JPH05150400A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material superior in rapid processability and improved in storage stability with the lapse of time. CONSTITUTION:The silver halide color photographic sensitive material has on a support at least >=2 silver halide emulsion layers and it is characterized by that the support is made of a polyester film having a haze value of <=3% and a water content of >=0.5weight%, and at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride of >=5mol%.

Description

The present invention relates to a silver halide color photographic light-sensitive material, and more specifically to a silver halide color photographic light-sensitive material having excellent rapid processability and improved storage stability. It is about materials.

[Prior Art] Conventionally, triacetyl cellulose (hereinafter referred to as "TA" has been used as a support for a roll-shaped color photographic light-sensitive material.
Films have been used. It is generally known that the TAC film has no optical anisotropy and high transparency, and further has an excellent property of decurling after development processing. The film quality was fragile and lacked in strength and dimensional stability, making it unsuitable for rapid processing. On the other hand, a polyester film having excellent mechanical properties, for example, a polyethylene terephthalate (hereinafter referred to as “PET”) film has a drawback that it tends to be curled and curled when stored in a roll state. It was not suitable as a support for use.

[Problems to be Solved by the Invention] Numerous studies have been conducted to solve these problems. For example, Japanese Patent Laid-Open No. 1-24
Japanese Patent No. 4446 discloses a technique for a roll-shaped photosensitive material in which the decurling property is improved by setting the water content in a polyester film to 0.5% by weight or more, but the haze value is high and the transparency is high. Was lacking in.
Further, JP-A-64-6941 and JP-A-2-43534 disclose a technique for a silver halide color photographic light-sensitive material obtained by coating a silver halide emulsion containing silver chloride on a triacetyl cellulose film. There is. However, the above-mentioned light-sensitive material coated with a silver halide emulsion containing silver chloride is inferior in storability with time, and particularly has a drawback that a fog increase after storability is large. Moreover, this tendency was particularly remarkable when the silver halide emulsion was gold-sensitized. Therefore, the technique disclosed in JP-A-62-168143 for a light-sensitive material having an improved storage stability at a relative humidity of 55% or less was used, and the above-mentioned silver halide emulsion containing silver chloride was used. It was not possible to improve the storability of the coated light-sensitive material. The present invention has been made to solve the above problems, and an object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in rapid processability and has improved storage stability over time.

[Means for Solving the Problems] The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least two silver halide emulsion layers on a support, the support having a haze value of 3% or less. A silver halide comprising a polyester film having a water content of 0.5% by weight or more, and at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 5 mol% or more. Achieved with color photographic light-sensitive materials. The present invention will be described in more detail below. The support used in the present invention comprises a polyester film having a haze of 3% or less and a water content of 0.5% by weight or more. Also preferably, the water content is 0.6
It consists of a polyester film in the range of 5.0% by weight. The water content of the polyester film is measured by conditioning the humidity of the film at 23 ° C., 30% RH for 3 hours,
The sample is dipped in distilled water at 23 ° C. for 15 minutes, and then dried at a temperature of 150 ° C. using a trace moisture meter (for example, CA-02 type manufactured by Mitsubishi Kasei Co., Ltd.). The haze of the polyester film is measured according to ASTM-D1003-52. The polyester used in the present invention is a polyester mainly composed of an aromatic dibasic acid and glycol. Typical dibasic acids are terephthalic acid and isophthalic acid, and glycols are ethylene glycol and propylene glycol. , Butanediol, neopentyl glycol, 1,4-cyclohexanediol, diethylene glycol and the like. Among the polyesters composed of these components, polyethylene terephthalate (PET) is most preferable from the viewpoint of easy availability. Below P
This will be explained using ET. The copolymerized polyethylene terephthalate film preferably used in the present invention comprises a copolymerized polyethylene terephthalate film containing an aromatic dicarboxylic acid component having a metal sulfonate as a copolymerization component. Specific examples of the aromatic dicarboxylic acid having a metal sulfonate include 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid. And compounds obtained by substituting these sodiums with other metals such as potassium and lithium. The copolymerization ratio of the aromatic dicarboxylic acid component having a metal sulfonate is preferably 2 to 15 mol%, and particularly preferably 4 to 10 mol% with respect to the terephthalic acid component as the main raw material. In the copolymerized polyethylene terephthalate film used in the present invention, the fact that an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms is further copolymerized is transparent, and particularly, suppression of whitening of the surface of the copolymerized polyethylene terephthalate film and resistance to It is preferable in terms of foldability. 4 carbon atoms
Specific examples of the aliphatic dicarboxylic acid component of to 20 include succinic acid, adipic acid, sebacic acid and the like, among which adipic acid is preferred. The copolymerization ratio of the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms is preferably 3 to 25 with respect to the terephthalic acid component.
Mol%, particularly preferably 5 to 20 mol%. In addition,
In the polyester film used in the present invention,
Other acid components or glycol components may be copolymerized as long as the transparency and mechanical properties are not impaired. For example, polyalkylene glycol, especially polyethylene glycol, can be copolymerized in an amount of 0 to 10% by weight. The polyalkylene glycol used for such a purpose preferably has a molecular weight in the range of 600 to 10,000. One of the properties that pose a problem when a polyester film is used as a support for a photographic light-sensitive material is a problem of fogging due to the high refractive index of the support. The refractive index of PET is about 1.6, and the refractive index of gelatin used exclusively for the subbing layer and the photographic emulsion layer is 1.50 to 1.55.
The refractive index ratio of gelatin and PET is 1.5 / 1.6
And less than 1, when light enters from the film edge,
Easily reflected at the interface between the base and the emulsion layer. Therefore, the polyester film is apt to cause a so-called light piping phenomenon (fogging). In the present invention, in order to avoid such a light piping phenomenon, a dye that does not increase the film haze is added. The dye used is not particularly limited, but is preferably a dye having a gray color tone due to the general property of the light-sensitive material, and also has excellent heat resistance in the film forming temperature range of the polyester film and has compatibility with polyester. Excellent ones are preferred. As a specific dye, from the above viewpoint, Mitsubishi Chemical's Diare
Examples include sin and Kayase manufactured by Nippon Kayaku.
The dyeing density is required to be at least 0.01 or more, preferably 0.03 or more, as measured by a Macbeth color densitometer. It is also possible to impart slipperiness to the polyester film depending on the application.
The slipperiness imparting means is not particularly limited, but kneading an inactive inorganic compound, coating a surfactant, or the like is generally used. Also, a method using an internal particle system in which a catalyst or the like added during the polyester polymerization reaction is precipitated can be used. Examples of the above-mentioned inert inorganic compound include SiO ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ , talc, kaolin and the like. Since transparency is an important requirement for a support for a photographic light-sensitive material, SiO ₂ having a refractive index relatively close to that of a polyester film, or an internal particle system capable of relatively reducing the precipitated particle size is selected. It is desirable to do. When imparting slipperiness by kneading, a method of laminating a layer imparted with a function in order to obtain more transparency of the film is also preferably used. Specific examples include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die. Depending on the copolymerization ratio, there may be a problem that a low-polymerization product is precipitated by heat treatment when forming the underlayer. In such a case, it can be solved by laminating an ordinary polyester layer on at least one surface of the support,
Also in this case, the coextrusion method is used as an effective means.
The raw material polymer for the copolymerized polyethylene terephthalate film can be synthesized according to a conventionally known polyester production method. For example, the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, an ester exchange reaction is first performed with the glycol component, and this is heated under reduced pressure to remove excess glycol component. As a result, copolymerized polyethylene terephthalate can be obtained. At this time, if necessary, it is possible to use a transesterification reaction catalyst or a polymerization reaction catalyst,
Further, a heat resistance stabilizer can be added. The obtained copolymerized polyethylene terephthalate is generally formed into particles, dried, melt-extruded into an unstretched sheet, and then biaxially stretched and heat-treated to form a film.
Biaxial stretching may be either longitudinal or transverse sequential stretching or biaxial simultaneous stretching, and the stretching ratio is not particularly limited, but usually 2.0 to 5.0 times is suitable. Further, after longitudinal or transverse stretching, it may be re-stretched in either longitudinal or transverse direction. As a drying method before melt extrusion, a vacuum drying method and a dehumidification drying method are preferable. The temperature during stretching is 7 for longitudinal stretching.
It is desirable that the temperature is 0 to 100 ° C. and the transverse stretching is 80 to 160 ° C. The heat setting temperature is 150 to 210 ° C, especially 1
It is preferably 60 to 200 ° C. The thickness of the copolymerized polyethylene terephthalate film can be appropriately set depending on the field of use of the photographic film, but is preferably 10 to 250 μm, more preferably 20 to 150 μm. The silver halide color photographic light-sensitive material of the present invention is preferably stored at a relative humidity of 55% or less. In the present invention, it is preferable to use a hermetically-sealed packaging means for storing the film at a relative humidity of 55% or less. The hermetically sealed packaging in the present invention is to perform moisture-proof packaging which is well known in the field of packaging. As the packaging material, aluminum plate, tin plate, metal and metal foil such as aluminum foil, glass, or polymer such as polyethylene, polyvinyl chloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate, polyamide, various polymers and cellophane, A composite laminated material (laminated material in packaging terms) made of materials such as paper and aluminum foil is used. As a sealing method for sealing, an adhesive method using various adhesives, a heat-bonding method such as heat sealing, or a method using a cartridge case which is common in the photographic industry can be used.
Details of these sealing methods are described in “Food Packaging Technology Handbook”, Japan Packaging Technology Association (ed.), P573 to p609. In the present invention, storage at a relative humidity of 55% or less means, for example, a weight W ₁ measured within 30 seconds after opening a sealed silver halide photosensitive material at 25 ° C. and 55% relative humidity.
W ₂ measured after storage under the same conditions as ⁵⁵ for 3 days or more
⁵⁵ difference ^{_{△ W 55 = W 2 55 -W}} 1 55 and is defined as not less than zero. The preferred condition of the present invention is 25 ° C.
Is that weight change △ W ³⁰ becomes negative more preferred conditions at a relative humidity of 30% is to become negative weight change △ W ³⁵ at 35% 25 ° C. relative humidity. In the present invention, the hermetic packaging may be doubled. In order to wrap under a low relative humidity condition as described above, the silver halide photographic light-sensitive material may be packaged in a low-humidity room, or may be slightly dried when the light-sensitive material is dried, Further, a desiccant such as silica gel may be placed in the closed container to reduce the humidity. The silver halide color photographic light-sensitive material of the present invention has at least two silver halide emulsion layers on a support. In the present invention, as a silver halide emulsion layer, a blue-sensitive emulsion layer spectrally sensitized to at least 400 to 500 nm, a green photosensitive emulsion layer spectrally sensitized to 500 to 600 nm and a spectrally sensitized spectrally sensitized layer to 600 to 700 nm are used. It is preferable to have a red photosensitive emulsion layer. Further, each photosensitive emulsion layer is preferably composed of a plurality of layers having high sensitivity, medium sensitivity, low sensitivity and the like. In the silver halide color photographic light-sensitive material of the present invention, at least one of the above silver halide emulsion layers contains silver halide grains having a silver chloride content of 5 mol% or more, and preferably all silver halides. The emulsion layer contains silver halide grains having a silver chloride content of 5 mol% or more. In the present invention, the silver chloride content of the silver halide grains is preferably 50 mol% or more, more preferably 70 mol% or more. The silver bromide content of the silver halide grains is preferably 90 mol% or less, more preferably 50 mol% or less, and particularly preferably 10 mol% or less. The silver halide emulsion used in the present invention preferably contains silver iodide, and the content thereof is preferably 0 to 20 mol%, more preferably 5 to 15 mol%. When the silver halide emulsion used in the present invention contains silver iodide, the silver halide grains are preferably those in which silver iodide is localized inside the grains. In the present invention,
Research Disclosure 30 for silver halide emulsions
8119 (hereinafter abbreviated as RD308119) can be used. The table below shows the relevant locations.

In the present invention, it is preferable to use a silver halide emulsion which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are
Disclosure No. 17643, No. 18716 and No. 308119 (Respectively RD1764
3, RD18716 and RD308119). The table below shows the locations.

Known photographic additives that can be used in the present invention are also described in the above Research Disclosure. The following table shows the relevant locations.

Various couplers can be used in the present invention, specific examples of which are described in Research Disclosure above. The following table shows the relevant locations.

The additive used in the present invention is RD308119X IV
It can be added by the dispersion method described in 1. The light-sensitive material of the present invention includes the above-mentioned RD308119V.
An auxiliary layer such as a filter layer or an intermediate layer described in the section II-K can be provided. In the present invention, the silver halide emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method or the like can be used. The light-sensitive material of the present invention can have various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above-mentioned item RD308119VII-K. The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. The light-sensitive material of the present invention is RD176 described above.
43 pages 28-29, RD 18716 pages 647 and R
Development processing can be performed by a usual method described in XIK of D308119.

[Examples] The present invention will be specifically described below with reference to Examples. It should be understood that the present invention is not limited to the examples described below.

Example-1 (Preparation of polyethylene terephthalate film) 100 parts by weight of dimethyl terephthalate, ethylene glycol 7
0 parts by weight, 10 parts by weight of dimethyl 5-sodium sulfoisophthalate and 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate and 0.1 part by weight of antimony trioxide.
03 parts by weight was added, and transesterification reaction was carried out by a conventional method. The product obtained was treated with phosphoric acid trimethyl ester 0.
05 parts by weight was added, the temperature was gradually raised and the pressure was reduced, and finally polymerization was carried out at 280 ° C. and 1 mmHg or less to obtain a copolymerized polyethylene terephthalate. The copolymerized polyethylene terephthalate was dried by a conventional method and then melt extruded at 280 ° C. to prepare an unstretched sheet. Then, the film was sequentially stretched 3.5 times in the longitudinal direction at 90 ° C. and 3.7 times in the lateral direction at 95 ° C., and then heat-set at 200 ° C. for 5 seconds to obtain a biaxially stretched film having a thickness of 100 μ. The film has a haze of 1.2.
%, Breaking strength 12 kg / mm, initial elastic modulus 340 k
It was g / mm. The transparency, breaking strength and initial elastic modulus were measured under the following conditions.

Transparency: Haze of film is ASTN-D1003-5
It measured according to 2.

Breaking strength and initial elastic modulus: JIS-Z1702-19
According to No. 76, a short fence piece with a width of 10 mm and a length of 100 mm, the pulling speed is 300 mm / when measuring the breaking strength.
The initial elastic modulus was measured at 20 mm / min.

Further, the thickness 5 according to the present invention prepared in the same manner as described above.
The water contents of the 0 μm PET film and the commercially available PET film (thickness 50 μm) were measured using a CA-02 type micro moisture meter manufactured by Mitsubishi Kasei Co., Ltd., respectively. The water content of the film was 0.4% of the commercially available PET film and 0.7% of the PET film according to the present invention.

Was subjected to corona discharge treatment on both surfaces of the PET film according to Coating invention (photosensitive creating materials) subbing layer (film A) and commercially available PET film (Film B), a subbing layer having the following composition Provided. The degree of corona discharge treatment was 0.02 KVA · min / m ² .

(Styrene - butyl acrylate - hydroxyethyl acrylate - butadiene emissions) Coating of a latex 3g of distilled water 250cc Sodium α- Suruhoji-2-ethylhexyl succinate 0.05g aziridine compound (C) 0.02 g Back layer (antistatic layer) Corona discharge was performed again on one surface of each of the PET films (film A, film B) after coating the coating layer, and then a conductive layer having the following composition was coated so that the dry film thickness was 1 μm.
However, the curing agent (H) was added while being applied. Dry air temperature 9
Dry for 30 seconds under parallel flow drying conditions of 0 ° C and overall heat transfer coefficient of 25 kg / m ² · hr · ° C, and then 140
Heat treatment was performed at 90 ° C. for 90 seconds.

Water-soluble conductive polymer (A) 60 g / l Hydrophobic polymer particles (B) 40 g / l Ammonium sulfate 0.5 g / l Curing agent (H) 12 g / l The total amount is 1 l. Gelatin was coated on the coated antistatic layer so as to have a concentration of 2.0 g / m ² . However, the following compounds were used as a hardener for gelatin.

Hardener: Glyoxal (Coating of Photographic Layer ) Preparation of Sample-1 (for Comparison) Commercially available PET film (Film B) On the side opposite to the back layer, each layer having the following composition was sequentially formed from the side of the support. A multilayer color photographic light-sensitive material sample-1 was prepared.

In each layer, in addition to the above composition, a dispersion aid SU-1, a coating aid SU-2, a hardener H-1, H-2, a dye AI-.
1, AI-2 were added appropriately. The emulsions used in the above samples are shown in Table 1.

Preparation of Samples-2 to 14 Samples-2 to 14 were prepared in the same manner as in Preparation of Sample-1, except that the type of silver halide emulsion was changed as shown in Table-1 and the support was changed as shown below. 14 was created. Samples 3, 5, 7, 9, 11 and 13 use the same commercially available PET film (film B) as Sample 1 as a support, and Samples 2, 4, 6, 8, 10, 12 and 14 use the present invention. A PET film according to (Film A) was used as a support. However, all the silver halide emulsions shown in Table 1 were optimally chemically sensitized with sodium thiosulfate and chloroauric acid.

The obtained photosensitive materials of Samples 1 to 14 were each divided into two, and each sample was sealed at a temperature of 25 ° C. and a relative humidity of 55%. One of the two divided samples-1 to 10 was heated at 25 ° C, and the other sample was heated to 65 ° C to check the storage stability.
After storage for a day, the wafer was exposed to a wedge of white light and the following development processing was performed. The sensitometric characteristics of each of the obtained developed samples were examined. The results of green light density are shown in Table-2.

Processing step Color development 35 ° C. 40 seconds Bleaching 38 ° C. 6 minutes 30 seconds Water washing 24-41 ° C. 3 minutes 15 seconds Settling 38 ° C. 6 minutes 30 seconds Water washing 24-41 ° C. 3 minutes 15 seconds Stabilization 38 ° C. 1 minute Drying for 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

(Color developer) triethanolamine 10 g N, N-diethylhydroxylamine 5 g potassium bromide 0.02 g potassium chloride 2 g potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g ethylenediaminetetraacetic acid 1. 0 g Catechol-3,5-diphosphonic acid disodium 1.0 g N-ethyl-N-β-methanesulfone amidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4′-diaminostilbene Disulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to adjust the total amount to 1 l, and the pH is adjusted to 10.10.

(Bleach) Ethylenediaminetetraacetic acid iron (III) ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10 g Ammonium bromide 150 g Glacial acetic acid 10 ml Water was added to make 1 l, and pH was adjusted to 6 with ammonia water.
Adjust to 0.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

(Stabilizer) Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

As is clear from Table 2, the sample of the present invention has excellent rapid processability and low fog, and has excellent storage characteristics over time with little increase in fog and decrease in sensitivity even when stored at high temperature. I found out that Further, by comparing Samples 3, 5 and 7, it is found that the degree of fog increase and the sensitivity decrease at high temperature are greater as the silver chloride content is higher. Further, it was shown that the sample 10 of the present invention containing silver iodide had the most excellent properties in all respects.

[Effects of the Invention] As described in detail above, the present invention can provide a silver halide color photographic light-sensitive material having excellent rapid processability and improved storability over time.

Claims (1)

[Claims] A silver halide color photographic light-sensitive material having at least two silver halide emulsion layers on a support, the support comprising a polyester film having a haze value of 3% or less and a water content of 0.5% by weight or more, and A silver halide color photographic light-sensitive material characterized in that at least one of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 5 mol% or more.