JPH0635138A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photosensitive material which hardly undergoes the lowering of the sensitivity during storage in spite of a magnetic recording layer included in the photosensitive material. CONSTITUTION:When at least one red-sensitive layer, at least one green-sensitive layer, at least one blue-sensitive layer and at least one nonphotosensitive layer are formed on a transparent base 32 as photographic constituent layers 31 and a magnetic layer 33 contg. ferromagnetic powder is further formed to obtain a color photosensitive material, the content of di- and higher valent metal ions in the photographic constituent layers 31 is regulated to <=1,000ppm.

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, improvement of raw storage stability of a silver halide color light-sensitive material having a magnetic recording layer (hereinafter also simply referred to as "light-sensitive material"). Regarding

[0002]

BACKGROUND OF THE INVENTION US Pat. No. 4,974,196 and International Patent Publication 9
No. 0/04254 discloses a photographing camera having a roll-shaped film having a magnetic layer containing magnetic particles capable of magnetic recording on the back surface of a photographic film and a magnetic head. According to this improved technology, identification information such as the type and manufacturer of the photosensitive material, information relating to the conditions at the time of shooting, information about the customer, information relating to printing conditions and print reprint conditions, etc. are magnetically recorded on the film in the magnetic layer. By inputting / outputting, it is possible to improve the print quality, improve the efficiency of printing work, and improve the efficiency of laboratory work processing.

However, a color photographic material having a magnetic recording layer has a sensitivity higher than that of a conventional photographic material having no magnetic recording layer when left under high temperature and high humidity after manufacturing, before photographing and developing. It was found to have the disadvantage of a large reduction. In particular, it has a photographic constituent layer on one side of the transparent support and a magnetic recording layer on the other side, and it has been found that it is remarkable when the photosensitive material is rolled and stored in a closed container or in a camera. It was These are problems caused by the magnetic recording layer, and improvement thereof is desired.

[0004]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide color light-sensitive material which has a magnetic recording layer and is less susceptible to sensitivity deterioration during storage.

[0005]

The above object of the present invention is to provide a transparent support,
Of the photographic constituent layers of the color photographic material, each having at least one photographic constituent layer consisting of a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-photosensitive layer, and having a magnetic layer containing a ferromagnetic powder. Content of polyvalent metal ion of divalent or more of 1000ppm
Achieved by the following silver halide color light-sensitive material.

The present invention will be described in more detail below.

In the present invention, the magnetic layer refers to JP-A-53-109.
No. 604, No. 60-45248, Japanese Patent Publication No. 57-6576, U.S. Pat.
7,196, WO90 / 04254, 91/11750, 9
1/11816, 92/08165, 92/08227, and the like, or a transparent magnetic layer as described in JP-A-4-124642 and 4-
A striped magnetic layer such as that shown in No. 124645 may be used.

When the magnetic layer of the present invention is transparent, the optical density is preferably 1.0 or less, more preferably 0.75 or less, and particularly preferably 0.02 to 0.3.

In the present invention, the magnetic layer is a layer in which ferromagnetic powder is dispersed in a binder. The coating amount of the ferromagnetic powder is 50 mg or less, preferably 20 mg or less, and particularly preferably 0.1 to 5 mg in terms of iron amount per 100 cm ² of the light-sensitive material.

Examples of the ferromagnetic powder include γ-Fe ₂ O ₃
Powder, Co deposited γ-Fe ₂ O ₃ powder, Co deposited Fe ₃ O ₄ powder, Co deposited F
eOx (4/3 <x <3/2) powder, other Co-containing iron oxides, and other ferrites such as hexagonal ferrites include, for example, M-type and W-type hexagonal Ba ferrites, Sr ferrites, Examples thereof include lead ferrite, Ca ferrite, and solid solutions or ion substitutes thereof.

In the hexagonal ferrite magnetic powder, at least some of Fe atoms, which are the constituent elements of these uniaxially anisotropic hexagonal ferrite crystals, are selected from divalent metals and Nb, Sb ₄ and Ta. One kind of pentavalent metal and 0.05 per chemical formula
Coercive force substituted with Sn atoms in the range of ~ 0.5 to 200 ~ 2,000
Oe element is used.

The divalent metal in the hexagonal ferrite is preferably an element such as Mn, Cu, or Mg which relatively well substitutes for the Fe atom in the ferrite.

In the hexagonal ferrite, divalent metal (M
The appropriate substitution amount of II) and pentavalent metal (Mv) varies depending on the combination of MII and Mv, but is preferably about 0.5 to 1.2 per chemical formula of MII.

Looking at the relationship of the substitution amount of the substitution element, for example, regarding magnetoplumbite type Ba ferrite, the chemical formula of the substitution product is represented by BaFe _{12- (x + y + z)} MII _x Mv _y Sn _z O _19. . Here, x, y and z are substitution amounts of MII, Mv and Sn elements per one chemical formula of ferrite. MII, Mv
And Sn are divalent, pentavalent, and tetravalent, respectively, and are substituted.
Since the Fe atom is trivalent, y =
The relationship of (x−z) / 2 is established. That is, the substitution amount of Mv is MI
It is uniquely determined from the substitution amount of I and the substitution amount of Sn.

The coercive force (Hc) of the ferromagnetic powder is usually 200.
It is not less than Oersted, preferably not less than 300 Oersted.

The size of the magnetic powder in the major axis direction is preferably 0.3 μm or less, more preferably 0.2 μm or less.

[0017] The specific surface area by the BET method of the ferromagnetic powder is usually 20 m ² / g or more, preferably 25~80m ² / g.

There is no particular limitation on the shape of the ferromagnetic powder, and for example, any shape such as needle-like, spherical or ellipsoidal shape can be used.

Fatty acids can be contained in the magnetic layer of the present invention.

The above-mentioned fatty acid may be monobasic or dibasic, and the preferred fatty acid in the present invention has 6 to 30, particularly 12 to 22 carbon atoms.

Preferred fatty acids include, for example, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid,
Linolenic acid, linoleic acid, oleic acid, elaidic acid,
Examples thereof include behenic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedicarboxylic acid and octanedicarboxylic acid.

Of these, myristic acid, oleic acid, and stearic acid are particularly preferable.

When a fatty acid ester is contained in the magnetic layer, the friction coefficient of the magnetic layer is lowered and the running property and durability of the magnetic recording medium of the present invention are further improved.

Examples of the fatty acid ester include oleyl oleate, oleyl stearate, isocetyl stearate, dioleyl maleate, butyl stearate, butyl palmitate, butyl myristate, octyl myristate, octyl palmitate, amyl stearate. , Amyl palmitate, stearyl stearate, lauryl oleate, octyl oleate, isobutyl oleate, ethyl oleate, isotridecyl oleate,
2-ethylhexyl stearate, 2-ethylhexyl myristate, ethyl stearate, 2-ethylhexyl palmitate, isopropyl palmitate, isopropyl myristate, butyl laurate, cetyl-2-ethyl hexalate, dioleyl adipate, diethyl adipate, diisobutyl Examples include adipate and diisodecyl adipate.

Of these, butyl stearate and butyl palmitate are particularly preferable.

The above various fatty acid esters may be used alone or in combination of two or more.

The magnetic layer of the present invention may contain the above fatty acid or further a lubricant in addition to the above fatty acid ester.

Examples of other lubricants include silicone lubricants, fatty acid-modified silicone lubricants, fluorine lubricants, liquid paraffin, squalane, carbon black and the like. These may be used alone or in combination of two or more.

As the binder, a transparent one such as cellulose ester or gelatin is used.

Dispersion of finely divided magnetically-receptive particles in a transparent binder such as cellulose ester or gelatin using an organic solvent for cellulose ester or a solvent for the binder such as water for gelatin. A liquid may be prepared.

As the organic solvent used in dispersing, kneading and coating the particles, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,
Ketones such as isophorone and tetrahydrofuran; alcohols such as methanol, ethanol, propanol, butanol, isobutyl alcohol, isopropyl alcohol, and methylcyclohexanol; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, ethyl lactate, glycol acetate. Esters such as monoethyl ether; ethers such as diethyl ether, tetrahydrofuran, glycol dimethyl ether, glycol monoethyl ether, dioxane; benzene,
Tar-based compounds (aromatic hydrocarbons) such as toluene, xylene, cresol, chlorobenzene, and styrene; chlorinated hydrocarbon-based compounds such as methylene chloride, ethylene chloride, carbon tetrachloride, chloroform, ethylene chlorohydrin, and dichlorobenzene; N , N-dimethylformaldehyde, hexane, etc. can be used.

The kneading method is not particularly limited, and the addition order of each component can be appropriately set.

In preparing the magnetic coating composition, a conventional kneading machine such as a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a tron mill, a sand grinder, a segegvari (Szegvari), an attritor, a high speed impeller disperser, and a high speed stone. Mill, High Speed Impact Mill, Disperser, Kneader, High Speed Mixer, Ribbon Brainer, Cokneader, Intensive Mixer, Tumbler,
A blender, a disperser, a homogenizer, a single screw extruder, a twin screw extruder, an ultrasonic disperser, etc. can be used. For details of the technology regarding kneading and dispersion, see T. C. By PATTON, "Paint Flow and Pigment Dispersion", 1964, John Wiley & Sons, John Tanaka Shin'ichi "Industrial Materials",
Vol. 25, 37 (1977) and the like, and the references cited in the book concerned. For continuous processing, these kneading and dispersing machines are appropriately combined and sent for application. In addition, U.S. Pat.
It is also described in No. 2,855,156. Also in the present invention, a magnetic coating material can be prepared by kneading and dispersing in accordance with the method described in the above-mentioned book or references cited in the book.

Prior to coating, the support may be subjected to corona discharge treatment, plasma treatment, undercoating treatment, heat treatment, dust removal treatment, metal vapor deposition treatment, and alkali treatment. Regarding these supports, for example, West German Patent No. 3,338,854A, JP-A-5959
-116926, U.S. Pat. No. 4,388,368, and Yukio Mitsuishi, "Fiber and Industry," Vol. 31, pp. 50-55 (1975).

Preferred embodiments of the support containing the magnetic particles of the present invention are shown below.

The support is preferably made of a natural or synthetic polymer, preferably cellulose ester, polyester, polycarbonate, polyethylene phthalate, polyethylene naphthalate, polyparaphenylene terephthalamide, etc., but cellulose acetate, polycarbonate, polyethylene terephthalate is more preferable. preferable.

Particularly, a copolymerized polyester film containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component as shown in JP-A-1-244446 is useful, and especially Japanese Patent Application No. 4-95654. As shown, a copolymerized polyester film having a content of diethylene glycol of 5 mol% or less is preferable.

In the present invention, the magnetic particles may be uniformly added to the support, may be concentrated on one surface side in the thickness direction of the support, or may be concentrated near the center. Although it is good, it is preferable to concentrate on the side of the support opposite to the side on which the photographic constituent layers are coated. As a method of concentrating on one surface side of the support, after casting a dope containing a support polymer and magnetic particles, the magnetic particles are concentrated on one surface side of the support by gravity, magnetic force, etc. As shown in Kosho 30-986, WO91 / 11750,
There is a method in which a dope containing magnetic particles and a dope not containing magnetic particles are simultaneously cast and concentrated on one surface side of the support, but the latter is preferable because it allows high-speed production.

In the present invention, it is preferable to cast the cellulose acetate triester dope containing the magnetic particles and the cellulose triacetate dope not containing the magnetic particles at the same time on a drum or belt and dry them to form a support. Two casting ports are provided on the endless belt, the cellulose acetate triacetate dope is cast first, and the cellulose acetate triacetate dope containing magnetic particles is then cast and dried to support the present invention. It can also form a body. (Fig. 1,
2) As a method for providing the stripe-shaped magnetic layer (see FIGS. 3 and 4), the methods described in JP-A-4-124642 and JP-A-4-124645 may be used.

The thickness of the support of the present invention is 50 to 200 μm, preferably 60 to 130 μm, particularly preferably 70 to 120 μm.
Is. If the thickness is less than this, the accuracy of writing and reading by the magnetic head is reduced with respect to the high-speed coating speed of the silver halide photosensitive material, which is not preferable. On the other hand, if it is thicker than this, the suitability for exposure / developing equipment as a silver halide photosensitive material is deteriorated.

In the support of the present invention, the thickness of the layer in which the magnetic particles are present is 2 μm or less, preferably 1.5 μm or less, particularly preferably 1 μm or less and 0.1 μm or more. The coating amount of the magnetic particles is 10 to 1000 mg / m ² , preferably 15 to 300 mg / m ² ,
Particularly preferred is 20-100 mg / m ² .

In the present invention, a photographic material is produced by coating a photographic constituent layer comprising at least one silver halide emulsion layer and a non-photosensitive layer on a support containing magnetic particles. The process has a magnetic writing unit and a magnetic reading unit, and the production control of the silver halide photosensitive material can be performed. That is, it is possible to perform on-line or off-line formatting and addressing by a magnetic writing means on a support coated with a magnetic recording material, and to control manufacturing by magnetic information in a coating step of a photographic constituent layer. Further, information (for example, product type, manufacturing number, manufacturing date, failure information, etc.) in the coating process can be additionally written by the magnetic writing means and applied to the subsequent drying process and cutting and packaging process. Further, in the cutting and packaging process, it is possible to write a shipping and sales code, perform reformatting in preparation for magnetic recording by a photographing camera, and write necessary information at the time of photographing, developing, printing, and the like.

In the present invention, a magnetic head is effective as the magnetic writing means and the magnetic reading means in the manufacturing process, and it is achieved by providing the head in a part or all of the width direction of the support of the present invention. Each magnetic head in the manufacturing process is connected to a computer to display read information, control the driving of the manufacturing apparatus, and write various kinds of information in necessary places. The above manufacturing method is a preferable method for manufacturing the light-sensitive material described in the claims of the present invention.

In the present invention, the magnetic particles are mainly composed of iron oxide, but those having a small amount of aluminum, calcium or silicon doped therein are preferably used for the purpose of the present invention. The acicular ratio of magnetic particles is 1
~ 7 are preferred.

In the process of casting a dope containing magnetic particles and drying it to form a magnetic layer, the magnetic particles may be regularly oriented by facing magnets, or a random magnetic field may be applied to obtain a so-called randomize. Treatment is also effective in the present invention.

In the present invention, the polymer forming the support is most preferably cellulose triacetate, but polyethylene terephthalate may be used. In this case, a so-called coextrusion method is used in the production of the support. Is preferred. Further, in the case of polyethylene terephthalate, JP-A 1-244446, 1-291248,
1-298350, 2-89045, 2-93641, 2-181749
No. 2-214852 and Japanese Patent Application No. 2-291135, it is preferable to use polyethylene terephthalate having a high water content because the dispersion stability of magnetic particles is improved.

In the present invention, it is preferable to add a small amount of a known dye or pigment to the support to prevent halation, irradiation and light piping.

In the present invention, the surface roughness is set to a certain region by adding an inorganic or organic matting agent to the dope containing the magnetic particles, or by matting the surface after forming the magnetic layer. By doing
The efficiency of writing and reading by the magnetic head can be improved.

In the present invention, by adjusting the viscosity balance, changing the solvent composition, adjusting the surface tension, and changing the plasticizer content of the dope containing magnetic particles and the dope not containing magnetic particles. The physical properties of the support of the present invention can be adjusted.

In the present invention, the steps can be simplified by applying an undercoat layer or a backing layer online after forming the support.

The color light-sensitive material of the present invention can be a full-color light-sensitive material. A full-color 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 adopted 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. 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 for the purpose of improving color reproduction. Regarding the layer structure using the fourth or more color-sensitive photosensitive layer,
JP 61-34541, JP 61-201245, JP 61-198236, JP
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. Also, the fourth
Alternatively, the photosensitive layer having a higher color sensitivity 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-61-43748 is used.
Issue 59-113438, Issue 59-113440, Issue 61-20037, Issue
It may contain a coupler, a DIR compound or the like as described in 61-20038, and may also contain a color mixing inhibitor as is commonly used. In addition, these non-photosensitive layers are research disclosure (referred to as RD) 308119 1
It may be an auxiliary layer such as a filter layer or an intermediate layer described on page 002, item VII-K.

Examples of the layer structure which can be adopted in the light-sensitive material of the present invention include the forward layer, the reverse layer and the unit structure described in RD No. 308119, page 1002, item VII-K.

When there are two light-sensitive layers having the same color sensitivity, these light-sensitive layers may be the same, and high sensitivity as described in West German Patent 1,121,470 or British Patent 923,045. It may have a two-layer structure of an emulsion layer and a low-sensitivity emulsion layer. 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 the emulsion layers. or,
JP-A-57-112751, 62-200350, 62-206541, 6
As described in 2-206543, 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, the 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 blue-sensitive layer / GH / RH from the side farthest from the support.
It is also possible to arrange in the order of / GL / RL. In addition,
As described in JP-A-56-25738 and JP-A-62-63936, from the side farthest from the support, the blue-sensitive layer / GL / RL /
It can also be arranged in the order of GH / RH.

Further, as described in JP-B-49-15495, three photosensitive layers having the same color sensitivity with different sensitivities are provided.
Layers 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,
Medium-sensitivity silver halide emulsion layer from the side remote from the support,
A high-sensitivity silver halide emulsion layer and a low-sensitivity silver halide emulsion layer may be arranged in this order. When it is composed of three layers having different sensitivities, the order of laminating these three layers is arbitrary. For example, as a laminating order, a high-sensitivity silver halide emulsion layer, a low-sensitivity silver halide emulsion layer, Examples thereof include a medium-sensitivity silver halide emulsion layer, a low-sensitivity silver halide emulsion layer, a medium-sensitivity silver halide emulsion layer, and a high-sensitivity silver halide emulsion layer. 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 1000 ppm or less, preferably 500 ppm or less, particularly preferably 300 ppm or less.

Usually, the silver halide emulsion contains polyvalent metal ions. The polyvalent metal ion contained is iron, manganese, zinc, copper, magnesium, calcium, etc., and in order to make these 1000 ppm or less in the photographic constituent layer, the polyvalent metal ion for preparing the silver halide emulsion is used. Used to remove gelatin, prevent contamination during the preparation process of silver halide emulsions, remove polyvalent metal ions as impurities in various additives, use ion-exchanged water for preparation, etc. This is done by preventing diffusion and penetration from the layer.

Particularly, it is most effective to reduce the polyvalent metal ion in gelatin used by processing a natural product.

Gelatin is generally Fe, Mn, Cu, Zn, Mg, Ca.
It contains metal ions such as, as impurities, far exceeding 1000ppm. The gelatin used for preparing the silver halide emulsion layer and the non-photosensitive layer in the present invention is preferably purified so that these metal ions will be 500 ppm or less.

Such gelatin can be obtained by deionization by ion exchange or the like. For example, the content of the metal ion can be reduced by heating the gelatin aqueous solution and bringing it into contact with the 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. In some cases, it can be removed by using an OH ^- type anion exchange resin. For these methods, see “Chemical Chemistry Course 2, Basic Technology II” edited by The Chemical Society of Japan, Maruzen (1956), 15
1-202, "New Experimental Chemistry Course 1, Basic Operation 1," edited by The Chemical Society of Japan, Maruzen (1975), pp. 463-497. 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. These methods are described in, for example, “Experimental Chemistry Course (Continued) Separation and Purification” (1967) edited by the Chemical Society of Japan.

On the other hand, various silver halide emulsions can be used in the photographic constituent layers of the present invention. The method for producing a silver halide emulsion and the additives used in the production are described in RD No. 17643, No. 18716 and No. 308119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively). This section describes the content and description of RD308119.

[Item] [Page of D308119] Iodine composition 993 I-A Manufacturing method 993 I-A and 994 E Crystal habit Normal crystal 993 I-A Twin twin 993 I-A Epitaxial 993 I -A term Halogen composition Uniform 993 IB term Non-uniform 993 IB term Halogen conversion 994 I-C term Halogen substitution 994 I-C Metal-containing 994 I-D term Monodisperse 995 I-F term Solvent addition 995 I-F item Latent image forming position Surface 995 I-G item Internal 995 I-G item Applicable negatives 995 I-H item Positive (including internal fog particles) 995 I-H item Emulsion mixture 995 I -J Item Desalination 995 II-A The silver halide emulsion used in the present invention is physically ripened,
Chemical ripening and spectral sensitization can be performed. Additives used in such processes are RD17643, RD18716 and RD30.
8119. The location of the description is shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, H, I, Item J 23-24 648-9 Supersensitizer 996 IV-AE, Item J 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Can be used in the present invention Known photographic additives are also described in Research Disclosure above. The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIIIC , XIII-C 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricants 1006 XII 27 650 Activators / Coating aids 1005 XI 26 to 27 650 Matte agents 1007 XVI Developers (contained in sensitive materials) 1011 XXB Various couplers can be used in the present invention. The specific examples are described in the following RD. The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VII C to G item Magenta coupler 1001 VII-D item VII C to G item Cyan coupler 1001 VII-D item VII C to G Item Colored coupler 1002 VII-G item VII G item DIR coupler 1001 VII-F item VII F item BAR coupler 1002 VII-F item Other useful residues 1001 VII-F item Emission coupler Alkali-soluble coupler 1001 VII-E item The additives used in the invention can be added by the dispersion method described in RD308119 page 1007, item XIV.

In the present invention, the above-mentioned RD17643 page 28,
The supports described in RD18716 pages 647-8 and RD308119 page 1009, section XIX can be used.

The color light-sensitive material of the present invention includes the above-mentioned RD30.
8119 Auxiliary layers such as a filter layer and an intermediate layer described in Item VII-K can be provided.

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

The color light-sensitive material of the present invention is 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. can do.

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.
Development can be carried out by a usual method described in page RD18716, page 647 and RD308119 XIX.

If necessary, the surface of the transparent support of the present invention on which the photographic constituent layer is to be formed is subjected to a surface activation treatment such as corona discharge and / or an undercoat layer prior to the formation of the photographic constituent layer. can do.

Examples of the undercoat layer include those disclosed in JP-A-59-199.
No. 41, No. 59-77439, No. 59-224841 and Japanese Patent Publication No. 58-5302
The undercoat layer described in No. 9 can be mentioned as a suitable example. The subbing layer provided on the surface of the transparent support opposite to the photographic constituent layer is also called a back layer.

[0080]

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

Example 1 (Production of Support-1) 100 parts of cellulose triacetate having a degree of acetylation of 61.4% and 15 parts of triphenyl phosphate are mixed solvent consisting of methylene chloride-methyl alcohol 738.
Completely dissolved in a part, and the following organic dyes (a), (b), (c)
Was added in a small amount to obtain a dope.

[0082]

[Chemical 1]

On the other hand, a cellulose triacetate dope containing magnetic particles was prepared as follows.

Co-deposited γ-Fe ₂ O ₃ 100 parts by weight (coercive force: 610 Oe BET surface area 35 m ² / g, major axis length 0.23 μm, acicular ratio 7) Cellulose triacetate 210 parts by weight Methylene chloride 2100 parts by weight Methyl ethyl ketone 1000 parts by weight The above components were mixed together with a dissolver and then dispersed with a sand grinder to obtain a dispersion liquid. The viscosity was measured with a Brookfield viscometer and was 8.8 poise.

20 parts by weight of the above dispersion was taken and thoroughly mixed with a dope having the following composition with a dissolver.

Cellulose triacetate 13.8 parts by weight Methylene chloride 163.1 parts by weight Cyclohexanone 55 parts by weight Ethanol 3.1 parts by weight Next, each dope was filtered and kept at 27 ° C., and two castings were provided on a rotating 6 m endless stainless band. The cellulose triacetate base containing magnetic particles and having a thickness of 90 μm was obtained by uniformly casting from the mouth, evaporating the solvent until peeling was possible, peeling from the stainless steel band, and further drying.

The cellulose triacetate dope containing magnetic particles was dried so that the dry film thickness was 1 μm, and after casting, it was dried while carrying out orientation treatment with a facing magnet. The coating amount of magnetic particles was 50 mg / m ² .

The coercive force of each support was 670 Oe.
The optical transmission density was 0.10.

On the side opposite to the magnetic particle-containing layer side of the triacetyl cellulose film support, layers having the following compositions were sequentially formed from the support side.

First layer Alumina sol AS-100 (aluminum oxide) 0.8 g (manufactured by Nissan Chemical Industries, Ltd.) Second layer diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg (Production of support-2) ) except that no addition the support Co- deposited in -1 γ-Fe ₂ O ₃ at all to create a support -2 in the same manner.

(Composition of Photographic Constituting Layer) The coating amount of silver halide and colloidal silver is g / m ² in terms of metallic silver.
The amounts are expressed in units, the amounts added in g / m ² for couplers, additives and magenta, and the sensitizing dyes are expressed in moles per mole of silver halide in the same layer.

First layer: Antihalation layer (HC) 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 (IL-1) Compound ( SC-1) 0.15 High boiling point solvent (Oil-2) 0.17 Gelatin 1.27 Third layer: Low sensitivity red sensitive layer (RL) 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 4th layer: Medium sensitivity red sensitive layer RM) Silver iodobromide emulsion (average grain size 0.52 μm) (silver iodide content 8.0 mol%) 0.62 Silver iodobromide emulsion (average grain size 0.38 μm) (silver iodide content 8.0 mol%) 0.27 Sensitization 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 (RH) 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 (IL-2) Compound (SC-1) 0.09 High boiling point solvent (Oil-2) 0.11 Gelatin 0.80 Seventh layer: Low sensitivity green sensitive layer (GL) Silver iodobromide emulsion (average) Grain size 0.38 μm) (Silver iodide content 8.0 mol%) 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 (GM) Silver iodobromide emulsion (average grain size 0.59 μm) (Silver iodide content 8.0 mol%) 0.87 Magenta coupler (M-2) 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 9th layer: High sensitivity green sensitive layer (GH) Silver iodobromide emulsion (average grain size 1.0 µm) (iodination) Silver content 8.0%) 1.27 Magenta coupler (M-2) 0.10 Colored magenta Taper (CM-1) 0.012 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00 10th layer: Yellow filter layer (YC) 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 11th layer: Intermediate layer (IL-3) Formalin scavenger (HS-1) 0.20 Gelatin 0.60 12th layer: Low sensitivity blue sensitive layer (BL) Silver iodobromide emulsion ( Average grain size 0.38 μm) (Silver iodide content 8.0 mol%) 0.22 Silver iodobromide emulsion (Average grain size 0.27 μm) (Silver iodide content 2.0 mol%) 0.03 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 13th layer: Medium sensitivity blue Sensitive layer (BM) Silver iodobromide emulsion (average grain size 0.59 μm) (iodination Content of 8.0 mol%) 0.30 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) 0.046 Gelatin 0.47 14th layer: High-sensitivity blue-sensitive layer (BH) Silver iodobromide emulsion (average grain size 1.00 μm) (Silver iodide content 8.0 mol%) 0.85 Sensitizing dye (SD -4) 7.3 × 10 ^-5 Sensitizing dye (SD-6) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.80 15th layer: 1st protective layer Iodour Silver halide (average grain size 0.08 μm) 0.40 (silver iodide content 1.0 mol%) UV absorber (UV-1) 0.026 UV 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 16th layer: 2nd protective layer Alkali-soluble matting agent (plain Particle size 2 [mu] m) 0.15 Polymethyl methacrylate (average particle size 3 [mu] m) 0.04 Slip agent (WAX-1) 0.04 Gelatin 0.55 The photosensitive material described above, further compounds Su-1, Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggants AF-1 and AF-2 (weight average molecular weights of 10,000 and 1.1 million), dyes AI-1 and AI
-2 and compound DI-1 (9.4 mg / m ² ).

The structures of the above additives are shown below.

Oil-1: dioctyl phthalate Oil-2: tricresyl phosphate Oil-3: dibutyl phthalate SC-2: 2-s-octadecyl-5-methylhydroquinone Su-1: dioctyl sulfosuccinate / sodium Su- 2: Sodium tri-i-propylnaphthalene sulfonate H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium H-2: Vinyl sulfonyl methyl ether ST-1: 4-hydroxy-6-methyl- 1,3,3a, 7-Tetrazaindene AF-1: 1-phenyl-5-mercaptotetrazole AF-2: Poly-N-vinylpyrrolidone

[0095]

[Chemical 2]

[0096]

[Chemical 3]

[0097]

[Chemical 4]

[0098]

[Chemical 5]

[0099]

[Chemical 6]

[0100]

[Chemical 7]

[0101]

[Chemical 8]

All the gelatins in the above photographic construction were replaced with the gelatins shown in Table 1, respectively.

[0103]

[Table 1]

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.

Further, 8 kinds of color light-sensitive material samples shown below were obtained by providing the above-mentioned Support-1 or 2 with a photographic constituent layer containing gelatin of the group shown in Table 1.

Sample No. Support Gelatin 101 2 A 102 1 A 103 1 B 104 1 C 105 1 D 106 1 E 107 1 F 108 2 D (preservation test) Each sample was cut to the standard of taking 135 sheets of 135 sizes. The photographic component layer was placed inside and rolled into a roll, which was then sealed in a polypropylene film container at 23 ° C. and 55% RH. Each sample was allowed to stand for 3 days in an atmosphere of 50 ° C. and 65% RH together with the container, and then exposed for sensitometry along with a blank sample to perform the following development processing.

Treatment process Treatment time Treatment temperature (℃) Replenishment amount * (mL) Color development 3 minutes 15 seconds 38 ± 0.3 780 Bleach 6 minutes 30 seconds 38 ± 2.0 150 Water washing 3 minutes 15 seconds 20 ± 10 200 Fixed 6 minutes 30 seconds 38 ± 2.0 830 Washing 3 minutes 15 seconds 20 ± 10 200 Stability 1 minute 30 seconds 38 ± 5.0 830 Drying 2 minutes 55 ± 5.0 − In the above, the replenishment amount is the value per 1 m ² of the photographic material. Is.

As the color developing solution, the bleaching solution, the fixing solution, the stabilizing solution and the replenishing solution thereof, those prepared as follows 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 and the pH was adjusted to 10.1.

<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 to 6 with ammonia water.
Adjusted to 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 (manufactured by 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 the pH was adjusted to 10.18 with potassium hydroxide or 20% sulfuric acid.

<Bleach Replenisher> Water 700 ml 1/3 Diaminopropane tetraacetate 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.

The relative sensitivity value of the blue-sensitive layer of each sample obtained by the development processing (blank sample of sample 101 was set to 100) and the increase in fog due to storage (ΔFog) were examined and shown in Table 2.

[0118]

[Table 2]

Therefore, it is clear that the light-sensitive material of the constitution of the present invention can input information magnetically and has little deterioration of photographic characteristics upon storage.

Example-2 (Production of Support-3) 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 transesterification reaction was carried out by a conventional method. . 5-sodium sulfodi (β
-Hydroxyethyl) isophthalic acid in ethylene glycol solution (concentration 35% by weight) 28 parts by weight, polyethylene glycol (number average molecular weight 3,000) 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, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out 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 is stretched 3.3 times in the machine direction at 80 ° C, then stretched 3.3 times in the transverse direction at 90 ° C, then heat set at 220 ° C for 30 seconds to obtain a thickness.
An 80 μm biaxially stretched film was obtained. The diethylene glycol content was 4 mol%.

An undercoat layer was provided on both sides of this biaxially stretched film as follows.

That is, 100 parts by weight of a resin liquid for undercoat layer obtained by emulsion polymerization of the following composition, the following surfactant (SF-
1) 0.2 parts by weight of hexamethylene-1,6-bis (ethyleneurea), 0.3 parts by weight, and 900 parts by weight of water were applied to a coating liquid for an undercoat layer so that a wet film thickness was 20 μm, and 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

[0125]

[Chemical 9]

Next, a coating liquid for the undercoating upper layer consisting of 10 parts by weight of gelatin, 0.2 parts by weight of saponin, and 1000 parts by weight of water was applied so as to have a wet film thickness of 20 μm, and then dried.

A magnetic layer having the following composition was provided on one surface of the support. It is shown by the coating amount per 1 m ² .

<Magnetic layer> γ-Fe ₂ O ₃ 200 mg (coercive force: 330 Oe, specific surface area 32 m ² / g) Gelatin 3.0 g Di- (2-ethylhexyl) sodium sulfosuccinate 200 mg Bis (vinylsulfonyl) methane 30 mg WAX-1 60 mg (Production of Support-4) γ-Fe ₂ O ₃ in Support- ₃
A support-4 was prepared in the same manner except that the above was not added at all.

Supports 3, 4 were prepared in the same manner as in Example 1.
And gelatin B, C, D in combination with the following samples 201-204
It was created.

Sample No. Support Emulsion Group Remark 201 3 B ratio comparison 202 3 C present invention 203 3 D present invention 204 4 B ratio comparison As a result of performing the same evaluation as in Example-1, the effect of the present invention was obtained. Was obtained.

[0131]

According to the present invention, a silver halide color light-sensitive material having a magnetic recording layer and having a small decrease in sensitivity during storage was obtained.

[Brief description of drawings]

FIG. 1 is a schematic view of a production example of a support using two casting ports.

FIG. 2 is a schematic view of a manufacturing example of a support using an integral casting port.

FIG. 3 is a plan view of a color photosensitive material in which a striped magnetic layer is provided on one side of a film.

FIG. 4 is a plan view of a color light-sensitive material in which a striped magnetic layer on both sides of a film and an optical recording layer are provided between shooting screens.

FIG. 5 is a sectional view showing an example of a color light-sensitive material of the present invention.

[Explanation of symbols]

 1,21 Stainless steel endless belt 2 Single-type casting port 3 Single-type casting port for magnetic dope 22 Composite type casting port 11 Magnetic layer 12 Optical recording layer 31 Photographic layer 32 Support 33 Magnetic recording layer

Claims (1)

[Claims] 1. At least one each on a transparent support.
A silver halide color light-sensitive material having a photographic constituent layer consisting of a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-photosensitive layer, and having a magnetic layer containing a ferromagnetic powder. The content of polyvalent metal ions with a valence of 2 or more is 1000 ppm
A silver halide color light-sensitive material characterized by the following.