JPH05307230A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To improve pressure resistance by forming photosensitive layers containing at least specified silver halide grains and a nonphotosensitive layer on a transparent base made of a specified copolymerized polyester. CONSTITUTION:At least one of red-, green-, and blue-sensitive silver halide emulsion layers and the nonphotosensitive layer are formed on the transparent base of <=120mmu thickness and at least one of the photosensitive layers contains silver halide grains formed with the photosensitive nuclei at the peculiar site on the surface of each grain or near to it. The transparent support contains the copolymerized polyester comprising repeating units each derived from aromatic dicarboxilic acid and those each derived from diethylene glycol in an amount of <=5mol%, and it is preferred to from the photosensitive nuclei at the peculiar site on the surface of each grain or localized to it, and >=60% of all the crystal faces of the silver halide grains formed with the photosensitive nuclei at the peculiar sites or near to them are the faces (III).

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 particularly to a silver halide color light-sensitive material having improved stability against variations in development processing conditions and improved pressure resistance.

[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. Although these proposals show some improvements, they are not sufficient for solving the above problems.

It has also been clarified that the thinning of the support makes the silver halide color light-sensitive material susceptible to fluctuations in the developing solution.

JP-A-63-305345, 64
-77047 discloses a silver halide photographic emulsion in which development is started at the vertex and / or in the vicinity of the vertex,
Although an improvement in development progress has been reported, there has been no suggestion of an improvement effect on fluctuations during development processing and an improvement in pressure resistance due to bending of the thin support.

An object of the present invention is to provide a silver halide color light-sensitive material having a thin support, which has high pressure resistance due to bending and is less susceptible to fluctuations in a developing solution. Is to provide.

[0009]

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, and at least one of the photosensitive layers is formed by biasing the photosensitizing nuclei to a specific location on the surface of the silver halide grain and its vicinity. The transparent support contains silver halide grains, and the transparent support contains an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component and 5 mol% of diethylene glycol.
A silver halide color light-sensitive material, characterized in that it is a copolyester contained in the following proportions. The invention according to claim 2 is characterized in that the photosensitive nucleus is present in a specific portion of the surface of the silver halide grain and in the vicinity thereof. The silver halide color light-sensitive material according to claim 1, wherein 60% or more of the total crystal surface of the silver halide grains formed by being biased toward (1) are (111) planes, and the invention according to claim 3 is The silver halide emulsion containing silver halide grains formed by biasing the photosensitized nuclei to a specific portion on the surface of the silver halide grain and its vicinity is monodisperse, and the diameter / thickness ratio of the silver halide grains is The silver halide color light-sensitive material according to claim 1 or 2, which is a silver halide emulsion in which tabular silver halide grains of 2 or more and less than 8 account for 70% or more in projected area.

The present invention will be described in more detail below.

-Photosensitive 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 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 that order from the support side. can do.

Further, 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, Japanese Patent Laid-Open No. 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 normal layer, the reverse layer, and the unit structure described in RD308119, 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.

Further, 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.

In the case of comprising three layers having different sensitivities, 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.

—Silver Halide Grains— In the present invention, the photosensitive layer contains silver halide grains formed by arranging the photosensitizing nuclei at specific sites on the surface of the silver halide grains and in the vicinity thereof.

The grain size of silver halide in the present invention is
Projected area diameter of about 10μ
Large size particles up to m may be used.

The grain shape of silver halide is one having a regular crystal such as a cube, octahedron or tetradecahedron, one having an irregular crystal shape such as a sphere or a plate, a twin plane. Those with crystal defects such as. Alternatively, a composite form of them may be used.

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

Of these, silver halide having a tabular crystal form is particularly preferable, and such a silver halide has a diameter / thickness ratio of 2 to 8, and particularly a diameter / thickness ratio of 3 to.
It is preferably 7. Tabular grains are described in Gutoff, Photographic Science and Engineering.
14: 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2. , 112, 157, etc., for easy preparation.

In the present invention, when a silver halide emulsion containing tabular silver halide grains is used, the tabular silver halide grains having a diameter / thickness ratio of 2 to 8 have a projected area as a whole. 70% or more of the grains preferably exist, and tabular silver halide grains having a diameter / thickness ratio of 3 to 7 make a projected area of 70% of all grains.
It is preferably present in the above proportion.

In the present invention, the photosensitized nuclei are formed so as to be biased to a specific portion on the surface of the silver halide grain and its vicinity.

Here, the peculiar portion on the surface of the silver halide grain means an area limited in area between the crystal planes occupying a wide area on the silver halide surface. The area limited between the crystal planes occupying a wide area on the surface of the silver halide is, specifically, the apex of the crystal, the ridge of the crystal, or the (111) plane, (100). )
Planes, planes having a small area ratio between wide crystal planes when two or more planes such as (110) plane coexist, and the like.

(111) plane, (100) plane, (110) plane
As a face having a small area ratio between the wide crystal faces when two or more faces coexist, for example, in an octahedral crystal formed by the (111) face, the ridge line is the (110) face. In the case where the area ratio between the wide (111) planes is small, the area ratio between the wide (111) planes when the (110) plane formed at the ridge position or the apex thereof is the (100) plane is Formed at a few vertex positions (10
0) surface can be mentioned.

As for the position of the photosensitive nucleus formed on the silver halide grain, the silver halide emulsion layer was exposed so that all the photosensitive nucleus became a latent image, and this was further diluted with a practical developing solution. It can be examined by developing using a dilute developer and observing the developed silver formed by an electron microscope. Specifically, the exposed silver halide emulsion layer is treated with a developing solution for a general camera color negative film, for example, C
NK-4-43 (manufactured by Konica Corporation) was developed with a 10-fold diluted developer at 20 ° C. for 3 minutes, then immersed in an acetic acid solution to stop the development and washed with water to gelatinize gelatin degrading enzyme. It can be examined by decomposing with a liquid, separating and collecting silver halide grains, and observing with an electron microscope.

The photosensitive nucleus is present in an amount of 20% or more, preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more of the surface area of the silver halide grain centering on a specific portion where the photosensitive nucleus is unevenly distributed. Is preferred. Also,
It is preferable that the photosensitive nucleus is present in an area of 10% or less of the surface area of the silver halide grain centering on a specific portion where the photosensitive nucleus is unevenly distributed.

In the silver halide emulsion containing the silver halide grains formed by biasing the photosensitive nuclei to the specific portions of the surface of the silver halide grains and the vicinity thereof in the present invention, the photosensitive nuclei are the apex of the silver halide grain crystals and A silver halide emulsion containing silver halide grains which are biased in the vicinity thereof is preferable. Further, the silver halide grains in the present invention are
It is preferable that 60% or more of the total crystal surface area is the (111) plane, more preferably 80%, and particularly preferably 95.
% Or more is (111).

The silver halide grains having a (111) plane of 60% or more in the present invention are preferably octahedral crystals or tabular twin crystals.

Conventionally known methods can be used to form the photosensitized nuclei on the surface of the silver halide grains in a specific portion and in the vicinity thereof.

The position at which the photosensitive nucleus is formed can be controlled by allowing a substance having adsorptivity to exist on the surface of the silver halide grain during chemical sensitization during the emulsion preparation process.
The substance having adsorptivity on the surface of the silver halide grains is
While the silver halide grains are being formed, they may be added at any time immediately after the grain formation, before the start of the cram school, or at the time of the cram school, but the photosensitizing nucleus is a specific site on the surface of the silver halide grain. In order to form it with bias to the vicinity thereof, it is preferable to add it before the chemical sensitization (for example, gold or sulfur sensitizer) is added, or simultaneously with the chemical sensitizer. Must exist in the process of progressing. It is generally preferred that the substance having adsorptivity on the surface of the silver halide grain is present in the emulsion preparation step at a ratio of 500 mg or more per mol of silver halide.

The substance having adsorptivity on the surface of the silver halide grain can be added at an arbitrary temperature, but the amount is from 30 to
It is preferably added at 80 ° C, and for the purpose of enhancing the adsorptivity, it is preferably added within the range of 50 to 80 ° C.
The values of pH and pAg may be arbitrary, but at the time of chemical sensitization, pH 6-9 and pAg 8-9 are preferable.

Any substance can be used as the substance having adsorptivity on the surface of the silver halide grain, but it is necessary in the emulsion preparation process such as a sensitizing dye, an antifoggant and a photographic performance stabilizer. Preference is given to using substances.

When a photographic performance stabilizer is used, its addition amount is 500 to 3,000 per mol of silver halide.
mg is preferable, and 1,000 to 2,500 mg is more preferable. When a sensitizing dye is used, its addition amount is preferably 500 to 2,000 mg, and more preferably 600 to 1,000 mg, per mol of silver halide.

As the photographic performance stabilizer, Research Disclosure (RD) No. 308119, page 998 VI, ibid. 17643, pp. 24-25,
Same No. 18716, page 649 can be mentioned. Examples of sensitizing dyes for photography include Research Disclosure (RD) No. 308119, page 996, VI-A-A, B, C, D, H, I, J items, ibid. 17643, pages 23-24, ibid. 1871
6, those described on pages 648 to 649 can be mentioned.

-Silver Halide Emulsion- The silver halide emulsion in the present invention may be either a polydisperse emulsion or a monodisperse emulsion, but a monodisperse emulsion having a uniform grain size is preferred.

The monodisperse emulsion preferred in the present invention is
The weight of silver halide contained within a grain size range of ± 20% around the weight average grain size d is 70% of the total weight of silver halide.
Those which occupy the above are more preferable, those which occupy 80% or more are more preferable, and those which occupy 90% or more are particularly preferable.

[0043] Here, the weight average particle diameter d, refers to a particle size d _i of when the product n _i × d _i ³ of the frequency n _i Metropolitan d _i ³ of particles having a particle size d _i is maximum (Three significant digits and the least significant digit are rounded off.). The particle size d _i is the diameter of the projected image of the particles converted into a circular image of the same area.
The particle diameter d _i is obtained by, for example, dispersing the particles so that they do not overlap on a flat sample table, enlarging the image with an electron microscope at a magnification of 10,000 to 50,000, and measuring the particle diameter or area on the print. Can be obtained (the number of measured particles is indiscriminately selected from 1,000 or more). When the grain size distribution of the silver halide emulsion has a single peak, the degree of monodispersion can also be represented by the breadth of the distribution calculated by the following formula.

{(Standard deviation of particle size) / (average particle size)} × 1
00 = breadth of distribution (%) Here, the particle size measuring method shall be in accordance with the above-mentioned measuring method,
The average particle size is an arithmetic average value calculated by the following formula.

Average particle size = (Σd ₁ n ₁ ) / (Σn ₁ ) The smaller the distribution size calculated by this equation, the greater the monodispersity.

When the monodispersity is represented by the above distribution, the silver halide emulsion of the present invention preferably has a distribution of 20% or less, more preferably 15% or less. ..

The silver halide emulsion used in the present invention is, for example, Research Disclosure (RD) No. 17
643, pp. 22-23 (December 1978), "I,
Emulsion preparation and types ", and (RD) No. 18716, p. 648, Graphide," The Physics and Chemistry of Photography, "published by Paul Montel (P.Gl).
afkides, Chemic et Phisique Photographique, Paul
Motel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chem
istry (Focal Press 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (V, L. Zelikma)
n etal, Making and Coating Photographic Emulsion,
Focal Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
665,394 and British Patent No. 1,413,748.
The monodisperse emulsions described in JP-A No. 1994-1999 are also preferable.

Additives used in the production of the silver halide emulsion layer in the present invention are Research Disclosure (RD) No. 17643, the same No. 1871
6, and No. 6 of the same. 308119. Table 1
~ Table 3 shows the location.

In particular, the additives shown in Table 2 are those capable of physical heat resistance, chemical heat resistance and spectral sensitization.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in No. 87 and No. 4,435,503 to the light-sensitive material.

The amount of silver halide used in the silver halide color light-sensitive material of the present invention is not particularly limited, but is preferably 10 g / m ² or less and 3 g / m ² or more in terms of silver amount, and further 7 g / m ^2. m ² or less, 3 g / m ²
The above is preferable.

The amount of silver with respect to the gelatin binder is not particularly limited, but depending on the high-sensitivity emulsion layer, the low-sensitivity emulsion layer, and other purposes, the silver amount (weight) / gelatin (weight) ratio is 0.01 to. It is preferably used in the range of 5.0.

The silver halide emulsion according to the present invention preferably contains silver iodobromide having an average silver iodide content of 4 to 20 mol%, and the average silver iodide content is 5 to 15 mol%. It is particularly preferred to contain some silver iodobromide. The silver halide emulsion in the present invention may contain silver chloride within the range not impairing the object of the present invention.

In the present invention, when a silver halide emulsion containing silver halide grains formed by deviating the development starting point to a specific portion on the surface of the silver halide grain or in the vicinity thereof is used, the other silver halide emulsion is used. Those silver halide emulsions include those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal forms such as spheres and plates, and crystals such as twin planes. It may have a defect or a composite form thereof.

The grain size of silver halide in the other silver halide emulsions described above may be fine grains of about 0.2 μm or less or large grains having a projected area diameter of up to about 10 μm, and are polydisperse. Although it may be either an emulsion or a monodisperse emulsion, a monodisperse emulsion is preferred as described above.

Various color couplers can be used in the present invention. Examples of yellow couplers include US Pat. Nos. 3,933,051 and 4,022,6.
No. 20, No. 4,326,024, No. 4,401,
No. 752, No. 4,248,961, Japanese Patent Publication No. 58-1
0739, British Patents 1,425,020, 1,476,760, U.S. Patent 3,973,968.
No. 4,314,023, 4,511,649
And those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferred, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
1,432, 3,725,067, Research
Disclosure (RD) No. 24220 (1984
June 60), JP-A-60-33552, Research Disclosure (RD) No. 24230 (June 1984).
Mon), JP-A-60-43659, JP-A 61-72238.
No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Pat. No. 4,500,63.
No. 0, No. 4,540, 654, No. 4,556, 6
No. 30, those described in International Publication WO88 / 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
52,212, 4,146,396, and 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,810,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
No. 4,775,616, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199, JP-A-61-42658 and the like are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are disclosed in US Pat. No. 4,163,670,
Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,9
29, 4,138,258, British Patent 1,1.
Those described in No. 46,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat. No. 4,744,181 and a reaction with a developing agent described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

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

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910 and British Patent 2,102,173.

A coupler that releases a photographically useful residue upon coupling is also preferably used in the present invention. DIR couplers that release development inhibitors are described in JP-A-5-58200.
7-151944, 57-154234, 60
Those described in U.S. Pat. Nos. 4,184,248 and 63-37346, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,093
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,4.
Competitive couplers as described in US Pat. No. 4,283,283.
No. 472, No. 4,338,393, No. 4,31
Multiequivalent couplers described in JP-A-0,618, JP-A-60-1
85950, D described in JP-A-62-24252, etc.
IR redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound, or DIR redox-releasing redox compound, coupler releasing a complex color dye after release described in EP 173,302A, Research Disclosure (R
D) No. 11449, 24241, JP-A-61-1.
Bleach accelerator releasing couplers described in 2012247, ligand releasing couplers described in US Pat. No. 4,553,477, etc., and leuco dye releasing couplers described in JP-A-63-75747.

Further, various couplers can be used in the present invention. Specific examples thereof are RD1764 shown below.
3 and RD308119. Table 4 shows the relevant locations.

[0070]

[Table 4]

Additives that can be used in the silver halide color light-sensitive material of the present invention are RD308119 1
It can be added by the dispersion method described in Section XIV, page 007.

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

Examples of the aromatic dibasic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the glycols include propylene glycol, butanediol, neopentyl glycol, 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.

[0075]

[Chemical 1]

The copolymerized polyester 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 5 mol% or less, preferably 4
The content is not more than mol%, particularly preferably not more than 3 mol%. The content of this diethylene glycol is 5mo
If it exceeds 1%, the heat resistance of the photographic support tends to be remarkably deteriorated. 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 diethylene glycol is
It is a value detected by hydrolyzing the copolyester. By containing this ethylene glycol in a proportion of 5 mol% or less, the transparent support of the present invention has
The curl recovery is excellent, and the flatness of the transparent support can be prevented from deteriorating even when various water-based coating liquids are applied to the surface of the transparent support and heat-treated at a high temperature.

The copolymerized polyester in 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. Of these, adipic acid is preferred.

When the copolymerized polyester 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 copolymerized polyester 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 copolyester 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 transesterifying the dicarboxylic acid component and the glycol component, a high temperature is used. And polycondensation under reduced pressure.

Examples of the catalyst used for this transesterification include acetates, fatty acid salts and 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 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 and thioester antioxidants. . 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 of the present invention is a photographic support for the purpose of preventing a light piping phenomenon (flickering) which occurs when light is incident on an edge of a transparent support coated with a photographic emulsion layer. 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 copolymer polyester, or an antioxidant optionally blended with this copolymer polyester, 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 specified because it varies depending on the copolymerization composition of the copolyester, but the stretching ratio in the longitudinal direction is from the glass transition temperature (Tg) of the copolyester to Tg + 100 ° C. 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 may be a film or sheet of another material formed 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, the strength and curl characteristics of the film after coating the photographic constituent layers are not caused, and the total thickness of the film is 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.

—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 this 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.

-Silver Halide Color Light-Sensitive Material- The silver halide color light-sensitive material of the present invention is a color negative film for general use or movies, a color reversal film for slides or televisions, a color paper, a color positive film, a color reversal paper. Can be applied to various color light-sensitive materials represented by.

In the silver halide color light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 24 μm or less, more preferably 20 μm or less, still more preferably 18 μm or less. . The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A. Green
Photographic Science and Engineering (Photogr.Sci.Eng.), Vol. 19, Vol.
Serometer of the type described on pages 24 to 129 (swelling meter)
T _1/2 is 90% of the maximum swollen film thickness reached when processed at 30 ° C. for 3 minutes and 15 seconds with a color developer, and the saturated film thickness is defined as 1/2 of the saturated film thickness. It is the time to reach the film thickness.

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

The silver halide color light-sensitive material of the present invention is described in RD17643, pp. 2829, and RD.
18716 Development processing can be carried out by a usual method described on page 615, left column to right column.

When the silver halide color light-sensitive material of the present invention is used in the form of a roll, it is preferable that it is housed in a cartridge. The most popular cartridge is the current 135 format cartridge. Other cartridges proposed in the following patents can also be used.

No. 58-67329, JP-A-58-67
181035, JP-A-58-182634, JP-A-58-195236, and U.S. Pat. No. 4,221,479.
Japanese Patent Application No. Sho 63-57785, Japanese Patent Application No. Sho 63-1833
No. 44, Japanese Patent Application No. 63-325638, Japanese Patent Application No. 1-25
362, Japanese Patent Application No. 1-21862, Japanese Patent Application No. 1-302
No. 46, Japanese Patent Application No. 1-20222, Japanese Patent Application No. 1-2186
No. 3, Japanese Patent Application No. 1-38171, Japanese Patent Application No. 1-33108
Japanese Patent Application No. 1-85198, Japanese Patent Application No. 1-172595
Japanese Patent Application No. 1-172594, Japanese Patent Application No. 1-172559
3, U.S. Pat. No. 4,846,418, U.S. Pat. No. 4,848,693, U.S. Pat. No. 4,832,275.
issue.

Also applied on January 31, 1992 (Yagi
The present invention can be applied to “Small-sized photographic roll film cartridge and film camera” by Toshihiko et al.

In order to obtain a dye image using the silver halide color light-sensitive material of the present invention, a commonly known color development process can be carried out after exposure. The silver halide color light-sensitive material of the present invention has the above-mentioned RD17643 28-29.
Pages, RD18716 647 pages and RD308119XI
The development process can be carried out by the usual method described in X.

[0108]

EXAMPLES Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

(Example 1) 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 mainly having a (111) plane 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 particles having a diameter / thickness ratio of 2.0 or more was 96%, and the distribution width was 14%. 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. Also a similar shape and core /
Em-20 having a shell structure and different average particle sizes
2 (0.86 μm) and Em-203 (0.51 μm) were prepared. Em-202 and Em-203 were prepared by changing the amounts of silver nitrate aqueous solution and halide aqueous solution added to the seed crystal.

(Control of development starting 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 starting 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 while continuing stirring, and 2
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 halogenated emulsion having a development start point mainly in the vicinity of the apexes of silver halide crystals, and the length 1 of the side connecting the adjacent apexes is 1 with the apex at the center. The distribution of the development start points contained in the circle having the length of / 3 was 82%.

SD-A, SD-B, SD-C and S
The chemical structures of T-1 and AF-1 are shown in (Chemical Formula 2).

[0121]

[Chemical 2]

(Transparent Support 1 in the Present 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,
The transesterification reaction was carried out by a conventional method. 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) 8 parts by weight, and Antimony oxide 0.05
Parts by weight, 0.13 parts by weight of phosphoric acid trimethyl ester and 0.02 parts by weight of sodium hydroxide 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.

The 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 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 sides of this transparent support 1 as follows.

That is, 100 parts by weight of a resin liquid for 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. 3 parts by weight of water and 900 parts by weight of water were applied to the undercoat layer coating solution so that the wet film thickness was 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>

[0127]

[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 in place 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%.

On both sides of this transparent support 2, an undercoat layer formed in the same manner as in the transparent support 1 is provided.

(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%.

On both sides of this transparent support 3, an undercoat layer formed in the same manner as in the transparent support 1 is provided.

(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.

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 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%.

On both surfaces of this transparent support 4, an undercoat layer formed in the same manner as in the transparent support 1 is provided.

(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%.

On both sides of this comparative support 1, an undercoat layer formed in the same manner as in the transparent support 1 is provided.

(Comparative support 2 outside the scope of the present invention) To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate was added, and a transesterification reaction was carried out by a conventional method. I went. The obtained product was added to an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35
% By weight) 28 parts by weight, polyethylene glycol (number average molecular weight 3000) 8 parts by weight, antimony trioxide 0.05
Parts by weight and 0.13 parts by weight of phosphoric acid trimethyl ester were added. Then, the temperature was gradually raised and the pressure was reduced to 280 ° C.
Polymerization was performed at 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 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 surfaces of the comparative support 2.

(Comparative support 3 outside the scope of the present invention) 100 parts of cellulose acetate (bound acetic acid amount: 61.4%) was dissolved in a mixed organic solvent of 550 parts of methylene chloride, 33 parts of methanol and 65 parts of cyclohexane, Further, 15 parts of triphenyl phosphate and a small amount of dye were added to and dissolved in this solution, followed by filtration and defoaming to prepare a cellulose acetate solution.

The cellulose acetate solution was cast from each of two casting ports located on an endless strip of 6 m stretched between two drums, and the casting layer was separated 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 prepare Comparative Support 3 Got

(Preparation of Silver Halide Color Light-Sensitive Material) Sample 101, which is a multi-layer color light-sensitive material, is prepared by providing each layer having the following composition on the transparent support 1 in the present invention.
It was created.

(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 units of ² is shown in moles per mole of silver halide in the same layer for sensitizing dyes.

<Sample 101> 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 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: Highly Sensitive 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 (Em-103) 0.80 Magenta coupler (M-1) 0.41 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 (Em-102) 0.87 Magenta Coupler (MA) 0.12 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.

Layer 9: Medium-Sensitivity Green Sensitive Layer Silver iodobromide emulsion (Em-101) 1.27 Magenta coupler (MA) 0.10 Colored magenta coupler (CM-1) 0.012 High boiling point solvent ( Oil-2) 0.10 gelatin 1.00.

Layer 10: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-1) 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 8.0 mol%) Silver iodobromide emulsion (average grain size 0 .27 μm) 0.03 (silver iodide content 2.0 mol%) Sensitizing dye (SD-4) 4.2 × 10 ⁻⁴ Sensitizing dye (SD-5) 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-4) 1. 6 × 10 ⁻⁴ Sensitizing dye (SD-6) 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-4) 7. 3 × 10 ^-5 sensitizing dye (SD-6) 2.8 × 10 ^-5 yellow coupler (Y-1) 0.11 high boiling 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 Absorber (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 11 below.

[0165]

[Chemical 4]

[0166]

[Chemical 5]

[0167]

[Chemical 6]

[0168]

[Chemical 7]

[0169]

[Chemical 8]

[0170]

[Chemical 9]

[0171]

[Chemical 10]

[0172]

[Chemical 11]

(Coating of Each Light-Sensitive Layer) The silver halide emulsions used in the seventh, eighth and ninth layers in the silver halide color light-sensitive material are represented by Group A and B as shown in Table 5 below.
There were groups, groups C and D.

[0174]

[Table 5]

Samples 101 to 115 as shown in Table 6 were prepared by combining the transparent support and the emulsion groups shown in Table 5.

[0176]

[Table 6]

(Development of silver halide color light-sensitive material) Samples 101 to 115 which are silver halide color light-sensitive materials
After being subjected to wedge exposure using white light, a pressure resistance test described below was performed using the bending tester shown in FIG. 1, and the treatment was performed according to the treatment steps shown in Table 7 below. In addition, p for investigating the stability of the developer against pH fluctuation
Processing was performed with color developing solutions having different H.

[0178]

[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 -Hydroxylethyl) 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 using 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.

(Bending Test) A bending test was performed as follows using the bending tester shown in FIG.
That is, the sample is placed on the sample setting part 23 of the bending tester so that the emulsion surface of the sample faces upward, and the plates 21 and 22 are folded in two with the hinge 24 so that the emulsion surface of the sample faces inside, and the width of 4
for 5 seconds pressure treatment in mm, bending remove the sample from the test machine, followed by the green transparent portion of the portion not bent by performing a development process, the pressure density differences [Delta] D _G of green transparent portion in the bent portion The resistance is shown in Table 8. The higher the value of the density difference [Delta] D _G is small is evaluated to be excellent in pressure resistance.

(Evaluation of Treatment Stability) The stability of magenta color development with respect to pH change was measured by the change width of the sensitometry curve, and the treatment 1 (pH 1) against γ _A in treatment 2 (pH 9.9).
The change width of γ _B at 0.1) was represented by Δγ (see the following equation).

Δγ = {(γ _B −γ _A ) / γ _A } × 100 (%) The results are shown in Table 8. It can be said that the smaller the value of Δγ, the better the stability.

[0191]

[Table 8]

[0192]

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 front view showing a bending tester.

[Explanation of symbols]

 21, 22 plate 23 sample setting part 24 hinge

Claims (3)

[Claims] 1. A transparent support having a thickness of 120 μm or less,
Each has at least one red-sensitive layer, a green-sensitive layer, a photographic constituent layer having a blue-sensitive layer and a non-photosensitive layer, at least one of the photosensitive layer, the photosensitive nucleus is a specific portion of the surface of the silver halide grains and A copolymerization containing silver halide grains formed biased in the vicinity thereof, and the transparent support containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component and diethylene glycol in an amount of 5 mol% or less. A silver halide color photosensitive material characterized by being polyester. 2. The method according to claim 1, wherein 60% or more of the total crystal surface of the silver halide grains formed by arranging the photosensitized nuclei on a specific portion of the surface of the silver halide grain and in the vicinity thereof are (111) planes. The described silver halide color light-sensitive material. 3. A silver halide emulsion containing silver halide grains formed by arranging the photosensitizing nuclei at specific sites on the surface of the silver halide grains and in the vicinity thereof is monodisperse, and The silver halide color light-sensitive material according to claim 1 or 2, which is a silver halide emulsion in which tabular silver halide grains having a diameter / thickness ratio of 2 or more and less than 8 occupy 70% or more in projected area.