JPH06130553A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a highly sensitive silver halide color photographic sensitive material with the improved sharpness and color reproducibility by forming perforations at the side edge (frame) of a film and specifying the area of the picture exposure part per picture and its aspect ratio. CONSTITUTION:At least one kind of the photosensitive silver halide emulsion layer with the photosensitive silver halide emulsion chemically sensitized by at least one kind among a selenium sensitizer, gold sensitizer and sulfur sensitizer is provided on a substrate. The substrate consists of a strip polyester base, >=4 perforations 5 per screen are formed in one or both of the frames 2 and 3, and the area of the picture exposure part 1 per screen is controlled to 3.0-7.0cm<2> and the aspect ratio to 1.40-2.50. The photosensitive layer consists of >=2 layers having different sensitivity, and a photosensitive layer having a different color sensitivity is formed between the lowest-sensitivity layer and the highest-sensitivity layer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material having high sensitivity and improved image quality, particularly sharpness and color reproducibility.

[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 widespread use of cameras equipped with zoom lenses or bifocal lenses have become common. More and more, we are getting more and more diverse photographs.

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

Therefore, as a means for solving the above problems,
For example, U.S. Pat. Nos. 3,490,844 and 4,58.
No. 3,831, and No. 4,650,304, a so-called pseudo-zoom method is proposed in view of 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 at the printing stage and stretches a portion of the negative film screen, resulting in a telescopic effect. To do. By adopting this pseudo zoom method, it becomes possible to shorten the focal length of the lens, and it is expected that the lens will be downsized.

However, this pseudo-zoom method is based on the silver halide color negative roll film housed in the 135-format cartridge which is currently the mainstream. Therefore, a lens having an image circle compatible with the 135 format and a cartridge compatible with the 135 format are required. For this reason, it was difficult to realize an epoch-making small camera as compared with the current 135 format camera.

Further, 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, there is a large variation in image quality between prints obtained from one film, which is one of the factors that cause user dissatisfaction.

In addition to this, there is a strong demand for a technique for increasing the sensitivity without deteriorating the sharpness of the color negative film, and various methods have been developed. For example, in order to obtain desired sensitivity and gradation, a silver halide emulsion used in a light-sensitive material is usually subjected to chemical sensitization using various chemical substances. As a typical method, for example, sulfur sensitization,
Selenium sensitization, sensitization with precious metals such as gold, reduction sensitization,
And various sensitizing methods by these combinations are known. In addition, various improvements have been made to these methods for increasing the sensitivity and improving the graininess.

Regarding selenium sensitization among the above-mentioned sensitization methods, for example, US Pat. Nos. 1,574,944, 1,602,592, 1,623,499, and 3, are disclosed. No. 297,446, No. 3,297,447,
No. 3,320,069, No. 3,408,196
No. 3,408,197, No. 3,442,65
No. 3, No. 3,420,670, No. 3,591,3
No. 85, French Patent Nos. 2,693,038 and 2,0
No. 93,209, Japanese Examined Patent Publication No. 52-34491, No. 44-
No. 15748, No. 52-34492, No. 53-295.
No. 57-22090, JP-A-59-180536.
No. 59-185330 and 59-181337.
No. 59-187338 and No. 59-192241.
Issue No. 60-150046, Issue No. 60-151637
No. 61-246738, British Patent No. 255546.
No. 86,1984 and H.H. E. Spencer
Et al., Journal of Photographi
c Science, Vol. 31, pp. 158-169 (1963).

[0009]

In order to solve the above problems of the pseudo zoom method, it is most effective to reduce the screen area of the color negative film to reduce the image circle of the lens. However, the reduction of the screen area of the film causes deterioration of print image quality (granularity, sharpness). According to the results of the market test on the image quality of the print, it is clear that it is not acceptable to general users unless the image quality is improved, and in particular, improvement of sharpness is strongly desired.

Image quality of color negative films, especially sharpness,
There are roughly two types of methods for improving color reproducibility: a method for improving a direct internal factor and a method for improving a direct external factor.

As a method for directly improving the internal factors, it is generally known that a development inhibitor releasing type coupler (so-called DIR coupler) has an effect of improving the sharpness of a color negative film. This DIR coupler is, for example, a research disclosure (RD) -176.
Patents described in paragraphs 43VII to F, JP-A-57-151
944, 57-154234, 60-1842.
48, 60-37346, U.S. Pat. No. 4,24.
No. 8,962. However, for a small format color negative product having a larger print magnification, the effect was insufficient with the DIR coupler alone.

Direct external factors that cause deterioration of sharpness include, for example, the flatness of the color photographic film in the camera at the time of photographing, or at the time of printing, particularly at high magnification and long-time exposure. The flatness of the color negative at the time of is mentioned. The major factors that impair the flatness are hygroscopicity and curling of cellulose triacetate (hereinafter abbreviated as TAC) which is generally used as a support (base) for color negatives. This TAC base has excellent properties that it has no optical anisotropy and has high transparency, and that it has high water absorption so that curling curls once formed after development processing can be eliminated. However, when it is stored in a roll form for a long period of time, curling curls strongly remain, and as described above, the poor flatness at the time of photographing greatly impairs the sharpness of the color negative. Also,
As described above, since the water absorption is high, the humidity dependency is large, and the curl state at the time of photographing differs depending on the humidity when stored in a roll form, which causes a serious problem that a constant image quality cannot be obtained. In addition, TAC bases also have the disadvantage of poor mechanical strength.

Further, it has been found that the number of perforations of the current 135 color photographic film also deteriorates sharpness and causes variations.

As described above, in the case of a small-format color negative having a small image exposure screen and therefore requiring a high expansion ratio, in addition to improving the sharpness of the photosensitive layer itself, a support constituting the color negative, Furthermore, comprehensive improvement with the processing form of color negative as a photographic film is important for higher image quality improvement.

Therefore, the object of the present invention is not only the photosensitive layer but also the support constituting the light-sensitive material, and the processed form as a film. The object of the present invention is to provide a silver halide color photographic light-sensitive material having improved properties and color reproducibility.

[0016]

Means for Solving the Problems Based on these circumstances, as a result of intensive research, the present inventor has found that the above problems can be achieved by the means described below. That is, the silver halide color photographic light-sensitive material of the present invention comprises
Halogen having at least one light-sensitive silver halide emulsion layer chemically sensitized with a selenium sensitizer, a gold sensitizer and a sulfur sensitizer on a support. In a silver halide color photographic light-sensitive material, the support comprises a belt-shaped polyester base,
Its side edges of one or both on one screen per 4 or less Pa - Foret - Deployment is formed, the area per one screen of the image exposure unit is 3.0 cm ² or more, 7.0 cm ² or less, an aspect ratio Is 1.40 or more and 2.50 or less.

In the silver halide color photographic light-sensitive material of the present invention, each of the light-sensitive silver halide emulsion layers is at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive halogen. At least one light-sensitive layer comprises two or more layers having different sensitivities, and in these layers having different sensitivities, the lowest sensitivity layer is located on the side closer to the support, It is preferable that the layers are arranged so that the layers become more sensitive in order with increasing distance from each other, and that a photosensitive layer having different color sensitivity is provided between the lowest sensitivity layer and the highest sensitivity layer.

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 of the present invention will be described.

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

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

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

The effect is exhibited when the treatment 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 the undercoat,
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 of more than 200 ° C. Therefore, the preferable Tg is 90 ° C. or higher and 200 ° C. or lower.

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

[0028]

[Chemical 1]

[0029]

[Chemical 2] 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,

[0031]

[Chemical 3]

[0032]

[Chemical 4] Can be mentioned.

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

Further, 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.

[0036]

[Chemical 5] 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.

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

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

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

In JP-A-3-041435, the polyester base according to the present invention is described in the description of the color sensitive material in which the thickness of the transparent base, the thickness of the back layer and the total thickness are defined. Although partly disclosed, there is no description that defines the exposure screen area and the number of perforations.

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

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

Polyester, particularly aromatic polyester, has a high refractive index of 1.6 to 1.7, while gelatin, which is the main component of the photosensitive layer coated on the polyester, 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 in view of the general properties 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 any of these polymer films is used as a 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).

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

Among the surface treatments of (1) above, corona discharge treatment is the most well-known method, and any conventionally known method, for example, Japanese Patent Publication Nos. 48-5043 and 47-43.
-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 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 direct current 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 multilayer 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, in many cases, good adhesion is achieved by swelling the support and interfacial mixing with the hydrophilic undercoating polymer.

Examples of the hydrophilic undercoating 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.

As the compound for swelling the support used in the present invention, for example, 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, the undercoating liquid may contain various additives, 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 generally 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 slip agent, 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 or less.
Ωcm or less, more preferably 10 ⁵ Ωcm or less.
The particle size is 0.01 to 0.7 μ, especially 0.0
It is desirable that it is 2 to 0.5 μ.

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

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

The silver halide color photographic light-sensitive material of the present invention forms perforations on one or both side edges in the lengthwise direction of 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 examples of the film according to the present invention, and FIG. 9 is FIGS.
It is a figure which shows the cross section of the thickness direction of the film shown in FIG.

As shown in FIGS. 1 to 8, the film is a 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 perforations is not particularly limited, and various shapes such as squares and hexagons such 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 particularly limited either, but it is preferable that it is smaller from the viewpoint that the frame portions 2 and 3 function as the information recording portion. The ratio of the total area of perforations is the area of one screen (A × B = S ₁ shown in FIG. 2)
Is 5% or less, preferably 3% or less,
It is particularly preferably 2% or less and 0.1% or more.

Further, in order to secure the area of the optical or magnetic information recording portion, 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 photographs are greatly increased. Have been found to increase. The three types of aspect ratios are the following three. (1) Low aspect ratio 1.40 to 1.60 (2) Medium aspect ratio 1.70 to 1.90 (3) High aspect ratio 2.00 to 3.00 Needless to say, even if the types of prints are increased. good.

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

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

On the other hand, considering that a high aspect ratio print has a high enlargement ratio, in order to maintain the print image quality, the area of one 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 film cartridge. However, it is difficult to achieve the effects of the present invention and achieve the object when the image area is made smaller than the existing half size. Therefore, the area of the image portion is 3.0 cm ² or more, is set to 7.0 cm ² or less, particularly preferably 4.0 cm ² or more, 6.0 cm ²
It is the following.

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

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

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

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

In the present invention, the silver halide grains contained in at least one photosensitive silver halide emulsion layer are chemically sensitized with at least one of a selenium sensitizer, a gold sensitizer and a sulfur sensitizer. Has been done. Hereinafter, the chemical sensitization and the sensitizer will be described in detail.

Here, selenium sensitization is carried out by a conventionally known method. That is, it is usually carried out by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Selenium sensitization using the unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Specific examples of unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, and selenophosphates. Particularly preferred unstable selenium compounds are shown below.

I. Colloidal metal selenium II. Organic selenium compound (selenium atom is double-bonded to carbon atom of organic compound by covalent bond) a isoselenocyanate For example, aliphatic isoselenocyanate such as allyl isoselenocyanate b selenourea (enol type For example, selenoureas and, for example, methyl, ethyl,
Propyl, isopropyl, butyl, hexyl, octyl, dioctyl, tetramethyl, N- (β-carboxyethyl) -N ′, N′-dimethyl, N, N-dimethyl,
Aliphatic selenoureas such as diethyl and dimethyl; aromatic selenoureas having one or more aromatic groups such as phenyl and tolyl; heterocyclic selenou having heterocyclic groups such as pyridine and benzothiazolyl Urea Particularly preferred selenoureas are 4-substituted selenoureas. Specific examples are shown in Chemical Formulas 6 to 7 below.

[0100]

[Chemical 6]

[0101]

[Chemical 7] c selenoketones, for example, selenoacetone, selenoacetophenone, selenoketone in which an alkyl group is bonded to -C (= Se)-, selenobenzophenone d selenoamides, for example, selenoamide.

E Selenocarboxylic acids and esters.

For example, 2-selenopropionic acid, 3-selenobutyric acid, methyl 3-selenobutyrate.

III. Others a. Selenides For example, diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide, triisopropylphosphine selenide, tri-n-butylphosphine selenide, diphenyl-pentafluorophenylphosphine selenide, di-n-butyl-phenylphosphine selenide, tris-2,4,6 -Trichlorophosphine selenide, phenyl-bis-pentachlorophenylphosphine selenide.

B selenophosphates For example, tri-p-tolylselenophosphate, tri-p-tolyl
n-Butylselenophosphate.

Preferred types of labile selenium compounds have been described above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and have no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, such a broad concept of unstable selenium compounds is advantageously used.

Japanese Patent Publication No. 46-4553, Japanese Patent Publication No. 52-3
Selenium sensitization using the non-labile selenium sensitizers described in JP-B-4492 and JP-B-52-34491 can also be used. Examples of the non-labile selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diaryl selenides,
Included are diaryl diselenides, 2-thioselenazolidinediones, 2-selenooxazolidinethiones and their derivatives.

The non-labile selenium sensitizer and thioselenazolidinedione compound described in JP-B-52-38408 are also effective.

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, and are added at the time of chemical sensitization. It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one kind, and two or more kinds of the above selenium sensitizers can be used in combination. A combination of an unstable selenium compound and a non-unstable selenium compound is preferred.

The addition amount of the selenium sensitizer used in the present invention varies depending on, for example, the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and preferably, The amount is 1 × 10 ^-8 mol or more per mol of silver halide. More preferably 1 × 10 ⁻⁷ mol or more and 5 ×
It is 10 ^-5 mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or higher and 80 ° C. or lower. pAg and p
H is arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9.

The selenium sensitization of the present invention is more effective when carried out in the presence of a silver halide solvent.

The silver halide solvent which can be used in the present invention is, for example, US Pat. No. 3,271,157.
No. 3,531,289, No. 3,574,62
No. 8, JP-A Nos. 54-1019 and 54-158917.
(A) organic thioethers described in JP-A Nos. 53-82408, 55-77737 and 5;
(B) thiourea derivative described in JP-A-5-2982, (c) silver halide having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in JP-A-53-144319. Solvent, JP-A-54-10071
(D) imidazoles described in No. 7, (e) sulfite, and (f) thiocyanate.

Particularly preferred solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1 per mol of silver halide.
It is not less than × 10 ^-4 mol and not more than 1 × 10 ^-2 mol.

In the chemical sensitization, the emulsion of the present invention uses sulfur sensitization and gold sensitization in addition to selenium sensitization.

The sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

For sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Rhodanine can be mentioned. In addition, for example, U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, and 2,728,668,
No. 3,501,313, No. 3,656,955
No. 1, German Patent 1,422,869, Japanese Patent Publication No. 56-2
The sulfur sensitizers described in JP-A-4937 and JP-A-55-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount will vary over a considerable range under various conditions, such as pH, temperature, size of silver halide grains, but will be 1 x 10 per mole of silver halide.
^It is preferably ^-7 mol or more and 5 × 10 ^-5 mol or less.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Representative examples include, for example, chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, and pyridyl trichlorogold.

The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is 1 × 10 ^-7 per mol of silver halide.
It is preferably not less than 5 and not more than 5 × 10 ⁻⁵ mol.

At the time of chemical ripening, for example, the timing and order of addition of a silver halide solvent, a selenium sensitizer, a sulfur sensitizer and a gold sensitizer need not be particularly limited. The above compounds can be added at the same time (preferably) or during the chemical ripening, or at different addition points. In addition, upon addition, an organic solvent capable of mixing the above compound with water or water,
For example, it may be added after being dissolved in a single liquid or a mixed liquid of methanol, ethanol, and acetone.

The silver halide emulsion used in the present invention is preferably reduction-sensitized during the grain formation process.

The fact that reduction sensitization is applied to the grain formation process of a silver halide emulsion basically means that it is performed during nucleation, ripening and growth. The reduction sensitization may be carried out at any stage of nucleation, physical ripening and growth which are the initial stages of grain formation. Most preferred is a method of reduction sensitization during the growth of silver halide grains. Here, the term "during growth" refers to a method in which the silver halide grains are physically ripened or subjected to reduction sensitization while they are growing by the addition of a water-soluble silver salt and a water-soluble alkali halide. It means that the method also includes a method of performing reduction sensitization in the above state and then further growing.

The above-mentioned reduction sensitization is a method in which a known reducing agent is added to a silver halide emulsion, pAg1 called silver ripening.
Method of growing or aging in a low pAg atmosphere of 7,
Any method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Examples of the reduction sensitizer include stannous salt,
Amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, and borane compounds are known. In the present invention, these known compounds can be selected and used, and two or more kinds of compounds can be used in combination. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and ascorbic acid derivatives are preferable compounds. The addition amount of the reduction sensitizer depends on the emulsion production conditions, so it is necessary to select the additive, but the range of 10 ^-8 to 10 ^-3 mol per mol of silver halide is suitable.

The reduction sensitizer may be dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain formation. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for particle formation. Further, particles may be formed using an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide. In addition, it is also a preferable method to add the solution of the reduction sensitizer in several batches or to add the solution continuously as the grains are formed.

In the silver halide emulsion of the present invention, more preferably 5 × 10 ^-5 mol or more of a palladium compound is added per mol of silver halide after the completion of the grain formation process and preferably before the desalting process.

Here, the palladium compound is palladium 2
It means a valent salt or a tetravalent salt. Preferably the palladium compound is represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, chlorine,
Represents a bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ )
₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K 2
PdBr ₄ is preferred.

Most preferably, these palladium compounds are used in combination with thiocyanate ions in an amount 5 times or more the molar amount of the palladium compound.

The silver halide emulsion of the present invention is preferably spectrally sensitized before use.

As the spectral sensitizing dye used in the present invention, a methine dye is usually used.
Included are merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemitoxonol dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, for example, pyrroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole, imidazole, tetrazole, pyridine; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring in these nuclei. A fused nucleus, ie, for example,
Indolenine, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole and quinoline can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one, thiohydantoin, 2-thiooxazolidine-2,4-dione, thiazolidine-2,4
-5- to 6-membered heterocyclic nuclei of dione, rhodanine, thiobarbituric acid can be applied.

Among the above dyes, the sensitizing dye particularly useful in the present invention is a cyanine dye. Specific examples of the cyanine dye useful in the present invention include dyes represented by the general formula (1) shown in the chemical formula 8 below.

[0135]

[Chemical 8] In the general formula (1), Z ₁ and Z ₂ are heterocyclic nuclei usually used for cyanine dyes, particularly, for example, thiazole, thiazoline, benzothiazole, naphthothiazole, oxazole, oxazoline, benzoxazole, naphthoxazole, tetrazole, pyridine. , Quinoline, imidazoline, imidazole, benzimidazole, naphthimidazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole or indolenine, is a group of atoms necessary for completion. These nuclei include, for example, lower alkyl such as methyl, halogen atom, phenyl,
It may be substituted with hydroxyl, an alkoxy group having 1 to 4 carbon atoms, carboxyl, alkoxycarbonyl, alkylsulfamoyl, alkylcarbamoyl, acetyl, acetoxy, cyano, trichloromethyl, trifluoromethyl, nitro.

L ₁ or L ₂ represents a methine group or a substituted methine group. For example, the substituted methine group includes, for example, a lower alkyl group such as methyl or ethyl, for example, a methine group substituted with phenyl, substituted phenyl, methoxy or ethoxy.

R _a and R _b are an alkyl group having 1 to 5 carbon atoms; a substituted alkyl group having a carboxyl group;
-Sulfoethyl, γ-sulfopropyl, δ-sulfobutyl, 2- (3-sulfopropoxy) ethyl, 2- [2-
(3-sulfopropoxy) ethoxy] ethyl, a substituted alkyl group having a sulfo group such as 2-hydroxysulfopropyl; an allyl group and other substituted alkyl groups usually used as N-substituents of cyanine dyes. Represent. m represents 1, 2 or 3. The anion of X represents an acid anion group usually used for cyanine dyes such as iodine ion, bromine ion, p-toluenesulfonate ion and perchlorate ion. n represents 1 or 2,
When taking a betaine structure, n is 1.

As the spectral sensitizing dye, those described below are used in addition to the above. For example, German Patent 929,080 and US Patent 2,493,748.
No. 2,503,776, 2,519,001
Nos. 2,912,329, 3,656,959
Issue No. 3,672,897 Issue No. 3,694,217
No. 4,025,349, No. 4,046,572
No. 2,688,545, 2,977,229
Issue No. 3,397,060 Issue 3,522,052
Issue 3, Issue 3,527,641, Issue 3,617,293
No. 3,628,964, 3,666,480
Issue 3, Issue 3,672,898, Issue 3,679,428
Issue 3, Issue 3,703,377, Issue 3,814,609
No. 3,837,862, 4,026,707
No., British Patent Nos. 1,242,588 and 1,344,2
No. 81, No. 1,507,803, Japanese Patent Publication No. 44-14,
No. 030, No. 52-24, 844, No. 43-4936.
No. 53-12,375, JP-A No. 52-110,6.
No. 18, No. 52-109, 925, No. 50-80, 8
No. 27.

The amount of the sensitizing dye added during the preparation of the silver halide emulsion cannot be unambiguously stated depending on, for example, the kind of the additive and the amount of silver halide, but the amount added by the conventional method. Can be used in approximately the same amount as.

That is, the preferable addition amount of the sensitizing dye is 0.001 to 100 mmol, and more preferably 0.01 to 10 mmol per mol of silver halide.

The sensitizing dye is added after chemical ripening or before chemical ripening. Most preferably, the sensitizing dye is added to the silver halide grains of the present invention during the chemical ripening or before the chemical ripening (for example, during grain formation and physical ripening).

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, an aminostill compound substituted with a nitrogen-containing heterocyclic group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), an aromatic organic acid formaldehyde condensate (for example, US Patent 3,743
No. 510), a cadmium salt, and an azaindene compound. US Patent 3,615,613
No. 3,615,641, No. 3,617,295
No. 3,635,721, the combination is particularly useful.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles [eg, benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds)]; heterocyclic mercapto compounds [eg, mercaptothiazoles, Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptotetrazole), mercaptopyrimidines]; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketone compounds [eg, oxazoline thione]; azaindenes [eg, tetraazaindenes (especially 4 -Hydroxy-substituted (1,3,3a, 7) tetraazaindenes)]; benzenethiosulfonic acids; benzenesulfinic acid; many compounds known as antifoggants or stabilizers can be added.

The antifoggant or stabilizer is usually added after the chemical sensitization, but more preferably during the chemical ripening or before the start of the chemical ripening. . That is, in the process of forming silver halide emulsion grains, during the addition of the silver salt solution, after the addition until the start of chemical ripening, during the chemical ripening (during the chemical ripening, preferably within the time from the start to 50%, Preferably within 20% of the time).

Specifically, a tetraazaindene compound having at least one hydroxy group, a benzotriazole compound, a heterocyclic compound substituted with at least one mercapto group and having at least two aza nitrogen atoms in the molecule. Can be mentioned.

As the tetraazaindene compound having at least one hydroxy group, compounds represented by the following general formulas (2) or (3) are preferable.

[0147]

[Chemical 9]

[0148]

[Chemical 10] Here, R ₁₁ and R ₁₂ in the general formulas (2) and (3) may be the same or different and each is a hydrogen atom; an aliphatic residue [an alkyl group (for example, methyl, ethyl, propyl,
Pentyl, hexyl, octyl, isopropyl, sec
-Butyl, t-butyl, cyclohexyl, cyclopentylmethyl, 2-norbornyl); an alkyl group substituted with an aromatic residue (eg, benzyl, phenethyl, benzhydryl, 1-naphthylmethyl, 3-phenylbutyl); an alkoxy group A substituted alkyl group (eg,
Methoxymethyl, 2-methoxyethyl, 3-ethoxypropyl, 4-methoxybutyl): an alkyl group substituted with a hydroxy group, a carbonyl group or an alkoxycarbonyl group (for example, hydroxymethyl, 2-hydroxyethyl, 3-hydroxybutyl, Carboxymethyl, 2-
Carboxyethyl, 2- (methoxycarbonyl) ethyl)] or an aromatic residue [aryl group (eg, phenyl, 1-naphthyl); aryl group having a substituent (eg, p-tolyl, m-ethylphenyl, m-) Cumenyl,
Mesityl, 2,3-xylyl, p-chlorophenyl, o
-Bromophenyl, p-hydroxyphenyl, 1-hydroxy-2-naphthyl, m-methoxyphenyl, p-ethoxyphenyl, p-carboxyphenyl, o- (methoxycarbonyl) phenyl, m- (ethoxycarbonyl) phenyl, 4- Carboxy-naphthyl)]. The total carbon number of R ₁₁ and R ₁₂ is preferably 12 or less. n represents 1 or 2.

Specific examples of the hydroxytetraazaindene compound represented by the general formula (2) or (3) are shown below. However, the compounds used in the present invention are not limited to these.

2-1 4-hydroxy-6-methyl-
1,3,3a, 7-Tetraazaindene 2-2 4-hydroxy-1,3,3a, 7-tetraazaindene 2-3 4-hydroxy-6-ethyl-1,2,3
a, 7-Tetraazaindene 2-4 4-hydroxy-6-phenyl-1,3,3
a, 7-Tetraazaindene 2-5 4-methyl-6-hydroxy-1,3,3
a, 7-Tetraazaindene 2-6 2,6-dimethyl-4-hydroxy-1,
3,3a, 7-Tetraazaindene 2-7 4-hydroxy-5-ethyl-6-methyl-
1,3,3a, 7-Tetraazaindene 2-8 2,6-dimethyl-4-hydroxy-5-ethyl-1,3,3a, 7-tetraazaindene 2-9 4-hydroxy-5,6- Dimethyl-1,
3,3a, 7-Tetraazaindene 2-10 2,5,6-trimethyl-4-hydroxy-1,3,3a, 7-tetraazaindene 2-11 2-methyl-4-hydroxy-6-phenyl- 1,3,3a, 7-Tetraazaindene 2-12 4-hydroxy-6-ethyl-1,2,3
a, 7-Tetraazaindene 2-13 4-hydroxy-6-phenyl-1,2,
3a, 7-Tetraazaindene 2-14 4-hydroxy-1,2,3a, 7-tetraazaindene 2-15 4-methyl-6-hydroxy-1,2,3
a, 7-Tetraazaindene 2-16 5,6-trimethylene-4-hydroxy-
1,3,3a, 7-Tetraazaindene Further, as the benzotriazole compound,
Examples thereof include those represented by the general formula (4).

[0151]

[Chemical 11] In general formula (4), p is 0 or an integer of 1-4. R ₁₃ is a halogen atom (chlorine, bromine or iodine) or an aliphatic group (including a saturated aliphatic group and an unsaturated aliphatic group), for example, preferably an unsubstituted alkyl group having 1 to 8 carbon atoms (eg, , Methyl, ethyl, n-propyl, hexyl); substituted alkyl groups (preferably having an alkyl radical (moiety) having 1 to 4 carbon atoms, for example, a vinylmethyl group}, an aralkyl group (for example, benzyl, phenethyl), Hydroxyalkyl groups (eg,
2-hydroxyethyl, 3-hydroxypropyl, 4-
Hydroxybutyl), acetoxyalkyl group (for example,
2-acetoxyethyl, 3-acetoxypropyl), an alkoxyalkyl group (for example, 2-methoxyethyl, 4
-Methoxybutyl); or an aryl group (eg, phenyl). R ₁₃ is more preferably a halogen atom (chlorine or iodine) or an alkyl group having 1 to 3 carbon atoms (methyl, ethyl or propyl).

Specific examples of the benzotriazole compound used in the present invention are listed below. However, the benzotriazole compound used in the present invention is not limited to these.

Compound 4-1 Benzotriazole Compound 4-2 5-Methyl-benzotriazole Compound 4-3 5,6-Dimethylbenzotriazole Compound 4-4 5-Bromo-benzotriazole Compound 4-5 5-chloro-benzotriazole Compound 4-6 5-Nitro-benzotriazole Compound 4-7 4-Nitro-6-chlorobenzotriazole Compound 4-8 5-Nitro-6-chlorobenzotriazole Addition of the antifoggant or stabilizer used in the present invention The amount cannot be uniquely determined by the addition method and the amount of silver halide, but is preferably 10 ^-7 mol to 10 ^-2 mol, and more preferably 10 ^-5 to 10 ^-2 mol per mol of silver halide. is there.

Next, a heterocyclic compound substituted with at least one mercapto group and having at least two aza nitrogen atoms in the molecule (hereinafter referred to as a nitrogen-containing heterocyclic compound having a mercapto group) explain. In addition to the nitrogen atom, the heterocycle of such a compound may have a heteroatom such as an oxygen atom, a sulfur atom, or a selenium atom. Preferred compounds are monocyclic heterocyclic compounds having at least two 5- or 6-membered aza nitrogen atoms, or two rings formed by condensing two or three heterocycles having at least one aza nitrogen atom, or A tricyclic heterocyclic compound in which a mercapto group is substituted on the carbon atom adjacent to the aza nitrogen.

In the nitrogen-containing heterocyclic compound having a mercapto group which can be used in the present invention, as the heterocycle, pyrazole, 1,2,4-triazole, 1,2,3-serialazole, 1,3,4-thiadiazole, 1, 2, 3
-Thiadiazole, 1,2,4-thiadiazole, 1,
2,5-thiadiazole, 1,2,3,4-tetrazole, pyridazine, 1,2,3-triazine, 1,2,4
-Triazine, 1,3,5-triazine, and a ring formed by condensing 2 to 3 of these rings, for example, triazolotriazole, diazaindene, triazaindene, tetrazaindene, pentazaindene can be applied. A heterocycle in which a monocyclic heterocycle and an aromatic ring are condensed, for example, a phthalazine ring or an indazole ring can also be applied.

Preferred among these rings are 1, 2,
4-triazole, 1,3,4-thiadiazole, 1,
2,3,4-tetrazole, 1,2,4-triazine,
Triazolotriazole and tetrazaindene.

The mercapto group may be substituted on any carbon atom of these rings, but preferred is when a bond as shown in the following chemical formula 12 is formed.

[0158]

[Chemical 12] The heterocycle may have a substituent other than the mercapto group.
Examples of the substituent include an alkyl group having 8 or less carbon atoms (eg, methyl, ethyl, cyclohexyl, cyclohexylmethyl), a substituted alkyl group (eg, sulfoethyl, hydroxymethyl), an alkoxy group having 8 or less carbon atoms (eg, methoxy). , Ethoxy), alkylthio groups having 8 or less carbon atoms (methylthio, butylthio), hydroxyl groups, amino groups, hydroxyamino groups, alkylamino groups having 8 or less carbon atoms (eg, methylamino, butylamino), and 8 or less carbon atoms Dialkylamino group (eg, dimethylamino, diisopropylamino), arylamino group (eg, anilino), acylamino group (eg,
Acetylamino), a halogen atom (eg chlorine, bromine), a cyano group, a carboxy group, a sulfo group, a sulfato group, and a phospho group can be applied.

The mercapto compound which is preferably used in combination with the selenium-sensitized emulsion in the present invention is represented by formula (A).

General formula (A) Q-SM ^{1 In the} formula, Q is directly or indirectly bonded to at least one member selected from the group consisting of —SO ₃ M ² , —COOM ² , —OH and —NR ¹ R ^2. Represents a heterocyclic residue represented by M ¹ ,
M ² independently represents a hydrogen atom, an alkali metal, a quaternary ammonium or a quaternary phosphonium, and R ¹ and R ² represent a hydrogen atom or a substituted or unsubstituted alkyl group.

Specific examples of the heterocyclic residue represented by Q in the general formula (A) include, for example, oxazole ring, thiazole ring, imidazole ring, selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring. , A pentazole ring, a pyrimidine ring, a thiadia ring, a triazine ring and a thiadiazine ring, or a ring bonded to another carbon ring or a heterocyclic ring, for example, a benzothiazole ring, a benzotriazole ring, a benzimidazole ring, a benzoxazole ring, a benzoselenazole ring. , Naphthoxazole ring, triazaindolizine ring, diazaindolizine ring, tetraazaindolizine ring.

Among the mercapto heterocyclic compounds represented by the general formula (A), particularly preferable compounds are shown below.
The compounds represented by the general formulas (B) and (C) shown in Chemical formula 14 can be mentioned.

[0163]

[Chemical 13]

[0164]

[Chemical 14] In the general formula (B), Y and Z each independently represent a nitrogen atom or CR ₂₂ (R ₂₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), and R ₂₁ -SO ₃ M ^2, -COOM ² -O
H and -NR ₂₃ R ₂₄ is an organic residue substituted with at least one selected from the group consisting of R ₂₄ , R ₂₃ and R ₂₄ represent an alkyl group and an aryl group, respectively, and R ₂₃ and R ₂₄ are the same. Or may be different. Specifically, an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl,
Propyl, hexyl, dodecyl, octadecyl), aryl groups having 6 to 20 carbon atoms (eg phenyl, naphthyl)
And L ¹ is -S-, -O-, -N-, -CO-,-.
SO- and -SO ₂ - shows a linking group selected from the group consisting of, n is 0 or 1.

In these alkyl groups and aryl groups,
For example, a halogen atom (eg, F, Cl, B
r), an alkoxy group (eg, methoxy, methoxyethoxy), an aryloxy group (eg, phenoxy group),
Alkyl group (when R ₂₄ is an aryl group), aryl group (when R ₂₄ is an alkyl group), amide group (eg acetamide, benzoylamino), carbamoyl group (eg unsubstituted carbamoyl, phenylcarbamoyl, methylcarbamoyl) , A sulfonamide group (eg, methanesulfonamide group, phenylsulfonamide group), a sulfamoyl group (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl), a sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), A sulfinyl group (eg, methylsulfinyl,
Phenylsulfinyl), cyano groups, alkoxycarbonyl groups (eg methoxycarbonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), and other substituents of the nitro group.

Here, the substituent of R ₂₁ is —SO ₃ M or —COO.
When two or more M ² , —OH and —NR ₂₃ R ₂₄ are present, they may be the same or different.

M ² has the same meaning as that represented by the general formula (A).

On the other hand, in the general formula (C), X represents a sulfur atom, an oxygen atom or —N (R ₂₅ ) —, and R ₂₅ is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. Represents an aryl group.

[0169] L ² is _{-CONR 26 -, - NR 26 CO-} ,
_{-SO 2 NR 26 -, - NR} 26 SO 2 -, - OCO -, -
COO -, - S -, - NR 26 -, - CO -, - SO-,
_{-OCOO -, - NR 26 CONR 27} -, - NR 26 COO
-, - OCONR ₂₆ - or -NR ₂₆ SO ₂ NR ₂₇ - represents a represents R _26, R ₂₇ are each a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

R ₂₁ and M ² have the same meanings as those represented by formulas (A) and (B), and n represents 0 or 1.

Further, as the substituent of the alkyl group and aryl group represented by R ₂₂ , R ₂₅ , R ₂₆ and R ₂₇ , the same substituents as those mentioned for R ₂₁ can be mentioned.

In the general formula, those in which R ₂₁ is —SO ₃ M ² and —COOM ² are particularly preferable.

Specific examples of preferred compounds represented by formula (A) used in the present invention are shown in the following chemical formulas 15 to 21.

[0174]

[Chemical 15]

[0175]

[Chemical 16]

[0176]

[Chemical 17]

[0177]

[Chemical 18]

[0178]

[Chemical 19]

[0179]

[Chemical 20]

[0180]

[Chemical 21] The compound represented by the general formula (A) is known, and can be synthesized by the methods described in the following documents.

For example, US Pat. No. 2,585,388
No. 2, 541, 924, Japanese Patent Publication No. 42-21, 84
No. 2, JP-A-53-50,169, British Patent Nos. 1 and 2.
75,701, D.I. A. Barges et al., “Journal of Heterocyclic Chemistry” (D.
A. Berges et. al. , "Journal
of the Heterocyclic Chemi
"Story") Vol. 15, No. 981 (No. 1978), "The
Chemistry of Heterocyclic Chemistry ", Imidazole and Derivatives, Part I (" The Chemistry of Hater
ocyclic Chemistry "Imidazo
le and Derivatives part
I), pp. 336-9, Chemical Abstracts (Ch
electronic Abstracts), 58, 7921
No. (1963), p. 394, E.I. Hogarth, “Journal of the Chemical Society (E. Hoggart
h, “Journal of Chemical So
ciety ") 1160-7 (1949), and S.
R. Sandler, W.D. Caro, "Organic Functional Group Preparations", Academic Press, Inc. (SR Sandler, W. kar
o, “Organic Functional Gro
up Preparations "Academic
Press, Inc.) 312-5 (1968), M.S. Shamdon et al. (M.Chamdon, et al.), Bourtan de la Sochette Simique de France (Bu
lletin de la Society Chim
issue de France), 723 (195)
4), D. A. Shirley, D.M. W. Alley, Journal of the American Chemical Society (DA Shirley, DW Alley.
Amer. Chem. Soc. ), 79, 4922 (1
954), A. Ball, W. Marchwald, Berichte (A. Wohl, W. Marchwald, Ber.)
(German Chemical Society), Vol. 22, 568 (1889),
Journal of American Chemical Society (J. Amer. Chem. Soc.), 44, 15
02-10, U.S. Pat. No. 3,017,270, British Patent No. 940,169, Japanese Patent Publication No. 49-8,334,
Japanese Patent Laid-Open No. 55-59,463, Advanced in Heterocyclic Chemistry (Advanced)
n Heterocyclic Chemistr
y), 9, 165-209 (1968), West German Patent No. 2,716,707, The Chemistry of Heterocyclic Compounds Imidazole and Derivatives (The Chemistry of Derivatives).
Heterocyclic Compounds I
midazole and Derivatives,
Vol 1, p. 384, organic synthesis (O
rg. Synth. ) IV. , 569 (1963), Berichte (Ber.), 9, 465 (1976), Journal of American Chemical Society (J.A.
mer. Chrm. Soc. ), 45, 2390 (19
23), JP-A-50-89,034, 53-28,
No. 426, No. 55-21,007, and JP-A No. 40-2.
No. 8,496.

The compound represented by the general formula (A) is a silver halide emulsion layer, a hydrophilic colloid layer (for example, an intermediate layer,
It is contained in a surface protective layer, a yellow field layer, an antihalation layer), but is preferably contained in a silver halide emulsion layer or its adjacent layer.

The addition amount is 1 × 10 ⁻⁷ to 1 × 1.
0 ^-3 mol / m ² , preferably 5 x 10 ^-7 to 1 x 10
^-4 mol / m ² , more preferably 1 × 10 ^{-6 to} 3 × 10 ^-5 mo
l / m ² .

The emulsion according to the present invention can be used as a mixture with other emulsions. The emulsion of the present invention can be used as a mixture of two or more kinds, or can be used as a mixture with one or two or more kinds of other emulsions. Those having different grain sizes can be mixed, those having different halogen compositions can be mixed, and those having different grain shapes can be mixed. Monodisperse emulsions can be mixed, polydisperse emulsions can be mixed, and monodisperse and polydisperse can be mixed. Preferably, the silver halide emulsion of the present invention contains at least 50% or more of the total projected area.

It is particularly preferable that the silver halide grains used in the present invention are mainly composed of (111) planes. The surface index of silver halide grains can be directly observed from, for example, an electron micrograph of silver halide emulsion grains, or more accurately, the Chemical Society of Japan, 198.
4. (6). P. It is also possible to perform the measurement by a quantitative method utilizing adsorption of a dye as described in 942-947. Mainly (111) plane means that the (111) plane occupies 50% or more of the total area of silver halide grains, preferably 60% or more, and more preferably 70%.
That is all.

Grains mainly composed of (111) planes include tabular silver halide grains (hereinafter also referred to as tabular grains), octahedral normal crystal grains and those lacking corners, and rounded. There are also particles of irregular shape.

In the present invention, tabular grains are most preferably used. The tabular silver halide emulsion preferably used in the present invention will be described in detail below.

In the tabular silver halide emulsion used in the present invention, the average aspect ratio means the average value of the ratio of the diameter to the thickness of the silver halide grains. That is,
It is the average of the values obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter means the diameter of a circle having an area equal to the projected area of a grain when the silver halide emulsion is observed with a microscope or an electron microscope. Therefore, the average aspect ratio of 2: 1 or more means that the diameter of the circle is twice or more the thickness of the particles.

In the present invention, the tabular silver halide grains used in the silver halide emulsion have a grain diameter of 2 times the grain thickness.
It is at least 3 times, preferably 3 to 20 times, more preferably 4 to 15 times, particularly preferably 5 to 10 times. or,
The proportion of tabular silver halide grains in the projected area of all silver halide grains is 50% or more, preferably 70% or more, and particularly preferably 85% or more.

By using such an emulsion, a silver halide photographic light-sensitive material having excellent sharpness can be obtained. The sharpness is excellent because the light scattering by the emulsion layer using such an emulsion is extremely small as compared with the conventional emulsion layer. This can be easily confirmed by those skilled in the art by experimental methods that can be routinely used. The reason why the light scattering of the emulsion layer using the tabular silver halide emulsion is small is not clear, but it is considered that the main surface of the tabular silver halide emulsion is oriented parallel to the support surface.

Further, the tabular silver halide grains have a diameter of 0.
The thickness is 2 to 20 μm, preferably 0.3 to 10.0 μm, and particularly preferably 0.4 to 5.0 μm. The thickness of the particles is preferably 0.5 μm or less. Here, the tabular silver halide grain diameter means the diameter of a circle having an area equal to the projected area of the grain. The grain thickness is represented by the distance between two parallel planes constituting a tabular silver halide grain.

In the present invention, more preferable tabular silver halide grains have a grain diameter of 0.3 μm or more and 10.0 μm or less.
m or less, the particle thickness is 0.3 μm, and the average aspect ratio is 5 or more and 10 or less. If it is more than this, the photographic performance may be abnormal when the light-sensitive material is bent, tightly wound, or touched with a sharp object, which is not preferable. More preferably, it is a silver halide photographic emulsion in which grains having a grain diameter of 0.4 μm or more and 5.0 μm or less and an average aspect ratio of 5 or more occupy 85% or more of the total projected area of all silver halide grains. .

The tabular silver halide grains used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide, but they are silver bromide or iodide. Silver iodobromide containing 15 mol% or less of silver, or 50 mol% or less of silver chloride and 2 mol% of silver iodide
The following silver chloroiodobromide and silver chlorobromide are more preferable, and the composition distribution in the mixed silver halide may be uniform or localized.

The tabular silver halide grains used in the present invention may have a narrow or wide grain size distribution.

The silver halide emulsion comprising tabular silver halide grains used in the present invention is a Cgnac, Chat.
Report of eau and "Photograph" by Duffin
icEmulsion Chemistry "(Foc
Al Press, New York 1966)
Pages 66-72, and A. P. H. Trivelli,
W. F. Smith edition “Photo. Journal” 8
0 (1940) 285, for example, JP-A-58-113927 and JP-A-58-11392.
It can be easily prepared by referring to the method described in No. 8 and No. 58-127921.

For example, a relatively high pA with pBr of 1.3 or less
The weight of tabular silver halide grains is 40 in a g-value atmosphere.
% Of the seed crystal is formed, and the seed crystal is grown by simultaneously adding the silver and halogen solutions while keeping the pBr value at the same level. In this grain growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated.

The size of tabular silver halide grains can be adjusted by, for example, controlling the temperature, selecting the type and quality of the solvent, and controlling the addition rate of the silver salt used during grain growth and the halide. .

During the production of the tabular silver halide grains of the present invention, a silver halide solvent is optionally used so that the grain size, the grain shape (for example, the aspect ratio), the grain size distribution, and the grain growth. You can control the speed. The amount of the solvent used is 10 in the reaction solution.
^{-3 to} 1.0% by weight is preferable, and particularly 10 ^-2 to 10
A range of ^-1 % by weight is preferred. In the present invention, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be promoted, while the thickness of particles also tends to increase with the amount of solvent used.

In the process of forming silver halide grains or physical ripening, for example, cadmium salt, zinc salt, lead salt,
Thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

When the tabular silver halide grains used in the present invention are produced, the addition rate and the addition amount of the silver salt solution (eg AgNO ₃ aqueous solution) and the halide solution (eg KBr aqueous solution) which are added to accelerate the grain growth. The method of increasing the addition concentration is preferably used. Regarding these methods, for example, British Patent No. 1,335,925, US Pat. No. 3,650,757, and US Pat.
No. 0, 4,242, 445, JP-A-55-142.
The descriptions in Nos. 329 and 55-158124 can be referred to.

In the emulsion used in the present invention, 50% of the number of silver halide grains preferably contains 10 or more dislocations per grain.

The dislocations of tabular grains are described, for example, in J. F. Ha
milton, Photo. Sci. Eng. , 11, 5
7, (1967) and T.S. Shiozawa, J .; So
c. Photo. Sci Japan, 35, 213 (1
It can be observed by a direct method using a transmission electron microscope at a low temperature described in 972). That is,
Carefully remove the silver halide grains from the emulsion so as not to apply pressure enough to cause dislocation, and place them on a mesh for electron microscope observation to prevent damage (eg, printout) by electron beams. The sample is cooled and then observed by the transmission method. At this time, the thicker the particles, the more difficult it is for an electron beam to pass therethrough.
It is possible to observe more clearly by using an electron microscope of 200 kV) for particles having a thickness of 25 μm. From the photograph of the grains obtained by such a method, it is possible to observe the position and number of dislocations in each grain when viewed from the direction perpendicular to the main plane.

The positions of dislocations in the tabular silver halide grains used in the present invention occur from the distance x% of the length from the center of the tabular grain in the major axis direction to the side to the side.
The value of x is preferably 10 ≦ x <100, more preferably 30 ≦ x <98, and further preferably 50 ≦ x <95. At this time, the shape formed by connecting the positions where the dislocations start is close to a shape similar to the particle shape, but may not be a perfect shape and may be distorted. The direction of the transition line is from the center to the side, but it often meanders.

Next, the layer arrangement is arranged so that the most sensitive emulsion layer of each of the red-sensitive emulsion layer and / or the green-sensitive emulsion layer located on the side closer to the support of the present invention is located as far as possible from the support. The changed photosensitive material will be described.

The specific photographic sensitivity of the color negative photographic material of the present invention in which the layer arrangement is changed as described above is preferably 320 or more. This is because in the case of a light-sensitive material having low sensitivity, the effect of the present invention is not exerted as much as in a light-sensitive material having high sensitivity. The specific photographic sensitivity is preferably 400 or more, more preferably 800 or more.

The specific photographic speed is a photographic speed obtained by a method according to JIS K 7614-1981 for measuring ISO speed, and the photographic material is not exposed for 5 days after being exposed for sensitometry. After 1 hour, it means the photographic sensitivity obtained by development processing according to the processing recipe described in Example 1 below. The reason for shortening the number of days left to be specified in the JIS test method is to obtain the result quickly, and the development processing is specified to be the processing specified by each company, and therefore it is specifically specified.

The details of the test method for measuring the specific photographic sensitivity are described in JP-A-63-226650 (Japanese Patent Application No. 62-159115, which claims priority based on Japanese Patent Application No. 61-201756). ), Page (4) [440
Page] upper left column to (6) page [442] upper right column.

The color photographic light-sensitive material of the present invention has a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer, and at least one of these emulsion layers is composed of two or more emulsion layers having different sensitivities. , These layers with different sensitivities are
It is preferable that the lowest sensitivity layer is located on the side closer to the support, and the layers are arranged so that the layers become more sensitive in order as the distance from the support increases. Further, it is preferable to provide a photosensitive layer having different color sensitivity between the lowest sensitivity layer and the highest sensitivity layer having the same color sensitivity.

It is more preferable that each color-sensitive layer has a three-layer structure in order to further improve the graininess. This technique is described in Japanese Examined Patent Publication No. 49-149,149. A non-photosensitive layer may be present between each photosensitive emulsion layer. This non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. When light-sensitive emulsion layers having different color sensitivities are adjacent to each other, it is preferable to provide a non-light-sensitive layer between them. Such non-photosensitive intermediate layers are disclosed in JP-A-59-113438, JP-A-59-113440 and JP-A-59-113440.
1-20037, 61-20038, 61-4
Couplers as described in 3748, D
An IR compound or the like may be contained, and a color mixing inhibitor may be contained as is commonly used. In addition, JP-A-59-
It is also preferred to provide a non-photosensitive reflective layer between the photosensitive emulsion layer and the support to improve the sensitivity as described in JP-A No. 160,135. The color photographic light-sensitive material of the present invention usually contains a yellow filter layer, though it is not always necessary.

Specific examples of the order of arranging the light-sensitive emulsion layers in the color photographic light-sensitive material of the present invention are shown below, but the invention is not limited thereto. Although the non-photosensitive layer is omitted here, it may be present at the position as described above.

(1) Support, low-sensitivity red-sensitive emulsion layer (hereinafter RL), low-sensitivity green-sensitive emulsion layer (hereinafter GL), low-sensitivity blue-sensitive emulsion layer (hereinafter BL), high-sensitivity red-sensitive emulsion layer (RH) ),
High sensitivity green sensitive emulsion layer (GH), high sensitivity blue sensitive emulsion layer (B)
H).

(2) Support, RL, GL, BL, GH,
RH, BH (3) support, RL, GL, BL, RH, intermediate green sensitive emulsion layer (GM) (GH), GH, BH (4) support, RL, GL, GM, BL, RH, GH,
BH (5) Support, RL, intermediate red-sensitive emulsion layer (hereinafter R
M), GL, GM, BL, intermediate blue sensitive emulsion layer (hereinafter B)
M), RH, GH, BH (6) Support, RL, GL, BL, RM, RH, GM,
GH, BM, BH (7) support, RL, GL, RH, GH, BL, BH (8) support, GL, RL, RH, GH, BL, BH (9) support, RL, GL, RH , GM, GH, BL,
BH (10) Support, RL, GL, GH, RH, BL, B
H.

In order to improve color reproducibility, US Pat. Nos. 4,663,271 and 4,705,744 are used.
No. 4,707,436, JP-A-62-1604.
48, 63-89850, BL described in the specification,
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 GL and RL, adjacent to or in proximity to the main photosensitive layer.

The silver halides used in the silver halide photographic light-sensitive material of the present invention other than the silver halide of the present invention include silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide. And any of silver chloride may be used. A preferred silver halide is silver iodobromide containing 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing 2 to 20 mol% silver iodide. Further, in order to achieve both high sensitivity and high image quality, the average silver iodide content of silver halide in all emulsion layers is 8 mol% or more as described in JP-A-60-128,443. Is preferred. It is known that if the average silver iodide content of silver halide is increased, the graininess is remarkably improved. However, when the silver iodide content exceeds a certain level, the development speed delay, desilvering and fixing speed Defects such as delay come out.

The silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention contain silver iodide in an amount of 5 mol%.
A core consisting essentially of silver iodobromide contained above and a shell consisting essentially of silver iodobromide or silver bromide having a lower silver iodide content than the core. It is preferable to have a double structure constituted by The silver iodide content of the core is more preferably 10 mol% or more, and most preferably 20 mol% or more and 44 mol% or less. The silver iodide content of the shell is preferably 5 mol% or less.

The core may contain silver iodide uniformly, or may have a multiple structure composed of phases having different silver iodide contents. In the latter case, the silver iodide content of the phase having the highest silver iodide content is 5 mol% or more, more preferably 10 mol% or more, and the silver iodide content of the shell is the core. It is better if it is lower than that of the highest silver iodide content phase. Further, "consisting essentially of silver iodobromide" is mainly composed of silver iodobromide, but other components are also 1 mol%.
It means that up to the order may be contained.

In a more preferred embodiment of the silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention, the diffraction angle (2θ) is 38 to 42 ° C.
When the curve of the diffraction intensity vs. the angle of diffraction of the (220) plane of silver halide was obtained using the Kβ ray of u, there were two diffraction maxima, a diffraction peak corresponding to the core part and a peak corresponding to the shell part. , A minimum appears between them, and the diffraction intensity corresponding to the core part is 1/10 to 3 of that of the shell part.
It is a particle having a structure such that it becomes / 1. Particularly preferably, the diffraction intensity ratio is 1/5 to 3/1, and further 1/3 to 3 /
This is the case of 1.

With such a double structure, it becomes possible to use a high iodine silver iodobromide emulsion without delaying the developing speed, and to obtain a light-sensitive material having excellent graininess even with a small coating amount of silver. Can be achieved.

The average grain size of the silver halide grains in the photographic emulsion (the grain diameter in the case of spherical grains or grains close to sphere,
In the case of cubic grains, the edge length is the grain size, and the average is based on the projected area. ) Is not particularly limited, but 0.05
It is preferably not less than 10 μm and not more than 10 μm. The average size of silver halide grains in each emulsion layer having the highest sensitivity is 0.5.
μm or more and 4 μm or less are preferable, and 0.6 μm or more and 2.5
More preferably, it is less than or equal to μm.

The particle size distribution may be narrow or wide.

The silver halide grains in the photographic emulsion may have regular crystal bodies such as cubes and octagons, or have irregular crystal bodies such as spherical and plate-like grains, or A composite form of these crystal forms may be used. It may consist of a mixture of particles of various crystal forms.

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

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

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

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

The 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. 307105.

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 developing treatment, 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, or mercapto-based compound or a 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.

The known photographic additives which can be used in the present invention or the color development processing of the light-sensitive material of the present invention are described in EP 482,552A, page 38, line 1 to page 41, page 32. The compounds, methods and the like described in the line, and page 41, line 40 to page 45, line 25 can be applied.

[0233]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. (Preparation of emulsion) 30 g of inert gelatin, potassium bromide 6
g, an aqueous solution prepared by dissolving 1 liter of distilled water was stirred at 75 ° C., and an aqueous solution prepared by dissolving 5.0 g of silver nitrate was added thereto.
cc and potassium bromide 3.2g, potassium iodide 0.98g
After adding 35 cc of an aqueous solution in which each was dissolved at a flow rate of 70 cc / min for 30 seconds, the pAg was raised to 10 and ripening was performed for 30 minutes to prepare a seed emulsion.

Successively, an aqueous solution 1 in which 145 g of silver nitrate was dissolved
A predetermined amount of liter and an aqueous solution of a mixture of potassium bromide and potassium iodide were added in equimolar amounts at a predetermined temperature and a predetermined pAg at an addition rate near the critical growth rate to prepare a tabular core emulsion. Further, subsequently, the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a different composition from the preparation of the core emulsion were added in equimolar amounts at an addition rate near the critical growth rate to form a core. Coated core / shell type silver iodobromide emulsions 1-5 were prepared. Emulsions 2 to 5 at this time correspond to tabular emulsions in the present invention.

The aspect ratio was adjusted by appropriately selecting pAg during core and shell preparation. The results are shown in Table 1 below.

In addition, 80% or more of these emulsion grains have 10% or more.
It was confirmed by a transmission electron microscope that there were more than two dislocation lines.

[0237]

[Table 1] Subsequently, the emulsions 1 to 5 were heated to 60 ° C., and the sensitizing dyes ExS-1 to ExS-7 shown in Chemical formulas 31 and 32 below were shown in the photosensitive layer compositions of the following examples according to the color sensitivity. Add quantity, 60
After keeping the mixture at 20 ° C for 20 minutes, at 60 ° C at pH 6.3, which is preferable for use in the present invention, compound (11), sodium thiosulfate, chloroauric acid and potassium thiocyanate are added in the amounts shown in the table. , Gold-sulfur sensitized. The gold-sulfur sensitization was performed so as to be optimum for each emulsion. Here, "to optimize gold-sulfur sensitization" means gold-
Chemical sensitization that maximizes the sensitivity when exposed to 1/100 second after sulfur sensitization. These emulsions 1a, 2
a, 3a, 4a and 5a.

Next, Emulsions 1 to 5 were subjected to gold-sulfur-selenium sensitization. The gold-sulfur-selenium sensitization is performed by the spectral sensitizing dye ExS-1 to ExS-1 represented by the structural formula as described below, as in the gold-sulfur sensitization.
ExS-7 was added in an amount shown in the composition of the photosensitive layer of the following examples according to the color sensitivity, and the mixture was kept at 60 ° C. for 20 minutes and then at 60 ° C.
The pH was adjusted to 6.0, and diphenylpentafluorophenylphosphine selenide was added in an amount shown in Table 2 below, in addition to the chemicals used for the "gold-sulfur" sensitization, to optimize the gold-sulfur-selenium sensitization. I made a sense. 1 of these emulsions
b, 2b, 3b, 4b, 5b and 5c.

[0239]

[Table 2] 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, PCT) in a ratio shown in Table 3 below. : Thickness 80 μm) Supports A-1 and A-2: Commercial polyethylene-2,
100 parts by weight of 6-naphthalate polymer and Tinuvin P.O. 2 parts by weight of 326 (manufactured by Ciba Geigy) were dried by a conventional method, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.3 times at 140 ° C., and then at 130 ° C. for 3. The film was transversely stretched 3 times and further heat-set at 250 ° C. for 6 seconds to obtain films having a thickness of 80 and 122 μm, respectively.

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

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

Supports D-1 to D-2: 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 coating the undercoat layer and the back layer by the above method, Table 3
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 3. As is clear from Table 3, PEN had a flexural modulus of 80 μm and PET had a thickness of 90 μm, which was approximately equivalent to 122 μm of TAC. Further, when the thickness of PEN was increased to 122 μm as in TAC, the flexural modulus was 3 times or more that of TAC.

[0250]

[Table 3] 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, the photosensitive material obtained by coating the photosensitive layer on the support A-1 is a multilayer 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, for the sensitizing dye and the compound represented by the formula (A), the coating amount per mol of silver halide in the same layer is shown in mol unit. (Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.15 Gelatin 0.80 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20 Second layer (intermediate) Layer) Emulsion G Silver 0.060 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-10 .10 HBS-2 0.020 Gelatin 0.70 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion C Silver 0.25 ExS-1 4.5 × 10 ^-4 ExS-2 1. 5 × 10 ^-5 ExS-3 4.5 × 10 ^-4 ExC-1 0.20 ExC-3 0.030 ExC-4 0.10 ExC-5 0.0050 ExC-7 0.0050 ExC-8 0. 020 Cpd-2 0.025 HBS 1 0.15 Gelatin 0.65 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion D silver ^{0.70 ExS-1 2.7 × 10 -4} ExS-2 1.1 × 10 -5 ExS-3 3. 5 × 10 ⁻⁴ ExC-1 0.22 ExC-2 0.060 ExC-4 0.060 ExC-7 0.0010 ExC-8 0.025 Cpd-2 0.023 HBS-1 0.10 Gelatin 0. 60 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion 1a Silver 0.85 ExS-1 1.3 × 10 ^-4 ExS-2 0.6 × 10 ^-5 ExS-3 1.9 × 10 ^-4 ExC- 1 0.10 ExC-3 0.040 ExC-6 0.020 ExC-8 0.007 Cpd-2 0.050 Exemplary compound (23) 4.0 × 10 ⁻⁴ HBS-1 0.25 HBS-20 .10 Gelatin 0.80 6th layer (intermediate layer) Cpd-1 0.10 HB S-1 0.50 Gelatin 0.80 Seventh layer (low-sensitivity green-sensitive emulsion layer) Emulsion A Silver 0.17 Emulsion B Silver 0.17 ExS-4 4.0 × 10 ⁻⁵ ExS-5 1.8 × 10 ⁻⁴ ExS-6 6.5 × 10 ⁻⁴ ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 Eighth layer (medium speed green emulsion layer) Emulsion D Silver 0.55 ExS-4 1.4 × 10 ^-5 ExS-5 1.0 × 10 ^-4 ExS-6 3.8 × 10 ^-4 ExM-2 0.16 ExM-3 0.045 ExY-1 0.01 ExY-5 0.030 HBS-1 0.16 HBS-3 8.0x10 ^-3 gelatin 0.65 9th layer (high sensitivity Green-sensitive emulsion layer) Emulsion 1a Silver 0.60 ExS-4 1.9 × 10 ⁻⁵ ExS-5 4.1 × 10 ^{−5 ExS-6 1.6 × 10 -4 ExC} -1 0.010 ExM-1 0.015 ExM-4 0.040 ExM-5 0.019 ExY-4 0.020 Cpd-3 0.020 exemplary compound (33 ) 3.0 × 10 ⁻⁴ HBS-1 0.25 HBS-2 0.10 Gelatin 0.80 10th layer (yellow filter layer) Yellow colloidal silver 0.010 Cpd-1 0.16 HBS-1 0. 60 gelatin 0.60 11th layer (low-sensitivity blue-sensitive emulsion layer) emulsion C silver 0.30 emulsion E silver 0.24 ExS-7 6.7 × 10 ⁻⁴ ExY-1 0.030 ExY-2 0.35 ExY-3 0.45 ExY-4 0.020 ExC-7 0.01 HBS-1 0.25 Gelatin 1.10 12th layer (high sensitivity blue-sensitive emulsion layer) Emulsion F Silver 0.30 Emulsion 1a Silver 0. 35 ExS-7 1. 5 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 ExY-4 0.015 Exemplified compound (24) 5.0 × 10 ⁻⁴ HBS-1 0.010 Gelatin 0.60 13th layer (third layer) 1 protective layer) Emulsion G silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 0.75 14th layer (second protective layer) H-1 0. 30 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 0.80 Further, each layer is appropriately used. , Storability, processability, pressure resistance, mildew-proof
To improve antibacterial property, antistatic property and coating property, W-
1 to W-4, 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. In the above composition,
The “exemplary compound” refers to the compound represented by the general formula (A) shown in Chemical formula 15 to Chemical formula 21 above.

[0251]

[Table 4] In Table 4, (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 are observed in the tabular grains by using a high voltage electron microscope.

[0252]

[Chemical formula 22]

[0253]

[Chemical formula 23]

[0254]

[Chemical formula 24]

[0255]

[Chemical 25]

[0256]

[Chemical formula 26]

[0257]

[Chemical 27]

[0258]

[Chemical 28]

[0259]

[Chemical 29]

[0260]

[Chemical 30]

[0261]

[Chemical 31]

[0262]

[Chemical 32]

[0263]

[Chemical 33]

[0264]

[Chemical 34]

[0265]

[Chemical 35]

[0266]

[Chemical 36] Subsequently, the fifth layer of the multilayer color light-sensitive material (red-sensitive emulsion layer)
Emulsion 1a used in the ninth layer (green sensitive emulsion layer) and the twelfth layer (blue sensitive emulsion layer) was replaced with emulsion 3b having the same amount of silver to prepare a multilayer color light-sensitive material.

Next, from the multilayer color light-sensitive material A-1 using the emulsion 3b to the fifth, ninth and twelfth layers, the exemplified compound (2) which is the compound represented by the formula (A) is used.
3), (33) and (24) were removed to prepare a multilayer color photosensitive material. This is designated as A-3.

The multi-layer color light-sensitive material produced above has 35
It is cut into a width of 1.1 mm and a length of 1.1 mm, and perforation holes of 2 mm x 2.8 mm are drilled at intervals of 4.75 mm at intervals of 2 mm from both ends in the width direction of the film, similar to the current 135 format. Wrap it around a 14mm spool and store it in a 135 cartridge.
The same color negative film for photography as in No. 5 was used. 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 were wound on a spool having a diameter of 8 mm. Similarly, it was a color negative film for photography. These films are group II.

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

In this photographing, when photographing the film of the group I, the distance for photographing the entire 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.

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

Conditions Light source Subject Contrast Background Others A Daylight (sunny) High trees, distant view of mountains Sunlit, shaded 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.

(Treatment process) Process treatment time Treatment temperature Replenishment amount * Tank capacity Color development phenomenon 3 minutes 5 seconds 38.0 ° C 600 ml 10 liters Bleach 50 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters fixing 50 seconds 38.0 ° C 420 ml 5 liters Washing with water 30 seconds 38.0 ° C 980 ml 3.5 liters Stable (1) 20 seconds 38.0 ° C −3 liters Stable (2) 20 seconds 38.0 ° C 560 ml 3 liters Dry 1 minute 30 seconds 60 ° C * Replenishment amount is photosensitive Amount per 1 m ^{2 of} material The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank. It was made to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water washing process are respectively per 1 m ² of the light-sensitive material. 65 ml, 50 ml, 50 ml, 50
It was milliliters. 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 treatment 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 3.95 .1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Hydroxylamine sulphate 2.4 3.3 2-Methyl-4- [N-ethyl-N-4. 0.5 6.0 (β-hydroxyethyl) amino aniline sulphate Add water 1.0 liter 1.0 liter pH (adjust with potassium hydroxide and sulfuric acid) 10.05 10.15 (bleaching solution) tank Liquid (g) Replenisher (g) 1,3-Diaminopropane tetraacetic acid 130 195 Ferric ammonium-hydrate Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxy Siacetic acid 50 75 Acetic acid 40 60 Water was added to 1.0 liter 1.0 liter pH (adjusted with ammonia water) 4.4 4.4 (bleach-fixing tank solution) 15 pairs of the above bleaching tank solution and the following fixing tank solution 85 (volume 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.

(Stabilizer) Common to tank liquid and replenisher (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 performed. These color negatives obtained by carrying out the tests were carried out using a Fuji enlarger A690 professional with a magnification of 5 times for the film I group, a magnification of 7 times for the film II group and a magnification of 9.5 times for the film III group. , Printed on Fuji Color Paper, Super FA and Type II, respectively. CP-43FA was used for the color development processing at this time.

The obtained print was cut so that only the image part 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 a print from a film which belongs to the group I and which is photographed with the multilayer color light-sensitive material C-1 using the emulsion 1a, and two prints of this reference and other prints are arranged side by side and sequentially compared. The arithmetic mean was determined by giving +1 to those judged to be better than the standard, 0 to those equal or difficult to judge, and -1 to those judged to be inferior to the standard.

On the other hand, regarding the color reproducibility, the yellow density of the magenta color image portion of the color checker chart was measured on a color negative, and the difference was taken based on the value of the multilayer color light-sensitive material C-1 which also used the emulsion 1a. The degree of color turbidity required was examined. In addition, three types of C-1 with different spool diameters
No difference was found in the yellow densities.

Some of the results are shown in Table 5.

[0284]

[Table 5] From the results of Table 5, a film using Emulsion 3b chemically sensitized with each of the selenium sensitizer, the gold sensitizer and the sulfur sensitizer of the present invention in a part of the light-sensitive silver halide emulsion, was obtained. It can be seen that the image quality is clearly improved as compared with the film using the emulsion 1a outside the present invention. In particular, the sharpness improving effect is great.

Further, even in the film using the chemically sensitized emulsion 3b of the present invention, the group II film having the polyester support has a sharpness higher than that of the current group 135 which is 135 format. It turns out to be excellent.

It is considered that this is because the flatness of the exposure screen at the time of shooting is insufficient for 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 TAC has a large water absorbency 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, where the exposure screen area is 3 cm ² or less, the sharpness judgment is obviously inferior, and reducing the exposure screen area to 3 cm ² or less maintains the sharpness obtained from the exposure screen area of the current 135 format. It shows that you cannot do it. Further, the use of the compound represented by the general formula (A) in the chemically sensitized emulsion according to the present invention is
It is clear from the comparison of A-1 and A-3 of the II group that it is effective for improving the image quality.

The multilayer 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 is equivalent 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 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, 4, shown in the example of polyester compound
5,6,8,9,10 and PBB-2,3,6,
Melting, biaxial stretching and heat setting were performed according to the method described in Example 1 to obtain a support having a thickness of 80 μm. 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 multi-layer color light-sensitive material prepared from these 11 types of polyester supports could obtain almost the same evaluation as A-1 belonging to the II group of Example 1. Example 3 Multilayer color photosensitive materials A-1, D- produced in Example 1
1, D-2 and D-3 were processed in the film storage cartridge described in JP-A-2-273740 so that the perforations had a width of 24 mm and one per side was formed on each side edge in the film length direction. Stowed. Also, the camera was modified so that this cartridge could be loaded, and the screen area of the exposure unit was 3.60 cm ² (30.0 mm × 1
2.0mm, aspect ratio 2.5),
According to the method of Example 1, the subject (one mannequin, the upper body, a resolution evaluation chart, and a Macbeth color checker chart were installed) was photographed.

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).

For photographing the subject, the distance was determined so that the subject was exactly in 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 had a good image quality comparable to the print obtained from the film of Group II of Example 1 above.

Considering this result together with the result of Example 1, 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. Further, from the results of this embodiment, it is apparent that the film storage cartridge can be downsized and the camera can be downsized by using the photosensitive material of the present invention. Example 4 Multilayer color photosensitive materials A-1 and C prepared in Example 1
-1, the emulsion 1a used in the fifth, ninth and twelfth layers was replaced by 1b, 2b, 4a, 4b, 5b and 5c.
To produce a multilayer color light-sensitive material.

These photosensitive materials produced were cut and processed in the same manner as in Example 3 so as to have a width of 24 mm and one perforation per screen in the length direction of the film. The film was housed in a cartridge, and the exposure size was set to 5.01 cm ² (30 mm × 16.7 mm, aspect ratio 1.8) and photographed in the same manner as in Example 3 (the film at this time was used). The single-frame feed was set to 31.7 mm feed in accordance with the screen area of the exposure unit).

The subject was photographed in the same manner as in Example 1 so that the subject was exactly in the vertical position of the screen of the exposure section.

The film that had been photographed was subjected to the same color development process as in Example 1, and the image quality was evaluated with C-1 of film group I as a reference.

The results are shown in Table 6.

[0300]

[Table 6] From Table 6, emulsions 1b, 2b, 4b, 5b according to the present invention chemically sensitized with a selenium sensitizer, a gold sensitizer and a sulfur sensitizer to a part of a light-sensitive silver halide emulsion and As in Example 1, it is clear that the film using 5c and using A-1 (PEN) as the support has improved image quality as compared with the film of Comparative Example.

Further, even in the case of emulsions subjected to the same chemical sensitization, in an emulsion in which silver halide is composed of tabular grains,
Emulsions 1b, 2b, 4b, 5 have a great effect of improving image quality.
It can be seen from the comparison of b.

Further, it is clear from the comparison between Emulsions 5b and 5c that it is more preferable to add the compound represented by the formula (A) to the chemically sensitized tabular grains. Example 5 The diphenyl-pentafluorophenylphosphine selenide used as the selenium compound in the preparation of the emulsion described before Example 1 was converted into diethyl selenide, tri-n-butylphosphine selenide, triphenylphosphine selenide, Tris-2,4,6-trichlorophenylphosphine selenide, phenyl-bis-pentafluorophenylphosphine selenide and exemplified compounds S-9 and S-10 were replaced in equimolar amounts, respectively, and chemically sensitized with selenium as in emulsion 4b. The tabular silver halide grains prepared above were prepared and used.

Each of the thus prepared seven kinds of emulsions was replaced by an equal weight of the emulsions 1a of the fifth, ninth and twelfth layers of the multilayer color photosensitive material A-1 prepared in Example 1 to obtain a multilayer color. -A photosensitive material was prepared.

These seven kinds of multi-layer color light-sensitive materials had a width of 24 mm and had one perforation on one side in the lengthwise direction of the film, as in Example 4. The image quality was evaluated after cutting, processing, photographing, color development processing and printing on a paper.

As a result, the film groups I and C of Example 1 were
In comparison with 1, the support A-1 in Example 4,
It was possible to obtain the same evaluation as that for the sharpness and color reproducibility of the light-sensitive material having the emulsion 4b. Example 6 The two-layer constitution consisting of the eleventh layer and the twelfth layer of the blue-sensitive emulsion layer in the layer constitution shown in the preparation of the multilayer color light-sensitive material of Example 1 was changed to the one-layer constitution shown below, and further, 5th layer, 9th
The emulsion of the layer was also replaced by 4b in the same amount and coated on the support A-1 in the same manner as in Example 1 to prepare a color light-sensitive material. The classification of the materials used, the coating amount, etc. were in accordance with the method described in Example 1. (Blue Sensitive Emulsion Layer) Emulsion B Silver 0.28 Emulsion D Silver 0.22 Emulsion F Silver 0.25 Emulsion 4b Silver 0.40 ExS-7 8.5 × 10 ⁻⁴ ExY-1 0.03 ExY-20 .40 ExY-3 0.60 ExY-4 0.03 ExC-1 0.01 Exemplified compound (40) 7.5 × 10 -4 HBS-1 0.35 Gelatin 1.45 The prepared multilayer color light-sensitive material is Then, the film was cut in the same manner as in Example 4, the same photographing as in Example 3 was performed, the same color development processing as in Example 1 and the peprint to the color paper were carried out to perform C-1 of film group I. Compared with.

As a result, the sharpness was the same as the result obtained from the light-sensitive material having the support A-1 and the emulsion 4b in Example 4.
It had excellent color reproducibility. Example 7 Using the support described in Example 1, each layer having the composition shown below was coated in multiple layers to prepare a multilayer color photosensitive material.
The symbols of the obtained multilayer color photographic material were the same as those of the support as in Example 1.

(Composition of Photosensitive Layer) First Layer (Antihalation Layer) Black Colloidal Silver 0.2 Gelatin 1.0 Ultraviolet Absorber UV-11 0.1 Ultraviolet Absorber UV-12 0.1 Ultraviolet Absorber UV- 13 0.1 Dispersion Oil Oil-1 0.2 Dispersion Oil Oil-2 0.1 Second Layer (Intermediate Layer) Gelatin 1.0 Coupler C-2 0.02 Dispersion Oil Oil-1 0.01 Third Layer ( Low-sensitivity red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain size 1.0 μm) 0.9 Gelatin 1.2 Sensitizing dye I 1.4 × 10 ⁻⁴ Sensitizing dye II 7 × 10 ^-5 coupler C-1 0.5 coupler C-2 0.05 coupler-C-7 0.03 dispersed oil Oil-3 0.03 dispersed oil Oil-4 0.03 4th layer (intermediate layer) ) Gelatin 1.0 Compound A 0.1 Compound B 0.05 min Oil Oil-1 0.05 Fifth layer (low-sensitivity green sensitive emulsion layer) Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain size 1.0 μm) 0.7 Monodisperse silver iodobromide emulsion (Silver iodide 3 mol%, average particle size 0.3 μm) 0.15 Gelatin 1.3 Sensitizing dye III 3 × 10 ⁻⁴ Sensitizing dye IV 1 × 10 ⁻⁴ Sensitizing dye V 1 × 10 ⁻⁴ Coupler C-3 0.6 Coupler C-4 0.2 Coupler C-5 0.1 Coupler-C-7 0.04 Dispersion oil Oil-3 0.2 Dispersion oil Oil-5 0.2 Sixth layer (intermediate layer) ) Gelatin 1.0 Compound A 0.1 Seventh layer (low-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 3 mol%, average particle size 1.0 μm) 0.5 Monodisperse iodine odor Silver halide emulsion (3 mol% silver iodide, average grain size 0.3 μm) 0.1 Gelatin 1.0 Sensitizing dye VI 2 × 10 ⁻⁴ Sensitizing dye VII 2 × 10 ⁻⁴ coupler C-6 0.9 Coupler C-10 0.2 Dispersion oil Oil-1 0.22 Eighth layer (intermediate layer) Gelatin 1.0 Compound A 0.1 Compound B 0.05 Dispersion oil Oil-1 0.05 9th layer (high-sensitivity red-sensitive emulsion layer) Polydisperse silver iodobromide emulsion (6 mol% silver iodide, average grain size 2.0 μm) 1.0 Gelatin 1.2 Sensitizing dye I 7 × 10 ⁻⁵ increase Sensitizing dye II 2 × 10 ^-5 coupler C-8 0.1 coupler C-1 0.2 Exemplified compound (12) 5.0 × 10 ^-4 Dispersion oil Oil-4 0.2 10th layer (intermediate layer) Gelatin 1.0 Coupler C-5 0.2 Compound A 0.1 11th layer (high-sensitivity green-sensitive emulsion layer) Polydisperse silver iodobromide emulsion (silver iodide 5 mol%, average grain size 2.0 μm) 1. 0 gelatin 1.0 sensitizing dye III 1 × 10 ⁻⁴ sensitizing dye IV 3 × 10 ⁻⁵ sensitizing dye V 3 × 10 ⁻⁵ coupler C-9 0. 2 Exemplified Compound (9) 5.0 × 10 ⁻⁴ Dispersion Oil Oil-1 0.4 12th Layer (Intermediate Layer) Fine grain silver bromide emulsion (average particle size 0.07 μm) 0.15 Gelatin 1.2 Compound A 0.1 13th layer (high-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain size 2.1 μm) 0.9 Monodisperse silver iodobromide emulsion (silver iodide 0.25 monodisperse silver iodobromide emulsion (3 mol% silver iodide, 0.3 μm average grain size) 0.1 fine grain silver bromide emulsion (average grain size of 0.3 μm) 09 μm) 0.1 Gelatin 1.2 Sensitizing dye VI 3 × 10 ^-4 Sensitizing dye VII 1 × 10 ^-4 Coupler C-10 0.35 Exemplified compound (17) 9.0 × 10 ^-4 Dispersion oil Oil- 1 0.15 14th layer (1st protective layer) UV absorber UV-11 0.05 UV absorber UV-12 0.05 UV absorber V-13 0.05 UV absorber UV-14 0.05 UV absorber UV-15 0.05 Gelatin 0.6 Dispersion oil Oil-4 0.1 Fifteenth layer (second protective layer) Gelatin 0.5 Poly Methyl methacrylate particles (diameter 1.5 μm) 0.2 In each layer, in addition to the above components, surfactant W-11 and hardener H
-11 was added. In addition, formalin scavenger was added.

The addition amount in the light-sensitive material is shown in grams per 1 m ² , the silver halide emulsion and colloidal silver are shown in terms of silver, and the sensitizing dye is expressed in moles with silver halide. The ratio is shown.

The compounds used in the examples are shown below in Chemical formulas 37 to 45.

[0310]

[Chemical 37]

[0311]

[Chemical 38]

[0312]

[Chemical Formula 39]

[0313]

[Chemical 40]

[0314]

[Chemical 41]

[0315]

[Chemical 42]

[0316]

[Chemical 43]

[0317]

[Chemical 44]

[0318]

[Chemical formula 45] Subsequently, the emulsion used for the ninth red-sensitive emulsion layer and the eleventh green-sensitive emulsion layer of the multilayer color light-sensitive material was 5b, and the silver iodide of the thirteenth blue-sensitive emulsion layer was 3 mol% and had an average grain size. A 1.2 μm monodisperse silver iodobromide emulsion was replaced by 3b with an equal amount of silver to prepare a multilayer color light-sensitive material. Where emulsion 3
For the preparation of b and 5b, sensitizing dyes I to VII were used in place of ExS-1 to ExS-7 in the preparation of the emulsion described in Example 1. The use of the selenium chemical sensitizer in addition to the gold-sulfur chemical sensitizer is the same as in Example 1.

These multilayer color light-sensitive materials thus produced were cut and processed according to the method described in Example 1, photographed and color-developed in the same manner, and then printed on a color paper. evaluated.

Some of the results are shown in Table 7.

The multi-layer color light-sensitive material consisting of the emulsion used first has Em1 in the emulsion column of the table, and the multi-layer color light-sensitive material using the emulsions 3b and 5b according to the present invention has Em2.
Was evaluated based on Em1, the film group I, and the support C-1 as a reference in comparison with other color photosensitive materials.

[0322]

[Table 7] From the results of Table 7, as in Example 1, emulsions chemically sensitized by using the selenium sensitizer, the gold sensitizer and the sulfur sensitizer according to the present invention in a part of the photosensitive silver halide emulsion. It can be seen that the image quality of the film using No. 1 is improved as compared with the film using the emulsion of the present invention. Also,
Even if the chemically sensitized emulsion according to the present invention is used, the film of Group II having a polyester support (exposure area: 5.01 cm ² , perforations: ² per screen) It turns out that it is particularly excellent in sharpness. Further, according to this example, the photosensitive layers having different color sensitivities consist of two layers having different sensitivities, and the low sensitivity layer is provided on the side closer to the support and the high sensitivity layer is provided on the side farther from the support. It can be seen that the same results as in Example 1 can be obtained with the photosensitive material. Example 8 Using the multilayer color light-sensitive material prepared in Example 1, a film photographed in the same manner as in Example 1 after being cut and processed into the forms of film group I and group II was used. The processing was carried out by changing the processing time of color development in the development processing and the composition of the color developing solution as shown in Table 8 below (the color developing time was adjusted by adjusting the depth of the immersion portion in the liquid of the film transporting section). Adjustment was made and the transportation speed was not changed). The obtained film was colored in the same manner as in Example 1.
Film I group C of Example 1 after printing on paper
The image quality (sharpness) was evaluated based on -1.

[0323]

[Table 8] Some of the results are shown in Table 9.

[0324]

[Table 9] From Table 9, a multilayer color light-sensitive material using diphenylpentafluorophenylphosphine selenide as a selenium chemical sensitizer and an emulsion containing tabular silver halide chemically sensitized with selenium-gold-sulfur is shown. Even if the processing was carried out by changing the factors such as the temperature of color development, the amount of color developing agent, pH and the replenishing amount, the emulsion 3b shown in Table 5 of Example 1 and the multilayer color light-sensitive material of film group II were obtained. It can be seen that it gives a comparable good image quality (sharpness).

Furthermore, the above selenium chemical sensitizer was used in Example 5.
The same good results can be obtained by carrying out an emulsion in which the seven kinds of selenium compounds shown in (3) are replaced by equimolar amounts.

[0326]

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

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 22, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0150

[Correction method] Change

[Correction content]

2-1 4-hydroxy-6-methyl-
1,3,3a, 7- tetrazaindene 2-2 4-hydroxy-1,3,3a, 7- tetrazaindene 2-3 4-hydroxy-6-ethyl-1, 3, 3
a, 7-Tetraazaindene 2-4 4-hydroxy-6-phenyl-1,3,3
a, 7-Tetraazaindene 2-5 4-methyl-6-hydroxy-1,3,3
a, 7-Tetraazaindene 2-6 2,6-dimethyl-4-hydroxy-1,
3,3a, 7-Tetraazaindene 2-7 4-hydroxy-5-ethyl-6-methyl-
1,3,3a, 7-Tetraazaindene 2-8 2,6-dimethyl-4-hydroxy-5-ethyl-1,3,3a, 7-tetraazaindene 2-9 4-hydroxy-5,6- Dimethyl-1,
3,3a, 7-Tetraazaindene 2-10 2,5,6-trimethyl-4-hydroxy-1,3,3a, 7-tetraazaindene 2-11 2-methyl-4-hydroxy-6-phenyl- 1,3,3a, 7-Tetraazaindene 2-12 4-hydroxy-6-ethyl-1,2,3
a, 7-Tetraazaindene 2-13 4-hydroxy-6-phenyl-1,2,
3a, 7-Tetraazaindene 2-14 4-hydroxy-1,2,3a, 7-tetraazaindene 2-15 4-methyl-6-hydroxy-1,2,3
a, 7-Tetraazaindene 2-16 5,6-trimethylene-4-hydroxy-
1,3,3a, 7-Tetraazaindene Further, as the benzotriazole compound,
Examples thereof include those represented by the general formula (4).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0165

[Correction method] Change

[Correction content]

Here, the substituent of R ₂₁ —SO ₃ M ² , —C
OOM ² 2, may be the same or different when -OH and _-NR 23 _{R 24} there are two or more.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0172

[Correction method] Change

[Correction content]

In the general formula (C) , R ₂₁ is —SO ₃
Those of M ² and —COOM ² are especially preferred.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0184

[Correction method] Change

[Correction content]

The emulsion according to the present invention can be used as a mixture with other emulsions. The emulsion of the present invention can be used as a mixture of two or more kinds, or can be used as a mixture with one or two or more kinds of other emulsions. Those having different grain sizes can be mixed, those having different halogen compositions can be mixed, and those having different grain shapes can be mixed. Monodisperse emulsions can be mixed, polydisperse emulsions can be mixed, and monodisperse and polydisperse can be mixed. Preferably it is preferable to contain at least 50% or more <br/> on 100% or less of the range of the silver halide emulsion of the present invention.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0185

[Correction method] Change

[Correction content]

It is particularly preferable that the silver halide grains used in the present invention are mainly composed of (111) planes. The surface index of silver halide grains can be directly observed from, for example, an electron micrograph of silver halide emulsion grains, or more accurately, the Chemical Society of Japan, 198.
4. (6). P. It is also possible to perform the measurement by a quantitative method utilizing adsorption of a dye as described in 942-947. Mainly (111) plane means that the (111) plane occupies 50% or more of the total area of silver halide grains, preferably 60% or more, and more preferably 70%.
The range is 100% or less .

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0189

[Correction method] Change

[Correction content]

In the present invention, the tabular silver halide grains used in the silver halide emulsion have a grain diameter of 2 times the grain thickness.
It is at least 3 times, preferably 3 to 20 times, more preferably 4 to 15 times, particularly preferably 5 to 10 times. or,
The proportion of tabular silver halide grains in the projected area of all silver halide grains is 50% or more, preferably 70% or more, particularly preferably 85% or more and 100% or less.
Is the range .

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0191

[Correction method] Change

[Correction content]

Further, the tabular silver halide grains have a diameter of 0.
The thickness is 2 to 20 μm, preferably 0.3 to 10.0 μm, and particularly preferably 0.4 to 5.0 μm. The thickness of the particles is preferably 0.1 μm or more and 0.5 μm or less. Here, the tabular silver halide grain diameter means the diameter of a circle having an area equal to the projected area of the grain. The grain thickness is represented by the distance between two parallel planes constituting a tabular silver halide grain.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0192

[Correction method] Change

[Correction content]

In the present invention, more preferable tabular silver halide grains have a grain diameter of 0.3 μm or more and 10.0 μm or less.
m or less, the particle thickness is 0.3 μm, and the average aspect ratio is 5 or more and 10 or less. If it is more than this, the photographic performance may be abnormal when the light-sensitive material is bent, tightly wound, or touched with a sharp object, which is not preferable. More preferably, grains having a grain diameter of 0.4 μm or more and 5.0 μm or less and an average aspect ratio of 5 or more and 10 or less account for 85% or more of the total projected area of all silver halide grains.
This is the case of a silver halide photographic emulsion occupying a range of 100% or less .

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0201

[Correction method] Change

[Correction content]

The emulsion used in the present invention is in the range of 50% to 100% of the number of silver halide grains.
It is preferable that each grain contains 10 or more dislocations.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0215

[Correction method] Change

[Correction content]

The silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention contain silver iodide in an amount of 5 mol%.
A core consisting essentially of silver iodobromide contained above and a shell consisting essentially of silver iodobromide or silver bromide having a lower silver iodide content than the core. It is preferable to have a double structure constituted by The silver iodide content of the core is more preferably 10 mol% or more, and most preferably 20 mol% or more and 44 mol% or less. The silver iodide content of the shell is preferably 0.1 mol% or more and 5 mol% or less.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0216

[Correction method] Change

[Correction content]

The core may contain silver iodide uniformly, or may have a multiple structure composed of phases having different silver iodide contents. In the latter case, the silver iodide content of the phase having the highest silver iodide content is 5 mol% or more, more preferably 10 mol% or more and 40 mol% or less , and
It suffices if the silver iodide content of the shell is lower than that of the highest silver iodide content phase of the core. Further, "consisting essentially of silver iodobromide" means that it is mainly composed of silver iodobromide, but other components may be contained up to about 0 to 1 mol%. .

[Procedure Amendment 12]

[Document name to be amended] Statement

[Name of item to be corrected] 0222

[Correction method] Change

[Correction content]

The silver halide photographic emulsions other than those described above which can be used in the present invention are described in, for example, Research Disclosure (RD) No. 17643 (December 1978)
Mon., pp. 22-23, "I. Emulsion production (Emulsio
n preparation and type
s) ”, and No. 18716 (11 November 1979).
Mon), page 648, ibid. 307105 (1989 1
January), pages 863-865, and "Graphics and Chemistry of Photography" by Graphide, published by Paul Montel (P. Glafk).
ideas, Chemie et Phisique P
photographique, Paul Monte
1, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photog.
radical Emission Chemistry
(Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et al., Maki).
ng and Coating Photograph
ic Emulsion, Focal Press, 1
It can be prepared using the method described in 964).

[Procedure Amendment 13]

[Document name to be amended] Statement

[Name of item to be corrected] 0323

[Correction method] Change

[Correction content]

[0323]

[Table 8] Some of the results are shown in Table 9.

Claims (2)

[Claims] 1. A photosensitive silver halide emulsion layer having a photosensitive silver halide emulsion chemically sensitized with at least one of a selenium sensitizer, a gold sensitizer and a sulfur sensitizer on a support. In a silver halide color photographic light-sensitive material having at least one layer of the above, the support is made of a belt-shaped polyester base, and one or both of side edges of the support is provided.
4. Perforations of 4 or less are formed per screen, and the area per screen of the image exposure portion is 3.0 cm ² or more.
A silver halide color photographic light-sensitive material having an aspect ratio of 0 cm ² or less and an aspect ratio of 1.40 or more and 2.50 or less. 2. The light-sensitive silver halide emulsion layer has at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer. At least one is composed of two or more layers having different sensitivities, and the layers having different sensitivities are such that the lowest sensitivity layer is located on the side closer to the support, and the layers become more sensitive as the distance from the support increases. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the light-sensitive layers are arranged, and a light-sensitive layer having different color sensitivity is provided between the lowest-speed layer and the highest-speed layer.