JPH0352846B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION [Technical Field] The present invention relates to a silver halide photographic material, particularly a color photographic material for printing. [Prior Art] One of the important characteristics of color photosensitive materials for printing (hereinafter referred to as color photosensitive materials) that greatly affects the image quality of prints is sharpness, and in order to improve this, Research has been carried out on anti-irradiation dyes, layer structure, supports, etc.Also, color reproducibility has been studied, and to improve this, research has been carried out on spectral sensitizing dyes, filter dyes. Therefore, the characteristics of anti-irradiation or filter dyes that greatly contribute to both of these characteristics are important, and the specific characteristics that they should have are as follows: Possess excellent spectral absorption characteristics. It must have excellent dissolution properties during development processing. It must not have any negative effects on silver halide, such as increasing fog that reduces sensitivity. Examples of dyes that nearly satisfy the above-mentioned requirements include oxonol dyes, Examples include azo dyes and anthraquinone dyes, and anthraquinone dyes in particular have excellent spectral absorption characteristics as described in U.S. Pat. This tends to cause fog to silver halide emulsions, especially to silver halide emulsions containing high silver chloride.Additionally, when antifoggants and stabilizers are added to remove this fog, significant desensitization occurs. On the other hand, most of the binders used in color sensitive materials for printing involve gelatin, and a hardening agent is used in combination with the binder.The desired properties of the hardening agent include rapid hardening. It is effective, does not cause fogging or other adverse effects on silver halide, does not cause problems with industrial hygiene or environmental pollution, is water soluble, is easy to synthesize, and is low cost. For this reason, studies were conducted on hardening agents such as vinyl sulfone, ethyleneimine, epoxy, N-methylol, cyanuric chloride, etc. 78788
No. 52-128130, No. 52-130326 and No. 56-
As described in No. 1043, the cyanuric chloride hardener has excellent properties, satisfying most of the above-mentioned desired properties. However, it has become clear that cyanuric chloride hardeners have major drawbacks. One of them is that color photosensitive materials for printing have poor storage stability over time until they are used, and are significantly desensitized over time.Furthermore, even if a desensitizing inhibitor is added, the effect is small or the desensitizing effect is small. Some inhibitors may even lead to fogging. Yet another characteristic is that it reduces the elution properties of anti-irradiation dyes or filter dyes during development processing, which impairs the whiteness of prints. In addition, when looking at the operating efficiency of color photosensitive materials for printing, it is important to increase the sensitivity of the color photosensitive materials for printing in order to shorten printing time. It is important for print yield to be small. For this purpose, studies have been carried out on silver halides, their chemical sensitization methods, spectral sensitization methods, etc., and silver halides that can be targeted include silver halides with high silver chloride content, which can easily be made highly sensitive by spectral sensitization. It is attracting attention as However, this silver halide containing high silver chloride has the property of being prone to fogging, which becomes noticeable during rapid processing at high temperatures or after aging of color sensitive materials, resulting in poor image quality of prints. Purpose of the Invention The present invention has been made in view of the above-mentioned circumstances, and its main objects are as follows: The first object is to provide a silver halide photographic light-sensitive material (hereinafter referred to as The aim is to provide photosensitive materials (abbreviated as photosensitive materials). The second object is to provide a photosensitive material with excellent whiteness. The third object is to provide a photosensitive material whose sensitivity changes little over time after its manufacture. The fourth objective is to provide a highly sensitive photosensitive material. Structure of the Invention As a result of various studies, it has been found that the above-mentioned objects of the present invention can be solved at once by the following structure of the present invention. That is, the structure of the present invention is a silver halide photographic material having at least one silver halide emulsion layer containing silver halide with a silver chloride content of 25 mol % or more, in which at least one of the silver halide emulsion layers is This is a photosensitive material characterized by containing a compound represented by the following general formula [] and further hardened with a compound represented by the following general formula [] and/or a compound represented by the following general formula []. General formula [] In the general formula [ ], R ₁ , R ₄ , R ₅ and R ₆ are each hydrogen atom, hydroxy group, -OR group or

[Formula] represents a group. Here, R represents an alkyl group or an aryl group, R' and R'' represent a hydrogen atom or an alkyl group or an aryl group having at least one sulfonic acid group or a carboxylic acid group, and R ₂ , R ₃ , R ₆ and R ₇ are each a hydrogen atom,
It represents a carboxylic acid group, a sulfonic acid group, or an alkyl or aryl group having at least one carboxylic acid group or sulfonic acid group. General formula [] In the general formula [ ], R ₉ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group,

[Formula] (R ₉ ′ and R ₉ ″ each represent a hydrogen atom, an alkyl group, or an aryl group.) -NHCOR ₉ (R ₉ represents a hydrogen atom, an alkyl group, an aryl group, or an alkylthio group.) or -OM Represents a group (M is a monovalent metal atom), and R ₁₀ has the same meaning as R ₉ excluding the chlorine atom. General formula [] In the general formula [], R ₁₁ and R ₁₂ are chlorine atoms,
It represents a hydroxy group, an alkyl group, an alkoxy group or an -OM group (M is a monovalent metal atom). Q,
Q' represents a linking group representing -O-, -S-, or -NH-, and L represents an alkylene group or an arylene group. l and m represent 0 or 1. The alkyl group represented by R in the -OR group represented by R ₁ , R ₄ , R ₅ and R ₈ in the general formula [] is, for example, a methyl group, an ethyl group or a butyl group, and the aryl group represented by R is, for example, a phenyl group. It is. Also-
The alkyl group having at least one sulfonic acid group or carboxylic acid group represented by R' and R'' of the NR'R'' group is, for example, -CH ₂ SO ₃ H, -(CH ₂ ) ₂ SO ₃ H, -
CH ₂ COOH, -(CH ₂ ) ₂ COOH or its sodium salt, potassium salt or ammonium salt. Furthermore, the aryl group represented by R′ and R″ is, for example,

【formula】

[Formula] etc. Further, the alkyl group or aryl group having at least one carboxylic acid group or sulfonic acid group represented by R ₂ , R ₃ , R ₆ and R ₇ is R′ and
The light-sensitive material of the present invention has a blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layer (hereinafter simply referred to as an emulsion layer) on a support. The compound represented by the general formula [] is contained in at least one layer or a plurality of layers selected from the emulsion layer or the auxiliary layer. It is possible to obtain an irradiation prevention or filter effect if the compound is contained in a red-sensitive emulsion layer or an auxiliary layer adjacent to the red-sensitive emulsion layer. Alternatively, it is used by dissolving it in alcohol, and the amount added is 1 to 1.
It is added at a concentration of 100 mg/m ² , preferably 5 to 50 mg/m ² . Next, typical examples of the compound represented by the above general formula [] will be listed. Next, the alkyl groups represented by R ₉ and R ₁₀ in the general formula [ ] are, for example, methyl, ethyl, butyl, etc., and the alkoxy groups represented by these are methoxy, ethoxy, butoxy, etc. Also

Specific examples of [Formula] include -NH ₂ , -NHCH ₃ , -NHC ₂ H ₅ , etc. Specific examples of -NHCOR ₉ include -HHCOOH ₃ ,

[Formula] etc. Furthermore, R ₉ and R ₁₀ are expressed. M in the OM group is, for example, a sodium atom, a potassium atom, or the like. Regarding the cyanuric chloride hardener represented by the above general formula [], US Pat. No. 3,645,743,
Special Publication No. 47-6151, No. 47-33380, No. 51-9607
No. 1978-19220, No. 51-78788, No. 52-
No. 60612, No. 52-128130, No. 52-130326, No. 60612, No. 52-128130, No. 52-130326, No.
No. 56-1043, which can be used in accordance with the above criteria. Next, the alkyl group represented by R ₁₁ and R ₁₂ in the general formula [] is, for example, a methyl group, an ethyl group, a butyl group, etc., and the alkoxy group is a methoxy group, an ethoxy group,
butoxy group, etc., and M in the -OM group is, for example, a sodium atom, a potassium atom, etc. Further, the alkylene group represented by L is, for example, -CH ₂
-, -( _CH2 ) _2- , -( _CH2 ) _3- , etc., and the arylene group is, for example, p-, o-, or m-phenylene group. The cyanuric chloride hardener represented by the general formula [] is described in Canadian Patent No. 895808, Japanese Patent Publication No. 58-33542, and Japanese Patent Application Laid-open No. 57-40244, and can be selected and used based on the above criteria. can be provided. The compounds represented by the general formulas [] and [] according to the present invention may be added to at least one layer or a plurality of layers selected from among the emulsion layer or auxiliary layer according to the present invention. The addition is dissolved in water or alcohol (e.g. methyl alcohol, ethyl alcohol, etc.),
1 to 100 mg, preferably 5 to 50 mg per gram of gelatin
mg added. The addition method may be either a batch method or an in-line method. Next, typical examples of compounds represented by the general formula [] or [] will be listed, but the present invention is not limited thereto. Compound represented by general formula []:

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] Compound represented by the general formula []: In the light-sensitive material of the present invention, the silver halide contained in at least one emulsion layer is a silver halide containing 25 mol% or more of silver chloride, and the remaining silver halide contains silver bromide and silver iodide. , silver bromide is 0~
75 mol%, silver iodide is preferably 0 to 5 mol%, particularly silver chloride is 25 to 60 mol%, and silver bromide is 40 to 75 mol%.
silver halide is preferred. The emulsion layer according to the present invention may be entirely composed of the above-mentioned silver halide, and does not necessarily need to be composed entirely of the emulsion layer, and any silver halide composition can be selected depending on the required characteristics. These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of (100) planes to (111) planes 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 with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. Furthermore, these silver halides may be produced by any of the neutral method, ammonia method, and acidic method, and may be produced by any of the simultaneous mixing method, forward mixing method, back mixing method, convergence method, etc. Silver halide grains manufactured by can also be applied. The particle size is preferably in the range of 0.1 to 1.0μ. It is preferable that soluble salts be removed from the silver halide emulsions used in the light-sensitive materials of the present invention, but those in which soluble salts have not been removed can also be used. Also,
It is also possible to use a mixture of two or more silver halide emulsions prepared separately. A silver halide photographic emulsion in which silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in combination in the present invention include noble metal sensitizers,
4 of sulfur sensitizers, selenium sensitizers and reduction sensitizers
It is broadly divided into species. As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used. In addition, when using a gold compound, it can be used in combination with ammonium thiocyanate and sodium thiocyanate. As the sulfur sensitizer, in addition to activated gelatin, sulfur compounds can be used. As selenium sensitizers, active and inactive selenium compounds can be used. Examples of reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium, and hydrazine derivatives. Further, these silver halide emulsions can be optically sensitized using various sensitizers in order to impart photosensitivity in a desired wavelength range. Preferred sensitizing dyes that can be used at this time include, for example, cyanine dyes, merocyanine dyes, or composite cyanine dyes, either singly or in combination of two or more. These various optical sensitizers are used for purposes other than their original purpose, such as preventing fogging, preventing deterioration of photographic performance due to storage of silver halide color sensitive materials, and controlling development (e.g.
It can also be used for purposes such as gradation control, etc. The constituent layers of the light-sensitive material according to the present invention may further contain chemical sensitizers such as thioether compounds, quaternary ammonium salt compounds, or polyalkylene oxide compounds, triazoles, imidazoles, azaindenes, benzothia Stabilizers such as zolium compounds, zinc compounds, cadmium compounds, and mercaptans can be used within the range that does not impair the effects of the present invention. When the present invention is applied to a color sensitive material, a diffusion-resistant coupler that develops color by coupling with an aromatic primary amine developing agent is used. Yellow dye image-forming couplers include acylacetamido-type benzoylmethane-type 4-equivalent or 2-equivalent couplers, and these include, for example, U.S. Pat.
3227155, 3227550, 3253924, 3227155, 3227550, 3253924,
No. 3265506, No. 3277155, No. 3341331, No.
No. 3369895, No. 3384657, No. 3408194, No. 3369895, No. 3384657, No. 3408194, No.
No. 3415652, No. 3447928, No. 3551155, No.
No. 3582322, No. 3725072, German patent publication
No. 1547868, No. 2057941, No. 2162899, No.
No. 2163812, No. 213461, No. 2219917,
2261361, 2263875, JP 49-13576, JP 48-29432, JP 48-66834, JP 49-10736,
No. 49-122335, No. 50-28834 and No. 50-
It is described in No. 132926 etc. As a magenta dye image-forming coupler, 5-
These are pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, indazolone, and cyanoacetyl 4-equivalent or 2-equivalent type magenta dye image-forming couplers, and these are described, for example, in U.S. Pat. 3127269
No. 3311476, No. 3152896, No. 3419391,
No. 3519429, No. 3558318, No. 3684514, No.
No. 3888680, No. 3907571, No. 3928044, No. 3928044, No. 3907571, No. 3928044, No.
No. 3930861, No. 3930866, No. 3933500, JP-A-Sho
No. 49-29639, No. 49-111631, No. 49-129538,
No. 50-13041, Special Publication No. 53-47167, No. 54-
No. 10491, No. 55-30615, British Patent No. 1247493,
It is described in Belgian Patent No. 792525, US Patent No. 3061432, West German Patent No. 2156111, Japanese Patent Publication No. 46-60479, Belgian Patent No. 769116, etc. The cyan dye image-forming coupler is a phenol-based or naphthol-based 4-equivalent or 2-equivalent type cyan dye image-forming coupler, and these include, for example, U.S. Pat.
No. 2474293, No. 2698794, No. 2706684,
Same No. 2772162, No. 2801171, No. 2895826, Same No.
No. 2908573, No. 3034892, No. 3046129, No. 3046129, No.
No. 3227550, No. 3253294, No. 3311476, No. 3227550, No. 3253294, No. 3311476, No.
No. 3386301, No. 3419390, No. 3458315, No. 3458315, No. 3419390, No. 3458315, No.
No. 3476563, No. 3516831, No. 3560212, No. 3560212, No. 3516831, No. 3560212, No.
No. 3582322, No. 3583971, No. 3591383, No. 3582322, No. 3583971, No. 3591383, No.
No. 3619196, No. 3632347, No. 3652286, No.
No. 3737326, No. 3758308, No. 3779763, No.
3839044, German Patent Publication No. 2163811, same
No. 2207468, Special Publication No. 39-27563, No. 45-28836,
JP-A-47-37425, JP-A No. 50-10135, JP-A No. 50-
No. 25228, No. 50-112038, No. 50-117422, No.
No. 50−130441 and Research Disclosure 1976
14853 etc. In the present invention, ultraviolet absorbers such as benzophenone or benzazole compounds may be used. Benzotriazole compounds are disclosed in Japanese Unexamined Patent Application Publication No. 1973-
No. 10466, No. 42-26187, No. 48-5496, No. 48-
No. 41572, US Pat. No. 3,754,919, and US Pat. No. 4,220,711. These hydrophobic additives, such as cyan dye-forming couplers, magenta dye-forming couplers, yellow dye-forming couplers, or photographic additives such as ultraviolet absorbers, are dispersed in an aqueous hydrophilic binder solution according to conventionally known methods. It is contained in the silver halide emulsion layer or non-photosensitive layer. Methods for dispersing these hydrophobic compounds include, for example, JP-A No. 49-74538, JP-A No. 51-59943, and JP-A No. 54-54.
No. 32552, Research Disclosure Magazine,
The latex dispersion method described in August 1976, No. 14850, pages 77-79, or the oil-in-water dispersion method may be used. As the oil-in-water type dispersion method, conventionally known methods for dispersing hydrophobic compounds such as couplers can be applied. Specifically, a hydrophobic compound is dissolved in a high boiling point organic solvent with a boiling point of 175°C or higher, and a low boiling point solvent such as ethyl acetate or butyl acetate, which is added as necessary. It is mixed with an aqueous solution containing a hydrophilic binder, emulsified and dispersed by a dispersing means such as a high-speed rotary mixer, a colloid mill, or an ultrasonic dispersion device, and incorporated into a hydrophilic colloid layer such as an emulsion layer or an auxiliary layer. Examples of high-boiling organic solvents used in this case include organic acid amides, carbamates, esters, ketones, urea derivatives, etc., especially dimethyl phthalate, diethyl phthalate, di-propyl phthalate, di-butyl phthalate, di-n-octyl phthalate, diisooctyl phthalate,
Phthalic acid esters such as diamyl phthalate, dinonyl phthalate, diisodecyl phthalate, phosphoric acid esters such as tricresyl phosphate, triphenyl phosphate, tri-(2-ethylhexyl) phosphate, trisononyl phosphate, dioctyl Sebaket, G (2
Sebacic acid esters such as -ethylhexyl) sebacate and diisodecyl sebacate, glycerin esters such as glycerol tripropionate and glycerol tributyrate, and other glycerin esters, adipate esters, glutaric acid esters, succinic acid esters, maleic esters, and fumaric esters. , citric acid ester, di-tert-acylphenol, n-octylphenol, and other phenol derivatives may be used singly or in combination. The binder used in the constituent layers of the light-sensitive material of the present invention is most commonly gelatin such as alkali-treated gelatin or acid-treated gelatin. derivative gelatin,
albumin, agar, gum arabic, alginic acid,
Partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of these vinyl compounds can also be used in combination. The emulsion layer and auxiliary layer of the light-sensitive material according to the present invention may contain various other photographic additives. For example, Research Disclosure Magazine
Antifoggants, dye image fading inhibitors, color stain inhibitors, fluorescent whitening agents, antistatic agents, surfactants, plasticizers, wetting agents, etc. described in No. 17643 can be used as appropriate. In the photographic material of the present invention, each constituent layer such as an emulsion layer and an auxiliary layer containing various photographic additives as described above is prepared on a support which has been subjected to corona discharge treatment, flame treatment or ultraviolet irradiation treatment. on the body,
Alternatively, it is manufactured by coating on a support via a subbing layer and an intermediate layer. Advantageously used supports include, for example, Paraita paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports provided with a reflective layer or in combination with a reflective material, such as glass plates, cellulose acetate, cellulose nitrate or printed materials. Polyester films such as ethylene terephthalate, polyamide films,
Examples include polycarbonate film and polysterene film, and these supports are appropriately selected depending on the intended use of the light-sensitive material. Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also US patent
Simultaneous coating of two or more layers by the method described in No. 2761791 and No. 2941898 can also be used. In the present invention, the coating position of each emulsion layer can be determined arbitrarily, but for example, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are arranged sequentially from the support side, or on the support side. A red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer can be sequentially arranged. Hydrophilic colloids that can be used in the emulsion as described above can be used as a binder in these constituent layers, and various types of colloids that can be contained in the emulsion layer as described above can be used as a binder. Photographic additives may similarly be included.
Further, an ultraviolet absorber layer may be provided in a layer adjacent to the support side of the emulsion layer furthest from the support, and if necessary, an ultraviolet absorber layer may be provided in a layer on the opposite side of the support. Particularly in the latter case, it is preferable to provide the uppermost layer with a protective layer consisting essentially of gelatin. When the present invention is applied to a color photosensitive material for printing, the photosensitive material is exposed to light through a negative photosensitive material having an image made of a coupling product, and then subjected to color development processing. The color development process is performed by a normal color development method. That is, first, it is processed with a color developing solution containing a color developing agent. Alternatively, a color developing agent or its precursor is contained in a color photosensitive material, and this is treated with a so-called activator liquid. Thereafter, a bleaching step and a fixing step are usually performed according to conventional methods. In this case, the color development process using a color developer or activator liquid, the bleaching process, and the fixing process may be performed independently, but instead of performing two or more processes independently, a process that has these functions is used. It is also possible to carry out once (one bath) using a liquid. For example, a one-bath processing method in which a color developing solution or an activator solution contains both a bleaching agent and a fixing agent as described below, and a bleaching and fixing method in which bleaching and fixing are carried out after the color development step. Methods include using a bath. Also, after processing with a color developer or activator solution, desilvering can be carried out by immediately processing with a bleach-fixing bath, etc., but an acidic stop step is provided between the color development step and the bleaching and fixing steps. You can also do that. For such an acidic stop bath, an aqueous solution of acetic acid, citric acid, etc. can be used. Further, steps such as predural mater, neutralization, washing with water, stabilization, etc. can be provided as necessary. Through such color development processing, a dye image is formed on the color sensitive material for printing by a coupling reaction. The color developing agent for the light-sensitive material of the present invention is typically an aromatic primary amine color developing agent. Aromatic primary amine color developing agents include aminophenol and p-phenylenediamine derivatives, and these compounds can be used in the free state or in their hydrochloride, sulfate, p-toluenesulfonate, Tetraphenylborate, p
It can be used as an organic acid salt such as -(t-octyl)benzenesulfonate. Specific aromatic primary amine color developing agents include o-aminephenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, 2-oxy-3-amino -1,4-dimethylbenzene, N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, N -ethyl-N-β-methanesulfonaminoethyl-3
-Methyl-4-aminoaniline and its sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, N,N-diethyl-3-(β-methanesulfonamidoethyl)-4-aminoaniline hydrochloride, 4 -amino-N-(2-methoxyethyl)
-N-ethyl-3-methylaniline-p-toluenesulfonate, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline tetraphenylborate, 4-amino- N-(2-methoxyethyl)-N-ethyl-3-
Methylaniline tetraphenylborate, p
Representative examples include -morpholinoaniline, p-piperidineaniline, and 4-amino-N,N-diethyl-3-chloroaniline. In some cases, the light-sensitive material of the present invention may contain a color developing agent precursor. The color developing agent precursor is a compound that can produce a color developing agent under alkaline conditions, and includes, for example, a Schiff base type breaker with an aromatic aldehyde derivative, a polyvalent metal ion complex breaker, a phthalic acid imide derivative breaker,
Examples include phosphoric acid amide derivative breaker, Shugar amine reaction breaker, and urethane type breaker. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat. No. 3,342,599;
No. 2507114, No. 2695234, No. 3719492, British Patent No. 803783, Japanese Patent Application Publication No. 1983-135628, No. 54-79035
No., Research Disclosure Magazine No. 15159,
It is described in No. 12146 and No. 13924. These aromatic primary amine color developing agents are
It is usually contained in a color developing solution in an amount of about 1 to 20 g/approx. When it is contained as a precursor in a photosensitive material, it is contained in an amount of about 0.5 to 3 moles per mole of silver halide. A water-soluble fluorescent whitening agent may be added to the color developer or activator solution used for the photosensitive material of the present invention in an amount of about 0.1 to 10 g/approx. The color developing solution or activator solution used for the photosensitive material of the present invention includes an alkaline agent such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, sodium sulfite, etc. , sulfites such as potassium sulfite, and bromide salts such as sodium bromide, potassium bromide, and ammonium bromide. Furthermore, if necessary, known development inhibitors, thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, chloride salts such as ammonium chloride, potassium chloride, and sodium chloride, ethylene glycol, diethylene glycol, methanol, ethanol,
Organic solvents such as n-butanol, benzyl alcohol, acetone, and dimethylformamide, amines such as hydroxylamine, ethanolamine, ethylenediamine, and diethanolamine, and water softeners such as sodium hexametaphosphate, sodium tripolyphosphate, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid. etc. may be included. The color developing solution or activator solution used in the present invention may contain an auxiliary developer. As such an auxiliary developer, 1-aryl-3-pyrazolindone derivatives are preferred, and the amount is 1 mg to 1 mg per color developer or activator solution.
g, preferably in the range of 10 mg to 500 mg. Typical auxiliary developers include 1-phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-
Phenyl-3-pyrazolidone, 4-methyl-4-
Hydroxymethyl-1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-
(p-tolyl)-3-pyrazolidone and the like. The color developing solution or activator solution used in the present invention is kept alkaline according to a conventional method, and its hydroxyl ion concentration is determined by the type of negative photosensitive material used in the present invention or color photosensitive material for printing to be processed. The pH can be selected as appropriate depending on the composition, purpose, and use, but the pH is generally 9.5 to 13.5. The color developing solution or activator solution used in the present invention is generally used within a certain temperature range. The temperature range can be appropriately selected depending on the type, composition, use, purpose, etc. of the color photosensitive material for printing according to the present invention to be processed, and is 15°C to 70°C.
is preferable, and 30°C to 50°C is more preferable. As the bleaching agent used in the bleaching or bleach-fixing bath, known compounds can be used, such as ferric complex salts of aminopolycarboxylic acids such as ferric sodium ethylenediaminetetraacetate and ferric ammonium ethylenediaminotetraacetate; Persulfates such as ammonium persulfate and sodium persulfate can be used. Further, as the fixing agent used in the fixing or bleach-fixing bath, known compounds can be used, such as thiosulfates such as sodium thiosulfate and ammonium thiosulfate, 3,6-dithia-
Water-soluble sulfur-containing diols such as 1,8-octanediol, 3,6,9,12-tetrathia-1,14-tetradecanediol, water-soluble sulfur such as ethylene bis-thioglycolic acid, ethylene bis-thioglycolic acid sodium salt, etc. Containing dibasic acids, etc. can be used. Specific Effects of the Present Invention When the present invention is applied to color photosensitive materials for printing, prints with excellent sharpness, color reproducibility, and whiteness can be obtained, that is, the quality of printed images can be significantly improved. Moreover, at the same time, the sensitivity of the photosensitive material can be increased and the change in sensitivity due to aging after production of the photosensitive material is small, and workability in the laboratory can be greatly improved. The present inventors confirmed the above effects of the present invention through Examples. Some examples are shown below. EXAMPLES Next, the present invention will be specifically explained using examples. Note that the present invention is not limited to the illustrated embodiments. Example 1 Color sensitive materials for printing (color photographic paper) were prepared as described in (1) below, and after imagewise exposure of these photographic papers, they were processed using the following color developer and bleach-fix solution. Performance was measured for each dye image formed. (1) Production of color photographic paper A paper support whose surface is coated with polyethylene containing anatase-type titanium oxide as a white pigment is pretreated with gelatin undercoating, and then the following layers are sequentially coated. Color photographic paper was produced. Layer 1: Blue-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 5 mol% of silver chloride, and the following yellow couplers (Y-1) and 2,
Coating was performed using an emulsified dispersion prepared by dissolving 5-di-tert-octylhydroquinone in dioctyl phthalate. Layer 2: First intermediate layer It was coated using an emulsified dispersion prepared by dissolving 2,5-di-tert-octylhydroquinone in dioctyl phthalate. Layer 3: Green-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 15 mol% of silver chloride, and the following magenta couplers (M-1) and 2,
Coating was carried out using an emulsified dispersion prepared by dissolving 5-di-tert-octylhydroquinone in dioctyl phthalate. Layer 4: Second intermediate layer The following ultraviolet absorber (UV-1) and 2,5-
Coating was performed using an emulsified dispersion prepared by dissolving di-tert-octylhydroquinone in dioctyl phthalate. Layer 5: Red-sensitive silver chlorobromide emulsion layer It was prepared by dissolving the silver chlorobromide emulsion shown in Table 1 and the following cyan coupler (C-1) and 2,5-di-tert-octylhydroquinone in dioctyl phthalate. The emulsified dispersion and the anti-irradiation dye shown in the table were added and coated. Layer 6: Protective layer Coated mainly with gelatin and the hardening agent shown in the table. Table showing the amount of ingredients in each layer (mg amount per ^100cm2 )
Shown in 1.

【table】

[Table] Based on the above layer structure, the types and coating amounts of silver halide and anti-irradiation dye in the red-sensitive silver chlorobromide emulsion layer, anti-irradiation dye, and hardener in the protective layer are changed as shown in the table 11. Seed samples were prepared.

[Table] Samples Nos. 1 to 11 thus prepared were evaluated as shown below. Fog The unexposed sample was subjected to the following treatment, and the cyan density was measured using a Greetak D-122 densitometer. Processing process (32.8℃) Processing time Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Washing with water 3 minutes 30 seconds Drying 1 minute [Color developer composition] N-ethyl-N-β-methanesulfonamidoethyl-3 -Methyl-4-aminoaniline sulfate 4.0g Hydroxylamine sulfate 2.0g Potassium carbonate 25.0g Sodium chloride 0.1g Sodium bromide 0.2g Anhydrous sodium sulfite 2.0g Benzyl alcohol 10.0ml Polyethylene glycol (average degree of polymerization 400)
Add 3.0ml of water to 1 and adjust the pH to 10.0 using sodium hydroxide. [Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron sodium salt
60.0g Ammonium thiosulfate 100.0g Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Add water to 1 and adjust to pH 7.0 using sulfuric acid. Redox potential -70mV N-ethyl-N- in color developer in stain due to residual anti-irradiation dye in sample
A similar experiment was conducted using a solution that did not use ethyl-3-methyl-4-aminoaniline sulfate of β-methanesulfonate amidoethyl sulfate. Sensitivity change over time after sample preparation The sample was left at 25℃ and 60% for one month.
Changes in sensitivity before and after time were measured by the method shown below. The sample was subjected to optical wedge exposure, and then the processing density was measured in the same manner as above to determine the sensitivity. The above results are shown in Table.

[Table] Coloring of white background in color photosensitive materials for printing
A value up to 0.005 is acceptable, but more than that will impair whiteness. Further, the change in sensitivity before and after aging is allowed to be within 5%, and if it is more than that, the yield during printing will be significantly reduced. That is, it can be seen that only samples Nos. 5, 6, 10, and 11 of the present invention satisfy both of these characteristics. Example 2 The following samples were prepared in the same manner as in Example 1, and the performance regarding dye images was measured. A paper support whose surface was coated with polyethylene containing anatase titanium oxide as a white pigment was pretreated with gelatin subbing, and then the following layers were sequentially coated to produce color photographic paper. Layer 1: Blue-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 5 mol% of silver chloride, and the yellow couplers (Y-1) and 2,
Coating was carried out using an emulsified dispersion prepared by dissolving 5-di-tert-octylhydroquinone in dioctyl phthalate. Layer 2: First intermediate layer It was coated using an emulsified dispersion prepared by dissolving 2,5-di-tert-octylhydroquinone in dioctyl phthalate. Layer 3: Green-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 15 mol% of silver chloride, and the magenta coupler (M-1) and
Coating was carried out using an emulsified dispersion prepared by dissolving 2,5-di-tert-octylhydroquinone in dioctyl phthalate. Layer 4: Second intermediate layer The ultraviolet absorber (UV-1) and 2,5-
Coating was performed using an emulsified dispersion prepared by dissolving di-tert-octylhydroquinone in dioctyl phthalate. Layer 5: Red-sensitive silver chlorobromide emulsion layer Prepared by dissolving the silver chlorobromide emulsion shown in the table, cyan coupler (C-1) and 2,5-di-tert-octylhydroquinone in di-octyl phthalate. It was coated using an emulsified dispersion liquid. Layer 6: Third intermediate layer The ultraviolet absorber (UV-1) and 2,5-
Coating was carried out using an emulsified dispersion prepared by dissolving di-tert-octylhydroquinone in di-octyl phthalate and the anti-irradiation dye shown in the table. Layer 7: Protective layer The amount of the main components (mg amount per 100 cm ² ) of each layer coated using mainly gelatin and the hardening agent shown in the table is shown in the table.

[Table] Based on the above layer structure, the coating amount of the anti-irradiation dye in the silver halide third intermediate layer in the red-sensitive silver chlorobromide emulsion layer and the hardening agent in the protective layer is determined. Twelve types of samples shown in the table were created by changing the temperature.

【table】

[Table] The results of the same evaluation as in Example 1 for Sample Nos.-12 to 23 prepared in this manner are shown in the table.

【table】

[Table] It can be seen that samples Nos. 15 and 18 to 23 of the present invention have excellent performance in terms of whiteness and change in sensitivity over time after producing the photosensitive material. Example 3 Samples Nos. 24 to 48 shown in the table were prepared in exactly the same manner as in Example 1, and the results of the same evaluations are shown in the table. The dyes and hardeners used for comparison are shown below. As is clear from the table, sample No. according to the present invention.
34, 35 and 45-48 have less fog and stain,
It can also be seen that the sensitivity fluctuation over time is small.

【table】

[Table] The present invention can only be achieved by combining a specific silver halide, a specific anti-irradiation or filter dye, and a specific hardener.
Both of the above characteristics were solved at once. Of course, it has been confirmed that the sharpness and color reproducibility are good, although this is not shown in the example.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing silver halide having a silver chloride content of 25 mol % or more, at least A silver halide photograph characterized in that one layer contains a compound represented by the following general formula [] and is further hardened with a compound represented by the following general formula [] and/or a compound represented by the following general formula [] photosensitive material. General formula [] [In the formula, R ₁ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, a hydroxy group, an -OR group or a [Formula] group. Here, R represents an alkyl group or an aryl group, R' and R'' represent a hydrogen atom or an alkyl group or an aryl group having at least one sulfonic acid group or at least one carboxylic acid group, and R ₂ , R ₃ , R ₆ and R ₇ each represent a hydrogen atom, a carboxylic acid group, a sulfonic acid group, or an alkyl group or aryl group having at least one carboxylic acid group or sulfonic acid group.] General formula [] [In the formula, R ₉ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, [Formula] (R ₉ ′ and R ₉ ″ each represent a hydrogen atom, an alkyl group, or an aryl group.) −NHCOR ₉ (R ₉ is represents a hydrogen atom, alkyl group, aryl group, or alkylthio group) or -OM group (M is a monovalent metal atom)
, and R ₁₀ has the same meaning as R ₉ excluding the chlorine atom. ] General formula [] [In the formula, R ₁₁ and R ₁₂ are chlorine atoms, hydroxy groups,
It represents an alkyl group, an alkoxy group or an -OM group (M is a monovalent metal atom). Q, Q' are -O-, -S
-, -NH-, a linking group, and L represents an alkylene group or an arylene group. l and m represent 0 or 1. ]