JPH04198931A - Method and device for image forming - Google Patents

Abstract

PURPOSE:To successively bring the exposed part of a photosensitive material into contact with developer before finishing the exposure of all the area of the photosensitive material and to prevent image density from changing between a leading edge and a trailing edge along the carrying direction of the photosensitive material by making the main scanning direction in scanning exposure a direction orthogonally crossed with the carrying direction of the photosensitive material. CONSTITUTION:The main scanning with a laser light beam is performed in the direction orthogonally crossed with the carrying direction A of the photographic photosensitive material 24 at a developing stage, and subscanning is performed in parallel with the carrying direction of the material 24. Then, a subscanning speed and the carrying speed of the material 24 at the developing stage are made substantially equal and further a time from scanning exposure till the start of developing is set <=20 seconds. Thus, the material 24 to which the scanning exposure has been performed is immediately developed to form the image and the density in the image is stably controlled.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method and apparatus for forming an image by exposing a silver halide photographic material to light by scanning exposure. More specifically, the present invention relates to an image forming method and apparatus that can provide a high-quality image with uniform density by performing a developing process immediately after scanning exposure. (Prior Art) Many techniques are known in which images are formed by scanning and exposing silver halide black-and-white photographic materials using gas lasers or semiconductor lasers (for example, Japanese Patent Laid-Open No. 61-245152,
(See No. 61-273534, No. 62-192736, No. 63-55541, No. 63-287849, and Japanese Unexamined Patent Publication No. 2037/1999). These techniques relate to a technique of performing high-intensity short-time exposure of lo-4 seconds or less using a scanning light source, and then rapidly processing with a black-and-white developer. Furthermore, a method of obtaining a color image by performing scanning exposure on a silver halide color photographic light-sensitive material is conventionally known (see, for example, Japanese Patent Publication No. 48018/1983). Recently, Japanese Patent Application Laid-open Nos. 61-137149 and 63-1
59840, a photosensitive material consisting of three silver halide emulsion layers each having a different maximum spectral sensitivity in the infrared region was scanned and exposed using a semiconductor laser, and then subjected to Eastman Kodunk EP2 processing (color development 33°). C210 seconds) to obtain a color image is disclosed. JP-A No. 63-18346 discloses that a photosensitive material consisting of three silver halide emulsion layers having different maximum spectral sensitivities in the visible region is scanned and exposed using a laser in the visible region, and then processed at 38° C. for 210 seconds. A method for obtaining a color image is disclosed. In all of these examples, the time required for color development processing is relatively long. Also, JP-A-61-233732 and JP-A-62-2950
No. 48 discloses that after scanning a silver dye bleaching silver halide color photographic light-sensitive material in the same manner as above, the first development (black and white development) of the silver dye bleaching process is carried out at 40°C for 20 seconds. A method is disclosed. On the other hand, developing color photographic materials as quickly as possible has always been an important issue from the viewpoint of workability. The easiest method for rapidly developing a photosensitive material is to increase the processing temperature to activate the reaction, and this method has already been used to shorten the processing time. In response to this, in recent years, many techniques have been proposed for rapid development using high silver chloride emulsions (for example, International Patent Publication No. WO37-04534, Japanese Patent Application Laid-Open No. 58-95353).
No. 59-232342 and No. 60-19140). These technologies process photographic materials using so-called high-silver chloride emulsions with a high silver chloride content with a color developing solution that does not substantially contain sulfite ions or Hensyl alcohol, allowing for color development that previously required more than 3 minutes. The developing time is shortened to 1 minute or less. Similarly, JP-A-1-19
Publication No. 6044 discloses a technology for improving the storage stability of white backgrounds and color images by using a high silver chloride emulsion and using a color development time of 25 seconds or less and a total time in liquid of all processing steps of 2 minutes or less. is disclosed. As mentioned above, various methods are known for forming black-and-white images or color images by scanning exposure, and methods for processing color photographic materials in a very short time. After scanning exposure using a light source,
When an experiment was conducted to form an image by immediately immersing the photosensitive material in a developer, a difference was found in the image density between the front and rear parts of the photosensitive material during scanning exposure, and the extent of this discrepancy could be determined by repeating the experiment. It turned out to be variable. Similarly, the present inventor developed a color photographic light-sensitive material having three silver halide emulsion layers having different spectral sensitivities, and after scanningly exposing it using a plurality of laser light sources corresponding to the spectral sensitivities of the light-sensitive material, immediately applied a color developer. When an experiment was conducted in which a color image was formed by immersing the photosensitive material in the photosensitive material, it was found that there was a difference in color balance between the front and rear parts of the photosensitive material during scanning exposure. In this case as well, the degree of deviation in color balance varied from experiment to experiment, which turned out to be a serious problem in practice. Comparing the above-mentioned density fluctuations in black and white photographic materials and color balance deviations in color photographic materials, the latter is easier to visually recognize (therefore, the problem seemed to be more important. Publication No. 18547 describes the deterioration of the latent image immediately after exposure when a photosensitive material containing high silver chloride is subjected to scanning exposure at high illuminance for a short period of time using a method in which silver halide emulsion grains have a localized phase with a high silver bromide content. According to this publication, the problem of latent image deterioration becomes apparent when the time from scanning exposure to the start of development processing is less than 60 seconds, and as a countermeasure, technology for improving the performance of photosensitive materials is proposed. Although this technique can improve the above-mentioned problems, the inventor's experiments have shown that it is time-consuming to study the method for preparing silver halide emulsions, and that it is difficult to develop color development. The degree of improvement becomes insufficient if the time or method changes, and furthermore, even though it has been improved, the deterioration tendency of the latent image that remains changes depending on the environmental conditions, so the improvement is insufficient for practical purposes. (Objective of the Invention) The first object of the present invention is to reduce the density in the image when an image is formed by immediately developing a photographic light-sensitive material that has been subjected to scanning exposure. It is an object of the present invention to provide an image forming method and an apparatus therefor that can stably control the image forming process.A second object of the present invention is to immediately develop a color photographic material that has been subjected to scanning exposure to form a color image. An object of the present inventor is to provide a color image forming method and an apparatus therefor that can stably control the color balance within an image when As a result of our research, we have found the following solution: (1) A halogenated emulsion layer consisting of silver halide grains with a silver chloride content of 95 mol% or more on a support. After scanning and exposing the silver photographic light-sensitive material using a laser beam having a wavelength corresponding to the color sensitivity of the silver halide emulsion,
In an image forming method for obtaining an image by drying after development processing, the laser beam is main-scanned in a direction perpendicular to the photosensitive material transport direction in the development processing step, sub-scanned in parallel to the photosensitive material transport direction, and the sub-scanning speed is An image forming method characterized in that the transport speed of the photosensitive material in the developing step is substantially the same, and the time from scanning exposure to the start of development is within 20 seconds. (2) an exposure section that scans and exposes a photographic light-sensitive material having a silver halide emulsion layer on a support using a laser beam corresponding to the color sensitivity of the silver halide emulsion; An image forming apparatus comprising: a means for generating a laser beam; a means for controlling the intensity and/or irradiation time of the laser arrow based on image information; a means for guiding the laser beam to the photosensitive material; means for scanning the photosensitive material with a laser beam, the laser beam is main scanned in a direction perpendicular to the photosensitive material conveyance direction in the development processing step, sub-scanned in parallel to the photosensitive material conveyance direction, and has a sub-scanning speed. An image forming apparatus characterized in that the transport speed of the photosensitive material in the development processing step is substantially equal to the transport speed of the photosensitive material in the development processing step, and the time from scanning exposure to the start of development is within 20 seconds. According to the present invention, since the main scanning direction of the scanning exposure is perpendicular to the direction in which the photosensitive material is transported, the exposed portions of the photosensitive material can be sequentially brought into contact with the developer before the exposure of the entire area of the photosensitive material is completed. I can do it. Then, the exposed photosensitive material is
By starting the development process by bringing the silver halide emulsion into contact with the developer within 0 seconds, the latent image on the silver halide grains of the silver halide emulsion in the light-sensitive material will not change, and especially the front edge along the transport direction The density of the image does not change at the rear end, and the color balance does not change to i in the case of multilayer color brightening materials. The photographic material in the present invention may be a black and white (B/W) photographic material or a color photographic material, but it is effective as a photographic material having a high silver chloride emulsion. This is particularly effective for color photographic materials. Here, examples of the photosensitive material include photosensitive materials for color printing such as color paper, color reversal paper, and direct positive photosensitive materials, color photosensitive materials for copying, black-and-white photographic paper, and black-and-white transmission type photosensitive materials. When exposing a color photographic material according to the present invention, a plurality of laser beams having wavelengths corresponding to the spectral sensitivity of the color photographic material are used. The plurality of laser beams are then converged into one beam and guided to the photosensitive material. The reason why a good color image with no deviation in color balance within the image can be obtained according to the present invention is not clear, but it can be estimated as follows. It is known that in photographic materials made of the above-mentioned high silver chloride emulsion, the so-called latent image immediately after exposure is unstable, and the finished image density tends to change depending on the time from exposure to the start of color development processing. It is being This provides the effect of not causing density fluctuations, which cannot be expected with light-sensitive materials made of silver chlorobromide emulsions or silver iodobromide emulsions. Particularly in the case of color photographic materials, it is thought that the magnitude of this variation does not match among a plurality of silver halide photographic emulsion layers having different photosensitivity, resulting in a shift in color balance. This phenomenon becomes more pronounced as the exposure conditions are higher and shorter.
Moreover, the longer the color development time, the more noticeable the problem was. Therefore, when a light-sensitive material made of a high silver chloride emulsion, especially a color photographic light-sensitive material, is exposed to high-intensity, short-time exposure such as scanning exposure using a laser beam, and then immediately subjected to color development, the problem arises as the color balance shifts. It will be easy. A deviation in color balance is easily recognized visually, and is therefore considered to be more likely to cause problems than in the case of black-and-white or monochromatic light-sensitive materials. In scanning exposure using a laser light source, the laser beam is scanned while rotating a polygon mirror, and at the same time the photosensitive material is exposed while moving in a direction perpendicular to the main scanning direction of the laser beam, that is, in the sub-scanning direction, so it is difficult to expose one color image. It takes several seconds to several tens of seconds. Therefore, if the entire exposed photosensitive material is instantaneously immersed in a color developing solution, the time from exposure to color development will be different between the front and rear parts in the sub-scanning direction, resulting in the above-mentioned deviation in color ratio. easy. At this time, if the time from exposure to color development is sufficiently long, such as 60 seconds or more, the rate of deterioration of the latent image formed on the silver halide grains will probably slow down and the image will become apparently stable. but,
According to experiments conducted by the present inventors, it has been found that the convergence level changes depending on the environmental conditions as a result of the time required for the above-mentioned apparent stabilization and fluctuations. Therefore, in order to stably obtain good images, day-to-day fluctuations cannot be resolved by simply waiting until the rate of deterioration of the latent image slows down before developing. In solving this problem, the present invention has investigated a method of shortening the time from scanning exposure to development as much as possible, and instead making the time from scanning exposure to the start of development substantially constant, resulting in significant improvements. This effect has been achieved. In addition, the shorter the development time, the smaller the deterioration of the latent image mentioned above.
It has been found that the problem is alleviated if the time is preferably 60 seconds or less, more preferably 20 seconds or less. In order to accurately equalize the time from exposure to the start of development, it is preferable to match the photosensitive material feeding speed in the sub-scanning direction and the photosensitive material feeding speed in the developing processor, but according to experiments conducted by the present inventor, this is not always the case. It is not necessary to make them match, and as long as the difference in time from exposure to the start of color development in the leading and trailing areas is within 20%, preferably within 10%, results in which the deviation in color balance is acceptable have been obtained. As the "development treatment" performed between exposure and drying, processing such as development-depositing one water wash, bath development fixing one water washing, development-demolition one stabilization, etc. can be carried out. Scanning exposure light sources that can be used in the present invention include He-Ne laser, argon laser, He-Ne laser,
Gas lasers such as Cd lasers, semiconductor lasers, L
There is a method of combining an ED, a semiconductor laser, and a nonlinear optical material to use the second harmonic of the laser oscillation wavelength and its sum frequency. Examples of how to use these scanning exposure light sources in combination with color development of light-sensitive materials are shown in the following table. However, the present invention is not limited to these implementations BIi. That is, the combination of the scanning exposure light sources to be used, the relationship with the photosensitivity of the photosensitive material, the number of scanning exposure light sources to be used, etc. can be arbitrarily selected. For example, JP-A-61-
As disclosed in No. 233732, when a photosensitive material capable of forming black images in addition to yellow, magenta, and cyan images is used, it is also possible to use four types of scanning exposure light sources. (Hereinafter, blank space) The scanning exposure apparatus of the present invention may use any known method, but preferably JP-A No. 1-097939,
Apparatuses disclosed in Japanese Patent No. 157749, Japanese Publication No. 2-074942, etc. can be used. In the present invention, it is preferable to use a jet stirring means to stir the treatment liquid, and various known methods can be used as the jet stirring means. Preferably JP-A-62-18
The method disclosed in Japanese Patent Application No. 3460 and Japanese Patent Application No. 2-268534 can be used. As the silver halide used in the present invention, silver chloride, silver bromide, silver (iod)chlorobromide, silver iodobromide, etc. can be used, but especially for the purpose of rapid processing, silver iodide can be used substantially. The silver chloride content is 95 mol% or more, more preferably 98 mol%.
It is preferable to use the above silver chlorobromide or silver chloride emulsion. In the photosensitive material according to the present invention, a hydrophilic colloid layer is incorporated into a hydrophilic colloid layer for the purpose of improving image sharpness, etc.
．． 337.49 OA2 specification, pages 27 to 76, dyes that can be decolorized by processing (especially oxonol dyes) are used in such a manner that the optical reflection density of the light-sensitive material at 680 nm is 0.70 or more. Titanium oxide surface-treated with a di- to tetrahydric alcohol (e.g. trimethylolethane) is added to the water-resistant resin layer of the support.
It is preferable to contain at least 14% by weight (more preferably at least 14% by weight). Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0.277.589A2 together with a coupler. Particularly preferred is the combination with a pyrazoloazole coupler. That is, compounds that chemically bond with aromatic amine-based developing agents remaining after color development processing to produce chemically inert and substantially colorless compounds and/or aromatic amines remaining after color development processing. For example, the use of a compound that chemically combines with the oxidized form of a color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly to reduce residual color development in the film during storage after processing. This is preferable in order to prevent staining and other side effects caused by the formation of colored pigments due to the reaction between the main drug or its oxidized product and the coupler. Furthermore, in order to prevent various types of mold and bacteria that propagate in the hydrophilic colloid layer and cause image deterioration, the photosensitive material according to the present invention is coated with an anti-mold agent as described in JP-A No. 63-271247. It is preferable to add The support used in the photosensitive material according to the present invention may be a white polyester support for display or a support in which a layer containing a white pigment is provided on the support on the side having a silver halide emulsion layer. In order to further improve sharpness, it is preferable to coat an antihalation layer on the side of the support coated with the silver halide emulsion layer or on the back side. In particular, it is preferable to set the transmission density of the support in the range of 0.35 to 0.8° so that the display can be viewed in both reflected light and transmitted light. The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or high illuminance short time exposure, and in the latter case in particular, a laser scanning exposure method in which the exposure time for one pixel is shorter than 10<-4> seconds is preferred. Further, during exposure, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. This eliminates optical color mixture and significantly improves color reproducibility. The exposed color photosensitive material may be subjected to color development processing, but for the purpose of rapid processing, it is preferable to carry out bleach-fixing processing after color development. In particular, when the high silver chloride pore side is used, the pH of the bleach-fix solution is preferably about 7.5 or less, more preferably about 7 or less, for the purpose of promoting desilvering. Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the photosensitive material of the present invention, and processing methods and processing materials applied to process this photosensitive material. As additives, the following patent publications,
In particular, European patent EP 0,355.66042 (patent application No. 1
-107011) those described in the specification are preferably used. 1 1 2 In addition, as a cyan coupler, in addition to the diphenylimidazole uncoupler described in JP-A-2-33144, the 3-hydroxypyridine cyan coupler described in European Patent EP 0,333.185A2
Among them, 4 of couplers (42) listed as specific examples
Particularly preferred are equivalent couplers with a chlorine leaving group to make them di-equivalent, couplers (6) and (9), and cyclic active methylene cyan couplers described in JP-A-64-32260 (among them, Particular preference is given to the coupler example 3.8.34 listed as an example). The color photographic material used in the present invention is preferably subjected to color development, bleach-fixing, and water washing treatment (or stabilization treatment). Bleaching and fixing may be performed in one bath or in separate baths. It's okay. Furthermore, one-bath development intensification may be used. The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. D-IN, N-diethyl-p-phenylenediamine D-24-amino-N, N-diethyl-3-methylaniline D-34-amino-N-(β-hydroxyethyl)-N
-Methylaniline D-44-amino-N-ethyl-N-(β-hydroxyethyl)aniline D-54-amino-N-ethyl-N-(β- and droxyethyl)-3-methylaniline D-64-amino -N-
Ethyl-N-(3-hydroxypropyl)-3-methylaniline D-74-amino-N-ethyl-N-(4-hydroxybutyl)-3-methylaniline D-84-amino-N-
Ethyl-N-(β-methanesulfonamidoethyl)-3
-Methylaniline D-94-Amino-N,N-diethyl-3-(β-hydroxyethyl)aniline D-104-Amino-N-ethyl-N-(β-methoxyethyl)-3methyl-aniline D-114 -amino-N-(β-ethoxyethyl)-N
-Ethyl-3-methylaniline D-124-amino-N-(3-carbamoylbutyl-N-n-propyl-3-methylaniline D-134-amino-N-(4-carbamoylbutyl-
N-n-propyl-3-methylaniline D-14N-(4-amino-3-methylphenyl)-3
-Hydroxypyrrolidine D-15N-(4-amino-3-methylphenyl)=3
-(Hydroxymethyl)pyrrolidine D-16N-(4-
Amino-3-methylphenyl)=3-pyrrolidinecarboxamide Among the above p-phenylenediamine derivatives, particularly preferred are exemplary compounds D-5, D-6, D-7, D-8 and D-
It is 12. Further, salts of these P-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, P-)luenesulfonic acid, etc. may also be used. The amount of the aromatic primary amine developing agent used is 11
The amount per mole is preferably 0.002 mol to 0.2 mol, more preferably 0.005 mol to 0.1 mol. In carrying out the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, "substantially free" means preferably 2 dl11 or less, more preferably 0.5 I11/f or less benzyl alcohol. alcohol concentration, most preferably no Hensyl alcohol. More preferably, the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency. Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" preferably means a sulfite ion concentration of 3.0 x 10 -' mol/l or less, and most preferably no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded. The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties. The expression "substantially not containing hydroxylamine" as used herein means preferably a hydroxylamine concentration of s, ox to -3 mol/l or less, and most preferably no hydroxylamine at all. It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion. The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. That is, organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-Hydroxyketones, α-aminoketones, *
Particularly effective organic preservatives include monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused cyclic amines. These are JP-A-63
-4235, 63-30845, 63-216
No. 47, No. 63-44655, No. 63-53551, No. 63-43140, No. 63-56654, No. 6
No. 3-58346, No. 63-43138, No. 6j-t
No. 46o4, No. 63-44657, No. 63-446
No. 56, U.S. Patent No. 3,615.503, U.S. Patent No. 2.49
No. 4,903, JP-A-52-143020, Special Publication No. 4, 1973
It is disclosed in various publications or specifications such as No. 8-30496. Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in JP-A No. 9-180588, alkanolamines described in JP-A-54-3532,
Polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544, etc. may be contained as necessary. In particular, it is preferable to add alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, hydrazine derivatives, or aromatic polyhydroxy compounds. Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides are particularly preferred; details thereof can be found in JP-A-1-9795).
No. 3, No. 1-186939, No. 1-186940,
It is described in Publication No. 1-187557 and the like. Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing. Examples of the above-mentioned amines include cyclic amines as described in JP-A-63-239447 and JP-A-63-1.
Examples include amines such as those described in Japanese Patent Publication No. 28340, and others such as those described in Japanese Patent Application Laid-open No. 1-186939 and Japanese Patent Application Laid-open No. 1-187557. In the present invention, 2×10 chloride ions are added to the color developer.
-"~3X10-'mol/1 is preferably contained,
Particularly preferably, it is 3×10−” to 2×10 u mol/i.If the chloride ion concentration is more than 3×10−′ mol/i, it has the disadvantage of delaying development, and the problem is that it is rapid and has a high maximum concentration. It is not preferable in achieving the object of the invention. Also, if it is less than 2×10-'' mole/1, it is not preferable in terms of preventing fogging. In the present invention, the bromine ion in the color developer is 1.0
X10-'mol/I! , or less is preferable. More preferably, it is 5×10 −′ mol/l or less. If the bromide ion concentration is greater than 1X10-3 mol/l, development will be delayed and the maximum density and sensitivity will be reduced. Here, the chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the photosensitive material into the developer during the development process. When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride. Alternatively, it may be supplied from an optical brightener added to the developer. As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among these, preferred are potassium bromide and sodium bromide. When eluted from the light-sensitive material during the development process, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion. The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds. In order to maintain the above pH, it is preferable to use various buffering agents. Examples of the buffering agents include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3゜4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1°3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are soluble at pH 9.0.
These buffering agents have excellent buffering capacity in the above high pttSI range, have no adverse effects on photographic performance (fogging, etc.) when added to color developers, and are inexpensive. Particularly preferred. Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (5-sulfosalicylic acid) sodium), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds. The amount of the buffer added to the color developer is 0.1 mol/2
It is preferably at least 0.1 mol/! ~0.
Particularly preferred is 4 mol/l. In addition, various chelating agents can be used in the color developer to prevent precipitation of calcium and magnesium, or to improve the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'
-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,
2,4-1-licarponic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N. Examples include N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid. Two or more of these chelating agents may be used in combination, if necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 1j
It is about 0.1g to 10g per 2. Any development accelerator can be added to the color developer if necessary. As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
, No. 247, etc., and thioether compounds disclosed in JP-A-52-49829 and JP-A-52-49829.
p-Fuynylenediamine compounds disclosed in Publication No. 15554, JP-A No. 137726-1983, and JP-A No. 1988-137726;
30074, JP-A-56-156826 and JP-A-56-156826
Quaternary ammonium salts disclosed in US Pat. No. 2,494,903 and US Pat. No. 3,128.
No. 182, No. 4,230,796, No. 3,253,9
No. 19, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,4
No. 82,546, No. 2゜596.926 and No. 3.5
Amine compounds described in each publication or specification such as No. 82.346, Japanese Patent Publication No. 37-16088, No. 42-2520
No. 1, U.S. Patent No. 3.128.183, Special Publication No. 1973-
No. 11431, No. 42-23883 and U.S. Patent No. 3
．． 532゜501 and other publications or specifications, and other 1-phenyl-3-
Virapritons, imidazoles, etc. can be added as necessary. In the present invention, any antifoggant can be added if necessary. As anti-capri agents, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic anti-capri agents can be used. Examples of the organic antifoggant include henctriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylhenzutriazole, 5-nitrohenzitriazole, 5-chloro-benzotriazole, 2-thiazolyl-henzimidazole. Representative examples include nitrogen-containing heterocyclic compounds such as , 2-thiazolylmethyl-henzimidazole, indazole, hydroxyazaindolizine, and adenine. The color developer applicable to the present invention preferably contains an optical brightener. As an optical brightener, 4.4'
-Diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 8 g/l, preferably 0.1 g to
It is 6g/l. Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary. The processing temperature of the color developer that can be applied to the present invention is 30~
50°C, preferably 35-50°C. Processing time is 5
The time is from 5 seconds to 30 seconds, preferably from 5 seconds to 20 seconds, and more preferably from 5 seconds to 15 seconds. Although it is preferable that the amount of replenishment is small, it is suitably 20 to 600 Ml, preferably 30 to 100 Ml, per 1 y of photosensitive material. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio/contact area between processing liquid and air (C4)/capacity of processing liquid (C4) The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. be. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, there is also a method using a movable lid as described in JP-A-1-82033; Pickpocketing described in Publication No. 63-216050,
Examples include development processing methods. It is preferable to reduce the aperture ratio not only in both color development and black-and-white development, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer. Next, a desilvering process that can be applied to the present invention will be explained. The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step. The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below. As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but especially iron (
Organic complex salts of [1) (e.g. aminopolycarbonate f such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid)
lIlf, complex salts of aminopolyphosphonic acids, phosphonocarboxylic acids and organic phosphonic acids) or citric acid,
Organic acids such as tartaric acid and malic acid; persulfates; hydrogen peroxide and the like are preferred. Among these, organic complex salts of iron(I) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (I[I) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1.3- Examples include diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like. These compounds may be sodium, potassium, thium or ammonium salts; among these compounds, iron salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodiacetic acid; The (n[) complex salt is preferred because it has a high bleaching edge. These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid.
It may be used in excess to form an iron ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/l, preferably 0.05 to 0.50 mol/l. Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. Specification No. 812, JP-A-53-95
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds having a mercapto group or disulfide bond, and Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
Thiourea compounds described in No. 5 and US Pat. No. 3,706,561, or halides such as iodine and bromide ions are preferred because they have excellent bleaching properties. In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention contains bromides (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. If desired, one or more inorganic acids having pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. , organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine. The fixing agent used in the bleach-fixing solution or fixing solution is a known fixing agent, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid. , 3,6-sithia-1,8-octanediol, and other water-soluble silver halide soluble compounds, such as thioureas, and these can be used alone or in combination of two or more. In addition, a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 can also be used.In the present invention, thiosulfuric acid Preference is given to using salts, especially ammonium thiosulfate salts. The amount of fixing agent per 11 is preferably from 0.2 to 2 mol, more preferably from 0.3 to 1.0 mol. The pH range of the bleach-fix solution or fix solution is preferably 3 to 9,
Furthermore, 4 to 8 are particularly preferable. Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
The content is preferably 1.0 mol/l, more preferably 0.04 to 0.6 mol/1. Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added. Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as desired. After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed. The amount of washing water in the washing step can be set over a wide range depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the intended use, the washing water temperature, the number of washing tanks (number of stages), and various other conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society.
Journal of Motion Picture and Television Engineers (Journal of the 5
Ociety of MotionPicture a
nd Te1vision Engineers), Vol. 64, p. 248-253 (May 1955 issue). Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 5. According to the multistage countercurrent method, the amount of washing water can be greatly reduced, for example, it is possible to reduce the amount of washing water to 500 d or less per 1 bottle of photosensitive material.
Although the effects of the present invention are remarkable, the increased residence time of water in the tank causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. As a solution to such problems, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Also, JP-A-57-85
Isothiazolone compounds and thiahendazoles described in Japanese Patent Application No. 42, chlorine-based sterilizers such as chlorinated sodium isocyanurate described in Japanese Patent Application Publication No. 61-120145, and benzene as described in Japanese Patent Application Laid-open No. 61-267761. Triazole, copper ion, etc. “Chemistry of antibacterial and antifungal” by Hiroshi Horiguchi (19)
1986) Sankyo Publishing, Hygiene Technique Complete Edition, "Microbial Sterilization, Disinfection, and Anti-Mold Technology J (1982)" Society of Industrial Engineers, Japan Antibacterial and Anti-Mold Research Line, "Encyclopedia of Antibacterial and Antifungal Agents J (1986)," In addition, a surfactant as a draining agent and a chelating agent such as EDTA as a water softener can be used in the rinsing water. Following the above rinsing step, or It is also possible to directly process with a stabilizing solution without going through the water washing process.Compounds with image stabilizing functions are added to the stabilizing solution, such as aldehyde compounds typified by formalin, membrane plating suitable for dye stabilization, etc.
Examples include buffers for preparing H and ammonium compounds. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used. Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without passing through a water washing step,
No. 8543, No. 58-14834, No. 60-2203
All known methods described in Japanese Patent No. 45 and the like can be used. In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds. A so-called rinsing liquid is also used as a washing liquid or stabilizing liquid used after the desilvering process. The preferred pH of the water washing step or stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is between 20°C and 5°C.
0°C, preferably 25°C to 45°C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time. Preferably it is 10 seconds to 60 seconds, more preferably 15 seconds to 45 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like. A specific preferable replenishment amount is 0.5 to 50 times the amount brought in from the previous bath per unit area of the photosensitive material, preferably 0.5 times.
It is 9 times to 10 times. or 500 per photosensitive material
It is smaller than a frog, preferably smaller than 100 d. Further, replenishment may be performed continuously or intermittently. The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to reduce the amount of waste liquid by using a multi-stage counter-current system to reduce the overflow of the wash water into a bleach-fixing bath which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid. (The following is a margin) [Embodiment] Hereinafter, one embodiment of the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to this embodiment. Figure 1 shows a silver halide photographic color printer to which the present invention is applied. This device develops, bleach-fixes, and washes exposed web-like color paper, then dries it to form an image on the color paper. It is something. The color paper C (hereinafter referred to as photosensitive material) processed by this device is 95
It is a color photographic light-sensitive material having at least one layer of a silver halide emulsion containing silver chloride in an amount of mol % or more on a support, and is color developed with a color developer containing an aromatic primary amine color developing agent. The apparatus main body 10 is provided with a paper feed section 12 on the right side, an exposure section 14 and a processing section 16 above, and a drying section 18 on the left side. In addition, a pair of magazines 20 and 22 can be loaded on the top and bottom of this silver halide photographic color printer.
Photosensitive materials 24 and 26 each having a width equal to 7+++n+) are housed in rolls, and are taken out from the leading end to the paper feed section 12. - For example, 24 is a photosensitive material based on paper, and 26 is a photosensitive material based on transparent film. In addition, two types of photosensitive materials 2
Since the configuration for processing 4.26 is the same, the configuration of the apparatus will be described below based on the processing of one photosensitive material 24. The photosensitive material 24 pulled out from the magazine 20 is fed to the paper feed section 1.
2 to the exposure window 28, and the image is exposed by an exposure device 36 provided in the exposure section 14. In the exposure device 36, the direction perpendicular to the conveyance direction of the photosensitive material 24 is the main scanning direction, and the moving direction of the photosensitive material 24 is the sub-scanning direction. Examples of devices that expose the photosensitive material 24 by main scanning in a direction perpendicular to the direction in which the photosensitive material is transported include a laser exposure device, a pick-pocket exposure device, and the like. In a laser exposure device, the scanning direction of laser light is the main scanning direction, and in a slit exposure device, the direction in which the slit extends is perpendicular to the photosensitive material transport direction and is the main scanning direction. The processing section 16 is successively provided with a developing tank 46, a bleach-fixing tank 47, and washing tanks 48 and 49. The photosensitive material 24 is immersed in a processing solution filled in a multi-tank, subjected to development, bleach-fixing, and washing, and then sent to the drying section 18. Moreover, the photosensitive material 24 after exposure is 20
The transport speed is set so that the film is immersed in the developer within seconds. Each processing liquid is appropriately replenished from replenishment tanks 60, 62, and 64. Although FIG. 1 shows a state in which two washing tanks 48 and 49 are provided for convenience, the number of washing tanks is not limited to this and can be changed. The drying section 18 dries the photosensitive material 24 after washing with water and sends it onto the take-out tray 54 . FIG. 2 is a block diagram of the exposure apparatus. The exposure device 300 emits a set of three colors of light to expose the photosensitive material 24. The g-light AT 300 performs image processing based on image data processed by an image processing device 240 connected to a computer or the like.
Drive circuits 242, 244, and 246 drive each semiconductor laser 25.
1,252.253 by driving the photosensitive material 24
to expose. In the exposure apparatus 300, light for developing magenta is generated by a semiconductor laser 251 that emits laser light with a wavelength of 150 nm. The semiconductor laser 251 is
An example is LTO30MF manufactured by Sharp ■. Laser light with a wavelength of 750 nm emitted from the semiconductor laser 251 is shaped through the collimator lens 258 and reflected by the total reflection mirror 261 toward the polygon mirror 270 . Light for producing cyan is generated by a semiconductor laser 252 that emits laser light with a wavelength of 810 nm. Laser light with a wavelength of 810 nm emitted from the semiconductor laser 252 is shaped through a collimator lens 259, and a gicroic mirror 26 passes the light for producing magenta and reflects the light for producing cyan.
2 toward the polygon mirror 270. The semiconductor laser 252 is, for example, ■Toshiba TOLD152.
R, LTO10MF manufactured by Sharp Corporation. Light for producing yellow color is generated by a semiconductor laser 253 that emits laser light with a wavelength of 670 nm. The semiconductor laser 253 is, for example, TOLD9 manufactured by Toshiba.
200, NDL3200 manufactured by NEC Corporation, 5L manufactured by Sony ■
It is D151U. Laser light with a wavelength of 670 nm emitted by the semiconductor laser 253 is shaped through a collimator lens 260, passes the light for producing magenta and the light for producing cyan, and reflects the light for producing yellow. It is reflected by the guichroic mirror 263 toward the polygon mirror 270 . The light for developing the cyan, magenta, and yellow colors described above passes through the same optical path 264, is reflected by the polygon mirror 270, passes through the rθ lens 280, is further reflected by the mirror 290, and reaches the photosensitive material 24. Then, as the polygon mirror 270 rotates around the axis 271, the image light scans and exposes the photosensitive material 24. Then, by moving the photosensitive material 24 in a direction (indicated by arrow A) perpendicular to the scanning direction of the laser beam, it is sub-scanned and an image is formed. Here, the moving speed of the photosensitive material 24 during exposure is equal to the moving speed during the developing process, and the developing process for the exposed portion of the photosensitive material 24 is started after an equal amount of time has elapsed. The exposure apparatus 300 does not rely only on the laser beam described above, but may also use a three-color liquid crystal shutter array, three linear plasma arrays, a light emitting diode, or the like. Further, the exposure device 300 is configured to expose the photosensitive material 24 based on image information processed by a computer or the like, but it can also expose the photosensitive material 24 based on image information obtained by reading an original. (Example) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. LBKP for photographic paper (bleached hardwood, sulfate pulp)
100χ (weighing 175g/bo, thickness approx. 180m);
A support was prepared by providing a white pigment-containing resin layer made of water-resistant titanium oxide having the following composition on the surface of a white base paper. That is, 16 parts by weight of a titanium oxide white pigment surface-treated with silicon oxide and aluminum oxide was added to 90 parts by weight of a polyethylene composition (density 0.920 g/cd, melt index (Ml) 5.0 g/10 min). After further adding a bluish dye (ulmarine blue) and kneading, a 30-water-resistant resin layer was obtained by melt extrusion coating. On the other hand, another polyethylene composition (density 0.950 g/c
j, Ml8.0g/10min) only coated 2
A water-resistant resin layer of 0- was obtained. A double-sided laminated paper support was thus prepared. 1. After corona discharge treatment was applied to the surface of the water-resistant paper support prepared above, a gelatin undercoat layer containing sodium dodecylhenzenesulfonate was applied, and various photographic constituent layers were further applied. Color photographic paper with each layer having the layer structure shown below was produced. The coating solution was prepared as follows. -th layer coating f1. AI yellow coupler (ExY) 19.1 g and color image stable side (Cpd-1) 4.4 g and color image stable side (Cpd
-7) 0.7 g to 27.2 cc of ethyl acetate and 4.0 ml each of solvents (Solv-3) and (Solv-7).
1 g was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate to prepare emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, average grain size 0
．． 3=7 mixture of 881.0 large size emulsion A and 0.7016 small size emulsion A (silver molar ratio) 0 Coefficient of variation of grain size distribution is 0.08 and 0.10 respectively, each size emulsion has bromination Contains 0.3 mol% silver locally on a part of the particle surface.
r) was prepared. This emulsion contains blue-sensitive enhancing dyes A and B shown below at a rate of 2.0% per mole of silver for large-sized emulsion A, respectively. OX 10-' mol, and for small size emulsion A, 2.5 x 10-' mol, respectively. Further, chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-3-triazine sodium salt was used. Further, Cpd-10 and Cpd-11 were added to each layer in a total amount of 25.0 .mu./i and 50.0 .mu./i, respectively. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer. Sensitizing dye A for blue-sensitive emulsion layer Sensitizing dye B for blue-sensitive emulsion layer (per mole of silver halide, 42.0 x 10-' mole each for large-size emulsion A, and for small-size emulsion A) are 2.5X 10-' mol each) Sensitizing dye C for the green-sensitive emulsion layer (4.OX 10-' mol for large size emulsion B and 4.OX 10-' mol for small size emulsion B per 1 mol of silver halide) (5.6 Sensitizing dye for red-sensitive emulsion layer E
X to-' moles, and for small size emulsion C 1.
(10 to 4 moles of IX) To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6XIO-3 moles per mole of silver halide. In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer per mole of silver halide.
, 5X10-' mol, 7.7 Xl0-' mol, 2.5
X10-' moles were added. In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added per mole of silver halide to lXl0-'
mol and 2XlO-' mol were added. In addition, the following dyes (indicated by the amount coated) were added to the emulsion layer to prevent irradiation. (10■/rrf) (10■/Bo) (40■/B) And (Layer structure) The composition of each layer is shown below. The number is the coating amount (g/rTr)
represents. The silver halide emulsion represents the coated amount in terms of silver. -th layer (blue-sensitive emulsion layer) Said silver chlorobromide emulsion A O,30 Gelatin 1.86 Yellow coupler (ExY) 0.76 Color image stabilizer (Cpd-1) 0.19 Solvent (
Solv-3) 0.18 Solvent (Solv-7) 0.18
Color image stabilizer (Cpd-7) 0.0
6 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.16
Solvent (Solv-4) 0.0
8 Fifth layer (green emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion B with an average grain size of 0.55- and small size grain B with an average grain size of 0.39-1=1)
3 mixture (^g molar ratio). The coefficient of variation of the particle size distribution is 0.1O and 0.08, respectively, and each size emulsion is AgB.
rO, 8 mol% was locally contained in a part of the particle surface)
0.12 gelatin
1.24 magenta coupler (ExM)
0.23 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-3)
0.16 color image stabilizer (Cpd-4)
0.02 color image stabilizer (Cpd-9)
0.02 solvent (Solv-2)
0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing inhibitor (Cpd-, 5) 0.05 Solvent (Solv-5) 0.2
4 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1 = large size emulsion C with an average grain size of 0.58- and small size C with an average grain size of 0.45-)
4 mixture (Ag molar ratio). The coefficient of variation of grain size distribution is 0.09 and 0.11, and each size emulsion is AgBrO,
(6 mol% was locally contained on a part of the particle surface)
0.23 gelatin
1.34 cyan coupler (EXC)
0.32 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-4)
0.02 color image stabilizer (Cpd-6)
0.18 color image stabilizer (Cpd-7)
0.40 color image stabilizer (Cpd-8)
0.05 solvent (Solv-6>
0.14 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (
Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic of polyvinyl alcohol 0.17 Modified copolymer (degree of modification 17%) Liquid paraffin 0.03 (Ex
Y) 1:l mixture (molar ratio) with yellow coupler ([41M) magenta coupler (ExC) cyan coupler! 1=1 mixture (molar ratio) with (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer Cs1L+(t) (Cpd-5) Color mixture prevention side I H (Cpd-6) 2:4:4 mixture (weight ratio) of color image stabilizer (Cpd-7) Color image stabilizer Ikko CH, -CH+- "C0NHC4H9 (t ) Average molecular weight 60,000 (Cpd-8) Color image stabilizer (Cpd-9) Color image stabilizer (Cpd-10) Preservative (Cpd-11) Preservative (UV-1) Ultraviolet absorber CJq(t) 4:2:4 mixture (weight ratio) (Sol Sea 1) Solvent (Solv-2) 1=1 mixture (volume ratio) of Solvent (Solv-3) Solvent (Solv-4) Solvent (Solv-5) Solvent C00C1lHI7 (CHz) a C00CIIHI7 (Sol Sea 6) Solvent (Solv-7) Solvent CsH,tCHcH (CHz)vcOOcsH+t A photosensitive material (lO) was prepared as described above.

[Production] An automatic developing machine shown in the attached Figure 1 was constructed and used for the following development processing. For the photosensitive material α0) cut to A3 size,
Scanning exposure was applied using (exposure apparatus-1) described in Example 1 of JP-A-2-157749. At that time, by electrically controlling the light intensity and emission time of the semiconductor laser used, the amount of exposure to the photosensitive material is adjusted so that the color density of cyan, magenta, and yellow after development is 1.0 each. adjusted. The exposed sample was processed according to the following development process (1). The above-mentioned automatic developing machine was used for this developing process. Processing ■ Star image processing A Soil L Color developer Bleach-fix at 38°C for 20 seconds Rinse at 38°C for 20 seconds ■ Rinse at 38°C for 7 seconds ■ Rinse at 38°C for 7 seconds ■ Rinse at 38°C for 7 seconds ■ Rinse at 38°C for 7 seconds ■ 38° Drying at 65°C for 15 seconds (5-tank countercurrent flow from rinsing ■ to ■) (The value includes the time in the air until it enters the next processing solution.) The composition of each processing solution is as follows. Water 800d Same as left Ethylenediamine-N,N,N',N'-mono-tetramethylenephosphonic acid 2.1g Same as left Triethanolamine 8.1g Same as left Potassium chloride
8.2g - potassium bromide
O,OLg - Sodium sulfite
0.14g Same as left potassium carbonate
18.7 g 37. Q g4-amino-
N-ethyl-N-(3-hydroquinepropyl)-3-methylaniline 12.8 g 27.
8 g Diethylhydroquinylamine 6.3 g Same as on the left (80χ) Fluorescent brightener (4,4'-diaminostirhene type) 0.5 g Same as on the left Add water 1000 d Same as on the left pH
(25°C) 10.05 1
0.95 The replenishment amount of the above replenisher is 30 per photosensitive material.
It was set as d. Water 400H
1400d Ammonium thiosulfate (70χ) 1001d
250ad ethylenediaminetetraacetic acid 3.4
g 8.5g Ethylenediaminetetraacetic acid M iron (I[[) Ammonium dihydrate 73.0g 183
g Sodium sulfite 40 g 10
0g ammonium bromide 20.0g
Add 50.0g water to 100M
1000dpH (25°C)
5.80 5°10 The replenishment amount of the above replenisher was 30 m per rrr of photosensitive material. Hisatoshi Yuno: Ion-exchanged water was used for both the tank liquid and the replenisher, and the replenishment amount was 40〆/pot. The automatic developing machine (FIG. 1) used in this example was provided with a blowout member for jet agitation at the bottom of each processing bath. The spouting member has a width of 30c+a and a length of 51 in the conveyance direction of the photosensitive material.
It has a diameter of 0.0 mm and is lined up at 5 gm intervals in the width direction.
4 rows of 5- nozzle holes were arranged at 10m+ intervals (
Figure 2). The processing liquid was supplied through this porous spouting member at a rate of 6N/min. The processing liquid supply rate at this time is
The value obtained by dividing 61 by the radius 30C1m, that is, the photosensitive material width ICI
It is expressed as 0.21 per I+. The jetting direction was perpendicular to the surface of the photosensitive material, and the distance between the jetting port and the surface of the photosensitive material was about 5 m. In addition, at this time, the position of the blowout member was set in the first half of 45 to 55% of the length of the submerged process in any bathtub. Further, as other features of the automatic developing machine of the present invention, (1) a plurality of liquid removal rollers are disposed between the final rinsing bath and the drying section to wipe off liquid adhering to the surface of the photosensitive material; ■In the drying section, drying air is blown onto the photosensitive layer surface of the photosensitive material at a wind speed of approximately 3 m/sec through a perforated plate or slit, and air circulation is carried out to quickly remove so-called return air containing moisture from the surface of the photosensitive material. One example is a drying section with a mechanism. The above-described A3 size photosensitive material 00) was subjected to scanning exposure and development processing, one sheet at any time every day, for a total of 5 sheets per day, and this was continued for 5 days to obtain a total of 25 gray colored samples. Next, arbitrarily select five locations on each sheet of the obtained A3-sized gray coloring sample, measure the B filter reflection density, G filter density, and R filter density, and measure the R, G, and B densities at each measurement location. (hereinafter, this density difference will be abbreviated as maximum color shift density difference). This maximum color difference density difference can be reduced by adjusting the exposure amount mentioned above, but if there is a problem where the color tone varies depending on the position on one sample, this maximum color difference density difference can be reduced. cannot be made smaller than a certain point. Therefore, the degree of the density variation problem that the present invention attempts to solve can be expressed by the magnitude of this maximum color shift density difference. When conducting the above experiment, the time from scanning exposure to the start of color development was 5 seconds, 10 seconds, 20 seconds, 40 seconds, 80 seconds, 5 minutes,
Table 1 shows the average value of the maximum color shift density difference of the 25 samples when the time was changed to 10 minutes. Table 1 As is clear from the results, by the method of the present invention, that is, by setting the time from scanning exposure to the start of color development within 20 seconds, it is possible to stably obtain an image with less white shift. Although the breakdown of the maximum color shift density difference in Table 1 is not clear, there was a tendency for the density difference to increase when the experimental environment was high and high. Fushien I The procedure was exactly the same as in Example 1, except that silver chlorobromide emulsions were used in which the silver chloride content of the silver halide emulsion used in Example 1 was changed to 90 mol%, 80 mol%, and 60 mol%. As a result of experiments carried out, it was found that the maximum color shift density difference showed a satisfactory value of 0.04 or less in all cases, regardless of the time from scanning exposure to the start of color development. However, in these cases, the color development speed was slower than in the case of using the high silver chloride emulsion of the present invention, and it was necessary to extend the development process. From the above, it can be seen that the present invention provides an image forming method and apparatus that can perform ultra-quick processing and stably obtain good images without color shift. [Real] 1 Color developing agent used in the color developing solution in development process (1) of Example 1. Except that exemplified compounds (D to 7) were used in an equimolar amount instead of exemplified compound (D-6). Example 1 was carried out in exactly the same manner as in Example 1 (this is referred to as development treatment (It)).
The same evaluation was performed and similar results were obtained. When the same evaluation as in Example 1 was performed except that the following development treatments (I[1-1) and (I[[-2)] were performed instead of development treatment (1) in Example 1, similar results were obtained. Got the results. Five press ■ Return 1 Process 11") Present 1 Back 1 Application 1") Color development I 40°C 15 seconds 40°C 15 seconds Bleach fixing 40°C 15 seconds 40°C 15 seconds Rinse ■ 40°C 7 seconds 40'C 7 seconds Rinse ■ 40°C for 7 seconds Rinse at 40°C for 7 seconds ■
40°C 7 seconds Rinse at 40°C 7 seconds ■
40°c 7 seconds 40°c 7 seconds rinse ■ 40
°C7 seconds 40°C7 seconds drying 65°
C: 15 seconds 65°C: 15 seconds (Rinse: 5-tank countercurrent flow from ■ to ■.) The composition of each treatment solution is as follows. Water 800 d Same as left Ethylenediaminetetraacetic acid 2.0 g Same as left 5.6-
Cyhydrokidihenzen-L2.4- Trisulfonic acid 0.3g Same as left Triethanolamine 8.0g Same as left Sodium chloride 2.5g Same as left Sodium sulfite 0.3g Same as left Potassium carbonate
25.0 g Same as left Exemplified compound D
8 10 mmol 5
mmol Exemplary Compound 1'ID 5
15 mmol 8 mmol Exemplary compound D
70 mmol
15mmol diethylhydroxylamine 4.2g
Same as left fluorescent whitening agent (4,4°-diaminostilhene type) 2. Og Same as on the left Add water 1000d Same as on the left pH (
25°C) 10.05 Same as on the left Here, the same bleach-fixing solution and rinsing solution as in the development process (1) of Example 1 were used. As mentioned above, the conditions for the development treatment, which were not particularly specified, were the same as in Example 1. Further, an automatic developing machine was manufactured and used based on the specifications of the developing machine shown in FIG. 1, with the sizes of each processing bath changed according to the processing time of this example. 1. When the evaluation was carried out in the same manner as in Example 1 except that the following development treatments (IV-1) and (IV-2) were performed instead of development treatment (1) in Example 1, the results were as follows. Obtained similar results. L-Kon process development processing NO. (■-1n (IV-2) Color development 48°C 20 seconds Bleach fixing at 35°C 20 seconds
38°C 20 seconds Rinse at 38°C 20 seconds ■
38°C 12 seconds Rinse at 38°C 12 seconds ■
38'CI 2 seconds 38°C 12 seconds rinse■
Dry at 38”C for 12 seconds at 38°C for 12 seconds.
65°C 15 seconds 65"C 15 seconds (3 tank countercurrent force type from rinsing ■ to ■) The above development process (
The compositions of the treatment solutions for TV-1) and (■-2) are the same and are as follows. Friend】Niri Natsumekyusui 800
Meethylenediaminetetraacetic acid 2.0g5.6-
Hydroxyhensen-1.2.4- Trisulfonic acid 0.3g Triethanolamine 8.0g Sodium chloride 1.4g Potassium carbonate
25 g Exemplary Compound D-85.0 g Diethylhydroxylamine 4.2 g Fluorescent brightener (4,4'-diaminostilhene type) 2.0 g Add water to 1000 dpH (25°C)
10.05 1n foot l water sprinkling 400
dAmmonium thiosulfate (70χ) 100a
+! Sodium sulfite 17g Iron (I[l) ethylenediaminetetraacetate Ammonium 75g Disodium ethylenediaminetetraacetate 5g Add water
1000fa1pH (25℃)5
68 Hiji 2 Kyu Ai Ion Exchange Water (Calcium, Magnesium 7um each 3pp
(II and following) As mentioned above, the conditions of the development treatment, which were not particularly specified, were the same as in Example 1. Further, an automatic developing machine was manufactured and used based on the specifications of the developing machine shown in FIG. 1, with the sizes of each processing bath changed according to the processing time of this example. In the method for preparing silver halide emulsion A in Example I, instead of using spectral sensitizing dyes A and B, the following spectral sensitizing dyes F and G were each used at 1.3X per mole of silver halide.
10-' mole and 1. Silver halide emulsion F was prepared in the same manner as silver halide emulsion A except that 10-' mol of OX was added.
was prepared. Spectral sensitizing dye F t Spectral sensitizing dye G t Next, in the method for preparing silver halide emulsion B of Example 1, instead of using spectral sensitizing dyes C and D, the following spectral sensitizing dye H was halogenated w & 1 mol. 4.5X10- per
Silver halide emulsion H was prepared in exactly the same manner as silver halide emulsion B, except that mol was added. Spectral sensitizing dye H Next, in the method for preparing silver halide emulsion C of Example 1, instead of using spectral sensitizing dye E, the following spectral sensitizing dye J
Silver halide emulsion J was prepared in exactly the same manner as silver halide emulsion C except that 5 x 10-'' mol of spectral sensitizing dye J ] 1 [Et was added per mol of silver halide. In the method for producing a photosensitive material (IO),
The photosensitive material was the same except that the use of the silver halide emulsion in the photosensitive layer was changed as shown in Table 3 below, and the following compound was added to the third layer in an amount of 2.6 x 10-3 mol per mol of silver halide. A photosensitive material (70) was prepared in exactly the same manner as (lO) to (12). Layer number Amount of silver halide emulsion used 1st layer (yellow color) F: 0.30 3rd layer (magenta color) H: 0.12 5th layer (cyan color) J:
0.24 These light-sensitive materials are infrared-sensitive color light-sensitive materials. The functions of each photosensitive layer are shown in Table 3 in comparison with the photosensitive layer of photosensitive material (1o). 1st layer Blue-sensitive yellow coloring layer Red-angry coloring layer 3rd layer Green-sensitive magenta coloring layer Infrared-sensitive magenta coloring layer Other layers are photosensitive material (1o) and photosensitive material (7o)
Same thing. The photosensitive material (70) prepared as described above was uniformly exposed over the entire surface using a semiconductor laser (hereinafter referred to as LD) shown in Table 4 below so that the density after development was the highest. . Exposure in this case means that three light beams obtained from the following three types of LDs are combined into one beam, and then scanned and exposed onto the photosensitive material using a rotating polyhedron. On this occasion,
Each laser beam has a bright spot diameter of approximately 0.03 on the photosensitive material.
The diaphragm, etc., were adjusted so that the image density was 100 m, and the intensity and irradiation time were electrically adjusted according to the required image density. The photosensitive material is imagewise exposed while being moved at a constant speed in a direction perpendicular to the scanning direction, and the time required for this exposure is 144
It took about 10 seconds for an image with a size of 20 meters and 297 pieces horizontally. LDm type LD for oscillation wavelength exposure (3) Noan coloring layer GaAZAs approx. 8
Example 1 was applied to the photosensitive material (70) that had been exposed to 10 nm.
Development treatment (I) in Example 3, development treatment (I) in Example 3
■), development treatment in Example 4 ([11) and (I
II-2), and further development treatment in Example 5 (IV-1
) and (■-2) were evaluated for the B density variation width of the black colored prints obtained. As in Examples 1 to 5, when the image forming method and apparatus of the present invention was used, the image Good images with little white shift were stably obtained. In this example, the exposure wavelength and coloring hue correspond as shown in Table 4, but this combination is not essential to obtain the effects of the present invention. [Effects of the Invention] According to the present invention, since the main scanning direction of scanning exposure is perpendicular to the direction in which the photosensitive material is conveyed, the exposed portions of the photosensitive material are sequentially developed before the exposure of the entire area of the photosensitive material is completed. It can be brought into contact with liquid. Then, the exposed photosensitive material is
By contacting the material with a developer for color development within 0 seconds, the latent image on the photosensitive material will not change, and the density of the image will not change, especially at the front and rear edges along the transport direction.
In color photosensitive materials, the color balance does not change.

[Brief explanation of the drawing]

FIG. 1 is a schematic sectional view of a color printer that is an embodiment of the present invention, and FIG. 2 is a configuration diagram of an exposure device. Codes in the figure: 10-・Main body 12-Feeding section 14-Exposure section
16 Processing section 18 Drying section 20.22 - Raw material magazine 24.26 Photosensitive material 28 - Exposure window 46 Developing tank 47 - Bleach-fixing tank 48.49 - Washing tank 54 - Take-out I/ray 240-
Image processing device 242, 244, 246 - Drive circuit 251, 252
,253 -Semiconductor laser 258.259.260-
Collimator lens 261-Life reflecting mirror 262.261-Dichroic mirror 264-One optical path 270-Polygon mirror 271-Axis
280-fθ lens 290- mirror 3o
o-Exposure device (3 others) Procedural amendment dated February 2, 1991

Claims (2)

[Claims] (1) A silver halide photographic light-sensitive material having on a support a silver halide emulsion layer consisting of silver halide grains having a silver chloride content of 95 mol% or more is used at a wavelength corresponding to the color sensitivity of the silver halide emulsion. After scanning exposure using a laser beam,
In an image forming method for obtaining an image by drying after development processing, the laser beam is main-scanned in a direction perpendicular to the photosensitive material transport direction in the development processing step, sub-scanned in parallel to the photosensitive material transport direction, and the sub-scanning speed is An image forming method characterized in that the transport speed of the photosensitive material in the developing step is substantially the same, and the time from scanning exposure to the start of development is within 20 seconds. (2) an exposure section that scans and exposes a photographic light-sensitive material having a silver halide emulsion layer on a support using a laser beam corresponding to the color sensitivity of the silver halide emulsion; An image forming apparatus comprising: a means for generating a laser beam; a means for controlling the intensity and/or irradiation time of the laser beam based on image information; a means for guiding the laser beam to a photosensitive material; means for scanning the photosensitive material, main scanning the laser beam in a direction perpendicular to the photosensitive material transport direction in the development processing step, sub-scanning parallel to the photosensitive material transport direction, and controlling the sub-scanning speed and development. An image forming apparatus characterized in that the transport speed of a photosensitive material in a processing step is substantially equal to that of a photosensitive material, and further, the time from scanning exposure to the start of development is within 20 seconds.