JPH0695313A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material with the quality, especially sharpness, of the obtained color image and color reproducibility improved and capable of miniaturizing the cartridge without damaging the picture. CONSTITUTION:At least one hydrophilic colloid layer contg. a compd. shown by the formula, A-(Time)n-W, is provided on a strip substrate consisting of a polyester base, <=4 perforations per picture plane are formed on one or both side edges of the substrate, and the area of the picture exposure part per picture plane is controlled to 3.0-7.0cm<2>. In the formula, A is a group capable of liberating (Time)n-W by the reaction with a color developing agent oxidant, Time is a timing group, W is a group inhibiting development after liberated from (Time)n-W, and (n) is 1, 2 or 3.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, the graininess, sharpness and color reproducibility of color photographic light-sensitive materials for photography (including color negatives and color reversal light-sensitive materials; hereinafter collectively referred to as color negatives) have been improved, and zoom lenses or bifocals have been used. With the widespread use of cameras equipped with lenses, more and more diverse photographs have been obtained.

However, in a camera equipped with a zoom lens or a bifocal lens, if the focal length on the telephoto side is extended, the camera becomes large and the portability deteriorates. It had the drawback of being a camera with no effect.

As means for solving the above problems, for example, US Pat. Nos. 3,490,844 and 4,583,831 are disclosed.
And No. 4,650,304, a proposal for a so-called pseudo-zoom method has been made, focusing on the recent progress in the performance of color negative films. The pseudo-zoom method detects the focal length information of the lens that was input to the film at some stage during the shooting stage, and at the stage of printing, stretches a portion of the negative film screen, resulting in a telescopic effect. It is what

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

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

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

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

On the other hand, in order to improve the image quality, a screen effective area per one exposed frame and its aspect ratio, which contains a compound releasing a precursor of a development inhibitor represented by the following general formula (A): (Ratio of horizontal length / vertical length of screen)
The color negative stored in the cartridge is described in JP-A-2-273743 and JP-A-2-273744.

General formula (A) A- (Time) _n -W (where A reacts with an oxidized product of a color developing agent to give (T
(ime) a group capable of releasing _n- W, Time is a timing group, W is a group which exhibits a development inhibitory action after being released from (Time) _n- W, and n represents 1, 2 or 3). A photographic film package containing a color negative containing a compound releasing a precursor of a development inhibitor represented by the general formula (A) in a flat surface holding cartridge is disclosed in JP-A-3-078.
No. 742. Although these methods have provided color negatives with improved image quality, they have not been satisfactory.

Cellulose triacetate (hereinafter abbreviated as TAC) is generally used as a support (base) for the color negative. 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 stored in a roll form for a long period of time, curling curls strongly remain, and poor flatness at the time of photography greatly impairs the sharpness of a color negative. Further, since the water absorbency is high as described above, 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.

Therefore, in the case of a small-format color negative having a small image exposure screen and therefore requiring a high enlargement ratio, in addition to improving the sharpness of the photosensitive layer itself, the support constituting the color negative and further Comprehensive improvement along with the processing form of color negative as a photographic film is important for higher image quality improvement.

[0013]

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

[0014]

The above-mentioned problems can be solved in a silver halide color photographic light-sensitive material having at least one hydrophilic colloid layer containing a compound represented by the following general formula (A) on a support. body is made of a belt-like polyester base, either or both on one screen per four or less perforations of the side edge portion is formed, and the image portion area is at 3.0 cm ² or more 7.0 cm ² or less,
It has been achieved by a silver halide color photographic light-sensitive material characterized in that its aspect ratio is 1.40 or more and 2.50 or less.

General formula (A) A- (Time) _n -W (where A reacts with an oxidized product of a color developing agent to give (T
(i) a group capable of releasing _n- W, Time is a timing group, W is a group exhibiting a development inhibitory action after being released from (Time) _n- W, and n is 1, 2 or 3). The present invention will be described in detail.

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

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

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

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

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

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

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

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

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

[0025]

[Chemical 1]

[0026]

[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,

[0028]

[Chemical 3]

[0029]

[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 may be mentioned as examples of such compounds.

[0033]

[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, especially 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 from 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 (() indicates weight ratio.) PBB-1 PEN / PET (60 / 40) Tg = 95 ° C. PBB-2 PEN / PET (80/20) Tg = 104 ° C. PBB-3 PAr / PEN (50/50) Tg = 42 ° C. PBB-4 PAr / PCT (50/50) Tg = 118 ° C. PBB-5 PAr / PET (60/40) Tg = 101 ° C. PBB-6 PEN / PET / PAr (50/25/25) Tg = 108 All polyesters above ℃ are triacetyl cellulose
It has a flexural modulus higher than that of TAC, and can realize a thinner film. However, PEN has the strongest bending elasticity among these, and by using it, it is possible to reduce the film thickness of PEN to 80 μm compared to 122 μm of TAC.

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

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

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

Polyester, particularly aromatic polyester, has a high refractive index of 1.6 to 1.7, whereas gelatin, which is the main component of the photosensitive layer coated 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 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, the objective can be achieved 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 its use.
The slipperiness imparting means is not particularly limited, but, for example, kneading an inert inorganic compound or coating a surfactant is used as a general method.

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

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

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

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

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

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

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

In general, the glow discharge treatment condition is that the pressure is 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 studied, and 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 as required. 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 a hydrophobic polymer or a hydrophilic polymer used in the subbing layer.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Next, the compound of the general formula (A) used in the present invention will be explained.

Formula (A) A- (Time) _n -W (In the formula, A represents a coupling component capable of reacting with an oxidized product of the color developing agent, and reacts with the oxidized product of the color developing agent (Time) _n. It is a component capable of releasing -W. Time represents a timing group, and W represents (Time).
Represents a group having a development inhibiting effect after being released from _n- W. n represents an integer of 1, 2 or 3. ) W is, for example,
Tetrazolylthio group, thiadiazolylthio group, oxadiazolylthio group, triazolylthio group, benzimidazolylthio group, benzthiazolylthio group, tetrazolylseleno group, benzoxazolylthio group, tetrazolyl group,
Examples thereof include a benzotriazolyl group, a triazolyl group, a benzoindazolyl group and derivatives thereof. These groups are described, for example, in US Pat.
Nos. 384,657, 3,615,506, 3,6
17,291, 3,733,201, 3,93
3,500, 3,958,993, 3,96
1,959, 4,149,886, 4,25
9,437, 4,095,984, 4,47
7,563 or British Patent 1,450,479 or Research Disclosure (Research
h Disclosure) Vol. 176, No. 1764
3, (December 1978).

Examples of the Time include groups utilizing the hemiacetal cleavage reaction described in US Pat. Nos. 4,146,396, 4,652,516, or 4,698,297, US Patent No. 4,248,96
A timing group for causing a cleavage reaction utilizing an intramolecular nucleophilic reaction described in U.S. Pat. No. 4,409,32
No. 3, or 4,421,845, a timing group for causing a cleavage reaction utilizing an electron transfer reaction, and a hydrolysis reaction of an iminoketal described in US Pat. No. 4,546,073. Or a group that causes a cleavage reaction by utilizing the hydrolysis reaction of the ester described in West German Patent Publication No. 2,626,317. Time is a hetero atom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom,
Combine with.

Preferred examples of Time are methyleneoxy group, 4-methylene-3-pyrazolyloxy group, 2 (or 4) -methylenephenoxy group, 2-carbonylaminomethylphenoxy group, carboxyl group or carbomethoxy group.

When n is 2 or 3, Time may be the same or different.

In the general formula (A), A represents a coupler residue in detail.

Examples of the coupler residue represented by A include a yellow coupler residue (for example, an open-chain ketomethylene type coupler residue such as acylacetanilide and malondianilide), a magenta coupler residue (for example, 5-
A coupler residue such as a pyrazolone type, a pyrazolotriazole type or a pyrazoloimidazole type), a cyan coupler residue (for example, a phenol type, a naphthol type or an imidazole type coupler residue described in European Patent Publication 249,453). Group) and a colorless coupler residue (for example, a coupler residue such as indanone type or acetophenone type). Also, US Pat.
315, 070, 4,183, 752, 4, 1
74,969, 3,961,959 or 4,
It may be a heterocyclic coupler residue described in No. 171,223.

The compound represented by formula (A) according to the present invention will be described in more detail.

The compound represented by the general formula (A) is preferably a compound represented by the general formula (A1) shown below.

[0102]

[Chemical 6] In the formula, A and W have the same meanings as A and W in the compound represented by the general formula (A).

[0103] X represents an oxygen atom or a sulfur atom, or a substituted imino group, organic substituents thereof are nitrogen-containing heterocyclic ring (the substituent of 5 to 7-membered ring together with the nitrogen atom and L ₁ bonded to L ₁ Or may be a condensed ring).

R ₁ and R ₂ are hydrogen atoms and have 1 to 36 carbon atoms.
Alkyl group (for example, methyl, ethyl, benzyl, dodecyl, cyclohexyl) or an aryl group having 6 to 36 carbon atoms (for example, phenyl, 4-methoxyphenyl, 4
-Chlorophenyl, 4-nitrophenyl, naphthyl).

[0105] L _1, in the compounds represented by the general formula (A1), after the coupling of the left L ₁ is cleaved, right coupling [-C of L ₁ by electron transfer reaction (R ₁₎ (R ₂₎ −
W] represents a linking group in which W is cleaved. a represents 0, 1 or 2, and when a is 2, L _1's may be the same or different.

Among the compounds represented by the general formula (A1), more preferred are the following general formulas (AI) to (A).
-IV) is a compound.

[0107]

[Chemical 7] Here, V ₁ and V ₂ are non-metal atoms necessary for forming a 5- to 7-membered nitrogen-containing heterocyclic ring (which may have a substituent or may be a condensed ring) with an atomic group to be bonded. And V ₃ represents a 5- to 7-membered heterocyclic ring (which may have a substituent or a condensed ring) or a benzene ring (which may have a substituent) together with an atomic group to be bonded. A fused ring may be used), and R ₃ represents a hydrogen atom or a monovalent group. However, R ₃ may be bonded to V ₂ to form a ring.

The basic part of the development inhibitor represented by W is the heterocyclic group or the heterocyclic thio group mentioned in the general formula (A), and examples thereof include the following.

[0109]

[Chemical 8]

[0110]

[Chemical 9] However, in the above formula, the substituent represented by Z (which is included in the portion of W in the general formula (A)) is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkaneamide group, an alkeneamide group. , An alkoxy group, a sulfonamide group or an aryl group. Y represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. L ₂ contains a chemical bond which is cleaved in the developing solution, and these chemical bonds include the examples shown in Table 1. Each of these is cleaved by a nucleophile such as hydroxylamine or hydroxyion which is a component in the color developer.

[0111]

[Table 1] m and n each represent an integer of 0 to 4.

Particularly preferable components represented by W for suppressing development are the following.

[0113]

[Chemical 10] Among the compounds represented by the general formulas (A-I) to (A-IV), particularly preferred are the compounds represented by the general formula (A-I), and further among the compounds represented by the general formula (AI), Preferred are compounds represented by the following general formula (A-V).

[0114]

[Chemical 11] In formula (A-V) A, R _1, R ₂ and W are A, respectively R _1, R ₂ and W synonymous in the general formula (A1), R ₉ is alkyl of 1 to 24 carbon atoms A group (for example, methyl, benzyl, dodecyl) or a carbon number of 6 to
36 aryl groups (eg, phenyl, 4-tetradecyloxyphenyl, 4-methoxyphenyl, 4-chlorophenyl, 2,5-dichlorophenyl, 4-methylphenyl, 4-nitrophenyl), R ₁₀ is a hydrogen atom, An alkyl group having 1 to 24 carbon atoms (eg, methyl, ethyl, undecyl), an aryl group having 8 to 36 carbon atoms (eg, phenyl, 4-methoxyphenyl), 1 to carbon atoms
24 alkoxy groups (eg, methoxy, ethoxy, dodecyloxy), cyano groups, amino groups having 0 to 36 carbon atoms (eg, amino, dimethylamino, piperidino, dihexylamino, anilino), carbonamides having 1 to 24 carbon atoms Group (for example, acetamide, benzamide, tetradecane amide), sulfonamide group having 1 to 24 carbon atoms (for example, methyl sulfonamide, phenyl sulfonamide), carboxy group, alkoxycarbonyl group having 2 to 24 carbon atoms (for example, methoxycarbonyl) , Dodecyloxycarbonyl) or a carbamoyl group having 1 to 24 carbon atoms (eg, carbamoyl, dimethylcarbamoyl, pyrrolidinocarbamoyl). As A in the general formula (A-V), a cyan dye-forming coupler residue (for example, a phenol-based cyan coupler residue, an α-naphthol-based cyan coupler residue) is preferable, and particularly, for example, the Journal of the Photographic Society of Japan, vol. 52 (1989). No. 2, No. 2, pp. 150-155 (Kida et al.), Those which flow out into the processing solution during the color development processing or the formed dye is bleached to be erased are preferable. R ₁ and R ₂ are preferably hydrogen atoms, R ₉ is preferably an aryl group, and R is
_An alkyl group is preferable as ₁₀ .

Specific examples of the compound represented by formula (A) are shown below, but the invention is not limited thereto.

[0116]

[Chemical 12]

[0117]

[Chemical 13]

[0118]

[Chemical 14]

[0119]

[Chemical 15]

[0120]

[Chemical 16]

[0121]

[Chemical 17]

[0122]

[Chemical 18]

[0123]

[Chemical 19]

[0124]

[Chemical 20]

[0125]

[Chemical 21]

[0126]

[Chemical formula 22]

[0127]

[Chemical formula 23]

[0128]

[Chemical formula 24]

[0129]

[Chemical 25]

[0130]

[Chemical formula 26]

[0131]

[Chemical 27]

[0132]

[Chemical 28]

[0133]

[Chemical 29]

[0134]

[Chemical 30]

[0135]

[Chemical 31]

[0136]

[Chemical 32]

[0137]

[Chemical 33]

[0138]

[Chemical 34] These compounds according to the present invention are described in US Pat.
No. 7,554, No. 3,617,291, No. 3,9
33,500, 3,958,993, 4,
149,886, 4,234,678, JP-A-51-13239, 57-56837, US Pat. Nos. 2,070,266, 2,072,363,
Research Disclosure 21st December 1981
No. 228, Japanese Patent Publication No. 58-9942, Japanese Patent Publication No. 51-16
141, JP-A-52-90932, US Pat. No. 4,
248,962, JP-A-56-114946, 5
7-154234, 58-98728, 58-
209736, 58-209737, 58-2
09738, 58-209740, 61-15
6043, 61-255342, JP-A-62-2
It can be easily synthesized by the method described in No. 4252.

In the present invention, the timing DIR compound represented by the general formula (A) is contained in at least one hydrophilic colloid layer.

The hydrophilic colloid layer as used in the present invention means a photosensitive layer and a non-photosensitive layer coated on the exposed surface side of the support except the above-mentioned support, back layer and undercoat (coating) layer. (For example,
Antihalation layer, intermediate layer, yellow filter layer, protective layer). Therefore, in the present invention, the timing DIR compound represented by the general formula (A) is contained in at least one of the photosensitive layer and the non-photosensitive layer.

When the timing DIR compound is added to the light-sensitive silver halide emulsion layer, the addition amount thereof is 0.01 to 20 mol% relative to 1 mol of silver halide in the layer, preferably 0. It is 0.05 to 10 mol%, and more preferably 0.1 to 5 mol%.

When the timing DIR compound is added to the non-photosensitive layer, the addition amount is 0.01 to 1 mol of silver halide in the nearest silver halide emulsion layer.
20 mol%, preferably 0.05 to 10 mol%
And more preferably 0.1 to 5 mol%.

Timing DI represented by general formula (A)
The R compound can be used by dividing itself into two or more layers, or can be used in combination of two or more kinds. It can also be used in combination with a known DIR compound. Known DIR
When used in combination with a compound, the ratio of the compound used can be arbitrarily determined depending on the performance required of the light-sensitive material.

Timing DI represented by general formula (A)
The R compound is used in the hydrophilic colloid layer, but it is preferably added to the light-sensitive silver halide emulsion and / or its adjacent layer.

The current color photographic material for photography is a print size of 135 format from service size (8c).
It is designed so that the best image quality can be obtained when stretched to m × 12 cm), and the use amount of the DIR compound is also selected from this viewpoint and the addition amount is determined.

When the area of the screen of the exposed portion of the color photographic material for photography becomes a small format, the enlargement ratio to the color print becomes high, and it is necessary to further improve the image quality, especially sharpness of the color photographic material for photography. . The timing DIR compound represented by the general formula (A) exhibits an excellent effect in improving the image quality.

[0147] Incidentally, the image exposure unit 1 screen 3.0 cm ² or more, 7.0 cm ² or less of the small follower - with to the mat,
It is important to maintain the flatness of the film during shooting. If the flatness is impaired, shift defects will occur, and especially when printing from small format negative film, the enlargement ratio will be large. It becomes a big obstacle to the exertion of sex. Therefore, in the present invention, a silver halide color light-sensitive material for photographing using the timing DIR compound represented by the general formula (A) is disclosed in, for example, JP-A-3-089.
It is particularly preferable to use a light-tight type cartridge provided with the attitude control mechanism disclosed in Japanese Patent No. 341 and preventing light fog and a camera adapted to the cartridge.

Further, the area of one screen of the image exposure unit is 3.0c.
It is also possible to change the aspect ratio in the range of 1.40 to 2.50 at the time of shooting while maintaining m ² or more and 7.0 cm ² or less, and for example, the means described in Japanese Patent Application No. 3-072779.・ The mechanism can be incorporated into a color sensitive material or a camera.

The silver halide color photographic light-sensitive material of the present invention (hereinafter simply referred to as light-sensitive material) will be further described below.

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

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

The intermediate layer may be formed, for example, in JP-A-61-43.
748, 59-113438, 59-1134
No. 40, No. 61-20037, No. 61-20038, the coupler and the DIR compound may be contained, and the color mixture inhibitor may be contained as it is usually used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Colored couplers for correcting unnecessary absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. 30710
5, section VII-G, U.S. Pat. No. 4,163,670,
Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,9
29, 4,138,258, British Patent 1,1.
Those described in JP-A No. 46-368 and JP-A-3-223750 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
The DIR coupler which releases a development inhibitor is, in addition to the compound represented by the general formula (A), the above-mentioned RD1764.
3, VII-F section and No. 307105, VII-
The compounds shown in the patents described in the section F, JP-A-57-
151944, 57-154234, 60-1
84248, 63-37346, 63-373.
50, US Pat. Nos. 4,248,962 and 4,78
The compounds described in No. 2,012 can be used in combination.

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

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

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl)). Phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2
-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecane amide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples thereof include aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). The auxiliary solvent has, for example, a boiling point of about 30 ° C or higher, preferably 50 ° C.
An organic solvent having a temperature of about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide.

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

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

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

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

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

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

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

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, for example, hydroxylamine,
Diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, various preservatives such as phenylsemicarbazides, triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol , Polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, amino polycarboxylic acids, amino poly Various chelating agents represented by phosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyl Iminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -N, N,
N-trimethylenephosphonic acid, ethylenediamine-N,
N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be added.

When the reversal process is carried out, the black and white development is usually carried out before the color development. This black and white developer contains dihydroxybenzenes such as hydroquinone,
Known black-and-white developing agents such as 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 L (liter) or less per square meter of the light-sensitive material, and it is possible to reduce the bromide ion concentration in the replenishing solution by 50%.
It can be 0 ml or less. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82 is available.
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

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

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

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

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid,
Propionic acid, hydroxyacetic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Is most commonly used, with ammonium thiosulfate being the most widely used. Further, for example, the combined use of a thiosulfate solution with a thiocyanate, a thioether compound or thiourea is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or EP 29476.
The sulfinic acid compounds described in No. 9A are preferable. Furthermore,
Various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

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

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

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

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

The silver halide photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society.
of Motion Picture and Tel
Evolution Engineers, Volume 64, 24
It can be determined by the method described on pages 8-253 (May 1955 issue). According to the multi-stage countercurrent method described in the above literature, the amount of washing water can be significantly reduced, but bacteria are propagated due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. The problem arises. In the processing of the light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
No. 8,542, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and benzotriazole, Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal agents" (1986). ) Sankyo Publishing,
Hygiene Technology Association, “Microbial Sterilization, Sterilization, and Antifungal Technology” (19
1982) It is also possible to use the bactericides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and the washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

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

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

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

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

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

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

[0221]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of Supports The following Supports A to D were prepared by the method described below.

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

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

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

Supports D-1 to D-2: According to the method for forming the support A, the mixture was kneaded and extruded at 280 ° C. using a biaxial kneading extruder, pelletized, and formed into a film having a thickness of 80 μm. . (2) Coating of Undercoat Layer Each of the supports A, B, and D was subjected to corona discharge treatment on both sides thereof, and then provided with an undercoat layer having 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 on which 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 of gelatin 27 parts by weight of water 60 parts by weight of methanol 2 parts by weight of resorcin 0.01 part by weight of polyoxyethylene nonyl phenyl ether [Coating liquid for coating layer (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 Support After coating the undercoat layer and back layer by the above method, 1
The heat treatment was performed under the conditions shown in. All the heat treatments were carried out with the core having a diameter of 30 cm and the outer surface of the undercoat surface wound. (5) Measurement of flexural modulus The flexural modulus, which is the most important of the 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%.

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

[0233]

[Table 2] (6) Coating of Photosensitive Layer On each support obtained by the above method, each layer having the following composition was multilayer coated to prepare a multilayer color photosensitive material. The same symbols as used for the support are used as they are for the obtained multilayer color light-sensitive material. For example, a photosensitive material obtained by coating a photosensitive layer on the support A-1 becomes a multi-layer color photosensitive material A-1. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. 1st layer (antihalation layer) Black colloidal silver 0.18 gelatin 1.40 ExM-1 0.18 ExF-1 2.0x10 ^-3 HBS-1 0.20 2nd layer (intermediate layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS- 2 0.020 Gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ⁻⁵ ExS-2 1.8 × 10 ^{− 5} ExS-3 3.1x10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 A- (44) 0.010 Cpd -2 0.025 HBS-1 0.050 BS-5 0.050 Gelatin 0.87 4th layer (medium sensitivity red-sensitive emulsion layer) Emulsion D silver ^{0.70 ExS-1 3.5 × 10 -4} ExS-2 1.6 × 10 -5 ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-8 0.094 ExC-5 0.025 ExC-7 0.0010 A- (44) 0. Cpd-2 0.023 HBS-1 0.060 HBS-4 0.050 Gelatin 0.75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0x10 ^-4 ExS-3 3.4x10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 A- (44) 0.025 Cpd-20 .050 HBS-1 0.22 HBS-2 0.10 Gelatin .20 Sixth layer (intermediate layer) Cpd-1 0.10 Cpd-4 0.050 HBS-1 0.50 Gelatin 1.10 Seventh layer (low-sensitivity green-sensitive emulsion layer) Emulsion C Silver 0.35 ExS- 4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-18 0.0 × 10 ⁻³ A- (30) 5.0 × 10 ⁻³ HBS-1 0.20 HBS-3 0.010 HBS-5 0.15 Gelatin 0.73 Eighth layer (medium-sensitivity green-sensitive emulsion layer) ) Emulsion D Silver 0.80 ExS- ⁴ 3.2x10 ^-5 ExS-5 2.2x10 ^-4 ExS-6 8.4x10 ^-4 ExM-2 0.13 ExM-3 0.030 A -(27) 7.0x10 ^-3 A- (23) 4.0x10 ^-3 HBS-1 0.16 HBS-3 8.0x10 ^-3 HBS-4 0.040 Gelatin 0.90 9th layer (high sensitivity green sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ⁻⁴ ExC-1 0.010 ExM-1 0.030 ExM-4 0.10 ExM-5 0.024 A- (12) 1.0 × 10 ⁻³ Cpd-3 0.040 HBS -1 0.25 HBS-2 0.10 HBS-3 8.0x10 ^-3 gelatin 1.44 10th layer (yellow filter layer) yellow colloidal silver 0.030 Cpd-1 0.16 HBS-10 .60 Gelatin 0.60 11th layer (low-sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.020 ExY-2 0.22 ExY-3 0. 50 ExY-4 0.020 HBS-1 0.15 HBS- 0.15 Gelatin 1.10 12th layer (Medium-speed blue-sensitive emulsion layer) Emulsion D silver ^{0.40 ExS-7 7.4 × 10 -4} ExC-7 5.0 × 10 -3 ExY-2 0.050 ExY-3 0.10 A- (35) 2.0 × 10 ⁻³ HBS-1 0.050 Gelatin 0.78 13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4. 0x10 ^-4 ExY-2 0.10 ExY-3 0.10 A- (42) 1.5x10 ^-3 HBS-1 0.040 HBS-5 0.030 Gelatin 0.86 14th layer 1 protective layer) Emulsion G silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00 15th layer (second protective layer) H-1 0. 40 B-1 (diameter ^{1.7μm) 5.0 × 10 -2 B-} 2 ( diameter 1.7μm) 0.10 B-3 0.1 S-1 0.20 Gelatin 1.20 In addition, appropriate in each layer, preservability, processability, pressure resistance, antifungal or
W-1 for improving antibacterial property, antistatic property and coating property
To W-3, B-4 to B-6, F-1 to F-
17 and iron salts, lead salts, gold salts, platinum salts, iridium salts,
Contains rhodium salt.

[0234]

[Table 3] In Table 3, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

(2) Emulsions A to F are described in JP-A-3-23745.
According to the Example of No. 0, the spectral sensitizing dye described in each photosensitive layer was subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of sodium thiocyanate.

(3) Preparation of tabular grains is described in JP-A-1-1.
Low molecular weight gelatin is used according to the Example of 58426.

(4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains and the normal crystal grains having a grain structure by using a high voltage electron microscope.

[0238]

[Chemical 35]

[0239]

[Chemical 36]

[0240]

[Chemical 37]

[0241]

[Chemical 38]

[0242]

[Chemical Formula 39]

[0243]

[Chemical 40]

[0244]

[Chemical 41]

[0245]

[Chemical 42]

[0246]

[Chemical 43]

[0247]

[Chemical 44]

[0248]

[Chemical formula 45]

[0249]

[Chemical formula 46]

[0250]

[Chemical 47]

[0251]

[Chemical 48]

[0252]

[Chemical 49] Subsequently, A- (30) used for the seventh layer of the green-sensitive emulsion layers and A- (27), A- (23) used for the eighth layer of each of the multilayer color light-sensitive materials A-1 and C-1. ), A- of the ninth layer
A multilayer color light-sensitive material was prepared in the same manner except that (12) was replaced with the comparative compound (1) shown in Chemical Formula 50 below in an equimolar amount. These multilayer color light-sensitive materials are designated as A-3 and C-2.

[0253]

[Chemical 50] The produced multilayer color light-sensitive materials have a width of 35 mm, 1.
Slit to a length of 15 m, and perforate holes of 2 mm x 2.8 mm like the current 135 format with 4.75 mm intervals at intervals of 2 mm from both ends in the width direction of the film, and spool with a diameter of 14 mm. It is rolled up and stored in the 135 Patrone, and the current 135
The same film for photography was used. These films are
Group.

Then, perforation holes of the same size were provided at intervals of 31.7 mm in the length direction of the film with a distance of 2 mm from both ends in the width direction of the film, and were wound on a spool having a diameter of 8 mm. It was also used as a film for photography. These films are group II.

Fuji Zoom Cardia 800 (manufactured by Fuji Photo Film Co., Ltd.) was used as it is for the film of group I, and Fuji Zoom Cardia was modified for the film of group II, and the area of the image exposure portion was 5.01 cm ² ( Three
It is 0.0mm x 16.7mm, aspect ratio is 1.80), and it is modified to a mechanism that can feed two perforations per screen, and the resolution evaluation chart and Macbeth color checker under the following shooting conditions. A mannequin (one body, upper body) with a chart was photographed. In addition, the film of Group II was used, and only the area of the image-exposed portion was set to 2.55 cm ² (21.4 mm × 11.9 mm, aspect ratio 1.8), and the same photographing was performed. This is III
Group.

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. The same view was taken by the zooming operation 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 (clear sky) High trees, mountain distant view, sun, sun shadows B Daylight (cloudy) Low trees, mountain distant view, C Strobe High light gray wall, for shooting The finished film was processed according to the following color development processing step using a processing solution having the composition shown below. However, the treatment was carried out with a treatment liquid after a sample (imagewise exposed) was continuously (running) treated at 1 m ² / day for 15 days.

The processing steps and processing liquid compositions are shown below. (Processing step) Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 23 ml 17 ml Bleach 50 seconds 38.0 ° C 5 ml 5 ml Bleach fixing 50 seconds 38.0 ° C-5 Milliliter constant 50 seconds 38.0 ° C 16 milliliter 5 milliliter Water wash 30 seconds 38.0 ° C 34 milliliter 3.5 milliliter Stability (1) 20 seconds 38.0 ° C-3 milliliter Stability (2) 20 seconds 38.0 ° C 20 ml 3 ml Dry 1 min 30 sec 60 ° C * Replenishment amount per 35 mm width of photosensitive material 1.1 m (equivalent to 24 Ex. 1) Stabilizer is countercurrent method from (2) to (1) All the overflow liquid of water was introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. It was made to flow in. The amount of developing solution brought into the bleaching step, the amount of bleaching solution brought into the bleach-fixing step, the amount of bleach-fixing solution brought into the fixing step, and the amount of fixing solution brought into the washing step were as follows. 2.5 ml, 2.0 ml, and 2.
It was 0 ml and 2.0 ml. Also,
The crossover time is 6 seconds in each case, 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 2.0 2.0-1,1-diphosphonic acid Sodium sulfite 3.9 5.1 Carbonic acid Potassium 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl 4.5 6.0- N- (β-hydroxyethyl) amino] aniline sulphate Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.15 (bleaching solution) Tank solution (g ) Replenisher (g) 1,3-diaminopropanetetraacetic acid 130 195 Ferric ammonium-hydrate Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 5 Acetic acid 40 60 Water was added to 1.0 liter 1.0 liter pH (prepared with ammonia water) 4.4 4.4 (Bleach-fixing tank solution) 15:85 (volume of the bleaching tank solution and the following fixing tank solution) Ratio) mixture.

(PH 7.0) (Fixer) Tank solution (g) Replenisher (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution 280 liters 840 liters (700 g / liter) Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water was added. 1.0 liter 1.0 liter pH (prepared 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 20mg / liter and sodium sulfate 150mg /
1 liter was 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-monononylphenyl ether 0.2 (Average degree of polymerization 10) Disodium salt of ethylenediaminetetraacetic acid 0. 05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazole 0.75-1-ylmethyl) piperazine Water was added to 1.0 liter pH 8.5 The above treatment was carried out. These color negatives obtained by using a Fuji enlarger A690 professional were used at 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, Type II. 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 the print from the film photographed with the multilayer color light-sensitive material C-1 belonging to the I group, and the two prints of this reference and other prints are arranged side by side and sequentially compared, and judged to be better than the reference. The arithmetic mean was calculated by giving +1 to those obtained, 0 to those equal or difficult to judge, and -1 to those judged to be inferior to the standard.

On the other hand, regarding the color reproducibility, the cyan density of the magenta color image portion of the color checker chart of the color negative was measured, and the difference was determined by taking the value of the multilayer color photosensitive material C-1 as a reference to determine the degree of color turbidity. Examined.

Some of the results are shown in Table 4.

[0266]

[Table 4] From the results in Table 4, the film of the group II having the polyester support has a better judgment as to the sharpness than the group I which is the current 135 format. this is,
It is considered that this is because the film of group I has a large number of perforations per screen, and therefore the flatness of the exposure screen at the time of shooting is not maintained. In fact, some monitors pointed out blurring in the peripheral and central areas of the print, which seems to support this. However, the screen is 3c
In the group C of m ² or less, the sharpness was clearly inferior,
It shows that it is difficult to reduce the screen size to 3 cm ² or less while maintaining the image quality. Further, the multilayer color light-sensitive materials A-1 and C-1 of the present invention and the multilayer color light-sensitive materials A-3 and C-2 in which the compound represented by the general formula (A) is replaced with the comparative compound (1), respectively. When compared, it is clear that A-1 and C-1 are superior in sharpness to A-3 and C-2.

Regarding color reproducibility, A- and C- in which A-1 and C-1 of the multilayer color light-sensitive material of the present invention using the compound represented by the general formula (A) are replaced with the comparative compound (1).
3, the color turbidity is clearly smaller than that of C-2 and the color reproducibility is excellent. Further, compared to the large-screen film of the I-group, the films of the II-group and the III-group, which are reduced screens, are small in difference but improved. The cause of this is unknown, but it is presumed that it is probably due to a mechanical factor added to the hydrophilic colloid layer when the film is wound on the spool.

The multilayer color photosensitive material A-1 slit to a width of 35 mm was used as
It was difficult to cut it to a length of 1.65 m, which corresponds to one for shooting a single image, to wind it into a spool having a diameter of 14 mm, and to store it in a 135 format patrone. On the other hand, the film wound on the spool having a diameter of 8 mm could be easily stored, and there was a room to store a longer film. This means that it is possible to increase the number of shots with the current Patrone, or to slim down the Patrone with the current number of shots. Combined with the fact that even if the area of the exposure screen is reduced compared to the current format, the image quality is not impaired at all, it is suggested that the camera can be downsized. Example 2 PBC-2, 3, 6, shown in the compound example of polyester
Using 9, 10 and PBB-3, 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, the glass transition point (Tg)
Heat treatment was carried out at a temperature lower by 10 ° C., and each of the layers having the composition shown in Example 1 was multilayer coated using these supports to prepare a multilayer color light-sensitive material.

The produced sample was cut and processed in the same manner as the film II group for photographing described in Example 1, and the performance in sharpness and color reproducibility was evaluated in the same manner as in Example 1. Comparative evaluation was performed based on C-1 of Group I.

As a result, the multi-layer color light-sensitive material prepared from these 6 kinds of polyester supports was able to obtain almost the same evaluation as A-1 belonging to the II group of Example 1. Example 3 Multilayer color photosensitive materials A-1 and D-1 produced in Example 1
And D-3 in a film storage cartridge described in JP-A-2-273740, and a perforation having a width of 24 mm is 1 per screen at each side edge in the film length direction.
It was processed and stored as an individual piece. The camera was also modified so that this cartridge could be loaded, and the screen size of the exposure unit was 30.0 mm x 12.0 mm (exposure screen area 3.60 cm ² , aspect ratio 2.5). The subject was photographed according to the method of Example 1.

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

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

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 as the print of the same sample obtained from the film of Group II of Example 1 above.

Also, by making the film 24 mm wide, it was possible to downsize the cartridge and further downsize the camera.

[0276]

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

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[Procedure amendment]

[Submission date] December 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0147

[Correction method] Change

[Correction content]

[0147] Incidentally, with the image exposure unit 1 screen 3.0 cm ² or more, to 7.0 cm ² or less of small format,
It is important to maintain the flatness of the film during shooting. If the flatness is impaired, it will lead to poor focus , and especially when printing from a small format negative film, the enlargement ratio will be large.Therefore, the poor flatness of the film as described above will bring out the sharpness of the color photosensitive material for photography. Will be a major obstacle to Therefore, in the present invention, a silver halide color light-sensitive material for photographing using the timing DIR compound represented by formula (A) is disclosed in, for example, JP-A-3-0893.
It is particularly preferable to use a light-tight type cartridge provided with the attitude control mechanism disclosed in No. 41 and preventing light fogging, and a camera adapted thereto.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0222

[Correction method] Change

[Correction content]

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

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0259

[Correction method] Change

[Correction content]

The processing steps and processing liquid compositions are shown below. The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. It was made to flow in. The amount of developing solution brought into the bleaching step, the amount of bleaching solution brought into the bleach-fixing step, the amount of bleach-fixing solution brought into the fixing step, and the amount of fixing solution brought into the washing step were as follows. 2.5 ml, 2.0 ml, and 2.
It was 0 ml and 2.0 ml. Also,
The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0266

[Correction method] Change

[Correction content]

[0266]

[Table 4] From the results in Table 4, the group II film having the polyester support has a better judgment as to the sharpness than the current 135 format I group. It is considered that this is because the film of Group I has a large number of perforations per screen, so that the flatness of the exposure screen at the time of shooting is not maintained. In fact, some monitors pointed out blurring in the peripheral and central areas of the print, which seems to support this. However, in the group III in which the screen is 3 cm ² or less, the sharpness determination is clearly inferior, which shows that it is difficult to reduce the screen size to 3 cm ² or less while maintaining the image quality. Also,
The multilayer color light-sensitive material A-1 of the present invention and comparative C-1,
When the multilayer color light-sensitive materials A-3 and C-2 in which the compound represented by the general formula (A) is replaced with the comparative compound (1) are respectively compared, A-1 and C-1 are clearly A-3,
From C-2 , it can be seen that A-1 is more excellent in sharpness than C-1 .

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one hydrophilic colloid layer containing a compound represented by the following formula (A) on a support, wherein the support comprises a belt-shaped polyester base. , one or four or less perforations per screen on both side edge portions are formed, and the image portion area is at 3.0 cm ² or more 7.0 cm ² or less, an aspect ratio of 1.40
A silver halide color photographic light-sensitive material characterized by being at least 2.50. General formula (A) A- (Time) _n- W Here, A reacts with an oxidized product of a color developing agent to form (Ti
me) _n -W-releasing group, Time is a timing group, W is a group exhibiting a development inhibitory action after being released from (Time) _n -W, and n is 1, 2 or 3.