JPH06123946A - Silver halide color photografic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photosensitive material excellent in the picture quarity of obtained color image, especially in sharpness and color reproducibility, and capable of making a supporting body thin and miniaturizing cartridge without damaging the picture quality. CONSTITUTION:The silver halide color photographic sensitive material is composed of at least one layer of the photosensitive silver halide emulsion layer containing an acylacetamide type coupler having an acyl group expressed by a general formula on the supporting body, and the supporting body is composed of a belt-like polyester base, and the perforation of <=4 member per 1 screen is formed on one side or both sides of the side edge, and the area of a image part is 3.0cm<2> to 7.0cm2, and an aspect ratio is 1.40 to 2.50. (In the formula, R1 is a substd. group, Q is a nonmetallic atom neccessary for forming a 3-5 ring hydrocarbon together with carbon or a 3-6 ring heterocyclic ring having at least one hetero atom selected from among N, O, S and P in a ring.).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as a color photographic film having improved image quality, particularly sharpness and color reproducibility, and having a specified screen area and number of perforations in an image exposure area, which is different from the conventional 135 format. The present invention relates to a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, the graininess, sharpness and color reproducibility of color photographic light-sensitive materials for photography (including color negatives and color reversal light-sensitive materials; hereinafter simply referred to as color negatives) have been improved, and zoom lenses or bifocal lenses have been developed. With the widespread use of cameras equipped with, the variety of photographs has been increasing.

However, in a camera equipped with a zoom lens or a bifocal lens, if the focal length on the telephoto side is extended, the camera becomes large and the portability deteriorates. On the contrary, if priority is given to downsizing the camera, a sufficient telephoto effect is obtained. It had the drawback of not having a camera.

As means for solving the above problems, attention has been paid to recent progress in the performance of color negative films in US Pat. Nos. 3,490,844, 4,583,831 and 4,650,304. Therefore, a so-called pseudo zoom method has been proposed. The pseudo-zoom method detects the focal length information of the lens that was input to the film at some stage during the shooting stage, and at the stage of printing, stretches a portion of the negative film screen, resulting in a telescopic effect. It is what

This pseudo-zoom method is currently used in 13
It is premised on a silver halide color negative roll film stored in a 5 format cartridge.

If the pseudo-zoom method is adopted, the size of the lens can be reduced by making the lens a single focal point.
It is difficult to realize an epoch-making compact camera compared to the current 135 format camera because it requires a lens having an image circle that can support the format and uses a cartridge compatible with the 135 format. Met. In addition, the pseudo zoom method is not preferable from the viewpoint of resource saving because the effective screen area / total film area ratio used at the time of making a print is reduced. Furthermore, the large variation in image quality between prints obtained from one film is one of user's complaints.
It was one.

In order to solve the above problems, it is most effective to reduce the image area of the lens by reducing the screen area of the color negative film. However, a market test on print image quality has revealed that it is not acceptable to general users unless the image quality (granularity, sharpness) of the print that deteriorates due to the reduction of the screen area of the film is improved. In particular, there was a strong demand for improvement in sharpness.

To improve the sharpness of color negative films, development inhibitor releasing compounds (so-called DIR compounds) are generally used.
Are known to have an effect. For example, the patents described in Research Disclosure (RD) 17643 VII to F, JP-A-57-151944, and JP-A-57-151944.
-154234, 60-184248, 60-
37346, U.S. Pat. No. 4,248,962 and the like. However, in the case of a small format color negative product in which the printing magnification becomes larger, the effect is insufficient when only the development inhibitor releasing compound is used.

On the other hand, in order to reduce the area of the exposed screen of the color negative film and improve the sharpness,
In addition to the above-mentioned use of the DIR compound, for example, a method of thinning the hydrophilic colloid layer of the color negative film, a method of using a dye that absorbs scattered light at the time of exposure, a method of coloring the base, or a photosensitive silver halide It has been proposed to apply a method of changing the shape of emulsion grains.

Although the introduction of these methods certainly improves the sharpness to some extent, these techniques alone are not yet satisfactory and further improvements are needed. To this end, in addition to the performance of the light-sensitive material itself, the state of the film in the camera at the time of shooting, and the deformation of the film due to long-time exposure due to high magnification enlargement when printing from a reduced screen of a color negative (for example, color The importance of taking into account

[0011]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to comprehensively consider the image quality, especially the color reproducibility in consideration of not only the photosensitive layer but also the support constituting the light-sensitive material, and further the processing form. Another object of the present invention is to provide a silver halide color photographic light-sensitive material having improved sharpness.

[0012]

In order to improve the sharpness of a color negative film, in addition to the improvement from the direct internal factors such as the use of a DIR compound and the use of a dye in the above-mentioned light-sensitive material, the indirect internal factors are improved. It can also be achieved by improvement. One of them is the “color contrast effect” relating to sharpness. In order to visually enhance sharpness by the color contrast effect, it is sufficient to increase the color purity of cyan, magenta, and yellow color images in the photographic material.

By the way, generally, as the yellow coupler, an acylacetamide coupler represented by a benzoylacetanilide coupler and a pivaloylacetanilide coupler is used. The benzoylacetamide type coupler has the excellent characteristics that the coupling activity with the aromatic primary amine developing agent at the time of development is higher than that of the pivaloylacetanilide coupler and that the yellow dye produced has a large molecular absorption coefficient. On the other hand, it has a drawback that spectral absorption on the long wavelength side (green light) is large and color image fastness during dark storage is low. The pivaloylacetamide type coupler is superior in color image fastness to the benzoylacetanilide coupler, but the coupling reactivity during development is low and the molecular extinction coefficient is small.
In order to obtain a sufficient color image density, more color-forming couplers have to be used, which is disadvantageous in terms of image quality and cost.

Further, studies have been made on the acyl group of the acylacetamide type yellow coupler.
US Patent Application No. 27,848 discloses a coupler having a 7,7-dimethylnorbornane-1-carbonyl group or a 1-methylcyclohexane-1-carbonyl group as a modification of the pivaloyl group. However, these couplers have low coupling activity, and the molecular extinction coefficient of the dye formed is small, so that they are not sufficiently satisfactory.

Further, Japanese Patent Application Laid-Open No. 47-26133 discloses a cyclopropane-1-carbonyl group, cyclohexane-1.
-Couplers having a carbonyl group are disclosed. However, these couplers were not sufficient in that the fastness of the dye formed was low and the spectral absorption characteristics were inferior.

Apart from this, as a direct external factor,
Analysis revealed that the flatness of the color negative film camera was maintained during shooting, the enlargement ratio was increased during printing, and the sharpness was deteriorated due to the flatness of the color negative when the exposure was performed for a long time. . It became clear that the major factors that impair the flatness are the hygroscopicity of the cellulose triacetate support, the curl, and the perforation number of the current 135 photographic film.
It was found that these also cause variations.

As a result of repeated studies for solving these problems, the present inventor has found that the object of the present invention can be achieved by the silver halide color photographic light-sensitive material described below.

(1) A halogen having at least one photosensitive silver halide emulsion layer containing an acylacetamide type coupler having an acyl group represented by the general formula (YI) represented by the following chemical formula 1 on a support. In a silver halide color photographic light-sensitive material, the support is made of a belt-shaped polyester base, and one or both side edges of the support is 4 per screen.
Pieces The following perforations formed and the image unit screen 3.0 cm ² or more, at 7.0 cm ² or less, the aspect ratio is 1.40 or more, the silver halide color, characterized in that it is 2.50 or less Photographic material.

General formula (YI)

[0020]

[Chemical 2] In the formula, R ₁ represents a substituent, Q together with C is a 3- to 5-membered hydrocarbon ring or a 3- to 6-membered hydrocarbon ring having at least one hetero atom selected from N, O, S, and P in the ring. Represents a group of non-metal atoms necessary to form a heterocycle.

(2) The photosensitive silver halide emulsion layer and /
Alternatively, the silver halide color photographic light-sensitive material according to (1), characterized in that the adjacent layer on the side closer to the support of the layer contains substantially non-photosensitive fine grain silver halide grains.

(3) The photosensitive silver halide emulsion layer has two or more red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers having different sensitivities, and the following (a) to (d) The silver halide color photographic light-sensitive material as described in (1), which satisfies all the conditions.

(A) The photosensitive silver halide emulsion layer provided on the side farthest from the support is the most sensitive blue-sensitive silver halide emulsion layer (BH), and (b) the most sensitive green. The sensitive silver halide emulsion layer (GH) and the most sensitive red sensitive silver halide emulsion layer (RH) are replaced by the BH and the blue sensitive silver halide emulsion layer (B) having a lower sensitivity than the BH.
h) and (c) with respect to Bh, the side farthest from the support has the least sensitive red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers (RL, GL and BL, respectively). ) Does not exist, and (d) has a non-photosensitive layer adjacent to the BH, and the BH and / or the non-photosensitive layer contains substantially non-photosensitive fine silver halide grains.

European Patent No. 447969A and US Pat. No. 5,118,599 describe couplers having an acyl group represented by the above general formula (YI), but the number of perforations as a support or a photographic film is not limited. There is no description about the screen size of the exposure unit.

The present invention will be described in more detail below.

First, the polyester base used for the support of the silver halide color photographic light-sensitive material according to the present invention will be described.

As a method for reducing the curl of the polyester film, a method described in JP-A-51-16358, that is, a method of heat treatment at a temperature lower than the glass transition temperature (Tg) by 30 to 5 ° C. is known. Has been. Here, the glass transition temperature is a temperature that starts to deviate from the baseline when the sample film 10 mg is heated at 20 ° C./min in a helium-nitrogen gas flow using a differential thermal analyzer (DSC). The average temperature of the temperature that returns to the baseline. However, when an endothermic peak appears, the temperature showing the maximum value of this endothermic peak is defined as Tg.

However, when this method is wound into a large diameter (14 mm) like a conventional 135 cartridge,
When I applied it to a small diameter (10 mm), I surprisingly found that the curl reduction rate when wound with a diameter of 10 mm shows a larger value than expected when wound with a diameter of 14 mm. Found in. Here, the curl reduction rate is a value calculated by (true core set curl / absolute core set curl) × 100. The core set is to wind the film around the spool to give a curl, and the core set curl means a curl in the length direction attached by the core set. The degree of winding is ANSI /
Test Meth of ASC PH1.29-1985
It is measured according to od A and is expressed as 1 / R [m] (R is the radius of the curl). True core set curl is (absolute core set curl)-(controlled core set curl)
The absolute core set curl is the core set curl of the photographic film before the curl improvement, and the controlled core set curl is the core set curl of the photographic film after the curl improvement. means.

This effect is desired to be achieved by heat treatment at a temperature as high as possible in a short time, but this effect disappears when Tg is exceeded. This effect becomes substantially remarkable at 50 ° C. or higher. Therefore, it is desirable to perform the heat treatment at a temperature between 50 ° C. and Tg.

The effect is exhibited when the processing time is 0.1 hours or more. The effect increases as the length increases, but the effect saturates after 1500 hours.

Further, since the effect disappears when exposed to a temperature of Tg or higher, this heat treatment is carried out by undercoating,
It is desirable to carry out between coating of the back layer and coating of the emulsion. This is because the support is usually 180
This is because the Tg of many general-purpose polyesters is lower than this value, although it is processed at a high temperature of ℃ or higher. Further, since this heat treatment is carried out at a high temperature of 50 ° C. or higher for a long time, if it is carried out after the emulsion is coated, it may cause deterioration of the performance of the emulsion layer. Therefore, it is desirable to do it before coating the emulsion layer.

As mentioned above, this effect disappears when exposed to temperatures above Tg. Therefore, the temperature in a passenger car under the sunshine in summer rises to nearly 90 ° C. Considering the actual conditions of use by such users, the Tg of 90 ° C or higher is considered.
It is preferable to have

On the other hand, there is no general-purpose, transparent polyester having a Tg exceeding 200 ° C. Therefore, the preferable Tg is 90 ° C. or higher and 200 ° C. or lower.

Used as a support in the present invention,
The polyester having a glass transition temperature of 90 ° C. or higher can be formed from, for example, a diol and a dicarboxylic acid. At this time, examples of usable dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, and maleic anhydride. Acid, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride, diphenylene p, p'-dicarboxylic acid, tetrachlorophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid,

[0035]

[Chemical 3]

[0036]

[Chemical 4] Can be mentioned.

Examples of usable diols include ethylene glycol, 1,3-propanediol, 1,2
-Propanediol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 1,
7-heptanediol, 1,8-octanediol,
1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1-cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4-benzenedimethanol,

[0038]

[Chemical 5]

[0039]

[Chemical 6] Can be mentioned.

If desired, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized.

In the polyester used in the present invention, a compound having a hydroxyl group and a carboxyl group (or its ester) at the same time in the molecule may be copolymerized.

The following are examples of such compounds.

[0043]

[Chemical 7] Among the polyesters composed of these diols and dicarboxylic acids, more preferred are polyethylene,
Homopolymers such as 2,6-dinaphthalate (PEN), polyacrylate (PAr), polycyclohexanedimethanol terephthalate (PCT), and 2,6-naphthalenedicarboxylic acid (ND) as dicarboxylic acid
CA), terephthalic acid (TPA), isophthalic acid (IP
A), orthophthalic acid (OPA), cyclohexanedicarboxylic acid (CHDC), paraphenylenedicarboxylic acid (PPDC), as a diol, ethylene glycol (EG), cyclohexanedimethanol (CHDM),
Neopentyl glycol (NPG), Bisphenol A
(BPA), biphenol (BP), parahydroxybenzoic acid (PHBA) as hydroxycarboxylic acid,
6-Hydroxy-2-naphthalenecarboxylic acid (HNC
The thing which copolymerized A) is mentioned. More preferred among these are naphthalene dicarboxylic acid, copolymers of terephthalic acid and ethylene glycol (mixing molar ratio of naphthalene dicarboxylic acid and terephthalic acid is 0.
It is preferably between 3: 0.7 and 1: 0, and 0.5: 0.
5 to 0.8: 0.2 is more preferable. ), A copolymer of terephthalic acid, ethylene glycol and bisphenol A (the mixing molar ratio of ethylene glycol and bisphenol A is preferably between 0.6: 0.4 and 0: 0.1, more preferably 0.5: 0.5). 0.1 to 0.9 is preferable), isophthalic acid, para-phenylenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of para-phenylenedicarboxylic acid is 1 terephthalic acid).
0.1 to 10.0, 0.1 to 20.
0, and more preferably 0.2 to 5.0 and 0.2, respectively.
.About.10.0), naphthalenedicarboxylic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is preferably 1: 0 to 0.7: 0.3, more preferably 0. 9: 0.1-0.6: 0.4) terephthalic acid,
Copolymer of ethylene glycol and biphenol (The molar ratio of ethylene glycol and biphenol is 0: 1.0.
.About.0.8: 0.2 is preferable, and more preferably 0.
It is 1: 0.9 to 0.7: 0.3. ), Para-hydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of para-hydroxybenzoic acid and ethylene glycol is preferably from 100: 0 to 0.1: 0.9, more preferably 0.9: 0). 0.1 to 0.2: 0.8), and PEN and PET.
(A composition ratio of 0.3: 0.7 to 1.0: 0 is preferable, and 0.
5: 0.5 to 0.8: 0.2 is more preferable), PET
And PAr (composition ratio 0.6: 0.4 to 0: 1.0 is preferable, 0.5: 0.5 to 0.1: 0.9 is more preferable)
Polymer blends such as

PEN is the most balanced of these polyesters, has a mechanical strength, particularly a high elastic modulus, and has a sufficiently high glass transition temperature of about 120 ° C.
However, it has the drawback of emitting fluorescence. On the other hand, P
CT has a high mechanical strength and a glass transition temperature as high as around 110 ° C., but has an extremely high crystallization rate, and has a drawback that it is difficult to obtain a transparent film. PAr has the highest glass transition temperature (190 ° C.) of these polymers, but has the disadvantage that mechanical strength is weaker than that of PET. Therefore, in order to make up for these drawbacks, it is preferable to use a blend of these polymers or a copolymer of the monomers forming them.

These homopolymers and copolymers can be synthesized according to conventionally known methods for producing polyesters. For example, when an acid component is directly esterified with a glycol component, or when a dialkyl ester is used as the acid component, first, an ester exchange reaction with the glycol component is performed, and this is heated under reduced pressure to remove excess glycol component. It can be synthesized by removing. Alternatively, the acid component may be an acid halide and reacted with glycol. At this time, if necessary, a transesterification reaction catalyst, a polymerization reaction catalyst, or a heat resistance stabilizer may be added. Regarding these polyester synthesis methods, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pp. 103-136.
Page, "Synthetic Polymer V" (Asakura Shoten, 1971), 18th
It can be performed with reference to the descriptions on pages 7 to 286.

The preferred average molecular weight range for these polyesters is about 10,000 to 500,000.

Polymer blends of the polymers thus obtained are disclosed in JP-A-49-5482 and JP-A-64-5482.
4325, JP-A-3-192718, Research Disclosure 283, 739-41, 284, 779.
-82, 294, 807-14, it can be easily formed.

Next, examples of preferable specific compounds of the polyester used in the present invention are shown, but the present invention is not limited thereto. Example of polyester compound Homopolymer PEN: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] Tg = 119 ° C. PCT: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) ) (100/100)] Tg = 93 ° C. PAr: [TPA / bisphenol A (BPA) (100/100)] Tg = 192 ° C. Copolymer (() represents a molar ratio.) PBC-12 , 6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. PBC-2 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C. PBC-3 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C. PBC-4 TPA / EG / BPA (100/50 50) Tg = 105 ° C. PBC-5 TPA / EG / BPA (100/25/75) Tg = 135 ° C. PBC-6 TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. PBC- 7 IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 ° C. PBC-8 NDCA / NPG / EG (100/70/30) Tg = 105 ° C. PBC-9 TPA / EG / BP (100 / 20/20) Tg = 115 ° C. PBC-10 PHBA / EG / TPA (200/100/100) Tg = 125 ° C. Polymer blend (() represents weight ratio.) PBB-1 PEN / PET (60 / 40) Tg = 95 ° C. PBB-2 PEN / PET (80/20) Tg = 104 ° C. PBB-3 PAr / PEN (50/50) Tg = 42 ° C. PBB-4 PAr / PCT (50/50) Tg = 118 ° C. PBB-5 PAr / PET (60/40) Tg = 101 ° C. PBB-6 PEN / PET / PAr (50/25/25) Tg = 108 All polyesters above ℃ are triacetyl cellulose
It has a flexural modulus higher than that of TAC, and can realize a thinner film. However, PEN has the strongest bending elasticity among these, and by using it, it is possible to reduce the film thickness of PEN to 80 μm compared to 122 μm of TAC.

The thickness of these polymer films is preferably 40 μm or more and 300 μm or less. Four
A transparent polymer film having bending elasticity capable of withstanding the shrinkage stress of the photosensitive layer at 0 μm or less has not yet existed, and if it is at least 300 μm, it is meaningless to use a fine spool. It is more preferably 40 μm or more and 150 μm or less, and particularly preferably 50 μm or more and 120 μm or less.

Further, an ultraviolet absorber may be kneaded into these polymer films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the UV absorber has no absorption in the visible region, and the amount thereof is usually 0.5% to 20% by weight, preferably about 1% to 10% by weight, based on the weight of the polymer film. Is. If it is less than 0.5% by weight, the effect of suppressing deterioration of ultraviolet rays cannot be expected. Examples of the ultraviolet absorber include 2,4-
Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, 2'-dihydroxy-
Benzophenone-based such as 4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5'-methylphenyl) benzotriazole, 2 (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-3'-t-butyl-5'
Examples include benzotriazole-based UV absorbers such as -methylphenyl) benzotriazole, salicylic acid-based UV absorbers such as phenyl salicylate and methyl salicylate.

Further, one of the properties which poses a problem when the polyester film is used as a support for a photographic light-sensitive material is the problem of fogging caused by the high refractive index of the support.

Polyester, especially aromatic polyester, has a high refractive index of 1.6 to 1.7, whereas gelatin, which is the main component of the photosensitive layer coated thereon, has a refractive index of 1.5.
It is 0 to 1.55, which is smaller than this value. Therefore, when light enters from the film edge, it is easily reflected at the interface between the base and the emulsion layer. Therefore, the polyester film causes a so-called light piping phenomenon (fogging).

As a method for avoiding such a light piping phenomenon, for example, a method in which a film contains inactive inorganic particles and a method in which a dye is added are known. The preferred method for preventing light piping in the present invention is a method by adding a dye that does not significantly increase the film haze.

The dye used for dyeing the film is not particularly limited, but the color tone is preferably gray dyeing due to the general property of the light-sensitive material, and the dye has heat resistance in the film forming temperature range of the polyester film. Those which are excellent and have excellent compatibility with polyester are preferable.

From the above viewpoints, as the dye, it is possible to achieve the object by mixing a commercially available dye for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Regarding the dyeing density, the color density in the visible light region was measured with a color densitometer manufactured by Macbeth Co., and at least 0.
It must be 01 or more. More preferably 0.
It is 03 or more.

The polyester film used in the present invention can be imparted with slipperiness depending on the use,
The slipperiness imparting means is not particularly limited, but, for example, kneading an inert inorganic compound or coating a surfactant is used as a general method.

Examples of such inert inorganic particles include Si
Examples are O ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ , talc, and kaolin. In addition to the lubricity imparted by the external particle system in which inert particles are added to the polyester synthesis reaction system, for example, the lubrication imparted by the internal particle system in which the catalyst added during the polymerization reaction of polyester is precipitated. Can be adopted.

These slipperiness imparting means are not particularly limited, but transparency is an important requirement for a support for a photographic light-sensitive material, and therefore external particles are included in the slipperiness imparting means. As the system, it is desirable to select SiO ₂ having a refractive index relatively close to that of the polyester film, or to select an internal particle system capable of relatively reducing the precipitated particle size.

Further, in the case of imparting slipperiness by kneading, a method of laminating a layer imparted with a function in order to obtain more transparency of the film is also preferable. Specific examples of the means include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die.

When these polymer films are used for the support, since each of these polymer films has a hydrophobic surface, a photographic layer comprising a protective colloid mainly containing gelatin on the support (for example, a photosensitive halogen). It is very difficult to firmly bond the silver halide emulsion layer, the intermediate layer and the filter layer). As conventional techniques attempted to overcome such difficulties, (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment , A method for surface activation treatment such as mixed acid treatment or ozone oxidation treatment, and then directly applying a photographic emulsion to obtain adhesive strength, and (2) after these surface treatments once or without surface treatment, A method of providing a subbing layer and coating a photographic emulsion layer thereon (for example, US Pat. No. 2,698,241,
2,764,520, 2,864,755, 3,462,335, 3,475,193, 3,143,421, 3,501,301, 3 , 460,944, 3,674,531, British Patents 788,365, 804,005, 89.
No. 1,469, Japanese Patent Publication No. 48-43122, No. 51-4
No. 46).

In all of these surface treatments, the surface of the support, which was originally hydrophobic, is made to have some polar groups, or the crosslink density of the surface is increased, and as a result, it is contained in the undercoat liquid. It is conceivable that the affinity of the component to be treated with the polar group is increased, or that the fastness of the adhesive surface is increased. In addition, various arrangements have been made for the composition of the undercoat layer. A layer that adheres well to the support (hereinafter referred to as the first undercoat layer) is provided as the first layer, and a second layer is used as a photograph. A so-called multi-layer method of applying a hydrophilic resin layer (hereinafter, abbreviated as the second undercoat layer) that adheres well to a layer, and a single layer of applying a single resin layer containing both a hydrophobic group and a hydrophilic group There is a law.

Among the surface treatments of (1) above, the corona discharge treatment is the most well known method, and any of the conventionally known methods, for example, Japanese Patent Publication Nos. 48-5043 and 47.
-51905, JP-A-47-28067, 49-
83767, 51-41770, 51-131.
It can be achieved by the method disclosed in No. 576. The discharge frequency is 50 Hz to 5000 kHz, preferably 5 kHz to several hundreds kHz. If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, which is not preferable. On the other hand, if the frequency is too high, a special device for impedance matching is required, and the cost of the device becomes high, which is not preferable. Regarding the treatment strength of the object to be treated, 0.001 KV · A · min / m ^{2 to 5} KV · A for improving the wettability of plastic films such as ordinary polyester and polyolefin.
Min / m ² , preferably 0.01 KV · A · min / m ² ~
1 KV · A · min / m ² is suitable. The gap clearance between the electrode and the dielectric roll is 0.5 to 2.5 mm, preferably 1.0 to 2.0 mm.

In many cases, the glow discharge treatment, which is the most effective surface treatment, is carried out by any conventionally known method, for example, Japanese Patent Publication Nos. 35-7578 and 36-103.
No. 36, No. 45-22004, No. 45-22005
Nos. 45-24040, 46-43480, U.S. Pat. Nos. 3,057,792 and 3,057,795.
Issue 3, Issue 3,179,482, Issue 3,288,638
No. 3,309,299, No. 3,424,735
No. 3, 3,462,335, 3,475,307
No. 3,761,299, British Patent 997,093
And JP-A-53-129262 can be used.

The glow discharge treatment conditions are generally pressure of 0.
005-20 Torr, preferably 0.02-2 Torr
r is suitable. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow and sparks will easily occur, which is dangerous and may damage the object to be treated. The discharge is generated by applying a high voltage between one or more pairs of metal plates or metal rods arranged in a space in a vacuum tank. This voltage is the composition of the atmosphere gas,
Although various values can be obtained depending on the pressure, in the pressure range described above, a stable steady glow discharge usually occurs between 500 and 5000V. A particularly suitable voltage range for improving the adhesion is 2000 to 4000V.

The discharge frequency is from DC to several thousand Hz, preferably 50 Hz to 2 as seen in the prior art.
0 MHz is suitable. Regarding the discharge treatment strength, 0.01 KV · A · min /
m ^{2 to 5} KV · A · min / m ² , preferably 0.15 KV
-A · min / m ^{2 to 1} KV · A · min / m ² is suitable.

Next, regarding the undercoating method (2), all of these methods have been well researched. For the first undercoating layer in the multi-layer method, for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid are used. , Itaconic acid, maleic anhydride, and many other polymers, including copolymers starting from monomers selected from
For example, polyethyleneimine, epoxy resin, grafted gelatin, and nitrocellulose have been investigated for their properties, and the second layer of the undercoat has mainly been investigated for their properties.

In the single-layer method, good adhesion is often achieved by swelling the support and interfacial mixing with the hydrophilic undercoat polymer.

Examples of the hydrophilic undercoat polymer used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Examples of the water-soluble polymer include gelatin, gelatin derivatives,
Examples thereof include casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer and maleic anhydride copolymer, and examples of the cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. As the latex polymer, for example, vinyl chloride-containing copolymer, vinylidene chloride-containing copolymer, acrylic acid ester-containing copolymer,
Examples thereof include vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable.

Examples of the compound for swelling the support used in the present invention include resorcin, chlorresorcin,
Methylresorcin, o-cresol, m-cresol,
p-cresol, phenol, o-chlorophenol,
Examples thereof include p-chlorophenol, dichlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred.

In the present invention, various gelatin hardeners can be used in the undercoat layer.

Examples of gelatin hardening agents include chromium salts (eg, chromium alum), aldehydes (eg,
Formaldehyde, glutaraldehyde), isocyanates, active halogen compounds (for example, 2,4-dichloro-6-hydroxy-S-triazine), epichlorohydrin resin can be mentioned.

In the present invention, the undercoat layer is made of SiO ₂ , T
Inorganic fine particles such as iO ₂ and matting agent or fine particles of polymethylmethacrylate copolymer (1 to 10 μm) can be contained.

In addition to the above, various additives may be contained in the undercoat liquid, if necessary. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants. In the present invention, when the undercoat liquid for the first undercoat layer is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, and chlorophenol in the undercoat liquid. However, if desired, an etching agent as described above may be contained in the base coat.

The undercoating liquid according to the present invention is a well-known coating method, for example, tip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. It can be applied by the extrusion coating method using the hopper described in the specification of 2,681,294. If desired, for example, US Pat. No. 2,761,
No. 791, No. 3,508,947, No. 2,941,8
No. 98 and No. 3,526,528, Yuji Harazaki, "Coating Engineering", page 253 (1973, published by Asakura Shoten), can coat two or more layers simultaneously. .

The binder for the back layer may be either a hydrophobic polymer or a hydrophilic polymer used in the subbing layer.

The back layer of the light-sensitive material of the present invention may contain, for example, an antistatic agent, a lubricant, a matting agent, a surfactant and a dye. In the present invention, the antistatic agent used in the back layer is not particularly limited, and examples of the anionic polymer electrolyte include polymers containing a carboxylic acid and a carboxylate salt, and a sulfonate salt. -22017, Japanese Patent Publication No. 46-24159,
JP-A-51-30725, JP-A-51-129216
And JP-A-55-95942. As the cationic polymer, for example, JP-A-49-121523 and JP-A-48-911 can be used.
65 and Japanese Patent Publication No. 49-24582. Further, ionic surfactants are also anionic and cationic, and are disclosed in, for example, JP-A-49-858.
26, JP-A-49-33630, and US Pat. No. 2,99.
2,108, 3,206,312, JP-A-48-
No. 87826, Japanese Patent Publication No. 49-11567, Japanese Patent Publication No. 49
Examples thereof include compounds described in JP-A-11568 and JP-A-55-70837.

The most preferable antistatic agent for the back layer of the present invention is ZnO, TiO ₃ , SnO ₂ or Al _2.
O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO
It is fine particles of at least one crystalline metal oxide selected from the group ₃ or a composite oxide thereof.

The fine particles of the conductive crystalline oxide or its composite oxide used in the present invention have a volume resistivity of 10 ⁷
Ωcm or less, more preferably 10 ⁵ Ωcm or less.
The particle size is 0.01 to 0.7 μ, especially 0.0
It is desirable that it is 2 to 0.5 μ.

Regarding the method for producing the fine particles of the conductive crystalline metal oxide or the composite oxide used in the present invention, see JP-A-56-143430 and JP-A-60-2585.
No. 41 is described in detail. For example, 1) a method in which metal oxide fine particles are produced by firing and heat treatment is performed in the presence of a heteroatom that improves conductivity, 2) a method for improving conductivity when producing metal oxide fine particles by firing. A method of coexisting different kinds of atoms, 3) a method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere when producing the metal fine particles by firing are easy. Examples of heteroatoms include Al for ZnO, N for In, and TiO ₂ .
Examples thereof include Sb, Nb and halogen elements for b, Ta and SnO ₂ . The addition amount of the hetero atom is preferably in the range of 0.01 to 30 mol%, and particularly preferably 0.1 to 10 mol%.

Next, the perforation number, screen, and image area in the silver halide color photographic light-sensitive material of the present invention will be described with reference to the drawings.

The silver halide color photographic light-sensitive material of the present invention forms perforations on one or both side edges in the lengthwise direction of a roll-shaped support. It is also possible to form a perforation only on one side and record information on the photosensitive material manufacturing and exposure conditions at the time of photographing, for example, magnetically or optically on the other side. In the case where the application is provided on both side edges, the above-mentioned information may be recorded between the perforations.

Examples of the structure of such a photosensitive material are shown in FIGS.

FIGS. 1 to 8 are plan views partially showing examples of the film according to the present invention, and FIG. 9 is FIGS.
It is a figure which shows the cross section of the thickness direction of the film shown in FIG.

As shown in FIGS. 1 to 8, the film is a strip-shaped long object, and a screen (image portion) 1 formed by photographing (exposure) and both end portions of the screen 1 in the film width direction. And frame portions 2 and 3 respectively formed in the. The frame portions 2 and 3 preferably function as an information recording portion, and for example, an optical information recording portion or a magnetic recording portion including a magnetic layer is formed. Specifically, the frame portion 2 can be provided with a magnetic recording track 4 along the longitudinal direction of the film F. As shown in FIG. 9, the magnetic recording track 4 is formed by coating a magnetic material 7 on the surface of the film F opposite to the surface on which the hydrophilic colloid layer 8 is provided. It can also be formed on the surface on which the layer 8 is provided. Further, the magnetic recording track 4 may be provided on the frame portion 3 or both side edge portions (frame portions 2 and 3). The magnetic recording track 4 is, for example, a maker at the time of film production, photographing, or film processing.
Name, film type, manufacturing date, film-specific information such as frame number, shooting date, presence / absence of flash, shutter speed, shooting information such as lens aperture, color lab company name, color development Laboratory processing information (hereinafter referred to simply as information) such as processing prescription name, developing device name, processing date, processing person in charge, and exposure condition for color paper is 1
Magnetic recording is performed for each film or image of a book.

When the information recorded on the magnetic recording track 4 is read, the film F is conveyed in the longitudinal direction and the reading means, for example, a magnetic head is brought into contact with the magnetic recording track 4 to read the information as an electric signal. You can take it out.

On the other hand, the frame portion 3 is provided with perforations (holes) 5 for feeding and aligning the film in the camera or the like.

In this case, it is preferable to reduce the number of perforations. Current cameras use perforation for film transport, but other film transport mechanisms that do not use perforation are used to provide only the number of perforations required for positioning within the camera or printer. If left, the number of perforations can be reduced. The preferable number of perforations is 1 to 4 per screen (S ₁ ), and the particularly preferable number is 1 or 2 per screen. Here, one screen corresponds to A × B in the film shown in FIG.

In the present invention, perforation 5 is used.
Is a film F as shown in FIGS.
Provided on the frame portions 2 or 3 formed on the side edges in the width direction of the frame, or may be provided on both the frame portions 2 and 3 as shown in FIGS. 3, 5, 7 and 8. .

The shape of the perforations is not particularly limited, and various shapes, for example, squares such as squares and hexagons as shown in FIGS. -The corners of the forations may be curves with a certain radius of curvature) or circular as shown in Figures 3 and 8 (may be elliptical or other circular variants). Can be applied. When a plurality of perforations are provided on one screen, the shapes of the plurality of perforations are:
It may be the same as shown in Figures 3, 4 and 8 or may be different as shown in Figures 5, 6 and 7.

The size of the perforation is not limited, either, but it is preferable that it is smaller from the viewpoint that the frame portions 2 and 3 function as the information recording portion. The ratio of the total area of perforations is the area of one screen (A × B = S ₁ shown in FIG. 2)
Is 5% or less, preferably 3% or less,
It is particularly preferably 2% or less and 0.1% or more.

Further, in order to secure the area of the optical or magnetic information recording portion, the area of the image portion (exposure portion screen) is set to 3 cm ² or more and 7 cm ² or less in the present invention. 4.0 cm ² or more, it is preferable that 6.0 cm ² or less.

The length of the strip-shaped long film F is 200.
cm or less, preferably 180 cm or less, and particularly preferably 165 cm or less. Conversely, film F
The lower limit of the length is 40 cm. The width of the film F is 35 mm or less, preferably 32 mm or less, 1
0 mm or more, particularly preferably 30 mm or less, 15
mm or more.

On the other hand, as a result of various investigations, if prints of the following three kinds of aspect ratios (ratio of horizontal length / vertical length of image part) can be provided, variations in the composition of photographs are greatly increased. Have been found to increase. The three types of aspect ratios are the following three. (1) Low aspect ratio 1.40 to 1.60 (2) Medium aspect ratio 1.70 to 1.90 (3) High aspect ratio 2.00 to 3.00 Needless to say, even if the types of prints are increased. good.

When the aspect ratio (b / a ratio in FIG. 2) of the image portion (exposure portion screen) of the color negative film is adjusted to the above-mentioned print of medium aspect ratio (2), it is compared with the conventional product. It is possible to improve the print quality by lowering the enlargement ratio of panorama print (high aspect ratio print). Therefore, in the present invention,
The aspect ratio of the image portion of the color negative film is 1.40.
It is preferably in the range of 1.50 to 2.50, more preferably in the range of 1.60 to 2.20, and most preferably in the range of 1.70 to 1.90.

It is preferable to set the aspect ratio to a value close to the aspect ratio of HDTV (1.78) because the silver salt photographic system and the electronic imaging system can be smoothly hybridized. That is, the most preferable aspect ratio value is 1.7.
5 to 1.85.

On the other hand, considering that a high aspect ratio print has a high enlargement ratio, in order to maintain the print image quality, the area of one screen of the image area is 3.0 cm ^2.
The above is desirable. However, if the area exceeds the area of the image portion of the current 135 film, the patrone or camera becomes large, which is not preferable. Therefore, the area of one screen of the image part is 3.0 cm ² or more and 8.6 cm ² or less.

As described above, in order to maintain the area of the optical or magnetic information recording portion, it is desirable that the upper limit of the area is low, and it is also desirable for the miniaturization of the cartridge for accommodating the film. However, it is difficult to achieve the effects of the present invention and achieve the object when the image area is made smaller than the existing half size. Therefore, the area of the image portion is 3.0 cm ² or more, is set to 7.0 cm ² or less, particularly preferably 4.0 cm ² or more, 6.0 cm ²
It is the following.

Further, in order to secure the area of the optically or magnetically recorded information portion, the area (A × b) of the image portion (a × b) with respect to the area (S ₁ ) of one screen A × B shown in FIG. S ₂ ratio) (S ₂ / S ₁₎ is 0.25 or more, 0.90
The following is preferable. In order to reduce the image area and the size of the image plane and the camera or the camera, S ₂ / S ₁ is preferably 0.50 or more and 0.90 or less, more preferably 0.60 or more and 0.80 or less, Particularly preferably 0.65
As described above, it is 0.75 or less.

The above-mentioned light-sensitive material using the polyester support according to the present invention is preferably used as a color photographic light-sensitive material for photographing. Particularly preferred is the use as a color negative photographic light-sensitive material for photography.

The image area is 3.0 cm ² or more,
With the small format of 7.0 cm ² or less, it is important to maintain the flatness of the film during shooting. When the flatness is impaired, it leads to poor focus, and especially when printing from a small format negative film, the enlargement ratio becomes large. It becomes a big obstacle. Therefore, it is particularly preferable to use a light-tight cartridge provided with an attitude control mechanism and preventing light fog, and a camera adapted thereto, as disclosed in, for example, Japanese Patent Laid-Open No. 3-089341.

Further, the image area is 3.0 cm ² or more,
The aspect ratio can be changed in the range of 1.40 to 2.50 while the image is kept at 7.0 cm ² or less. For example, the means / mechanism described in Japanese Utility Model Application No. 3-072779 can be photographed. Color sensitive materials can also be loaded into the camera.

Next, the acylacetamide type yellow coupler having an acyl group represented by formula (YI) used in the present invention will be described in more detail.

The acylacetamide type yellow coupler used in the present invention is preferably represented by the following general formula (YII).
Is represented by General formula (YII)

[0105]

[Chemical 8] In the general formula (YII), R ₁ represents a substituent excluding a hydrogen atom, Q represents a 3- to 5-membered hydrocarbon ring together with C or at least one hetero atom selected from N, S, O and P in the ring. R ₂ is a hydrogen atom or a halogen atom (F, Cl, B), which is a group of non-metal atoms necessary to form a 3- to 6-membered heterocycle.
r, I), an alkoxy group, an aryloxy group, an alkyl group or an amino group, R ₃ is a group capable of substituting on the benzene ring, and X is a hydrogen atom or an oxidized product of an aromatic primary amine developer. A group capable of splitting off by a coupling reaction (hereinafter referred to as splitting group) represents k and an integer of 0 to 4, respectively.
However, when k is plural, plural R ₃ may be the same or different. R ₁ is preferably an organic residue containing no metal atom, and more preferably a hydrocarbon group which may have a substituent. In the following description of the acylacetamide type yellow coupler of the present invention, the halogen atom means F, Cl, Br or I.

Here, as an example of R ₃ , a halogen atom,
Alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonyl group, aryloxysulfonyl group, acyloxy group, nitro group, heterocyclic group, cyano group, acyl group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy Examples of the leaving group include a heterocyclic group bonded to the coupling active position at a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, and a heterocyclic group. There are ring thio groups and halogen atoms.

In formula (YII), when the substituent is an alkyl group or contains an alkyl group, the alkyl group is linear, branched or cyclic, unless otherwise specified. Or an alkyl group which may contain an unsaturated bond (for example, methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl,
2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, allyl, 3-cyclohexenyl, oleyl, benzyl, trifluoromethyl,
Hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, phenoxyethyl).

In formula (YII), when the substituent is an aryl group or contains an aryl group, the aryl group may be a monocyclic or complex aryl group which may be substituted (unless otherwise specified). For example, phenyl, 1-naphthyl, p-tolyl, o-tolyl, p-chlorophenyl,
4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl, pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecylphenyl, 2,4-di-t-pentylphenyl, p-
Methanesulfonamidophenyl, 3,4-dichlorophenyl).

In formula (YII), when the substituent is a heterocyclic group or contains a heterocyclic ring, the heterocyclic group is selected from O, N, S, P, Se and Te unless otherwise specified. A 3- to 8-membered optionally substituted monocyclic or condensed-ring heterocyclic group containing at least one hetero atom in the ring (for example, 2-furyl, 2-pyridyl, 4-pyridyl,
1-pyrazolyl, 1-imidazolyl, 1-benzotriazolyl, 2-benzotriazolyl, succinimide, phthalimide, 1-benzyl-2,4-imidazolidindione-3-yl) is meant.

The substituents preferably used in formula (YII) are described below.

In the general formula (YII), R ₁ is preferably a halogen atom, a cyano group or a monovalent group having a total carbon number (hereinafter abbreviated as C number) 1 to 30 which may be substituted (for example, C number). , An alkyl group, an alkoxy group, an alkylthio group) or a monovalent group having a C number of 6 to 30 (for example, an aryl group, an aryloxy group, an arylthio group), and the substituent thereof is, for example, a halogen atom, There are alkyl groups, alkoxy groups, nitro groups, amino groups, carbonamide groups, sulfonamide groups, and acyl groups. R ₁ may be a so-called ballast group. When Q together with C forms a heterocycle having at least one heteroatom selected from N, O, S and P in the ring, R ₁ is Q
May combine with to form a bicyclo ring.

In the general formula (YII), Q is preferably C together with C which may be substituted with any of 3 to 5 members.
A hydrocarbon ring of the number 3 to 30 or at least one N, S,
C number 2-3 containing a hetero atom selected from O and P in the ring
Represents a group of non-metal atoms necessary to form a 0 heterocycle. The ring formed by Q together with C may contain an unsaturated bond in the ring, and may be substituted or unsubstituted. Examples of the ring formed by Q together with C include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopropene ring, cyclobutene ring, cyclopentene ring, oxetane ring, oxolane ring, oxane ring, 1,3-dioxolane ring, dioxane ( 1,3- or 1,4-) ring, thietane ring, thiolane ring, thiane ring, 1,3-dithiolane ring, dithiane (1,3- or 1,4-) ring, 1,4-
There are oxathian ring and pyrrolidine ring. Examples of the substituent are the same as those described for R ₃ , but they may be further substituted with an oxo group (═O), or the substituents may be bonded to each other to form a ring.

In the general formula (YII), R ₂ is preferably a halogen atom, an optionally substituted alkoxy group having 1 to 30 C atoms, an aryloxy group having 6 to 30 C atoms, or 1 to C atoms. It represents an alkyl group of 30 or an amino group having a C number of 0 to 30, and the substituent thereof is, for example, a halogen atom, an alkyl group, an alkoxy group or an aryloxy group.

In the general formula (YII), R ₃ is preferably a halogen atom, which may have a C number of 1-3.
0 alkyl group, 6-30 C aryl group, 1-C number
30 alkoxy groups, C2-30 alkoxycarbonyl groups, C7-30 aryloxycarbonyl groups,
Carboxamide group having 1 to 30 C number, sulfonamide group having 1 to 30 C number, carbamoyl group having 1 to 30 C number, 0 number of C
To 30 sulfamoyl group, C 1-30 alkylsulfonyl group, C 6-30 arylsulfonyl group, C
An ureido group having a number of 1 to 30, a sulfamoylamino group having a C number of 0 to 30, an alkoxycarbonylamino group having a C number of 2 to 30, a heterocyclic group having a C number of 1 to 30, an acyl group having a C number of 1 to 30, It represents an alkylsulfonyloxy group having a C number of 1 to 30, an arylsulfonyloxy group having a C number of 6 to 30, and the substituent thereof is, for example, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group. , Heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, acyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoyl Amino group, ureido group, cyano group, nitro group, acyloxy group, alkoxycarbonyl group, Lumpur aryloxycarbonyl group, an alkylsulfonyloxy group, an arylsulfonyloxy group.

In the general formula (YII), k preferably represents an integer of 1 or 2, and the substitution position of R ₃ is preferably meta or para to the acylacetamido group.

In formula (YII), X preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position with a nitrogen atom.

When X represents a heterocyclic group, X is preferably a 5- to 7-membered monocyclic or condensed-ring heterocyclic group which may be substituted, and examples thereof include succinimide,
Maleinimide, phthalimide, diglycolimide,
Pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-
Dione, thiazolidine-2,4-dione, imidazolidin-2-one, oxazolidin-2-one, thiazolidin-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5
On, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-
3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,4
-Thiazolidin-4-one, these heterocycles being optionally substituted.

Examples of the substituents of these heterocycles include halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, sulfo group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group. Group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, There is a sulfamoylamino group.

When X represents an aryloxy group, X preferably represents an aryloxy group having a C number of 6 to 30,
It may be substituted with a group selected from the substituent group mentioned when X is a heterocycle. The substituent of the aryloxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group,
An arylsulfonyl group or a cyano group is preferable.

Next, the substituents particularly preferably used in formula (YII) will be described.

R ₁ is particularly preferably an alkyl group having a C number of 1 to 30 (eg methyl, ethyl, n-propyl, n-).
(Butyl, isobutyl, n-octyl, n-dodecyl, phenoxymethyl, phenylthiomethyl, p-toluenesulfonylmethyl, benzyl, cyclohexylmethyl, methoxyethyl), most preferably an alkyl group having 1 to 4 C atoms. .

Q is particularly preferably a group of non-metal atoms whose ring formed with C forms a 3- to 5-membered hydrocarbon ring,
For example, it is an ethylene group, a trimethylene group, or a tetramethylene group, both of which may be substituted. Here, as the substituent, for example, an alkyl group, an alkoxy group,
There are aryl groups and halogen atoms.

Q is most preferably a substituted or unsubstituted ethylene group.

R ₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having a C number of 1 to 6 (for example, methyl, trifluoromethyl, ethyl, isopropyl, t-butyl), an alkoxy group having a C number of 1 to 30. (For example, methoxy, ethoxy, methoxyethoxy, butoxy, hexadecyloxy), or an aryloxy group having a C number of 6 to 24 (for example, phenoxy group, p-tolyloxy, p-methoxyphenoxy), most preferably a chlorine atom. , A methoxy group or a trifluoromethyl group.

R ₃ is particularly preferably a halogen atom,
Cyano group, trifluoromethyl group, alkoxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group or sulfamoyl group, most preferably chlorine atom, alkoxy group, alkoxycarbonyl group, sulfamoyl A group, a carbonamido group, or a sulfonamide group.

X is particularly preferably the following formula (Y-
1), (Y-2), or (Y-3).

[0127]

[Chemical 9]

[0128]

[Chemical 10]

[0129]

[Chemical 11] In formula (Y-1), Z is _{-O-CR 4 (R 5)} -,
_{-S-CR 4 (R 5)} -, - NR 6 -CR 4 (R 5)
_{-, - NR 6 -NR 7 -} , - NR 6 -C (= O) -, -
_{CR 4 (R 5) -CR 8} (R 9) - or -CR ₁₀ = C
Represents R ₁₁ −.

Here, R ₄ , R ₅ , R ₈ and R ₉ are a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group. the stands, R ₆ and R ₇ are a hydrogen atom, an alkyl group,
It represents an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or an aryl group. R ₁₀ and R ₁₁ may combine with each other to form a benzene ring. R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ or R
₄ and R ₈ may combine with each other to form a ring (for example, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).

Among the heterocyclic groups represented by the formula (Y-1), particularly preferable ones are those in which Z in the formula (Y-1) is-.
_{O-CR 4 (R 5)} -, - NR 6 -CR 4 (R 5) - or -NR ₆ -NR ₇ - is a heterocyclic group which is. Expression (Y
The C number of the heterocyclic group represented by -1) is 2 to 30, preferably 4 to 20, and more preferably 5 to 16.

In formula (Y-2), at least one of R ₁₂ and R ₁₃ is a halogen atom, a cyano group, a nitro group,
A group selected from a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and the other is a hydrogen atom or an alkyl group. It may be a group or an alkoxy group. R ₁₄ represents a group having the same meaning as R ₁₂ or R _13, and m represents an integer of 0-2. The C number of the aryloxy group represented by the formula (Y-2) is 6 to.
30, preferably 6 to 24, more preferably 6 to 15
Is.

In the formula (Y-3), W represents a nonmetallic atom group necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring together with N.
Here, the ring represented by formula (Y-3) may have a substituent, and preferred examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an alkyl group and an aryl group. , An amino group, an alkoxy group, an aryloxy group or a carbamoyl group. The C number of the heterocyclic group represented by the formula (Y-3) is 2 to 30, preferably 2 to 24, more preferably 2 to 16.

X is most preferably a group represented by the formula (Y-1).

The coupler represented by formula (YII) is
The substituents R ₁ , R ₂ , R ₃ , Q or X may form a dimer or a multimer which is bonded to each other through a bond or a divalent or higher valent group. in this case,
It may be out of the range of the number of carbon atoms shown in each of the above substituents.

Specific examples of the yellow coupler represented by formula (YII) are shown below.

[0137]

[Chemical 12]

[0138]

[Chemical 13]

[0139]

[Chemical 14]

[0140]

[Chemical 15]

[0141]

[Chemical 16]

[0142]

[Chemical 17]

[0143]

[Chemical 18]

[0144]

[Chemical 19]

[0145]

[Chemical 20]

[0146]

[Chemical 21]

[0147]

[Chemical formula 22]

[0148]

[Chemical formula 23]

[0149]

[Chemical formula 24]

[0150]

[Chemical 25] The yellow coupler represented by the general formula (YII) can be obtained by a conventionally known synthesis method, for example, European Patent Application (EP) 4479.
69A and US Pat. No. 5,118,599.

The coupler represented by formula (YII) can be used in any layer in the light-sensitive material. That is, any of a photosensitive layer (blue-sensitive emulsion layer, green-sensitive emulsion layer, red-sensitive emulsion layer) and a non-photosensitive layer (for example, protective layer, yellow filter layer, intermediate layer, antihalation layer) can be used. In particular, it is preferably used in a blue-sensitive emulsion layer or a non-light-sensitive layer adjacent thereto.

[0152] The preferred amount of the coupler represented by Formula (YII) is 0.05 to 5.0 mmol / m ^2, more preferably from 0.1 to 2.0 mmol / m ^2.

When the coupler represented by formula (YII) is used in the photosensitive layer, the preferred molar ratio of the coupler to silver halide is in the range of 1: 0.1 to 1: 200, more preferably It is 1: 2-1: 150. Also,
When used in the non-photosensitive layer, the molar ratio of the adjacent silver halide emulsion layers to the silver halide is preferably 1: 2 to 2.
It is 1: 200.

The coupler represented by the general formula (YII) is
Of course, they may be used alone or in combination with other yellow couplers (for example, benzoylacetanilide type yellow couplers, pivaloylacetanilide type yellow couplers, couplers described in EP 482,552A).

In the present invention, the coupler represented by the general formula (YII) exhibits high color-forming property and excellent color image fastness, but has excellent spectral absorption characteristics, in particular, small spectral absorption on the long wavelength side (green light region). By providing the above, excellent color reproducibility is imparted to the color photographic material for photographing, and in combination with this, sharpness is also improved by the color contrast effect.

Further, in the present invention, the coupler represented by the general formula (YII) is prepared by applying an oil-in-water dispersion method to prepare a fine emulsified dispersion using a high-boiling point organic solvent, which will be described later, and introducing it into a light-sensitive material. At this time, even if the amount of the high boiling point organic solvent with respect to the coupler is reduced, it has excellent performance of exhibiting high color development. Therefore, this coupler is preferably on the side farther from the support of the color photosensitive material for photographing (the side closer to the incident light).
Is used for the blue-sensitive layer, which contributes to the reduction of the film thickness and has an advantageous effect on the sharpness.

Next, the layer structure of the light-sensitive material of the present invention will be described.

The light-sensitive material of the present invention preferably has three light-sensitive layers: a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer. Further, for example, a yellow filter layer for reducing the blue sensitivity of the green-sensitive emulsion layer and the red-sensitive emulsion layer, or a same-color-sensitive layer for reducing color mixture during development between photosensitive layers having different color sensitivities. It may have a non-photosensitive layer such as an intermediate layer provided between the layers and an antihalation layer for preventing halation, and for improving color reproducibility, for example, US Pat. No. 4,663,271. , No. 4,70
5,744, 4,707,436, JP-A-62.
-160448 and 63-89850, a donor layer having a multi-layer effect having a spectral sensitivity distribution different from that of a main photosensitive layer such as a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer is adjacent to the main photosensitive layer. Alternatively, they may be arranged close to each other.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each silver halide emulsion layer. Further, JP-A-57-112751, JP-A-62-20035.
No. 0, No. 62-206541 and No. 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support, the low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (B
H) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH
/ RL, or BH / BL / GH / GL / RL / R
It can be installed in the order of H.

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, JP-A-56-25738 and 62-63.
As described in Japanese Patent No. 936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

As described in JP-B-49-15495, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a middle layer in the lower layer. A silver halide emulsion layer having a lower photosensitivity than that of the silver halide emulsion layer may be disposed, and the photosensitivity may be sequentially decreased toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In the present invention, various layer structures and layer arrangements can be selected as described above according to the purpose of each light-sensitive material.

The light-sensitive material of the present invention preferably has at least one of the above various layer constitutions and layer arrangements.
In a layer on the side close to the support adjacent to the photosensitive silver halide emulsion layer and / or the photosensitive silver halide emulsion layer,
It contains substantially non-photosensitive fine grain silver halide grains. This will be described in more detail.

Of the various layer configurations and layer arrangements described above,
Typical basic preferred examples are shown in Table 1 below.

[0167]

[Table 1] In the representative basic layer structure and layer arrangement shown in Table 1, each color-sensitive layer is shown as a two-layer structure of high sensitivity and low sensitivity, but three layers (for example, high sensitivity, medium sensitivity, (Low sensitivity) or above. In this case, for example, RH may be RH-1 and RH-2, and RL
May be RL-1 and RL-2. At this time, it is preferable to arrange the low-sensitivity layer, the medium-sensitivity layer, and the high-sensitivity layer from the side closer to the support. An intermediate layer M may be provided between RH-1 and RH-2 and between RL-1 and RL-2, if necessary.
Further, RL and RH, GL and GH, B in Example 1 in Table 1
An intermediate layer M may be provided between L and BH. Furthermore, AH
An intermediate layer may be provided between RL and RL or on the side of the YF close to the support or on the side distant from the support, and these non-photosensitive layers including a protective layer may be adjacent to each other as necessary. Can be provided.

Explaining in accordance with the representative basic layer constitution and layer arrangement shown above, the photosensitive silver halide emulsion layer is B
H, BL, GH, GL, RH, RL, at least one of these photosensitive silver halide emulsion layers and / or a layer adjacent to the photosensitive silver halide emulsion layer and close to the support. It is preferable to contain substantially non-photosensitive fine grain silver halide grains.

The layers adjacent to the support, which are adjacent to the light-sensitive silver halide emulsion layer, including the layers adjacent to the support shown in Table 1, may be provided as described above. It also includes a non-photosensitive layer such as a possible intermediate layer.

In the present invention, the light-sensitive silver halide emulsion layer containing substantially non-light-sensitive fine silver halide grains is preferably the blue-sensitive emulsion layer (BH and BL in Table 1) or the green-sensitive emulsion layer. The high sensitivity layer (GH in Table 1) and the highest sensitivity layer (RH in Table 1) of the red-sensitive emulsion layers. More preferred are blue-sensitive emulsion layers (BH and BL in Table 1). Most preferred is the most sensitive layer of the blue-sensitive emulsion layers.

The layer adjacent to the support adjacent to the light-sensitive silver halide emulsion layer is preferably a non-light-sensitive layer. The intermediate layer described above is more preferable, and the hydrophilic colloid layer containing no coupler or other compound is most preferable.

Next, the substantially non-photosensitive fine grain silver halide grain will be described.

In the present invention, substantially non-photosensitive fine grain silver halide grains are substantially non-photosensitive in that they are lower by 0.5 or more in log unit than the sensitivity of the lowest sensitive layer of the adjacent photosensitive silver halide layers. Means that. More preferably, it is lower than 1.0.

The substantially non-photosensitive fine grain silver halide grain in the present invention may be pure silver chloride, pure silver bromide, pure silver iodide, silver chlorobromide, silver iodobromide or silver chloroiodobromide. But,
Since it is preferable that these silver halide grains are not dissolved during development, it is desirable that the silver chloride content is low.
It is preferably 0 mol% or less. On the other hand, it is desirable that the content of silver bromide is high, and it is preferably 60 mol% or more. The silver iodide content is 40 mol% or less, preferably 10 mol% or less. Particularly, silver iodobromide grains having a silver iodide content of 10 mol% or less are preferable.

The particle size is not particularly limited, but is preferably 0.6 μm or less. More preferably 0.0
It is in the range of 4 to 0.4 μm. When the layer containing the substantially light-insensitive fine grain silver halide grains is a blue-sensitive emulsion layer, a blue-sensitive emulsion layer or a layer of the lowest-sensitivity blue-sensitive emulsion layer on the side closer to the support, it is preferably 0. It is in the range of 0.08 to 0.25 μm. When the layer containing the substantially non-photosensitive fine grain silver halide grains is the green-sensitive emulsion layer, the green-sensitive emulsion layer or the layer of the lowest-sensitivity green-sensitive emulsion layer closer to the support, it is preferably 0.1 to When the content layer is in the range of 0.3 μm, and the content layer is a layer closer to the support than the red-sensitive emulsion layer, the red-sensitive emulsion layer or the red-sensitive emulsion layer having the lowest sensitivity, preferably 0.1 to 0. Four
It is in the range of μm. The substantially non-photosensitive fine grain silver halide grains used in the present invention can have a relatively wide grain size distribution, but it is preferable that they have a narrow grain size distribution, especially with respect to the weight or number of silver halide grains. It is preferable that the size of particles occupying 90% is within ± 40% of the average particle size.

The coating amount of the substantially non-photosensitive fine grain silver halide grain of the present invention is 0.03 to 5.0 g, and preferably 0.05 to 1.0 g per 1 m ³ . When the layer containing the substantially non-photosensitive fine grain silver halide grains is a non-photosensitive layer other than the photosensitive emulsion layer, the binder of this layer may be any hydrophilic polymer, but gelatin is particularly preferable. The binder amount is preferably less than 250 g per 1 mol of fine grain silver halide.

The substantially non-photosensitive fine grain silver halide grain used in the present invention can be prepared by a known method. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method for reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. . As one of the simultaneous mixing methods, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a control double jet method can be used. Since this method has a narrow grain size distribution, it is preferable as a method for preparing substantially non-photosensitive fine grain silver halide grains used in the present invention.

The substantially non-photosensitive fine grain silver halide grain used in the present invention may have a regular crystal form such as a cube, an octahedron, a dodecahedron and a tetradecahedron, and may have a spherical or tabular shape. Particles having a crystal form such as Tabular grains having an aspect ratio of 2 or more are preferred.

The aspect ratio of the substantially light-insensitive tabular fine grain silver halide grain used in the present invention means the ratio of the diameter to the thickness of the silver halide grain. That is, it is a value obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter means the diameter of a circle having an area equal to the projected area of the grain when the silver halide grain is observed with an electron microscope. Therefore, an aspect ratio of 2 or more means that the diameter of this circle is twice or more the thickness of the particles.

The tabular silver halide grains used in the present invention have a grain diameter of 2 times or more the grain thickness, more preferably 2 to 15 times, more preferably 3 to 10 times, particularly preferably 4 times. ~ 8 times. The proportion of tabular grains in the projected area of all substantially non-photosensitive silver halide grains is preferably 50% or more, more preferably 70% or more, and particularly preferably 85% or more.

The tabular silver halide emulsion used in the present invention is described by Cugnac and Chateau, and Duf.
Fin “Photographic Emulsio”
nChemistry ”(published by Focal Press,
New York 1966) pp. 66-72, and A. P. H. Trivelli, W.C. F. Smith edited "Phot. Journal" 80 (1940) 28
Although it is described on page 5, for example, JP-A-58-113
927, 58-113928, 58-1279.
It can be easily prepared by referring to the method described in No. 21.

The substantially non-photosensitive fine grain silver halide grain used in the present invention may have a halogen composition in which the inside and the surface of the grain are different, or may have a uniform halogen composition. The substantially non-photosensitive silver halide grains may contain, for example, cadmium ions, lead ions, zinc ions, iridium ions, rhodium ions, thallium ions, and iron ions as impurities.

The substantially non-photosensitive fine grain silver halide grain may be a surface latent image type or an internal latent image type, and may have a fog nucleus inside.

The substantially non-photosensitive fine grain silver halide grains may be subjected to usual chemical sensitization, that is, sulfur sensitization, gold sensitization and reduction sensitization, but it is desirable to restrain the degree of chemical sensitization as much as possible. . In the present invention, an emulsion that is not chemically sensitized (so-called unripened) is preferable. The preparation method and shape of these silver halide grains will be described in more detail later.

The substantially non-photosensitive fine grain silver halide grain used in the invention may be spectrally sensitized. That is, known dyes such as cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styrene dyes and hemioxonol dyes may be included. Further, a desensitizing dye which has a large desensitization and is not preferable in a normal negative emulsion can be used.

The substantially non-photosensitive fine grain silver halide grains may contain known antifoggants and stabilizers. For example, azoles, heterocyclic mercapto compounds, thioketo compounds,
Antifoggants or stabilizers such as azaindenes, benzenethiosulfonic acids, benzenesulfinic acid can be added.

In the present invention, a dye may be added to the layer containing substantially non-photosensitive fine grain silver halide grains, or a dispersion of a slightly soluble synthetic polymer may be contained.

As described above, at least one of the acylacetamide type couplers having an acyl group represented by the general formula (YI) is replaced with at least one of the photosensitive silver halide emulsion layers.
Adjacent to the silver halide color photographic light-sensitive material of the present invention contained in a layer, at least one light-sensitive silver halide emulsion layer and / or adjacent to the light-sensitive silver halide emulsion layer, adjacent to the support. High sensitivity can be imparted and image quality (color reproducibility, sharpness) can be improved by incorporating substantially non-photosensitive fine grain silver halide grains into the layer. Moreover, in the constitution of the present invention, the stability of the light-sensitive material over time is high.

Next, the silver halide of the photosensitive silver halide emulsion layer used in the light-sensitive material of the present invention will be described.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or iodochloroodor containing about 30 mol% or less of silver iodide. It is silver oxide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), page 648, ibid. Thirty
7105 (Nov. 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemie et.
Phisique Photographique,
Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duf).
fin, Photographic Emulsion
Chemistry (Focal Press, 19
66)), "Production and Coating of Photographic Emulsions" by Zelikmann et al.,
Published by Focal Press (VL Zelikman e
tal. , Making and Coating P
photographicEmulsion, Focal
It can be prepared using the method described in Press, 1964).

For example, US Pat. No. 3,574,628
No. 3,655,394 and British Patent No. 1,41
The monodisperse emulsions described in 3,748 are also preferred.

Also, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described, for example, by Gatov, Photographic Science and Engineering (Gutoff, Photog.
radical Science and Engine
ering), Volume 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It must be a negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-
No. 133542. The thickness of the shell of this emulsion is, for example, 3 to 40, although it depends on the development process.
nm is preferred and 5-20 nm is particularly preferred.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and the same No. No. 307105, and the relevant parts are summarized in the table below.

The light-sensitive material of the present invention contains the grain size, grain size distribution, halogen composition, and
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
The thickness is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). (Having a particle size of 1).

The amount of silver coated on the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention page 24 to 25 page 649 right column 868 to 870 page agents and stabilizers 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, to page 650, left column, ultraviolet absorbers 7. Stain page 25 right column page 650 left column page 872 Inhibitor to right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder page 26 page 651 left column 873 to page 874 11. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 right column 876 to 877 inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

The light-sensitive material of the present invention can be incorporated into US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention has the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 be contained.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and the same No. 307105, VII-C to G.

Examples of the yellow coupler include, in addition to the acylacetamide type coupler having an acyl group represented by the general formula (YI) used in the present invention, for example, US Pat. Nos. 3,933,501 and 4, 022,62
No. 0, No. 4,326,024, No. 4,401,7
No. 52, No. 4,248,961, Japanese Patent Publication No. 58-10
739, British Patent Nos. 1,425,020 and 1,
476,760, U.S. Pat. No. 3,973,968,
No. 4,314,023, No. 4,511,649
No., European Patent Nos. 249,473A and 482,55.
Those described in No. 2A are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and examples thereof include US Pat. Nos. 4,310,619 and 4,35.
No. 1,897, European Patent No. 73,636, US Patent Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (198
June, 4), JP-A-60-33552, Research Disclosure No. 24230 (June 1984)
Mon), JP-A-60-43659, JP-A 61-72238.
No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Pat. No. 4,500,63.
No. 0, No. 4,540, 654, No. 4,556, 6
No. 30, those described in International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,052,212 and 4,146,396.
No. 4,228,233, No. 4,296,200
No. 2, No. 2,369,929, No. 2,801,17
No. 1, No. 2,772, 162, No. 2,895, 8
No. 26, No. 3,772,002, No. 3,758,
No. 308, No. 4,334, 011 and No. 4,32
7,173, West German Patent Publication No. 3,329,729,
European Patent Nos. 121,365A and 249,453A
U.S. Pat. Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
Those described in 690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
No. 64-554, No. 64-555, and No. 64-556.
The pyrazoloazole-based couplers described in U.S. Pat. No. 4,849,639 and the imidazole-based couplers described in U.S. Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, and European Patent 341,188A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. 30710
5, section VII-G, U.S. Pat. No. 4,163,670,
Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,9
29, 4,138,258, British Patent 1,1.
46,368, JP-A-3-177837 and EP 423,727A are preferable. Also,
The coupler described in US Pat. No. 4,774,181 which corrects unnecessary absorption of a coloring dye by the fluorescent dye released during coupling, and the reaction with the developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD1 above.
7643, VII-F section and No. 307105, V
Patents described in the section II-F, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248.
No. 63-37346, No. 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012.
No., European Patent Nos. 464,612A and 482,55.
Those described in No. 2A are preferable.

For example, R.I. D. No. 11449 and 2
The bleaching accelerator-releasing couplers described in JP-A No. 4241 and JP-A No. 61-201247 are effective for shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when added to. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
The compounds described in JP-A-45687, which release a fogging agent, a development accelerator, and a silver halide solvent by a redox reaction with an oxidized product of a developing agent are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat.
Competitive couplers as described in US Pat. No. 4,427, for example US Pat.
No. 283,472, No. 4,338,393, No. 4,310,618, and multi-equivalent couplers, such as JP-A-60-185950 and JP-A-62-24252.
REDOXOXIDE COMPOSITION RELEASE COUPLERS
R coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A and 313,30
8A, a coupler that releases a dye that undergoes color recovery after release, such as a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, and a leuco dye-releasing coupler described in JP-A-63-75747. U.S. Pat. No. 4,77
The coupler which emits the fluorescent dye described in 4,181 can be mentioned.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described, for example, in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid Esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di- - ethylhexyl phenyl phosphonate), benzoic acid esters (e.g., 2
-Ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (For example, isostearyl alcohol, oleyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, Isostearyl lactate, trioctyl citrate), aniline derivatives (eg,
N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, the boiling point is about 30 ° C.
Above, preferably, an organic solvent having a temperature of 50 ° C. or more and about 160 ° C. or less can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

The photographic material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-272.
248, and 1, described in JP-A No. 1-80941.
2-benzisothiazolin-3-one, n-butyl p
-Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various preservatives or antifungal agents such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports which can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een) and others in Photographic Science and Engineering (Photogr. Sci. E.
ng. ), Vol. 19, No. 2, can be measured by using a type of Swellometer described (swelling meter) pp 124-129, T _1/2 is 30 ° C. with a color developing solution, and treated for 3 minutes 15 seconds 90% of the maximum swollen film thickness that reaches at time is the saturated film thickness,
It is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or by changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-described conditions according to the formula: (maximum swollen film thickness-film thickness) / film thickness.

The photographic material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer preferably contains, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. .. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, page 651, left column to right column, and the same No. Thirty
The development can be carried out by a usual method described in 7105, pages 880 to 881.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
N-ethyl-β-methoxyethylaniline, 3-methyl-4-amino-described in EP 410,450A.
N-ethyl-N-4-hydroxybutylaniline, 1- (4-amino-3-ethylphenyl) -2,5-bis- (2-hydroxyethyl) pyrrolidine described in JP-A-4-11255 and their derivatives. Sulfate, hydrochloride or p
-Toluene sulfonate. Two or more of these compounds can be used in combination depending on the purpose.

The color developing solution contains, for example, a pH buffering agent such as an alkali metal carbonate, borate or phosphate,
It is common to include development inhibitors or antifoggants such as chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, for example, hydroxylamine, diethylhydroxylamine, sulfite, N, N-
Hydrazines such as biscarboxymethylhydrazine,
Various preservatives such as phenylsemicarbazides, triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye formation Coupling agents, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids ,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,
N, N-trimethylenephosphonic acid, ethylenediamine-
N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be added.

When the reversal processing is carried out, the black and white development is usually carried out before the color development. This black-and-white developer contains known black-and-white developing agents, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or amino acids such as N-methyl-p-aminophenol. Phenols can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers is
Depending on the color photographic light-sensitive material to be processed, it is generally less than 3 L (liter) per square meter of light-sensitive material,
The bromide ion concentration in the replenisher may be reduced to 500 ml or less. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-
The method using a movable lid described in 82033 and the slit development processing method described in JP-A-63-216050 can be mentioned. Reducing the aperture ratio is
It is preferable to apply not only to both the color development and the black and white development but also to the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of a color developing agent. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents are iron (III) complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid,
Complex salts of aminopolycarboxylic acids such as glycol ether diamine tetraacetic acid, citric acid, tartaric acid, or malic acid can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath.
Specific examples of useful bleaching accelerators include, for example, U.S. Pat. No. 3,893,858 and West German Patent 1,290,81.
2, No. 2,059,988, JP-A-53-3273.
No. 6, No. 53-57831, No. 53-37418,
53-72623, 53-95630, 53
-95631, No. 53-104232, No. 53-1
No. 24424, No. 53-141623, No. 53-28
No. 426, Research Declosure No. 1712
No. 9 (July 1978), compounds having a mercapto group or a disulfide group; JP-A-50-1401.
Thiazolidine derivatives described in No. 29; JP-B-45-85
06, JP-A-52-20832, and JP-A-53-3273.
5, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-5
Iodide salts described in 8-16,235; West German Patent No. 96
6,410, 2,748,430, polyoxyethylene compounds; JP-B-45-8836, polyamine compounds; and others, JP-A-49-40,943.
No. 49-59,644, and 53-94,927.
No. 54, 35-727, 55-26, 506.
No. 58-163940, and bromide ions. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858,
West German Patent No. 1,290,812, JP-A-53-95,
The compounds described in No. 630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid and hydroxyacetic acid are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Is most commonly used, with ammonium thiosulfate being the most widely used. Further, for example, a combined use of a thiosulfate solution and a thiocyanate, a thioether compound, or thiourea is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294769.
The sulfinic acid compounds described in No. A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add imidazoles such as methylimidazole in an amount of 0.1 to 10 mol / L.

The total time for the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method of strengthening the stirring, a method of causing a jet stream of a processing solution to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and a rotating means described in JP-A-62-183461 are used. To improve the stirring effect, and further to move the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution to make the emulsion surface turbulent, thereby further improving the stirring effect, the entire processing solution. There is a method of increasing the circulation flow rate of. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the development processing of the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A-191258 and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the deterioration of the performance of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the material used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent and forward flow, and various other types. It can be set in a wide range depending on the condition. Among these, the relationship between the number of washing tanks and the water amount in the multi-stage counterflow method is as follows.
tty of Motion Picture
Television Engineers, 64th
Volume, pages 248-253 (May 1955 issue). According to the multi-stage countercurrent method described in the above literature, the amount of washing water can be significantly reduced, but bacteria are propagated due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. The problem arises. In the processing of the light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. Also, isothiazolone compounds described in JP-A-57-8542, siabendazoles, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, such as those described by Hiroshi Horiguchi, "Antibacterial Control" Mold Chemistry "(1986
Sankyo Shuppan, Hygiene Society, edited by "Microbial sterilization, sterilization, and fungicide technology" (1982), Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) A bactericide can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be set variously depending on, for example, the characteristics of the light-sensitive material and the application, but generally 15 to 45 ° C. and 20 seconds to 1 are used.
A range of 0 minutes, preferably 25 to 40 ° C. and 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543,
All known methods described in JP-A-58-14834 and JP-A-60-220345 can be used.

In some cases, the washing treatment is further followed by a stabilizing treatment. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. Can be mentioned. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in another step such as a desilvering step.

For example, in the processing using an automatic processor, when each processing solution described above is concentrated by evaporation,
It is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material according to the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, No. 3,342,599, Research Disclosure No. 14, 850 and the same No. 15,159
Examples thereof include the Schiff base type compounds described in JP-A No. 13-324, the aldol compounds described in JP-A No. 13,924, the metal salt complexes described in US Pat. No. 3,719,492, and the urethane compounds described in JP-A-53-135628. .

The silver halide color light-sensitive material according to the present invention contains various kinds of 1-type dyes for the purpose of promoting color development, if necessary.
-Phenyl-3-pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339 and JP-A-57-1.
44547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

[0249]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 1) Preparation of Supports The following Supports A to D were prepared by the method described below.

Support A-1 (polyethylene naphthalate (PEN): thickness 80 μm) Support A-2 (polyethylene naphthalate (PEN):
Thickness 122 μm Support B-1 (polyethylene terephthalate (PE
T): thickness 90 μm) support C-1 (triacetyl cellulose (TAC): thickness 122 μm) supports D-1 to D-3 (PEN, PET, PAr, PC)
Mixture containing T in the proportion shown in Table 2 below: thickness 80 μm
m) Supports A-1 and A-2: commercially available polyethylene-2,
100 parts by weight of 6-naphthalate polymer and Tinuvin P.O. 2 parts by weight of 326 (manufactured by Ciba Geigy) were dried by a conventional method, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.3 times at 140 ° C., and then at 130 ° C. for 3. The film was transversely stretched 3 times and further heat-set at 250 ° C. for 6 seconds to obtain films having a thickness of 80 and 122 μm, respectively.

Support B-1: A commercially available polyethylene terephthalate polymer was biaxially stretched and heat-set according to a conventional method to obtain a film having a thickness of 90 μm.

Support C-1: Methylene chloride / methanol = 82/8 wt ratio of triacetyl cellulose, T
AC concentration 13% and plasticizer (TPP / BDP = 2 /
1: Where TPP is triphenyl phosphate, BDP
Of 15% by weight of biphenyldiphenyl phosphate) was treated by a conventional band casting method to prepare a support.

Supports D-1 to D-2: In accordance with the method for forming Support A, the mixture was kneaded and extruded at 280 ° C. using a biaxial kneading extruder, pelletized, and formed into a film having a thickness of 80 μm. . 2) Coating of undercoat layer Each of the supports A, B and D was subjected to corona discharge treatment on both sides thereof, and then provided with an undercoat layer of the following composition. For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm wide support is treated at 20 m / min. At this time, it was observed from the readings of current and voltage that the object to be treated was treated at 0.375 KV · A · min / m ² . The discharge frequency during treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 m.
It was m.

Gelatin 3 g Distilled water 250 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g For Support C, an undercoat layer having the following composition was provided.

Gelatin 0.2 g Salicylic acid 0.1 g Methanol 15 cc Acetone 85 cc Formaldehyde 0.01 g 3) Coating of back layer On the surface opposite to the side where the undercoat layer of Supports A to D after undercoating is provided, The back layer was applied by the following procedure. 3-1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid): 230 parts by weight of stannic chloride hydrate and 23 parts by weight of antimony trichloride were added to 300 parts of ethanol.
It was dissolved in 0 part by weight to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, the precipitate was washed with water by adding water and centrifuging. This operation was repeated 3 times to remove excess ions.

Colloidal precipitate 20 with excess ions removed
0 part by weight was redispersed in 1500 parts by weight of water and sprayed in a baking furnace heated to 600 ° C. to obtain a bluish average particle size of 0.2 μm.
A fine particle powder of a tin oxide-antimony oxide composite of m was obtained. The specific resistance of this fine particle powder was 25 Ω · cm.

A mixed solution of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, roughly dispersed with a stirrer, and then
Horizontal sand mill (trade name: Dyno Mill; WILLY A.
It was prepared by dispersing with BACHOFENAG) until the residence time reached 30 minutes. 3-2) Preparation of back layer: The following formulation A was used to obtain a dry film thickness of 0.
It was applied so as to have a thickness of 3 μm and dried at 130 ° C. for 30 seconds. The following coating solution (B) for coating layer was further applied thereon so that the dry film thickness was 0.1 μm, and dried at 130 ° C. for 2 minutes. [Formulation A] 10 parts by weight of the conductive fine particle dispersion liquid 1 part by weight gelatin 1 part by weight water 27 parts by weight methanol 60 parts by weight resorcin 2 parts by weight polyoxyethylene nonylphenyl ether 0.01 parts by weight [coating layer coating solution (B)] Cellulose triacetate 1 part by weight Acetone 70 parts by weight Methanol 15 parts by weight Dichloromethylene 10 parts by weight p-Chlorophenol 4 parts by weight 4) Heat treatment of the support 4) After coating the undercoat layer and the back layer by the above method, Table 2
The heat treatment was performed under the conditions shown in. All the heat treatments were carried out with the core having a diameter of 30 cm and the outer surface of the undercoat surface wound. 5) Measurement of flexural modulus The flexural modulus, which is the most important mechanical strength of the support for thinning the support, was measured. The flexural modulus was measured by a method called a ring method. That is, width 35m
A slit of 10 m in the length direction, that is, a sample cut to make a ring with a circumference of 10 cm is placed horizontally, and the load when deforming 12 mm in the diameter direction of the ring is measured and used as a guide for the bending elastic modulus. did. All the measurements were performed so that the undercoat layer was the inner circumference of the ring, and the measurement environment was 25 ° C. and the relative humidity was 60%.

The measurement results are shown in Table 2. As is clear from Table 2, the PEN was 80 μm and the PET was 90 μm, and the flexural modulus was almost equivalent to 122 μm of TAC. Further, when the thickness of PEN was increased to 122 μm as in TAC, the flexural modulus was 3 times or more that of TAC.

[0260]

[Table 2] 6) Coating of photosensitive layer On each support obtained by the above-mentioned method, each layer having the following composition was multilayer coated to prepare a multilayer color photosensitive material. The same symbols as used for the support are used as they are for the obtained multilayer color light-sensitive material. For example, a photosensitive material obtained by coating a photosensitive layer on the support A-1 becomes a multi-layer color photosensitive material A-1. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. 1st layer (antihalation layer) Black colloidal silver 0.18 gelatin 1.40 ExM-1 0.18 ExF-1 2.0x10 ^-3 HBS-1 0.20 2nd layer (intermediate layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS- 2 0.020 Gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion C Silver 0.25 ExS-1 4.5 × 10 ⁻⁴ ExS-2 1.5 × 10 ^{− 5} ExS-3 4.5 × 10 ⁻⁴ ExC-1 0.13 ExC-3 0.030 ExC-4 0.10 ExC-5 0.0050 ExC-7 0.0050 ExC-8 0.020 ExC-9 0.050 Cpd-2 0.025 BS-1 0.10 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion D silver ^{0.80 ExS-1 3.0 × 10 -4} ExS-2 1.2 × 10 -5 ExS-3 4.0 × 10 ^-4 ExC-1 0.12 ExC-2 0.060 ExC-4 0.11 ExC-7 0.0010 ExC-8 0.025 ExC-9 0.040 Cpd-2 0.023 HBS -1 0.10 Gelatin 0.75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3 0.0 × 10 ^-4 ExC-1 0.095 ExC-3 0.040 ExC-6 0.020 ExC-8 0.007 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1 .20 6th layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10 7th layer (low-sensitivity green-sensitive emulsion layer) Emulsion A Silver 0.17 Emulsion B Silver 0.17 ExS-4 4.0 × 10 ⁻⁵ ExS-5 1.8 × 10 ⁻⁴ ExS-6 6.5x10 ^-4 ExM-1 6.0x10 ^-3 ExM-2 0.130 ExM-3 5.8x10 ^-2 ExM-6 0.130 ExM-7 0.135 ExY- 1 0.015 HBS-1 0.25 HBS-3 4.0 × 10 ⁻³ HBS-4 0.15 Gelatin 0.85 Eighth layer (medium-speed green emulsion layer) Emulsion D Silver 0.80 ExS-4 2.0 × 10 ⁻⁵ ExS-5 1.4 × 10 ⁻⁴ ExS-6 5.4 × 10 ⁻⁴ ExM-2 0.060 ExM-3 0.030 ExM-6 0.065 ExM-7 0. 068 ExY-1 0.01 ExY-3 0.030 HBS-1 0.15 HBS-3 3.0 × 10 ^-3 HBS-5 0.10 Gelatin 0.90 9th layer (high sensitivity green sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ⁻⁵ ExS-5 8.1 × 10 ⁻⁵ ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.015 ExM-4 0.040 ExM-5 0.019 ExY-2 3.0 × 10 ^-3 Cpd-3 0.020 HBS-1 0.20 HBS-2 0.10 HBS-5 0.050 Gelatin 1.20 10th layer (yellow filter layer) Yellow colloidal silver 0.010 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60 Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.25 Emulsion D Silver 0.40 ExS-7 8.0 × 10 ⁻⁴ ExY-1 0.030 ExY-2 0.020 Y-23 0. 82 ExC-7 0.01 HBS-1 0.3 Gelatin 1.30 12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F silver ^{1.38 ExS-7 3.0 × 10 -4} Y-23 0.21 ExY-2 1.2 × 10 -2 HBS-1 0.070 gelatin 0.86 thirteenth layer (first protective layer) emulsion G silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00 fifteenth Layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ⁻² B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20 Furthermore, the storability, processability, pressure resistance, and mildew-proofing properties of each layer are appropriately adjusted.
To improve antibacterial property, antistatic property and coating property, W-
1 to W-4, B-4 to B-6, F-1 to F
-18 and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt are contained.

[0261]

[Table 3] In Table 3, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0262]

[Chemical formula 26]

[0263]

[Chemical 27]

[0264]

[Chemical 28]

[0265]

[Chemical 29]

[0266]

[Chemical 30]

[0267]

[Chemical 31]

[0268]

[Chemical 32]

[0269]

[Chemical 33]

[0270]

[Chemical 34]

[0271]

[Chemical 35]

[0272]

[Chemical 36]

[0273]

[Chemical 37]

[0274]

[Chemical 38]

[0275]

[Chemical Formula 39]

[0276]

[Chemical 40] Subsequently, the magenta coupler (M-13) used in the seventh layer of the green-sensitive emulsion layers of the multilayer color light-sensitive materials A-1 and C-1 was used as the comparative coupler (1) and the magenta coupler used in the eighth layer. (M-3) and (M-16) were used as comparison couplers (1) and (2), and a magenta coupler (M
-21) and (M-20) are compared with couplers (2) and (3).
A multilayer color light-sensitive material was prepared in the same manner as above, except that the same molar amounts were substituted. These multilayer color light-sensitive materials are designated as A-3 and C-2. The comparison coupler (1),
(2) and (3) are shown in Chemical formula 59.

[0277]

[Chemical 41] The produced multilayer color light-sensitive materials have a width of 35 mm, 1.
It is slit to a length of 2m and has a 2mm x 2.8mm perforation hole of 4.7 as in the current 135 format.
2m from each widthwise end of the film at 5mm intervals
The film was pierced at an interval of m, wound on a spool having a diameter of 14 mm, and stored in a 135 cartridge, to obtain a color negative film for photographing similar to the current 135. These films are group I.

Next, perforation holes of the same size were provided at a distance of 2 mm from both ends in the width direction of the film at intervals of 31.7 mm in the length direction of the film, and were wound on a spool having a diameter of 8 mm. Similarly, it was a color negative film for photography. These films are group II.

Fuji Zoom Cardia 800 (manufactured by Fuji Photo Film Co., Ltd.) was used as it was for the film of group I, and the same camera was modified for the film of group II, and the area of the image exposure part was 5.01 cm ² (30 0.0 mm
× 16.7 mm, aspect ratio 1.80), and
A mannequin (one body, one upper body) having a resolution evaluation chart and a Macbeth color checker chart installed thereon was photographed under the following photographing conditions by modifying a mechanism capable of feeding two perforations per screen. Also, using the film of group II, only the area of the image exposure part is 2.55
The same photographing was performed with a cm ² (21.4 mm × 11.9 mm, aspect ratio 1.8). This is group III.

In this shooting, when shooting the film of the group I, the distance for shooting the whole view of the main part of the subject is set in the image section (exposure section screen), and for the film of the group II and the group III, it is set. Shooting was performed with the zooming operation performed so that the entire view fits in the image section without changing the distance.

Further, in order to evaluate the color reproducibility, the color checker chart was separately photographed closer.

Conditions Light source Subject Contrast Background Others A Daylight (sunny) High trees, distant view of mountains Hinata, Sunlit B B Daylight (cloudy) Low trees, distant view of mountains C Strobe High Light gray wall Film finished Was processed according to the following color development processing step using a processing solution having the following composition. However, the treatment was carried out with a treatment liquid after 30 samples / day separately subjected to continuous (running) treatment for 30 days / day for 15 days. Each processing was carried out using an automatic processor.

The treatment steps and treatment liquid compositions are shown below. (Processing step) Processing time Processing temperature Replenishment amount * Tank capacity Color development phenomenon 3 minutes 5 seconds 38.0 ° C 23 ml 10 liters Bleach 50 seconds 38.0 ° C 5 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters Fixing 50 seconds 38.0 ° C. 16 ml 5 liters Washing with water 30 seconds 38.0 ° C. 34 ml 3.5 liters Stable (1) 20 seconds 38.0 ° C.-3 liters Stable (2) 20 seconds 38.0 ° C. 20 ml 3 Liter Drying 1 minute 30 seconds 60 ° C. * Replenishment amount per 1 m ² of light-sensitive material The stabilizing solution is a countercurrent system from (2) to (1), and the overflow solution of washing water is all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank. It was made to flow in. The amount of developing solution brought into the bleaching step, the amount of bleaching solution brought into the bleach-fixing step, the amount of bleach-fixing solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 1. 2.5 ml, 2.0 ml, 2.0 ml per meter,
It was 2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-3.3 3.3 Diphosphonic acid Sodium sulfite 3.9 5.1 Carbonic acid Potassium 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N-4.5 6 0.0 (β-hydroxyethyl) amino] aniline sulfate Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.15 (bleaching solution) Tank solution (g ) Replenisher (g) 1,3-diaminopropanetetraacetic acid 130 195 Ferric ammonium-hydrate Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 5 Acetic acid 40 60 Water was added 1.0 liter 1.0 liter pH (adjusted with ammonia water) 4.4 4.4 (Bleaching fixing tank liquid) 15:85 (volume of the bleaching tank liquid and the following fixing tank liquid) Ratio) mixture.

(PH 7.0) (Fixer) Tank solution (g) Replenisher (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution 280 ml 840 ml (700 g / l) Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water was added. 1.0 liter 1.0 liter pH (adjusted with ammonia water and acetic acid) 7.4 7.45 (wash water) Tap water is used as an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas).
And an OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through the column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by isocyanuric dichloride. Sodium acid 20 mg / liter and sodium sulfate 150 mg / liter were added. The pH of this liquid was in the range of 6.5 to 7.5. (Stabilizing liquid) Tank liquid and replenishing liquid are common (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononyl 0.2 Phenyl ether (Average degree of polymerization 10) Disodium salt of ethylenediaminetetraacetic acid 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazole 0.75-1-ylmethyl) piperazine Water was added to 1.0 liter pH 8.5 The above treatment was carried out. These color negatives thus obtained were measured using a Fuji enlarger A690 professional, with a film I group having a magnification of 5 times, a film II group having a magnification of 7 times, and a film III group having a magnification of 10 times. Printed on Super FA, TypeV. CP-45X was used for the color development processing at this time.

The obtained print was cut so that only the image portion was formed, and the sharpness was evaluated by a monitor of 10 men and women on a gray plate (reflection density 0.18) and under a fluorescent lamp for color evaluation. .

The evaluation is based on the print from the film photographed with the multilayer color light-sensitive material C-1 belonging to the group I, and two prints of this reference and other prints are arranged side by side and sequentially compared, and judged to be better than the reference. The arithmetic mean was calculated by giving +1 to those obtained, 0 to those equal or difficult to judge, and -1 to those judged to be inferior to the standard.

On the other hand, regarding the color reproducibility, the G density (λ _max 520
nm, an interference filter having a half-value width of 20 nm was used), the difference was determined by similarly using the value of the multilayer color photosensitive material C-1 as a reference, and the degree of color turbidity was examined.

Some of the results are shown in Table 4.

[0290]

[Table 4] From the results in Table 4, the film of Group II having the polyester support has a large screen (36 mm × 24 m) in terms of sharpness.
It is clear that it is superior to the current 135 format I group with m). It is considered that this is because the flatness of the exposure screen at the time of shooting is insufficient in the I group, which has a large number of perforations per screen. In fact, the fact that some monitors pointed out the blurring of the image around the print and in the center seems to support this.

On the other hand, the area of one screen of the screen exposure unit is 3 cm ²
In the following III group (2.55 cm ² ), when the enlargement ratio is increased at the time of printing to make it the same size as the previous I and II prints, the sharpness judgment is obviously inferior and the exposure screen Reducing the area below 3 cm ² indicates that the sharpness obtained from the current 135 format exposed screen area cannot be maintained.

Further, A-3 and C-2 in which the acylacetamide type coupler represented by the general formula (YI) is replaced by the comparative coupler (1) are the corresponding A-1 and C-1.
Sharpness is remarkably deteriorated when compared with. This result is in agreement with the result of color reproducibility, and the use of the acylacetamide type coupler represented by the general formula (YI) provides excellent color purity of a yellow color image, resulting in "color contrast effect".
It seems that there is an improvement in visual sharpness.

The manufactured A-1 multilayer color light-sensitive material was slit into a width of 35 mm, cut into a length of 1.65 m, which is equivalent to 36 sheets of the current 135 format, and wound on a spool having a diameter of 14 mm. I tried to store it in a 135 format Patrone, but it was difficult. On the other hand, the film wound on the spool having a diameter of 8 mm could be easily stored, and there was a room to store a longer film.

This means that it is possible to increase the number of images to be taken with the current patrone or to slim the patrone with the current number of images to be taken. Combining this with the fact that even if the area of the exposure screen is made smaller than the current 135 format does not impair the image quality, it is suggested that the camera can be downsized.

Example 2 PBC-2, 3, 8, shown in the example of polyester compound,
Melting, biaxial stretching, and heat setting were performed according to the method described in Example 1 using 9, 10 and PBB-2, 3, 5, 6 to obtain a base having a thickness of 80 μm. After applying an undercoat layer, a back layer and the like to these bases, heat treatment was performed at a temperature 10 ° C. lower than the glass transition point (Tg) to obtain a support.

Using these supports, each layer having the composition shown in Example 1 was coated in multiple layers to prepare a multilayer color light-sensitive material.

These prepared samples were similarly cut and processed in the same manner as in the color film group II for photographing described in Example 1, and the performance of sharpness and color reproducibility was evaluated according to the same method. Comparative evaluation was performed based on C-1 of group I.

As a result, the multilayer color light-sensitive material prepared by using these 9 types of polyester supports was prepared as in Example 1.
It was possible to obtain almost the same evaluation as A-1 belonging to Group II.

Example 3 Multilayer color photosensitive materials A-1 and D-1 prepared in Example 1
And D-3 were processed so that the perforations had a width of 24 mm and there were two perforations per screen in the film length direction, and the film storage cartridge described in JP-A-2-273740 was modified and stored. The camera is also modified so that this cartridge can be loaded, and the screen area of the exposure unit is 30.0 mm x 12.0 mm (exposure screen area 3.60 cm ² , aspect ratio 2.50). The subject was photographed according to the method of Example 1.

Separately from this, the same sample is
It is processed so that the perforation is one per side in the length direction of the film per m width and is stored in the cartridge described in JP-A-2-273740 in the same manner as above, and the perforation is Area is 30.0 mm x 21.4 m
m (exposure screen area 6.42 cm ² , aspect ratio 1.
40) and the subject was photographed in the same manner as in Example 1 (at this time, one frame of the film was fed in common according to the above screen size and 31.7 mm.
And).

For photographing the subject (one mannequin, upper body, resolution evaluation chart and color checker chart), the photographing distance was determined so that the subject was exactly in the vertical position of the screen of the exposure section.

The film thus photographed was subjected to the treatment described in Example 1 and printed on a color paper at the same magnification in the same manner as in Example 1 to obtain a sample having the same size without a border.

The prints obtained were compared with the prints obtained from the Group II films of Example 1 above and Group C-1 (reference). The results are shown in Table 5.

[0304]

[Table 5] From the results of Table 5, the print obtained from the group C film C-1 of Example 1 used for comparison, the screen size of the exposed portion was set to 3.60 cm ² or 6.42 cm ² , and the perforation number was set to 1 screen. When compared with prints obtained from multilayer color light-sensitive materials A-1, D-1 and D-3 taken as 2 or 1 per hit, Group II A-1, D- of Example 1 above. It is clear that it gives excellent sharpness as well as the evaluation of sharpness of 1, D-3.

Example 4 No. 11 of the multilayer color light-sensitive material A-1 described in Example 1
Yellow coupler Y-23 used for the first layer and the twelfth layer
Multilayer color light-sensitive materials 401 to 407 were prepared in exactly the same manner except that (and a part of ExY-11 of the 11th layer) was replaced with a coupler shown in Table 6 below in an equimolar amount.

The multi-layer color light-sensitive material thus prepared was used in 24
The film was cut into a width of mm and a length of 1.65 m, and perforations were perforated on one side of the film at intervals of 31.7 mm in the length direction (one per screen) to obtain a color negative film for photographing.

This film was stored in the cartridge described in Example 3, and the area of the exposure screen was 30.0 mm × 1.
The image was taken at 6.7 mm (exposure screen area 5.01 cm ² , aspect ratio 1.80) under the same shooting conditions as in Group II of Example 1.

After the film having been photographed was subjected to the treatment described in Example 1, it was printed on a color paper and the same evaluation was carried out with C-1 of the film group I as a reference.
The results are shown in Table 6.

[0309]

[Table 6] From Table 6, PEN was used as the polyester base, and the screen area of the exposed portion was 5.01 cm ² (aspect ratio 1.8
0), by using an acylacetamide type coupler having an acyl group represented by the general formula (YI) in the blue-sensitive layer of a multilayer color light-sensitive material in which the number of perforations is one per screen, sharpness and color reproducibility are improved. It is clear from the comparison with Group I C-1 and Group II A-3 that it improves.

Example 5 In the layer structure of the multilayer color light-sensitive material described in Example 1, an intermediate layer containing only gelatin was provided between the eleventh layer and the twelfth layer of the blue-sensitive emulsion layer. The coating amount of gelatin in this intermediate layer was 0.40 g / m ² . The base used was the PEN shown in Example 1, and the thickness was 80 μm. The multi-layer color light-sensitive material thus produced is
Set to 1.

Then, using the control double jet method, the average particle size is 0.20 μm and the average aspect ratio is 5.
A tabular non-photosensitive fine-grain silver halide containing 0 silver iodobromide (2 mol% silver iodide) was prepared, and a multi-layer color photosensitive film was prepared so that the coated silver amount was 0.2 g / m ^2. A multilayer color light-sensitive material was prepared by adding the material 501 to the intermediate layer and the twelfth layer. This is a multilayer color photosensitive material 502. The support is the same as 501 described above.

These multilayer color light-sensitive materials thus produced were cut and processed in the same manner as in Example 4 to obtain a color negative film for photography, which was also stored in the same cartridge as in Example 4, the exposure screen was the same, and the same photography conditions were used. A color print was obtained in the same manner as above. These prints are C-1 of film group I of Example 1, film group
It compared with A-1 and A-3 of II, and evaluated similarly using C-1 as a reference.

The results are shown in Table 7.

[0314]

[Table 7] From Table 7, the sharpness and color reproducibility are improved by incorporating a non-photosensitive fine grain silver halide in the adjacent layer on the side closer to the support of the photosensitive silver halide emulsion layer of the present invention. Is clear.

Example 6 On the support formed into a film in Example 1, a multi-layer color light-sensitive material having the following compositions was prepared.

The addition amount in the light-sensitive material is shown in grams per m ² , and the silver halide emulsion and colloidal silver are shown in terms of silver, and the sensitizing dye is expressed in moles with silver halide. The ratio is shown. (Composition of photosensitive layer) First layer (antihalation layer) Black colloidal silver 0.3 Gelatin 1.0 Ultraviolet absorber UV-I 0.1 Ultraviolet absorber UV-II 0.1 Ultraviolet absorber UV-III 0. 1 Dispersion Oil Oil-1 0.2 Dispersion Oil Oil-2 0.1 Second Layer (Intermediate Layer) Gelatin 1.0 Coupler C-2 0.02 Dispersion Oil Oil-1 0.01 Third Layer (Low Sensitivity Red) Sensitive emulsion layer) Monodisperse silver iodobromide emulsion 1.8 (3 mol% silver iodide, average grain size 1.0 μm) Gelatin 1.2 Sensitizing dye I 1.4 × 10 ⁻⁴ Sensitizing dye II 7 × 10 ^-5 Coupler C-1 0.5 Coupler C-2 0.05 Coupler C-11 0.04 Compound D 0.1 Dispersion oil Oil-3 0.03 Dispersion oil Oil-4 0.03 Fourth layer (intermediate layer) Layer) Gelatin 1.0 Compound A 0.1 Fifth layer (low sensitivity green sensitive milk) Agent layer) Monodisperse silver iodobromide emulsion 1.4 (3 mol% silver iodide, average grain size 1.0 μm) Monodisperse silver iodobromide emulsion 0.3 (3 mol% silver iodide, average grain size 0) .3 μm) Gelatin 0.8 Sensitizing dye III 3 × 10 ⁻⁴ Sensitizing dye IV 1 × 10 ⁻⁴ Sensitizing dye V 1 × 10 ⁻⁴ Coupler C-3 0.7 Coupler C-4 0.1 Coupler C -5 0.1 Coupler C-13 0.05 Coupler C-15 0.08 Compound C 0.1 Dispersion oil Oil-3 0.3 Sixth layer (intermediate layer) Gelatin 1.0 Compound A 0.1 Seventh Layer (low-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion 0.7 (silver iodide 3 mol%, average grain size 1.0 μm) Monodisperse silver iodobromide emulsion 0.2 (silver iodide 3 mol %, Average particle size 0.3 μm) Gelatin 1.0 Sensitizing dye VI 2 × 10 ⁻⁴ Sensitizing dye VII 2 × 10 ⁻⁴ Coupler C-6 0.75 Coupler C-10 0. 40 Coupler C-12 0.05 Dispersion oil Oil-1 0.20 Eighth layer (intermediate layer) Gelatin 1.0 Compound B 0.1 Ninth layer (high-sensitivity red-sensitive emulsion layer) Polydisperse silver iodobromide emulsion 2.3 (Silver iodide 6 mol%, average particle size 2.0 μm) Gelatin 1.2 Sensitizing dye I 7 × 10 ⁻⁵ Sensitizing dye II 2 × 10 ⁻⁵ Coupler C-8 0.15 Coupler C- 1 0.15 Compound D 0.1 Dispersion oil Oil-4 0.2 10th layer (intermediate layer) Gelatin 1.0 Coupler C-5 0.2 Compound A 0.1 11th layer (high-sensitivity green-sensitive emulsion layer) ) Polydisperse silver iodobromide emulsion 2.0 (5 mol% silver iodide, average grain size 2.0 μm) Gelatin 1.0 Sensitizing dye III 1 × 10 ⁻⁴ Sensitizing dye IV 3 × 10 ⁻⁵ Sensitizing Dye V 3 × 10 ⁻⁵ Coupler C-9 0.22 Coupler C-14 0.04 Compound C 0.1 Dispersion Oil Oil-1 0.45 12th layer (intermediate layer) Gelatin 1.2 Compound A 0.1 13th layer (high-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion 1.8 (3 mol% silver iodide, average grain) Diameter 2.1 μm) Monodisperse silver iodobromide emulsion 0.5 (3 mol% silver iodide, average grain size 1.2 μm) Monodisperse silver iodobromide emulsion 0.2 (3 mol% silver iodide, average grain) Diameter 0.3 μm) Gelatin 1.2 Sensitizing dye VI 3 × 10 ⁻⁴ Sensitizing dye VII 1 × 10 ⁻⁴ Coupler C-6 0.32 Dispersion oil Oil-1 0.11 14th layer (first protective layer) ) Coupler C-7 0.1 UV absorber UV-I 0.05 UV absorber UV-II 0.05 UV absorber UV-III 0.05 UV absorber UV-IV 0.05 UV absorber UV-V 0.05 Gelatin 0.6 Dispersion oil Oil-4 0.1 Fifteenth layer (second protective layer) Gelatin 0.5 Polymethyl The data acrylate particles (diameter 1.5 [mu] m) compounds used in the 0.2 present embodiment will be described below of 42 to reduction 52.

[0317]

[Chemical 42]

[0318]

[Chemical 43]

[0319]

[Chemical 44]

[0320]

[Chemical formula 45]

[0321]

[Chemical formula 46]

[0322]

[Chemical 47]

[0323]

[Chemical 48]

[0324]

[Chemical 49]

[0325]

[Chemical 50]

[0326]

[Chemical 51]

[0327]

[Chemical 52] In addition to the above components, each layer contains a surfactant WI and a hardener H-.
I was added. In addition, formalin scavenger was added.

Then, using the control double jet method, tabular non-photosensitive fine grain silver halide grains having an average grain size of pure silver bromide of 0.15 μm and an average aspect ratio of 4.0 and silver iodobromide ( Silver iodide (2 mol%) average grain size 0.20
tabular non-photosensitive fine grain silver halide grains having an average aspect ratio of 4.0 μm and 0.25 μm were prepared respectively, and the eighth layer of the intermediate layers of the above multi-layer color photosensitive material had a grain size of 0.25 μm. To give a coating amount of 0.30 g / m ² , a particle size of 0.20 μm for the 10th layer to 0.25 g / m ^2, and a particle size of 0.15 μm for the 12th layer. Was coated so as to be 0.20 g / m ² to prepare a multilayer color light-sensitive material.

These multilayer color light-sensitive materials were used in Example 4
In the same manner as the above, the film was cut into a width of 24 mm and a length of 1.2 m, and perforations were perforated on one side of the film at intervals of 31.7 mm in the length direction (one per screen) to obtain a color negative film for photographing.

These films were placed in the cartridge described in Example 3, and the area of the exposure screen was 5.01 cm ^2.
The subject was photographed in the same manner as in Example 1 with an (aspect ratio of 1.80).

The photographed film was subjected to the treatment described in Example 1 and then printed on a color paper to prepare a C using a TAC support containing no non-photosensitive fine grain silver halide grain in the intermediate layer. Evaluation was performed in the same manner as in Example 1 based on the sample printed from -1.

Some of the results are shown in Table 8.

[0333]

[Table 8] From the results shown in Table 8, the sharpness of the photosensitive silver halide emulsion layer in the multilayer color light-sensitive material according to the present invention can be improved by adding non-photosensitive fine grain silver halide grains to the adjacent layer on the side close to the support. It is possible to obtain a color negative film for photography that has excellent image quality with color reproducibility, especially sharpness.
It is clear that the quality of the resulting print is excellent.

[0334]

INDUSTRIAL APPLICABILITY As described above, the silver halide color photographic light-sensitive material of the present invention is excellent in image quality of the obtained color image, particularly in sharpness and color reproducibility, and the support can be thinned. is there. Therefore, the area of the image portion can be reduced and the cartridge can be downsized without degrading the image quality, which contributes to downsizing of the camera.

[Brief description of drawings]

FIG. 1 is a plan view partially showing the constitution of one embodiment of a film produced by using the light-sensitive material of the present invention, in which one rectangular perforation per screen is provided on one side edge portion of the film. -Figure showing an example in which an option is formed.

FIG. 2 is a plan view partially showing the constitution of another embodiment of a film produced by using the light-sensitive material of the present invention, in which one rectangular pattern per screen is provided on one side edge portion of the film. The figure which shows the example in which the formation was formed.

FIG. 3 is a plan view partially showing the constitution of another embodiment of a film produced by using the light-sensitive material of the present invention, in which two circular patterns per screen are provided on both side edges of the film. The figure which shows the example in which the formation was formed.

FIG. 4 is a plan view partially showing the constitution of another embodiment of a film produced by using the light-sensitive material of the present invention, in which two rectangular patterns per screen are provided on one side edge portion of the film. The figure which shows the example in which the formation was formed.

FIG. 5 is a plan view partially showing the constitution of another embodiment of a film produced by using the light-sensitive material of the present invention, in which two perforations per screen are provided on both side edges of the film. FIG. 6 is a diagram showing an example in which a perforation is formed, and the shape of the perforation formed on one side edge portion is square and the other is circular.

FIG. 6 is a plan view partially showing the constitution of another embodiment of a film produced by using the light-sensitive material of the present invention, in which three perforations per screen are provided at one side edge portion of the film. FIG. 6 is a diagram showing an example in which a partition is formed and the shape of a perforation is a circle and a triangle.

FIG. 7 is a plan view partially showing the constitution of another embodiment of a film produced by using the light-sensitive material of the present invention, in which three perforations per screen are provided on both side edges of the film. FIG. 6 is a view showing an example in which a segment is formed and the shape of the perforation is a circle and a rectangle.

FIG. 8 is a plan view partially showing a constitution of another embodiment of a film produced by using the light-sensitive material of the present invention, in which four elliptical patterns per screen are provided on both side edges of the film. -A diagram showing an example in which a formation is formed.

9 is a view showing a cross section in the thickness direction of the film shown in FIGS.

[Explanation of symbols]

F ... Film, 1 ... Exposure section screen, 2, 3 ... Frame section,
4 ... Magnetic track, 5 ... Perforation, 6 ... Support, 7 ... Magnetic material, 8 ... Hydrophilic colloid layer, 9 ... Undercoat layer

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[Procedure amendment]

[Submission date] December 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0276

[Correction method] Change

[Correction content]

Subsequently, the supports A-1 and C-1 were used.
Of the multi-layer color light-sensitive material prepared by
The coupler Y-23 used in the 11th and 12th layers is described below.
In the comparative coupler (1) shown in Chemical formula 41, an equimolar amount is replaced,
A multilayer color light-sensitive material was produced in the same manner except the above. these
Are A-3 and C-2.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction item name] 0283

[Correction method] Change

[Correction content]

The treatment steps and treatment liquid compositions are shown below. The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank. It was made to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water washing process are respectively per 1 m ² of the light-sensitive material. 65 ml, 50 ml, 50 ml, 5
It was 0 ml. The crossover time is 6 seconds in any case, and this time is included in the processing time of the previous step.

Claims (6)

[Claims] 1. A halogenation having at least one photosensitive silver halide emulsion layer containing an acylacetamide type coupler having an acyl group represented by the general formula (YI) represented by the following chemical formula 1 on a support. In the silver color photographic light-sensitive material, the support is made of a strip-shaped polyester base, and at least one of the side edges thereof has 4 or less perforations per screen, and the screen of the image area is 3.0 cm ² or more, A silver halide color photographic light-sensitive material characterized by having an aspect ratio of not less than 7.0 cm ^{2 and not} less than 1.40 and not more than 2.50. General formula (YI) In the formula, R ₁ represents a substituent, Q together with C is a 3- to 5-membered hydrocarbon ring or a 3- to 6-membered hydrocarbon ring having at least one hetero atom selected from N, O, S, and P in the ring. Represents a group of non-metal atoms necessary to form a heterocycle. 2. A light-sensitive silver halide emulsion layer and / or an adjacent layer on the side closer to the support of the layer contains substantially light-insensitive fine grain silver halide grains. Item 1. A silver halide color photographic light-sensitive material according to Item 1. 3. The silver halide color photographic light-sensitive material according to claim 2, wherein the light-sensitive silver halide emulsion layer is a blue-sensitive silver halide emulsion layer. 4. The silver halide color photographic light-sensitive material according to claim 2, wherein the layer adjacent to the support of the light-sensitive silver halide emulsion layer is a non-light-sensitive layer. 5. The silver halide according to claim 3, wherein the photosensitive layer closest to the support of the photosensitive silver halide emulsion layer is a photosensitive layer other than blue-sensitive. Color photographic light-sensitive material. 6. The photosensitive silver halide emulsion layer has two or more red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers having different sensitivities, and the following conditions (a) to (d) are satisfied. 2. All of the above are satisfied.
A silver halide color photographic light-sensitive material described in 1. (A) The photosensitive silver halide emulsion layer provided on the side farthest from the support is the most sensitive blue-sensitive silver halide emulsion layer (BH), and (b) the most sensitive green-sensitive halogen. The silver halide emulsion layer (GH) and the most sensitive red-sensitive silver halide emulsion layer (RH) are the same as the above BH and B.
It is provided between the blue-sensitive silver halide emulsion layer (Bh) having a lower sensitivity than H, and (c) with respect to the Bh, on the side farther from the support, the red-sensitive, green-sensitive and blue having the lowest sensitivity. Sensitive silver halide emulsion layers (RL, GL and B, respectively)
L) is absent, and (d) a non-photosensitive layer is provided adjacent to the BH, and the BH and / or the non-photosensitive layer contains substantially non-photosensitive fine grain silver halide grains. .