containing an oil-soluble coupler dispersion having an average particle size of oil droplets of 150 to 600 nm, wherein at least one layer is provided. Film surface of the obtained photosensitive material cured with two vinyl sulfone type curing agents
It is achieved by a silver halide color photographic light-sensitive material characterized by having a pH of 5.5 to 7.0.

 Hereinafter, the present invention will be described in more detail.

The oil-soluble coupler dispersion having an average oil droplet diameter of 150 to 600 nm used in the present invention can be emulsified and dispersed by a known oil-in-water emulsion dispersion method.

That is, the oil-soluble coupler is usually dissolved in a high-boiling point organic solvent having a boiling point of about 150 ° C. or more in combination with a low-boiling point and / or water-soluble organic solvent, if necessary, and the surfactant is added to a hydrophilic binder such as an aqueous gelatin solution. Using a stirrer, homogenizer,
When emulsifying and dispersing using a dispersing means such as a colloid mill, a flow jet mixer, an ultrasonic device, etc., a coupler dispersion having an oil droplet average diameter of 150 to 600 nm depending on the operation of the emulsifying device and the setting of conditions such as emulsifying time. Can be made.

A homogenizer is preferable as the emulsifying device, a homogenizer manufactured by Manton Gorin Co. can control the particle size by changing the pressure during dispersion, and a high-speed stirring homogenizer can easily control the particle size by changing the stirring rotation.

A Coulter model N4 submicron particle analyzer with a particle size measurement method using laser Doppler was used to measure the oil drop average particle size. When the average particle size of the coupler dispersion is smaller than the average oil droplet size of 150 nm of the present invention, sufficient effect cannot be obtained with respect to the progress of hardening, and when it is 600 nm or more, deterioration of photographic performance and the like is observed. It was

The oil droplet average particle diameter of the coupler dispersion of the present invention is preferably 250 to 600 nm.

Oil drop average particle size is also within the scope of the present invention, even in the photographic constituent layer containing a coupler dispersion, if the oil drop content is 0.5 or less, the effect on the film progress was observed, but if it is higher than 0.5, the effect is not so great. There wasn't.

Next, the vinyl sulfone-based curing agent used in the present invention may be any compound as long as it has at least two vinyl sulfone groups in one molecule. Examples thereof include compounds represented by [I].

General formula [I] Here, R represents a hydrogen atom or a lower alkyl group, preferably a hydrogen atom or a methyl group. Z is an n-valent group containing at least one of oxygen, nitrogen and sulfur atoms, and the atoms contained in Z are preferably oxygen atoms or nitrogen atoms. m is 1 or 2, and n is 2 or 3.

Next, specific examples of the vinyl sulfone type curing agent according to the present invention will be given. However, the present invention is not limited to these.

_{H-1 CH 2 = CHSO 2} CH 2 OCH 2 SO 2 CH = CH 2 H-2 CH 2 = CHSO 2 CH 2 CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CH 2 SO 2 CH = CH 2 H- 3 CH ₂ = CHSO ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ CH = CH ₂ H-4 CH ₂ = CHSO ₂ CH ₂ CH ₂ OCH ₂ CH ₂ NHCONHCH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ CH = CH _{2 H-8 CH 2 = CHSO 2} CH 2 OCH 2 CH 2 SO 2 CH 2 CH 2 OCH 2 SO 2 CH = CH 2 H-9 CH 2 = CHSO 2 CH 2 SO 2 CH = CH 2 H-10 CH 2 = CHSO ₂ CH ₂ CH ₂ SO ₂ CH = CH _{2 H-13 CH 2 = CHSO 2} CH 2 CONHCH 2 CH 2 NHCOCH 2 SO 2 CH = CH 2 H-14 (CH 2 = CHSO 2 CH 2 CH 2 O-CH 2 CH 2 2 SO 2 H-15 [(CH ₂ = CHSO ₂ CH _{2 3} CCH ₂ SO ₂ CH ₂ CH ₂ ] ₂ N-CH ₂ CH ₂ SO ₃ K H-17 (CH ₂ = CHSO ₂ CH _{2 2} C ₂ CH ₂ SO ₂ CH ₂ CH ₂ OSO ₃ Na) H-20 (CH ₂ = CHSO ₂ CH _{2 4} C) The amount of the curing agent used in the present invention can be arbitrarily selected according to the purpose. Usually, a hydrophilic colloid such as dry gelatin to be hardened is used. On the other hand, it can be used in the range of 0.01 to 20% by weight, particularly preferably in the range of 0.05 to 10% by weight.

Since these hardeners have diffusibility, all layers can be hardened by adding them to one of the photographic constituent layers. Generally, it is preferably added to the outermost layer or a layer adjacent to the outermost layer at the time of coating multiple layers.

In the silver halide photographic light-sensitive material of the present invention, the layer using these curing agents is not particularly limited, and a silver halide emulsion layer as well as a non-photosensitive layer such as an antihalation layer, a back layer, a filter layer, an intermediate layer, It can be used in any gelatin-containing photographic layer such as a protective layer.

The curing agent according to the present invention may be used alone, or two or more curing agents according to the present invention may be used in combination. It may be used in combination with other conventionally known curing agents. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine, and others. U.S. Pat.Nos. 3,288,775, 2,732,303, British Patents 974,723, 1,167,207 and the like, compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1, 3,5-triazine, other U.S. Patent 3,635,718,
3,232,763, British Patent 994,869, JP-A-53-41221
Nos. 53-57257 and the like, compounds having a reactive olefin, N-hydroxymethylphthalimide, and other N-methylol compounds described in US Pat. Nos. 2,732,316 and 2,586,168, US patents 3,10
Isocyanates described in 3,437, etc., U.S. Patents 3,017,280, aziridine compounds described in 2,983,611, etc., U.S. Patents 2,725,294, acid derivatives described in 2,725,295, etc., U.S. Patents Carbodiimide compounds described in 3,100,704 and the like, epoxy compounds described in U.S. Pat.No. 3,091,537, isoxazole compounds described in U.S. Pat. Dioxane derivatives such as halogenocarboxaldehydes, dihydroxydioxane and dichlorodioxane, the above-mentioned dihydroquinoline compounds, compounds having a phosphorus-halogen bond, N-sulfonyloxyimide compounds, N
-Acyloxyimino compounds, N-carbonyloxyimide compounds described in JP-A-56-433535, 2-sulfonyloxypyridinium salts, N-carbamoyl palidinium salts and the like. Alternatively, as an inorganic compound curing agent, there are chromium alum, zirconium sulfate and the like. or,
Those in the form of precursors (precursors) instead of the above compounds, for example, alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic nitro alcohols, methyloxyethylsulfonyl compounds, chloroethyl You may use together with a sulfonyl-type compound.

When the curing agent according to the present invention is used in combination with another curing agent, the proportion of the curing agent according to the present invention to be used can be selected arbitrarily according to the purpose and effect, but is 50 mol% or more. It is preferable.

As the silver halide emulsion used in the light-sensitive material of the present invention, any conventional silver halide emulsion can be used. The emulsion can be chemically sensitized by a conventional method, and a desired wavelength region can be optically sensitized by using a sensitizing dye.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion.

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

Commonly used couplers and other couplers are used in the emulsion layer of the color photographic light-sensitive material.

Furthermore, development couplers, bleaching accelerators, developers, silver halide solvents, toning agents, hardeners, and fogging agents by coupling with colored couplers, competing couplers, and oxidized products of developing agents that have the effect of color correction. , Antifoggant, chemical sensitizer,
Compounds that release photographically useful fragments such as spectral sensitizers and desensitizers can be used.

The light-sensitive material can be provided with an auxiliary layer such as a filter layer, an antihalation layer, and an anti-irradiation layer. In these layers and / or the emulsion layers, dyes which flow out or bleach from the light-sensitive material during the development processing may be contained.

To the light-sensitive material, a formalin scavenger, a fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder and a bleaching accelerator can be added.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate film, or the like can be used.

In order to obtain a dye image using the light-sensitive material of the present invention, generally known color photographic processing can be performed after exposure.

In the method of the present invention, the hydrophilic binder layer containing the oil-soluble coupler dispersion is coated on a support, and then the pH of the film surface is measured.

Membrane pH is 20 per 1 cm ^{2 of} sample using a commercially available flat electrode.
μ of pure water is dropped, the flat surface of the electrode is applied thereto, and measurement is performed.

The method of adjusting the pH of the film surface is as follows.
Potassium hydroxide, sodium carbonate, potassium carbonate, sodium oxalate, potassium citrate, lithium citrate,
The effect of the present invention can be obtained by appropriately adding an alkaline solution such as sodium acetate or potassium acetate or an acidic solution such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, citric acid or boric acid so as to have a desired film surface pH. .

The range of the film surface pH of the present invention is 5.5 or more, 7.0 or less, 5.5
In the following cases, the effect of the present invention is small, and in the case of 7.0 or more, the storage stability of the silver halide photographic light-sensitive material is affected, which is not preferable. Further, when the membrane surface pH is 6.0 or more, the effect of the present invention is remarkable, which is more preferable.

The film surface pH of the light-sensitive material in the present invention means the film surface pH of the surface in the multi-layer color light-sensitive material.

That is, an oil-soluble coupler dispersion having a particle diameter of oil droplets according to the present invention, and a photosensitive material having a hydrophilic binder layer containing a vinyl sulfone type curing agent, the film surface pH after drying of the layer is Of course, it means the pH of the outermost surface film surface after drying of the color light-sensitive material completed by coating other constituent layers such as an intermediate layer, a filter layer, an emulsion layer and a protective layer on the upper layer of the layer.

〔Example〕

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example-1 A multilayer color photographic light-sensitive material sample 1 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

Sample-1 (reference) First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer: Intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Monodisperse emulsion (Emulsion I) consisting of AgBr I containing 0.40 μm average grain size () and 6 mol% Ag I. Silver coating amount 1.8 g / m ² Sensitizing dye I: 5.0 × 10 ^-4 mol per mol of silver Sensitizing dye II: 0.8 × 10 ^-4 mol per mol of silver TCP ... 0.8g against 1.0g of total of (C-1) and (CC-1) 4th layer; High-sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size () 0.8μm, Ag I Monodisperse emulsion consisting of AgBr I containing 6.0 mol% (Emulsion II): Silver coating amount 1.3 g / m ² Sensitizing dye I: 2.5 × 10 ^-4 mol per mol of silver Sensitizing dye II: 1 mol of silver Against 0.8 × 10 ^-4 mol TCP ... 0.8g against 1.0g of total of (C-1) and (CC-1) 5th layer; Intermediate layer (IL) The same gelatin layer as the 2nd layer.

Sixth layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion I ... Coating amount of silver 1.5 g / m ² sensitizing dye III ... 2.0 × 10 ^-4 mol sensitizing dye IV per mol of silver ... 1.0 × 10 ^-4 mol per mol of silver TCP ... 1.0g against 1.0g total of (M-1) and (CM-1) 7th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion II ... Coating amount 1.4g silver / m ² Sensitizing dye III: 1.2 × 10 ^-4 mol per mol of silver Sensitizing dye IV: 0.8 × 10 ^-4 mol per mol of silver TCP ... 1.2g against 1.0g of total of (M-1) and (CM-1) 8th layer; Yellow filter layer (YC-1) Emulsification of yellow colloidal silver and 2,5-di-t-octylhydroquinone And a gelatin layer containing the dispersion.

Layer 9: Low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion (Emulsion III) consisting of AgBr I containing 0.48 μm average grain size and 6 mol% Ag I ... Silver coating amount 0.9 g / m ² Sensitizing dye V: 1.3 × 10 ^-4 mol per mol of silver TCP ... (Y-1) 0.5g against 1.0g 10th layer; High-sensitivity blue-sensitive emulsion layer (BH-1) Monodisperse emulsion consisting of AgBr I containing 0.8 μm average grain size and 7 mol% Ag I ( Emulsion IV) ... Silver coating amount 0.5 g / m ² Sensitizing dye V ... 1.0 × 10 ^-4 mol per mol of silver TCP ... (Y-1) 0.3 g per 1.0 g 11th layer; 1st protective layer (Pro-1) Silver iodobromide (Ag I 1 mol% average particle diameter 0.07 μm) ... Silver coating amount
Gelatin layer containing 0.5g / m ² UV absorber UV-1, UV-2 12th layer; 2nd protective layer (Pro-2) Polymethylmethacrylate particles (diameter 1.5μm) and formalin scavenger (HS-1) Sample-1 was prepared with the above layer structure.

In each layer, 0.1 mmol of hardener per 1 g of gelatin was added as shown in Table 1.

In addition, each coupler dispersion was added with ethyl acetate using tricresyl phosphate as a high boiling point solvent and sodium dodecylbenzene sulfonate was used as an activator.After emulsifying and dispersing with a high-speed rotating mixer, ethyl acetate was removed and dispersed. A liquid was prepared. The dispersed particle size was adjusted to the target particle size by changing the rotation speed of the mixer. The particle size of the sample is shown in Table 1.

The pH of the film surface of the sample should be adjusted by using an aqueous solution such as sodium carbonate or citric acid at the time of coating liquid.
A pH sample was prepared.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; Anhydro-5.5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; Anhydro-9-ethyl-3,3'- The- (3
-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide sensitizing dye III; anhydro-5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl Propyl) oxacarbocyanine hydroxide Sensitizing dye IV; anhydro-9-ethyl-3,3'-di- (3
-Sulfopropyl) -5,6,5 ', 6'-dibenzoxacarbocyanine hydroxide sensitizing dye V; anhydro-3,3'-di- (3-sulfopropyl) -4,5-benzo-5' -Methoxythiocyanine hydroxide The sample thus obtained was allowed to stand under humidity control at 40 ° C. and 60% relative humidity, and then the sample was immersed in pure water at 38 ° C. to measure water absorption. The time during which this absorption was almost constant was defined as the curing time.

Further, the reciprocal of the absorption amount during the curing time of Sample-1 was used as the denominator, and the reciprocal of the absorption amount during the curing time of the sample using the same curing agent as other Sample-1 was used as the numerator to calculate the ultimate curing degree. .

Similarly, the ultimate curing degree was calculated for the samples using the curing agents, with the absorption amount of Samples 2, 3, and 4 as the denominator.

 The obtained results are shown in Tables 1-1 and 1-2 below.

As is clear from Table 1, in the sample having a coupler dispersion particle size of 150 nm or more and a film surface pH of 5.5 or more, the hardening time is shortened and the reduction of the achieved curing degree is improved. In particular, when the particle size is 250 nm or more, the hardening time is shortened sharply. At pH 6.0 or above, no decrease in the achieved dura is observed.

Sample 2 using a curing agent other than vinyl sulfone-based curing agent
Looking at 8, 29 and 30, the effect of the present invention is not recognized. Further, among the vinyl sulfone-based curing agents, the magnitude of the effect of the present invention varies depending on the type, and in particular, Samples 9, 15, 17, 19, 21 cured with the curing agent represented by the general formula described in the specification.
The effect of the present invention is remarkably greater than those of Samples 23, 25 and 27 cured with other curing agents.

〔The invention's effect〕

As described above, according to the curing method of the present invention, it is possible to obtain a silver halide color photographic light-sensitive material having a low post-curing property without lowering the ultimate curing degree.

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Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one hydrophilic binder layer containing gelatin containing an oil-soluble coupler dispersion having an average particle size of oil droplets of 150 to 600 nm, wherein at least one layer is provided. Cured with two vinyl sulfone type curing agents, and
A silver halide color photographic light-sensitive material characterized by being 5.5 to 7.0.