JPH07191427A - Silver halide color photograzphic sensitive material - Google Patents

Abstract

PURPOSE:To facilitate workability to take out the tongue end of a film in spite of core setting, to obviate generation of nonuniform developing, breaking at the rear end and rubbing flaws and to improve the preservable property and color reproducibility of color images by using a specific base which has a layer contg. specific couplers on a base and consists of a poly(alkylene arom. carboxylate). CONSTITUTION:This silver halide color photographic sensitive material has the layer contg. the couplers expressed by the formula. The base thereof consists of the poly(alkylene arom. carboxylate) and its glass transition temp. is >=50 to <=200 deg.C. The base is heat treated at a temp. above 40 deg.C and below the glass transition temp. during the time before application of an under coating layer or after the application of the under coating layer and before application of a silver halide photosensitive agent. In the formula, R1 denotes a hydrogen atom or substituent. Z denotes a nonmetal atom group forming a 5-membered azole ring contg. 2 to 3 pieces of nitrogen atoms; X denotes a hydrogen atom or a group which is eliminatable at the time of coupling reaction with the oxidant of a developing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention improves color reproducibility, color image fastness, storability of a light-sensitive material with time, improves curling and makes it easier to extract a tongue end of a film, and develops uneven development. ,
The present invention relates to a silver halide color photographic light-sensitive material that reduces scratches and film breakage during development processing.

[0002]

BACKGROUND OF THE INVENTION Silver halide color photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials) are generally produced by coating at least one light-sensitive silver halide emulsion layer on a plastic film support. . Examples of the plastic film include fibrin-based polymers represented by tri (acetyl cellulose) (hereinafter referred to as “TAC”) and poly (ethylene terephthalate) (hereinafter referred to as “P”).
A polyester-based polymer represented by "ET") is used. These are, for example, Research Disclosure No. 307, 10.
5 (1989, Nov.), XVII.

In general, the light-sensitive material using such a support is a sheet-like material such as a cut film, and a roll film typified by a width of 35 mm, which is housed in a cartridge and loaded into a camera for photographing. . TAC is mainly used as a support for a roll film, but the greatest feature of TAC is that it has no optical anisotropy and high transparency. Furthermore, it has the property of being excellent in decurling after one-point development processing. That is, the characteristic of the molecular structure of the TAC film is that it has a relatively high water absorption as a plastic film. Therefore, the curling curl that occurs over time in the state of being wound as a roll film causes water absorption in the development process to cause a molecular chain. It has an excellent property that the molecular chains that have flowed and fixed with time of winding undergo rearrangement, and as a result, curling curls once formed are eliminated.

However, in a photosensitive material using a film having no curling curl eliminating property such as TAC, when used in a roll state, for example, "processing unevenness" or "scratch" or a film is generated during development processing. "Break" may occur in
Problems such as the occurrence of scratches, defocusing, and jamming during transportation may occur in the printing process of forming an image on photographic printing paper after development.

On the other hand, since TAC has a relatively high water absorption,
It decomposes gradually during long-term storage and releases acid (acetic acid). The cyan, magenta, and yellow dye-forming couplers used in the light-sensitive material and the dyes formed from these couplers are affected by the released acid to cause a decrease in the coloring ability of the coupler and fading of the formed dye. Among them, the magenta dye forming coupler and the formed magenta dye are
Compared with other cyan and yellow dye-forming couplers and the formed dyes, the change in color tone when subjected to the action of this acid is particularly large. Among the magenta dye-forming couplers, the coupler according to the present invention has a smaller absorption of an unnecessary yellow component of the formed dye as compared with the conventional 5-pyrazolone coupler and is excellent in color reproducibility. Therefore, if the coupler having this excellent color reproducibility can be prevented from deteriorating the storage stability and color image storage stability of the light-sensitive material due to the use of the TAC support, the magenta dye-forming coupler can be dramatically improved, The development of these technologies has been long awaited.

In recent years, the use of photosensitive materials has been diversified,
The speed of film transport during shooting, the increase in shooting magnification, and the downsizing of cameras have been significantly advanced. In response to this progress, the support of the light-sensitive material is required to have properties such as strength, dimensional stability, and thin film formation. Further, as the camera becomes smaller, the miniaturization of the cartridge becomes stronger.

There are two problems in reducing the size of the cartridge. The first problem is a decrease in mechanical strength that accompanies thinning of the film. In particular, bending elasticity decreases in proportion to the cube of the thickness.
The light-sensitive material is generally coated with gelatin, and this layer causes shrinkage at low humidity to generate a curl in the width direction (U-shape). Therefore, the support needs to have bending elasticity enough to withstand the contraction stress.

The second problem is the curl that occurs during storage over time due to the miniaturization of cartridges and spools. In the conventional 135 system, the roll diameter is 14 mm even for the 36-shot film having the smallest roll diameter inside the cartridge.
Attempting to reduce the size to 12 mm or less, and further to 9 mm or less causes a marked curl, which causes various troubles. For example, when developing with a minilab automatic developing machine, one end is fixed to the reader and the other end is not fixed, so the film rolls up, and the supply of the processing liquid is delayed in this part. Cause the occurrence of. Also, the roll-up of this film is crushed by the rollers in the minilab, causing "folds" and "scratches." In addition, when the unexposed film drawn from the cartridge is wound into a roll and loaded into the supply room (this is called the core set), if a long film (36 frames is taken), it is compared to 12 frames or 24 frames. As a result, the number of windings is large and a tight winding state (hard to loosen) occurs. Moreover, in this case, the diameter of the innermost layer of the film in the supply chamber is naturally small. Therefore, in the case of a long film, the winding start end (the tongue end of the film) has a sharp curl. As a result, the tongue end of the film stored in the patrone after the end of photographing is tightly curled and adheres closely to the inner wall of the patrone, making it extremely difficult to pull out the tongue end by a jig during development.

In order to achieve the above-mentioned two problems, that is, high mechanical strength and low curl, there are two methods. The first method is a method of modifying the TAC having a curl-eliminating property to improve the mechanical strength. The second method is a method of improving the polyester support represented by poly (ethylene terephthalate) (PET) of the present invention, which is excellent in mechanical strength, so that it is hard to be wound.

To achieve this task by the former method,
The thickness of the TAC support, which is commonly used in current light-sensitive materials, is 122 μm, and when it is thinned to 100 μm, the flexural modulus is proportional to the cube of the thickness, so a support with approximately twice the elastic modulus is achieved. It is very difficult to do. Even if the spool diameter is reduced to 10 mm or less, even TAC, which has a curl-eliminating property, cannot be fully recovered during the development process, causing the above-mentioned “processing unevenness”, “folding” and “scratch marks”. Tongue tip work becomes difficult.
In this way, it is considered difficult to simultaneously solve the three problems of "improving elastic modulus twice", "improving curl curl" and "improving tongue tip workability".

On the other hand, when the latter method is used, for example, when PET is used, because of the inherently high elastic modulus, a bending elasticity equivalent to 122 μm of TAC of 100 μm,
Furthermore, it can be achieved at 90 μm. In addition, it was revealed as a result of the study that the use of a polyester support typified by PET markedly reduces the deterioration with time of the light-sensitive material derived from the TAC support and the deterioration of color image storability. To achieve these objects, a polyester support represented by PET, which is inexpensive and has excellent productivity, mechanical strength, and dimensional stability, has been considered as a substitute for TAC. In the roll form widely used as above, curling curl remains strongly, so that the handleability after development processing is poor, and the range of use is limited while having the above-mentioned excellent properties.

[0012]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to facilitate the workability of taking out the tongue end of a film even when the core is set, and to prevent uneven development, back end bending, and scratches in the developing process. Another object of the present invention is to provide a light-sensitive material having improved storage stability of a light-sensitive material, further improved storage stability of a color image, and excellent color reproducibility.

[0013]

The above objects of the present invention can be achieved by the silver halide color photographic light-sensitive material described below. A silver halide color photographic light-sensitive material having a layer containing a coupler represented by the general formula [M] shown in the following chemical formula 1 on a support, wherein the support is composed of poly (alkylene aromatic dicarboxylate). The glass transition temperature is 50 ° C. or higher and 200 ° C. or lower, and heat treatment is performed at a temperature of 40 ° C. or higher and lower than the glass transition temperature before coating the undercoat layer or after coating the undercoat layer and before coating the silver halide photosensitive layer. A silver halide color photographic light-sensitive material characterized in that

[0014]

[Chemical 2]

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

The silver halide color photographic light-sensitive material as described above, wherein the poly (alkylene aromatic dicarboxylate) support is composed of polyester having benzenedicarboxylic acid or naphthalene dicarboxylic acid and diol as essential components. .

The silver halide color photographic light-sensitive material as described in (1) or (2) above, wherein the polyester of the polyester support is made of poly (ethylene terephthalate) or poly (ethylene naphthalate).

The silver halide color photographic light-sensitive material as described in any one of (1) to (5) above, wherein the poly (alkylene aromatic dicarboxylate) support has a thickness of 50 μm to 100 μm.

The silver halide color photographic light-sensitive material as described in any one of (1) to (4), which is used by being wound in a roll shape on a spool having a core diameter of 3 mm or more and 10 mm or less.

The present invention will be described in detail below. First, the polyester of the present invention will be described. Although there are various polyesters of the present invention, a polyester having benzenedicarboxylic acid or naphthalenedicarboxylic acid and a diol as a main component has a high performance by balancing the difficulty of curling, mechanical strength, and cost. Of these, polyethylene-terephthalate (PET) polyethylene naphthalate-based polyester is particularly preferable. The naphthalate used in the description of the present invention means naphthalene dicarboxylate.

The polyester of the present invention is formed by using aromatic dicarboxylic acid and diol as essential components. The aromatic dicarboxylic acid is a dicarboxylic acid having at least one benzene nucleus, and specific compounds thereof include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride,
1,4- or 1,5- or 2,6- or 2,7-
Naphthalenedicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, tetrachlorophthalic anhydride,

[0022]

[Chemical 3]

And the like. Dibasic acids that can be used in addition to the essential aromatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, itaconic acid, and citraconic anhydride. Acid, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid

[0024]

[Chemical 4]

And the like.

Next, as diols, 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,

[0027]

[Chemical 5]

[0028]

[Chemical 6]

And the like. If necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. The polyester of the present invention may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or an ester thereof) at the same time in the molecule, and examples thereof include the following.

[0030]

[Chemical 7]

Among the polyesters composed of these diols and dicarboxylic acids, more preferred are homopolymers such as poly (ethylene terephthalate), poly (ethylene naphthalate) and poly (cyclohexanedimethanol terephthalate) (PCT). And 2,6-naphthalenedicarboxylic acid (NDCA) and terephthalic acid (TP) as particularly preferable essential aromatic dicarboxylic acids.
A), isophthalic acid (IPA), orthophthalic acid (OP
A), biphenyl-4,4'-dicarboxylic acid (PPD
C), ethylene glycol (EG) as a diol,
Cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (BP
A), biphenol (BP), and para-hydroxybenzoic acid (PHB) as hydroxycarboxylic acid which is a copolymerization component.
A), 6-hydroxy-2-naphthalenecarboxylic acid (H
NCA) is copolymerized.

Among these, more preferable are:
Copolymer of terephthalic acid, naphthalenedicarboxylic acid and ethylene glycol (mixing molar ratio of terephthalic acid and naphthalenedicarboxylic acid is 0.9: 0.1 to 0.1: 0.9)
Is preferable, and 0.8: 0.2 to 0.2: 0.8 is more preferable. ), Terephthalic acid and ethylene glycol,
Copolymer of bisphenol A (mixing molar ratio of ethylene glycol and bisphenol A is 0.6: 0.4 to 0:
It is preferably between 1.0 and more preferably 0.5: 0.5 to 0.1.
~ 0.9 is preferred. ), Isophthalic acid, biphenyl-4,4'-dicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; biphenyl-
The molar ratio of 4,4'-dicarboxylic acid is 0.1 to 0.5, 0.1 to 0.5, and more preferably 0.2 to 0.3, 0. 2 to 0.3
Is preferred. ), Terephthalic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is 1: 0 to 0.
7: 0.3 is preferable, and 0.9: 0.1 is more preferable.
To 0.6: 0.4) terephthalic acid, copolymer of ethylene glycol and biphenol (the molar ratio of ethylene glycol and biphenol is preferably 0: 1.0 to 0.8: 0.2, more preferably 0.1 : 0.9 to 0.7:
It is 0.3. ), Para-hydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of para-hydroxybenzoic acid, ethylene glycol is 1: 0 to
0.1: 0.9 is preferable, and 0.9: is more preferable.
Copolymers such as 0.1 to 0.2: 0.8) are preferable. These homopolymers and copolymers can be synthesized according to conventionally known polyester production methods. For example, when the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, first, the transesterification reaction with the glycol component is performed, and this is heated under reduced pressure to remove the excess glycol component. By doing so, it can be synthesized. 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. For these polyester synthesis methods, for example,
Polymer Experiments Vol. 5 "Polycondensation and polyaddition" (Kyoritsu Publishing, 1
980) 103-136, "Synthetic Polymer V"
(Asakura Shoten, 1971) 187 to 286 can be referred to. The preferred average molecular weight (weight) range for these polyesters is about 10,000 to 500,5000. In addition, these polyesters may be partially blended with another polyester to improve adhesion with another type of polyester,
It is possible to copolymerize a monomer constituting another polyester, or to copolymerize a monomer having an unsaturated bond in these polyesters and radically crosslink them. Polymer blends prepared by mixing two or more kinds of the obtained polymers are disclosed in JP-A-49-5482 and JP-A-64-5482.
-4325, JP-A-3-192718, Research Disclosure, 283, 739-41, 284, 7;
It can be easily molded according to the method described in 79-82 and 294,807-14.

The glass transition temperature (Tg) in the present invention means that when 10 mg of a sample film is heated in a helium nitrogen stream at a temperature of 20 ° C./minute using a differential thermal analyzer (DSC), it is measured from a baseline. It is defined as the arithmetic mean temperature of the temperature at which eccentricity begins and the temperature returning to a new baseline.
However, when an endothermic peak appears, the temperature at which this endothermic peak has a maximum value is defined as Tg. The polyester of the present invention has a Tg of 50 ° C. or higher, but the use conditions thereof are not generally handled with sufficient caution, and in particular, the temperature is often exposed to 40 ° C. outdoors in the midsummer, in many cases. From this viewpoint, the Tg of the present invention is preferably 55 ° C. or higher in consideration of safety. More preferably, Tg is 60 ° C. or higher, and particularly preferably 70 ° C. or higher. This is because the effect of improving the curling habit by this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature, so that the temperature is a severe condition when used by general users, that is, the temperature in summer exceeds 40 ° C. Polyesters having a glass transition temperature above the temperature are preferred. On the other hand, the upper limit of the glass transition temperature is 200 ° C. A polyester having a glass transition temperature of higher than 200 ° C. cannot provide a film having good transparency. Therefore, the Tg of the polyester used in the present invention needs to be 50 ° C. or higher and 200 ° C. or lower.

Next, examples of preferable specific compounds of the polyester used in the present invention are shown, but the present invention is not limited thereto. Polyester compound example P-0: [terephthalic acid (TPA) / ethylene glycol (EG)) (100/100)] (PET) Tg = 80 ° C P-1: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene Glycol (EG) (100/100)] (PEN) Tg = 119 ° C. P-2: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. P-3: [TPA / Bisphenol A (BPA) (100/100)] Tg = 192 ° C. P-4: 2,6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. P-5: 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C. P-6: 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 12 ℃ P-7: TPA / EG / BPA (100/50/50) Tg = 105 ℃ P-8: TPA / EG / BPA (100/25/75) Tg = 135 ℃

P-9: TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. P-10: IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 C P-11: NDCA / NPG / EG (100/70/30) Tg = 105C P-12: TPA / EG / BP (100/20/80) Tg = 115C P-13: PHBA / EG / TPA (200/100/100) Tg = 125 ° C. P-14: PEN / PET (60/40) Tg = 95 ° C. P-15: PEN / PET (80/20) Tg = 104 ° C. P-16: PAr / PEN (50/50) Tg = 142 ° C. P-17: PAr / PCT (50/50) Tg = 118 ° C. P-18: PAr / PET (60/40) Tg = 101 ° C. P-19: PEN / PET / PAr (50/25 25) Tg = 108 ℃ P-20: TPA / 5- sulfonium isophthalate (SIP) (100)

The polyester support (film base) preferably has a thickness of 50 μm or more and 100 μm or less. 5
If it is less than 0 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated during drying, while if it exceeds 100 μm, it is inconsistent with the purpose of reducing the thickness for compactness.
However, when used as a sheet-shaped photosensitive material, 10
The thickness may exceed 0 μm. The upper limit is 30
It is 0 μm. All of the polyesters of the present invention as described above have a flexural modulus higher than that of TAC, and it was possible to realize the original thinning of the film. However, of these, PET and PEN have strong bending elasticity, and by using them, it is possible to reduce the film thickness required for 122 μm for TAC to 100 μm or less. Next, the polyester support of the present invention is characterized by being subjected to a heat treatment, and in that case, it is necessary to perform the treatment at a temperature of 40 ° C. or higher and lower than the glass transition temperature for 0.1 to 1500 hours. This effect progresses faster as the heat treatment temperature increases. However, when the heat treatment temperature exceeds the glass transition temperature, the molecules in the film move rather disorderly and conversely the free volume increases, and the molecules tend to flow, that is, the film is easily curled. Therefore, this heat treatment needs to be performed below the glass transition temperature.

Therefore, this heat treatment is preferably carried out at a temperature slightly below the glass transition temperature for the purpose of shortening the processing time, and is 40 ° C. or more and less than the glass transition temperature, more preferably,
It is at least 30 ° C. below the glass transition temperature and less than the glass transition temperature. On the other hand, when performing heat treatment under these temperature conditions,
The effect is recognized after 0.1 hour. Further, at 1500 hours or more, the effect is almost saturated. Therefore, 0.
It is preferable to perform heat treatment for 1 hour or more and 1500 hours or less. In the method for heat-treating the polyester of the present invention, in order to shorten the time, it is previously heated to Tg or more for a short time (preferably Tg of 20 ° C or more and 100 ° C or less for 5 minutes to 3
It is also possible to carry out heat treatment at 40 ° C. or higher and below the glass transition temperature after heat treatment. In the heating method, the film roll may be left as it is in a heating warehouse for heat treatment, but it may be further transferred to a heating zone for heat treatment, and the latter is preferred in view of the suitability for production. Further, the roll core used in the heat treatment preferably has a structure in which an electric heater is built-in or a high-temperature liquid can be poured so that the film can be hollow or heated in order to efficiently propagate the temperature to the film. The material of the roll winding core is not particularly limited, but it is preferable that the material does not undergo strength reduction or deformation due to heat, and examples thereof include stainless steel and glass fiber-containing resin.

Next, in order to further enhance the function of the polyester of the present invention as a photographic support, it is preferable to coexist with various additives. An ultraviolet absorber may be kneaded into these polyester films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the addition amount thereof is usually 0.01% by weight to 20% by weight, preferably 0.05% by weight based on the weight of the polyester film.
It is about 10% by weight to 10% by weight. If it is less than 0.01% by weight, the effect of suppressing deterioration of ultraviolet rays cannot be expected. 2,4-dihydroxybenzophenone as an ultraviolet absorber,
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
Benzophenone-based compounds such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
Benzotriazoles such as 3'-di-t-butyl-5'-methylphenyl) benzotriazole, salicylates such as phenyl salicylate and methyl salicylate 2,4,6
-Tris [2'-hydroxy-4 '-(2 "-ethylhexyloxy) phenyl] triazine, 2-phenyl-
Examples thereof include triazine-based UV absorbers such as 4,6-di [2′-hydroxy-4 ′-(2 ″ -ethylhexyloxy) phenyltriazine.

In addition, one of the properties which are problematic when the polyester film of the present invention is used as a support for a photographic light-sensitive material is a problem of fogging due to the high refractive index of the support. The polyester of the present invention, particularly the aromatic polyester has a high refractive index of 1.6 to 1.7, while the gelatin which is the main component of the photosensitive layer coated thereon has a refractive index of 1.50 to 1.50. It is smaller than this value, which is 1.55. 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 of avoiding such a light piping phenomenon, a method of adding inert inorganic particles and the like to the film, a method of adding a dye, and the like 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 film dyeing is not particularly limited, but the color tone is preferably gray dyeing due to the general property of the light-sensitive material, and the dye is excellent in heat resistance in the film forming temperature range of the polyester film, and polyester Those having excellent compatibility with are preferable. As the dye, from the above viewpoint, Diaresin manufactured by Mitsubishi Kasei, manufactured by Nippon Kayaku
The purpose can be achieved by mixing a commercially available dye such as Kayaset for polyester.
Regarding the dyeing density, it is necessary to measure the color density in the visible light region with a color densitometer manufactured by Macbeth Co. and be at least 0.01 or more. More preferably, it is 0.03 or more.

The polyester film according to the present invention can be imparted with slipperiness according to the intended use, and the slipperiness imparting means is not particularly limited.
A general method is kneading an inactive inorganic compound or coating a surfactant. Examples of such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ , talc, kaolin and the like. Further, in addition to the slipperiness imparted by an external particle system in which inert particles are added to the polyester synthesis reaction system described above, a slipperiness imparting method by an internal particle system in which a catalyst or the like added during the polyester polymerization reaction is precipitated can also be adopted. Is. These slipperiness imparting means are not particularly limited, but transparency is an important requirement for a support for a photographic light-sensitive material. It is desirable to select SiO ₂ having a refractive index relatively close to, or an internal particle system capable of relatively reducing the precipitated particle size.

Further, when 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 this means include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die. When any of these polymer films is used as a support, since each of these polymer films has a hydrophobic surface, a photographic layer comprising a protective colloid mainly containing gelatin on the support (for example, a photosensitive silver halide emulsion layer). , The intermediate layer, the filter layer, etc.) are very difficult to adhere firmly. As conventional techniques attempted to overcome such difficulties, (1) chemical treatment, mechanical treatment,
Corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment,
After performing surface activation treatment such as glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., a method of directly applying a photographic emulsion to obtain adhesive strength,
(2) There are two methods, that is, a method of forming an undercoat layer and coating a photographic emulsion layer on the undercoat layer after the surface treatment is once performed or without the surface treatment. (For example, US Pat. No. 2,698,2
No. 41, No. 2,764,520, No. 2,864,75
No. 5, No. 3,462, 335, No. 3, 475, 193
No. 3, 3, 431, 421, 3, 501, 301
Nos. 3,460,944, 3,674,531
No., British Patent Nos. 788,365, 804,005
No. 891, 469, Japanese Patent Publication No. 48-43122,
51-446, etc.).

All of these surface treatments are thought to be caused by the formation of polar groups on the surface of the support which was originally hydrophobic, and the increase of the crosslink density of the surface. It is considered that the affinity of the component contained in the undercoat liquid with the polar group is increased, or 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) in good contact with the layer, and a single layer of applying only one resin layer containing both a hydrophobic group and a hydrophilic group There is a law.

Among the surface treatments of (1), corona discharge treatment is the most well known method, and any conventionally known method, for example, Japanese Patent Publication Nos. 48-5043 and 47-5.
1905, JP-A-47-20867, 49-83.
No. 767, No. 51-41770, No. 51-13157.
This can be achieved by the method disclosed in No. 6 or the like.
The standing frequency is 50 Hz to 5000 KHz, preferably 5
KHz to several hundred KHz is suitable. 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. If the frequency is too high,
A special device for impedance matching is required, which increases the cost of the device, 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 · min / m ² , preferably 0 in order to improve the leakage property of ordinary polyester, polyolefin and other plastic films. 0.01 KV · A · min / m ^{2 to 1} KV · A · min / m ² is suitable. The gap clearance between the electrode and the derivative 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 36-1033.
No. 6, No. 45-22004, No. 45-22005,
45-2440, 46-43480, U.S. Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638 and 3,309. No. 299, No. 3,424,735, No. 3,462,335, No. 3,475,307, No. 3,761,299, British Patent 997,093, JP-A No. 53-129262, etc. Can be used.

The glow discharge treatment conditions are generally such that the pressure is 0.005 to 20 Torr, preferably 0.02 to 2 Torr. 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 electric discharge is generated by applying a high voltage between metal plates or metal rods arranged in a vacuum tank with one or more pairs of spaces. This voltage can take various values depending on the composition of the atmospheric gas and the pressure, but normally, within the above pressure range, stable steady glow discharge occurs between 500 and 5000V. A particularly suitable voltage range for improving the adhesion is 2000 to 4000V. Further, as seen in the prior art, the discharge frequency is from DC to several tens of degrees.
00 MHz, preferably 50 Hz to 20 MHz is suitable. Regarding the discharge treatment strength, 0.01 KV · A · min / m ^{2 to 5} KV · A · min /
m ² is preferably 0.15 KV · A · min / m ^{2 to 1} KV · A · min / m ² .

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 other copolymers starting from monomers selected from polyesterimine, epoxy resin, grafted gelatin, nitrocellulose, and many other polymers The properties of the two layers have been investigated mainly for gelatin.

In the single layer method, good adhesion is often achieved by swelling many supports and interfacially mixing with the hydrophilic undercoat 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, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, and the like.
Examples of the cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, 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, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, di-resin. Examples include chlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred. Various known gelatin hardening agents can be used in the subbing layer of the present invention. Gelatin hardening agents include chromium salts (chrome alum, etc.), aldehydes (formaldehyde,
Glutaraldehyde, etc., isocyanates, epichlorohydrin resins, cyanuric chloride compounds (for example, Japanese Patent Publication Nos. 47-6151 and 47-33380,
54-25411, compounds described in JP-A-56-130740), vinyl sulfone or sulfonyl compounds (for example, JP-B-47-24259 and 50-).
35807, JP-A-49-24435, 53-4.
Nos. 1221 and 59-18944),
Carbamoyl ammonium salt compounds (for example, JP-B-56-12853, JP-A-58-32699, JP-A-4)
9-51945, 51-59625, 61-9
No. 641), amidinium salt-based compounds (for example, compounds described in JP-A-60-225148), carbodiimide-based compounds (for example, JP-A-51-
Nos. 126125 and 52-48311), pyridinium salt compounds (for example, Japanese Examined Patent Publication No. 58-
50699, JP-A-52-54427, JP-A-57.
-44140, 57-46538), other Belgian Patent No. 825,726, U.S. Patent No. 3,321,313, JP-A-50-38540.
No. 52-93470, No. 56-43353, No. 58-113929, and the like.

The subbing layer of the present invention may contain fine particles of inorganic or organic as a matting agent to the extent that the transparency and graininess of the image are not substantially impaired. As a matting agent for inorganic fine particles, silica (SiO ₂ ), titanium dioxide
(TiO ₂ ), calcium carbonate, magnesium carbonate and the like can be used. Examples of organic fine particle matting agents include polymethylmethacrylate, cellulose acetate propionate, polystyrene, and US Pat. No. 4,142,8.
The treatment solution-soluble substances described in US Pat. No. 94, and the polymers described in US Pat. No. 4,396,706 can be used. The average particle size of these fine particle matting agents is preferably 1 to 10 μm.

In addition to the above, the undercoat layer may contain various additives as required. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. 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, chlorophenol, etc. in the undercoat liquid. However, if desired, an etching agent as described above may be contained in the base coat.

The undercoating liquid according to the present invention is a well-known coating method, for example, dip 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, US Pat. No. 2,761,791
Issue No. 3,508,947 Issue 2,941,898
, And 3,526,528, Yuji Harasaki,
Two or more layers can be coated simultaneously by the method described in "Coating Engineering", page 253 (1973, published by Asakura Shoten).

The binder of 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 an antistatic agent, a slip agent, a matting agent, a surfactant, a dye and the like. The antistatic agent used in the back layer of the present invention is not particularly limited, and for example, as the anionic polymer electrolyte, carboxylic acid and carboxylic acid salt,
A polymer containing a sulfonate is disclosed in, for example, JP-A-48-220.
17, JP-B-46-24159, JP-A-51-30
725, JP-A-51-129216, JP-A-55-
It is a polymer as described in No. 95942. Examples of the cationic polymer include, for example, JP-A-49-12152.
3, JP-A-48-91165, JP-B-49-245.
No. 82 is available. Further, the ionic surfactant has anionic property and cationic property, and is disclosed in, for example, JP-A-49-85826 and JP-A-49-33630.
U.S. Pat. No. 2,992,108, U.S. Pat. No. 3,
206,312, JP-A-48-87826, JP-B-49-11567, JP-B-49-11568, JP-A-55-70837 and the like.

The most preferable antistatic agent for the back layer of the present invention is ZnO, TiO ₂ , 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 or a composite oxide thereof selected from ₃ V ₂ O ₅ .
The fine particles of the conductive crystalline oxide or the composite oxide thereof used in the present invention have a volume resistivity of 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less. The particle size is 0.002-0.7 μm, especially 0.005-0.3 μm.
It is desirable to set to μm.

Further, the silver halide color photographic light-sensitive material of the present invention may have a magnetic recording layer for recording various information. A known ferromagnetic material can be used. The magnetic recording layer is preferably used on the back surface of the support layer and can be provided by coating or printing. Further, a space for optically recording may be provided in the photosensitive material for recording various information.

The smaller the hollow portion or spool in the center of the film of the film used in the camera of the light-sensitive material of the present invention, the smaller it is. Can not. Therefore, in the present invention, the hollow or spool in the center of the film which is preferable in the camera is 3 mm or more, and the upper limit is 12 mm.
Is more preferable, 3 mm to 10 mm is more preferable, and 4 mm to 9 mm is particularly preferable. Also, the smaller the winding inner diameter of the spool, the more preferable. Therefore, in the present invention, the preferable inner diameter of the spool in the camera is 5 mm or more for the spool, and the upper limit is preferably 15 mm.
More preferably 6 mm to 13.5 mm, even more preferably 7
mm to 13.5 mm, particularly preferably 7 mm to 13 mm.

First, the compound of the formula [M] according to the present invention will be explained in detail. Among the coupler skeletons represented by the general formula [M] used in the present invention, preferred ones are 1H-imidazo [1,2-b] pyrazole, 1H-
Pyrazolo [1,5-b] [1,2,4] triazole,
1H-pyrazolo [5,1-c] [1,2,4] triazole and 1H-pyrazolo [1,5-d] tetrazole, each of formula [MI], [M-II], [M- II
I] and [M-IV]. More preferably, it is a compound represented by [M-II].

[0057]

[Chemical 8]

The substituents R ₁₁ , R ₁₂ , and R in these formulas
₁₃ and X will be described in detail. R ₁₁ is a hydrogen atom,
Halogen atom, alkyl group, aryl group, heterocyclic group,
Cyano group, hydroxyl group, nitro group, carboxyl group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino Group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group , A sulfinyl group, a phosphonyl group,
It represents an aryloxycarbonyl group, an acyl group or an azolyl group, and R ₁₁ may be a divalent group to form a bis form.

More specifically, each R ₁₁ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). Group, alkynyl group, cycloalkyl group, cycloalkenyl group, and specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 4-tetradecanamidophenyl), a heterocyclic group (for example, 2
-Furyl, 2-thiethyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-
Dodecylethoxy, 2-methanesulfonylethoxy),
Aryloxy group (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (eg, acetamide, benzamide, tetradecane) Amide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide) , An alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-). 5- Decyloxycarbonyl anilino, N- acetyl anilino, 2-chloro-5-{alpha-
(3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (for example, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (for example, N, N-dipro). Pilsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio group (eg, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-
(4-t-butylphenoxy) pspyruthio), an arylthio group (for example, phenylthio, 2-butoxy-5-).
t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, ,
Methanesulfonamide, hexadecanesulfonamide,
Benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-
5-t-butylbenzenesulfonamide), carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl))
Carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-di-t-amylphenoxy)
Propyl} carbamoyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocycle An oxy group (eg,
1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminofetylazo, 2-hydroxy-4-propanoylphenylazo) ), An acyloxy group (eg, acetoxy),
Carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, , N-succinimide, N-phthalimide,
3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-
Pyridylthio), a sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl,
3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, Benzoyl, 4-dodecyloxybenzoyl), and an azolyl group (eg, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl).

Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. Of these substituents, preferred R ₁₁
Examples thereof include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a ureido group, a urethane group and an acylamino group. R ₁₂ is R
It is the same group as the substituent exemplified for ₁₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, an acyl group and a cyano group. R ₁₃ is the same group as the substituent exemplified for R ₁₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group. , A carvimol group and an acyl group, and more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group and an arylthio group.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. The splitting off group is described in detail below. A halogen atom, an alkoxy group, an aryloxy group, an acyloxy group. Group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5-membered or 6-membered group There are a nitrogen heterocyclic group, an imide group, an arylazo group and the like, and these groups may be further substituted with a group which is allowed as a substituent for R ₁₁ . However, X does not contain a photographically useful group (for example, a development inhibitor and a group which releases it).

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

Examples of compounds of the magenta coupler represented by the general formula [M] are shown below, but the invention is not limited thereto.

[0064]

[Chemical 9]

[0065]

[Chemical 10]

[0066]

[Chemical 11]

[0067]

[Chemical 12]

[0068]

[Chemical 13]

[0069]

[Chemical 14]

[0070]

[Chemical 15]

[0071]

[Chemical 16]

[0072]

[Chemical 17]

[0073]

[Chemical 18]

Documents which describe a method for synthesizing the coupler represented by the formula [M] are listed below. The compound of the formula [M-I] is represented by the formula [M-I] such as in US Pat. No. 4,500,630.
The compounds of I] are disclosed in U.S. Pat. Nos. 4,540,654 and 4,705,863, JP-A-61-265155, JP-A-61-265457, and JP-A-62-1209457.
The compound of the formula [M-III] is disclosed in JP-B-47-27411,
The compound of the formula [M-IV] such as US Pat. No. 3,725,067 can be synthesized by the method described in JP-A-60-33552. The magenta coupler represented by formula [M] of the present invention can be used in any layer of a light-sensitive material. That is, it can be used as any of a photosensitive layer (blue-sensitive emulsion layer, green-sensitive emulsion layer, red-sensitive emulsion layer) and non-photosensitive layer (for example, protective layer, yellow filter layer, intermediate layer, antihalation layer). . Particularly preferred is the green-sensitive emulsion layer and / or its adjacent layer. The total amount added is 0.01 to 1.0 g / m ² , preferably 0.05 to 0.8 g / m ² , and more preferably 0.1.
~ 0.5 g / m ² . The method for adding the magenta coupler of the present invention to the light-sensitive material is based on the method for other couplers described below, but the amount of the high-boiling organic solvent used as the dispersion solvent is
The weight ratio to all couplers added to the magenta coupler-containing layer is 0 to 4.0, preferably 0 to
2.0, more preferably 0.1 to 1.5, and further preferably 0.3 to 1.0.

Regarding the technology and inorganic / organic materials applicable to the light-sensitive material using the support of the present invention,
It is described in European Patent No. 436,938A2 at the following points and in the patents cited below. 1. Layer composition: Page 146, Line 34 to Line 147
Page 25 line 2. Silver halide emulsion: pp. 147, line 26-148.
Page 12th line 3. Yellow coupler: Page 137, line 35 to line 146
3. Coupler described on page 33, line 149, lines 21-23. Magenta coupler: As a coupler which can be used together with the compound of the formula [M] of the present invention, see page 149, line 24 to line 28.
Line: Examples include couplers described on page 3, line 5 to page 25, line 55 of EP 421,453A1. 5. Cyan coupler: page 149, lines 29 to 33; coupler described in page 3, line 28 to page 40, line 2 of EP 432,804A2. Polymer coupler: page 149, lines 34-38; EP 435,334A2, page 113, 39.
6. Coupler described in lines 1 to 123, page 123. 7. Colored couplers: page 53, line 42 to page 137, line 34, page 149, lines 39 to 45; couplers described in EP 423,727A. Other functional couplers: page 7, line 1 to page 53, line 41, page 149, line 46 to page 150, line 3; EP 435,334A2, page 3, line 1 to line 29
Page 50 line; European Patent Nos. 520,496A, 52
9. Couplers described in Nos. 2,371A and 525,396A. Antiseptic / antifungal agent: compound described on page 150, lines 25 to 28. 10. Formalin casvenger: page 149, line 15 to
17th line; compounds described in U.S. Pat. No. 4,414,309 11. Other additives: page 153, lines 38 to 47; European Patent 421,453A1, page 75, line 21 to Page 84, Line 56, Page 27, Line 40 to Page 37, Line 4
Compound described in line 0 12. Dispersion method: Page 150, lines 4 to 24 13. Film thickness / film properties: Page 150, lines 35 to 49 14. Color development step: 150 Page 50th line-151st
Page 47 line; color developing agent described in JP-A-5-072691 15. desilvering process: page 151, line 48-152.
Page 53, Line 16. Automatic processor: Page 152, Line 54-153
Page 2nd line 17. Water washing / stabilization process: Page 153, line 3 to line 37

[0076]

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

Example 1 (1) Material of Support, etc. Each support used in this example was prepared by the following method. PEN: 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinuvin P. as an ultraviolet absorber.
2 parts by weight of 326 (manufactured by Geigy) were dried by a conventional method, melted at 300 ° C., and then extruded from a T-shaped die 140.
Longitudinal stretching of 3.3 times at ℃, followed by 3.3 at 130 ℃
Double stretching was performed, and heat setting was further performed at 250 ° C. for 6 seconds. PET: 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.・ TAC: Methylene chloride / methanol = 82/8 wt by a normal solution casting method of triacetyl cellulose
Ratio, TAC concentration 13%, plasticizer TPP / BDP = 2/1
(Here TPP; triphenyl phosphate, BD
15% by weight of P; biphenyl diphenyl phosphate)
The band method was used.・ PEN / PET = 4/1 (weight ratio); PE in advance
The N and PET pellets were vacuum dried at 150 ° C. for 4 hours, kneaded and extruded at 280 ° C. using a twin-screw kneading extruder, and then pelletized.

This polyester was formed into a film under the same conditions as the above PEN. (2) Coating of Undercoat Layer Each of the above supports was subjected to corona discharge treatment on both sides thereof, and then an undercoat liquid having the following composition was applied to provide the undercoat layer on the high temperature surface side during stretching. For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm width support is treated at 20 m / min. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during processing is 9.6KHz,
The gap clearance between the electrode and the dielectric roll is 1.6.
It was mm.

Gelatin 3 g Distilled water 250 cc Sodium-α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Further, an undercoat layer having the following composition was provided on the TAC support. Gelatin 0.2g Salicylic acid 0.1g Methanol 15cc Acetone 85cc Formaldehyde 0.01g

(3) Coating of Back Layer A back layer having the following composition was coated on the surface opposite to the side on which the undercoat layer of the above support was provided after undercoating. (3-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol 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, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. Colloidal precipitate from which excess ions have been removed 2
100 parts by weight of water 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 0.1.
A fine powder of tin oxide-antimony oxide composite having a size of μm was obtained. The specific resistance of this fine particle powder was 25 Ω · cm.

A mixed solution of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, roughly dispersed with a stirrer, and then
Horizontal sand mill (trade name Dyno Mill; WILLYA. BACHOFEN
It was prepared by dispersing with AG) until the residence time reached 30 minutes.

(3-2) Preparation of Back Layer: The following formulation [A] was applied so that the dry film thickness would be 0.3 μm, and dried at 115 ° C. for 60 seconds. The following coating solution (B) for coating layer was further applied onto this so that the dry film thickness would be 1 μm.
It was dried at ℃ for 3 minutes. [Formulation A] 10 parts by weight of the conductive fine particle dispersion liquid 1 part by weight gelatin 1 part by weight water 27 parts by weight methanol 60 parts by weight resorcin 2 parts by weight polyoxyethylene nonylphenyl ether 0.01 part by weight [coating layer coating solution (B)] Cellulose triacetate 1 part by weight Acetone 70 parts by weight Methanol 15 parts by weight Dichloromethylene 10 parts by weight p-Chlorophenol 4 parts by weight Silica particles (average particle size 0.2 μm) 0.01 parts by weight Polysiloxane 0.005 parts by weight C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H = (8 / 2J weight ratio) 0.01 parts by weight Dispersion (average particle size 20 nm)

(4) Heat Treatment of Support After the undercoat layer and the back layer were applied by the above method, heat treatment was carried out under the conditions shown in Tables 3 to 6 below. 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. On the other hand, the support PEN, PET, PEN / PET = 4
A support which was not heat-treated at / 1 (weight ratio) was also prepared.

(5) Coating of Photosensitive Layer On the support obtained by the above method, each layer having the composition as shown below was coated in multiple layers to prepare a multilayer color photosensitive material. (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 hardener ExS; sensitizing dye coating amount represents the amount of silver for the silver halide and colloidal silver, expressed in units of g / m ² of silver and coupler, for additives and gelatin in the unit of g / m ² The amount is shown, and for the sensitizing dye, it is shown in mol per mol of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver 0.15 Gelatin 1.90 ExM-1 2.0 × 10 ^-2 HBS-1 3.0 × 10 ^-2

Second layer (intermediate layer) Gelatin 2.10 UV-1 3.0 × 10 ^-2 UV-2 5.0 × 10 ^-2 UV-3 5.0 × 10 ^-2 UV-5 3.0 × 10 ^-2 ExF-1 4.0 × 10 ^-2 HBS-2 7.0 x 10 ^-2 HBS-4 5.0 x 10 ^-2

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Silver 0.15 Silver iodobromide emulsion B Silver 0.25 Gelatin 1.50 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS- 3 1.0 x 10 ^-5 ExC-1 0.11 ExC-3 0.11 ExC-4 3.0 x 10 ^-2 ExC-7 1.0 x 10 ^-2 HBS-1 7.0 x 10 ^-3 HBS-3 3.0 x 10 ^-3

Fourth layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.25 Silver iodobromide emulsion D Silver 0.45 Gelatin 2.00 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS- 3 1.0 × 10 ^-5 ExC-1 0.16 ExC-2 8.0 × 10 ^-2 ExC-3 0.17 ExC-7 1.5 × 10 ^-2 ExC-8 1.8 × 10 ^-2 ExY-2 1.0 × 10 ^-2 Cpd-10 1.0 × 10 ^-4 HBS-1 0.10

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E Silver 0.60 Gelatin 1.60 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 ExC- 5 7.0 x 10 ^-2 ExC-6 8.0 x 10 ^-2 ExC-7 1.5 x 10 ^-2 ExC-8 1.2 x 10 ^-2 HBS-1 0.15 HBS-2 8.0 x 10 ^-2

Sixth layer (intermediate layer) Gelatin 1.10 P-2 0.17 Cpd-1 0.10 Cpd-4 0.17 HBS-1 5.0 × 10 ^-2

7th layer (low-sensitivity green emulsion layer) Silver iodobromide emulsion F Silver 0.08 Silver iodobromide emulsion G Silver 0.12 Gelatin 0.50 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS- 6 0.3 × 10 ^-4 ExM-1 2.0 × 10 ^-2 M-22 0.26 ExM-3 3.0 × 10 ^-2 ExY-1 1.0 × 10 ^-2 ExC-9 2.0 × 10 ^-2 Cpd-11 0.15 HBS-1 0.10

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.55 Gelatin 1.00 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 3.0 × 10 ^-5 ExM- 1 3.0 x 10 ^-2 M-22 0.15 ExM-3 1.5 x 10 ^-2 ExY-1 2.0 x 10 ^-2 ExC-9 2.0 x 10 ^-2 HBS-1 0.20

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 0.45 Gelatin 0.90 ExS-4 2.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 2.0 × 10 ^-5 ExS- 7 3.0 × 10 ^-4 ExM-1 1.0 × 10 ^-2 M-21 3.9 × 10 ^-2 M-23 2.6 × 10 ^-2 ExC-9 1.5 × 10 ^-2 Cpd-2 1.0 × 10 ^-2 Cpd-9 2.0 × 10 ^-4 Cpd-10 2.0 × 10 ^-4 HBS-1 0.20 HBS-2 5.0 × 10 ^-2

10th layer (yellow filter layer) Gelatin 0.90 Yellow colloid 5.0 × 10 ^-2 Cpd-1 0.10 Cpd-13 0.10 HBS-1 0.20

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.10 Silver iodobromide emulsion K Silver 0.20 Gelatin 1.00 ExS-8 2.0 × 10 ^-4 ExY-1 3.0 × 10 ^-2 ExY- 3 0.95 YB-33 7.0 × 10 ^-2 Cpd-2 1.0 × 10 ^-2 HBS-1 0.23

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 0.40 Gelatin 0.60 ExS-8 1.0 × 10 ^-4 ExY-3 1.2 × 10 ^-1 Cpd-2 1.0 × 10 ^-3 HBS- 1 4.0 x 10 ^-2

Thirteenth layer (first protective layer) Fine grain silver iodobromide (average particle size 0.07 μm, AgI 1 mol%) 0.20 Gelatin 1.00 UV-2 0.10 UV-3 0.10 UV-4 0.10 UV-5 0.10 Cpd- 12 0.20 HBS-3 4.0 x 10 ^-2 P-3 9.0 x 10 ^-2

14th layer (second protective layer) Gelatin 0.70 B-1 (diameter 1.5 μm) 0.10 B-2 (diameter 1.5 μm) 0.10 B-3 2.0 × 10 ^-2 H-1 0.36

In addition, storability, processability, pressure resistance, mildew resistance
In order to improve antibacterial properties, antistatic properties, and coating properties, the following Cpd-3, Cpd-5 to Cpd-8, P-
1, P-2, W-1 to W-4 were added. In addition to the above, B-4, F-1 to F-13, iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt are further contained in each layer as appropriate. Next, a list of emulsions used in the present invention and the chemical structural formulas or chemical names of the compounds are shown below.

[0101]

[Table 1]

[0102]

[Table 2]

In Tables 1 and 2, (1) each emulsion was reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Each emulsion was subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each light-sensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. There is. (3) Low molecular weight gelatin is used for the preparation of tabular grains according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0104]

[Chemical 19]

[0105]

[Chemical 20]

[0106]

[Chemical 21]

[0107]

[Chemical formula 22]

[0108]

[Chemical formula 23]

[0109]

[Chemical formula 24]

[0110]

[Chemical 25]

[0111]

[Chemical formula 26]

[0112]

[Chemical 27]

[0113]

[Chemical 28]

[0114]

[Chemical 29]

[0115]

[Chemical 30]

[0116]

[Chemical 31]

[0117]

[Chemical 32]

[0118]

[Chemical 33]

(6) Processing of photographic film sample The photographic film sample produced in this manner was 35 mm
A film-integrated camera was manufactured by slitting the film to a width of 1.8 m, punching it, and incorporating it into a unit as shown in FIG. 1 or 2. These are designated as Samples 101 to 138. Figure 1
[FIG. 3] is a top view showing the internal structure of a film-integrated camera. In this camera 1, a unit 3 is housed inside a camera outer box 2. In this unit 3, the unexposed film 8 drawn from the cartridge 6 is wound and loaded in the supply chamber 4. Then, the film is pulled out from the supply chamber 4 and wound up in the cartridge 6 each time a photograph is taken. Reference numeral 7 is a taking lens, and 9 is a film supporting surface.

Further, FIG. 2 shows only the unit 13 portion of another type of film-integrated type camera, which is a spool 21 in the cartridge 16 (a description of the spool is omitted in FIG. 1). ) Outside the supply room 1
4 also has a spool 22. The film 18 uses 36 frames.

Next, as a comparative sample, one in which the temperature / time of the heat treatment of the support PEN, the spool diameter of the film-integrated camera, and the winding diameter were changed as shown in Table 6 was prepared.
This is designated as Samples 139-142. (7) Core set The above film-integrated camera was heated at 40 ° C. for 24 hours to have a curl. This temperature condition is a condition assuming outdoor in summer. (8) Extraction of tongue end, development process, curl measurement After the film-integrated camera with a curled curl under the above conditions was left to cool overnight in a room at 25 ° C, the tongue end was extracted with a jig. Automatic processor (Minilab FP-56
0B: made by Fuji Photo Film Co., Ltd.) and immediately processed to 25
Curl measurement was performed at 60 ° C. and 60% RH.

The development processing conditions are as follows. The sample used for the measurement was separately processed by running the sample which was previously subjected to imagewise exposure, and was processed using the processing solution which was used until the replenishment amount for color development was replenished by 3 times the tank volume. I did.

(Processing process) Process processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 300 ml 5 liters Bleaching 50 seconds 38.0 ° C 140 ml 5 liters Bleaching fixing 50 seconds 38.0 ° C-5 liters Settling 50 seconds 38.0 ° C 420 ml 5 liters Washing with water 30 seconds 38.0 ° C 980 ml 3.5 liters Stable (1) 20 seconds 38.0 ° C −3 liters Stable (2) 20 seconds 38.0 ° C 560 ml 3 liters Dry 1 minute 30 seconds 60 ℃ ^* Replenishment amount per 1 m ² of light-sensitive material The stabilizing solution was a countercurrent method 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 at the top of the bleaching tank of the automatic developing machine and at 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. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water washing process are respectively per 1 m ² of the light-sensitive material. They were 65 ml, 50 ml, 50 ml and 50 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 2.0 3.2 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.2 Potassium carbonate 37.5 39.0 Potassium bromide 1.7-Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 4.2 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.7 7.5 Add water to 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid Adjust) 10.05 10.45

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-Diaminopropanetetraacetic acid ferric ammonium monohydrate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 40 60 Water Add 1.0 liter 1.0 liter pH (prepared with ammonia water) 4.4 4.4

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (P
H7.0)

(Fixing solution) Tank solution (g) Replenishing solution (g) Ammonium sulfate 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 280 Millitottle 840 Millitottle imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH [ Prepared with aqueous ammonia and acetic acid] 7.4 7.45

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by 20 mg / liter sodium dichloroisocyanate and 150 sodium sulfate
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Fixer) Common to tank and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The results are shown in Tables 3 to 6.

[0131]

[Table 3]

[0132]

[Table 4]

[0133]

[Table 5]

[0134]

[Table 6]

In Tables 3 to 6, "post-treatment ANSI curl value" means ANSI / ASC, pH 1.29-19.
The degree of curl measured according to Test Method A of No. 85 is 1 / R (R is the radius of curl [unit.m]. The results shown in Tables 3 to 6 indicate that In a film-integrated camera that uses a film made of heat-treated polyester support, the curl value is small even when the spool diameter is small, and the tongue tip can be easily pulled out. Trouble of rear end breakage did not occur, whereas polyester film without TAC or heat treatment, tongue end extraction work,
It was not possible to satisfy all of development unevenness, scratches, and trailing edge break at the same time. Although not shown in Tables 3 to 6, even if the type of the support is PET or PEN, when the thickness of the support is less than 50 μm, the support may have bending elasticity capable of withstanding the contraction stress of the photosensitive layer. However, a gutter-like curl was generated, and scratches were generated in the development processing step. The same was true for other polyesters. Further, when the support has a thickness of 100 μm or more, it is difficult to wind it up in a spool and store it in a cartridge or a supply chamber. Therefore, it becomes impossible to downsize the camera and the cartridge.

As a polymer having a glass transition temperature Tg of more than 200 ° C., poly (oxyisophthalooxy-2,6-dimethyl-1,4-phenyleneisopropylidene-3,5-dimethyl-1,4) having a Tg of 225 ° C. is used. -Phenylene) could not be applied to a light-sensitive material because a transparent support was not obtained. Further, in all the preparations of the photosensitive material using water in place of the conductive fine particle dispersion in [Formulation A] of the back layer, static marks were observed, and in the present invention, the conductive layer should be provided. Is essential to enhance the commerciality of the sensitive material.

Example 2 Thickness 12 used when producing the sample 103 of Example 1
2 μm TAC support, 90 μm thick heat treated PET support used to make samples 121-126, 75 μm thick heat treated PEN support used to make samples 127-132 Body and sample 1
The couplers of the 7th to 9th layers of Example 1 were prepared by using the four kinds of heat-treated PEN / PET = 4/1 (weight ratio) used to prepare Nos. 33 to 137 and having a thickness of 75 μm. Samples 201 to 212 were prepared in the same manner as in Example 1 except that the values were changed as shown in Tables 7 to 8. Samples 203, 2
Couplers ExM-2, E used in 06, 209, 212
xM-4 and ExM-5 are shown in Chemical formula 53.

[0138]

[Chemical 34]

Next, P-4 to P-7, P-11, P-12 and P listed in the preferred specific examples of polyesters.
-16 and P-19 are used, and (1) PEN of Example 1 is used.
According to the method described for the support, an ultraviolet absorber is added and melted, and extrusion molding, longitudinal stretching and transverse stretching are performed to obtain a thickness of 85.
A μm support was obtained. These supports are the same as in Example 1.
After coating the undercoat layer and the back layer described in 1 above and applying the heat treatments shown in Table 9, the photosensitive layers shown in Example 1 were coated to prepare samples 213 to 220.

[0140]

[Table 7]

[0141]

[Table 8]

[0142]

[Table 9]

These prepared samples 201 to 220 include the coated samples of samples 103, 123, 129 and 135,
According to the processing of the film sample of (6) described in Example 1, the film was placed in a supply chamber having an inner diameter of 13.02 mm.
After the core setting treatment of (7) was performed to give a curl, the sample was taken out from these film-integrated cameras and left for use in the following use after allowing to cool overnight in a room at 25 ° C.

First, in order to examine the storability of the light-sensitive material with time, two sets of each sample were prepared, and one set was 5
Another set is 40 under conditions of ℃ and relative humidity of 35%.
After storing for 2 months under the conditions of ℃ and relative humidity of 80%, white light (color temperature of light source: 4800 ° K) wedge exposure was performed to perform the color development processing used in Example 1,
The characteristic curve was obtained. From these characteristic curves, each sample was stored at 5 ° C. and a relative humidity of 35%. From the point of the exposure amount giving the minimum density +0.2 on the characteristic curve of the sample to the high exposure amount side, logE = 1.5. Density at the point (D
₁ ) while reading the density (D ₂ ) at the same exposure point of the sample stored under the conditions of 40 ° C. and 80% relative humidity,
The ratio D ₂ / D ₁ of the color density was obtained, and the storability of the light-sensitive material with time was examined from the change in color density.

Regarding the storability of color images, the density of the samples obtained by subjecting the samples to color development processing by subjecting them to wedge exposure of white light separately was measured.
After storing in 0% condition for 2 months, perform density measurement again, and give the density of minimum density +1.5 before storing in high temperature and high humidity condition. The density at the same exposure dose point was read and the density difference (ΔD) was determined. With respect to the storage stability of these light-sensitive materials with time and the storage stability of color images, the results of magenta color image density are shown.

Next, a green filter was applied and wedge exposure of green light was applied to perform color development and development, and ordinary magenta densities of these samples were measured to obtain characteristic curves thereof. The yellow density of the same sample was also measured. However, the transmission wavelength of 4 is used to measure the yellow density.
The concentration was measured by changing to a polarizing filter of 30 nm (half-value width of 10 nm). From these two characteristic curves, the yellow density at the point of the exposure amount that gives the minimum density + 2.0 density on the characteristic curve measured with the magenta density is read, and the difference (ΔD _B ) is obtained with the value of the sample 203 as a reference. It was The smaller the value is, the smaller the absorption in the blue region is, which is preferable for color reproduction, and the image quality is improved. The results are also shown in Tables 7 to 9.

From the results shown in Tables 7 to 9, the light-sensitive materials produced by using the heat-treated polyester support of the present invention were obtained by storing these light-sensitive materials under high temperature and high humidity conditions for a long period of time. However, no decrease in magenta color density was observed, and it is clear from comparison with the comparative sample that it is a preferable support for storage of the light-sensitive material. Further, it is apparent that the use of the support of the present invention is also preferable in terms of storage stability of a magenta color image, because it is a preferable support with a small decrease in density. Regarding the magenta coupler, it is preferable to use the coupler represented by the general formula [M] for further improving the storability of the light-sensitive material and the storability of a color image and being advantageous for color reproducibility and preferable for improving image quality. Samples 204, 205 satisfying the constitution of the present invention,
207, 208, 210, 211, 123, 129, 1
This can be known by comparing 35 with the comparative samples 206, 209 and 212.

Example 3 PET, PEN, PEN / PET = 4/1 were prepared in the same manner as in Example 1, except that the stretching and casting methods were changed so that the thickness was 180 μm.
A support of (weight ratio) and TAC was prepared. Samples 301 to 316 shown in Table 10 were prepared by applying the same coating composition as Sample 101 of Example 1 and Samples 201 to 203 of Example 2 using these four types of supports.

These prepared samples 301 to 316 are
The storability as a light-sensitive material, the storability of a color image and the color reproducibility were examined according to the method described in Example 2. Regarding the color reproducibility, the difference was found with reference to the sample 313. The results are also shown in Table 10.

[0150]

[Table 10]

From the results shown in Table 10, the thickness of the support is 180
When the thickness was set to μm, the color reproducibility was the same as that of the thin support of Example 2 and there was no change due to the thickness of the support, but the storage stability of the light-sensitive material and the storage stability of the color image were The comparative TAC supports show further deterioration of these performances, but the heat-treated polyester-based supports of the present invention do not change with the thickness of the supports, and have excellent sensible material storability and color image storability. It can be seen that In addition, T
The greater deterioration of these performances due to the increase in the thickness of the AC support is considered to be due to the increase in the amount of acid (acetic acid) produced by the decomposition of TAC.

Example 4 75 μm PEN, 90 μm, capable of coating a photosensitive layer according to the methods (1) to (4) described in Example 1
PET, 75 μm PEN / PET = 4/1 (weight ratio), 115 μm and 122 μm TAC, five kinds of supports were wrapped around a hollow core with a diameter of 9 cm and a length of 50 m,
After being stored under conditions of high temperature and high humidity of 60 ° C. and relative humidity of 70% for 1 month, the same photosensitive layer as in Example 1 was applied using these supports to obtain samples 101 to 142. Samples 401 to 442 were produced in the same manner (the last two digits of the numbers correspond to the samples of Example 1 and this example).

The prepared samples were processed according to the method described in Example 1, one set was given a curl and then allowed to cool, and the tongue was taken out, and the development process and curl measurement were carried out. In the other set, the storability of the light-sensitive material and the storability of the color image were examined according to the method described in Example 2.

As a result, as the sample prepared from the polyester support heat-treated in the temperature range of the present invention, the support stored under the conditions of high temperature and high humidity before coating the photosensitive layer was used. Even though the tongue-extracting workability, curl value, development unevenness, scratches, and trailing edge fold were the same as in Example 1,
Even in the case of the TAC support and the polyester support which were not heat-treated, the workability of extracting the tongue tip was more difficult and the curl value was high. In addition, uneven development, scratches, and breakage of the trailing edge were often seen. On the other hand, regarding the storability and color image storability of the light-sensitive material, the sample using the polyester support was sample 12 of Table 7 and Table 8 shown in Example 2.
3, 129, and 135, but the samples using the TAC support showed a deterioration of 0.94 and 0.17, respectively, as compared with the results of the sample 103 in Table 7.

From these results, in the support of the present invention, the support before coating the photosensitive layer was stored under conditions of high temperature and high humidity, after which the photosensitive layer was coated to prepare the support. As described above, it can be seen that the sample gives good results without any problems in handleability, color development processability, sensitizing material and storability of color image.

[0156]

EFFECT OF THE INVENTION A silver halide color photographic light-sensitive material having a layer containing a coupler represented by the general formula [M] on a support, which is used in the form of a roll, is a polyester type. Which has a glass transition temperature of 5
Halogenation using a support having a temperature of 0 ° C. or higher and 200 ° C. or lower and heat-treated at a temperature of 40 ° C. or higher and a glass transition point or lower before applying the undercoat layer or after applying the undercoat layer and before applying the silver halide photosensitive layer. The silver color photographic light-sensitive material is easy to pull out from the tongue end, is hard to curl up, and has little curl after development processing. Further, there is little development unevenness, scratches, and trailing edge breakage during color development processing. Furthermore, the use of a polyester support improves the storage stability of the light-sensitive material and the storage stability of color images.

[Brief description of drawings]

FIG. 1 is a top view showing the internal structure of one type of film-integrated camera of the present invention.

FIG. 2 shows a partial cross-sectional top view of the unit of another type of film-integrated camera of the present invention.

[Explanation of symbols]

 1-Camera with integrated film 2-Camera box 3,13 ... Unit 4,14 ... Supply room 5,15 ... Hoisting room 6,16 ... Patrone 7 ...・ ・ Shooting lens 8 ・ ・ ・ Film 9 ・ ・ ・ Film support surface 17 ・ ・ ・ ・ Lens unit 18 ・ ・ ・ ・ Film (36 frames taken) 20 ・ ・ ・ ・ ・ ・ Exposed frame 21, 22 ・ Spool

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 7/38 // B32B 27/36 7421-4F C08J 5/18 CFD 9267-4F

Claims (5)

[Claims] 1. A general formula [M] represented by the following chemical formula 1 on a support.
A silver halide color photographic light-sensitive material having a layer containing a coupler represented by the above, wherein the support is made of poly (alkylene aromatic dicarboxylate), and its glass transition temperature is 50 ° C. or higher and 200 ° C. or lower. A silver halide color photographic light-sensitive material, which is heat-treated at a temperature of 40 ° C. or more and less than the glass transition temperature before coating the undercoat layer or after coating the undercoat layer and before coating the silver halide light-sensitive layer. [Chemical 1] R ₁ in the formula represents a hydrogen atom or a substituent. Z is
It represents a group of non-metal atoms necessary to form a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. 2. The silver halide according to claim 1, wherein the poly (alkylene aromatic dicarboxylate) support is a polyester containing benzenedicarboxylic acid or naphthalenedicarboxylic acid and a diol as essential components. Color photographic light-sensitive material. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the polyester of the polyester support is poly (ethylene terephthalate) or poly (ethylene naphthalate). 4. The poly (alkylene aromatic dicarboxylate) support having a thickness of 50 μm to 100 μm.
A silver halide color photographic light-sensitive material as described in the above item. 5. The silver halide color photographic light-sensitive material according to claim 1, which is used by being wound in a roll on a spool having a core diameter of 3 mm or more and 10 mm or less. material.