JPH0619530B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has improved rapid development processability, process stability and image sharpness, and suppresses fog formation. And a silver halide color photographic light-sensitive material which can be used

In general, a silver halide color photographic light-sensitive material has three kinds of photographic silver halide emulsion layers, which are selectively spectrally sensitized to have sensitivity to blue light, green light and red light, coated on a support. ing. For example, in a silver halide photographic light-sensitive material for color negative, a blue light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer, and a red light-sensitive silver halide emulsion layer are generally coated in this order from the exposed side. Between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer, there is a bleachable yellow filter layer for absorbing blue light transmitted through the blue-sensitive silver halide emulsion layer. It is provided. Further, each emulsion layer is provided with another intermediate layer for various special purposes and a protective layer as the outermost layer. Furthermore, for example, in a silver halide photographic light-sensitive material for color photographic paper, a red light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer, and a blue light-sensitive silver halide emulsion layer are generally arranged in this order from the exposed side. In the same manner as in the silver halide photographic light-sensitive material for color negative, an intermediate layer such as an ultraviolet absorbing layer and a protective layer are provided for each special purpose. It is also known that each of these silver halide emulsion layers is provided in an arrangement different from that described above, and further, as each silver halide emulsion layer, it is photosensitive to each color light in substantially the same wavelength range. It is also known to use a photosensitive silver halide emulsion layer having two layers. In these silver halide color photographic light-sensitive materials, the exposed silver halide grains are developed by using, for example, an aromatic primary amine type color developing agent as a color developing agent, and the generated color developing agent is oxidized. The reaction of the product with the dye-forming coupler forms a dye image. In this method, usually, in order to form a dye image of cyan, magenta and yellow, a phenol or naphthol type cyan coupler, a 5-pyrazolone type, a pyrazolinobenzimidazole type, a pyrazolotriazole type, an indazolone type or a cyano type, respectively. Acetyl magenta couplers and acylacetamide yellow couplers are used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developing solution. The present invention relates to a silver halide color photographic light-sensitive material in which these couplers have been previously contained in a silver halide emulsion layer to make them non-diffusible.

[Prior Art] In recent years, a silver halide color photographic light-sensitive material capable of rapid processing, high image quality, excellent processing stability, and low cost has been demanded in the art.

That is, silver halide color photographic light-sensitive materials are run by an automatic developing machine provided in each laboratory, but as part of improving service to users, development is done within the day of development acceptance. It is required to process and return to users, and in recent years, it is even required to return within a few hours from reception, and development of silver halide color photographic light-sensitive materials capable of rapid processing is urgently required. It is peeling. Further, in the running process, there is a problem in that stable photographic performance cannot be obtained because the photographic characteristics greatly change due to the composition change of the processing liquid and the change of conditions even between the laboratories or even in the same laboratories. Changes in the composition of the processing liquid and changes in conditions are
It is considered that this is due to elution / accumulation of the photographic active substance from the light-sensitive material during development processing (running) and other causes. Therefore, in order to cope with fluctuations in processing conditions, it is required that the developing time, the temperature and pH of the developing solution, and the halogen concentration in the developing solution, particularly the bromide concentration, be highly controlled. However, compared with the development time or the temperature and pH of the developing solution, the concentration of bromide ions in the developing solution is difficult to quantify, and it is difficult to control because of poor measurable property. Therefore, in particular, it is necessary to develop a silver halide color photographic light-sensitive material whose photographic performance has little dependence on the brom concentration and which is highly process-stabilized. Although processing stability is problematic even at the current processing time, processing stability becomes more problematic in rapid processing. Further, it is a matter of course that such a processing-stabilized silver halide color photographic light-sensitive material is required to be provided economically at low cost.

In view of the prior art, a silver halide color photographic light-sensitive material that can be rapidly processed is disclosed in, for example, Japanese Patent Laid-Open No.
Fine graining technique of silver halide as described in JP-A No. 1-77223, JP-A-58-184142 and JP-B-56-1.
A technique for reducing silver bromide of silver halide as described in JP-A-8939, and 1-aryl-3-pyrazolidone having a specific structure as described in JP-A-56-64339 are added to a silver halide color photographic light-sensitive material. Technology, and JP-A-5
7-144547, 58-50534, 58-
50535, 58-50536, 1-
A technique for adding an arylpyrazolidone to a silver halide color photographic light-sensitive material is known, and in addition, an exposed silver halide color photographic light-sensitive material is used by using an aromatic primary amine type color developing agent. A technique of using a color development accelerator when performing development is also known. For example, as such a color development accelerator, U.S. Pat.
No. 0, No. 2,515,147, No. 2,496,903, No. 4,038,075,
4,119,462, British Patents 1,430,998, 1,455,413
JP-A Nos. 53-15831 and 55-62450.
No. 55, No. 55-62451, No. 55-62452, No. 55-62453, No. 51-12422, No. 55-.
No. 62453, Japanese Patent Publication Nos. 51-12422, 55-4
There are compounds described in 9728 and the like.

However, when using one of these conventional techniques,
Although the processing time was shortened, the processing stability was poor, and there were problems with fog and storage stability in the same day performance.

When the above low silver bromide emulsion is used, the amount of brom ions eluted from the silver halide color photographic light-sensitive material containing the low silver bromide emulsion into the processing liquid is small, and the concentration of brom ions in the processing liquid is set low. Although rapid processing can be achieved, the processing stability is poor when a silver halide color photographic light-sensitive material containing a low silver bromide emulsion is processed using a processing solution having a low bromide concentration. Here, the processing stability is the degree of fluctuation of the processing solution composition, pH, temperature, bromine ion concentration, etc., and the fluctuation of sensitometry due to the incorporation of other compounds other than the processing solution composition.

Further, when the above fine grain silver halide was used, there was a drawback that the processing stability was inferior and that the finer the grain, the lower the sensitivity.

On the other hand, regarding the conventional technique for improving the processing stability, as disclosed in, for example, JP-A Nos. 59-121036 and 59-120250, there is an improvement in the processing liquid. As far as is known, there is no example in which the processing stability is substantially improved by the improvement of the silver halide color photographic light-sensitive material.

Therefore, the present inventor previously proposed the technique disclosed in Japanese Patent Application No. 59-158782. The previously proposed technique is a silver halide color photographic light-sensitive material having a blue light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer and a red light-sensitive silver halide emulsion layer on a support. The average grain size of silver halide in the silver halide emulsion layer is 0.20 to 0.55 μm, and the silver bromide content of silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 5 A silver halide color photographic light-sensitive material having a content of ~ 65 mol%,
It is possible to perform a rapid color development process, have excellent process stability, and obtain a high-quality image.

The present inventor has found that there is room for further improvement in terms of image sharpness as a result of continuing research on such a previously proposed technique.

On the other hand, in order to improve the image sharpness, a method has been proposed in which a coating layer curable by electron beam irradiation is applied onto a paper base material and then irradiated with an electron beam to cure it. 57-27257, 57-30830, 57-
49946).

When a silver halide color photographic light-sensitive material is produced using the photographic paper support produced by the above-mentioned method, for example, a gelatin-based hydrophilic colloid such as a gelatin-silver halide emulsion layer is used. A photographic image forming or constituting layer (hereinafter, simply referred to as a photographic constituting layer), which is a hydrophilic colloid layer having a continuous layer, is coated on a support having the above-mentioned coating layer. A silver halide color photographic light-sensitive material using a support coated with a resin cured by irradiating with a ray has a drawback that fogging is remarkable.

[Problems to be Solved by the Invention] The present invention has been made in view of the above, and has rapid developability,
It is a technical object to provide a silver halide color photographic light-sensitive material which is improved in processing stability and image sharpness and can suppress the occurrence of fog.

[Means for Solving the Problems] The silver halide color photographic light-sensitive material of the present invention which solves the above technical problems is a blue-sensitive material containing silver chlorobromide or silver chloroiodobromide on a reflective support. In a silver halide color photographic light-sensitive material having a silver halide emulsion layer, a green light-sensitive silver halide emulsion layer and a red light-sensitive silver halide emulsion layer in this order and one layer each, the support is irradiated with an electron beam. Is coated with a resin which has been cured by the above method, and the average grain size of silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 0.55 μm, and the green-sensitive silver halide emulsion layer and The silver bromide content of silver halide in the red-sensitive silver halide emulsion layer is 5 to 65 mol%.

According to the present invention, the technical problem of the present invention can be solved,
In particular, it was found that not only the fogging on the same day but also the fogging after the raw storage can be suppressed.

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

In the present invention, the resin cured by irradiating with an electron beam means to start the polymerization reaction in the presence of a polymerization initiator by irradiating with an electron beam to start the polymerization reaction without the cured resin or the polymerization initiator. It includes both of the cured and cured resins.

When a polymerization initiator is used, examples of the compound that initiates the polymerization reaction by electron beam irradiation include compounds having at least two epoxy groups in one molecule. That is,
A compound having at least two epoxy groups in one molecule (hereinafter, referred to as an epoxy compound according to the present invention) is a compound which does not undergo ring-opening polymerization by itself even when irradiated with an electron beam, and is capable of undergoing cationic polymerization. The polymerization reaction occurs when the substance to be started is made to coexist.

When a polymerization initiator is not used, the resin polymerizable by electron beam irradiation may be, for example, a compound having a double bond in the molecule, preferably a compound having a plurality of double bonds in the molecule, and more preferably Examples thereof include compounds containing an acryloyl group, methacryloyl group, acrylamide group, allyl group, vinyl ether group, vinyl thioether group, and unsaturated polyesters. Particularly preferably A. Vranck
Unsaturated polyesters, unsaturated acrylics, unsaturated polycarbonates cited in en Fatipec Congress 1119 (1972), with a molecular weight of about 1,000-20,000.

An inorganic white pigment may be contained in the coating layer of the support of the light-sensitive material according to the present invention. As the inorganic white pigment, those commonly used in the field of photographic printing paper can be used, and examples thereof include titanium oxide (anatase type, rutile type), barium sulfate, calcium carbonate, aluminum oxide, magnesium oxide, and the like. Can be used,
Titanium oxide, barium sulfate and calcium carbonate are particularly preferable.

Further, the surface of the support may be partially coated with titanium oxide with a metal oxide compound such as metal oxide hydroxide, for example, metal oxide oxide such as alumina oxide hydroxide. However, the inorganic white pigment is not limited to these.

The inorganic white pigment is a compound 10 that is curable by the electron beam.
It is preferably in the range of 20 to 200 parts by weight with respect to 0 parts by weight. The average particle size of the pigment is preferably 0.1 to 10 μm.

The layer of the composition containing an electron beam-polymerizable resin according to the present invention, a polymerization initiator optionally used and an inorganic white pigment (hereinafter referred to as the composition according to the present invention) is a single layer on a support. It may be applied as one photographic constituent layer, or may be applied as a plurality of photographic constituent layers.

Examples of the paper support used in the present invention include paper made of natural pulp, synthetic pulp or a mixture thereof.

If desired, various paper strength enhancers, sizing agents, inorganic pigments, colorants, optical brighteners, etc. may be added to these papers.

In addition to the above, synthetic papers such as polypropylene and polyester, and film bases such as polyethylene terephthalate can be used as the support according to the present invention. Furthermore, a support formed by forming a composite material on the surface of the paper can be used. The body can also be used.

The coating layer (hereinafter referred to as the coating layer according to the present invention), which is provided on these supports and is obtained by curing the layer of the composition according to the present invention by electron beam irradiation, is subjected to smoothing treatment to be mirror-finished. It is possible, and if necessary, it can be imprinted.

In order to perform mirror finishing, the treated surface can be brought into contact with a mirror surface roll, and the back surface thereof can be irradiated with an electron beam to be cured to perform mirror finishing. Alternatively, a method may be used in which preliminary irradiation is performed in advance to partially cure the surface, contact with a mirror surface roll, peeling, secondary irradiation, and complete curing.

As the mirror surface roll, there are a chrome-plated roll, a stainless roll, and the like.

In addition, as the patterning roll used in place of the mirror surface roll when performing patterning, a roll such as a stainless roll or a chrome plating roll is subjected to surface polishing, vapor deposition method, etching method, plating method, etc. A roll having a pattern formed thereon can be used.

To apply mirror finishing and patterning, after applying the composition liquid,
It may be applied after removing a part or all of the organic solvent,
After imprinting, the organic solvent may be removed.

In the present invention, the electron beam accelerator used for electron irradiation may be an electro curtain system, a van de Graaff type scanning system, a double scanning system, or the like.

In terms of electron beam characteristics, 100 to 750K in terms of penetrating power.
It is preferable to use an electron beam accelerator of V, preferably 150 to 300 KV, so that the absorbed dose is 0.5 to 20 Mrad.

The electron beam may be irradiated in an atmosphere of an inert gas such as N ₂ , He or CO ₂ .

The coating layer according to the present invention shows good adhesiveness to the photographic constituent layer as it is, but more excellent adhesiveness can be obtained by subjecting the coating layer to surface activation treatment such as corona discharge treatment or glow discharge treatment. The same adhesive effect as above can be obtained by a simple undercoating treatment using gelatin or the like.

At least one of the coating layers according to the present invention is present on the side of the support having a photographic constituent layer (for example, a silver halide emulsion layer, an image receiving layer in a dye diffusion method, etc.).

In addition, the coating layer according to the present invention is preferably on both sides of the support from the viewpoint of waterproofing. Further, when there is no photographic constituent layer on one side of the support, this covering layer on this side can be a covering layer having a constitution in which the inorganic white pigment is removed from the covering layer according to the present invention, or an antistatic layer is used. You can also

The support coated with the resin cured by irradiation with the electron beam of the present invention is described in JP-A-57-27257.
57-49946, 59-124336, Japanese Patent Application Nos. 58-53042, 58-54948 and 58.
174980, 58-175885, 58-
176696, 58-177752, 58-1
No. 78794, No. 59-32237, No. 59-426.
Those described in No. 23 and the like are preferably used.

The production examples of the support coated with the resin cured by irradiation with the electron beam of the present invention are shown below.

Production Example (1) Acrylic terminal modified polybutadiene (average molecular weight 1000, Nippon Soda Co., TEA-1000) 70 parts by weight CH ₂ = CH-COO- (CH ₂ ) ₆ -OOC-CH = CH ₂ 20 parts by weight trimethylol Propane triacrylate 10 parts by weight Titanium oxide (rutile type, average particle size 0.2 μm) 50 parts by weight Tetraisopropylbisdioctyl phosphite titanate (Plenact 41B, manufactured by Kenrich Petrochemical, titanium coupling agent) 5 parts by weight Methyl ethyl ketone / toluene (1) 1 mix) 30 parts by weight The above composition liquid was mixed and dispersed in a ball mill for 48 hours, and then coated on one surface of a high-quality paper having a basis weight of 150 g / m ² with a curtain coater to a thickness of 30 μm.

Then, after removing the solvent of this coating by drying (100 ° C., 1 minute), using an electron beam accelerator under a nitrogen gas atmosphere,
The coating was irradiated with an electron beam at a dose of 150 KV and 5 Mrad.

The cured coating layer is wound up once, and on the side opposite to the coating layer, the above composition containing no titanium oxide is coated to a thickness of 30 μm, dried and cured by the same operation. Then, the substrate was wound up and irradiated with the electron beam of the present invention to obtain a support coated with a resin cured.

Production Example (2) Titanium oxide (anatase type, average particle size 0.2 μm) 100 g
Was washed with acetone and dried, then put in 500 ml of methanol in which 3 g of γ-glycidoxypropyltrimethoxysilane (KBM 403 Shin-Etsu Chemical Co., Ltd.) was dissolved and mixed and stirred for 2 hours, and then left for about 6 hours. did.

After removing the solvent under reduced pressure and air drying titanium oxide, 130
Heat treatment was performed at ℃ for 10 minutes.

Next, 60 parts by weight of the above surface-treated titanium oxide CH ₂ = CH-COO-CH ₂ CH ₂ CH _2- [NHCO- (CH ₂ ) ₄ -CON
H-CH ₂ CH _2] Urethane acrylate oligomer represented by the -OOC-CH = CH ₂ [Exemplified Compound (3), n = 8]
80 parts by weight Trimethyl roll propane triacrylate 20 parts by weight Methyl ethyl ketone / cyclohexane (1: 1 mixture) 50 parts by weight of a composition liquid was mixed and dispersed in a ball mill for 36 hours, and then the basis weight was 180 g / m ² on both sides of a high-quality paper. Each was coated with a curtain coater to a thickness of 30 μm.

Then, after removing the solvent of this coating by drying (100 ° C., 1 minute), the electron beam was applied to this coating at a dose of 150 KV and 7 Mrad under a nitrogen gas atmosphere using two electron beam accelerators. After irradiation and curing, the film was wound up and irradiated with the electron beam of the present invention to obtain a support coated with the resin cured.

The silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention has an average grain size (average grain size) of 0.20 to 0.55μ.
m, preferably 0.30 to 0.50 μm. Average particle size is 0.55
When it exceeds μm, the processing stability is poor, and particularly when the amount of potassium bromide varies, the processing stability is significantly deteriorated. on the other hand,
If the average grain size is less than 0.20 μm, the sensitivity of the blue-sensitive silver halide emulsion layer is insufficient and magenta color turbidity occurs.

The average grain size of the silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention can be measured by various methods generally used in the technical field for the above purpose. A typical method is Loveland's "Particle Size Analysis" ASTM Symposium on Light Microscopy,
1955, pp. 94-122 or "Theory of Photographic Process" by Mies and James, 3rd edition, Chapter 2 published by Macmillan, Inc. (1966).

The silver halide used in the present invention may be a polydisperse emulsion having an average grain size distributed in a wide range, but a substantially monodisperse emulsion is preferable.

The above-mentioned substantially monodisperse silver halide grains in the present invention mean that most of the silver halide grains appear to have the same shape when the emulsion is observed by an electron micrograph, and the grain sizes are uniform, and It has a particle size distribution as defined by the following formula. That is, when the standard deviation s of the particle size distribution is divided by the average particle size, the value is 0.15 or less.

The grain size referred to here is the length of one side of a cubic silver halide grain, or the length of one side when converted to a cube having the same volume in the case of a grain having a shape other than a cube. Therefore, when the individual particle size in this sense is ri and the number thereof is ni, is defined by the following formula.

The relationship between particle size distributions is described in "The Empirical Relationship between Sensitometric and Particle Size Distributions in Photography", The Photographic Journal, LXXIX (1949), pages 330-338, by Tribel and Smith. You can decide this in a way.

The silver halide contained in the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer of the present invention may be silver chlorobromide, silver chloroiodobromide or a mixture thereof. The content is 5 to 65 mol%. Silver bromide content is 65 mol%
If it exceeds the range, the processing stability becomes poor, magenta color turbidity occurs, and the image quality deteriorates. On the other hand, when the silver bromide content is less than 5 mol%, the processing stability is significantly deteriorated.

When the silver halide contained in the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer of the present invention is silver chloroiodobromide, the silver iodide content thereof exceeds 2 mol%. Those that do not exist are preferred.

The preferable silver bromide content of the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer is preferably 20 to 60 mol%, more preferably 30 to 55 mol%.

The silver halide contained in the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer of the present invention is substantially the same as the silver halide contained in the blue light-sensitive silver halide emulsion layer. Monodisperse ones are preferred.

The composition of the silver halide contained in the blue-sensitive silver halide emulsion layer may be either silver chlorobromide or silver chloroiodobromide, or a mixture thereof, preferably silver chlorobromide. And the silver bromide content is 30 to 95 mol%.

The average grain size of silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is not particularly limited, but is preferably 0.1 to 2 μm, more preferably 0.2.
˜1 μm, particularly preferably 0.25 to 0.8 μm.

The silver amount (silver coating amount) of the silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention is not limited, and the total amount of the light-sensitive silver halide emulsion layers is 0.3 to 1 g / m ² . Is preferred. That is, in order to obtain excellent image quality, the silver amount is preferably 1 g / m ² or less, while in order to obtain high maximum density and high sensitivity, the silver amount is 0.3 g or less.
/ M ² or more is preferable.

The silver halide composition preferably used in the present invention is silver chlorobromide or silver chloroiodobromide. Furthermore, it may be a combination mixture of these. That is, when the silver halide emulsion according to the present invention is used for color photographic paper, particularly fast developing property is required. Therefore, it is preferable that the halogen composition of the silver halide contains a chlorine atom, and the halogen composition is at least 1%. Particularly preferred is silver chlorobromide or silver chloroiodobromide containing silver chloride.

The substantially monodisperse silver halide grains preferably used in the present invention may be those obtained by any preparation method such as an acidic method, a neutral method or an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing the silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled so that the amount of silver ions corresponding to the growth rate of the silver halide grains as described in, for example, JP-A-54-48521. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The crystals of these silver halide grains may be normal crystals, twin crystals or others, and any ratio of [1.0.0] face to [1.1.1] face can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-59-170070) can also be used.

The silver halide grains according to the present invention are prepared as described above. The composition containing the silver halide grains is hereinafter referred to as a silver halide emulsion.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Polyamine, etc .; Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-
Sensitizers of methylbenzothiazolium chloride and the like or water-soluble salts such as ruthenium, palladium, platinum, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (these or Some of them act as sensitizers or antifoggants depending on the amount.) Etc. alone or in combination (for example, gold sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer). It may be chemically sensitized by the combined use with a sensitizer).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one kind of nitrogen-containing heteroaryl having a hydroxytetrazaindene and a mercapto group. You may make it contain at least 1 sort (s) of a ring compound.

The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × 10 ^{−3 with} respect to 1 mol of silver halide in order to impart photosensitivity to a desired wavelength region. It may be optically sensitized by adding a mole. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, as the sensitizing dye used in the blue-sensitive silver halide emulsion layer, for example, West German Patent No. 929,080, U.S. Pat.
1,658, 2,493,748, 2,503,776, 2,519,001
No., No. 2,912,329, No. 3,656,959, No. 3,672,897,
No. 3,694,217, No. 4,025,349, No. 4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 4414030, No. 52
The thing described in No. 24844 etc. can be mentioned. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201 and 2,072,908.
No. 2,739,149, No. 2,945,763, British Patent 505,979
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in No. Further, as the sensitizing dye used in the red-sensitive silver halide emulsion, for example, US Pat.
269, 234, 2,270,378, 2,442,710, and
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes such as those described in Nos. 2,454,629 and 2,776,280. Furthermore, U.S. Patents 2,213,995, 2,493,748 and 2,519,001
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in U.S. Pat. No. 1979,080 and West German Patent can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used especially for the purpose of supersensitization. A typical example is a US patent
2,688,545, 2,977,229, 3,397,060, 3,52
2,052, 3,527,641, 3,617,293, 3,628,964
No., No. 3,666,480, No. 3,672,898, No. 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,8
37,862, 4,026,707, British Patent 1,344,281, 1,
No. 507,803, Japanese Patent Publication No. 43-4936, No. 53-123
75, JP-A Nos. 52-110618 and 52-109.
No. 925.

The silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patents 584,609, 1,277,429, JP-A-48-85130, 49-99620 and 49.
-114420, 49-129537, 52-
108115, 59-25845, U.S. Pat.
4,782, 2,533,472, 2,956,879, 3,125,448
No. 3,148,187, No. 3,177,078, No. 3,247,127,
3,540,887, 3,575,704, 3,653,905, 3,7
18,472, 4,071,312 and 4,070,352.

Each silver halide emulsion layer according to the present invention may contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

In the present invention, conventionally known yellow couplers, magenta couplers and cyan couplers can be used as the above-mentioned couplers. These couplers may be so-called 2-equivalent type or 4-equivalent type couplers, and it is also possible to use diffusible dye releasing type couplers in combination with these couplers.

As the yellow coupler, a closed ketomethylene compound which has been used conventionally, an active point-o-aryl substituted coupler, an active point-o-acyl substituted coupler, an active point hydantoin compound-substituted coupler, which is called a so-called 2-equivalent type coupler, Active point urazole compound-substituted couplers, active point succinimide compound-substituted couplers, active point fluorine-substituted couplers, active point chlorine- or bromine-substituted couplers, active point-o-sulfonyl-substituted couplers, etc. can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.
5,057, 3,265,506, 3,408,194, 3,551,155
No., No. 3,582,322, No. 3,725,072, No. 3,891,445,
West German Patent 1,547,868, West German Published Application 2,219,917, 2,
261,361, 2,414,006, British Patent 1,425,020, JP-B-51-10783, JP-A-47-26133,
48-73147, 51-102636, 5
0-6341, 50-123342, 50-1
No. 30442, No. 51-21827, No. 50-876
No. 50, No. 52-82424, No. 52-115219
No. 58-95346 and the like.

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based compounds.

These magenta couplers are the same as the yellow couplers 4
Not only the equivalent type coupler but also a two equivalent type coupler may be used. As a specific example of the magenta coupler, US Pat.
600,788, 2,983,608, 3,062,653, 3,127,2
No. 69, No. 3,311,476, No. 3,419,391, No. 3,519,429
No., No. 3,558,319, No. 3,582,322, No. 3,615,506,
No. 3,834,908, No. 3,891,445, West German patent 1,810,464
Issue, West German patent application (OLS) 2,408,665, 2,417,945
No. 2,418,959, 2,424,467, Japanese Patent Publication No. 40-60
31, JP-A-51-20826, and JP-A-52-5892.
2, No. 49-129538, No. 49-74027.
No. 50-159336, No. 52-42121,
49-74028, 50-60233, 51
No. 26541, No. 53-55122, Japanese Patent Application No. 55-
Examples thereof include those described in No. 110943.

Further, useful cyan couplers used in the present invention include, for example, phenol type and naphthol type couplers. And these cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Patents 2,369,929 and 2,434,272.
No. 2, 2,474,293, 2,521,908, 2,895,826,
3,034,892, 3,311,476, 3,458,315, 3,4
76,563, 3,583,971, 3,591,383, 3,767,41
No. 1, 4,004,929, West German patent application (OLS) 2,414,83
0, 2,454,329, JP-A-48-59838, 5
1-26034, 48-5055, 51-14
No. 6827, No. 52-69624, No. 52-9093.
No. 2, No. 58-95346 and the like can be mentioned.

In the silver halide emulsion layer and other photographic constituent layers of the present invention, a so-called DIR compound, a coupler such as a non-diffusible coupler or a polymer coupler which reacts with an oxidized product of a developing agent to form a diffusible dye having an appropriate degree of bleeding. You may use together. Regarding the non-diffusible DIR compound and the non-diffusible coupler which reacts with the oxidized product of the developing agent to form a diffusible dye which is appropriately bleeding, the description in Japanese Patent Application No. 59-193611 by the present applicant, and regarding the polymer coupler, Japanese Patent Application No. 5 by the applicant
For the DIR compound, the description of Japanese Patent Application No. 59-158782 by the present applicant can be referred to.

In order to include these couplers and the like in the silver halide emulsion according to the present invention, when the couplers and the like are alkali-soluble, they may be added as an alkaline solution, and when they are oil-soluble, for example, US Patent 2,322,027
No. 2, No. 2,801,170, No. 2,801,171, No. 2,272,191 and No. 2,304,940 according to the method described in each specification couplers and the like in a high-boiling solvent, if necessary dissolved in combination with a low-boiling solvent, in the form of fine particles It is preferably dispersed and added to the silver halide emulsion. At this time, other hydroquinone derivatives, ultraviolet absorbers, browning inhibitors and the like may be used in combination if necessary. It is also possible to use a mixture of two or more couplers. Further, in the present invention, the addition method of couplers and the like will be described in detail. One or more of such couplers and the like may be added together with other couplers, hydroquinone derivatives, browning inhibitors, ultraviolet absorbers and the like as organic acids. Amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, tricresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n -Butyl sebacate, tri-n
-Hexyl phosphate, N, N-di-ethyl-caprylamidobutyl, N, N-diethyllaurylamide, n
-Pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether, monophenyl-di-o-chlorophenyl phosphate, fluorine paraffin, etc. Boiling point solvent and / or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, Anionic surfactants such as alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid which are soluble in low boiling point solvents such as methyl ethyl ketone And / or an aqueous solution containing a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate and / or a hydrophilic binder such as gelatin, and mixed with a high-speed rotary mixer, colloid mill or ultrasonic dispersion device. The emulsion is dispersed and added to the silver halide emulsion.

In addition, the above-mentioned couplers and the like may be dispersed by using a latex dispersion method. The latex dispersion method and its effects are described in JP-A-49-74538, JP-A-51-59943, and JP-A-51-59943.
4-32552 and Research Disclosure, August 1976, No. 14850, pp. 77-79.

Suitable latices include, for example, styrene, acrylates,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2- (methacryloyloxy) ethyltrimethylammonium methosulfate, 3- (methacryloyloxy) propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N- [2- (2-methyl-4) -Oxopentyl)] acrylamide, 2-acrylamido-2-
Homopolymers, copolymers and terpolymers of monomers such as methyl propane sulfonic acid and the like.

The silver halide color photographic light-sensitive material of the present invention may further contain various photographic additives, for example, antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure Magazine 17643. A color stain preventing agent, a fluorescent whitening agent, a color image browning preventing agent, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent and the like can be used.

In the silver halide color photographic light-sensitive material of the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxy. Any one of ethyl cellulose derivative, cellulose derivative such as carboxymethyl cellulose, starch derivative, single or copolymer synthetic hydrophilic polymer such as polyvinyl alcohol, polyvinyl imidazole, polyacrylamide and the like is included.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the emulsion layers and other constituent layers used in the present invention. Further, a simultaneous coating method of two or more layers by the method described in US Pat. Nos. 2,761,791 and 2,941,898 can also be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photosensitive material for photographic paper, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer are sequentially arranged from the support side.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and further, a filter layer,
Various layers such as a cursor prevention layer, a protective layer and an antihalation layer can be appropriately combined and used as a photographic constituent layer. In these photographic constituent layers, a hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder, and in the layer, the hydrophilic colloid can be contained in the emulsion layer as described above. Various photographic additives can be included.

The processing method of the photographic light-sensitive material using the silver halide emulsion according to the present invention is not particularly limited, and any processing method can be applied. For example, as a typical one,
After color development, bleach-fixing treatment followed by washing and / or stabilizing treatment if necessary; after color development, bleaching and fixing treatment are carried out separately, and if necessary, further washing and / or stabilizing treatment; or Pre-hardening, neutralization, color development, stop-fixing, washing, bleaching, fixing, washing, post-hardening, washing in this order, color development, washing, supplemental color development, stopping, bleaching, fixing, washing, stabilizing Any of the above methods may be used, such as a method in which the developed silver is developed in this order, halogenated bleaching of the developed silver is performed, and then color development is performed again to increase the amount of dye formed.

The color developing solution used for processing the silver halide emulsion of the present invention is an alkaline aqueous solution containing a color developing agent, preferably having a pH of 8 or more, more preferably 9 to 12. The aromatic primary amine developing agent as the color developing agent is
It is a compound having a primary amino group on the aromatic ring and capable of developing exposed silver halide, and if necessary, a precursor for forming such a compound may be added.

Typical examples of the color developing agent include those of p-phenylenediamine type, and the following are preferred examples.

4-amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methanesulfonamide ethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-
Hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-
Acetamide-4-amino-N, N-dimethylaniline, N-ethyl-N-β- [β- (β-methoxyethoxy) ethoxy] ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β -(Β-methoxyethoxy) ethyl-3-methyl-4-aminoaniline and salts thereof such as sulfate, hydrochloride, sulfite, p-toluenesulfonate and the like.

Further, for example, JP-A-48-64932 and 50-1.
Nos. 31526, 51-95849 and Bent et al., Journal of the American Chemical Society, Volume 73, pages 3100 to 3125 (1951), are also representative.

The amount of these aromatic primary amino compounds used depends on where the activity of the developer is set, but it is preferable to increase the amount of use in order to increase the activity. The amount used is 0.0002 mol / to 0.7 mol /. Further, two or more compounds can be used in an appropriate combination depending on the purpose. For example 3-methyl-4
-Amino-N, N-diethylaniline and 3-methyl-4
-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline and 3-
A combination of methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline and the like can be freely used in combination according to the purpose.

The color developer used in the present invention may contain a monochrome developing agent described in Japanese Patent Application No. 59-2455 by the present applicant. Further, various components that are usually added, for example, alkali agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites, alkali metal hydrogen sulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners. , A thickening agent, a development accelerator and the like may be optionally contained.

Examples of additives other than the above that are added to the color developing solution include potassium bromide, bromide such as ammonium bromide, alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, and 1-phenyl. Examples include compounds for rapid processing liquids such as -5-mercaptotetrazole, stain inhibitors, anti-sludge agents, preservatives, layering effect accelerators, chelating agents and the like.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution in the bleaching step, aminopolycarboxylic acids or acids, organic acids such as citric acid, and those in which metal ions such as iron, cobalt and copper are coordinated are generally known. There is. And the following can be mentioned as a typical example of said amino polycarboxylic acid.

Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Iminodiacetic acid Ethyldiaminediaminetetraacetic acid Ethylenediaminetetrapropionic acid Ethylenediaminetetraacetic acid disodium salt Diethylenetriaminepentaacetic acid pentasodium salt Nitrilotriacetic acid sodium salt You may contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution having a composition containing a silver halide fixing solution in addition to the bleaching agent is applied. Further, the bleach-fixing solution may further contain a halogen compound such as potassium bromide. And, as in the case of the bleaching solution, various other additives such as pH buffer, fluorescent whitening agent, defoaming agent, surfactant, preservative, chelating agent, stabilizer, organic solvent, etc. Addition,
It may be contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc. Compounds forming a silver salt of

Color development of the silver halide color photographic light-sensitive material of the present invention,
From the viewpoint of rapid processing, it is preferable that the processing temperature of bleach-fixing (or bleaching / fixing) and, if necessary, various processing steps such as washing with water, stabilization and drying is carried out at 30 ° C. or higher.

The silver halide color photographic light-sensitive material of the present invention is described in JP-A-58 / 58.
No. 14834, No. 58-105145, No. 58-1
34634 and 58-18631 and Japanese Patent Application No. 5
You may perform water washing alternative stabilization treatment as shown by 8-2709 and 59-89288 etc.

[Effects of the Invention] According to the silver halide color photographic light-sensitive material of the present invention, a blue-sensitive silver halide emulsion layer and a green light-sensitive layer each containing silver chlorobromide or silver chloroiodobromide on a reflective support. In a silver halide color photographic light-sensitive material having a silver halide emulsion layer and a red light-sensitive silver halide emulsion layer in this order and one layer each, the support is coated with a resin cured by irradiation with an electron beam. And the average grain size of the silver halide in the blue-sensitive silver halide emulsion layer is 0.02 to 0.55 μm.
m, which is characterized in that the silver bromide content of silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 5 to 65 mol%. Property, processing stability and image sharpness are improved, and the occurrence of fog can be suppressed.

[Examples] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

Example 1 The following layers were sequentially coated from the support side on a support coated with a resin cured by irradiation with the electron beam of the present invention prepared in the above Production Example (2), and a silver halide color was prepared. Photographic photosensitive materials Nos. 1 to 6 were prepared.

Layer 1 ... 1.2 g / m ² gelatin, 0.32 g / m ² (silver equivalent, the same applies below) blue-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), A layer containing 0.80 g / m ² of yellow coupler (Y-1) dissolved in 0.50 g / m ² of dioctyl phthalate.

Layer 2 An intermediate layer comprising 0.7 g / m ² gelatin, 20 mg / m ² irradiation dye (AI-1) and 10 mg / m ² (AI-2).

Layer 3: 1.25 g / m ² gelatin, 0.22 g / m ² green-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), 0.30 g / m ² dioctyl Dissolved in phthalate.
A layer containing 62 g / m ² of magenta coupler (M-1).

Layer 4 ... an intermediate layer consisting of 1.2 g / m ² of gelatin.

Layer 5: 1.4 g / m ² gelatin, 0.20 g / m ² red-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), 0.20 g / m ² dioctyl Dissolved in phthalate.
Layer containing 45 g / m ² of cyan coupler (C-1).

Layer 6 ... Layer containing 0.30 g / m ² of UV absorber (UV-1) dissolved in 1.0 g / m ² of gelatin and 0.20 g / m ² of dioctyl phthalate.

Layer 7 ... A layer containing 0.5 g / m ² of gelatin.

(Y-1) (M-1) (C-1) (AI-1) (AI-2) (UV-1) As a hardening agent, 2,4-dichloro-6-hydroxy-S-triazine sodium was added in layers 2, 4 and 7,
Each of them was added in an amount of 0.017 g per 1 g of gelatin.

Next, layers 1 to 7 in Sample Nos. 1 to 6 were sequentially coated on a polyethylene-laminated paper support to prepare a sample.
Sample Nos. 7 to 12 corresponding to Nos. 1 to 6 were created.

Each of the above photosensitive material sample Nos. 1 to 12 is divided into two, and one is divided into 30
After storing for 10 days under the condition of ℃, 60% RH, the other is instant,
After exposure through an optical wedge, each was processed in the next step.

Processing step (38 ° C.) Color development 3 minutes Bleach fixing 1 minute Washing with water 1 minute Drying 60 to 80 ° C. 2 minutes The composition of each processing solution is as follows.

[Color developer] Pure water 800 ml Benzyl alcohol 15 ml Hydroxyamine sulfate 2.0 g Potassium bromide 1.5 g Sodium chloride 1.0 g Potassium sulfite 2.0 g Triethanolamine 2.0 g N-ethyl-N-β-methanesulfone amidoethyl-3-methyl- 4-Aminoaniline sulfate 4.5g 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5ml Potassium carbonate 32g Whitex BB (50% aqueous solution) 2ml (Fluorescent brightener, Sumitomo Chemical Co., Ltd.) Add pure water to make 1 and adjust the pH to 10.1 with 20% potassium hydroxide or 10% dilute sulfuric acid.

[Bleach-fixing solution] Pure water 550 ml Ethylenediaminetetraacetic acid iron (III) ammonium 65 g Ammonium thiosulfate 85 g Sodium hydrogen sulfite 10 g Sodium metabisulfite 2 g Ethylenediaminetetraacetic acid-2 sodium 20 g Sodium bromide 10 g Add pure water to 1 and ammonia water Or pH with dilute sulfuric acid
Adjust to 7.0.

Sensitometry was performed on each of the obtained samples by a conventional method. The sample obtained by the development process is the Sakura densitometer PV
Table 2 shows the fog obtained by measurement using an A-60 type (manufactured by Konishi Rokusha Kogyo Co., Ltd.).

The results of Table 2 show that Sample Nos. 1 and 5 according to the present invention are equivalent to the case of using polyethylene laminated paper, and Sample N using an emulsion other than the present invention and using an electron beam curable resin support.
It can be seen that the fog is remarkably improved compared to o.2, 3, 4, and 6.

Example 2 In order to see the effect of improving the sharpness of an image, MTF (Modulatio Tran
sfer Function) with a microdensitometer,
The MTF values at the spatial frequency of 5 lines / mm were compared. In addition, MTF
It is well known to those skilled in the art to judge the sharpness of an image by using "The theory of the photographic process 3".
"rd edition". The results are shown in Table 3.

As is apparent from Table 3, the sharpness is improved by using the emulsion or electron beam curable resin of the present invention. That is,
The effect of the emulsions of the invention can be seen, for example, by comparing samples No. 7 and 8, and the effect of the support, for example, by comparing sample Nos. 2 and 8. However, the sharpness of the sample using both the emulsion of the present invention and the electron beam effect resin support was remarkably improved. From the above results, it can be seen that the silver halide color photographic light-sensitive material of the present invention is excellent in image sharpness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeto Hirabayashi 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Industry Co., Ltd. (56) Reference JP-A-58-126530 (JP, A) JP-A-57 -30830 (JP, A) JP 59-74548 (JP, A) JP 59-102229 (JP, A)

Claims (1)

[Claims] 1. A blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer each containing silver chlorobromide or silver chloroiodobromide on a reflective support. A silver halide color photographic light-sensitive material having one layer each in this order, the support being coated with a resin cured by irradiation with an electron beam, and the blue-sensitive silver halide emulsion The average grain size of silver halide in the layer is 0.20 to 0.55 μm, and the silver bromide content of silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 5 to 65 mol. %, A silver halide color photographic light-sensitive material.