JPH05307231A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material improved in both a preservation of freshness and a coating film adhesion at a high temp. and a high humidity. CONSTITUTION:A photographic constituting layer having at least one red sensitive layer, one green sensitive layer, one blue sensitive layer and one insensitive layer are provided respectively on a transparent base having <=120mum thickness, the transparent base consists of a copolymeric polyester contg. <=5mol% diethylene glycol in a ratio together with providing an arom. dicarboxylic acid as a copolymeric component having a metal sulfonate group, and a content of a polyvalent metal ions of >=2 valents in the photographic constituting layer is to be <=500ppm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color light-sensitive material, and more specifically to a silver halide color light-sensitive material having improved raw storage stability under high temperature and high humidity and improved coating adhesion. ..

[0002]

2. Description of the Related Art In recent years, downsizing and simplification of cameras have been advanced, portability has been improved, and opportunities for taking photographs have been greatly increased. However, further miniaturization is desired by users, and miniaturization while maintaining high image quality has been widely studied. The so-called 135 size roll film for general use is currently loaded in a standard format patrone, which is an obstacle to making the camera thinner. In order to reduce the size of the cartridge, it is most effective and convenient to thin the film, that is, the light-sensitive material, and this can be achieved by making the thickness of the support of the light-sensitive material thinner than before.

On the other hand, the standard size Patrone of 135 size is currently limited to 36 pictures. There is a desire to put more image information in one Patrone,
This can also be achieved by making the support of the photosensitive material thinner than before.

However, there is a drawback that the silver halide color light-sensitive material is easily bent by making the support thin, and the image density of the bent portion is changed. This is a peculiar problem that occurs when a pressure is locally applied to the photographic constituent layers, and the occurrence frequency is low in the conventional thick support.

On the other hand, Japanese Patent Laid-Open No. 1-244446.
Nos. 3-54551 and 3-84542 disclose a thin support useful for a silver halide color light-sensitive material. According to the supports described in these publications, the occurrence of wrinkles can be reduced. However, when a photographic constituent layer containing a silver halide emulsion is coated and stored under high temperature and high humidity, the photographic sensitivity decreases. It has been clarified that a new problem is caused such that the occurrence of defects occurs and the coating film adhesion between the photographic constituent layer and the support is deteriorated.

Since characteristics such as photographic sensitivity and coating film adhesiveness are extremely important as a photographic light-sensitive material, it is desired to overcome such new problems.

An object of the present invention is to provide a silver halide color light-sensitive material having a thin support which can contribute to miniaturization of a camera, and further, even if it has a thin support. It is an object of the present invention to provide a silver halide color light-sensitive material having a small deterioration in raw storability and a decrease in coating film adhesion.

[0008]

The invention according to claim 1 for solving the above-mentioned problems comprises a transparent support having a thickness of 120 μm or less, and at least one red-sensitive layer,
It has a photographic constituent layer having a green-sensitive layer, a blue-sensitive layer and a non-photosensitive layer, wherein the transparent support contains an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component and a diethylene glycol content of 5 mol. %, And the content of polyvalent metal ions having two or more values in the photographic constituent layer is 500 ppm or less.

The present invention will be described in more detail below.

-Transparent Support- The transparent support in the silver halide color light-sensitive material of the present invention comprises an aromatic dicarboxylic acid having a metal sulfonate group and a small amount of diethylene glycol as a copolymerization component,
A preferred example is a copolyester having an aromatic dibasic acid and a glycol as main constituents.

Examples of the aromatic dibasic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the glycols include propylene glycol, butanediol, neopentyl glycol and 1,4-. Cyclohexane dimethanol, p-xylylene fricol etc. can be mentioned. Among these, terephthalic acid is preferable as the aromatic dibasic acid.

Examples of the aromatic dicarboxylic acid having a metal sulfonate group include 5-sodium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-sodium sulfo-2,6.
-Naphthalenedicarboxylic acid, or an ester-forming derivative represented by the following (Chemical formula 1), and compounds obtained by substituting these sodiums with other metals such as potassium and lithium can be given.

[0013]

[Chemical 1]

The copolyester having an aromatic dicarboxylic acid having a metal sulfonate group can be detected by hydrolyzing the aromatic polyester, and the amount of the aromatic dicarboxylic acid having a metal sulfonate group can be determined based on the total acid component. It is preferably 2 to 7 mol%. If the amount of the aromatic dicarboxylic acid having a metal sulfonate group is less than 2 mol%, the curl of the photographic film may not be sufficiently recovered, and if it exceeds 7 mol%, a transparent support having poor heat resistance is obtained. May be.

The copolymerized polyester in the present invention is
Diethylene glycol is contained in an amount of 5 mol% or less, preferably 4 mol% or less, and particularly preferably 3 mol% or less. When the content of this diethylene glycol exceeds 5 mol%, the heat resistance of the photographic support tends to remarkably deteriorate. In this case, the reason why it deteriorates is not clear, but it is presumed that the reason is that the copolyester cannot be sufficiently crystallized in the step of heat fixing the film of the copolyester as the transparent support. ..

The amount of this diethylene glycol is
It is a value detected by hydrolyzing a co-weight polyester. By containing this ethylene glycol in a proportion of 5 mol% or less, the transparent support in the present invention is excellent in curl recovery, and moreover, various water-based coating liquids are applied to the surface of this transparent support. Even if heat-treated at a high temperature, the reduction of the flatness of the transparent support can be prevented.

The copolyester of the present invention is
As long as it has an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit and diethylene glycol, and does not impair the object of the present invention, polyalkylene glycol and / or C 4-20
The above aliphatic dicarboxylic acid may be contained as a copolymerization component.

As the polyalkylene glycol,
Examples thereof include polyethylene glycol and polytetramethylene glycol. What is important in the present invention is that polyethylene glycol is preferred among the polyalkylene glycols. Further, the molecular weight thereof is usually 600 to 20,000, and 1,000 to
It is preferably 5,000.

Examples of the aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, adipic acid and sebacic acid, among which adipic acid is preferred.

When the copolyester having an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit and diethylene glycol in the present invention contains an aliphatic dicarboxylic acid as a monomer unit, the copolyester is hydrolyzed. The amount of aliphatic dicarboxylic acid thus detected is usually 3 to 25 mol% based on all ester bonds. When the aliphatic dicarboxylic acid as a monomer unit is contained in the copolyester so that the amount of the aliphatic dicarboxylic acid is within the above range, the curl of the photographic film can be easily eliminated, and the transparent The support can have heat resistance in practical use.

The copolyester used in the present invention may have other types of monomer units as long as the object of the present invention is not impaired.

The copolymerized polyester having an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit is not particularly limited in its production method. For example, after the dicarboxylic acid component and the glycol component are transesterified, a high temperature is used. And polycondensation under reduced pressure.

Examples of the catalyst used for the transesterification include acetates, fatty acid salts, carbonates of metals such as manganese, calcium, zinc and cobalt. Among these, hydrates of manganese acetate and calcium acetate are preferable, and a mixture of these is preferable.

It is also effective to add a hydroxide, a metal salt of an aliphatic carboxylic acid, a quaternary ammonium or the like to the extent that the reaction is not inhibited or the polymer is colored during the transesterification and / or polycondensation. Among them, sodium hydroxide, sodium acetate and tetraethylhydroxyammonium are preferable, and sodium acetate is particularly preferable. The addition amount of these is 1 × 10 ^-2 to 2 with respect to all acid components.
0 × 10 ^-2 mol% is preferable.

The copolyester used in the present invention includes phosphoric acid, phosphorous acid,
And their esters and inorganic particles (for example, silica, kaolin, calcium carbonate, calcium phosphate, titanium dioxide, etc.), or the inorganic particles appropriately added after the polymerization.

Further, the copolyester may contain a dye, an ultraviolet absorber, an antioxidant, etc., which are appropriately added at any of the polymerization stage and the post-polymerization stage.

The transparent support in the present invention preferably contains a specific copolymerized polyester and an antioxidant.

The type of the antioxidant is not particularly limited, and specific examples thereof include hindered phenol compounds, allylamine compounds, phosphite compounds, thioester antioxidants and the like. .. Among these, hindered phenol compounds are preferable.

The content of the antioxidant in the transparent support is usually 0.01 to 2% by weight, preferably 0.1 to 0.5% by weight, based on the copolyester. If the content of the antioxidant is less than 0.01% by weight, the effect of photographic performance is inferior, and if it exceeds 2% by weight, the turbidity of the copolyester increases and it may not be preferable as a transparent support. The antioxidants may be used alone or in combination of two or more.

The transparent support according to the present invention is used for the purpose of preventing a light piping phenomenon (flickering) which occurs when light is incident on the transparent support provided with a photographic emulsion layer from an edge thereof. It is preferable to include a dye therein. The dye to be blended for such a purpose is not particularly limited in its type, but a dye having excellent heat resistance is preferable in the film forming process of the film, and examples thereof include anthraquinone chemical dyes. You can Further, as the color tone of the transparent support, gray dyeing is preferable as seen in general light-sensitive materials, and one kind or two or more kinds of dyes can be mixed and used. SUMIPL manufactured by Sumitomo Chemical Co., Ltd.
AST, Diaresin, Ba manufactured by Mitsubishi Kasei Co., Ltd.
A dye such as MACROLEX manufactured by yer can be used alone or in an appropriate mixture.

The transparent support in the present invention is selected from the group consisting of, for example, the above-mentioned copolyester, or an antioxidant optionally blended with this copolyester, or sodium acetate, sodium hydroxide and tetraethylhydroxyammonium. The copolyester composition containing at least one of the following is sufficiently dried, and then melt-extruded into a sheet form through an extruder, a filter and a die controlled at a temperature range of 260 to 320 ° C., and the molten polymer is rotated. It is cooled and solidified on a cooling drum to obtain an unstretched film. After that, the unstretched film is biaxially stretched in the machine direction and the transverse direction, and heat-fixed to produce the film.

The stretching conditions of the film cannot be uniformly defined because it varies depending on the copolymerization composition of the copolyester, but the stretching ratio in the temperature range from the glass transition temperature (Tg) of the copolyester to Tg + 100 ° C. in the machine direction. 2.5-6.0 times, Tg + 5 ° C to Tg + 50 in the lateral direction
The draw ratio is in the range of 2.5 to 4.0 times in the temperature range of ° C. The biaxially stretched film obtained as described above is usually heat set at 150 ° C. to 240 ° C. and cooled. In this case, if necessary, it may be relaxed in the vertical direction and / or the horizontal direction.

The transparent support in the present invention may be a single-layer film or sheet formed by the above-mentioned method, or a film or sheet of another material by a coextrusion method or a laminating method. It may have a multilayer structure in which a film or sheet formed by the method is laminated.

The thickness of the transparent support thus obtained in the present invention is not particularly limited, but is usually 1
It is 20 μm or less, preferably 40 to 120 μm, and more preferably 50 to 110 μm. The local variation in the thickness of the transparent support is preferably within 5 μm, more preferably within 4 μm, and particularly preferably 3 μm.
It is below.

When the thickness of the transparent support is set within the above range, there will be no problem in the strength and curl characteristics of the film after coating the photographic constituent layers, and the total thickness of the film should be within the above range. You can Further, when the local variation in the thickness of the transparent support is within 5 μm, it is possible to prevent the occurrence of coating unevenness and drying unevenness when the photographic constituent layer is applied.

-Photographic Constituting Layer- The silver halide color photographic light-sensitive material of the present invention can be a full-color photographic light-sensitive material. A full-color photographic light-sensitive material generally has a photographic constituent layer consisting of a red-sensitive layer containing a cyan coupler, a green-sensitive layer containing a magenta coupler, and a blue-sensitive layer containing a yellow coupler. Each of these sensitive layers may be a single layer, may have a plurality of layers, or may be composed of a plurality of layers. The stacking order of the sensitive layers is not particularly limited, and various stacking orders can be taken according to the purpose. For example, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer can be laminated in this order from the support side, and conversely,
A blue-sensitive layer, a green-sensitive layer and a red-sensitive layer can be laminated in this order from the support side.

The photosensitive layers having different color sensitivities may be sandwiched between two photosensitive layers having the same color sensitivity. Further, for the purpose of improving color reproduction, in addition to the three layers of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer, a fourth or more photosensitive layer having a color sensitivity can be provided. Regarding the layer structure using a fourth or more color-sensitive photosensitive layer, JP-A-61-34541 and JP-A-61-201245 are available.
No. 61-198236 and No. 62-160448, which can be referred to. In this case, the photosensitive layers of the fourth or more color-sensitive layers may be arranged at any laminating position. Further, the fourth or more color-sensitive photosensitive layer may be composed of a single layer or a plurality of layers.

Various non-photosensitive layers may be provided between the sensitive layers and as the uppermost layer and the lowermost layer.

For these non-photosensitive layers, JP-A-61-43 is used.
748, 59-113438, 59-1134
No. 40, No. 61-20037, No. 61-20038, the coupler, the DIR compound, etc. may be contained, and the color mixture inhibitor may be contained so that it may be usually used. In addition, these non-photosensitive layers are RD3
08119, page 1002, auxiliary layers such as a filter layer and an intermediate layer described in the item VII-K may be used.

Examples of the layer structure that can be used in the light-sensitive material of the present invention include the forward layer, the reverse layer and the unit structure described in RD-308119, page 1002, item VII-K.

When there are two photosensitive layers having the same color sensitivity, these photosensitive layers may be the same, and
West German Patent No. 1,121,470 or British Patent No. 9
It may have a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer as described in No. 23,045. In this case, it is usually preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each emulsion layer. Also, JP-A-57-112751
No. 62-200350, No. 62-206541.
No. 62-206543, etc., a low-sensitivity emulsion layer may be arranged on the side farther from the support, and a high-sensitivity emulsion layer may be arranged on the side closer to the support.

As a specific example, from the side farthest from the support, a low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green sensitive layer (GH) / Low sensitivity green sensitive layer (GL) /
High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH. Installation can be mentioned.

As described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in Japanese Patent Publication No. 6, a blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

As described in JP-B-49-15495, three photosensitive layers having different sensitivities and having the same color sensitivity can be used. These three layers are arranged with a high-sensitivity silver halide emulsion layer as an upper layer, a middle-sensitivity silver halide emulsion layer as an intermediate layer, and a low-sensitivity silver halide emulsion layer as a lower layer. Further, as described in JP-A-59-202464, a medium-sensitivity silver halide emulsion layer, a high-sensitivity silver halide emulsion layer, and a low-sensitivity silver halide emulsion from the side distant from the support. You may arrange | position in order of a layer.

When three layers having different sensitivities are formed, the order of laminating these three layers is arbitrary. For example, the laminating order may be a high-sensitivity silver halide emulsion layer and a low-sensitivity silver halide. An emulsion layer and a medium-sensitivity silver halide emulsion layer are listed in this order, or a low-sensitivity silver halide emulsion layer, a medium-sensitivity silver halide emulsion layer, a high-sensitivity silver halide emulsion layer and the like. Further, the number of photosensitive layers having the same color sensitivity can be four or more. Also in this case, the arrangement is arbitrary as described above.

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

In the present invention, it is important that the content of divalent or higher polyvalent metal ions present in the photographic constituent layer is 500 ppm or less, preferably 400 ppm or less, and particularly preferably 200 ppm or less.

Usually, a silver halide emulsion contains polyvalent metal ions. The polyvalent metal ion contained is iron, manganese, zinc, copper, magnesium, calcium, etc., and these are 500 ppm in the photographic constituent layer.
To do the following, use gelatin from which polyvalent metal ions have been removed in the preparation of silver halide emulsions, prevent contamination during the preparation process of silver halide emulsions, and use polyvalent metal as impurities in various additives. It is carried out by removing metal ions, using ion-exchanged water for preparation, and preventing diffusion and penetration from other layers.

Particularly, it is most effective to reduce polyvalent metal ions in gelatin used by processing natural products.

Gelatin is generally Fe, Mn, Cu, Z.
500 as metal impurities such as n, Mg and Ca
It contains much more than ppm. The gelatin used for preparing the silver halide emulsion layer and the non-photosensitive layer in the present invention is preferably purified so that the content of these metal ions is 500 ppm or less.

Such gelatin can be obtained by deionization by ion exchange or the like. For example, the content of the metal ions can be reduced by heating an aqueous gelatin solution and contacting it with an ion exchange resin while stirring.

Since the metal elements in gelatin are usually cations in many cases, they can be removed by using an H ⁺ type cation exchange resin. However, among the metal elements, negative complex salts are included. Since it may be formed in some cases, in such a case, it can be removed using an OH ⁻ type anion exchange resin. These methods are described in "Chemical Chemistry Lecture 2, Basic Technology II" edited by The Chemical Society of Japan, Maruzen (195).
6), pp. 151-202, edited by The Chemical Society of Japan, "New Experimental Chemistry Lecture 1, Basic Operation 1," Maruzen (1975), 463-497.
It is described in detail on pages and the like. Further, when this alone is not sufficient, the content of metal impurities can be further reduced by utilizing a chelate resin and by means such as solvent extraction and foaming separation. Regarding these methods, for example, “Chemical Chemistry Lecture (continued) Separation and Purification” edited by The Chemical Society of Japan (1967)
Etc.

On the other hand, various silver halide emulsions can be used in the photographic constituent layers of the present invention. A method for producing a silver halide emulsion and additives used in the production are described in Research Disclosure No. 17643,
Same No. 18716 and the same No. 308119 (hereinafter referred to as RD17643, RD18716 and RD30, respectively)
(Abbreviated as 8119)). Table 1 shows RDN
o. The following describes the description content and description location of 308119.

[0054]

[Table 1]

The silver halide emulsion used in the present invention can be subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RD176.
43, RD18716 and RD308119. Table 2 shows the location of the description.

[0056]

[Table 2]

Known photographic additives which can be used in the present invention are also RD17643, RD18716 and RD308119.
It is described in. Table 3 shows the relevant description locations.

[0058]

[Table 3]

Various couplers may be used in combination in the present invention, specific examples of which are given below in RD17643 and RD.
308119. Table 4 shows the relevant locations.

[0060]

[Table 4]

The additive used in the present invention is RD3081.
19 1007 page XIV can be added by the dispersion method or the like.

In the present invention, the above-mentioned RD17643 is used.
28, RD18716, pages 647-8 and RD30.
8119 The support described in page 1009, section XIX can be used.

The silver halide color light-sensitive material of the present invention may be provided with auxiliary layers such as the filter layer and the intermediate layer described in the above-mentioned RD308119 VII-K.

The silver halide color light-sensitive material of the present invention comprises
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in RD308119 VII-K can be adopted.

The silver halide color light-sensitive material of the present invention comprises
It can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.

To obtain a dye image using the light-sensitive material of the present invention, a commonly known color development process can be carried out after exposure.

The light-sensitive material of the present invention is the above-mentioned RD17643.
28-29, RD18716647 and RD30
Development can be carried out by a usual method described in 8119 XIX.

—Undercoat Layer— The surface of the transparent support of the invention on which the photographic constituent layers are formed is
If necessary, a surface activation treatment such as corona discharge and / or an undercoat layer can be applied prior to the formation of the photographic constituent layer.

As the undercoat layer, for example, JP-A-59 is used.
-19941, 59-77439, 59-22
Preferred examples are the undercoat layers described in JP-A-4841 and JP-B-58-53029. The undercoat layer provided on the surface of the transparent support opposite to the photographic constituent layer is also referred to as a back layer.

[0070]

EXAMPLES Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. (Examples and Comparative Examples) A. Preparation of Silver Halide Emulsion An octahedral silver iodobromide emulsion mainly having a (111) plane was prepared by the double jet method according to the method described in JP-A-60-138538.

The average grain size of the obtained emulsion was 1.05 μm,
The breadth of the distribution is 9%, the silver iodide content of the core is 30%, the silver iodide content of the shell is 0.1 mol%, the average silver iodide content is 9 mol%, and the ratio of (111) faces is Was 98%. This emulsion is called Em-101. In addition, Em having a similar shape and core / shell structure but different average particle size
-102 (0.71 μm), Em-103 (0.40 μm
m) was prepared. Em-102 and Em-103 were prepared by changing the amounts of the silver nitrate aqueous solution and the halide aqueous solution added to the seed crystal.

A tabular silver iodobromide emulsion having mainly (111) faces was prepared by the double jet method according to the method described in JP-A-3-94248. The average grain size of the obtained emulsion was 1.32 μm, the average diameter / thickness ratio was 3.3, the projected area of grains having a diameter / thickness ratio of 2.0 or more was 96%, and the distribution was 14%. there were. The silver iodide content of the core was 30%, the silver iodide content of the shell was 0.1 mol%, the average silver iodide content was 9.0 mol%, and the ratio of (111) faces was 94%. . This emulsion is called Em-201. It also has a similar shape and core / shell structure,
Em-202 (0.86μ with different average particle size)
m) and Em-203 (0.51 μm) were prepared. Em
-202 and Em-203 were prepared by changing the amounts of the aqueous silver nitrate solution and the aqueous halide solution added to the seed crystal.

(Control of development start point) In the process of chemical sensitization and color sensitization of the obtained emulsion, the sensitizing dye is added at the time of addition, that is, prior to the addition of the chemical sensitizer or the chemical sensitization is performed. The position of the development start point was controlled depending on whether to add after completion.

<Sensitizer 1> Sodium thiosulfate <Sensitizer 2> Chloroauric acid (0.3 mg) and ammonium thiocyanate (N15 mg) <Methanol solution of sensitizing dye> SD-A (70 mg),
Methanol solution containing SD-B (70Mg) and SD-C (70Mg) <Stabilizer> ST-1 (1.0 g) Silver halide emulsion Em-101 (containing 1 mol of silver halide) at 55 ° C. and pAg of 8. After adjusting to 0, an aqueous solution of sensitizer 1 and an aqueous solution of sensitizer 2 were sequentially added while stirring, and aging was performed for 120 minutes. After aging, set the temperature to 4
The temperature was lowered to 0 ° C., a methanol solution of a sensitizing dye was added, stirring was further performed for 20 minutes, and finally, an antifoggant AF-1 and a stabilizer ST-1 were added.

Similar silver halide emulsion Em-10
2, Em-103, Em-201, Em-202, Em
-203 was also sensitized. The amounts of the sensitizer 1 and the sensitizer 2 are adjusted according to the change in the crystal size of the silver halide so that the highest photographic sensitivity can be obtained, and the amount of the sensitizing dye is also used. Was prepared according to the change in crystal size of.

The emulsion obtained by this method was a halogenated emulsion having a development starting point mainly on the (111) plane of silver halide crystals.

The silver halide emulsion Em-101 (containing 1 mol of silver halide) was adjusted to 55 ° C. and pAg of 8.0, and a methanol solution of a sensitizing dye was added to the mixture while stirring.
It was aged for 0 minutes, and then an aqueous solution of sensitizer 1 and an aqueous solution of sensitizer 2 were sequentially added to perform aging for 90 minutes. Next, the antifoggant AF-1 was added to lower the temperature to 40 ° C., and finally the stabilizer ST-1 was added. The amounts of the sensitizer 1 and the sensitizer 2 were adjusted so that the highest photographic sensitivity was obtained.

Similar silver halide emulsion Em-10
2, Em-103, Em-201, Em-202, Em
-203 was also sensitized. The amounts of the sensitizer 1 and the sensitizer 2 are adjusted according to the change in the crystal size of the silver halide so that the highest photographic sensitivity can be obtained, and the amount of the sensitizing dye is also used. Was prepared according to the change in crystal size of.

The emulsion obtained by this method is a halide emulsion having a development start point mainly in the vicinity of the vertices of silver halide crystals, and the length 1 of the side connecting adjacent vertices is 1 with the vertices as the center. The distribution of the development start points contained in the circle having the length of / 3 was 82%. SD-
The chemical structures of A, SD-B, SD-C, ST-1 and AF-1 are shown in (Chemical Formula 2).

[0080]

[Chemical 2]

B. Preparation of transparent support (Transparent support 1 in the invention) 0.1 part by weight of calcium acetate hydrate was added to 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, and transesterification reaction was carried out by a conventional method. It was 28 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight), polyethylene glycol (number average molecular weight: 3,000) were added to the obtained product.
0) 8 parts by weight, antimony trioxide 0.05 parts by weight, phosphoric acid trimethyl ester 0.13 parts by weight and sodium hydroxide 0.02 parts by weight were added. Then gradually raise the temperature,
The pressure was reduced and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain polyester.

The polyester was vacuum dried at 150 ° C., melt-extruded at 280 ° C., and rapidly solidified on a cooling drum to prepare an unstretched film. Using this unstretched film, it was stretched 3.3 times in the machine direction at 80 ° C., then 3.3 times in the transverse direction at 90 ° C. and then at 220 ° C. for 30 times.
It was heat set for 2 seconds to obtain a biaxially stretched film having a thickness of 80 μm. The diethylene glycol content was 4 mol%.
This biaxially stretched film was used as a transparent support 1, and an undercoat layer was provided on both surfaces of this transparent support 1 as described below.

That is, 100 parts by weight of a resin liquid for an undercoat layer obtained by emulsion polymerization of the following composition, 0.2 part by weight of the following surfactant, hexamethylene-1,6-bis (ethyleneurea) 0. An undercoat layer coating solution comprising 3 parts by weight and 900 parts by weight of water was applied so as to have a wet film thickness of 20 μm,
It was then dried. In the following, the transparent support having the undercoat layer may be simply referred to as a transparent support.

<Composition> 2-hydroxyethyl methacrylate 75 parts Butyl acrylate 90 parts t-Butyl acrylate 75 parts Styrene 60 parts Sodium dodecylbenzene sulfonate 6 parts Ammonium persulfate 1 part Water 700 parts <Surfactant>

[0085]

[Chemical 3]

Next, 10 parts by weight of gelatin and 0.
An undercoating upper layer coating liquid consisting of 2 parts by weight and 1,000 parts by weight of water was applied so as to have a wet film thickness of 20 μm, and then dried.

(Transparent support 2 in the present invention) In the production examples of the transparent support described in the section of the transparent support 1 in the present invention, 0.07% by weight of tetraethylhydroxyammonium was added instead of sodium hydroxide. A biaxially stretched film having a thickness of 80 μm was obtained in the same manner as above. The diethylene glycol content was 5 mol%.
An undercoat layer formed in the same manner as in the transparent support 1 is provided on both surfaces of the transparent support 2.

(Transparent Support 3 in the Present Invention) In the production examples of the transparent support described in the section of the transparent support 1 in the present invention, 0.04% by weight of sodium acetate was used as an ester instead of sodium hydroxide. A biaxially stretched film having a thickness of 80 μm was obtained by the same method except that it was added during the exchange reaction. The diethylene glycol content was 3 mol%. An undercoat layer formed in the same manner as in the transparent support 1 is provided on both surfaces of the transparent support 3.

(Transparent support 4 in the present invention) To 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, and 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate hydrate was added, followed by a conventional method. A transesterification reaction was performed. 32 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration 35% by weight), antimony trioxide 0.05 parts by weight, phosphoric acid trimethyl ester 0.13 parts by weight were obtained. Parts and 0.04 parts by weight of sodium acetate were added. Then gradually raise the temperature and reduce the pressure to 280 ° C.,
Polymerization was performed at 0.5 mmHg to obtain polyester.

This polyester was vacuum dried at 150 ° C., melt-extruded at 280 ° C., and rapidly cooled and solidified on a cooling drum to prepare an unstretched film. Using this unstretched film, it was stretched 3.3 times in the longitudinal direction at 80 ° C., then 3.3 times in the transverse direction at 90 ° C., and then at 200 ° C. for 30 times.
It was heat set for 2 seconds to obtain a biaxially stretched film having a thickness of 80 μm.
The diethylene glycol content was 3 mol%. An undercoat layer formed in the same manner as in the transparent support 1 is provided on both surfaces of the transparent support 4.

(Comparative support 1 outside the scope of the present invention) To 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol and 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate hydrate was added. The transesterification reaction was carried out by a conventional method. 32 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight) was added to the obtained product.
0.05 parts by weight of antimony trioxide and 0.13 parts by weight of trimethyl phosphate were added. Then gradually raise the temperature,
The pressure was reduced and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain polyester.

The polyester was vacuum dried at 150 ° C., melt-extruded at 280 ° C., and rapidly solidified on a cooling drum to prepare an unstretched film. Using this unstretched film, it was stretched 3.3 times in the machine direction at 80 ° C., further stretched 3.3 times in the cross direction at 90 ° C., and then at 180 ° C. for 30 times.
It was heat set for 2 seconds to obtain a biaxially stretched film having a thickness of 80 μm.
The diethylene glycol content was 9 mol%. An undercoat layer formed in the same manner as in the transparent support 1 is provided on both surfaces of the comparative support 1.

(Comparative support 2) Dimethyl terephthalate 1
To 100 parts by weight of ethylene glycol and 64 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate was added, and transesterification reaction was carried out by a conventional method. 28 parts by weight of an ethylene glycol solution (concentration: 35% by weight) of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid was added to the obtained product.
8 parts by weight of polyethylene glycol (number average molecular weight 3000), 0.05 parts by weight of antimony trioxide, and 0.13 parts by weight of trimethyl phosphate ester were added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was performed at 280 ° C. and 0.5 mmHg to obtain a polyester.

This polyester was vacuum dried at 150 ° C., melt-extruded at 280 ° C., and rapidly cooled and solidified on a cooling drum to prepare an unstretched film. Using this unstretched film, it was stretched 3.3 times in the longitudinal direction at 80 ° C., then 3.3 times in the transverse direction at 90 ° C., and then at 200 ° C. for 30 times.
It was heat set for 2 seconds to obtain a biaxially stretched film having a thickness of 80 μm.
The diethylene glycol content was 8 mol%. An undercoat layer formed in the same manner as in the transparent support 1 is provided on both sides of the comparative support 2.

(Comparative support 3) 100 parts of cellulose acetate (bound acetic acid content: 61.4%) was dissolved in a mixed organic solvent of 550 parts of methylene chloride, 33 parts of methanol and 65 parts of cyclohexane, and triphenylphosphine was added to this solution. After 15 parts of fate and a small amount of dye were added and dissolved, the mixture was filtered and defoamed to prepare a cellulose acetate solution.

The cellulose acetate solution was cast from each of two casting ports located on a 6 m endless strip stretched between two drums, and the casting layer was peeled from the stainless strip, and then it was rolled by a number of rolls. Drying was completed while being conveyed, and a cellulose acetate film having a thickness of 127 μm was produced.

On both sides of this cellulose acetate, a coating solution for an undercoat layer consisting of 20 g of gelatin, 40 g of water, 20 g of salicylic acid, 600 g of methanol, 1,200 g of acetone and 200 g of methylene chloride was applied, and dried to obtain a comparative support 3 Got

C. Preparation of silver halide color light-sensitive material Each layer having the composition shown below is applied and formed on the transparent support 1 in the present invention by a coating method described below to prepare a silver halide color light-sensitive material which is a multilayer color light-sensitive material. did.

(Composition of photosensitive layer) The coating amount is the amount expressed in g / m ² unit in terms of metallic silver for silver halide and colloidal silver, and g / m for couplers, additives and magenta. ^The amount added in ² units is shown in mol per mol of silver halide in the same layer for the sensitizing dye.

First layer; antihalation layer Black colloidal silver 0.16 UV absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.20 Gelatin 1.23.

Second layer; intermediate layer Compound (SC-1) 0.15 High boiling point solvent (Oil-2) 0.17 Gelatin 1.27.

Third Layer: Low Sensitivity Red Sensitive Layer Silver iodobromide emulsion (average grain size 0.38 μm) (silver iodide content rate 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0 .27 μm) (silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.9 × 10 ⁻⁴ Sensitizing Dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan Coupler (CC-1) 0.021 DIR compound (D-2) 0.020 High boiling point solvent (Oil-1) 0.53 Gelatin 1.30.

Fourth Layer: Medium Sensitive Red Sensitive Layer Silver iodobromide emulsion (average grain size 0.52 μm) (silver iodide content rate: 8.0 mol%) 0.62 Silver iodobromide emulsion (average grain size 0 0.38 μm) (silver iodide content 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.2 × 10 ⁻⁴ Sensitizing Dye (SD-3) 1.6 × 10 ^-5 Sensitizing dye (SD-4) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan Coupler (CC-1) 0.030 DIR compound (D-2) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93.

Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm) (silver iodide content: 8.0 mol%) 1.27 Sensitizing dye (SD-1) 1. 3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.3 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.6 × 10 ⁻⁵ Cyan coupler (C-2) 0.12 Colored cyan coupler (CC -1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91.

Sixth layer: intermediate layer Compound (SC-1) 0.09 High boiling point solvent (Oil-2) 0.11 Gelatin 0.80.

Seventh Layer: Low Sensitivity Green Sensitive Layer Silver iodobromide emulsion (average grain size 0.38 μm) 0.61 (silver iodide content 8.0 mol%) Silver iodobromide emulsion (average grain size 0 0.27 μm) 0.20 (silver iodide content 2.0 mol%) Sensitizing dye (SD-4) 7.4 × 10 ⁻⁵ Sensitizing dye (SD-5) 6.6 × 10 ⁻⁴ Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.33 Gelatin 1.95.

Eighth Layer: Medium-Sensitivity Green Sensitive Layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.87 Sensitizing dye (S-6) 2.4 × 10 ^-4 Sensitizing dye (S-7) 2.4 × 10 ^-4 Magenta coupler (M-1) 0.12 Magenta coupler (M-2) 0.06 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00.

Ninth layer: Medium-sensitive green sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm, silver iodide content: 8.0 mol%) 1.27 Sensitizing dye (S-6) 1.4 × 10 ^-4 Sensitizing dye (S-7) 1.4 × 10 ^-4 Magenta coupler (M-1) 0.10 Magenta coupler (M-2) 0.05 Colored magenta coupler (CM-2) 0.012 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00.

10th layer: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10.

Eleventh layer; Intermediate layer Formalin Scavenger (HS-1) 0.20 Gelatin 0.60.

Twelfth layer; low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm) 0.22 (silver iodide content rate 8.0 mol%) Silver iodobromide emulsion (average grain size 0 .27 μm) 0.03 (silver iodide content 2.0 mol%) Sensitizing dye (SD-8) 4.2 × 10 ⁻⁴ Sensitizing dye (SD-9) 6.8 × 10 ⁻⁵ Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20.

Thirteenth layer; low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm) 0.30 (silver iodide content 8.0 mol%) Sensitizing dye (SD-8) 1. 6 × 10 ⁻⁴ Sensitizing dye (SD-10) 7.2 × 10 ⁻⁵ Yellow coupler (Y-1) 0.10 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 046 Gelatin 0.47.

Fourteenth layer: high-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm) 0.85 (silver iodide content rate: 8.0 mol%) Sensitizing dye (SD-8) 7. 3 × 10 ⁻⁵ Sensitizing dye (SD-10) 2.8 × 10 ⁻⁵ Yellow coupler (Y-1) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.80.

Fifteenth layer; first protective layer Silver iodobromide (average particle size: 0.08 μm) 0.40 (silver iodide content: 1.0 mol%) UV absorber (UV-1) 0.026 UV light Absorbent (UV-2) 0.013 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31.

Sixteenth Layer; Second Protective Layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 .

The above-mentioned light-sensitive material further comprises compounds SU-1, Su-2, a viscosity adjusting agent, a film hardener H-1, and H-.
2, stabilizer ST-1, antifoggant AF-1, AF-2
(With a weight average molecular weight of 10,000 and 1,100,
000), dyes AI-1, AI-2 and compound DI-1 (9.4 mg / m ² ).

The above UV-1, Oil-1, SC-1,
Oil-2, SD-1, SD-2, SD-3, SD-
4, C-1, C-2, CC-1, D-1, D-2, M-
A, CM-1, D-3, CM-2, SC-2, HS-
1, SD-5, Y-1, SD-6, UV-2, WAX-
1, SU-1, Su-2, H-1, H-2, ST-1,
The structures of AF-2, AI-1, AI-2 and compound DI-1 are shown in Chemical Formulas 4 to 12 below.

[0118]

[Chemical 4]

[0119]

[Chemical 5]

[0120]

[Chemical 6]

[0121]

[Chemical 7]

[0122]

[Chemical 8]

[0123]

[Chemical 9]

[0124]

[Chemical 10]

[0125]

[Chemical 11]

[0126]

[Chemical formula 12]

All the gelatins in the above photographic constituent layers are gelatins of any one of A, B, C and D shown in Table 5. The content of divalent or higher polyvalent metal ions in gelatin shown in Table 1 was determined by adjusting the degree of ion exchange treatment in the gelatin manufacturing process.

[0128]

[Table 5]

Further, a silver halide color light-sensitive material as a sample shown in Table 6 was obtained by providing the above-mentioned support with a photographic constituent layer containing gelatin of the group shown in Table 5.

[0130]

[Table 6]

D. Development of silver halide color light-sensitive material For each sample which is a silver halide color light-sensitive material shown in Table 6, the sample was left to stand at 40 ° C. and 70% RH atmosphere for 1 week to be subjected to forced deterioration treatment for raw preservation evaluation. The processed sample and the untreated sample were prepared, and each of the treated and untreated samples was subjected to wedge exposure using white light, and thereafter, development processing was performed by the following processing steps.

[0132]

[Table 7]

In Table 7, the replenishment amount is 1 m of the photographic light-sensitive material.
It is a value per ² . As the color developing solution, the bleaching solution, the fixing solution, the stabilizing solution and the replenishing solution thereof, those prepared as described below were used.

<Color Developer> 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water was added to make 1 liter, pH 10.1 (treatment 1) and pH 9 9 (treatment 2).

<Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150 g Glacial acetic acid 10 ml Water was added to make 1 liter, and pH was adjusted with aqueous ammonia.
It was adjusted to 6.0.

<Fixer> Ammonium thiosulfate 175 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to make 1 liter, and pH was adjusted to 6.0 with acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (Konica Corporation) 7.5 ml Water was added to make 1 liter.

<Color development replenisher> Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyl ethyl) aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water was added to make 1 liter and potassium hydroxide or 20
The pH was adjusted to 10.18 with% sulfuric acid.

<Bleach replenisher> Water 700 ml 1/3 Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g pH adjusted to 4.0 with aqueous ammonia or glacial acetic acid After that, water was added to make 1 liter.

<Fixing Replenisher> Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Ammonium water or glacial acetic acid was used to adjust the pH to 6.5 and then water was added to make 1 liter.

<Stable Replenisher> Same as the stabilizer.

E. Evaluation <Evaluation of coating film adhesiveness in a dry state> Each of the samples cut into strips with a width of 35 mm was subjected to film splicer (MS
650D, manufactured by Sanyu Co., Ltd., the photographic constituent layers were joined with a splice tape, and a load of 1 kg was applied to the joined portion in the longitudinal direction of the film under an atmosphere of 23 ° C. and 20% RH.
After being applied for a second, the state of film peeling at the joint was observed and evaluated through a loupe. The evaluation ranks are shown below. The evaluation result is shown in FIG.

A: No film peeling occurred. B: The film peeled slightly. C ... Film peeling can be clearly confirmed even with the naked eye.

<Evaluation of Adhesiveness of Coating Film in Wet State> Each sample was immersed in the color developing solution at 45 ° C. for 3 minutes and 15 seconds, and then the surface of the sample on which the photographic constituent layer was coated was coated as shown in FIG.
Make a 2 mm-wide lattice-like scratch using the stainless steel tool shown in, and immediately rub the scratched part strongly with the belly of your thumb, dry the sample as it is, and remove the remaining area of the surface of the photographic constituent layers. It was evaluated visually. Figure 2 shows a model of a scratched surface. Figure 2 shows a model of a scratched surface. The black portion in FIG. 2 is the coated portion of the photographic constituent layer of the sample, and the white portion is the scratched portion. The evaluation ranks are shown below. The evaluation result is shown in FIG.

A ... Even if it is rubbed, it remains as shown in FIG.

B ... Rubbing shows that the remaining portion is 1 /
It disappears about 4.

C: When rubbed, the remaining portion is 1 according to FIG.
/ 3 to 1/2 is lost.

<Evaluation of Raw Preservability> The relative sensitivity value of the sample subjected to the forced deterioration treatment is shown as a numerical value when the sensitivity of the unprocessed sample of the green-sensitive layer is set to 100 for each sample. It was evaluated as storability. The evaluation result is shown in FIG. In addition,
Samples 115 and 116 have a transparent support having a thickness of 127 μm.
Therefore, it is impossible to form a thin silver halide color light-sensitive material.

[0149]

[Table 8]

[0150]

According to the present invention, it is possible to provide a silver halide color light-sensitive material in which the occurrence of coating unevenness is reduced to the extent that there is no practical problem and the production efficiency is high.

[Brief description of drawings]

FIG. 1 is a perspective view showing a stainless steel tool for making lattice-shaped scratches on the surface of a photographic constituent layer.

FIG. 2 is a front view showing a model of a scratched surface in a photographic constituent layer.

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

[Procedure amendment]

[Submission date] May 7, 1992

[Procedure Amendment 1]

[Document name to be corrected] Drawing

[Correction target item name] All drawings

[Correction method] Change

[Correction content]

[Figure 1]

[Fig. 2]

Claims (1)

[Claims] 1. A transparent support having a thickness of 120 μm or less,
Each has a photographic constituent layer having at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer, and the transparent support contains an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component. And a content of diethylene glycol of 5 mol% or less, and a polyvalent metal ion content of binary or more in the photographic constituent layer of 500 ppm or less. material.