JPH0695296A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance image sharpness and color reproduction performance by incorporating a specified coupler in one of the layers of the silver halide color photographic sensitive material and forming a support made of a belt- formed polyester base perforated on its sides by a specified number per one image and specifying an image part area. CONSTITUTION:The silver halide color photographic sensitive material has the layer containing the coupler represented by formula I and the support made of the polyester base belt perforated on one side or both sides by <=4 holes per one image and it has an image part area of 3.0-7.0cm<2> and an aspect ratio of 1.40-2.50. In formula I, R1 is H or a substituent; Z is a nonmetallic atomic group necessary to form a 5-membered azole ring having 2-3 N atoms; and X is H or a group to be released by coupling with the oxidation product of a color developing agent.

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, improvements in graininess, sharpness, and color reproducibility of color photographic light-sensitive materials for photography (hereinafter simply referred to as color negatives) and the spread of cameras equipped with zoom lenses or bifocal lenses have been combined. Then, I got more and more variety of photos.

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. It had the drawback of being a camera with no effect.

As means for solving the above problems, for example, US Pat. Nos. 3,490,844 and 4,583,831 are disclosed.
And No. 4,650,304, a proposal for a so-called pseudo-zoom method has been made, focusing on the recent progress in the performance of color negative films. 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, it is expected that the lens can be downsized by shortening the focal length of the lens.
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. Further, one of the user's dissatisfaction points is that there is a large variation in image quality between prints obtained from one film.

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.

It is known that development inhibitor releasing couplers (so-called DIR couplers) are generally effective in improving the sharpness of color negative films.
Chi Disclosure (RD) -17643VII-F
Patents described in paragraphs Nos. 57-151944, 57-154234, 60-184248 and 6
0-37346 and U.S. Pat. No. 4,248,962. However, the effect was insufficient for a small format color negative product, which has a larger print magnification.

On the other hand, as a method of improving sharpness without using a DIR compound, for example, a method of thinning a hydrophilic colloid layer of a color negative film, a method of using a dye which absorbs scattered light at the time of exposure, A method of coloring the lower layer or the base or a method of changing the shape of the photosensitive silver halide emulsion grains has been proposed. However, although these methods do improve some sharpness, these techniques alone are still unsatisfactory for small format color negative products and need further improvement.

Furthermore, in addition to the performance of the photosensitive material itself,
It has become clear that it is important to consider the film state at the time of shooting and the film deformation (for example, curl) that occurs during long-time exposure due to high magnification stretching from a small screen when printing from a color negative.

[0011]

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material containing a specific magenta coupler, which is provided as a photographic film for photography in a specific format. Another object of the present invention is to provide a silver halide color photographic light-sensitive material having improved physical properties of the film and improved image quality, particularly sharpness and color reproducibility.

[0012]

In order to improve the sharpness of a color negative film, it is conceivable to improve it by an indirect internal factor in addition to the improvement by a direct internal factor such as the use of the above-mentioned DIR compound or dye. One of them is the “color contrast effect” relating to sharpness. The visual increase in sharpness due to this color contrast effect is yellow,
This can be achieved by increasing the color saturation of magenta and cyan images. This effect is most prominent especially when the saturation of the magenta color image is increased.

Conventionally, a so-called pyrazolone type coupler has been used as a magenta coupler, but as is well known, this type of coupler has a second absorption around a wavelength of 430 nm and is not preferable for color reproduction. On the other hand, in recent years, a pyrazoloazole-based coupler has been proposed, and it is known that the color reproducibility is remarkably improved by the absence of the second absorption and the good bottoming of the absorption on the long wavelength side. Examples of pyrazoloazole-based couplers include U.S. Pat. No. 3,725,067.
No. 4,500,630, No. 4,540,65
4, JP-A-60-33552 and 60-43659.
No. 61-72238.

Further, as a direct external factor, it is possible to maintain the flatness of the color photographic film during photographing in the camera. That is, increase the enlargement ratio during printing,
It was revealed from the analysis that the sharpness was deteriorated due to the flatness of the color negative upon long-time exposure.
The major factors that impair the flatness are the hygroscopicity and curl of the cellulose triacetate support, and the perforation number of the current 135 color photographic film is also a factor that deteriorates the sharpness and causes variations. did.

Based on these circumstances, as a result of earnest research, the present inventor has found that the above-mentioned problems can be achieved by the means described below. (1) In a silver halide color photographic light-sensitive material having a layer containing a coupler represented by the general formula (M) shown in the following chemical formula 1 on a support, the support is a belt-shaped polyester base. Becomes 1 on one or both of its side edges
Is formed with four or less perforations per screen, and halogenation image unit area at 3.0 cm ² or more 7.0 cm ² or less, the aspect ratio is characterized in that 1.40 to 2.50 Silver color photographic light-sensitive material.

[0016]

[Chemical 9] R ₁ in the formula represents a hydrogen atom or a substituent. Z is
It represents a group of non-metal atoms necessary to form a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

(2) At least one selected from the group of non-color-forming and diffusion-resistant compounds represented by the general formulas (I) to (VII) shown in the following chemical formulas 10 to 16 is used. (3) The silver halide color photographic light-sensitive material described in (1) above, which is contained in the hydrophilic colloid layer of the silver halide color photographic light-sensitive material.

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical 12]

[0021]

[Chemical 13]

[0022]

[Chemical 14]

[0023]

[Chemical 15]

[0024]

[Chemical 16] In the formula, R ²¹ is a hydrogen atom, an aliphatic group or a heterocyclic group,
R ³¹ and R ⁴¹ are a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R ¹² , R ²² , R ³² , and R ⁷¹ are a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocycle. Group, alkoxy group, aryloxy group, amino group, alkenyl group,
Alkynyl group or hydrazino group, R ⁴² is cyano group, nitro group, perfluoroalkyl group or thioacyl group, G ³¹ is —SO ₂ —, —SO—, —PO (R
³⁵ )-, iminomethylene or -COCO-, and R ³⁵
Is an alkyl group or an aryl group, and G ⁵¹ and G ⁷¹ are G ³¹
And the addition of --CO-- to R ¹³ , R
²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁷³ , R ¹⁴ , R ²⁴ , R ³⁴ ,
R ⁴⁴ , R ⁵⁴ , and R ⁷⁴ are hydrogen atoms or groups that can be removed under alkaline conditions, R ⁷³ may be an alkyl group, R ¹¹ is a substituent on the benzene ring, and Z ⁵¹ forms a ring. Y ⁶¹ is a divalent group having a hydrazine or hydroxylamine structure, L ⁶¹ and L ⁶² are divalent linking groups, and n, m and q are 0, 1 or 2 Yes, j and k are 0 or 1. The groups described above may have a substituent.

The present invention will be described in 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 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. In this case, usable dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, 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 17]

[0036]

[Chemical 18] 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 19]

[0039]

[Chemical 20] 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 21] 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 (() indicates 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 the 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. Also, various arrangements have been made for the composition of the undercoat layer, and a layer that adheres well to the support (hereinafter referred to as the first undercoat layer) is provided as the first layer, and the second layer is photographed as the second layer. 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.

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 the 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 an example of the film according to the present invention, and FIG. 9 is a plan view.
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 long strip-shaped 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 perforation is not particularly limited, and various shapes such as a square and a hexagon such as a hexagon 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 in the same way, 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, in the present invention, the area of the image portion (exposure portion screen) is set to 3 cm ² or more and 7 cm ² or less. 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 types of aspect ratios (horizontal length / vertical length ratio of image part) can be provided, variations in the composition of the photograph will be large. 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 was adjusted to the above-mentioned print of medium aspect ratio (2), it was 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 image screen 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) relative 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.Thus, the poor flatness of the film as described above causes the sharpness of the color negative photosensitive material for photography to be exhibited. 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 compound of the general formula (M) according to the present invention will be described in detail.

In the general formula (M), R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary to form a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

Among the coupler skeletons represented by the general formula (M) used in the present invention, preferable ones are 1H-imidazo [1,2-b] pyrazole and 1H-pyrazolo [1,5.
-B] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] triazole and 1H
-Pyrazolo [1,5-d] tetrazole, represented by the following formulas (M-I), (M-II),
It is represented by (M-III) and (M-IV).

Preferably (M-II) or (M-III)
And more preferably (M-II)
Is a compound represented by.

[0106]

[Chemical formula 22] The substituents R ₁₁ , R ₁₂ , R ₁₃ and X in these formulas will be described in detail.

R ₁₁ is hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group. , Anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxy Carbonyl group,
It represents an acyl group or an azolyl group, and R ₁₁ may be a divalent group to form a bis form.

More specifically, each R ₁₁ is a hydrogen atom, a halogen atom (eg chlorine, bromine), an alkyl group (eg a straight chain or branched chain alkyl group having 1 to 32 carbon atoms),
An aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and more specifically, for example,
Methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 4-tetradecanamidophenyl), a heterocyclic group (for example, 2-
Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group,
Carboxyl group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butyl). Phenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3
-Methoxycarbamoyl), an acylamino group (for example,
Acetamide, benzamide, tetradecanamide, 2
-(2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino A group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino),
Anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino, 2-chloro-5- {α- (3-
t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoyl) Amino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-)
t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-
Butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N-
{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group (for example, N-
Ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N
-Diethylsulfamoyl), a sulfonyl group (for example,
Methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (eg, 1-phenyltetrazole-5-oxy) , 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo,
2-hydroxy-4-propanoylphenylazo), acyloxy group (eg acetoxy), carbamoyloxy group (eg N-methylcarbamoyloxy, N-
Phenylcarbamoyloxy), silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg,
Phenoxycarbonylamino), imide group (eg, N
-Succinimide, N-phthalimide, 3-toctadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl) , Phenylphosphonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), acyl groups (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl groups (eg, imidazolyl, pyrazolyl, 3- Chloro-pyrazol-1-yl, triazole).

Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁₁ is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group or an acylamino group. Can be mentioned.

R ₁₂ is a group having the same meaning as the substituent exemplified for R ₁₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group or an acyl group. And a cyano group.

R ₁₃ is a group similar to the substituents exemplified for R ₁₁ , preferably a hydrogen atom, an alkyl group,
An aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group and an acyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group and an arylthio group. It is a base.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent. The splitting off group is described in detail, for example, a halogen atom, an alkoxy group, an aryl group. Oxy group, acyloxy group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5 member or There are 6-membered nitrogen-containing heterocyclic groups, imide groups, arylazo groups and the like, and these groups may be further substituted with a group acceptable as the substituent for R ₁₁ .

More specifically, for example, a halogen atom (eg, fluorine, chlorine, bromine), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryl. An oxy group (for example, 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl. Sulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg, dichloroacetylamino, heptafluorobutyrylamino), alkyl or aryl sulfonamide groups (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryl Oxycarbonyl group (e.g., phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio group (e.g., dodecylthio, 1
-Carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio), a carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino),
5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazole, pyrazolyl, triazolyl, tetrazolyl, 1,
2-dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), and an arylazo group (eg, phenylazo, 4-methoxyphenylazo). In addition to these, X is a leaving group bonded via a carbon atom, which is an aldehyde or a ketone.
In some cases, it may take the form of a bis-type coupler obtained by condensing an equivalent coupler. Further, X may contain a photographically useful group such as a development inhibitor or a development accelerator. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom.

Compound examples of the magenta coupler represented by the general formula (M) are shown in the following Chemical Formulas 23 to 33.
It is not limited to these.

[0116]

[Chemical formula 23]

[0117]

[Chemical formula 24]

[0118]

[Chemical 25]

[0119]

[Chemical formula 26]

[0120]

[Chemical 27]

[0121]

[Chemical 28]

[0122]

[Chemical 29]

[0123]

[Chemical 30]

[0124]

[Chemical 31]

[0125]

[Chemical 32]

[0126]

[Chemical 33] The following documents describe the method for synthesizing the coupler represented by the general formula (M).

The compound of the formula (M-I) is described in, for example, US Pat. No. 4,500,630, and the compound of the formula (M-II) is described in, for example, US Pat. No. 4,540,654. No. 4,705,863, JP-A Nos. 61-65245, 62-209457 and 62-249155, compounds of the formula (M-III) are described, for example, in JP-B-47-274.
11, U.S. Pat. No. 3,725,067, the formula (M-
The compound of IV) can be synthesized, for example, by the method described in JP-A-60-33552.

The magenta coupler represented by formula (M) used in the present invention is preferably used in the green-sensitive emulsion layer. It can also be added to a non-photosensitive layer adjacent to the green-sensitive emulsion layer. The total amount of the magenta coupler added is 0.01 to 1.0 g / m ² , preferably 0.0.
5 to 0.8 g / m ² , more preferably 0.1 to 0.5 g
/ M ² . The method for adding the magenta coupler in the light-sensitive material according to the present invention is based on the method for other couplers described below, but the amount of the high boiling organic solvent used as the dispersion solvent is the weight relative to all the couplers added to the magenta coupler-containing layer. The ratio is 0 to 4.0, preferably 0 to 2.
0, more preferably 0.1 to 1.5, still more preferably 0.3 to 1.0.

Next, the compounds represented by formulas (I) to (VII) will be described in more detail.

The aliphatic group of R ²¹ , R ³¹ and R ⁴¹ is a linear, branched or cyclic alkyl group, aralkyl group, alkenyl group or alkynyl group having 1 to 30 carbon atoms, and R ¹² is There is something to mention.

The aromatic group for R ³¹ and R ⁴¹ is, for example, phenyl or naphthyl, with phenyl being preferred.

The heterocyclic group for R ²¹ , R ³¹ and R ⁴¹ may be a saturated or unsaturated monocyclic or condensed ring, and examples thereof include pyridyl, imidazolyl, thiazolyl, quinolyl, morpholino and thienyl.

R ¹¹ is, for example, an alkyl group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an alkoxy group, an aryloxy group, a hydroxy group, a carboxyl group, an aryl group, a carbamoyl group, a sulfamoyl group, an alkylthio group or an arylthio group. , A sulfonyl group, a sulfinyl group, an acyl group, a halogen atom, a cyano group, a heterocyclic group, or a sulfo group, and further preferably an acylamino group, a sulfonylamino group, a ureido group, a urethane group, or an alkoxy group.

The alkyl group of R ¹² , R ²² , R ³² and R ⁷¹ is
A straight chain, branched chain or cyclic group having 1 to 30 carbon atoms, for example, methyl, cyclohexyl, 2-octyl or octadecyl. The aralkyl group has a carbon number of 7 to 30, and examples thereof include benzyl, phenethyl and trityl.
The aryl group has 6 to 30 carbon atoms and is, for example, phenyl or naphthyl. The heterocyclic group is as described for R ²¹ . The alkoxy group has 1 to 3 carbon atoms.
0, for example, methoxy, octyloxy, 2-pentyloxy, benzyloxy, cyclohexyloxy. The aryloxy group has 6 to 30 carbon atoms, and examples thereof include phenoxy and naphthyloxy. The amino group is a substituted or unsubstituted group, and the substituent is an alkyl, aryl or heterocycle having 1 to 30 carbon atoms. The alkenyl group has 2 to 30 carbon atoms, and examples thereof include vinyl and 1-dodecenyl. The alkynyl group has 2 to 30 carbon atoms, and examples thereof include ethynyl, 1-octynyl and 2-phenylethynyl. Examples of the hydrazino group include R ³¹ —N (R ³³ ) N (R ³⁴ ) — in the general formula (III).

The perfluoroalkyl of R ⁴² has 1 to 30 carbon atoms, and examples thereof include trifluoromethyl and perfluorooctyl. Thioacyl has 2 to 30 carbon atoms, and examples thereof include thioacetyl and thiobenzoyl.

R ¹³ , R ²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁷³ , R
^{The group of 14} , R ²⁴ , R ³⁴ , R ⁴⁴ , R ⁵⁴ , and R ⁷⁴ , which is removed under alkaline conditions, has a carbon number of 20 or less, and examples thereof include an alkylsulfonyl group, an arylsulfonyl group, and an acyl group. , A dialkylaminomethyl group and a hydroxymethyl group. R ¹³ , R ²³ , R ³³ , R ⁴³ , R
^A hydrogen atom is preferable as ⁵³ , R ⁷³ , R ¹⁴ , R ²⁴ , R ³⁴ , R ⁴⁴ , R ⁵⁴ , and R ⁷⁴ .

Z ^{51 in the} general formula (V) is methylene,
It is a divalent linking group consisting of ethylene, trimethylene, -CO-, 1,2-phenylene, -O-, -S-, -NH-, -NHNH-, and a combination thereof, and the ring has 5-8.
Member rings are preferred.

Of the general formula (VI), the following general formula (VI-
Those represented by 1) are more preferable.

[0139]

[Chemical 34] In the formula, R ⁸¹ is a hydrogen atom, a halogen atom or an alkyl group, and L ⁸¹ is —CO—, —SO ₂ —, —NH—, —O.
-, -S-, phenylene, alkylene and a divalent linking group consisting of a combination thereof, L ⁸² is represented by the general formula (III
) R ³¹ is a divalent group obtained by removing a hydrogen atom from R ³¹ , and G
⁸¹ and R ⁸³ have the same meanings as G ³¹ and R ^{33 in} formula (III).
X is a group derived from an amino group or hydroxyl group, respectively general formula (III) -N of ^{(R 34) - (G 31} )
_m -R ³² and in formula -O-R ⁷⁴ of (VII) synonymous. r, t, and u are 0 or 1.

The above groups may be substituted with the groups described for R ¹¹ . The molecular weight of the general formulas (I) to (V) and (VII) is preferably 300 to 1500, more preferably 4
It is 50 to 1000, and more preferably 500 to 800.

Two or more of these may be combined to form an oligomer (for example, a bis form or a tris form).

R ¹¹ , R ²¹ , R ³¹ , R ⁴¹ , R ⁷¹ , R ¹² , R
It is preferable that each of ²² , R ³² and R ⁴² incorporates a ballast group commonly used in a non-moving photographic material such as a coupler therein. In that case, it is more preferable to have a polar group as a substituent. The polar group is a group having a π value smaller than −1.0 in combination, and examples thereof include hydroxyl, sulfonamide, amino, carboxy, carbamoyl, sulfamoyl, ureido and heterocyclic groups.

The compounds represented by the general formulas (I) to (VII) may have as a substituent a group (for example, thiourea, mercaptoheterocycle or azole) which enhances adsorption on the surface of silver halide. As a diffusion resistant group, a ballast group is more preferable than an adsorption group on silver halide. Of the compounds represented by the general formulas (I) to (VII), the compounds represented by (I), (II), (III) and (VI) are preferable.

Specific examples of the compounds represented by formulas (I) to (VII) used in the present invention are shown below, but the invention is not limited thereto.

[0145]

[Chemical 35]

[0146]

[Chemical 36]

[0147]

[Chemical 37]

[0148]

[Chemical 38]

[0149]

[Chemical Formula 39]

[0150]

[Chemical 40]

[0151]

[Chemical 41]

[0152]

[Chemical 42]

[0153]

[Chemical 43] The synthesis of these compounds is described, for example, in JP-A-3-16473.
5, 3-154051, 3-150560, 3-
It can be easily performed according to the method of the patent described or cited in 150562 and 1-315731.

The compounds represented by the above general formulas (I) to (VII) (color mixing inhibitors) in the present invention can be used in any of the hydrophilic colloid layers constituting the light-sensitive material.

The hydrophilic colloid layer as used in the present invention means a photosensitive layer or a non-photosensitive layer coated on the exposed surface side of the support except the above-mentioned support, back layer and undercoat (undercoat) layer. (For example, an antihalation layer, an intermediate layer, a yellow filter layer, a protective layer). In the present invention, the general formula (I)
It is preferable that at least one of the photosensitive layer and the non-photosensitive layer contains the compound represented by formula (VII) to (VII).

These color mixing inhibitors, when used for the purpose of preventing color fog, are provided between a color coupler and a layer containing a photosensitive silver halide or a silver halide emulsion layer having the same color sensitivity. Provided non-photosensitive layer (intermediate layer)
Is preferably added to. When used for the purpose of preventing color turbidity, it is preferably added to a non-photosensitive layer (intermediate layer) provided between silver halide emulsion layers having different color sensitivities.

Further, when it is used for both the purpose of preventing color fogging and preventing color turbidity, it can be added to two or more layers of both the silver halide emulsion layer and the intermediate layer.

Further, a plurality of color mixing inhibitors can be mixed and used.

The color mixing inhibitor is used in an amount of 1 × 10 ⁻³ to 1 per layer.
It is used in the range of × 10 ^-6 mol / m ² . When this color mixing inhibitor is used for the purpose of preventing color fog, one layer is used per layer.
The range of × 10 ^-4 to 1 × 10 ^-6 mol / m ² is preferable, and when used for the purpose of preventing color turbidity, it is 1 × 10 ^-3 to 1 × 1.
A range of 0 ^-5 mol / m ² is preferred.

Further, in the present invention, it may be used in combination with the above color mixing inhibitor. These can be used as a mixture, or can be used individually in separate layers.
Examples of color mixing inhibitors other than the above include hydroquinone derivatives, gallic acid derivatives, aminophenol derivatives, ascorbic acid derivatives, and sulfonamide derivatives.

Introduction of the color-mixing inhibitor into the constituent layers of the light-sensitive material can be carried out by various methods used when introducing a coupler or the like described later into the constituent layers. For example, a high boiling organic solvent and / or a low boiling point (at normal pressure, 30 to
150 ° C.) A method of dissolving in an organic solvent and dispersing in a hydrophilic colloid medium, a polymer latex dispersion method, or the like can be applied.

The color mixing inhibitors represented by the above general formulas (I) to (VII) can improve the color reproducibility of the light-sensitive material of the present invention. It is particularly effective for the light-sensitive material of the present invention which uses the coupler represented by the general formula (M). Further, the color developer has a high pH, that is, pH 10.0.
Above, especially when treated with a liquid of 10.5 or more and 13.0 or less, the effect is further increased.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities is provided on a support. A silver halide photographic light-sensitive material is a unit photosensitive layer having a color sensitivity to any of blue light, green light and red light. In the multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in the order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the support side.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer may be formed, for example, in JP-A-61-43.
748, 59-113438, 59-1134
No. 40, No. 61-20037, No. 61-20038, and a coupler and a DIR compound may be contained.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of 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, No. 62-206543
As described in the publications, etc., 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 farthest side 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 or the like.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the silver halide emulsion layer having the highest photosensitivity in the upper layer, the silver halide emulsion layer having a lower photosensitivity in the middle layer, and the 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 order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
Nos. 63-89850 and BL, G
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

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

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 a photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and 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 the 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.

Tabular grains having an aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of about 3 or more can also be used in the present invention. Tabular grains are written by Gatov,
Photographic Science and Engineering (Gutoff, Photographic S
Science and Engineering), Volume 14, 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520. No. 2,112,157 and the like, and can be easily prepared.

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 which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain, or a type which has a latent image both on the surface and 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 varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

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,
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 the fogged core / shell type silver halide grain 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 grains (at least 95% of the weight or number of silver halide grains are within ± 40% of the average grain size) (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferably silver iodide,
The content is 0.5 to 10 mol%.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

Fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The silver coating amount of 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.

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 are described in Research Disclosure No. 17643, VII-CG, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
European Patent Nos. 249,473A and 447,969A
Nos. 482,552A are preferable.

As the magenta coupler, in addition to the coupler represented by the above general formula (M) of the present invention, 5-pyrazolone compounds and pyrazoloazole compounds other than the present invention may be used depending on the purpose. You can For example, U.S. Pat. Nos. 4,310,619 and 4,351,897,
European Patent No. 73,636, US Patent No. 3,061,4
32, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-
No. 43659, No. 61-72238, No. 60-357.
No. 30, No. 55-118034, No. 60-18595
1, U.S. Pat. Nos. 4,500,630 and 4,54.
0,654, 4,556,630, International Publication W
The compounds described in O88 / 04795 can be used.

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.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

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. 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, a silver halide solvent and the like 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 US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , A ligand releasing coupler described in US Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in US Pat. No. 4,774,181. Examples thereof include releasing couplers.

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 in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (eg, 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-2-ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecane amide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples thereof include aniline derivatives (for example, N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-Ethoxyethyl acetate and dimethylformamide can be mentioned.

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 antiseptics or antifungal agents such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

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 hardening agent to gelatin as a binder or 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 light-sensitive 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. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

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 for 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 a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, for example, hydroxylamine,
Diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, various preservatives such as phenylsemicarbazides, triethanolamine and 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-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, amino polycarboxylic acids, amino poly Various chelating agents represented by phosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyl Iminodiacetic 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 process is carried out, the black and white development is usually carried out before the color development. This black and white developer contains dihydroxybenzenes such as hydroquinone,
Known black-and-white developing agents such as 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol 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 replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 L (liter) or less per square meter of the light-sensitive material, and it is possible to reduce the bromide ion concentration in the replenishing solution by 50%.
It can be 0 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 expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷
[Treatment Liquid Volume (cm ³ )] The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to
It is 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, The slit developing treatment method described in No. 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The time of color development processing 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 adjusting the pH, 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 for the development processing of the light-sensitive material of the present invention is disclosed 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 has a high effect of 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 subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society.
of Motion Picture and Tel
Evolution Engineers, Volume 64, 24
It can be determined by the method described on pages 8-253 (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. In addition, JP-A-57-
Isothiazolone compounds and siabendazoles described in No. 8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles by Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Hygiene Technology Society, "Microbial sterilization, sterilization, and antifungal technology" (198
2 years) The bactericides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Agents 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 the washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C is preferably 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 stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and as an example thereof, a stabilizing bath containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing. 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 washing with water and / or the replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

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-color image forming materials for the purpose of accelerating color development.
-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.

[0234]

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 1 below: thickness 80 μ
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: Triacetyl cellulose was added to methylene chloride / methanol = 82/8 wt ratio, 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: According to the method of forming the support A, the mixture was kneaded and extruded at 280 ° C. using a twin-screw 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 mixture 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 applying the undercoat layer and the back layer by the above method, Table 1
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 1. As is clear from Table 1, PEN has a flexural modulus of 80 μm and PET has a flexural modulus of 90 μm, which is almost equivalent to TAC of 122 μm. 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.

[0245]

[Table 1] 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 point 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 B Silver 0.25 ExS-1 6.9 × 10 ⁻⁵ ExS-2 1.8 × 10 ^{− 5} ExS-3 3.1 × 10 ⁻⁴ ExC-1 0.12 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 ExC-9 0.070 Cpd-2 0.025 H S-1 0.10 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion D silver ^{0.70 ExS-1 3.5 × 10 -4} ExS-2 1.6 × 10 -5 ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.10 ExC-2 0.060 ExC-3 0.070 ExC-4 0.070 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 ExC -9 0.065 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 2.4 × 10 ^-4 ExS- 2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 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 Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS- 5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 M-13 0.28 ExM-1 0.010 ExM-2 0.10 ExM-3 0.086 ExM-4 0.015 HBS- 1 0.30 HBS-3 6.0 × 10 ⁻³ HBS-4 0.050 Gelatin 0.73 Eighth layer (medium sensitivity green sensitive emulsion layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^{− 5} ExS-5 2.2x10 ^-4 ExS-6 8.4x10 ^-4 M-3 0.080 M-16 0.070 ExM-3 0.030 ExM-4 0.010 ExY-1 8. ^{0 × 10 -3 HBS-1 0.16} HBS-5 0.050 gelatin 0.90 ninth layer (high sensitivity 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 .030 M-21 0.040 M-20 0.020 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44 10th layer (yellow filter layer) Yellow colloidal silver Silver 0. 030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60 11th layer (low-sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10 12th layer (medium-sensitivity blue emulsion layer) Emulsion D Silver 0.40 ExS-7 7. ^{4 × 10 -4 ExC-7 7.0} × 10 -3 E Y-2 0.050 ExY-3 0.10 ExY-4 0.015 HBS-1 0.050 Gelatin 0.78 13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4. 0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 HBS-1 0.070 Gelatin 0.86 14th 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 mold resistance of each layer are appropriately adjusted.・
To improve antibacterial property, antistatic property and coating property, W-
1 to W-3, B-4 to B-6, F-1 to F
-17 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained.

[0246]

[Table 2] In Table 2, (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.

[0247]

[Chemical 44]

[0248]

[Chemical formula 45]

[0249]

[Chemical formula 46]

[0250]

[Chemical 47]

[0251]

[Chemical 48]

[0252]

[Chemical 49]

[0253]

[Chemical 50]

[0254]

[Chemical 51]

[0255]

[Chemical 52]

[0256]

[Chemical 53]

[0257]

[Chemical 54]

[0258]

[Chemical 55]

[0259]

[Chemical 56]

[0260]

[Chemical 57]

[0261]

[Chemical 58] 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.

[0262]

[Chemical 59] 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 with 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 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, upper body) on which a resolution evaluation chart and a Macbeth color checker chart were installed 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 photographing, when photographing the film of the group I, the distance for photographing the whole view of the main part of the subject is set in the image part (exposure part screen), and the film of the group II and the group III is set. Shooting was performed with the zooming operation performed so that the entire view fits in the image section without changing the distance.

In order to evaluate the color reproducibility, the color checker chart was photographed separately at a closer distance.

Conditions Light source Subject Contrast Background Others A Daylight (sunny) High trees, distant view of mountains, sun, shadows B Daylight (cloudy) Low trees, distant view of mountains C Strobe High light gray wall Film that has been taken 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.

The processing steps and processing 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 35 mm width of photosensitive material 1.1 m (24E
x. (One equivalent) 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 so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. 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-1,1-2.0 2.0 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. The obtained color negatives were produced using a Fuji enlarger A690 professional, with the film I group having a magnification of 5 times, the film II group having a magnification of 7 times, and the film III group having a magnification of 9.5 times. Printed on paper, Super FA, Type II. CP-43FA 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 I group, and the 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, with respect to color reproducibility, the yellow density of the magenta color image portion of the color checker chart was measured on a color negative, and the difference was calculated based on the value of the multilayer color light-sensitive material C-1 as well. I checked. No difference was observed in the yellow densities of the three types of C-1 having different spool diameters.

Some of the results are shown in Table 3.

[0275]

[Table 3] From the results in Table 3, it is clear that Group II films with polyester support are superior in sharpness to Group 135 which is the current 135 format. 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 particular, when the support is TAC other than the present invention, it is remarkable, and it is considered that this is because the TAC has a large water absorption and further disturbs the flatness retention due to the influence of temperature and humidity at the time of photographing. In fact, it seems that this is supported by the fact that some monitors pointed out the blurring in the image around the print and the center. On the other hand, in the group III in which the exposure screen area is 3 cm ² or less, the sharpness determination is obviously inferior, and reducing the exposure screen area to 3 cm ² or less is the sharpness obtained from the exposure screen area of the current 135 format. Indicates that it cannot maintain. Furthermore, A-3 and C-2 in which the coupler represented by the general formula (M) according to the present invention is replaced with a comparative coupler have markedly deteriorated sharpness when compared with the corresponding A-1 and C-1. . By using the coupler represented by the general formula (M), a magenta color image with less yellow density component on the short wavelength side can be obtained, and it is considered that the visual sharpness is improved by the "color contrast effect".

Regarding the color reproducibility, the coupler represented by the general formula (M) has less color turbidity than the comparative coupler and is excellent in color reproducibility as compared with A-1, C-1 and A.
It can be known from the comparison with -3 and C-2.

The multi-layer color light-sensitive materials C-1 and C-2 of the prepared film I group were slit into a width of 35 mm and cut into a length of 1.65 m which corresponds to 36 sheets of the current 135 format. It was difficult to wrap it up in a spool with a diameter of 14 mm and store it in a 135 format patrone. In contrast, the diameter is 8m
The film wound on the spool of m 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 down 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, 5, shown in the example of polyester compound
No. 6,8 and PBB-2,3,6 were melted, biaxially stretched and heat-fixed according to the method described in Example 1 to obtain 80 μm.
A support having a thickness of m was obtained. After applying an undercoat layer, a back layer, etc. to these supports, heat treatment was carried out at a temperature 10 ° C. lower than the glass transition point (Tg), and these supports were used to obtain the composition shown in Example 1. Each layer was coated in multiple layers to prepare a multilayer color light-sensitive material.

The produced multilayer color light-sensitive material was cut and processed in the same manner as the color film II group for photographing described in Example 1, and photographed by the same method to obtain the performances of sharpness and color reproducibility in Example 1. The film group I was evaluated based on C-1.

As a result, the multilayer color light-sensitive material prepared from these eight types of polyester supports was able to obtain almost the same evaluation as A-1 belonging to the II group of Example 1. Example 3 Multilayer color photosensitive materials A-1 and D-1 produced in Example 1
And D-3 were processed and stored in a film storage cartridge described in JP-A-2-273740 with a width of 24 mm so that the perforations were 1 per screen at each side edge in the film length direction. The camera was also modified so that this cartridge could be loaded, and the screen area of the exposure unit was 3.60 cm ² (30.0 mm × 12.0 m).
m, aspect ratio 2.5), and
The subject (one mannequin, upper body, resolution evaluation chart, and Macbeth color checker chart were installed) was photographed according to the above method.

Further, the same sample is similarly used in Japanese Patent Laid-Open No. 2-273.
The cartridge described in No. 740 is processed and accommodated in a cartridge having a width of 35 mm so that the perforation is one on each side with respect to the film length direction, and the screen size of the exposure section is 6.42 cm ² (30.0 mm). × 21.4m
m, aspect ratio 1.4), and similar photography was carried out (at this time, the frame advance of the film was set to 31.7 mm in accordance with the screen area of the exposure section).

[0282] Note that in photographing the subject, the distance was determined so that the subject would exactly enter the vertical position of the screen of the exposure section.

These photographed films were processed as described in Example 1 and printed on color paper in the same manner as in Example 1.

It was confirmed that the obtained print was a print of good image quality comparable to the print obtained from the film of Group II of Example 1 above.

Considering this result and the result of Example 1 together, the multilayer color light-sensitive material according to the present invention has the number of perforations of 1 or 2 per screen, and the area of the screen of the exposed portion is 3.60 cm. ² to 6.42 cm ²
As a result, it is apparent that it is preferable to use it as a color film for photographing. Example 4 Multilayer color photosensitive materials A-1 and B- produced in Example 1
Film group II using 1, D-1, D-2 and D-3
Using a color negative film obtained from (two perforations per screen, the screen area of the exposed portion is 5.01 cm ² ), using a stretcher similar to that in Example 1, these were used for Fuji Color Crystal Paper and Fuji Color High Film. It was printed on a metallic paper at the same magnification (the processing of the paper at this time was carried out by using CP-45X).

The obtained prints were evaluated in the same manner as in Example 1 by using the prints obtained from C-1 of film group I as a reference.

The results are shown in Table 4.

[0288]

[Table 4] From the results of Table 4, the film group II of Table 3 shown in Example 1
It can be seen from the comparison with the result of the sharpness of No. 1 that the sharpness can be further improved by printing on paper which gives excellent smoothness, good sharpness and three-dimensional effect even with the same film.

As a result, the sharpness improved by the "color contrast effect" can be further improved.

Further, in comparison of magenta color to red color of the print, it was found that the color was more vivid and excellent in color reproducibility. Example 5 Multilayer color photosensitive materials A-1 and C- prepared in Example 1
1, the magenta coupler used in the seventh to ninth green-sensitive emulsion layers was replaced with another coupler represented by the general formula (M) in an equimolar amount, as shown in Table 5, and further,
Samples 501 to 510 were prepared by adding the color mixing inhibitors represented by the general formulas (I) to (VII) to the sixth intermediate layer, the ninth green emulsion layer and the tenth yellow filter layer. . The coating amount at this time is 2.0 × for the sixth layer and the tenth layer.
The green sensitive emulsion layer of the ninth layer had a concentration of 1.0 × 10 ⁻⁵ mol / m ² so that the concentration was 10 ⁻⁴ mol / m ² . However, in the polymer compound represented by the general formula (VI), the constituent unit unit of the monomer was converted into mol.

[0291]

[Table 5] These prepared samples were subjected to film processing in the same manner as in the film group II of Example 1, the subject was photographed and color developed in the same manner as in Example 1, and sharpened with C-1 of film group I as a reference. And the color reproducibility were evaluated.

The results are shown in Table 6.

[0293]

[Table 6] From Table 6, it can be seen that the samples printed from the Group II film having the PEN support show excellent sharpness and good color reproducibility, but further contain the color mixture inhibitors represented by the general formulas (I) to (VII). By doing so, it is possible to improve both sharpness and color reproducibility by using samples 504 and 505 and samples 501 to 5
It is clear by comparing 03. Example 6 Multilayer color photosensitive material A-1 prepared in Example 1
D-1, D-2 and D-3, and Samples 501 to 505 produced in Example 5 are described in JP-A-2-27374.
The film storage cartridge described in No. 0 was processed and stored in a width of 24 mm so that the perforations were one on each side edge in the film length direction per screen.
Also, the camera was modified so that this cartridge could be loaded, and the screen size of the exposure unit was 30.0 mm × 12.
The subject was photographed according to the method of Example 1 so that the distance was 0 mm (the exposed screen area was 3.60 cm ² and the aspect ratio was 2.5).

Further, the same sample is similarly used in JP-A-2-273.
The cartridge described in No. 740 is processed and stored so that the perforation has a width of 24 mm and one per side per one screen in the film length direction, and the screen size of the exposure part is 30.0 mm × 21.4 mm ( Exposure screen area 6.42 cm ² , aspect ratio 1.4) and 30.0
mm × 16.7 mm (exposure screen area 5.01 cm ² ,
The same photographing was carried out so that the aspect ratio was 1.80) (the film one frame feed at this time was set to 31.7 mm in accordance with the screen area of the above-mentioned exposure part).

Subject (one mannequin, upper body, resolution evaluation chart and color checker chart)
In each of the shootings, the shooting distance was determined so that the subject was exactly in the vertical position of the screen of the exposure unit.

These photographed films were processed as described in Example 1 and printed on color paper in the same manner as in Example 1.

The prints obtained are of similar good print quality as compared to the prints of the same samples obtained from the films of group II of example 1 and samples 501 to 505 of example 5 above. Was confirmed.

By making the film 24 mm wide, it was possible to reduce the size of the cartridge and the size of the camera.

[0299]

INDUSTRIAL APPLICABILITY The silver halide color photographic light-sensitive material of the present invention is excellent in image quality of a color image to be obtained, particularly in sharpness and color reproducibility, and the support can be thinned. Therefore, the screen area can be reduced and the cartridge can be downsized without deteriorating the image quality, which is useful for downsizing 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

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having a layer containing a coupler represented by the general formula (M) shown in the following chemical formula 1 on a support, wherein the support is a belt-shaped polyester base. In this way, 4 or less perforations are formed per screen on one or both of the side edges, and the image area is 3.0 cm ² or more and 7.0 c or less.
m ² or less and the aspect ratio is 1.40 or more and 2.50
A silver halide color photographic light-sensitive material characterized by the following. [Chemical 1] R ₁ in the formula represents a hydrogen atom or a substituent. Z is
It represents a group of non-metal atoms necessary to form a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. 2. The silver halide containing at least one selected from the group of non-color forming and diffusion resistant compounds represented by the general formulas (I) to (VII) shown in the following chemical formulas 2 to 8. The silver halide color photographic light-sensitive material according to claim 1, which is contained in a hydrophilic colloid layer of the color photographic light-sensitive material. [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] In the formula, R ²¹ is a hydrogen atom, an aliphatic group or a heterocyclic group,
R ³¹ and R ⁴¹ are a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R ¹² , R ²² , R ³² , and R ⁷¹ are a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocycle. Group, alkoxy group, aryloxy group, amino group, alkenyl group,
Alkynyl group or hydrazino group, R ⁴² is cyano group, nitro group, perfluoroalkyl group or thioacyl group, G ³¹ is —SO ₂ —, —SO—, —PO (R
³⁵ )-, iminomethylene or -COCO-, and R ³⁵
Is an alkyl group or an aryl group, and G ⁵¹ and G ⁷¹ are G ³¹
And the addition of --CO-- to R ¹³ , R
²³ , R ³³ , R ⁴³ , R ⁵³ , R ⁷³ , R ¹⁴ , R ²⁴ , R ³⁴ ,
R ⁴⁴ , R ⁵⁴ , and R ⁷⁴ are hydrogen atoms or groups that can be removed under alkaline conditions, R ⁷³ may be an alkyl group, R ¹¹ is a substituent on the benzene ring, and Z ⁵¹ forms a ring. Y ⁶¹ is a divalent group having a hydrazine or hydroxylamine structure, L ⁶¹ and L ⁶² are divalent linking groups, and n, m and q are 0, 1 or 2 Yes, j and k are 0 or 1. The groups described above may have a substituent.