JPH07181650A - Method for forming color photographic image - Google Patents

Abstract

PURPOSE:To obtain the color image forming method superior in development processing stability and image storage stability after development by processing a color photographic sensitive material with a development processing solution containing a specified compound. CONSTITUTION:The photosensitive material has photographic constitution layers comprising at least each one of red-, green-, and blue-sensitive layers and nonphotosensitive layer on one side of a transparent support, and a magnetic recording layer on the other side and it is processed with the development processing solution containing at least one of the compounds represented by formulae I and II in which R1 is alkyl or hydroxyalkyl; R2 is alkylene or hydroxyalkylene; R3 is a substituent; (m) is an integer of 0-4; R11 is alkyl; R12 is alkylene; R13 is Hor alkyl; R14 is a substituent; and (n) is an integer of 0-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic image forming method, and more particularly to a color photographic image forming method with improved development processing stability, and a color photographic image forming excellent in image storability after development. Regarding the method.

[0002]

2. Description of the Related Art In recent years, a silver halide color light-sensitive material (hereinafter, simply referred to as "color light-sensitive material") is used to more efficiently and highly accurately perform development processing after photographing (image exposure) and printing on photographic paper. There is a proposal to record the information at the time of photographing on a color light-sensitive material so that it can be effectively used.

US Pat. No. 4,947,196 and International Patent Publication 90 /
No. 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 the above-mentioned improved technology, the magnetic layer is provided with identification information such as the type and manufacturer of the photosensitive material, information relating to the conditions at the time of shooting
By magnetically inputting / outputting information on customers, information on print conditions, information on print reprint conditions, etc. on the film, it is possible to improve print quality, improve the efficiency of print work, and process work at a laboratory (laboratory). It is possible to improve the efficiency of.

On the other hand, in contrast to the above magnetic recording, a method of optically recording information, that is, a method of recording information on a photographic film by using a light source and fixing the information by a developing process is known. In JP-A-3-96635 and JP-A-3-116137, there is a method of recording image trimming information on a film by an LCD for imprinting, and in JP-A-3-61727, position information of a subject is recorded on a film as a bar code. An optical recording method is disclosed in Japanese Patent Laid-Open No. 3-135535, in which the shooting information is optically recorded on a film using a dot code, and in Japanese Patent Laid-Open No. 4-125543, information on the photographed area is converted into numbers and characters. The method of optical recording on a film is shown respectively.

These are mainly optically recorded on the non-image portion of the film, and devised so that information can be effectively recorded on a small area.

Due to the recent miniaturization of the light source, a compact and inexpensive camera can be realized even if it is provided as an optical recording unit in the camera.

However, it has been revealed that when the color light-sensitive material has the magnetic recording layer, the stability of the development processing level in the laboratory is inferior to that of the conventional light-sensitive material having no magnetic recording layer. The cause is not clear, but it is considered that the magnetic substance in the magnetic recording layer influences the redox balance in the development processing step. The quality of color light-sensitive materials that general users have is largely dependent on the quality when shipped from this lab, and for laboratories processing a large amount of light-sensitive materials, this deterioration in processing stability is fatal. It becomes a problem.

Further, it has been revealed that a color photosensitive material in which information at the time of photographing is optically recorded outside the photographing screen is inferior in stability of development processing level in a laboratory as compared with a conventional photosensitive material. Normally, an automatic processor in a lab is replenished with a processing solution according to the length or the number of developed photosensitive materials. It is considered that the balance of the unexposed portion, that is, the balance of the developed / undeveloped portion is lost, and the stability of the development processing level is deteriorated. It may be possible to deal with it by adjusting the supply balance of the replenisher, but it is complicated and difficult in the situation where the conventional color photosensitive material and the optically recorded color photosensitive material are mixed. The quality of color light-sensitive materials that general users have is largely dependent on the quality at the time of shipment from this laboratory, and for laboratories processing a large amount of color light-sensitive materials, this deterioration in processing stability is fatal. Problem.

Furthermore, the roll width of the color light-sensitive material is 20 to
It was revealed that the small format photosensitive material having a size of 35 mm and a photographing screen area of 300 to 700 mm ² is inferior in stability of the development processing level in the laboratory as compared with the conventional photosensitive material. Normally, in an automatic developing machine in a laboratory, the processing solution is replenished according to the length or the number of color light-sensitive materials after development processing, but compared with conventional light-sensitive materials, the area of the light-sensitive material, the shooting screen area, It is considered that when the ratio of the image-capturing screen area to the area of the photosensitive material is different, the balance between exposed / unexposed portions, that is, the balance between developed / undeveloped portions is lost, and the stability of the development processing level deteriorates.
It may be possible to deal with it by adjusting the supply balance of the replenisher, but it is complicated and difficult in the situation where the conventional color photosensitive material and the small-format color photosensitive material are mixed. The quality of color light-sensitive materials that general users have is largely dependent on the quality when shipped from this lab, and this deterioration of processing stability is fatal to laboratories that develop a large amount of light-sensitive materials. It becomes a problem.

Further, it has been found that the light-sensitive material having the magnetic recording layer and the light-sensitive material having the optical recording portion also have a problem that so-called dark fading is more likely to occur than the conventional light-sensitive materials. It is considered that this is due to the fact that it has a layer / portion that is not present in the light-sensitive material up to now and that reading and retrieval of information are repeated. In addition, since the printing conditions are constant for a photosensitive material having such information, the frequency of re-baking increases and the frequency of use of a negative film after development such as reproduction on a monitor increases. However, even from such a situation, stricter dark fading resistance is required as compared with the conventional negative film.

[0011]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a method for forming a color photographic image excellent in development processing stability. A second object of the present invention is to provide a method of forming a next-generation color photographic image that can improve print quality, improve print work efficiency, and improve lab work processing efficiency by using information at the time of shooting. Is. A third object of the present invention is to provide a color image forming method using a small-format color light-sensitive material that can contribute to miniaturization and high functionality of a camera. Furthermore, the fourth
It is an object of the invention to provide a color image forming method having excellent image storage performance after development of a photosensitive material having a magnetic recording layer and a photosensitive material having an optical recording portion.

[0012]

Therefore, as a result of earnest research, the present inventor has found that the above object of the present invention can be achieved by the following constitution.

(1) On one side of a transparent support, there is provided a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer, and on the other side. In a color photographic image forming method using a silver halide color photographic light-sensitive material having a magnetic recording layer, a development treatment in which the color photographic light-sensitive material contains at least one of compounds represented by the following general formulas (I) and (II) A method for forming a color photographic image treated with a liquid.

[0014]

[Chemical 3]

In the formula, R ₁ represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms or a straight-chain or branched hydroxyalkyl group having 3 to 6 carbon atoms, and R ₂ represents a straight-chain or branched hydroxyalkyl group having 1 to 6 carbon atoms. It represents a chain or branched alkylene group or a linear or branched hydroxyalkylene group having 3 to 6 carbon atoms. R ₃
Represents a substituent, and m represents an integer of 0 to 4. When m is 2 or more, a plurality of R _3's may be the same or different.

[0016]

[Chemical 4]

In the formula, R ₁₁ represents an alkyl group, R ₁₂ represents an alkylene group whose main chain has 2 or more carbon atoms, and R ₁₃ represents a hydrogen atom or an alkyl group. R ₁₄ represents a substituent, n is 0
Represents an integer of 4; When n is 2 or more, a plurality of R _14's may be the same or different. X is -CON (R ₁₅ ) (R ₁₆ ), -C
Represents OOR ₁₇ or —SO ₂ N (R ₁₅ ) (R ₁₆ ). R ₁₅ and R ₁₆ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. R ₁₇ represents an alkyl group or an aryl group.

(2) A silver halide color photographic light-sensitive material having a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer on one side of a transparent support. In a color photographic image forming method using a material, the color photographic light-sensitive material is one in which information at the time of photographing is optically recorded outside the photographing screen, and at least the compound represented by the general formula (I) or (II). A method for forming a color photographic image, which is processed with a developing solution containing one of them.

(3) A silver halide color photographic light-sensitive material having a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer on one side of a transparent support. In a color photographic image forming method using a material, the color photographic light-sensitive material has a roll width of 20 to 35 mm, a photographing screen area of 300 to 700 mm ² , and is represented by the general formulas (I) and (II). A method for forming a color photographic image, which is processed with a developing solution containing at least one compound.

It is a preferred embodiment that the transparent support is composed of naphthalene dicarboxylic acid and polyester containing ethylene glycol as a main component.

The present invention will be described in more detail below.

The magnetic recording layer in the present invention refers to JP-A-53.
-109604, Japanese Examined Patent Publication No. 57-6576, Japanese Patent Laid-Open No. 60-45248, U.S. Pat. No. 4,947,196, International Publication No. 90/04254, 91/1175.
No. 0, No. 91/11816, No. 92/08165, No. 92/08227, and the like, or a transparent magnetic layer as described in JP-A-4-124642.
No. 4,124,645 and the like may be stripe-shaped magnetic layers.

When the magnetic layer of the present invention is a transparent layer, the optical density is preferably 1.0 or less, more preferably 0.75 or less, and particularly preferably 0.02 to 0.30.

In the present invention, the magnetic layer is a layer formed by dispersing ferromagnetic powder in a binder.

The coating amount of the magnetic powder is 50 mg or less, preferably 20 mg or less, particularly preferably 0.1 mg to 5 mg as the amount of iron per 100 cm ^{2 of the} silver halide color 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 Fe atoms, which are the constituent elements of the uniaxially anisotropic hexagonal ferrite crystal, 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
The element Oe is used.

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

In the hexagonal ferrite, divalent metal (M
The appropriate substitution amount of II) and pentavalent metal (Mv) depends on the combination of MII and Mv, but is approximately 0.5 per one chemical formula of MII.
~ 1.2 is preferable.

Looking at the relationship of the substitution amount of the substitution element, for example, for 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.

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

The shape of the ferromagnetic powder is not particularly limited and, for example, any of needle-like, spherical or ellipsoidal shapes 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, especially 12 to 22 carbon atoms.
Particularly preferred are myristic acid, oleic acid and stearic acid.

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. Butyl stearate and butyl palmitate are preferred.

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

The magnetic layer of the present invention may contain other fatty acid together with the above fatty acid or the above fatty acid ester.

Examples of other lubricants include silicone lubricants, fatty acid-modified silicone lubricants, fluorine lubricants, liquid paraffin, squalane, and carbon black. 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.

A dispersion of finely divided magnetic 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. Can be prepared.

As the organic solvent used in the dispersion, kneading and coating of the particles, acetone, methyl ethyl ketone, cyclohexanone and other ketones; propanol, butanol, isobutyl alcohol and other alcohols; ethyl acetate, butyl acetate An ester system such as isopropyl acetate; an ether system such as glycol dimethyl ether; a tar system (aromatic hydrocarbon) such as xylene; a chlorinated hydrocarbon system such as methylene chloride and ethylene chloride.

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 preferably comprises a natural or synthetic polymer, such as cellulose ester, polyester, polycarbonate, polyethylene terephthalate,
Polyethylene naphthalate, polyparaphenylene terephthalamide and the like are preferable, but a polyester support containing 2,6-naphthalenedicarboxylic acid and ethylene glycol as main components is more preferable.

The polyethylene naphthalate support in the present invention is described in JP-A-4-93937, JP-A-6-35114, US Pat.
By having a laminated multi-layer structure as shown in No. 288,601 or a mixed polyester mixed with other polyester, it is possible to provide a color light-sensitive material having less problem of curl. .

Further, for the purpose of reducing the curl of the photographic support made of polyester, JP-A-51-16358 and JP-A-6-35.
The method described in No. 118 and the like can be preferably used. That is, it is a method of heat treatment at a temperature of 50 ° C. to glass transition temperature for 0.1 to 1500 hours.

Since this heat treatment is performed at a high temperature of 50 ° C. or higher,
If it is performed after coating the emulsion, it tends to cause deterioration of the performance of the emulsion layer. Therefore, it is desirable to do it before coating the emulsion layer.

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, the cellulose acetate triacetate dope containing magnetic particles and the cellulose triacetate ester dope not containing magnetic particles can be simultaneously cast on a drum or belt and dried to form a support.
Two casting ports are provided on the endless belt, the cellulose triacetate ester dope is cast first, and then the cellulose triacetate ester dope containing magnetic particles is further cast and dried,
It is also possible to form the support of the present invention.

The thickness of the support of the present invention is 50 to 150 μm, preferably 60 to 130 μm, particularly preferably 70 to 120 μm.
Is. If it is thinner than this, the accuracy of writing and reading by the magnetic head with respect to the high-speed coating speed of the photosensitive material decreases, which is not preferable. On the other hand, if it is thicker than this, the suitability for exposure / developing equipment as a photosensitive material is deteriorated.

In the support of the present invention, the thickness of the layer containing magnetic particles 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 production method for producing a silver halide light-sensitive material by coating a support containing magnetic grains with a photographic constituent layer comprising at least one silver halide emulsion layer and a non-photosensitive layer. In the above, it is preferable that the manufacturing process has a magnetic writing unit and a magnetic reading unit to control the manufacturing of the photosensitive material. That is, after the support of the present invention is manufactured, the support that is also a magnetic recording material is subjected to online and offline formatting and addressing by a magnetic writing means, and the manufacturing control is performed by magnetic information in the coating step of the photographic constituent layer. It can be carried out. Further, information in the coating process (for example, product type, manufacturing number, manufacturing date, failure information, etc.) can be additionally written by the magnetic writing means and fed back to the subsequent drying process and cutting and packaging process. Furthermore, in the cutting and packaging process, shipping and sales codes can be written, formatting can be performed again in preparation for magnetic recording by a shooting camera,
It is also possible to write necessary information at the time of shooting, developing, printing, etc.

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 the whole 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. In the production method of the present invention, in producing the color light-sensitive material of the present invention,
This is the preferred method.

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, cellulose triacetate may be used as the polymer forming the support, but polyethylene terephthalate or polyethylene naphthalate is preferred. In this case, in the production of the support, the so-called coextrusion method is used. Is preferably used.
Further, in the case of polyethylene terephthalate or polyethylene naphthalate, JP-A 1-244446, 1-291248,
1-298350, 2-89045, 2-93641, 2-181749
It is preferable to use polyethylene terephthalate or polyethylene naphthalate having a high water content as shown in JP-A No. 2-214852 and Japanese Patent Application No. 2-291135, 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 of the dope containing magnetic particles and the dope not containing magnetic particles, changing the solvent composition, adjusting the surface tension, and changing the plasticizer content. 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.

In the present invention, the roll width of the roll color light-sensitive material for photographing is 20 to 35 mm, preferably 20 to 30 mm.
mm. By narrowing the film width, not only can the camera and the cartridge be miniaturized, but also resources can be saved and the storage space for the developed negative film can be reduced.

In the present invention, the photographing screen area is 300 to 700.
a mm ^2, preferably 400 to 600 mm ^2. Within the above range, the small format can be achieved without deteriorating the image quality of the final photographic print, and the camera can be downsized, especially the camera can be made thin.

In the present invention, the aspect ratio of the photographic screen can be arbitrarily selected such as the conventional 135 standard of 1: 1.5, the high definition type of 1: 1.8, and the panoramic type of 1: 3. Further, the aspect ratio of the photographing screen may be fixed, and trimming may be performed by cutting the top and bottom or the left and right according to the customer's request at the time of printing.

In the present invention, the above-mentioned prior art can be referred to for a method of optically recording information at the time of photographing outside the photographing screen of the color light-sensitive material.

In the camera, a light emitting diode is particularly preferable as a light source for optically recording on a photosensitive material.

In the present invention, it is preferable that the optical recording by the light emitting diode is performed from the photographic constituent layer side of the color light-sensitive material. When done from the side opposite to the photographic component layer side,
This is because the backing layer, the antihalation layer, the antistatic layer, the undercoat layer, the magnetic recording layer, and the like of the light-sensitive material are affected by the optical effects of the support itself, and the recording accuracy is reduced or varies.

Therefore, the position of the light emitting diode provided in the camera is preferably on the side where the image is exposed, that is, on the camera body side, and not on the back cover side.

In the present invention, the red light emitting diode has a maximum emission wavelength of 620 nm or more, preferably 650 nm to 70 nm.
It is 0 nm. Any red light emitting diode can be used within the above range.

As typical ones, GaAsP (650 nm), AlG
There are aAs (660 nm), GaPZnO (700 nm), etc. Other red light-emitting diodes are described in Furuike et al., "High brightness and multi-coloring of visible light-emitting diodes", Applied Physics, 53, 132 (1984) and the like.

In the present invention, the red light emitting diode is installed in the camera as an optical recording unit, but at this time, it is preferable to additionally install an optical system such as a lens and an optical fiber. In the case of optically recording on a photographic film (color light-sensitive material) with a red light emitting diode, it is preferable to perform recording from the photosensitive layer side of the photographic film. From the back side, that is, the backing layer side, the effective sensitivity is insufficient and variations occur depending on the type of the photographic film due to the influence of dyes contained in the antihalation layer and the backing layer of the photographic film, which is not preferable.

In the present invention, the light beam used for reading the information is most preferably the light beam having the same maximum emission wavelength as when the information was recorded, but the present invention is not limited to the case where the maximum emission wavelength is within ± 5 nm. Produce the effect of.

As the optically recorded code in the present invention, a two-dimensional bar code can be used in addition to a one-dimensional bar code such as a normal bar code and a dot code.

The conventional one-dimensional bar code is only read by a one-dimensional line sensor, whereas the two-dimensional bar code is a stacked bar code that is scanned by a one-dimensional line sensor and read in multiple stages. , CCD
There is a matrix code by an optical recognition device such as a camera. That is, the two-dimensional bar code system is a means for recognizing two-dimensional shape information, and the recognition system usually includes a light source, an optical system, a two-dimensional sensor, and an intelligent terminal. As a concrete example of one stacked barcode of the two-dimensional barcode, CODE16K, C
There are ODE49, PDF417, etc., and other specific examples of matrix code are data code, Veri code, Carla code, etc.

Of the two-dimensional bar codes, the one suitable for the optical recording of the present invention is the Carla code.

The Carla Code is Communication for Al
It is a code system named after the initial letter "CALRA" of Language Radical Application, and was invented by Tomioka in 1986.

Next, the compound represented by formula (I) or (II) of the present invention will be explained.

In the general formula (I), R ₁ has 1 to 6 carbon atoms.
Represents a straight-chain or branched alkyl group or a straight-chain or branched hydroxyalkyl group having 3 to 6 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, Hexyl, neopentyl,
Examples include groups such as 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 4-hydroxypentyl, 3-hydroxybutyl, 4-hydroxy-4-methylpentyl and 5,6-dihydroxyhexyl. To be

R ₂ represents a linear or branched alkylene group having 3 to 6 carbon atoms or a linear or branched hydroxyalkylene group having 3 to 6 carbon atoms, and specific examples thereof include trimethylene, tetramethylene, Pentamethylene,
Hexamethylene, 1-methylethylene, 2-methylethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-
Examples thereof include groups such as methyltrimethylene, 3-methylpentamethylene, 2-methylpentamethylene, 2-ethyltrimethylene and 3-hydroxypentamethylene.

The substituent represented by R ₃ is not particularly limited, but a halogen atom, a lower alkyl group and the like are preferable.

Next, R _{11 to} R ₁₇ and X in the compound represented by the general formula (II) will be described in detail.

R ₁₄ is a substituent, and more specifically, a halogen atom, alkyl, aryl, heterocycle, cyano, nitro, hydroxyl, carboxyl, alkoxy, aryloxy, acylamino, alkylamino, anilino,
Ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamide, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocycleoxy, azo, acyloxy, carbamoyloxy, silyl, silyloxy, aryloxycarbonylamino, imide, hetero Ring thio, sulfinyl, phosphonyl, aryloxycarbonyl,
Represents each group such as acyl.

The alkyl group represented by R ₁₁ has 1 to 16 carbon atoms.
A straight chain, branched chain or cyclic alkyl group of alkenyl group, alkynyl group, aryl group, hydroxyl group,
Nitro group, cyano group, halogen atom or other, oxygen atom, nitrogen atom, may be substituted with a substituent linked with a sulfur atom or a carbon atom, for example, methyl, ethyl, propyl, i-propyl, t-butyl, 2-hydroxyethyl,
3-hydroxypropyl, benzyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl, 3 -Carbamoylpropyl, hexyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl, 4- Examples include groups such as nitrobutyl.

R ₁₂ represents an alkylene group, and more specifically, an alkylene group having a main chain of 2 or more carbon atoms (a linear or branched alkylene group, which is a hydroxyl group, a nitro group, a cyano group, a halogen atom or other, Oxygen atom, nitrogen atom,
It may be substituted with a substituent linked by a sulfur atom or a carbon atom, for example, ethylene, 2-methylethylene, 2-fluorotrimethylene, trimethylene, tetramethylene,
Groups such as pentamethylene, hexamethylene, 2-methyltrimethylene, 2-methoxytrimethylene, 1-methyltetramethylene, 1-methylethylene and the like can be mentioned.

R ₁₃ is a hydrogen atom or an alkyl group, and the alkyl group is a linear or branched alkyl group having 1 to 16 carbon atoms, and these are alkenyl group, alkynyl group, aryl group, hydroxyl group, nitro group, carboxyl group. Group, cyano group, halogen atom or other, oxygen atom, nitrogen atom,
It may be substituted with a substituent linked with a sulfur atom or a carbon atom, for example, methyl, ethyl, propyl, t-butyl, 2-hydroxyethyl, 2-carboxyethyl, 3-sulfopropyl, i-propyl, 3- Examples include groups such as (N, N-dimethyl) aminopropyl.

X is --CON (R ₁₅ ) (R ₁₆ ), --COOR ₁₇ , --SO ₂ N
(R ₁₅ ) (R ₁₆ ) is a group selected from the group consisting of
₁₅₎ (R ₁₆₎ and _{-SO 2 N (R 15) (} R 16) are preferred. R ₁₅ and R
Each of ₁₆ is a hydrogen atom, an alkyl group or an aryl group, and more specifically, a hydrogen atom or an alkyl group (having 1 to 16 carbon atoms).
A linear or branched alkyl group, which is an alkenyl group,
Alkynyl group, aryl group, hydroxyl group, nitro group, carboxyl group, cyano group, halogen atom or other, may be substituted with a substituent linked with an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom, for example, methyl,
Ethyl, propyl, t-butyl, 2-hydroxyethyl, 2-
Carboxyethyl, 3-sulfopropyl, i-propyl, 3-
{(N, N-dimethyl) amino} propyl, etc.), aryl groups (aryl groups having 6 to 24 carbon atoms, which are alkyl groups,
Alkenyl group, alkynyl group, aryl group, hydroxyl group, nitro group, cyano group, halogen atom or other,
It may be substituted with a substituent linked by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom, and represents, for example, phenyl, naphthyl, p-methoxyphenyl and the like.

R ₁₇ is an alkyl group or an aryl group,
More specifically, an alkyl group (a linear or branched alkyl group having 1 to 16 carbon atoms, which is a hydroxyl group, a nitro group, a carboxyl group, a cyano group, a halogen atom or others, an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom). May be substituted with a substituent linked with, for example, methyl, ethyl, propyl, t-butyl, 2-hydroxyethyl, 2-carboxyethyl, 3-sulfopropyl, isopropyl, 3-
{(N, N-dimethyl) amino} propyl), aryl groups (aryl groups having 6 to 24 carbon atoms, which are alkyl groups, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, nitro groups, cyano groups, halogens) Or may be substituted with a substituent linked by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom, such as phenyl, naphthyl, p-methoxyphenyl and the like).

Specific examples of the compound (I) or (II) of the present invention are shown below, but the present invention is not limited thereto.

[0090]

[Chemical 5]

[0091]

[Chemical 6]

[0092]

[Chemical 7]

[0093]

[Chemical 8]

[0094]

[Chemical 9]

[0095]

[Chemical 10]

[0096]

[Chemical 11]

[0097]

[Chemical 12]

[0098]

[Chemical 13]

Among the compounds represented by the general formula (I) or (II), (I-1), (I-2), (I-3) and (I-
4), (I-5), (I-12), (II-1), (II-
2), (II-4), (II-7) and (II-11) are preferably used.

The compound represented by the general formula (I) or (II) (hereinafter referred to as the color developing agent of the present invention) is usually used in the form of sulfate, hydrochloride, p-toluenesulfonate, etc.

The color developing agents used in the present invention may be used alone or in combination of two or more depending on the purpose, and the color developing agents disclosed in JP-A-5-188549 and 5-188550. Can also be used together. Furthermore, the color developing agent may be incorporated in the color light-sensitive material. In this case, the light-sensitive material can be processed with an alkaline solution (activator solution) instead of the color developing solution.

The color developing agent of the present invention is used in a concentration of preferably 0.1 to 30 g, more preferably 1 to 10 g per liter of color developing solution.

The color developer is an alkaline agent usually used in developers, such as sodium hydroxide or potassium hydroxide,
Ammonium hydroxide, sodium carbonate, potassium carbonate,
It may contain sodium sulfate, sodium metaborate, borax and the like, and further various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or a development modifier such as citrazic acid. Alternatively, hydroxylamine or sulfite may be contained as a preservative. Further, various defoaming agents and surfactants, and an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide, etc. can be appropriately contained.

The pH of the color developer is usually 7 or more, preferably about 9-13.

The color developing solution used in the present invention includes
As an antioxidant, diethylhydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, if necessary.
Hydroxamic acid, pentose or hexose, pyrogallol-1,3-dimethyl ether and the like may be contained.

In the color developing solution, various chelating agents can be used together as a sequestering agent. For example, as the chelating agent, ethylenediaminetetraacetic acid, aminopolycarboxylic acid such as diethylenetriaminepentaacetic acid, 1-
Organic phosphonic acid such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acid such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as oxalic acid or gluconic acid,
Examples thereof include phosphonocarboxylic acid such as 2-phosphonobutane-1,2,4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compound.

The bleaching process may be carried out simultaneously with the fixing process or may be carried out individually. As the bleaching agent, a metal complex salt of an organic acid is used. For example, polycarboxylic acid, aminopolycarboxylic acid or oxalic acid, iron with an organic acid such as citric acid,
Those in which metal ions such as cobalt and copper are coordinated are used. Among the above-mentioned organic acids, the most preferable organic acid is polycarboxylic acid or aminopolycarboxylic acid. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N
-(Β-Oxyethyl) -N, N ', N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine oxalic acid (or tartaric acid), ethyl ether diamine Examples thereof include tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, and phenylenediamine tetraacetic acid.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

These bleaching agents are preferably 5-450 g /
Use in liters.

As the bleaching solution, in addition to the bleaching agent as described above, a solution having a composition containing sulfite as a preservative can be used if necessary. The bleaching solution may be a solution containing an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and having a composition in which a large amount of a halide such as ammonium bromide is added. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

For the bleaching solution, Japanese Examined Patent Publication Nos. 45-8506 and 45-8836
No. 46-556, 53-9854, Belgium Patent 770,910
Various bleaching accelerators described in JP-A-46-280, JP-A-54-7163 and JP-A-49-42349 can be added.

The pH of the bleaching solution is 2.0 or more, but it is generally 4.0 to 7.0, preferably 4.0 to 6.5, and most preferably 4.0 to 6.0.

The main bleaching agent preferably used in the bleaching solution or the bleach-fixing solution is the second organic acid represented by the following general formula (C).
It is an iron complex salt.

[0114]

[Chemical 14]

In the formula, A _{1 to} A ₄ may be the same or different and each represents —CH ₂ OH, —COOM or —PO ₃ M ₁ M ₂ . M, M ₁ ,
M ₂ each represents a hydrogen atom, an alkali metal or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.

The compound represented by formula (C) is described in detail below.

Incidentally, A _{1 to} A ₄ in the formula are Japanese Patent Application No. 1-260628.
Since it has the same meaning as A _{1 to} A ₄ described on page 12, line 15 to page 15, line 3, detailed description thereof will be omitted.

In the present invention, in the bleaching solution or the bleach-fixing solution, a ferric iron complex salt of the following compound can be used as the bleaching main agent, in addition to the iron complex salt of the compound represented by the general formula (C).

[A′-1] Ethylenediaminetetraacetic acid [A′-2] trans-1,2-cyclohexanediaminetetraacetic acid [A′-3] Dihydroxyethylglycinic acid [A′-4] Ethylenediaminetetrakismethylenephosphonic acid [A′-4] A'-5] Nitrilotrismethylenephosphonic acid [A'-6] diethylenetriaminepentakismethylenephosphonic acid [A'-7] diethylenetriaminepentaacetic acid [A'-8] ethylenediaminedioltohydroxyphenylacetic acid [A'-9] hydroxy Ethyl ethylenediamine triacetic acid [A'-10] ethylenediamine dipropionic acid [A'-11] ethylenediamine diacetic acid [A'-12] hydroxyethyliminodiacetic acid [A'-13] nitrilotriacetic acid [A'-14] nitrilo Tripropionic acid [A'-15] triethylene ether Tramine hexaacetic acid [A′-16] ethylenediaminetetrapropionic acid [A′-17] β-alaninediacetic acid The ferric organic acid complex salt is added in an amount of 0.01 mol to 2.0 mol per liter of the bleaching solution or the bleach-fixing solution. It is preferably contained in the range, more preferably in the range of 0.05 to 1.5 mol / liter.

The bleaching solution, the bleach-fixing solution, and the fixing solution include imidazole and its derivatives described in JP-A-64-295258, compounds represented by the general formulas [I] to [IX] described in the same publication, and their compounds. By containing at least one of the exemplified compounds, it is possible to exert an effect on promptness.

In addition to the above-mentioned accelerator, JP-A-62-123459 51
-Exemplary compounds described on page 115 and JP-A-63-17445, 22-2
Exemplified compounds described on page 5, JP-A Nos. 53-95630 and 53-2842
The compounds described in No. 6 and the like can be used as well.

In addition to the above, the bleaching solution or the bleach-fixing solution may contain halides such as ammonium bromide, potassium bromide and sodium bromide, various fluorescent whitening agents, defoaming agents or surfactants. it can. The bleaching treatment time using the bleaching solution of the present invention is preferably within 1 minute, particularly preferably 15 seconds to 45 seconds.

As the fixing solution, those having a generally used composition can be used. As the fixing agent, a compound which reacts with silver halide to form a water-soluble complex salt as used in a general fixing process, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate,
Typical examples thereof include thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g / liter or more, which can be dissolved, but generally 70 to 250 g / liter. A part of the fixing agent can be contained in the bleaching solution, and conversely, a part of the bleaching agent can be contained in the fixing solution.

The bleaching solution and the fixing solution include boric acid, borax,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Various pH of potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
It may contain a buffering agent, an antifoaming agent, or a surfactant. Further, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, hardening agents such as water-soluble aluminum salts, An organic solvent such as methanol, dimethylformamide, dimethylsulfoxide or the like may be appropriately contained.

The fixing solution is used at a pH of 3.0 or more, and is generally used at 4.5-10, preferably 5-9.5, and most preferably 6-9.

As the bleaching agent used in the bleach-fixing solution, the metal complex salts of the organic acids described in the bleaching step can be mentioned, and preferably the compound and the concentration in the processing solution are the same as in the bleaching step.

As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of an iron diamine tetraacetate (III) complex salt bleaching agent and a halide such as ammonium bromide other than the above silver halide fixing agent are added in a small amount, or conversely, a halogenating agent such as ammonium bromide is used. It is also possible to use a special bleach-fixing solution having a composition containing a large amount of a compound added. Examples of the halides include ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide,
Ammonium iodide or the like can also be used.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the fixing agents described in the above fixing processing step. The concentration of the fixing agent and the pH buffer and other additives which can be contained in the bleach-fixing solution are the same as those in the fixing processing step.

The pH of the bleach-fixing solution is used at 4.0 or more, but is generally 5.0 to 9.5, preferably 6.0 to 8.5.
And most preferably 6.5 to 8.5.

[0130]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example 1 (Production of Support) 100 parts by weight of cellulose triacetate having a degree of acetylation of 61.4% and 15 parts by weight of triphenyl phosphate were completely dissolved in 738 parts of a mixed solvent of methylene chloride-methyl alcohol, and the following organic dye was prepared. (A), (b),
A small amount of (c) was added to obtain a dope.

[0132]

[Chemical 15]

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

Co-adhered γ-Fe ₂ O ₃ (coercive force: 610 Oe BET surface area 35 m ² / g, major axis length 0.23 μm, acicular ratio 7) 100 parts by weight 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 liquid was taken and thoroughly mixed with a dope having the following composition by 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 performed on a rotating 6 m endless stainless steel band. The cellulose triacetate base containing magnetic particles and having a thickness of 110 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 the support was 670 Oe. or,
The optical transmission density was 0.10.

On the surface of the above base, gelatin 20 g and water 40
g, salicylic acid 20 g, methanol 600 g, acetone 1200
and 200 g of methylene chloride were applied and dried.

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 (Preparation of silver halide emulsion) An octahedral silver iodobromide emulsion having mainly (111) faces was prepared by the double jet method according to the method described in JP-A-60-138538.

The resulting emulsion had an average grain size of 1.05 μm, a distribution of 9%, a core silver iodide content of 30 mol%, a shell silver iodide content of 0.1 mol%, and an average iodide content. The silver content is 9 mol% and the relative standard deviation of silver iodide content between emulsion grains is 17
%, The ratio of the (111) plane was 98%. This emulsion is Em-
Called A.

(Sensitization of Silver Halide Emulsion) Em-A prepared as described above was sensitized as follows. To the emulsion
At 60 ° C, the sensitizing dye described below was added per mol of silver halide, and 20 minutes after that, sodium thiosulfate 1.5 x 1 was added.
After adding 0 ^-6 mol and N, N-dimethylselenourea 5.0 × 10 ^-7 mol and aging for 60 minutes, further chloroauric acid 5.0 × 10
A mixed aqueous solution of ^-7 mol and 1.0 × 10 ^-4 mol of ammonium thiocyanate was added and aging was continued for 30 minutes.

Next, after completion of aging, stabilizer ST was added to each.
-1 and the inhibitor AF-1 per 1 mol of silver halide,
500 mg and 10 mg were added respectively.

(Preparation of Silver Halide Color Photosensitive Material) Sample 101, which is a multilayer color photosensitive material, was prepared by providing each layer having the following composition on the transparent support.

[0146] The coating amount (Composition of photosensitive layer) The silver halide and colloidal silver, the amount expressed in terms of metallic silver in the unit of g / m ^2, also, the coupler, the additive g / m ² The amount expressed in units is also shown for the sensitizing dye in terms of the number of moles per mole of silver halide in the same layer.

Sample 101 First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High Boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: low-sensitivity red sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye ( SD-2) 1.4 × 10 ^-4 sensitizing dye (SD-3) 1.4 × 10 ^-5 sensitizing dye (SD-4) 0.7 × 10 ^-4 cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) ) 0.04 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 4th layer: Medium-sensitive red sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD- 1) 1.7 × 10 ^-4 sensitizing dye (SD-2) 0.86 × 10 -4 sensitizing dye (SD-3) 1.15 × 10 -5 sensitizing dye (SD 4) 0.86 × 10 ^-4 Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.013 DIR compound (D-1) 0.02 High boiling solvent (OIL-1) 0.16 Gelatin 0.79 Fifth Layer: High Sensitivity Red Sensitive layer Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-1) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.2 × 10 ⁻⁵ Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Sixth layer: intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 7th layer: low-sensitivity green-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta Coupler (M-1) 0.14 Magenta Coupler (M-2) 0.14 Colored Magenta Coupler (CM-1) 0.06 High Boiling point solvent (OIL-4) 0.34 Gelatin 0.70 Eighth layer: Intermediate layer Gelatin 0.41 Ninth layer: Medium-sensitive green sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-6) 1.2 × 10 ^-4 Sensitizing dye (SD-7) 1.2 × 10 ^-4 Sensitizing dye (SD-8) 1.2 × 10 ^-4 Magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler ( CM-1) 0.017 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 10th layer: high sensitivity green sensitive layer Silver iodobromide emulsion D 0.95 Sensitization Dye (SD-6) 7.1 × 10 ^-5 Sensitizing Dye (SD-7) 7.1 × 10 ^-5 Sensitizing Dye (SD-8) 7.1 × 10 ^-5 Magenta Coupler (M-1) 0.09 Colored Magenta Coupler (CM) -1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow Id silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 12th layer: Low sensitivity blue sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling point solvent (OIL-2) 0.42 Gelatin 1.40 13th layer: High sensitivity blue sensitive layer Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9 ) 8.0 × 10 ^-5 Sensitizing dye (SD-11) 3.1 × 10 ^-5 Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide Emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 High boiling solvent (OIL-1) 0.07 High Point solvent (OIL-3) 0.07 Gelatin 0.65 Fifteenth 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 In addition to the above composition, coating aid Su-1, dispersion aid S
u-2, viscosity modifier, hardener H-1, H-2, stabilizer S
T-1, antifoggant AF-1, two kinds of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and preservative DI-1 were added.

The emulsions used in the above samples are as follows. The average particle size is shown as a particle size converted into a cube.
Further, each emulsion was optimally subjected to gold and sulfur sensitization.

[0149]

[Table 1]

Emulsions F to M each contain 1 of the metals listed in the remarks column.
Containing × 10 ^-5 mol / 1 mol Ag, iodine or PTTS during grain formation
(Paratoluenethiosulfonic acid) is added.

The samples were simultaneously coated with a multi-slide hopper type coater at the first time from the first layer to the eighth layer, and at the second time onto the ninth to 16th layers. Sample 101 had a silver coating amount of 6.25 g / m ² , a dry film thickness of 18 μm, and a specific photographic sensitivity of 420. This sample is designated as a.

[0152]

[Chemical 16]

[0153]

[Chemical 17]

[0154]

[Chemical 18]

[0155]

[Chemical 19]

[0156]

[Chemical 20]

[0157]

[Chemical 21]

[0158]

[Chemical formula 22]

Separately, the support has a thickness not containing magnetic particles.
Sample b was prepared in the same manner as sample a except that the film was changed to a 110 μm triacetyl cellulose film.

For samples a and b, the usual 135
Cut to size of 24 sheets, stored in a film cartridge, and stored in a polypropylene closed container at 25 ° C and relative humidity 55
Sealed under an atmosphere of%.

Each of the cameras (Konica Big Mini NE
The test pattern was photographed. This test pattern is a pattern obtained by statistically processing the exposure level, color balance, etc. of the scene shot by general users and averaging it. It is designed so that the development processing level of can be reproduced.

(Evaluation of Development Processing and Processing Variation) The following development processing line A was prepared for one series and B was prepared for two series, and as shown in Table 2 below, samples were combined and continuously processed, and a so-called running test was carried out. I made a rotation.

The development processing line B is the same as the development processing line A except that the color developing agent in the color developing solution and the color replenishing solution described later is changed to II-25 of the present invention. (Processing process) Processing time Temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 780cc Bleach 45 seconds 38 ± 2.0 ℃ 150cc Fixed 1 minute 30 seconds 38 ± 2.0 ℃ 830cc Stability 60 seconds 38 ± 5.0 ℃ 830cc Dry 1 minute 55 ± 5.0 ℃ － * Replenishment amount is the value per 1m ² of photographic material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer and color replenisher (A ) Developer replenisher Water 800cc 800cc Potassium carbonate 30g 35g Sodium hydrogencarbonate 2.5g 3.0g Potassium sulfite 3.0g 5.0g Sodium bromide 1.3g 0.4g Potassium iodide 1.2mg- Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate) 2.3 × 10 ^-2 mol 3.2 × 10 ^-2 mol Diethylenetriamine Pentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Water was added to make 1 liter, and potassium hydroxide or 20% sulfuric acid was used to adjust the color developer to pH 10.06 and the replenisher to pH 10.18.
Adjust to.

Bleaching solution and bleach replenishing solution Bleaching solution Replenishing solution Water 700cc 700cc 1,3-Diaminopropanetetraacetic acid (III) iron ammonium 125g 175g Ethylenediaminetetraacetic acid 2g 2g Sodium nitrate 40g 50g Ammonium bromide 150g 200g Glacial acetic acid 40g 56g Water Then, the bleaching solution is adjusted to pH 4.4 and the replenisher is adjusted to pH 4.0 using ammonia water or glacial acetic acid.

Fixing Solution and Fixing Replenishing Solution Fixing Solution Replenishing Solution Water 800 cc 800 cc Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid was used as the fixer at pH 6.2,
Adjust the replenisher to pH 6.5 and add water to make 1 liter.

Stabilizer and stable replenisher water 900 cc p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzisothiazolin-3-one 0.1 g siloxane (UC-L-77 ) 0.1g Ammonia water 0.5cc Add water to make 1 liter, then use ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

The processing variation was evaluated by the relative sensitivity value at 1/2 rotation and 1 rotation when the sensitivity value of the green sensitive layer at the start of the running test was 100 for each sample. The sensitivity value was determined according to a conventional method.

(Evaluation of Image Preservability) Running Test 1
This sample is 50 ℃ ・ 80% RH in the dark when rotating.
After storage for 3 days under the conditions described above, the fluctuation range (%) of the density of the green sensitive layer
It was evaluated by. The fluctuation range was calculated at the point where the density of the green sensitive layer of the sample before forced deterioration was 1.0 (the density before forced deterioration was 100
And).

The above results are summarized in Table 2.

[0172]

[Table 2]

As is clear from Table 2, in the present invention, magnetic recording is possible, but processing variability and image storability are excellent.

Example 2 A camera incorporating a light emitting diode (GaAsP) having an emission maximum at 655 nm and a magnetic recording head shown in FIG. 1 was used to photograph a test pattern using the above sample and to perform optical recording by the light emitting diode (see FIG. 2) was performed.

For comparison, the running test of A was also conducted in the case of b which was not optically recorded.

The same development processing lines A and B as in Example 1 were used.
One series was prepared for each, and a running test was performed in the same manner as in Example 1 using the photographed and optically recorded samples a and b. The results are shown in Table 3.

[0177]

[Table 3]

As is clear from Table 3, in the present invention, optical recording is possible, but processing variability and image storability are excellent.

Example 3 Samples 101 and 102 were film width 28 mm, one side perforation type, and the photographing screen area was 20 mm in length and 36 in width.
It was cut into 24 shots in mm and stored in a compact size with a height of 7 mm lower. The Konica Big Mini NEO was remodeled by attaching an adapter for a cartridge and a 20m x 36mm picture frame, and photographed the test pattern.

A development test was conducted in the same manner as in Example 1 by using the developing treatments A and B. However, film width 28 mm
The number of samples was 25% and the number of samples with a film width of 35 mm was 75%. The results are as follows.

Sample No. Development Treatment 1 / 2R 1R b (Comparison) A 92 90 b (Invention) B 96 95 a (Invention) B 95 94 As is apparent from the above results, the processing method of the present invention Then, it can be seen that the development processing level is stable even if small format films are mixed.

Example 4 (Production of Polyethylene Naphthalate Support) 100 parts by weight of a commercially available polyethylene-2,6-naphthalate polymer and 2 parts by weight of TINUVIN326 (manufactured by Ciba Geigy) as an ultraviolet absorber were dried by a conventional method. After that, it was melted at 300 ° C, extruded from a T-die, longitudinally stretched 3.3 times at 140 ° C, then laterally stretched 3.3 times at 130 ° C, and further heat set at 250 ° C for 6 seconds to obtain a thickness. A film having a thickness of 80 μm was obtained. Next, a magnetic layer and an undercoat layer were provided in the same manner as the support of Example 1. Further, heat treatment was carried out at 55 ° C. for 2 days to enhance curl resistance.

Sample c was prepared by coating the silver halide photosensitive layer of sample a of Example 1 on the side of the support opposite to the magnetic layer.

Table 4 shows the results of evaluation of processing stability and image storability by treating the developers A and B in the same manner as in Example 1.

[0185]

[Table 4]

As is apparent from Table 4, the effect of the present invention is large even with the polyethylene naphthalate support.

[0187]

According to the present invention, it is possible to provide a color photographic image excellent in processing stability and image storability while allowing magnetic recording.

[Brief description of drawings]

FIG. 1 is a schematic view of a camera incorporating a light emitting diode.

FIG. 2 is a schematic diagram of a film on which dot matrix optical recording is performed.

[Explanation of symbols]

 1 Optical Recording Camera 2 Light Emitting Diode 3 Magnetic Recording Head 4 Buffer Member 10 Camera Body 11 Camera Back Cover

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03C 7/00 510

Claims (4)

[Claims] 1. A transparent support having on one side thereof a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer, and a magnetic layer on the other side. In a color photographic image forming method using a silver halide color photographic light-sensitive material having a recording layer, the color photographic light-sensitive material contains a developing solution containing at least one of compounds represented by the following general formulas (I) and (II). And a color photographic image forming method. [Chemical 1] [In the formula, R ₁ represents a linear or branched alkyl group having 1 to 6 carbon atoms or a linear or branched hydroxyalkyl group having 3 to 6 carbon atoms, and R ₂ represents a linear or branched alkyl group having 1 to 6 carbon atoms or It represents a branched alkylene group or a linear or branched hydroxyalkylene group having 3 to 6 carbon atoms. R ₃ represents a substituent, and m represents an integer of 0-4. When m is 2 or more, a plurality of R _3's may be the same or different. ] [Chemical 2] [In the formula, R ₁₁ represents an alkyl group, R ₁₂ represents an alkylene group whose main chain has 2 or more carbon atoms, and R ₁₃ represents a hydrogen atom or an alkyl group. R ₁₄ represents a substituent, and n represents an integer of 0-4. When n is 2 or more, a plurality of R _14's may be the same or different. X is _{-CON (R 15) (R 16} ), - COOR 17 or -SO ₂ N (R ₁₅₎ represents the (R _16). R ₁₅ and R ₁₆ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. R ₁₇ represents an alkyl group or an aryl group. ] 2. A silver halide color photographic light-sensitive material having, on one side on a transparent support, a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer. In the method for forming a color photographic image using, the color photographic light-sensitive material is one in which information at the time of photographing is optically recorded outside the photographing screen, and at least one of the compounds represented by the general formulas (I) and (II). A method for forming a color photographic image, characterized in that the color photographic image is processed with a development processing solution containing 3. A silver halide color photographic light-sensitive material having, on one side on a transparent support, a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer. In the method for forming a color photographic image using, the roll width of the color photographic light-sensitive material is 20 to 35 mm, the screen area for photography is 300 to 700 mm ² , and the compound represented by the general formula (I) or (II). A color photographic image forming method, wherein the color photographic image is formed by processing with a developing solution containing at least one of the above. 4. The color photographic image forming method according to claim 1, 2 or 3, wherein the transparent support is made of a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main components.