JPH1165051A - Color picture forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve overall picture quality by bettering both graininess and sharpness without damaging other picture quality factors, by conducting color development under the existence of competitive compounds. SOLUTION: A picture obtained by development under the existence of competitive compounds is processed. As competitive couplers among competitive compounds, there are a non-coloration coupler, which is harmless if it remains in a developed photographic material after a coupling reaction with an oxidant of a color developing agent, and a water-soluble pigment producing coupler, which is highly water-soluble and does not remain in a photographic material, and either of them can be used. Among competitive compounds, the competitive couplers are especially effective among which a competitive coupler, a compound expressed by an expression is effective. In the expression, R and R', which can be substituted for one or more of a second to sixth position of a benzene ring, denote alkyl radicals or the like the number of whose carbon atoms is 1 to 5. A competitive developer is required to have a moderately weak developing action for controlling moderately a developing reaction of the color developing agent, and a preferable competitive developer is a hydroquinone derivative or its salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color image forming method for obtaining a high quality color print from a photographed silver halide color photographic material.
In particular, the present invention relates to a method for obtaining a high-quality color print excellent in graininess and sharpness.

[0002]

2. Description of the Related Art The most widely used form of color photography at present is a so-called negative print, in which a color negative film that has been photographed is developed in a photo lab and the resulting film image is printed on photographic paper to obtain a color print. It is a paper system (hereinafter, referred to as an N / P system). With the spread of color photography and the increasing sensitivity of color negative films, this system has been established as a practical international common process, and a development and print service network has been completed. is there.

At present, products having various sensitivities are supplied to color negative films, so that the sensitivity required for most photographing purposes has been satisfied. Therefore, improvement in image quality rather than sensitivity is demanded. The image quality is
Although it is composed of many factors such as graininess, sharpness, gradation, and color tone, graininess and sharpness are particularly important factors of image quality. Sensitivity and granularity are incompatible because one is improved and the other is degraded.
well known. In the past, emphasis has been placed on higher sensitivity, but now that high-sensitivity color negative film products have been prepared, there is a growing demand for improved graininess. By the way, it is generally recognized that, under the same sensitivity, graininess and sharpness are incompatible with each other and are incompatible. For image quality, both the graininess and sharpness are important factors, and it is not allowed to sacrifice one and improve the other. Therefore, in the current NP system in which an image is printed on a paper from a developed negative by light-surface exposure to obtain a print, the NP system is designed to optimize both graininess and sharpness.

[0004] In recent years, systems have been introduced that obtain digital image information from the image of the developed film and then obtain a print. In this system, image processing means for enhancing sharpness by means of image processing means for enhancing edge portions of digitized electrical image information and image processing means for selectively increasing contrast of legs (highlight portions of prints). Is possible. However, edge enhancement and local hardening of contrast still affect graininess in a worsening direction, although the degree is different, and neither graininess nor sharpness can be increased. .

On the other hand, when the graininess or sharpness is to be improved by a development process, a reciprocal relationship between the two is observed, and no means for improving both the graininess and the sharpness has been found. Further, if development conditions are changed to improve graininess or sharpness, photographic characteristics such as gradation, color balance, sensitivity, and stain are also changed, thereby deteriorating overall image quality. After all, the processing of the current general-purpose NP system, which sets the graininess and sharpness to the optimal conditions, has been optimized for other photographic characteristics as well, and changes from these processing conditions are different from those for graininess and sharpness. However, it causes adverse effects and it is difficult to improve the image quality.

[0006] Therefore, although it has been strongly demanded to improve both the sharpness and the graininess to enhance the overall image quality, there is still no solution yet.

[0007]

In view of the above-mentioned conventional technical background and the demands of the photographic market, the problem to be solved by the present invention is to develop a photographic light-sensitive material for color photography, and then to develop a positive material such as a color print. When getting the image,
An object of the present invention is to provide a color image forming method in which both graininess and sharpness are improved without impairing other image quality factors to improve overall image quality.

[0008]

As a result of repeated studies, the inventors of the present invention have found that the above-mentioned object is achieved by a specific combination of the development processing and the image processing. And improved sharpness. Specifically, in the presence of a specific competitor compound, even if the sharpness is improved by image processing, no accompanying deterioration in graininess is observed.
Even under the processing conditions with improved graininess, it was found that there would be no change such as a decrease in sharpness, a decrease in development sensitivity, or a loss of gradation or color balance that would otherwise occur. This has led to the present invention. Therefore, the present invention is as follows.

1. Performing color development in the presence of a competitive compound in a method of developing a photographed silver halide color photographic material, photoelectrically reading the obtained image information, converting it into digital image information, and outputting it to a printer A color image forming method comprising: 2. 2. The method for forming a color image as described in 1 above, wherein color development is performed using a color developer to which a competitor compound has been added. 3. 3. The method for forming a color image as described in 1 or 2 above, wherein the competitor compound is a coupler. 4. Competing compounds are dihydroxybenzophenone derivatives, naphthoic acid derivatives and acetophenone derivatives and 2,6-dihydroxyisonicotinic acid derivatives, 3,5-
4. The color image forming method according to the above item 3, wherein the color coupler is a competitive coupler selected from dihydroxybenzoic acid derivatives. 5. 5. The color image forming method according to any one of the above items 1 to 4, wherein the silver halide color photographic light-sensitive material has been developed so that the gamma value of the light-sensitive material is 0.2 to 0.7. 6. 6. The color image forming method according to any one of the above items 1 to 5, wherein the photographed silver halide color photographic light-sensitive material is a color negative film.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described in detail below. First, the basic feature of the present invention is to develop a conventionally photographed silver halide color photographic material to develop a positive image. When obtaining, the relationship between graininess and sharpness has traditionally been considered to be reciprocal,
When an image obtained by developing in the presence of a specific competitor is subjected to image processing, it has been discovered that the image is not reciprocal and that it has been skillfully linked to a color image forming method.

The competing compound of the present invention refers to a compound which causes a competitive reaction to the coupling reaction between the oxidized product of the color developing agent and the coupler in the color developing process to inhibit the formation of a dye by the coupling. . Competing compounds are classified into the following compound groups in terms of the mechanism of action. (1) Competitive coupler: Coupling reaction with an oxidized color developing agent suppresses the coupling reaction of the original coupler contained in the photosensitive material,
Inhibits pigment formation. (2) Competitive developing agent: Competitively develops with a color developing agent to form a non-coupling oxidant, thereby inhibiting dye formation.

Competitive couplers, after a coupling reaction with the oxidized form of the color developing agent, become colorless products and are colorless as harmless colorless couplers even if they remain in the developed photographic material. There are water-soluble dye-forming couplers which have high water solubility and do not remain in the photographic material, and any of them can be used in the present invention. Specific examples of the compound of the competitive coupler will be described later.

Competitive developers are required to have a moderately weak developing action to moderately suppress the development reaction of the color developing agent. If the activity is too strong, the original color development is stopped, and if the activity is too weak, no effect is exhibited. . Preferred competitive developers are hydroquinone derivatives and N-substituted aminophenols or salts thereof, the latter N-substituent being an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms. A carboxyalkyl group having 1 to 12 carbon atoms and an aryloxy group having 7 to 12 carbon atoms. Specifically, they are N-benzylaminophenol, N-hydroxybutylaminophenol, N-carboxyethylaminophenol, hydroquinone monosulfonic acid, hydroquinone disulfonic acid, and a group of compounds which are later represented by the general formula [VIII].

The competitive compounds used in the present invention do not include derivatives of hydroxylamines, sulfites and sulfinates.

Of the above-mentioned competing compounds, a competing coupler is particularly effective in the present invention. Among them, the competitive couplers which are effective are the compounds represented by the following general formulas [I] to [VII] and the compounds listed as IX-1 to IX-4. Also,
The competing developer of the general formula [VIII] is also effective and is shown here.

The general formulas and specific examples are shown below for nine groups of competing couplers and competing developers. (1) Arylsulfonylacetophenone derivative General formula [I]

[0017]

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In the general formula [I], R and R 'may each be substituted on one or more of the 2- to 6-positions of the benzene ring. Or R ′ may be the same or different, and include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a carboxyalkyl group or a hydroxyalkyl group having 1 to 5 carbon atoms, an amino group, and chlorine. , Bromine and the like, COOM, SO ₃ M ₂ (M is H, Na, K, NH ₄ or other monovalent positive atoms or atomic groups). Hereinafter, specific examples of the compound represented by this general formula will be shown.

[0019]

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(2) Indazolone derivative General formula [II]

[0021]

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In the general formula [II], R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, R 'is a hydrogen atom or an acyl group having 1 to 5 carbon atoms. Formyl groups are preferred. R ″ is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a carboxyalkyl group or a hydroxyalkyl group having 1 to 5 carbon atoms, a halogen atom such as chlorine or bromine, CO 2
OM, SO ₃ M ₂ (M is H, Na, K, NH ₄ or another monovalent positive atom or atomic group) or an amino group, which is substituted at positions 4, 5, 6, and 7 of the indazolone structure; A plurality of the same groups may be substituted. Hereinafter, specific examples of the compound represented by this general formula will be shown.

[0023]

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(3) Polyhydroxybenzoketone derivative General formula [III]

[0025]

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In the general formula [III], X represents an alkyl group having 1 to 5 carbon atoms or a phenyl group which may be substituted (the substituent is an alkyl group having 1 to 5 carbon atoms, chlorine,
Halogen atom such as bromine, amino group, hydroxyl group, carboxyl group, sulfo group). X may be substituted at a plurality of substitution positions, in which case each X may be the same or different. Hereinafter, specific examples of preferred compounds represented by this general formula will be shown.

[0027]

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(4) Naphthoic acid derivative General formula [IV]

[0029]

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In the general formula [IV], X may be substituted at any of the 3- to 8-positions, the same X group may be substituted plurally, and a straight-chain or branched alkyl having 1 to 5 carbon atoms. A halogen atom such as a group, an amino group, chlorine and bromine, or a hydroxyl group. However, when substituting at the 4-position, the substituent is a halogen atom. Hereinafter, specific examples of the compound represented by this general formula will be shown.

[0031]

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(5) Pyrazolone derivative General formula [V]

[0033]

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In the general formula [V], R¹Is a hydrogen source
, An alkyl group having 1 to 5 carbon atoms which may be substituted,
Amino group, cyano group, chlorine, bromine, etc.
A logen atom, a carboxyl group, and a sulfonic acid group. R
¹Is an alkyl group which may be substituted, the substituent is
It is a hydroxy group or a carboxy group. R¹Is replaced
In the case of an amino group, the substituent may have 1 to 1 carbon atoms.
3 alkyl groups. R^TwoIs a hydrogen atom,
A good amino group, which may have 1 to 20 carbon atoms
Represents an alkylthio group or an arylthio group which may be substituted;
You. R^TwoIs an amino group which may be substituted,
Is a phenyl group and the phenyl group has a carboxyl
Group, alkyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms
Alkoxy groups, halogen atoms such as chlorine and bromine,
The amino group may be substituted. Also R^TwoMay be replaced
In the case of an alkylthio group, the substituent is an alkoxy group,
A hydroxy group or an alkyl group having 1 to 4 carbon atoms
It is an amino group which may be substituted two times. Also, R^TwoBut
In the case of an arylthio group which may be substituted, phenylthio
A phenyl group is a carboxyl group, a carbon atom
An alkyl group having 1 to 20 carbon atoms, an alcohol having 1 to 20 carbon atoms
An xyl group, an alkoxyalkyl group having 1 to 20 carbon atoms,
Halogen atoms such as chlorine and bromine, and cyano groups
You may. R^ThreeIs a hydrogen atom, a substitution having 1 to 5 carbon atoms.
A branched or straight-chain alkyl group which may be substituted,
Shows a mino group. R^ThreeFor an alkyl group which may be substituted
The substituent is a hydroxy or carboxy group
is there. R^ThreeIs an amino group which may be substituted,
The group is a phenyl group and the phenyl group has carboxyl
Group, alkyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms
Alkoxy groups, halogen atoms such as chlorine and bromine,
The amino group may be substituted. R¹, R^Two, R^ThreeOf the substituent
If the number of carbon atoms exceeds 9, the competitive coupler
Is not used for adding color developer,
Is added. Also, R ¹, R^TwoHas at least one
Contains acid groups. Hereinafter, compounds represented by this general formula
The following shows a specific example.

[0035]

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(6) Gallic acid derivative General formula [VI]

[0037]

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In the general formula [VI], R is a straight-chain or branched alkyl group having 1 to 18 carbon atoms. Specific examples of preferred alkyl esters of gallic acid of the general formula [VI] include the following. VI-1 Gallic acid methyl ester VI-2 Gallic acid ethyl ester VI-3 Gallic acid n-propyl ester VI-4 Gallic acid isopropyl ester VI-5 Gallic acid n-butyl ester VI-6 Gallic acid isoamino ester VI-7 Gallic acid t-amyl ester VI-8 Gallic acid n-hexyl ester VI-9 Gallic acid n-heptyl ester VI-10 Gallic acid t-octyl ester VI-11 Gallic acid n-nonyl ester VI-12 Gallic acid n-decyl Esters VI-13 Gallic acid n-undecyl ester VI-14 Gallic acid n-dodecyl ester VI-15 Gallic acid n-tetradecyl ester VI-16 Gallic acid n-hexadecyl ester VI-17 Gallic acid n-octadecyl ester

(7) Gallic acid amide derivative General formula [VII]

[0040]

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In the general formula [VII], R ¹ and R ² each represent a hydrogen atom, a substituted or unsubstituted aliphatic group. Also R ¹
And R ² may form a ring. R ¹ and R ² do not simultaneously take a hydrogen atom. In the general formula [VII], R
Examples of the aliphatic group represented by ¹ and R ² include a linear or branched alkyl group, a linear or branched alkenyl group, a cycloalkyl group, and a linear or branched alkynyl group. The carbon number of the linear or branched alkyl group is 1 to 30, preferably 1 to 20,
For example, methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, n-hexyl, 2-ethylhexyl, n-octyl, t-octyl, n-dodecyl, n-
Hexadecyl, n-octadecyl, isostearyl, eicosyl and the like can be mentioned. The linear or branched alkenyl group has 2 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as allyl, butynyl,
Prenyl, octenyl, dodecenyl, oleyl and the like can be mentioned. As the cycloalkyl group, 3 to 12
And preferably 5 to 7 members, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclododecyl. As a straight-chain or branched alkynyl group, a alkynyl group having 3 to 3 carbon atoms
0, preferably 3 to 22, such as propargyl or butynyl. What forms a ring together with R ¹ and R ² includes those having 3 to 12 members, preferably 5 to 12 members, such as ethylene, tetramethylene, pentamethylene, hexamethylene and dodecamethylene.

Further, each of these groups may have a suitable substituent. Examples of the substituent include an alkoxy group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, and a carboxy group. Group, sulfo group, cyano group, alkyl group, alkenyl group, aryl group, alkylamino group, arylamino group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, acyl group, sulfonyl group, acyloxy group and acylamino group. Can be These gallic acid derivatives having a ballast group in the molecule are preferably added to the photosensitive material. Next, specific examples will be described below.

[0043]

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(8) Hydroquinone derivative General formula [VIII]

[0045]

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In the general formula [VIII], R ³ and R ⁴ each represent a hydrogen atom or a group which can be hydrolyzed by an alkali, and may be the same or different. R ⁵ , R ⁶ , R ⁷
Represents a hydrogen atom, a sulfo group, a carboxyl group, a sulfoalkyl group, a carboxyalkyl group, or an alkyl group, respectively. The alkyl group portion contained in R ⁵ , R ⁶ , and R ⁷ is a linear or branched alkyl group having 1 to 5 carbon atoms,
At least one of R ⁵ , R ⁶ , and R ⁷ is a group selected from a sulfo group, a carboxyl group, a sulfoalkyl group, and a carboxyalkyl group.

In the above general formula [VIII], R ³ , R
Examples of the case where ⁴ is a group that can be hydrolyzed by an alkali include an acetyl group, a trichloroacetyl group, an ethoxycarbonyl group, and a benzoyl group. Also R ⁵ ,
Examples where R ⁶ and R ⁷ are sulfoalkyl groups are 1,1-dimethyl-2-sulfoethyl groups, and examples where R ⁶ and R ⁷ are carboxyalkyl groups are 5-carboxypentyl groups and alkyl groups. Examples are methyl, ethyl, t-octyl, n-octyl, sec-
A dodecyl group, an n-pentadecyl group, a sec-octadecyl group and the like. In the general formula [VIII], R ³ and R ⁴
Is preferably a hydrogen atom, and R ⁵ , R ⁶ and R ⁷ are preferably a sulfo group and an alkyl group. Further, it is more preferable that R ⁷ represents a sulfo group or a carboxyl group, one of R ⁵ and R ⁶ is an alkyl group, and the other is a hydrogen atom.

Most preferably, R ⁵ is a hydrogen atom, R ⁶ is an alkyl group, and R ⁷ is a sulfo group. Preferred are hydroquinone monosulfonic acid and hydroquinone disulfonic acid. These hydroquinone derivatives are preferably added to the light-sensitive material. General formula (VII
The compound of the formula [I] can be synthesized by the methods described in British Patent No. 891,158, US Patent No. 2,701,197 and the like, and methods analogous thereto. Next, specific examples of the compound will be shown.

[0049]

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(9) Other Competitive Couplers Having Great Effects

Other competitive couplers having great effects include the following 2,6 dihydroxyisonicotinic acid and 3,5-dihydroxybenzoic acid for adding a developing solution and salts thereof, and a coupling-off group for adding a photosensitive material. And 4-phenylthionaphthol having a ballast group and pivaloylacetoanilide.

[0052]

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Among the above-mentioned competing couplers and competing developers, the compounds represented by the formulas I, III and IV, and the compounds of the formulas IX-1 and IX-2 are particularly preferred. The competitor compound of the present invention may be added to the light-sensitive material, may be added to a color developer, or may be added to a prebath prior to color development. Is preferred.

The effect is particularly large when the compounds represented by the general formulas I, III and IV and the compounds of the formulas IX-1 and IX-2 are added to a color developer. When these competing compounds are added to a color developer, they can be added directly to an alkaline developer.However, depending on the compound, they are separately dissolved in a highly alkaline aqueous solution and then added to the color developer, or hexylene glycol, In some cases, it may be preferable to take a dissolution promoting means such as adding together with a dissolution aid such as ethylene glycol.

The concentration of the above compound added to the color developer varies greatly depending on the kind of the compound, but is usually 0.1 × 10 ⁻³ mol to 0.2 mol per liter of the developer, more preferably 1 liter of the developer. 0.5x1 per
0 ^-3 mol to 0.1 mol is good. The addition of a large amount of a compound having a relatively weak effect of suppressing color development is often more effective than the addition of a small amount of a compound having a strong effect, and thus the above-mentioned general formulas I and 2, which are particularly effective, are particularly effective. In the case of the competing couplers of the general formulas III and IV and the chemical formulas IX-1 and IX-2, the preferable addition amount is 0.005 to 0.05 mol per liter of the developing solution.

The compounds having a ballast group in the competitive coupler represented by formulas V to VIII are added to the light-sensitive material. These compounds belong to the general formulas VII and VIII, which undergo a coupling reaction with the oxidized form of the developing agent during the color development process to release the ballast group and become water-soluble. There are compounds belonging to the general formula VI which are washed away from the light-sensitive material during the process, and all of them are added to the emulsion by a method of adding a usual coupler to the emulsion.

Next, description will be made on the development of the photosensitive material for photography so that the gradation becomes soft. FIG.
Fig. 2 shows a characteristic curve obtained by using a standard color negative film according to an internationally standardized developing recipe according to the method defined in the international standard for sensitivity determination method (ISO 5800). As shown in this figure, a normal gradation has a gamma value (△ D / △ LogE) of 0.6 to 0.9.

The color density of the light-sensitive material to be processed is suppressed by the presence of the competitor compound, and the Dmax and the gamma value are reduced. Therefore, if applied directly to the current NP system that obtains color prints by the light-surface exposure method established in the color photographic market, soft prints can be produced. By performing the processing, a print having a normal gradation is obtained. Further, it was found that the prints obtained by image processing from the photographing material softly developed with the competitor compound in this way had a greater improvement in sharpness and graininess.
In order to bring about such an effect of improving both image quality characteristics, the gradation of the photographic material should be 0.2 to 0.7, preferably 0.30 to 0.70, more preferably 0.40 to 0 in gamma value. .7
It is better to set to 0. In particular, when each layer is softened to about one-half to three-fourths of a normal gamma value, an effect is particularly recognized.

The present invention can be applied to a photographed silver halide color photographic light-sensitive material. Among them, the present invention is particularly effective when applied to a color negative film. The color negative film is effective for general photographing, movies, business photographers, and the like, and can be applied to roll films and sheet films of various formats. Further, the present invention can be applied to any color negative film of each sensitivity ranging from low sensitivity to high sensitivity.

The developing processing apparatus to which the image forming method of the present invention can be applied is a roller transport type, a cine type roller rack transport type, or a hanging development, if it can be used in combination with an image processing apparatus to output a positive image. The method may be applied to any of a large-scale developing laboratory and a minilab, but it is particularly advantageous to apply the present invention to a roller-transfer type minilab developing processing apparatus.

In the present specification, the standard development processing refers to a substantially common processing generally used in most development laboratories worldwide, and specifically, processing of a color negative film. In the process, CN16 series (Fuji Photo Film Co., Ltd.), C41 series (Eastman Kodak Company)
These are prescriptions for development processing, which are substantially common and most commonly performed, even though they have different names. On the other hand, in a lab, the standard processing is usually performed to achieve standard photographic performance, but the processing performed by the lab as a standard within the lab is referred to as a reference process from the viewpoint of the lab. May be distinguished from the international standard processing even if the actual contents are the same.
Also in this specification, when reference is made in relation to the inside of a laboratory,
Although terms such as reference development and reference photographic characteristics are sometimes used, the meanings are as described above. The non-standard development is, in the present invention, development with a color developer to which a competitor compound has been added.

In the present invention, the term “development processing” refers to all the processing starting from the development step and being completed in the drying step.
Will be used. Further, in the following description, there are two completely different operations even though the common terms “processing” of “development processing” and “image processing” are attached. Expressions are distinguished from “development processing” and “image processing”.

Now, the general flow of the method of the present invention will be described. FIG. 1 is a block diagram showing a development processing apparatus to which the present invention can be applied and the flow of operations in the processing apparatus. The example of this figure shows the processing (non-processing) of the present invention in addition to the standard processing (reference processing) described above. (Reference processing).
The film is taken into the developing device from the left end of the diagram. First, the type of the film is read (01). This reading is for knowing the type of film described in the perforation symbol for identification called DX code on the film, and by using this “type” information, it is possible to select the setting conditions of image processing described later, Processing (03)
Or the competitive compound addition treatment (03A) of the present invention can be selected (02). This choice is
It is also possible by an operator (04). Also, a dedicated processor that does not perform such development selection is used.

After selecting the developing conditions, the film is conveyed through a series of processing tanks in the developing machine. The developing machine is of a roller transport type, and includes, for example, a dedicated machine for a reference process which is at least substantially common to the world described above, and a device capable of performing a rapid process of one or more levels in addition to the reference process. FIG. 3 shows an apparatus having a reference processing step (03) and a non-reference processing step (03A). The development step (03) includes color development,
It consists of an immersion step consisting of bleaching, fixing, washing or stabilizing, followed by a drying step. After the development, the process proceeds to the image reproducing process. The image reproducing process includes reading image information (block 1 in FIGS. 1 and 2), image processing (block 5 in FIG. 2), and outputting a reproduced image (block 8 in FIG. 2).
Divided into steps.

In the image information reading step (1), the transmission density (may be the reflection density) is measured for each small area unit (usually called a pixel) constituting the image of the developed film, and the image information is stored in the pixel. It is read as the density for each. As a result of the reading, the image information is converted into an electric image signal based on the density value.
The digital signal is converted by a / D (nalog / digital) converter 18. This information signal is sent to the image processing device 5 via the log converter 20 after the CCD function correction 19 such as the correction of sensitivity variation and dark current for each pixel.

In the image processing apparatus, the image information converted into the digital signal is subjected to electrical processing and converted into a digital image signal that would have been obtained when the reference development processing was performed. When the film is subjected to the reference development, this image processing simply means correcting the variation in the photographing conditions, development processing or film characteristics, and correcting it to a statistical center value. Importantly, it is not the subject of the present invention. When developed in the presence of a competitor compound, the developed film has contrast, image area density, color balance or Dmin
Photographic characteristic values such as (density value of unexposed portion) are deviated from the values at the time of reference development. The present invention is characterized in that the correction of the bias is performed by image processing as described later. The above image processing operation is performed by a method and an arithmetic unit which are applied for in Japanese Patent Application Nos. 8-174022 and 8-182551.

The image signal of the processed film of the present invention converted into the normal photographic characteristic value at the time of the reference development is output to the printer (8), and as a result, a normal positive image is obtained. The printer may be any printer that inputs an electric image signal or a photoelectric image signal, and particularly preferable printers are color print, instant photograph, silver salt color print such as dye thermal transfer type, ink jet, sublimation type thermal transfer, wax. It is a printer for each positive image such as mold thermal transfer and color electrophotography. The apparatus and method of the present invention for obtaining a normal positive image obtained by reference processing from a photographic image having abnormal photographic characteristics of a film processed in the presence of a competitive compound have been described above. Give an explanation.

In the case where the photographic characteristic values obtained by the non-reference development processing in the present invention are converted to the normal photographic characteristic values at the time of the reference development, the gradation and the color equivalent to the image information obtained by the reference development are obtained. This means that the balance is obtained, that is, the image quality is substantially the same except for sharpness and granularity. Specifically, whether or not the image quality in this sense is equivalent is basically determined by observing and evaluating a photographic image. However, when objectivity is emphasized, the image density is represented as a characteristic value that can represent photographic characteristics. Can be used. More specifically, if the density value is within ± 10% of the gamma value or the color balance value based on the density value, it can be said that it is the same as in the standard development processing. In other words, the one-key correction amount of a normal surface exposure type color printer is about 8%, and a difference within this range is usually allowed, so that the photographic characteristic value obtained by the non-reference development processing is different from the reference value. If it is within 10%, it can be determined that it is acceptable.

Having described the features of the present invention, the present invention will be described in more detail in the following order. 1. 1. Development processing to which the present invention is applied 2. Image reproduction of the present invention Positive material for output Color photography material to which the present invention is applied

1. Development Processing to which the Present Invention is Applied The standard development processing described above is CN16
International common processing and common processing such as C41 system and C41 system have been premised, but the development processing to which the image forming method of the present invention can be applied is not necessarily limited to this international common processing. Less than,
The color development processing to which the present invention is applied will be supplemented.

The color developing tank solution and the color developing replenisher used in the developing process of the color negative film of the present invention include:
This is an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl ) Aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-
Amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-
Propyl-N- (3-hydroxypropyl) aniline,
4-amino-3-propyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3- Methyl-N-ethyl-N- (4-
(Hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-
Hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-NN-bis (5-hydroxypentyl) aniline, 4-amino-3
-Methyl-N- (5-hydroxypentyl) -N- (4
-Hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis (5-
(Hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among them, in particular, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N-
(3-hydroxypropyl) aniline, 4-amino-3
-Methyl-N-ethyl-N- (4-hydroxybutyl)
Aniline and their hydrochlorides, p-toluenesulfonates or sulfates are preferred. These compounds can be used in combination of two or more depending on the purpose.

The amount of the aromatic primary amine developing agent to be used is preferably from 0.0002 mol to 0.2 mol, more preferably from 0.001 mol to 1 mol per liter of color developing solution.
0.1 mol.

Color developing solutions (color developing solutions) include pH buffers such as alkali metal carbonates, borates or phosphates, and 5-sulfosalicylates, chloride salts, bromide salts and iodides. Salt, benzimidazoles, benzothiazo-
It generally contains a development inhibitor or an antifoggant such as a compound or a mercapto compound. If necessary, besides hydroxylamine and diethylhydroxylamine, the compound represented by the general formula (I) of JP-A-3-144446 can be used.
Hydroxylamines, sulfites, N, N-
Hydrazines such as biscarboxymethylhydrazine,
Various preservatives such as phenylsemicarbazides, triethanolamine, catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, and dye formation Couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids. Agent
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,
N, N-trimethylenephosphonic acid, ethylenediamine-
Various compounding materials typified by N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be included.

Among the above, as the preservative, unsubstituted hydroxylamine and substituted hydroxylamine are most preferred. Among them, diethylhydroxylamine, monomethylhydroxylamine or alkyl substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group is preferred. Those having a group as a substituent are preferred. The most preferred example is
N, N-bis (2-sulfoethyl) hydroxylamine and its alkali metal salts.

As the antifoggant, bromine ions are preferable, and the addition amount thereof is preferably 0.002 to 0.1 mol / l, more preferably 0.005 to 0.03 mol / l.

As the chelating agent, a compound having biodegradability is preferable. An example of this is disclosed in JP-A-63-1.
No. 46998, No. 63-199295, No. 63-26
Nos. 7750 and 63-267751, JP-A-2-22
Nos. 9146 and 3-186841, German Patent No. 3,7
39,610 and European Patent No. 468,325.

It is preferable that the processing solution in the replenishment tank of the color developing solution is shielded with a liquid agent such as a high boiling organic solvent to reduce the area of contact with air. Liquid paraffin is most preferred as the liquid shielding agent.

The processing temperature of the color developer is 20 to 55 °
C, preferably 30-55 ° C. The processing time is 30 seconds to 4 minutes, preferably 45 seconds to 3 minutes 20 seconds. Most preferably, it is in the range of 60 seconds to 3 minutes 15 seconds.

In this embedding method, the photosensitive material is desilvered after color development. In the desilvering step, it is desirable that both photosensitive materials be filled with a common tank solution and a common replenisher. However, the replenishment amount can be set differently for each photosensitive material. Less than,
Details of the desilvering step will be described.

The desilvering step generally includes a bleaching step, a bleach-fixing step, and a fixing step, and includes a winter type step. Specific steps are shown below, but are not limited thereto.

(Step 1) Bleaching and Fixing (Step 2) Bleaching and Bleaching and Fixing (Step 3) Bleaching and Bleaching and Fixing (Step 4) Fixing and Bleaching and Fixing (Step 5) Bleaching and Fixing If necessary, the solution may be divided into two or more baths, or may be replenished by a cascade method.

As the bleaching agent used in the processing solution having the bleaching ability, aminopolycarboxylic acid iron (III) complex, persulfate, bromate, hydrogen peroxide, erythrocyte and the like are used. The iron (III) polycarboxylate complex can be most preferably used.

The ferric complex used in this treatment method is
It may be added and dissolved as a pre-complexed iron complex salt, or a complex-forming compound and a ferric salt (eg, ferric sulfate, ferric chloride, ferric bromide, iron nitrate (III ), Iron (III) sulfate and the like) to form a complex salt in a solution having bleaching ability.

The amount of the complex-forming compound may be slightly larger than the amount required for complex formation with ferric ion, and when it is added in excess, it is usually in the range of 0.01 to 10%. preferable.

The compound forming a ferric complex salt in the solution having bleaching ability is ethylenediaminetetraacetic acid (E
DTA), 1,3-propanediaminetetraacetic acid (1,3-
PDTA), diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid,
Nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-carboxymethyl) iminodipropionic acid, β-alanine diacetate, α-methyl-nitrilotriacetic acid, 1,4-diaminobutanetetraacetic acid , Glycol ether diamine tetraacetic acid, N- (2-carboxyphenyl)
Iminodiacetic acid, ethylenediamine-N- (2-carboxyphenyl) -N, N ', N'-triacetic acid, ethylenediamine-N, N'-disuccinic acid, 1,3-diaminopropane-N, N'-disuccinic acid, Ethylenediamine-N,
N'-dimalonic acid, 1,3-diaminopropane-N,
Examples thereof include N'-dimalonic acid, but are not particularly limited thereto.

The concentration of the ferric complex salt in the processing solution having the bleaching ability is suitably in the range of 0.005 to 1.0 mol / l, preferably in the range of 0.01 to 0.50 mol / l. , More preferably 0.02 to 0.3
The range is 0 mol / liter.

The concentration of the ferric complex salt in the replenisher of the processing solution having the bleaching ability is preferably 0.005 to 2
Mol / l, more preferably 0.01 to 1.0 mol / l.

Various compounds can be used as a bleaching accelerator in a bath having bleaching ability or a prebath thereof. For example, US Pat. No. 3,893,858,
German Patent No. 1,290,812, JP-A-53
-95630, Research Disclosure No. 1
No. 7129 (July, 1978), a compound having a mercapto group or a disulfide bond,
-8506, JP-A-52-20832 and 53-3
No. 2,735, U.S. Pat. No. 3,706,561, and the like, or thiourea compounds or halides such as iodine and bromide ions are preferred because of their excellent bleaching ability.

Other baths having bleaching ability include bromide (eg, potassium bromide, sodium bromide, ammonium bromide), chloride (eg, potassium chloride, sodium chloride, ammonium chloride), or iodide (eg, potassium chloride, sodium chloride, ammonium chloride). For example,
Rehalogenating agents such as ammonium iodide). Sand, sodium metaborate, acetic acid,
At least one inorganic acid or organic acid having a pH buffering capacity such as sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid, etc. And their alkali metal or ammonium salts, or
Corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The bath having bleaching ability may contain various other types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The fixing agent component in the bleach-fixing solution or the fixing solution is
The use of thiosulfates is preferred. Examples of the thiosulfate include sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate. Other known fixing agents, thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid,
Thioether compounds such as 3,6-dithia-1,8-octanediol, mesoionic compounds, and water-soluble silver halide dissolving agents such as thioureas can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfate, potassium thiosulfate and sodium thiosulfate is preferred. The total amount of the fixing agent per liter is preferably from 0.3 to 3 mol, more preferably from 0.5 to 20 mol.

It is preferable that the bleach-fixing solution or the fixing solution contains a sulfite (or bisulfite or metabisulfite) as a preservative.
Liter, more preferably 0.05 to 0.3 mol / liter.

The bleach-fixing solution and the fixing solution may be any of the above-mentioned sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite) as preservatives. In addition to containing a sulfite ion releasing compound such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite),
Aldehydes (such as benzaldehyde and acetaldehyde), ketones (such as acetone), ascorbic acids, hydroxylamines, benzenesulfinic acids, and alkylsulfinic acids can be added as necessary. Particularly, use of benzenesulfinic acid, p-methylbenzenesulfinic acid, p-aminobenzenesulfinic acid and the like is also preferable. The preferable addition amount is 0.005 mol to 0.1 mol.
It is about 3 mol / liter.

Further, a buffer, a fluorescent brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added to the bleaching solution, the bleach-fixing solution, and the fixing solution as needed.

In the bleaching solution, the bleach-fixing solution and the fixing solution, the preferable pH range is 4 to 8, and more preferably 4.5 to 6.
5 is preferred.

The replenishment amount for the bleaching solution, bleach-fixing solution and fixing solution is 50 to 2000 ml per 1 m ² of the light-sensitive material. Further, washing water as a post-bath or overflow solution of a stabilizing bath may be replenished as necessary.

The processing temperature of the bleaching solution, bleach-fixing solution and fixing solution is from 20 to 50 ° C., preferably from 30 to 45 ° C.
The processing time of each step is 10 seconds to 3 minutes, preferably 20 seconds to
2 minutes.

In the processing solution having bleaching ability, it is particularly preferable to carry out aeration during processing, since photographic performance is extremely stably maintained. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. Aeration may be performed directly in the processing tank, but in a preferred embodiment, aeration is performed in the stock tank in order to prevent mixing of other liquids.

In blowing air, it is preferable to discharge air into the liquid through an air diffuser having fine pores. Such a diffuser is widely used for an aeration tank in activated sludge treatment. Regarding aeration, Z-121 issued by Eastman Kodak Company,
USING PROCESS C-41 3rd Edition (1982
Year), and the items described on pages BL-1 and BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that stirring is strengthened, and the processing is carried out as described in JP-A-3-33847, page 8, upper right column, line 6 to lower left. The contents described in the column and the second line can be used as they are. In the developing apparatus of the present invention, when aeration is performed, it is preferable to use a circulation system, a stock tank, or the like.

The photographic material generally undergoes a washing and / or stabilizing step after desilvering. In washing and / or stabilizing steps, it is desirable that residual thiosulfate concentration of the processed light-sensitive material is prepared to be 30 to 1500 micromoles / m ^2. Specifically, it is desirable to adjust the concentration of the thiosulfate in the final bath to be about 0.001 to 0.04 mol / liter. That is, the above-mentioned concentration may be added to the final bath, or when a thiosulfate is used as a fixing component, the amount of replenishment in the subsequent washing and stabilization steps is reduced, so that the final bath has the above-mentioned concentration. It is also a desirable embodiment to prepare such a solution.

The specific amount of replenishment varies depending on the concentration of thiosulfate in the fixing step, the number of baths in the washing step and the stabilization step, and the like.
Generally, the amount is about 100 to 1000 ml, preferably about 130 to 700 ml, per m ^{2 of} the photosensitive material.

[0102] The amount of water to be washed in the washing step is as follows.
The relationship between the number of washing tanks and the amount of water in the multi-stage
urnal of the Society of Motion Picture and Televis
ionEngineers vol. 64, p. 248-253 (1955)
May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises.

In the processing of a color light-sensitive material, a method for reducing calcium ions and magnesium ions described in JP-A-62-28838 can be used very effectively as a solution to such a problem. Also,
JP-A-57-8542, isothiazolone compounds, thiabendazoles, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles. (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology"
(1982) The germicidal agent described in "Encyclopedia of Bacterial and Fungicides" (ed. 1986), edited by the Industrial Technology Society of Japan and the Japan Society of Bacterial and Fungicide can also be used.

The pH of the final bath in the processing of the photosensitive material is as follows:
It can be set to any value, preferably 3.5-8,
More preferably, it is 4-7. The pH is preferably set so as to reflect the film pH of the processed photosensitive material,
Various buffers may be used for that purpose. Specific examples include acetic acid, malonic acid, succinic acid, malic acid, maleic acid, and phthalic acid.

The washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, and the like.
A range of 20 seconds to 5 minutes at 5 ° C, preferably 30 seconds to 3 minutes at 25 to 40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization treatment, JP-A-57-8543, JP-A-58-14834, and JP-A-60-14.
All known methods described in No. 20345 can be used.

The stabilizing solution contains a compound for stabilizing a dye image, for example, a benzaldehyde such as formalin or m-hydroxybenzaldehyde, an adduct of formaldehyde bisulfite, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffers are included. The preferable addition amount of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution. The lower the concentration of free formaldehyde in the stabilizing solution, the less the formaldehyde gas is scattered. From these viewpoints, examples of the dye image stabilizer include N-methylolazoles described in JP-A-4-270344, such as m-hydroxybenzaldehyde, hexamethylenetetramine and N-methylolpyrazole, and N, N'-bis (1 4,3,4-triazol-1-ylmethyl) piperazine and the like.
Azolylmethylamines described in 13753 are preferred. In particular, azoles such as 1,2,4-triazole and 1,4-bis (1,2,4) described in JP-A-4-359249 (corresponding to EP-A-519190A2).
A combination of azolylmethylamine and its derivatives such as (-triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. Further, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, a fluorescent brightener, a hardener, and US Pat.
No. 86,583, and a preservative which can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-31051 is also preferable. .

The washing water and / or the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets during drying of the processed photosensitive material. Among them, a nonionic surfactant is preferably used, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl, and dinonylphenol are particularly preferred as the alkylphenol, and the number of moles of ethylene oxide added is particularly preferably 8 to 14. It is also preferable to use a silicon surfactant having a high defoaming effect.

The washing water and / or the stabilizing solution preferably contain various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N '.
-Trimethylene phosphonic acid, diethylene triamine-
Organic phosphonic acids such as N, N, N ', N'-tetramethylenephosphonic acid, or EP 345,172A
The hydrolyzate of the maleic anhydride polymer described in No. 1 can be used.

2. Image Reproduction of the Present Invention Image reproduction comprises image information reading from a developed film, image processing of the read image information, and output of image information corrected by the image processing.

2.1 Reading Image Information from Developed Film FIG. 2 is a block diagram showing the basic configuration of an image reproducing system according to the present invention. As shown in FIG. 2, the image reproducing system includes an image reading device 1 that reads a color image and generates digitized image data.
An image processing device 5 that performs predetermined image processing on image data generated by the image reading device 1 and an image output device 8 that reproduces a color image based on the image data that has been subjected to image processing by the image processing device 5 are provided. Have.

Image reading can be performed mainly by the following three methods. (I) While irradiating a measuring film combined with a color separation filter by wrapping a film around a rotating drum, the drum is rotated, and at the same time, sub-scanning is performed in the direction of the drum, and the reflection density of each pixel is photoelectrically converted by a photomultiplier tube. (Ii) using a line CCD in which light receiving elements are arranged one-dimensionally, and sub-scanning the image on the developed film to determine the transmission or reflection density using a line CCD.
D, which is converted into an electric signal by an electric scan by a line CCD-scanning method, and (iii) an area C
Any area CCD method may be adopted in which the density of pixels is read two-dimensionally using a CD and converted into electric signals rearranged in time series by electric scanning from the area CCD. The area CCD system is particularly preferable, and the following description will be made on the premise of this system. However, the present invention can be implemented without any problem in the other two systems.

The appearance of the image reproducing system shown in FIG. 2 is shown in FIG.
As shown in FIG. 3, in an actual image reproducing system, as an image reading apparatus 1, a transmission type image reading apparatus 10 for photoelectrically reading a color image recorded on a film, and a color printing apparatus A reflective image reading device 30 that photoelectrically reads a color image recorded in
Optionally, it is configured to be connected to the image processing device 5, so that both the color image recorded on the film and the color image recorded on the color print can be reproduced. However, here, an image reading apparatus will be described for a color negative film according to the present invention.

FIG. 4 is a schematic diagram of a transmission type image reading apparatus 10 for a color image reproducing system for generating image data based on a color image. As shown in FIG. 3, the transmission type image reading device 10 irradiates a color image recorded on the film F with light and detects the light transmitted through the film, thereby reading the color image photoelectrically. The light source 11, a light amount adjustment unit 12 capable of adjusting the light amount of the light emitted from the light source 11, and the light emitted from the light source 11 are output to R (red), G (green), and B (blue). A) a color separation unit 13 for separating light into three colors, a diffusion unit 14 for diffusing light so that light emitted from the light source 11 is uniformly irradiated on the film F, and light transmitted through the film F. CCD area sensor 15 for photoelectrically detecting and CCD area sensor 15 for transmitting light transmitted through film F
Is provided with an electric zoom lens 16 for forming an image. The transmission-type image reading apparatus 10 is configured to exchange 135 film negative (135)
Positive film, Advanced Photo System (APS)
Various types of films such as films can be read.

As the light source 11, a halogen lamp was used.
The light amount adjustment unit 12 moves the two aperture plates,
The amount of light changes exponentially with respect to the moving distance. The color separation unit 13 performs color separation into three colors in a plane sequence by rotating a disk having three filters of R, G, and B. The CCD area sensor 15 has a light receiving element of 920 pixels long and 1380 pixels wide,
Image information on film can be read with high resolution. When reading a color image, the CCD area sensor 15 sequentially converts odd-field image data consisting of odd-line image data and even-field image data consisting of even-line image data of the photoelectrically read image. It is configured to transfer.

The transmission type image reading apparatus 10 further includes a CC
The amplifier 17 amplifies the generated R, G, B image signals that are photoelectrically detected and generated by the D area sensor 15, the A / D converter 18 that digitizes the image signals, and digitized by the A / D converter 18. A CCD corrector 19 for correcting the sensitivity of each pixel and a dark current with respect to the obtained image signal and a log converter 20 for converting R, G, B image data into density data are provided. Log converter 2
0 is connected to the interface 21.

The film F is held by the carrier 22, and the film F held by the carrier 22 is
The printer is configured to be fed to a predetermined position by a drive roller 24 driven by the printer 3, press-held in a stopped state, and fed by one frame when reading of one frame of color image is completed. As an auto carrier for handling a negative film, a carrier used in a conventional minilab such as Fujifilm NC135S is used. It is possible to read an image in a range corresponding to a print mode, such as a full size, a panorama size, and a powerful size. In addition, when a carrier used in a conventional minilab is used as a trimming carrier, the magnification can be increased by about 1.4 times around the center. Also, as a reversal carrier, Japanese Patent Application Hei 7-
No. 271048, No. 7-275358, No. 7-275
No. 359, No. 7-277455, No. 7-285015
Use what is disclosed in the above item.

The screen detecting sensor 25 detects the density distribution of the color image recorded on the film F, and transmits the detected density signal to the CPU 26 for controlling the transmission type image reading apparatus 10.
The CPU outputs a signal based on the density signal.
26 is configured to calculate the screen position of the color image recorded on the film F, and stop the driving of the motor 23 when determining that the screen position of the color image has reached a predetermined position. The image reading device may be at any location such as an entrance or an exit of a drying unit of the developing machine, an independent reading / image processing device or attached to a printer unit.

2.2 Image Processing of Read Image Information The image reading apparatus 1 shown in FIGS. 1 and 2 has been described in detail above. Next, the image processing apparatus 5 also shown in FIGS. 1 and 2 will be described. I do.

FIGS. 5 and 6 are block diagrams showing the structure of the image processing apparatus 5 divided into two figures. As shown in these drawings, the image processing apparatus 5 is provided with an interface 2 of the transmission type image reading apparatus 10.
1 or an interface 48 connectable to the interface 41 of the reflection type image reading device 30 and the value of two adjacent pixel data of the image data generated by the image reading device 1 and transmitted for each line, Averaging means 49 for averaging and making one pixel data;
A first line buffer 50a and a second line buffer 50b for alternately storing pixel data in each line of the image data sent from the averaging means 49.
And the line data stored in the line buffers 50a and 50b are transferred and the 1
First for storing image data corresponding to a color image of a frame
Frame memory unit 51, second frame memory unit 52, and third frame memory unit 53
It has. Here, the first line buffer 50a and the second line buffer 50b store the odd-numbered pixel data of each line of the image data in one line buffer.
It is configured to store even-numbered pixel data alternately in the other line buffer.

In this embodiment, first, for one frame of color image recorded on film F, first reading (hereinafter referred to as pre-reading) by image reading device 1 and digital image of the read image are performed. Conversion to data is performed. At this time, based on the image data obtained by the pre-reading, the image processing device 5 performs a second
An image reading condition for reading (hereinafter referred to as main reading) is set. Then, based on the set reading conditions, reading of the color image, that is, main reading, is executed again, thereby generating digital image data to be subjected to image processing for reproduction. In order to perform such processing, the image processing device 5 stores image data obtained by pre-reading in the first frame memory unit 51, and stores image data obtained by main reading in the second frame memory unit 52 and The third frame memory unit 53 is configured to store the information.

Before describing the other components shown in FIGS. 5 and 6, these frame memory units will be described in detail. FIG. 7 is a block diagram showing details of the first frame memory unit 51, the second frame memory unit 52, and the third frame memory unit 53. As shown in FIG. 7, the image processing apparatus 5 processes a first frame memory unit 51, a second frame memory unit 52, and a third frame memory unit 52 for processing image data generated by reading a color image.
Of the frame memory units 53
R data memory 51R, G data memory 51G, B data memory 51B, R data memory 52R, and G for storing image data corresponding to (red), G (green), and B (blue).
A data memory 52G and a B data memory 52B, an R data memory 53R, a G data memory 53G and a B data memory 53B are provided. Note that, as described above, the first frame memory unit 51 stores the image data obtained by prefetching, and stores the second and third image data.
In FIG. 7, the image data obtained by prefetching is input from the input bus 63 to the first frame memory unit 51, and the second frame data is stored in the first frame memory unit 51. The state where the image data stored in the memory unit 52 is output to the output bus 64 is shown.

The structure of the image processing apparatus 5 will be described again with reference to FIGS. The image processing device 5 includes a CPU 60 that controls the entire image processing device 5. C
The PU 60 is a CPU that controls the transmission type image reading device 10.
26 (FIG. 4) and a communication line (not shown) that can communicate with each other and controls an image output device 8 described later.
It is configured to be able to communicate with U via a communication line (not shown). With this configuration, the CPU 60 changes the image reading conditions for performing the main reading of the color image based on the image data obtained by the pre-reading stored in the first frame memory unit 51, and further reads as necessary. It is possible to change image processing conditions for image processing to be performed on a subsequent image.

That is, based on the image data obtained by the pre-reading, the CPU 60 sets the image reading conditions for the main reading so that the dynamic range of the CCD area sensor 15 or the CCD line sensor 35 can be used efficiently at the time of the main reading. Is determined, and the reading control signal is sent to the CPU 26 of the transmission type image reading device 10 or the CPU of the reflection type image reading device 30 (which is not related to the present invention).
Output to 46. At this time, C of the transmission type image reading apparatus 10
PU 26 or CPU 46 of the reflection type image reading device 30
When the reading control signal is input, the light amount controlling unit 12 or the light amount adjusting unit 34 controls the light amount and the accumulation time of the CCD area sensor 15 or the CCD line sensor 35. At the same time, CPU6
0 denotes a first image processing means and a second image processing means which will be described later so that a color image having an optimum density, gradation and color tone can be reproduced on a color paper based on the obtained image data. A control signal for changing image processing conditions such as image processing parameters by the means is output to the first image processing means and the second image processing means as necessary. At this time, the image reading conditions or the image processing conditions determined by the CPU 60 are stored in the memory 66.

When the CPU 60 performs the above control, if the image reading condition or the image processing condition is held by the instruction of the operator, the CPU 60 does not determine the condition based on the pre-read image data as described above. Various control signals are input based on the held conditions. When the operator sets various conditions by using an input device such as the keyboard 69, and further instructs to hold these conditions,
These conditions are stored in the memory 66, and when the operator subsequently instructs to release the holding of these conditions, the conditions stored in the memory 66 become invalid. Therefore, when performing the above-described control, the CPU 60 first refers to the condition stored in the memory 66, and if the condition is stored, it follows the condition. Determine these conditions based on the data. Therefore, the operator can read from the DX code, instruct the condition setting according to each film type according to a special order of the customer, or automatically set the conditions for each film type in advance and automatically set the conditions. It is also possible to perform the processing according to the instruction. It is not always necessary to hold such conditions in large units such as image reading conditions or image processing conditions, and it is necessary to store the above conditions in the memory 66 or refer to them in more detail. For example, the setting of the saturation may be maintained, and the sharpness may be set using an automatically determined condition.

The configuration of the image processing apparatus 5 in the range shown in FIG. 5 has been described above. Here, the image data generated in the image reading apparatus 1 is input to the image processing apparatus 5 through the interface 48, and the first The processing performed on the image data from the time when the image data is stored in the third frame memory unit will be described in detail.

Next, as described above, an image processing apparatus for performing image processing on the image data stored in the second frame memory unit 52 and the third frame memory unit 53 as a result of the actual reading. 5 will be described.

The image processing device 5 includes a second frame memory unit 52 and a third frame memory unit 53
The look-up table and matrix operation are performed so that the color image can be reproduced on the color paper with the desired density, gradation and color tone in the image data stored in
First to perform image processing such as gradation correction, color conversion, and density conversion
The image processing means 61 (FIG. 6) and the image data stored in the first frame memory unit 51 are stored in a look-up table so that a color image can be reproduced on a CRT screen described later with desired image quality. And a second image processing means 62 (FIG. 6) for performing image processing such as gradation correction, color conversion, density conversion, and the like by matrix operation.
The outputs of the second frame memory unit 52 and the third frame memory unit 53 are connected to a selector 55, and the selector 55 stores the output in one of the second frame memory unit 52 and the second frame memory unit 53. The image data is selectively inputted to the first image processing means 61.

FIG. 8 is a block diagram showing details of the first image processing means 61. As shown in FIG. 8, the first image processing unit 61 includes a color density gradation conversion unit 100 that converts density data, color data, and gradation data of image data, and a color conversion unit that converts saturation data of image data. Digital conversion unit 102 for converting the number of pixel data of image data, frequency processing unit 103 for performing frequency processing on image data, and dynamic range conversion unit 104 for converting the dynamic range of image data. I have. Each of these conversion means,
As generally called pipeline processing, each processing means operates simultaneously, and after the operation is completed, the next processing is performed, so that high-speed processing is possible.

The image processing means shown in FIG. 8 can perform not only processing such as gradation correction, color conversion, and density conversion, but also processing for improving sharpness while suppressing graininess of the film. (This technology is pending as Japanese Patent Application No. 7-337510). In addition, an automatic dodging process that provides good image reproduction can be performed on an image having a high contrast between light and dark areas (this technique is also applied for Japanese Patent Application No. 7-165965). In the present invention, the graininess of the film itself is improved, but (i) the gradation is remarkably softened,
(Ii) Sharpness has deteriorated, and (iii) color balance has also deteriorated. Accordingly, in each of the above-described processing means, image processing conditions for correcting the read image information digitized with respect to these photographic characteristics to the standard image quality are set, and based on the conditions, standard photographic characteristics are set as described in the next section. Then, the converted image information is stored once, and then proceeds to the stage of outputting to a printer a positive image.

In this series of image processing for image reproduction, the correction of the soft gradation, which is particularly mentioned in (i), is performed by the gradation conversion means 100, and particularly when the degree of nonlinearity is large, the gradation conversion is performed. Means 100, dynamic range conversion means 10
This is performed by modifying the shape of the characteristic curve of the leg portion and the high-density portion in a direction approaching the characteristics of the reference development by a combination of the density amplification degree 4 and the spatial frequency change described below. At the same time, to improve the sharpness described in (ii), after increasing or decreasing the number of pixel data of the pixel data by the digital magnification conversion means 102 according to the size of the output positive image, the frequency processing means 103 contributes to the sharpness of the pixel data. It is improved by performing frequency processing such as hardening of a part or edge emphasis. Regarding (iii), the adjustment is made by a combination of the saturation conversion means 101 and the color density gradation conversion means 100. The leg growth directly related to the sensitivity is also corrected by the saturation enhancement of the saturation conversion means 101 and the combination of the dynamic range conversion means 104 and the gradation conversion means 100. In addition, the image sharpness is improved by modifying the shape of the characteristic curve of the leg and the high density portion in combination with the change of the density amplification of the high spatial frequency component. Also in this case, similarly to the reproduction of the gradation (high contrast), if the reproduction to the reference development processing characteristics is insufficient under the already set image processing conditions, the image processing conditions are reset.

Further, processing for enhancing the fringe of the image,
The image sharpness of the entire and fine image portions can be improved by incorporating the process of increasing the gradation of the low density portion, but this is performed by the frequency processing means 103. That is, the spatial frequency of the image portion is analyzed, and an emphasis process is set for a fringe portion where the frequency greatly changes and a fine image portion where the frequency increases. The accuracy of the correction of the gradation and the color balance by the above image processing may be within 10% of the target value set as the density value as described above, and is preferably within 8%. If the color balance and the gradation characteristics are within the above ranges as the density values, it is determined that the image has been reproduced. To convert to standard photo characteristic values, set conversion conditions for each type of film,
The condition may be automatically selected by reading the type of the film to be processed, or the operator may specify the conversion processing condition for each film to be processed. The operation contents of the image processing apparatus used for the above image processing are described in JP-A-8-174022 and 8-18255.
No. 1.

In addition to the above, the image processing apparatus 5 has a data bus separate from the input bus 63 and the output bus 64 of the first frame memory unit 51, the second frame memory unit 52, and the third frame memory unit 53. 65
The data bus 65 includes a CPU 60 for controlling the entire color image reproduction system, a memory 66 for storing an operation program of the CPU 60 or data relating to image processing conditions, and a hard disk capable of storing and storing image data. 67, CRT68, keyboard 6
9, a communication port 70 connected to another color image reproducing system via a communication line, and a C of the transmission type image reading apparatus 10.
A communication line with the PU 26 is connected.

2.3 Output of Image Signal after Image Processing to Printer The configuration of the image processing apparatus 5 shown in FIGS. 2 and 3 has been described in detail. Next, the image output device 8 shown in FIGS. 2 and 3 will be described. In the present invention, focusing on color paper, which is the main output target,
The output of the image information will be described, but the output target of the image information in the present invention is not limited to this. FIG. 9 is a schematic diagram of an image output device 8 for a color image reproduction system that reproduces a color image on a color paper based on image data processed by the image processing device according to the preferred embodiment of the present invention. is there.

In FIG. 9, the image output device 8 includes an interface 78 connectable to the interface 77 of the image processing device 5 and a CPU 79 for controlling the image output device 8.
And an image data memory 80 composed of a plurality of frame memories for storing image data input from the image processing device 5.
A D / A converter 81 for converting image data into an analog signal; a laser light irradiation means 82; and a modulator driving means 83 for outputting a modulation signal for modulating the intensity of the laser light. The CPU 79 is configured to be able to communicate with the CPU 60 of the image processing apparatus 5 via a communication line (not shown).

FIG. 10 is a schematic view of the laser light irradiating means 82 shown in FIG. 9. The laser light irradiating means 82 includes semiconductor laser light sources 84a, 84b and 84c, and emits laser light emitted from the semiconductor laser light source 84b. The light is converted into green laser light having a wavelength of 532 nm by the wavelength conversion means 85, and the laser light emitted by the semiconductor laser light source 84 c is converted by the wavelength conversion means 86 into blue laser light having a wavelength of 473 nm.

6 emitted from the semiconductor laser light source 84a
Red laser light of any wavelength between 70 nm and 690 nm,
The green laser light whose wavelength has been converted by the wavelength converting means 85 and the blue laser light whose wavelength has been converted by the wavelength converting means 86 are respectively converted into an acousto-optic modulator (AO).
M) and the like so as to be incident on the optical modulators 87R, 87G, 87B.
B is configured such that a modulation signal is input from the modulator driving unit 83 and the intensity of the laser beam is modulated according to the modulation signal. At this time, if the semiconductor laser light source 84a can operate at high speed, the optical modulator 87R can be omitted by directly modulating the semiconductor laser light source 84a.

The laser light whose intensity has been modulated by the optical modulators 87R, 87G, 87B is reflected by the reflection mirror 88R,
The polygon mirror 89 is reflected by 88G and 88B.
Incident on. Here, the paper is transported at a speed of about 75 mm per second, the scanning line density is 600 lines per inch, and each pixel is modulated every 100 nsec.

The image output device 8 includes a magazine 91 in which color paper 90 is stored in a roll shape. The color paper 90 having a paper width is conveyed at a speed of about 110 mm per second in the sub-scanning direction along a predetermined conveyance path. It is configured to: A color paper with a width of 89 mm to 210 mm can be used, and it may be a color paper used in ordinary mini-labs or a special color suitable for high-intensity short-time exposure unique to laser exposure. Paper may be used. As the magazine 91, a magazine used in a normal minilab, for example, Japanese Patent Application No. Hei 4-317051
Use the one described in the item. The transport path of the color paper 90 is provided with perforation means 92 for making a reference hole at a side edge of the color paper 90 at intervals corresponding to the length of one color print. In the device 8, according to the reference hole, the color paper 90
Is synchronized with the driving of other means.

The laser light modulated by the light modulators 87 R, 87 G, and 87 B is scanned in the main scanning direction by the polygon mirror 89, and exposes the color paper 90 via the fθ lens 93. Here, color paper 90
Is transported in the sub-scanning direction, so that the entire surface is exposed by laser light. Here, the transport speed of the color paper 90 in the sub-scanning direction is the main scanning speed of the laser beam,
That is, it is controlled by the CPU 79 so as to synchronize with the rotation speed of the polygon mirror 89.

The color paper 90 exposed by the laser beam is sent to the developing section 94 at a speed of about 29 mm per second, and is subjected to predetermined color developing processing, bleach-fixing processing, and rinsing processing. A color image is reproduced on the color paper 90 based on the image data subjected to the image processing. The color paper 90 that has been subjected to the color development processing, the bleach-fixing processing, and the water-washing processing by the color developing tank 94, the bleach-fixing tank 95, and the washing tank 96 is sent to the drying unit 97, where the color paper 90 is dried. Based on the reference holes formed in the side edges, the color paper 9
By the cutter 98 driven in synchronization with the conveyance of 0, it is cut into a length corresponding to a color image recorded on one frame of the film F or one color paper P, sent to the sorter 99, and sent to the sorter 99. The number of sheets corresponding to the film F of the book or the number of customers is accumulated. A sorter has been filed separately (Japanese Patent Application No. 2-332146).
issue).

Here, the color developing tank 94 and the bleach-fixing tank 9
5. As the washing tank 96, the drying unit 97, the cutter 98, and the sorter 99, those used in an ordinary minilab automatic developing machine can be used. In this embodiment, the processing method CP47L is adopted.
CP43FA (both processing and photosensitive material manufactured by Fuji Photo Film Co., Ltd.) can be used, and other general processing may be used.

Further, in the present embodiment, the characteristic variation and characteristic variation of the color paper used, the laser light source,
Calibration can be performed in order to absorb characteristic variations of the modulator and the development processor and perform stable image reproduction. First, the density data stored as digital data is converted into a single color of each of the three colors cyan, magenta, and yellow, and a gray color obtained by superimposing the three colors.
After exposure and development with each of a plurality of density step patterns, the developed densities are automatically measured using a densitometer. Based on the difference between the target density and the measured density, the table storing the characteristics of the electric signal given to the modulator at the time of exposure is rewritten for the density data to be reproduced. As a result, it is possible to always stably reproduce an image without being affected by changes in the paper used, the device, the environment, and the like. The input device has a calibration function for keeping the characteristics constant independently of absorbing the characteristic fluctuation due to the replacement of the halogen lamp light source or the like in a constant state. As described above, by independently managing the input device and the output device, stable image reproduction can be always performed.

3. Positive materials for output As described above, the materials for output to obtain positive images are inkjet, sublimation type thermal transfer, color diffusion transfer, color electrophotography, heat development type silver halide color diffusion transfer, and heat development type multilayer color. Any image signal such as diazo, silver halide color paper or the like can be input as long as it is an electric or optical signal that is time-series.

Among them, a color paper is particularly preferable. All of the photosensitive silver halide emulsions in the light-sensitive material preferably have silver chloride content of at least 95 mol%, the balance being silver bromide, and preferably comprise silver halide grains substantially free of silver iodide. Here, “substantially free of silver iodide” means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less, more preferably 0 mol%. From the viewpoint of rapid processing, the silver halide emulsion is preferably a silver halide emulsion having a silver chloride content of 98 mol% or more. Among such silver halides, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable because high sensitivity can be obtained and photographic performance can be stabilized.

The silver halide emulsion contained in at least one photosensitive silver halide emulsion layer has a coefficient of variation of grain size distribution (standard deviation of grain size distribution divided by average grain size) of 15% or less. Some are preferred and 1
Monodispersed emulsions of 0% or less are more preferred. It is preferable to use two or more of the above monodispersed emulsions in the same layer for the purpose of obtaining a wide latitude. At this time, the monodispersed emulsions preferably differ in average grain size by 15% or more, more preferably differ by 20 to 60%, and particularly preferably differ by 25 to 50%. The sensitivity difference between the monodispersed emulsions is preferably from 0.15 to 0.50 logE, more preferably from 0.20 to 0.40 logE, even more preferably from 0.25 to 0.35 logE. . To obtain the desired image gradation of the present invention,
Iron and / or ruthenium and / or osmium compounds are added to silver chlorobromide having a silver chloride content of 95 mol% or more substantially containing no silver iodide at 1 × / mol of silver halide.
A silver halide emulsion containing 10 ^-5 to 1 × 10 ^-3 mol and containing 1 × 10 ^-7 to 1 × 10 ^-5 mol of an iridium compound per mol of silver halide in a silver bromide localized phase. It is effective to use

As the silver halide photographic light-sensitive material for output used in the present invention, conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transparent support include transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyesters of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) and polyesters of NDCA, terephthalic acid and EG. And the like provided with an information recording layer such as a magnetic layer are preferably used. For the purpose of the present invention, a reflective support is preferred, in particular laminated on a paper base or the plastic film base with a plurality of polyethylene or polyester layers, and at least one such water-resistant resin layer (laminate layer). A reflective support containing a white pigment such as titanium oxide is preferred. Alternatively, a paper colloid or a film base coated with a hydrophilic colloid layer containing a white pigment may be used. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio in the case of mixing with the water-resistant resin is preferably 0.0005 to 3% by weight with respect to the resin, and more preferably 0.1 to 3% by weight.
001 to 0.5% by weight.

In order to make the image reproducing system of the present invention compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) combining a semiconductor laser or a solid-state laser with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The maximum wavelength of the spectral sensitivity of the output color photosensitive material can be arbitrarily set depending on the wavelength of the scanning exposure light source to be used. In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. When the exposure time in such scanning exposure is defined as the exposure time for the pixel size when the pixel density is 400 dpi, the preferred exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less. Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table.

4. Color photographic material for photography to which the present invention is applied In the color photographic material for photography used in the present invention, a color negative film is particularly preferred. As the color negative film of the present invention, as described above, general color negative films from various manufacturers sold in the market can be used.

As a typical example of the color negative film of the present invention, at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities is provided on a support. This is a silver halide photographic light-sensitive material. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light. The red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer are provided in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in DE 1,121,470 or GB923,0.
As described in No. 45, it is preferred that two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer are arranged so that the sensitivity gradually decreases toward the support. Also, Japanese Patent Application Laid-Open No. 57-112
No. 751, No. 62-200350, No. 62-2065
As described in JP-A Nos. 41 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on. In addition, Japanese Patent Publication No. 55-34
As described in JP-A-932, a blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the farthest side from the support. Japanese Patent Application Laid-Open No. 56-25738
No. 62-63936, the blue-sensitive layer / GL / RL / GH from the side farthest from the support.
/ RH may be arranged in this order. In addition, Tokubiko 49-
No. 15,495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the silver halide emulsion having a lower sensitivity than the middle layer. An example is an arrangement in which an emulsion layer is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-speed emulsion layer / They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers. In order to improve color reproducibility, US Pat.
No. 3,271, No. 4,705,744, No. 4,70
7,436, JP-A-62-160448, JP-A-63-160448
It is preferable to dispose a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL described in the specification of 89850, adjacent to or adjacent to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (197
December, 8), pp. 22-23, "I. Emulsion production (Emulsi
on preparation and types) ”and No. 187
16 (November 1979), p. 648, ibid. 307
105 (11/1989), pp. 863-865, and "The Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Chemie et Phisique Photographiq).
ue Paul Montel, 1967), Duffin's "Emulsion Chemistry", Focal Press (GFDuffinPhotograph)
ic Emulsion Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zeligman et al., published by Focal Press (VLZelikman et al., Making and Coating Ph.
otographic Emulsion, Focal Press, 1964).

US Pat. Nos. 3,574,628 and 3,65
Monodisperse emulsions described in US Pat. No. 5,394 and GB 1,413,748 are also preferred. The aspect ratio is about 3
The tabular grains as described above can also be used in the present invention. Tabular grains are written by Gatoff, Photographic Science and Engineering (Gutoff Photographic S
Science and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,434,226;
14,310, 4,433,048, 4,43
No. 9,520 and GB 2,112,157 can be easily prepared.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is RD No. 17643,
No. No. 18716 and the same No. 307105, and the corresponding portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions different in at least one property of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion,
They can be mixed and used in the same layer. US4,0
No. 82,553, and silver halide grains having a fogged surface described in US Pat. No. 4,626,498;
No. 14,852, the inside of which is covered with silver halide grains and colloidal silver may be applied to a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer according to circumstances. it can. The term “silver halide particles having a fogged interior or surface” refers to silver halide particles that can be uniformly (non-imagewise) developed regardless of the unexposed portions and exposed portions of the photosensitive material. The preparation method is US4
626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. Silver chloride, silver chlorobromide,
Both silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm, particularly 0.05 to 0.75 μm.
~ 0.6 µm is preferred.

The color negative film according to the present invention can also use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing process, and is preferably not fogged in advance. The fine grain silver halide has a silver bromide content of 0 to 100 mol%,
If necessary, it may contain silver chloride and / or silver iodide. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average particle size (average value of the equivalent circle diameter of the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide.

The photographic additives which can be used in the color negative film according to the present invention are also described in RD, and the relevant portions are shown in Table 1 below.

[0158]

[Table 1]

Although various dye-forming couplers can be used in the color negative film of the present invention, the following couplers are particularly preferred. Yellow coupler: Formula (I) of EP502,424A,
A coupler represented by formula (1) or (2) of EP513,496A (particularly Y
-28); couplers of the formula (I) in claim 1 of EP 568,037A; US 5,066,576
A coupler represented by the general formula (I) in column 1 of the line 45 to 55; a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; EP 498,381
The couplers described in claim 1 on page 40 of A1 (especially 18
D-35 on page 4); Couplers represented by formula (Y) on page 4 of EP447,969A1 (especially Y-1 (page 17),
Y-54 (page 41)); couplers represented by formulas (II) to (IV) in columns 7 to 36 of US Pat. No. 4,476,219 (particularly II-17, 19 (column 17), II- 2
4 (column 19)). Magenta coupler: JP-A-3-39737 (L-57)
(Page 11, lower right), L-68 (page 12, lower right), L-77
(Page 13 lower right); A-4-63 of EP456,257
(Page 134), A-4-73, -75 (page 139); E
P-486,965, M-4, -6 (p. 26), M-7
(Page 27); M-45 of EP 571,959A (19
(M-1) of JP-A-5-204106 (page 6);
M-22 in paragraph 0237 of JP-A-4-36231.

Cyan coupler: JP-A-4-208443
CX-1,3,4,5,11,12,14,15 (1
4 to 16); JP-A-4-43345, C-7,10
(P. 35), 34, 35 (p. 37), (I-1), (I-1)
7) (pages 42 to 43); a coupler represented by the formula (Ia) or (Ib) according to claim 1 of JP-A-6-67385. Polymer coupler: P-1, P of JP-A-2-44345
-5 (page 11).

US Pat. No. 4,366,237, GB 2,125, and US Pat.
570, EP 96,873B, DE 3,234,533
Are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456, 257 A1 (particularly Y on page 84).
C-86), yellow colored magenta coupler ExM-7 (p. 202) and EX-1 (249) described in the EP.
EX-7 (page 251), US Pat. No. 4,833,069.
Magenta colored cyan couplers CC-9 (column 8), CC-13 (column 10), US Pat.
7,136 (2) (column 8), WO92 / 1157
Colorless masking couplers of formula (A) of claim 1 of claim 5 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of compounds (including couplers) which release a photographically useful compound residue by reacting with an oxidized developing agent include the following.

Development inhibitor releasing compound: EP 378,23
Formulas (I), (II), (III) and (IV) described on page 11 of 6A1
(Particularly T-101 (p. 30), T-
104 (page 31), T-113 (page 36), T-131
(Page 45), T-144 (page 51), T-158 (58
Page)), EP 436, 938 A2, page 7 (particularly D-49 (51
P.)), Compounds represented by formula (1) of EP568,037A (especially (23) (p.11)), EP440,19.
Compounds represented by formulas (I), (II) and (III) described on pages 5 to 6 of 5A2 (especially I- (1) on page 29);

Bleaching accelerator releasing compound: EP 310,12
Compounds of formulas (I) and (I ') on page 5 of 5A2 (especially (60) and (61) on page 61) and JP-A-6-59.
411. The compound represented by formula (I) of claim 1 (particularly (7) (p. 7); Ligand releasing compound: US 4,55
Compound represented by LIG-X described in claim 1 of US Pat.
Compounds 1 to 6 of columns 3 to 8; fluorescent dye releasing compounds:
C0UP-DY of claim 1 of US 4,774,181
Compound represented by E (particularly, compound 1 in columns 7-10)
-11);

Development accelerator or fogging agent releasing compound: U
Formulas (1) and (2) of column 3 of S4, 656, 123,
The compound represented by (3) (particularly, (I-2) in column 25
2)) and EP450, 637A2, page 75, 36-38.
ExZK-2 in row: Compound that releases a group that becomes a dye only after leaving: a compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (especially, Y-1 to Y- 19).

The following are preferred as additives other than the coupler. Dispersion medium of oil-soluble organic compound: JP-A-62-215272
P-3, 5, 16, 19, 25, 30, 42, 49,
54, 55, 66, 81, 85, 86, 93 (140 to
144)); Latex for impregnation of oil-soluble organic compound: U
Latex described in S4, 199, 363; oxidized developing agent scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. , (6), (12) (columns 4-5),
US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3);
Formulas (I) to (II) on page 4, lines 30 to 33 of 98321A
I), especially I-47, 72, III-1, 27 (24-48
Page); Anti-fading agent: A-6,7, of EP298321A
20, 21, 23, 24, 25, 26, 30, 37, 4
0, 42, 48, 63, 90, 92, 94, 164 (6
9-118), column 25 of US 5,122,444.
II-I to III-23, especially III-10, EP47
1347A, pages 1 to 12 I-1 to III-4, especially II-
2, US 5,139,931 Columns 32-40 A-
1-48, especially A-39, 42;

Material for Reducing the Use of Color Enhancing Agent or Color Mixing Prevention: I- on page 5-24 of EP 411324A
1-II-15, especially I-46; Formalin scavenger: SCV-1 on pages 24-29 of EP 477932A.
28, especially SCV-8; hardener: JP-A-1-21484
5, page 17, H-1, 4, 6, 8, 14, US 4, 61
Compounds (H-1 to 54) represented by Formulas (VII) to (XII) in columns 13 to 23 of 8,573, JP-A-2-214
852, page 8, lower right compound (H-
1-76), especially the compounds described in claim 1 of H-14, US 3,325,287; development inhibitor precursors:
JP-A-62-168139, P-24, 37, 39 (6)
Compounds described in claim 1 of US Pat. No. 5,019,492, especially 28, 29 of column 7; Preservatives and fungicides: I-1 of columns 3 to 15 of US Pat. No. 4,923,790.
~ III-43, especially II-1, 9, 10, 18, III-2
5; Stabilizer, antifoggant: I-1 to (14) of columns 6 to 16 of US Pat. No. 4,923,793, particularly I-1,6
0, (2), (13), compounds 1-65, especially 36, from columns 25-32 of US 4,952,483.

Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; Dye: JP-A-3-156450, pages 15-18, pages a-1 to b-2
0, especially a-1, 12, 18, 27, 35, 36, b-
V-1 to 23 on pages 5, 27 to 29, especially V-1, EP4
F-I-1 to F-II-4 on page 33 to 55 of 45627A
3, especially FI-11, F-II-8, EP457153
A, pages III-36 on pages 17-28, especially III-1,3
Dye-1 to 124 of 8-26 of WO88 / 04794
Of EP 319999A, compounds 1 to 22 on pages 6 to 11, especially compound 1, compounds D-1 to 87 of EP519306A represented by formulas (1) to (3).
(Pages 3 to 28), compounds 1 to 22 (columns 3 to 10) represented by formula (I) of US Pat.
Compounds (1) to (31) represented by the formula (I) of 4,923,788 (columns 2 to 9);

UV absorbers: Compounds (18b) to (18r), 1 represented by formula (1) of JP-A-46-3335.
Compounds (3) to (66) represented by the formula (I) of Nos. 01 to 427 (pages 6 to 9) and EP520938A (10 to 4).
4) and the compounds HBT-1 to HBT-1 represented by the formula (III).
10 (p. 14), compounds (1) to (31) represented by the formula (1) in EP521823A (columns 2-9).

The color negative film of the present invention may be a film unit with a lens described in JP-B-2-32615 and JP-B-3-39784.
Suitable supports that can be used in the present invention are, for example, the aforementioned R
D. No. No. 17643, page 28; No. 18716, from the right column on page 647 to the left column on page 648; 307
105, page 879, it is preferred to use a polyester support.

Color negative film used in the present invention
Preferably has a magnetic recording layer. Used in the present invention
The magnetic recording layer obtained will be described. Used in the present invention
A magnetic recording layer is a layer in which magnetic particles are dispersed in a binder.
Aqueous or organic solvent-based coating liquid was applied on the support
Things. The magnetic particles used in the present invention are γFe
_TwoO_ThreeSuch as ferromagnetic iron oxide, Co-coated γFe_TwoO_Three, Co
Magnetite, Co-containing magnetite, ferromagnetic dioxide
Chromium, ferromagnetic metal, ferromagnetic alloy, hexagonal BaFe
Light, Sr ferrite, Pb ferrite, Ca ferrite
Can be used. Co deposited γFe_TwoO_ThreeSuch as Co
Deposited ferromagnetic iron oxide is preferred. Needle shape, rice grain
Shape, spherical shape, cubic shape, plate shape, etc. Specific surface area
Then S_BETAt 20m^Two/ g or more, preferably 30 m^Two/ g or more
Particularly preferred. The saturation magnetization (σs) of the ferromagnetic material is preferable.
Or 3.0 × 10^Four~ 3.0 × 10^FiveA / m, especially
Preferably 4.0 × 10^Four~ 2.5 × 10^FiveA / m
You. Ferromagnetic particles, such as silica and / or alumina
Surface treatment with an organic material may be performed. In addition, magnetic
The body particles are as described in JP-A-6-160332.
Silane coupling agent or titanium coupling agent on the surface
May be processed. JP-A-4-259911, 5
No. 81652 coated with inorganic or organic material
Magnetic particles can also be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural material described in JP-A-4-219569. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is from 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. As the isocyanate-based crosslinking agent, isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate,
Reaction products of these isocyanates with polyalcohols (for example, a reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane), and polyisocyanates formed by condensation of these isocyanates are mentioned. No. 6-59357.

The magnetic recording layer is provided with lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. US Pat. Nos. 5,336,589 and 5,25 for photosensitive materials having a magnetic recording layer
0,404, 5,229,259, 5,215,8
74, EP 466,130.

The polyester support used in the present invention will be described. For details including photosensitive materials, treatments, cartridges, and examples described later, see Japanese Patent Publication No.
4-6023 (Invention Association; 1994. 3.15.). The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components,
2,6-, 1,5-, 1,4 as aromatic dicarboxylic acids
-And 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

In the present invention, an antistatic agent is preferably used. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Zn
O, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , Si
A particle size of at least one selected from O ₂ , MgO, BaO, MoO ₃ and V ₂ O ₅ having a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. .00
Fine particles of crystalline metal oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), furthermore, sol-like metal oxides or composite oxides thereof Particles. 5 to 5%
500 mg / m ² is preferred, particularly preferably 10 to 350 mg / m ²
a m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% PH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Slip agents usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and the like, and the additional layer is preferably the outermost layer of the emulsion layer or the back layer. .

[0176]

【Example】

[Embodiment 1] Hereinafter, the present invention will be specifically described with reference to embodiments, but the present invention is not limited thereto.
First, the photosensitive material, the developing processor, and the contents of the working which are used will be described. 1. Tested color negative film: A color negative film equivalent to the sample 101 described in Example 1 of JP-A-8-339063 as a sample that can represent a general-purpose color negative film is 135-24E specified in the international standard (ISO 1007).
x (normal 35 mm, containing 24 cartridges). The ISO sensitivity of this film is 400.

[0177] 2. Method of photographic property test Photographing a person and a Macbeth chart with standard exposure under the illumination of a standard C light source described in ISO 5800 (sensitivity measuring method for color negative film) on each test film. The photographic image reproduction characteristics were visually determined. At the same time, exposure was performed through a continuous tone carbon wedge for sensitometry, and the photographic characteristics of the developed color negative film, particularly the gamma value, were measured.

[0178] 3. Developing Processor Used The image processing mechanism described in Section 2 of this specification (filed in Japanese Patent Application Nos. 8-174022 and 8-182551) and a color negative, except for the developing processor for comparative experiments. Film processing machine (FP560, Fuji Photo Film Co., Ltd.)
(Image processing combination type).
However, the drive motor was modified so that the film transport speed was variable.

[0179] 3. Development Processing The processing steps and processing solution compositions used as the standards for color negative development are shown below.

(Processing process) Process Processing time Processing temperature Color development 3 minutes 5 seconds 38.0 ° C Bleaching 50 seconds 38.0 ° C Fixed (1) 50 seconds 38.0 ° C Fixed (2) 50 seconds 38.0 ° C Water washing 30 seconds 38.0 ℃ Stable (1) 20 seconds 38.0 ℃ Stable (2) 20 seconds 38.0 ℃ Drying 1 minute 30 seconds 60 ℃

The stabilizing solution was of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing (2). The fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 2.5 ml and 2.0 ml, respectively, per 1.1 mm width of 35 mm photosensitive material. , 2.0 ml. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developing solution A) Tank solution (g) Diethylenetriaminepentaacetic acid 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 0.012 mol Potassium iodide 1.3 mg Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 2.0 hydroxylamine sulfate 2.4 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate (color developing agent) 0.0145 mol Add water 1.0 Liters pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

(Bleaching solution) Tank solution (g) 1,3-diaminopropanetetraacetic acid ferric ammonium ammonium monohydrate 118 Ammonium bromide 80 Ammonium nitrate 14 Succinic acid 40 Maleic acid 33 Water was added to add 1.0 liter pH [ammonia water 4.4)

(Fixing solution) Tank solution (g) Ammonium methanesulfinate 10 Ammonium methanethiosulfonate 4 Aqueous solution of ammonium thiosulfate (700 g / L) 280 mL Imidazole 7 Ethylenediaminetetraacetic acid 15 Add water and add 1.0 L pH [Ammonia water, Adjust with acetic acid) 7.4

(Washing Water) Tap water was washed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strong basic anion exchange resin (Amberlite IR-400). Water was passed through the packed mixed-bed column to adjust the concentration of calcium and magnesium ions to 3 mg / l or less, and then 20 mg / l of sodium diisocyanurate and 150 mg / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Tank liquid (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1,2,4- Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-Benzoisothiazolin-3-one 0.10 Add water 1.0 liter pH 8.5 8.5

Next, a competing coupler was added to the color developing solution A as described below to prepare color developing solutions B to Q.

[0188]

[Table 2]

The photographed color negative film was developed under the above-described color development conditions and printed on color paper.

5. Output device A laser printer / paper processor LP-10 is an example of a commercially available printer that can generate a positive image by inputting an electrical image signal output from the FP560B.
00P (Fuji Photo Film Co., Ltd.) was used. For the comparison sample, a commercially available surface exposure type color printer / paper processor PP728A (manufactured by Fuji Mini Lab Champion Fuji Photo Film Co., Ltd.) was used.
The printer of this device is of the type commonly used in the current market where the color balance is controlled by controlling the filter by the simultaneous full-surface exposure method in which the developed color negative is transmitted through and printed on color paper. It is. In each case, color paper uses commercially available Fujicolor Pepper Super FA3 (manufactured by Fuji Photo Film Co., Ltd.), and the development process is a general-purpose CP47L formulation (development process formulation and processing agent for color paper, Fuji Photo Film Co., Ltd.) Made)
It went according to.

6. Tests The following tests were performed. (1) Sensory evaluation of image quality The color negative films treated with the color developers A to H were printed with LP1000 and PP728A, respectively. The printed image is a randomly extracted 1
The sensory evaluation of the image quality was performed by 0 persons, and each person gave a score on a five-point scale of 1 to 5. (Evaluation content) (Score) Poor ----------------------------------------- ------ 1 point Somewhat inferior ---------------------------------------- --- 2 points Normal (the same level of print quality as you are used to in everyday life) --- 3 points Somewhat good ------------------------- ------------------ 4 points good ----------------------------- ------------------ 5 points The average of the obtained scores was calculated.

(2) Evaluation of Granularity and Sharpness The same observer observed the same print for the same print, paying attention to the edge sharpness of the outline of the human image and the granularity of the skin.
Visual evaluation was performed by a graded scoring method.

[0193] 7. Test results The test results of the sensory evaluation are shown in Table 3 below.

[0194]

[Table 3]

Prints subjected to digital image processing have obtained higher image quality evaluation points than ordinary light-surface exposure prints. However, in the method of the present invention in which a competitive coupler is added and further image processing is performed, further evaluation is performed. The points are higher. The effects are particularly remarkable in the compound III. IV group and IX-1 IX-2. On the contrary, in the comparative example in which the image processing was not performed by adding the competing coupler, the image quality was deteriorated.

Next, the test results of the visual evaluation of graininess and sharpness are shown in Table 4 below. The granularity is rated higher for the finer (the better).

[0197]

[Table 4]

In ordinary light-surface exposure printing, sharpness is improved by performing digital image processing printing, but graininess is reduced, and graininess is reduced by using a developing solution containing a competitive coupler. Better, but lower sharpness. On the other hand, in the method of the present invention in which the processing in which a competitive coupler is added and the image processing is performed, the sharpness is improved and the graininess is excellent. Table 5 below shows the gamma values of the samples under each developing condition.

[0199]

[Table 5]

When the gamma values in Table 5 are compared with those in Tables 3 and 4, when the gamma value is reduced by using a developing solution to which a competing coupler is added, the graininess improves, but the image quality or Although the sharpness is reduced, it can be seen that the combination of the addition of the competitive coupler and the image processing improves both the sharpness and the graininess, resulting in a favorable evaluation of the overall image quality.

Example 2 1. Color negative film On a cellulose triacetate film support with an undercoat,
Each layer having the composition shown below was applied in multiple layers to prepare a negative type multilayer color photosensitive material for photography. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye A number corresponding to each component, and indicates a coating amount expressed in g / m ² unit. For silver halide, it indicates a coating amount in terms of silver.
However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Comparative Sample 101) This sample is a color negative film of substantially the same type as a general-purpose color negative film that is commercially available and is developed at developing sites around the world. Therefore, both the mask density (Dmin) and gradation are different. Equivalent to ordinary film. First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02

Second Layer (Intermediate Layer) Silver iodobromide emulsion M silver 0.065 ExC-2 0.04 polyethyl acrylate latex 0.20 gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 gelatin 0.87

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-10 .10 gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10.

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E silver 0.15 silver iodobromide emulsion F silver 0.10 silver iodobromide emulsion G silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS- 3 0.010 Gelatin 0.73

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY- ⁴ 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4 0.0 × 10 ^-3 gelatin 0.80

Ninth Layer (High Sensitive Green-Sensitive Emulsion Layer) Silver Iodobromide Emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.10 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1. 33

Tenth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.015 Cpd-1 0.16 Solid Disperse Dye ExF-5 0.060 Solid Disperse Dye ExF-6 0.060 Oil-soluble Dye ExF-7 010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J silver 0.09 silver iodobromide emulsion K silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-40 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.8

Fourteenth layer (second protective layer) Silver iodobromide emulsion M silver 0.10 H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (diameter 1 0.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, W-1 to W-3, B-4 to B-B may be suitably added to each layer in order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability. 6, F-
1 to F-17, and iron salts, lead salts, gold salts, platinum salts, palladium salts, iridium salts, and rhodium salts.

[0219]

[Table 6]

In Table 6, (1) Emulsions J to L were reduction-sensitized during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to I were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Have been. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope. (5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

(Preparation of Dispersion of Organic Solid Disperse Dye) ExF-2 shown below was dispersed by the following method. That is, water 21.
70 ml of 7 ml and a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) were mixed with 70 ml.
In a 0 ml pot mill, 5.0 g of dye ExF-2 and 500 zirconium oxide beads (1 mm in diameter) were added.
Milliliter was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used.
After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameter of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
m. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP-A-549,489A. The average particle size was 0.06 μm.

[0221]

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[0225]

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[0229]

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[0230]

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[0232]

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[0233]

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[0234]

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[0235]

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[0236]

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(Sample 102) Next, Competitive Coupler VII-2 was applied to the following emulsion layer of Sample 101 at the following coating amount (mol / mol).
m ² ) A sample was prepared in the same manner as the sample 101 except that it was added, and was used as a sample 102. Additive compound Additive layer Coating amount VII-2 Third layer 0.03 VII-2 Fourth layer 0.03 VII-2 Fifth layer 0.03 VII-2 Seventh layer 0.06 VII-2 Eighth layer 06 VII-2 9th layer 0.01 VII-2 11th layer 0.08 VII-2 12th layer 0.04

(Sample 103) Next, the following emulsion of Sample 101
The following application amount (mol / m) of the competitor compound VIII-3 ^Two)
A sample was prepared in the same manner as sample 101, except that it was added.
This was used as Sample 103. Additive compound Additive layer Coating amount VIII-3 Third layer 0.03 VIII-3 Fourth layer 0.03 VIII-3 Fifth layer 0.03 VIII-3 Seventh layer 0.06 VIII-3 Eighth layer 06 VIII-3 9th layer 0.01 VIII-3 11th layer 0.08 VIII-3 12th layer 0.04

[0239] 2. Developing Process and Photographic Property Measurements Photographic characteristic values (Dmin and gamma value) obtained by using the color developing solution A for the samples 101 to 103 and otherwise using the same developing process recipe and test method as in Example 1 are shown in the following table. It was as follows. (Photo characteristic value) Sample No. Dmin Gamma value BGRBGR101.90 0.58 0.24 0.90 0.68 0.68 102 0.82 0.51 0.22 0.65 0.45 0.55 103 0.82 0.52 0.23 0.55 0.42 0.50

The values of graininess and sharpness similarly obtained by the same method are as shown in Table 7.

[0241] 5. Test results

[0242]

[Table 7]

Table 7 shows that both the sharpness and the graininess could be improved by developing a color negative film containing a competitive coupler and a competitive developer according to the present invention and subjecting the image to image processing. Have been.

[0244]

According to the present invention, there is provided an image forming method in which a color development is performed in the presence of a competing compound, particularly a competing coupler, and the obtained image is image-processed and the image information is output to a positive material. Can improve both sharpness and graininess, which have been difficult with a conventional method of producing a positive material by light-surface exposure without image processing. The effect is remarkable when a print is made from a color negative film.

[Brief description of the drawings]

FIG. 1 is a block diagram showing a basic configuration and an overall flow of an image forming method and apparatus according to the present invention.

FIG. 2 is a block diagram showing a basic configuration of an image reproduction system according to the present invention.

FIG. 3 is a diagram illustrating an appearance of an image reproducing system according to an embodiment of the present invention.

FIG. 4 is a diagram schematically showing a transmission type image reading apparatus.

FIG. 5 is a block diagram showing a part of the configuration of the image processing apparatus 5 shown in FIG. 2;

FIG. 6 is a block diagram showing another part of the configuration of the image processing apparatus 5 shown in FIG. 2, which is not shown in FIG. 5;

FIG. 7 is a block diagram showing details of a first frame memory unit, a second frame memory unit, and a third frame memory unit shown in FIG. 5;

FIG. 8 is a block diagram showing details of the first image processing means shown in FIG. 6;

FIG. 9 is a diagram schematically showing the image output device shown in FIG. 2;

FIG. 10 shows a laser beam irradiation unit of the image output apparatus shown in FIG.

FIG. 11 is a characteristic curve of a representative color negative film obtained according to an international standard (ISO 5800).

[Explanation of symbols]

 Description of reference numerals in FIGS. 1 to 11 F film P color print or color paper 01 DX code 02 development selection instructing unit 03 reference development process 03A non-reference development process 04 manual development selection 1 image reading device 5 image processing device 8 image output device 10 Transmission type image reading device 11 Light source 12 Light amount adjustment unit 13 Color separation unit 14 Diffusion unit 15 CCD area sensor 16 Lens 17 Amplifier 18 A / D converter 19 CCD correction means 20 Log converter 21 Interface 22 Carrier 23 Motor 24 Drive roller 25 Screen detection sensor 26 CPU 48 Interface 49 Averaging operation means 50a First line buffer 50b Second line buffer 51 First frame memory unit 51R R data memory 51 GG data memory 51B B data memory 52 second frame memory unit 52R R data memory 52G G data memory 52B B data memory 53 third frame memory unit 53R R data memory 53G G data memory 53B B data memory 55 selector 60 CPU 61 first image processing means 62 second image processing means 63 input bus 64 output bus 65 data bus 66 memory 67 hard disk 68 CRT 69 keyboard 70 communication port 75 data synthesizing means 76 synthesized data memory 76R R data memory 76G G data memory 76B B data memory 77 interface 78 interface 79 CPU 80 image data memory 81 D / A converter 82 laser light irradiation means 83 modulator driving means 84a b, c Semiconductor laser light source 85 Wavelength conversion means 86 Wavelength conversion means 87R, G, B Light modulator 88R, G, B Reflection mirror 89 Polygon mirror 90 Color paper 91 Magazine 92 Perforation means 94 Color developing tank 95 Bleaching and fixing tank 96 Rinse with water Tank 97 Drying section 98 Cutter 99 Sorter 100 Color density gradation conversion means 101 Saturation conversion means 102 Digital magnification conversion means 103 Frequency processing means 104 Dynamic range conversion means

Claims (6)

[Claims] 1. A method for developing a photographed silver halide color photographic light-sensitive material, photoelectrically reading the obtained image information, converting it into digital image information, and outputting the digital image information to a printer, in the presence of a competitive compound. A color image forming method comprising performing color development. 2. The color image forming method according to claim 1, wherein color development is performed using a color developer to which a competitor compound has been added. 3. The color image forming method according to claim 1, wherein the competitor compound is a coupler. 4. A competitor compound comprising a dihydroxybenzophenone derivative, a naphthoic acid derivative and an acetophenone derivative and a 2,6-dihydroxyisonicotinic acid derivative;
The color image forming method according to claim 3, wherein the color coupler is a competitive coupler selected from 3,5-dihydroxybenzoic acid derivatives. 5. The color image according to claim 1, wherein the color image is developed so that the gamma value of the photographed silver halide color photographic material is 0.2 to 0.7. Forming method. 6. The color image forming method according to claim 1, wherein the photographed silver halide color photographic light-sensitive material is a color negative film.