JPH07209810A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To facilitate operation of drawing out the tongue tip of the film and to restrain occurrences of uneven development and scratches in development processing and to reduce lateral curling, and to enhance mechanical strength by specifying a thickness ratio of the support film to the total dried film. CONSTITUTION:The photographic sensitive material rolled on a spool has silver halide emulsion layers on a support and the thickness ratio of the support film to the dried films of the total hydrophilic colloidal layers on the side of the emulsion layers of 3 to 7 and this support is made of a polyethylene aromatic dicarboxylate having a glass transition point of 50 to 200 deg.C and heat treated at a temperature from 40 deg.C up to a point near the lowest limit of its glass transition point before and after undercoating and before application of the silver halide emulsion layers, and it is preferred to heat-treat it at a temperature a little, that is, 30 degree, lower than the glass transition point.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is, firstly, to improve the winding curl so as to facilitate the work of extracting the tongue end of a long film, and to prevent uneven development, scratches during development and film breakage. Secondly, the present invention relates to a silver halide color photographic light-sensitive material in which curl in the width direction is reduced and blurring in the peripheral portion of an image during photographing is reduced.

[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 recent years, the use of photosensitive materials has been diversified, and the downsizing of cameras and the speeding up of film transport during shooting have been promoted. In addition, the number of roll film shots is being increased. There are two problems in increasing the number of roll film shots.

The first problem is a reduction in mechanical strength associated with 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 a strong curl that occurs during storage over time in a cartridge or in a spool or the like. In the 135 system, when an attempt is made to increase the number of images to be taken, the winding diameter becomes small, so that the winding movement becomes very strong and various troubles occur. 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 processing liquid is delayed in this part, causing "processing unevenness". Cause. 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), the length of film is larger than the number of windings of 12 or 24 frames when the film is long. Closed winding (hard to loosen). 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. Due to this, the tongue end with a tight curl on the film stored in the cartridge after the end of shooting adheres tightly to the inner wall of the cartridge, making it extremely difficult to pull out the tongue with a jig during development, and processing unevenness, May cause scratches.

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. On the other hand, when the latter method is used, the mechanical strength of PET is sufficient, for example, when PET is used.
Due to its higher elastic modulus than that of the AC support, the width direction (U-shaped) curl when the support thickness is reduced is reduced to some extent. However, the shrinkage due to the gelatin coated on the support becomes more severe as the film thickness increases, and even if a PET support is used, in order to improve the curl in the width direction, the thickness of the support and the gelatin coated As a result of examination, it became clear that it is necessary to control the layer thickness to a certain ratio. Further, a polyester support typified by PET has a strong curl curl in a roll form widely used as a light-sensitive material, so that it is difficult to handle after development and its use range is limited.

[0008]

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, to prevent uneven development, scratches and folds of the film in the developing process, and to reduce the curl in the width direction. Another object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent mechanical strength by reducing the blurring of the image in the peripheral portion of the image.

[0009]

The above problems have been solved by the following silver halide color photographic light-sensitive material. In a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and being wound into a spool on a roll, a total hydrophilic colloid layer on the side having the emulsion layer. The ratio of the dry total film thickness to the support film thickness (support film thickness / dry total film thickness) is 3 or more and 7 or less, the support is made of polyalkylene aromatic dicarboxylate, and its glass transition temperature is Is 50 ° C. or more and 200 ° C. or less, and heat treatment is performed 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 emulsion layer. Silver halide color photographic light-sensitive material.

First, the polyether 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. Among them, polyethylene-terephthalate (PET) and polyethylene naphthalate-based polyester are 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, anhydrous water phthalic acid,
1,4- or 1,5- or 2,6- or 2,7-
Naphthalenedicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, tetrachlorophthalic anhydride,

[0012]

[Chemical 1]

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

[0014]

[Chemical 2]

And the like.

Next, as the diol, 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,

[0017]

[Chemical 3]

[0018]

[Chemical 4]

And the like. Further, 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.

[0020]

[Chemical 5]

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 0.5: 0.5-0.
1: 0.9 is preferable. ), Isophthalic acid, biphenyl-4,4'-dicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; biphenyl-4,4'-dicarboxylic acid in a molar ratio of 1 terephthalic acid).
0.1 to 0.5, 0.1 to 0.5, and more preferably 0.2 to 0.3 and 0.2 to 0.
3), 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 500,000. Further, in order to improve the adhesiveness with another type of polyester, these polyesters may be partially blended with another polyester, or the monomers constituting the other polyester may be copolymerized,
Alternatively, these polyesters may be copolymerized with a monomer having an unsaturated bond and radically crosslinked. Polymer blends prepared by mixing two or more kinds of the obtained polymers are disclosed in JP-A-49-5482 and JP-A-64-4.
325, JP-A-3-192718, Research Disclosure 283, 739-41, 284, 779-.
82, 294, 807-14, and can be easily molded.

The glass transition temperature (Tg) in the present invention means that when 10 mg of a sample film is heated at 20 ° C./min in a helium nitrogen stream using a differential thermal analyzer (DSC), the temperature changes from the 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 showing the maximum value of this endothermic peak is defined as Tg.

The polyester of the present invention has a Tg of 50 ° C.
As described above, the conditions of use are not generally handled with sufficient caution, and the temperature is often exposed to 40 ° C. especially in the midsummer outdoors. From this viewpoint, the Tg of the present invention is safe. The temperature is preferably 55 ° C or higher. 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 is 50 ° C or higher and 200 ° C or higher.
It must be:

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) T = 112 ° C P-7: TPA / EG / BPA (100/50/50) Tg = 105 ° C P-8: TPA / EG / BPA (100/25/75) Tg = 135 ° C 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 = 105 ° C. P-12 : TPA / EG / BP (100/20/80) Tg = 115 ° C. 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 ° C P-20: TPA / 5-sulfoi Phthalic acid (SIP) / EG (95/5/100) Tg = 65 ℃

The thickness of these polyester supports (film base) is preferably 50 μm or more and 100 μm or less. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated at the time of drying, while if it exceeds 100 μm, it contradicts the purpose of thinning the film in order to elongate it. 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 had strong bending elasticity, and using them, the film thickness required for TAC was 122 μm.
It is possible to reduce the thickness to less than 00 μm. 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 easily flow,
That is, it becomes a film that is easy to curl. Therefore, this heat treatment needs to be performed below the glass transition temperature.

Therefore, this heat treatment is preferably performed 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. Furthermore, in the method of 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 is treated at 20 ° C. or higher and 100 ° C. or lower for 5 minutes to 3 hours), and then 40 ° C. It is also possible to perform heat treatment at a temperature lower than the glass transition temperature. Further, 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 preferably one that 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, various additives are preferably coexistent. An ultraviolet absorber may be kneaded into these polyester films for the purpose of preventing fluorescence and imparting stability with time. As the UV absorber, one that does not have absorption in the visible region is desirable, and its addition amount is usually relative to the weight of the polyester film.
0.01% to 20% by weight, preferably 0.05% by weight
Or about 10% by weight. If it is less than 0.01% by weight, the effect of suppressing deterioration of ultraviolet rays cannot be expected. As the ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2 ', 4.
Benzophenone-based compounds such as 4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy 3 ', 5'-di-t-butylphenyl) benzotriazole, benzotriazole compounds such as 2 (2'-hydroxy-3'-di-t-butyl-5'-methylphenyl) benzotriazole, phenyl salicylate, methyl salicylate, etc. Salicylic acid type 2,4,6-tris [2-hydroxy-4- (2 "-ethylhexyloxy) phenyl]
Examples thereof include triazine-based UV absorbers such as triazine and 2-phenyl-4,6-di [2'-hydroxy-4 '-(2 "-ethylhexyloxy) phenyl] triazine.

Further, one of the properties which becomes a problem when the polyester film of the present invention is used as a support for photographic light-sensitive materials is a problem of fogging caused by the high refractive index of the support. The polyester of the present invention, in particular, the aromatic polyester has a high refractive index of 1.6 to 1.7, whereas the gelatin which is the main component of the photosensitive layer coated thereon has a refractive index of 1.50 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 of avoiding such a light piping phenomenon, a method of incorporating inert inorganic particles and the like into a 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 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 polyester film, and polyester Those having excellent compatibility with are preferable. From the above viewpoints, as the dye, it is possible to achieve the object by mixing commercially available dyes 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 according to the present invention can be imparted with slipperiness depending on the application, and the slipperiness imparting means is not particularly limited.
A general method is kneading an inactive inorganic compound or coating a surfactant. Such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaC.
Examples are O 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. Therefore, in the slipperiness imparting method means, a polyester film is used as an external particle system. 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 these polymer films are used for a support, since each of these polymer films has a hydrophobic surface, a photographic layer (for example, a photosensitive silver halide emulsion layer containing a protective colloid mainly containing gelatin) is provided on the support. , 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, glow discharge treatment, active plasma treatment, laser treatment , A method of surface activation such as mixed acid treatment, ozone oxidation treatment, etc., and then directly applying a photographic emulsion to obtain adhesive strength, and (2) after these surface treatments once or without surface treatment, There are two methods: a method of providing an undercoat layer and a method of coating a photographic emulsion layer on the undercoat layer. (For example, US Pat. No. 2,69
8,241, 2,764,520, 2,86
4,755, 3,462,335, 3,47
5,193, 3,143,421, 3,50
1,301, 3,460,944, 3,67
4,531, British Patents 788,365, 80
No. 4,005, No. 891,469, Japanese Patent Publication No. 48-43
122, 51-446, etc.).

All of these surface treatments are considered to be caused by the formation of polar groups on the surface of the support, which was originally hydrophobic, to some extent, and by increasing the crosslink density of the surface. As a result, 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 that adheres well to a layer (hereinafter, abbreviated as the second undercoat 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-47-28067 and JP-A-49-83.
No. 767, No. 51-41770, No. 51-13157.
This can be achieved by the method disclosed in No. 6 or the like.
Discharge 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 for improving the wettability of ordinary polyester, polyolefin and other plastic films.
m ² , preferably 0.01 KV · A · min / m ^{2 to 1} KV
・ A · min / m ² is appropriate. 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 performed 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 pressure of 0.
005-20 Torr, preferably 0.02-2 Torr
r is suitable. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow and sparks will easily occur, which is dangerous and may damage the object to be treated. The 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 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. Further, as seen in the prior art, the discharge frequency is preferably DC to several 1000 MHz, preferably 50 Hz to 20 MHz. Regarding the discharge treatment strength, 0.01KV · A · min / m ² to 5KV is obtained because the desired adhesion performance can be obtained.
・ A · min / m ² , preferably 0.15 KV · A · min / m
^{2 to 1} KV · A · min / m ² is suitable.

Next, regarding the undercoating method (2), all of these methods have been well researched. For the first undercoating layer in the multi-layer method, for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid are used. , Itaconic acid, maleic anhydride, etc., starting with copolymers selected from monomers, polyethyleneimine, 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 substrates 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
641), amidinium salt-based compounds (for example, compounds described in JP-A-60-225148),
Carbodiimide compounds (for example, JP-A-51-126)
125, 52-48311) and pyridinium salt compounds (for example, Japanese Patent Publication No. 58-50699).
JP-A-52-54427, JP-A-57-4414
0, No. 57-46538), other Belgian Patent No. 825,726, US Patent No. 3,32.
No. 1,313, JP-A Nos. 50-38540 and 52-9.
No. 3470, No. 56-43353, No. 58-1139.
Examples thereof include compounds described in No. 29.

The subbing layer of the present invention may contain inorganic or organic fine particles as a matting agent to such an extent that the transparency and graininess of an 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. As an organic fine particle matting agent,
Polymethylmethacrylate, cellulose acetate propionate, polystyrene, US Pat. No. 4,142,
The treatment solution-soluble compounds described in US Pat. No. 894, the polymers described in US Pat. No. 4,396,706, and the like can be used. The average particle size of these fine particle matting agents is preferably 1 to 10 μm.

Other than the above, the undercoating liquid may contain various additives, if necessary. 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 generally 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 3, Issue 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 for the back layer may be either a hydrophobic polymer or a hydrophilic polymer used in the subbing layer. The back layer of the light-sensitive material of the present invention may contain 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. 3,2
06, 312, JP-A-48-87826, JP-B-49
-11567, JP-B-49-11568, JP-A-5
The compound as described in 5-70837 etc. can be mentioned.

Most preferred as an antistatic agent for the back layer of the present invention
Preferred are ZnO and TiO₂, SnO₂, Al₂
O₃, In₂O₃, SiO₂, MgO, BaO, MoO
₃V ₂O_FiveAt least one crystalline gold selected from
It is a fine particle of a group oxide or a complex oxide of these.
Conductive crystalline oxide used in the present invention or composite thereof
Oxide particles have a volume resistivity of 10⁷Ωcm or less,
More preferably 10^FiveΩcm or less. Also its particles
The size is 0.002-0.7 μm, especially 0.005-
It is desirable to set it to 0.3 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 silver halide color photographic light-sensitive material of the present invention is described on page 35, line 38 to page 40, line 13 of EP 482,552A; page 40, line 20 to 41.
Page 32, line 41; page 41, line 40 to page 45, line 25, layer composition, silver halide grains, photographic additives, couplers and the like, and their use, and color development processing and processing. Can be applied.

In the present invention, the total dry film thickness of all hydrophilic colloid layers on the side having the photosensitive silver halide emulsion layer is 30 μm.
m or less is preferable, 12 μm to 23 μm is more preferable, and 15 μm to 20 μm is particularly preferable. Also,
Since the widthwise curl occurs due to the shrinkage of the coated gelatin, the thicker the film, the more the curl, and the thinner the support, the lower the elastic modulus and the more curl. In order to improve the curl in the width direction, it is necessary to control the film thickness of both, and as a result of the investigation, the ratio of the total dry film thickness of the hydrophilic colloid layer to the support film thickness (support film thickness / dry total film thickness) Is 3 or more, preferably 3.
It has been found that the widthwise curl can be improved if it is 0 or more. On the other hand, in order to use the long film in a roll shape, the thickness of the support cannot be increased more than necessary, and the thickness of the support / total dry film thickness is 7 or less, preferably 7.0 or less. The sum of body thickness and total dry thickness is 115 μm or less 6
It is preferably 0 μm or more, more preferably 110 μm or less and 60 μm or more. Here, the dry total film thickness is a value measured by a commercially available contact-type film thickness meter (Anritsu Electric Co. Ltd. K-402B STAND) under the condition that the humidity is controlled at a temperature of 25 ° C. and a humidity of 55% for 2 days. Display with. Total dry film thickness of all hydrophilic colloid layers on the side having the emulsion layer (that is, total dry film thickness)
Is determined by the difference between the thickness of the dried sample and the thickness after removing the coating layer on the support having the emulsion layer. Further, in the present invention, the length of the silver halide color photographic light-sensitive material which is wound around a spool and used is preferably 1.9 m or more from the viewpoint of increasing the number of photographed sheets, and 2.4 m.
The above is more preferable.

The silver halide color photographic light-sensitive material of the present invention can be applied to the film unit with a lens described in JP-B-2-32615, JP-B-3-39784 and the like.

[0049]

【Example】

Example 1 (1) Material of Support, etc. Each support used in this example was manufactured by the following method. PEN: 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinuv as an ultraviolet absorber
inP. 2 parts by weight of 326 (manufactured by Geigy Co.) 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 130 times.
The film was transversely stretched 3.3 times at 0 ° C., and further heat set 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 / 8w by a normal solution casting method of triacetyl cellulose
t ratio, TAC concentration 13%, plasticizer TPP / BDP = 2 /
1 (where TPP; triphenyl phosphate, BD
P; biphenyl diphenyl phosphate) 15 wt
% Band method.・ 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.

A film of this polyester was formed under the same conditions as for 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 solution 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 wide 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 the treatment was 9.
At 6 KHz, the gap clearance between the electrode and the dielectric roll was 1.6 mm.

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 0.2g 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 of the support after the undercoating, which was opposite to the side on which the undercoating layer was provided. (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 mixture of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0 and roughly dispersed with a stirrer, and then a horizontal sand mill (trade name: Dynomill; WILLYA.BA).
CHOFENAG) and dispersed 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 coating solution (B) for coating layer described below was further applied thereon to give a dry film thickness of 1 μm, and dried at 115 ° C. 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 shown below was multilayer coated 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 Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of 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.

First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 2.30 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 2.75

Third Layer (Low-Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C 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-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 2.81

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion E 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I 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 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 2.31

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0073]

[Table 1]

In Table 1, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
was μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0077]

[Chemical 6]

[0078]

[Chemical 7]

[0079]

[Chemical 8]

[0080]

[Chemical 9]

[0081]

[Chemical 10]

[0082]

[Chemical 11]

[0083]

[Chemical 12]

[0084]

[Chemical 13]

[0085]

[Chemical 14]

[0086]

[Chemical 15]

[0087]

[Chemical 16]

[0088]

[Chemical 17]

[0089]

[Chemical 18]

[0090]

[Chemical 19]

[0091]

[Chemical 20]

[0092]

[Chemical 21]

(6) Processing of photographic film sample The photographic film sample produced in this way is 35 m long.
The film was integrated with a unit as shown in FIG. 1 by slitting and perforating the film with a width of m. These are designated as Samples 101 to 114. FIG. 1 is a top view showing the internal structure of a film-integrated camera which is one form of the present invention. In this camera 1, a unit 3 is housed inside a camera outer case 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 of the supply room 4 every time a photograph is taken, and the cartridge 6
It is designed to be rolled up inside. Reference numeral 7 is a taking lens, and 9 is a film supporting surface.

The emulsion layer thickness of the photographic film sample prepared here was 25 μm, and the thickness was 31 μm and 20 μm.
, 19 μm film samples were prepared by changing the coating amount of gelatin for the first, second, sixth, and tenth layers. (7) Core set The above-mentioned film-integrated camera was heated at 40 ° C. for 24 hours so as 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. went.

(Processing step) Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 300 ml 5 liters Bleach 50 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters Fixed 50 seconds 38.0 ° C 420 ml 5 liters Water wash 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 560ml 3 liters Dry 1 minute 30 seconds 60 ° C ^* The replenishment amount was per 1 m ² of the light-sensitive material, the stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided 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. 65 ml, 50 ml, 50 ml, 5
It was 0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank 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 Water was added 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-Diaminopropaneferric acid ferric ammonium monohydrate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 40 60 Water 1.0 liter 1.0 liter pH (prepared with ammonia water) 4.4 4.4

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

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH [Prepared with ammonia water 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 sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizing Solution) Tank Solution and Replenishing Solution Common (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 Table 2. In Table 2, "ANSI curl value after treatment" means ANSI / AS
C pH 1.29 Indicates the degree of curl measured according to Test Method A of 1985, which is expressed by 1 / R (R is a curl radius [unit: m]).

[0104]

[Table 2]

From the results shown in Table 2, in the film-integrated camera using the film having the constitution of the present invention, the curl value is small, the tongue end extraction work can be easily performed, and the development unevenness and scratches on the film are Also, no blurring occurred in the peripheral area of the image.

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.

[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.

[Explanation of symbols]

 1 ・ ・ ・ ・ Film integrated camera 2 ・ ・ ・ ・ ・ ・ Camera outer box 3 ・ ・ ・ ・ Unit 4 ・ ・ ・ ・ Supply room 5 ・ ・ ・ ・ ・ ・ Winding room 6 ・ ・ ・ ・ ・ ・ Patrone 7 ・ ・ ・Lens 8 ... Film 9 ... Film support surface

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, which is wound around a spool and used.
The ratio of the total dry film thickness of the hydrophilic colloid layer on the side having the emulsion layer to the support film thickness (support film thickness / dry total film thickness) is 3 or more and 7 or less, and the support is polyalkylene. Made of aromatic dicarboxylate, its glass transition temperature is 50 ℃
40 ° C. or higher and between 200 ° C. or lower and before coating the undercoat layer or after coating the undercoat layer and before coating the silver halide emulsion layer.
A silver halide color photographic light-sensitive material, which is heat-treated at a temperature of not less than ° C and less than a glass transition temperature. 2. The sum of the dry total film thickness of the hydrophilic hydrophilic colloid layer on the side having the silver halide emulsion layer and the support film thickness is 115 μm.
The silver halide color photographic light-sensitive material according to claim 1, which is not more than m. 3. The halogen 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. Silver halide color photographic light-sensitive material. 4. The silver halide color photograph according to claim 1, wherein the polyester of the polyester support is poly (ethylene terephthalate) or poly (ethylene naphthalate). Photosensitive material. 5. The silver halide color photograph according to claim 1, wherein the poly (alkylene aromatic dicarboxylate) support has a thickness of 50 μm to 100 μm. Photosensitive material.