JP2005283985A - Automatic developing processor for silver halide photographic sensitive material and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an automatic developing processor for a silver halide photographic sensitive material capable of removing dirt on a roll causing paper stain and a residual sensitizing dye causing problem on a white background in an automatic developing processor for a silver halide photographic sensitive material using a jet development system. <P>SOLUTION: In the automatic developing processor for a silver halide photographic sensitive material, a step of jetting a processing solution containing an oxidizing agent is carried out after a step of jetting a processing solution having fixing capacity. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an automatic developing machine for silver halide photographic light-sensitive materials for developing a silver halide photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material or a light-sensitive material). The present invention relates to an automatic developing machine for silver halide photographic light-sensitive materials and a developing method using a jet development system excellent in continuous injection stability.

  Due to the rapid increase in minilab shops in recent years, the amount of photosensitive material processed per one silver halide photographic light-sensitive material automatic developing machine in a photographic development processing shop is decreasing. A decrease in the processing amount of the photosensitive material per automatic processor causes a decrease in the renewal rate of the processing liquid in the processing tank of the automatic processor, and a decrease in the reprocessing rate of the processing liquid causes deterioration of the processing liquid. It is easy to keep stable processing performance. For this reason, there is an increasing demand for equipment that does not require frequent maintenance and daily management such as equipment cleaning even when the amount of photosensitive material processed per automatic processor is low.

  On the other hand, as a method for developing a silver halide photographic light-sensitive material without providing a processing tank, the processing solution is stored in a highly airtight container (for example, an ink jet head), and this processing solution is exposed to the emulsion surface of the photosensitive material. A developing system based on a jet developing system that supplies and processes a phase is disclosed (see Patent Document 1).

  In the jet development method, small droplets are jetted onto the light-sensitive material for development processing. Therefore, it is difficult to supply a sufficient amount of processing liquid, and stable jetting is continuously performed due to air bubbles mixed in. However, there has been proposed a technique that solves these problems by providing an on-off valve in the treatment liquid supply channel or improving the injection nozzle for the treatment liquid (Patent Document 2). reference).

  The development system based on the jet development method always develops a new processing solution on the surface of the photosensitive material compared to the conventional immersion development method in which the photosensitive material is immersed in the processing solution in the processing tank. It has the advantages that there are few variations in the finish, excellent maintainability, and that the amount of waste liquid is small and the environmental load is small, and the spread is widening.

  By the way, with the recent increase in small-volume processing stores and the spread of 24-hour services such as kiosks, white background problems and paper stains have emerged as new problems. This problem is also a problem that has occurred in the development system of the jet development system. In particular, when the number of processed sheets is small, the white background problem has appeared remarkably. The white background problem mentioned here refers to a phenomenon in which the remaining sensitizing dye colors and contaminates the white background portion of the color print because the sensitizing dye cannot be sufficiently removed from the photosensitive material during the development process.

  As a method for removing the sensitizing dye remaining in the photosensitive material, there is a method in which an oxidizing agent is brought into contact with the photosensitive material after the fixing process to efficiently decompose the sensitizing dye (see Patent Document 3). It did not work well when applied to other development systems.

  Also, in color paper development processing by the jet development method, the color developing agent that adheres to the surface of members such as the conveyance roller in the developing device becomes tar by oxidation, and if it adheres to the surface of the photosensitive material, it can be easily removed in the water washing process. It became impossible to generate paper stains.

Also, in today's so-called digitization era, image information obtained by optically reading a film image formed by performing post-shooting development processing with a film scanner, etc., converting it to an electrical signal, and performing digitization processing Is formed on a separate recording material. After forming a color image of at least three colors by film development processing, the image is converted into optical information or electrical information, and the image is formed on another recording material. An image forming method for forming a color image has also been proposed (see Patent Document 4). Even in such an image forming method in which an image is read from the film after the development processing, if the processing amount is reduced, the developing performance deteriorates in the jet development method, resulting in low-density color development. However, there was a problem that it was difficult to capture images.
JP-A-6-324455 JP 2002-16725 A JP 2003-121974 A JP 11-65054 A

  Automatic development for silver halide photographic light-sensitive materials capable of removing roller stains that cause paper stains and residual sensitizing dyes that cause white background problems in an automatic developing machine for silver halide photographic light-sensitive materials using a jet development system Image information obtained from a film that has been developed by a jet development system and optically read by a film scanner, etc., converted into an electrical signal, and digitized. An image forming method for forming an image on another recording material is to provide a developing method with good scanner reading characteristics that eliminates the influence of residual silver.

  The inventors have made various studies in order to solve the above problems, and found that the problem can be achieved by injecting an oxidizing agent onto the processed photosensitive material.

  The present invention is achieved by the following configurations described in the claims.

That is, the invention according to claim 1 is the following: "In an automatic developing machine for silver halide photographic light-sensitive materials for performing development processing by sequentially jetting a plurality of kinds of processing liquids onto an exposed silver halide photographic light-sensitive material,
An automatic developing machine for a silver halide photographic light-sensitive material, comprising a step of spraying a processing solution containing an oxidizing agent after a step of spraying a processing solution having fixing ability. It is.

  According to the second aspect of the present invention, “having squeeze means for squeezing the silver halide photographic light-sensitive material immediately before the step of injecting the processing solution containing the oxidizing agent onto the silver halide photographic light-sensitive material. 2. An automatic developing machine for silver halide photographic light-sensitive materials according to claim 1 characterized by the above-mentioned.

  The invention described in claim 3 is the “automatic developing machine for silver halide photographic light-sensitive materials according to claim 1 or 2, wherein the oxidizing agent is a peroxide”.

  The invention according to claim 4 is “at least the treatment liquid containing the oxidizing agent is selected from compounds represented by the following general formula [1], [S1] or [S2], or water-soluble organosiloxane compounds” The automatic developing machine for silver halide photographic light-sensitive materials according to any one of claims 1 to 3, which contains one kind.

In the formula, Rf represents a saturated or unsaturated alkyl group containing at least one fluorine atom.
X is sulfonamide,

Represents one of the following. Y represents an alkylene oxide group. Rf ′ represents a saturated or unsaturated hydrocarbon group containing at least one fluorine atom. A represents any hydrophilic group such as —SO ₃ M, —OSO ₃ M, —COOM, —OPO ₃ (M ₁ ) (M ₂ ), —PO ₃ (M ₁ ) (M ₂ ). M, M ₁ and M ₂ represent H, Li, K, Na or NH ₄ . m represents 0 or 1, and n represents 0 or an integer of 1 to 10.

In the formula, R ¹ represents a hydrogen atom, an aliphatic group or an acyl group, and R ² represents a hydrogen atom or an aliphatic group. E ¹ represents ethylene oxide, E ² represents propylene oxide, E ³ represents ethylene oxide, X represents an oxygen molecule or —R ³ N— group, and R ³ represents an aliphatic group, hydrogen molecule or

R ⁴ represents a hydrogen atom or an aliphatic group. _{l 1, l 2, m 1} , m 2, n 1, n 2 represents an integer of respective 0-300.

In the formula, A ₂ is a monovalent organic group. B or C is ethylene oxide or propylene oxide or

Represents. (However, n _1, m ₁ and l ₁ .X ₁ .m and n represents an integer of 0 to 100 each represent 0, 1, 2 or 3 is a hydrogen atom or an alkyl group, an aralkyl group, an aryl group ")".

  The invention as set forth in claim 5 is: “having a heating means for heating the silver halide photographic light-sensitive material to a temperature of 45 ° C. or higher. An automatic processor for silver photographic materials. "

The invention according to claim 6 has a control means for controlling the supply amount of the processing liquid sprayed onto the silver halide photographic light-sensitive material to ⁵ ml to 100 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material. The automatic developing machine for silver halide photographic light-sensitive materials according to any one of claims 1 to 5.

The invention according to claim 7, “After performing color development processing by sequentially jetting a plurality of kinds of processing solutions onto the exposed silver halide photographic light-sensitive material,
In the image forming method of converting image information on the silver halide photographic light-sensitive material into optical information or electrical information and forming a color image on the recording material based on the information,
An image forming method comprising a step of spraying a processing solution containing an oxidizing agent to a silver halide photographic light-sensitive material after color development processing. It is.

  The image forming method according to claim 7, wherein the silver halide photographic light-sensitive material is squeezed before the step of spraying the processing solution containing the oxidizing agent. . "

  The invention according to claim 9 is: "at least the treatment liquid containing the oxidizing agent is selected from the compound represented by the general formula [1], [S1] or [S2], or a water-soluble organosiloxane compound" 9. The image forming method according to claim 7 or 8, which comprises one kind.

The invention according to claim 10, “After performing development processing by sequentially jetting a plurality of types of processing solutions to the exposed silver halide photographic material,
In the image forming method for converting the dye image information of the silver halide photographic light-sensitive material into optical information or electrical information and forming a color image on the recording material based on the information,
A method of forming an image, comprising the step of jetting a processing solution containing an oxidizing agent onto a silver halide photographic material processed with a processing solution having fixing ability. It is.

  According to the first aspect of the present invention, the oxidant contains the sensitizing dye in the silver halide photographic light-sensitive material by injecting a processing solution containing the oxidant onto the silver halide photographic light-sensitive material being developed. Since it decomposes, it can prevent the occurrence of white background problems, and it also removes the processing agent adhering to the conveyance rollers of the automatic processor and removes the oxide of the color developing agent. Dirt can be prevented.

  According to the second aspect of the present invention, squeezing removes the processing solution from the previous step and allows the oxidant to permeate the photosensitive material well, thereby enhancing the effect of improving the white background problem. Become.

  According to the invention described in claim 3, by using a peroxide having a particularly stable oxidizing power as an oxidizing agent, the sensitizing dye in the light-sensitive material can be decomposed quickly and surely to generate a white background problem. Achieve prevention.

  According to the invention described in claim 4, the treatment liquid containing an oxidizing agent is at least one selected from a compound represented by the general formula [1], [S1] or [S2], or a water-soluble organosiloxane compound. By adding seeds, the sprayed oxidizing agent is uniformly applied to the silver halide photographic light-sensitive material, so that the effect of the oxidizing agent can be improved and the removal of dirt can be promoted.

  According to the fifth and sixth aspects of the invention, the development processing can be performed under preferable conditions.

  According to the invention described in claim 7, by injecting a processing solution containing an oxidizing agent onto the silver halide photographic light-sensitive material after color development processing, the influence of residual silver in the photographic light-sensitive material is reduced, Improved image scanner reading. In particular, the formed image can be read accurately even when the amount of processing is small.

  According to the invention described in claim 8, since the processing liquid in the color development step is removed by squeezing, the permeability of the oxidant-containing liquid to the photosensitive material is improved, and the effect of using the oxidant-containing liquid is improved. Can be improved.

  According to the ninth aspect of the present invention, at least one selected from the compound represented by the general formula [1], [S1] or [S2], or a water-soluble organic siloxane compound is used as the treatment liquid containing an oxidizing agent. By adding the seed, the injected oxidant is uniformly applied to the photographic material, so that the effect of the oxidant can be improved and the scanner reading characteristics can be improved.

  According to the invention described in claim 10, by injecting a processing solution containing an oxidizing agent onto the silver halide photographic light-sensitive material that has been processed with the processing solution having fixing ability, ε can be reduced and the scanner reading characteristics can be improved.

  Embodiments of the present invention will be described below. These embodiments show specific examples of the present invention and do not limit the meaning of the terms of the present invention. Although there are assertive descriptions, these are also preferable examples as examples, and do not limit the meaning of the present invention or terms.

  Examples of the photosensitive material processed in the present invention include silver halide color photographic photosensitive materials containing silver iodobromide or silver bromide, and silver halide monochrome photographic photosensitive materials. More preferred examples include chloride. Examples thereof include a silver halide color photographic light-sensitive material containing a silver emulsion and a silver halide monochrome photographic light-sensitive material. Furthermore, it is preferable to have at least one emulsion layer containing a silver halide emulsion comprising 90% mol or more of silver chloride. More preferred is a silver halide emulsion comprising 95 to 100 mol%, most preferably 98 to 100 mol%, consisting of silver chloride, from the viewpoint of processing progress.

  First, an example in which the automatic developing machine for silver halide photographic light-sensitive materials of the present invention is applied to a color paper automatic developing machine will be described.

  1 is a schematic configuration diagram of a color paper automatic developing machine according to the present invention, FIG. 2 is a perspective view of a processing liquid supply unit, FIG. 3 is a configuration diagram of processing liquid supply means, FIG. 4 is a configuration diagram of a supply device, and FIG. It is sectional drawing of a nozzle.

  As shown in FIG. 1, the color paper automatic developing machine 1 includes an original scanner 110, a film scanner 112, an MO drive 114, and a digital camera terminal 116, from which image information to be recorded on a silver halide photographic light-sensitive material is stored. Entered. The input image information is displayed on the CRT 120, and the image is confirmed on the CRT 120.

  The color paper automatic developing machine 1 includes a paper feeding unit 130, a cutter unit 140, an exposure unit 150, a development processing unit 160, a fixing processing unit 170, an oxidant injection unit 173, a stabilization processing unit 175, and a drying unit 190. Has been.

  The development processing unit 160, the fixing processing unit 170, the oxidant injection unit 173, and the stabilization processing unit 175 are horizontally arranged on the lower side, the paper feeding unit 130 is arranged on the upper side, and the cutter unit 140 and the exposure unit 150 are dried on both sides. The part 190 is arranged, and the apparatus has a compact structure.

  The paper supply unit 130 is loaded with a paper magazine 11 containing color paper P, which is a silver halide photographic light-sensitive material. The color paper P delivered from the paper magazine 11 is cut into a predetermined length by the cutter unit 140, and is nipped and conveyed by a conveying means such as a plurality of conveying rollers.

  The color paper P is sent to the exposure unit 150, and the exposure unit 150 forms a latent image on the color paper P by exposure. The color paper P that has passed through the exposure unit is heated by a heater 30 that is a heating means for the photosensitive material disposed in the transport path. By heating the photosensitive material, the reaction by the sprayed processing solution is promoted so that rapid processing is possible and the processing solution can be applied uniformly at high speed, so that stable processing without any processing unevenness is always possible. It is said. The temperature of the heated photosensitive material is preferably 35 ° C. or higher, and more preferably 40 ° C. or higher from the viewpoint of rapid processing. Therefore, it is preferable that the heater 30 as a heating means has a capability of heating the photosensitive material P to a temperature of 45 ° C. or higher.

  The development processing unit 160, the fixing processing unit 170, the oxidant injection unit 173, and the stabilization processing unit 175 on the downstream side of the heater 30 are each provided with processing liquid supply means 20. The color paper P is conveyed to these processing units with the emulsion surface facing upward, and a processing solution having a developing ability is jetted onto the emulsion surface side, and a processing solution having a fixing capability is ejected to the fixing processing unit. The oxidant spraying unit 173 sprays the processing liquid containing the oxidant, passes through the stabilization processing unit 175, and is dried by the drying unit 190, and then discharged as a photographic print.

  Here, the sensitizing dye remaining in the color paper P is decomposed by spraying and applying the treatment liquid containing the oxidant to the color paper P in the oxidant spraying unit 173, so that the white background can be improved. Further, since the excessive processing liquid is also decomposed, it is no longer possible to generate tar-like dirt on the surface of the roller due to the excessive processing liquid adhering to the conveying roller.

  Reference numeral 40 denotes a squeeze roller 40 that removes the processing liquid remaining on the color paper P, and is disposed immediately before the oxidant injection unit 173. The squeeze roller 40 removes the processing liquid remaining on the color paper P conveyed to the oxidant spraying unit 173, so that the permeability of the oxidant to the color paper P is improved and the effect of the oxidant spray is improved. Can do.

  As shown in FIG. 2, the processing liquid supply means 20 provided in each processing step supplies a processing pipe pressurized by a compressor, a supply pipe 275, a solenoid 181, an on-off valve 182, and a processing liquid. The supply device 183 includes a nozzle for spraying, and the supply device 183 is reciprocated in a direction orthogonal to the conveyance direction of the photosensitive material P by the drive mechanism 280 to spray the processing liquid onto the surface of the photosensitive material P.

  As shown in FIG. 3, the drive mechanism 280 has a pair of pulleys 281 and 282, a timing belt 283 stretched over the pulleys 281 and 282, and a drive motor M1 that drives the pulley 281. The drive motor M1 The supply device 183 fixed to the timing belt 283 is moved in the direction orthogonal to the conveyance direction of the photosensitive material P by forward and reverse rotation.

  Further, as shown in FIG. 4, the on-off valve 182 is disposed on the downstream side of the processing liquid flow path of the liquid supply pipe 275 that is a supply path for supplying the processing liquid, and the supply device 183 is arranged downstream of the on-off valve 182. Branch flow paths 183a provided on the side and nozzles 183b provided in the respective branch flow paths 183a. The processing liquid is ejected from the nozzles 183b by the opening / closing operation of the on-off valve 182. Apply to. The opening / closing of the on-off valve 182 is driven by a solenoid 181, and in the embodiment, one on-off valve branches into four flow paths, and a nozzle is formed at the end.

  The four nozzles are arranged at a pitch of 35 mm, the branching section and the nozzle are fixed to the movable base, and are controlled by a control means (not shown) so as to reciprocate a movement distance of 40 mm five times per second. The on-off valve is operating at a constant speed during the reciprocating motion of the movable table. The open / close valve does not operate during acceleration / deceleration.

  As shown in FIG. 5, the nozzle 183b includes a chamber 183b1 for storing the processing liquid and an orifice 183b2 for injecting the processing liquid in the chamber 183b1, and the inner diameter of the chamber 183b1 is R1, and the diameter of the orifice 183b2 is set. R2, and the ratio of the cross-sectional area of the orifice 183b2 to the cross-sectional area of the chamber 183b1 is 2 to 150, and the cross-sectional area of the chamber 183b1 is increased so that the loss of pressure transmission is suppressed and the response is delayed. Can be eliminated. Further, a taper 183b3 is provided at a joint portion between the chamber and the orifice, and by this taper 183b3, bubbles are not mixed from the orifice 183b2, and once entered, the bubbles can be easily removed.

The processing liquid supply amount to the photosensitive material by the processing liquid supply means 20 is preferably 10 ml to 100 ml (10 ml / m ^{2 to} 100 ml / m ² ) per 1 m ² of the photosensitive material. In the embodiment of the automatic developing machine for silver halide photographic light-sensitive material according to the present invention, a control (not shown) for controlling the supply amount of processing solution to 5 ml to 100 ml (5 ml / m ^{2 to} 100 ml / m ² ) per 1 m ² of the light-sensitive material. Have means.

  Specific examples of the oxidizing agent used in the present invention include organic peracids and organic peroxides, oxidizing organic compounds, peracids, oxygen, hypochlorite, chlorine, bromine, iodine, bromine-hexamethyl. Examples include phosphoramide, orthoperiodic acid, nitric acid, nitrous acid, nitrogen dioxide, potassium nitrodisulfonate, tetrabutylammonium periodate, potassium periodate, microorganisms, enzymes, etc., but the present invention is not limited thereto. Is not to be done.

  Specific examples of the organic peracid and the organic peroxide include m-chloroperbenzoic acid (MCPBA), perbenzoic acid, peracetic acid, t-butyl hydroperoxide, and the like.

  Specific examples of the oxidizing organic compound include dimethyl sulfoxide / oxalyl chloride, dimethyl sulfoxide / trifluoroacetic anhydride, dimethyl sulfoxide / dicyclohexylcarbodiimide, quinones (2.3-dichloro-5.6-dicyano-1.4- Benzoquinone etc.), nitrobenzene, p-nitrosodimethylaniline, dimethylaminopyridine N-oxide, triphenylmethyl cation, diethyl azodicarboxylate, diphenylnitroxide, 2-sulfonyloxaziridine, iodosobenzene diacetate, N-bromosuccin Examples thereof include imide, chloramine T, chloramine B thiosulfonate, and the like.

Specific examples of the peroxide include hydrogen peroxide, persulfate, percarbonate, perborate, and a belloxy complex compound (for example, K ₂ [Ti (O ₂ ) C ₂ O ₂ ] · 3H ₂ O, 4K ₂ SO ₄ · Ti (O ₂ ) OH · SO ₄ · 2H ₂ O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ ] · 6H ₂ O), and the like.

  Among these peroxides, hydrogen peroxide, persulfate, percarbonate, and perborate are particularly preferable from the viewpoint of environmental suitability.

  Moreover, it is desirable that the treatment liquid containing an oxidizing agent contains at least one selected from a compound represented by the following general formula [1], [S1] or [S2], or a water-soluble organosiloxane compound.

In the formula, Rf represents a saturated or unsaturated alkyl group containing at least one fluorine atom. X is sulfonamide,

And Y includes an alkylene oxide group. Rf ′ represents a saturated or unsaturated hydrocarbon group containing at least one fluorine atom. Furthermore, A represents a hydrophilic group such as —SO ₃ M, —OSO ₃ M, —COOM, —OPO ₃ (M ₁ ) (M ₂ ), —PO ₃ (M ₁ ) (M ₂ ). M, M ₁ and M ₂ represent H, Li, K, Na or NH ₄ . m represents 0 or 1, and n represents 0 or an integer of 1 to 10.

Wherein, R1 represents a hydrogen atom, an aliphatic group, an acyl group, R ² represents a hydrogen atom, an aliphatic group. E ¹ represents ethylene oxide, E ² represents propylene oxide, E ³ represents ethylene oxide, X represents an oxygen molecule or —R ³ N— group, and R ³ represents an aliphatic group, hydrogen molecule or

R ⁴ represents a hydrogen atom or an aliphatic group. _{l 1, l 2, m 1} , m 2, n 1, n 2 each represents an value from 0 to 300.

In the formula, A ₂ is a monovalent organic group. B or C is ethylene oxide or propylene oxide or

(Where n ₁ , m ₁ and l ₁ represent 0, 1, 2 or 3 respectively). m and n represent an integer of 0 to 100. X ₁ is a hydrogen atom, an alkyl group, an aralkyl group or an aryl group.

  These compounds are surfactants, and by adding the surfactant to the processing solution, the sprayed oxidant is uniformly applied to the silver halide photographic light-sensitive material, improving the effect of the oxidant and preventing contamination. Removal removal can be achieved.

  The addition amount of these surfactants is preferably 0.0001 g / l to 2.0 g / l, and more preferably 0.01 g / l to 0.5 g / l.

  In addition, although the said Example is an example which applied this invention to the color paper automatic processor, the photosensitive material made into a process target may be color paper, In that case, oxidizing agent process liquid injection is, After the color development processing, after the bleaching processing, after the fixing processing, or after the bleach-fixing processing, it may be any, preferably after the fixing processing.

  Next, according to another embodiment of the present invention, image information is optically read by a film scanner or the like after being photographed and developed, and converted into an electrical signal for digitization. An image forming method for forming an image of the obtained image information on another recording material will be described.

  FIG. 6 is a conceptual diagram of an automatic film developing machine based on the image forming method according to the present invention. In FIG. 6, members having the same functions as those in FIG.

  In FIG. 6, F is a photographed color film F which is conveyed from the right side to the left side of the drawing with the emulsion surface on the upper side by conveying means such as a plurality of conveying rollers.

  In the conveyance path of the color film F, a development processing unit 160 and an oxidant injection unit 173 are disposed, and a processing liquid supply unit 20 is disposed in each. In the development processing unit 160, a processing solution having developing ability is sprayed onto the color film F to perform color development, and a dye image of Y (yellow), M (magenta), and C (cyan) is formed along with the formation of a silver image. Is done. Next, the color film F is conveyed to the oxidant injection unit 173, and after the treatment liquid containing the oxidant is injected by the oxidant injection unit 173, the color film F is washed by the water washing processing unit and conveyed to the film scanner 112. Here, reference numeral 40 denotes a squeeze roller 40 that removes the processing liquid remaining on the color paper P, and is disposed immediately before the oxidant injection unit 173. The squeeze roller 40 removes the processing liquid remaining on the color film F transported to the oxidant injection unit 173, so that the permeability of the oxidant to the color paper P is improved and the effect of the oxidant injection is improved. Can do. The film scanner 112 reads the dye image on the color film F, converts it into an electrical signal, digitizes it, sends the obtained image information to the thermal transfer printer 220, and the thermal transfer printer 220 images the image information on the recording material P. Form and eject as an image print. Here, the CRT 12 is a CRT monitor for confirming an image to be printed, and 210 is a CPU 210 for controlling the scanner 112, the thermal transfer printer 220, and the CRT monitor.

  In addition to decomposing the sensitizing dye remaining in the color film F by spraying and applying a treatment liquid containing an oxidant to the color film F in the oxidant spraying unit 173, even if there is residual silver, Absorption is reduced and scanner reading characteristics can be improved. That is, by jetting a processing solution containing an oxidizing agent, the high ε of the sensitizing dye remaining in the silver halide photographic light-sensitive material and the residual silver is reduced, and the scanner reading characteristics are improved. Further, since the oxidant decomposes the surplus processing liquid, the surplus processing liquid does not adhere to the transport roller, and tar-like dirt is not generated on the surface of the roller.

  Examples of the oxidizing agent contained in the treatment liquid include the above organic peracids and organic peroxides, oxidizing organic compounds, peracids, oxygen, hypochlorite, chlorine, bromine, iodine, bromine-hexamethyl. Examples include phosphoramide, orthoperiodic acid, nitric acid, nitrous acid, nitrogen dioxide, potassium nitrodisulfonate, tetrabutylammonium periodate, potassium periodate, microorganisms, enzymes, and the like.

  Further, by adding at least one selected from the compound represented by the general formula [1], [S1] or [S2], or a water-soluble organic siloxane compound in the treatment liquid, the injected oxidizing agent can be made homogeneous. Since it is applied on the photosensitive material, the effect of using the oxidizing agent can be enhanced and the scanner reading characteristics can be improved. The addition amount of these surfactants is preferably 0.01 g / l to 2.0 g / l, more preferably 0.1 g / l to 1.0 g / l.

  Reference numeral 40 denotes a squeeze roller 40 for removing the processing liquid remaining on the color film F after the development processing. By providing the squeeze roller 40 immediately before the oxidant injection unit 173 and removing the processing liquid remaining on the color film F, the permeability of the oxidant to the color film is improved and the effect of the oxidant is improved. Can do.

  FIG. 7 is a conceptual diagram of an automatic film developing machine based on another image forming method according to the present invention. In FIG. 7, members having the same functions as those in FIG.

  In FIG. 7, F is a photographed color film F which is conveyed from the right side to the left side of the drawing with the emulsion surface on the upper side by conveying means such as a plurality of conveying rollers.

  A developing processing unit 160, a bleaching processing unit 161, a fixing processing unit 170, and an oxidant injection unit 173 are disposed on the conveyance path of the color film F, and each is provided with a processing liquid supply unit 20. In the development processing unit 160, a processing solution having developing ability is sprayed and applied to the color film F to perform color development, and a dye image of Y (yellow), M (magenta), and C (cyan) is formed along with the formation of a silver image. Then, the color film F is conveyed to the oxidant spraying unit 173 through bleaching and fixing processes, and after receiving the spray of the treatment liquid containing the oxidant in the oxidant spraying unit 173, the color film F is washed in the water washing processing unit. And conveyed to the film scanner 112. Here, reference numeral 40 denotes a squeeze roller 40 that removes the processing liquid remaining on the color paper P, and is disposed immediately before the oxidant injection unit 173. The squeeze roller 40 removes the processing liquid remaining on the color film F transported to the oxidant injection unit 173, so that the permeability of the oxidant to the color paper P is improved and the effect of the oxidant injection is improved. Can do. The film scanner 112 reads the dye image on the color film F, converts it into an electrical signal, digitizes it, sends the obtained image information to the thermal transfer printer 220, and the thermal transfer printer 220 images the image information on the recording material P. Form and eject as an image print. Here, the CRT 12 is a CRT monitor for confirming an image to be printed, and 210 is a CPU 210 for controlling the scanner 112, the thermal transfer printer 220, and the CRT monitor.

  In addition to being able to decompose the sensitizing dye remaining in the color film F by spraying and applying the treatment liquid containing the oxidant to the color film F in the oxidant injection unit 173, absorption of silver even when there is residual silver Can be reduced and the scanner reading characteristics can be improved. That is, by jetting a processing solution containing an oxidizing agent, the high ε of the sensitizing dye remaining in the silver halide photographic light-sensitive material and the residual silver is reduced, and the scanner reading characteristics are improved. Further, since the oxidant decomposes the surplus processing liquid, the surplus processing liquid does not adhere to the transport roller, and tar-like dirt is not generated on the surface of the roller.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this.
[Example 1]
The color paper was developed using the automatic developing machine for silver halide photographic light-sensitive materials shown in FIG. 1 under the following conditions. Here, QA-A6 color paper (manufactured by Konica Minolta, size 127 mm × 178 mm) was used as the silver halide color photographic light-sensitive material. The color paper is heated to 45 ° C. by a heater.
(Processing conditions)

  Table 1 shows the development processing conditions. Table 2 shows the oxidizing agent processing conditions in the development processing shown in Table 1. That is, Experiment No. In the case of no oxidant treatment, Experiment No. 1 In No. 2, when hydrogen peroxide is used as the oxidizing agent and the oxidizing agent treatment is performed under the condition that no additive is added, Experiment No. 2 is performed. No. 3 is an experiment No. 3 when additive A is added to a treatment solution containing hydrogen peroxide. No. 4 is an experiment No. 4 when additive B is added to a treatment solution containing hydrogen peroxide. No. 5 is an experiment No. 5 when the additive C is added to the treatment liquid containing hydrogen peroxide. 6 shows the oxidizing agent treatment conditions when the additive D is added to the treatment liquid containing hydrogen peroxide.

  The processing time in Tables 1 and 2 refers to, for example, supplying the processing solution in the next step (for example, bleach-fixing step) after the photosensitive material in the color development processing step is first supplied with the color developer on the emulsion surface. It means the time until it is immersed in the treatment liquid of the next step.

Each treatment solution used was composed of the following formulation.
(Color developer formulation: per liter)
30 g of diethylene glycol
50 g of sodium p-toluenesulfonate
Bishydroxylamine disodium 15g
CD-3 15g
40g potassium carbonate
Potassium hydroxide 6g
Chinovar SFP 3g
The pH was adjusted to 11.5 using potassium hydroxide or sulfuric acid.
(Prescription for bleach-fixing solution: per liter)
55 g of ammonium salt of ferric salt of ethylenediaminetetraacetic acid
Ethylenediaminetetraacetic acid 5g
60g ammonium thiosulfate
20g ammonium sulfite
The pH was adjusted to 6.0 using aqueous ammonia or acetic acid.
(Prescription of oxidant-containing liquid: per liter)
Hydrogen peroxide solution 30ml
(Prescription of additives to be added to oxidant-containing liquid)
Experiment No. 3, C ₇ F ₁₅ CONHC ₂ H ₄ NC ₅ H ₄ Cl 0.2 g
Experiment No. 4, C ₁₂ H ₂₅ COO— (C ₂ H ₄ O) ₁₀ —H 0.2 g
Experiment No. 5, C ₁₂ H ₂₅ —O— (C ₂ H ₄ O) ₁₀ —H 0.2 g
Experiment No. 6

0.5g
Were added respectively.

Here, Experiment No. C ₇ F ₁₅ CONHC ₂ H ₄ NC ₅ H ₄ Cl formulated in No. 3 is an example of the compound represented by the general formula [1]. C ₁₂ H ₂₅ COO— (C ₂ H ₄ O) ₁₀ —H formulated in No. 4 is an example of the compound represented by the general formula [S1]. C ₁₂ H ₂₅ —O— (C ₂ H ₄ O) ₁₀ —H formulated in No. 5 is an example of the compound represented by the general formula [S2]. Prescription in 6

Is an example of the water-soluble siloxane compound.

Evaluation 50 color photographic light-sensitive materials as described above were processed, and the state of the roller after the oxidant treatment was observed.
○ No deposits △ There are slight deposits, but there are no problems in practical use. × There are deposits and there are actual damages. Further, the soil was evaluated on the white background of the treated paper, and evaluated according to the following criteria.

○ Dirt is not recognized. △ There is slight dirt, but there is no problem in practical use.

  Evaluation results

As shown in Table 3, the experiment No. in which the oxidizing agent treatment containing a peroxide was performed. In Nos. 2 to 6, it was confirmed that no paper white background stain was generated and that the roller stain could be improved, and it was confirmed that the effects of the present invention could be achieved. In addition, in Experiment No. 1 in which the compound represented by the general formulas [1], [S1], and [S2] and the water-soluble siloxane compound were added to the oxidizing agent treatment liquid. In 3-6, it was confirmed that the effect of this invention can be show | played more favorably.
[Example 2]
According to another aspect of the present invention, image information is optically read by a film scanner or the like from a film that has been developed after photographing and image-formed, converted into an electrical signal, and digitized to obtain an image. With respect to the image forming method in which an oxidizing agent treatment is added to the development processing step in the image forming method for forming an image of information on another recording material, the following experiment was conducted with the configuration shown in FIG.

  A color negative film (Centuria 400 (manufactured by Konica Minolta)) subjected to wedge exposure is developed under the conditions shown in Table 4, and the processed film wedge is read using a film scanner (film scanner DS1000, manufactured by Konica). The obtained digital information was subjected to image processing and then output by an ink jet printer (ink jet printer PM-3300C manufactured by Seiko Epson Corporation), and the obtained image was visually confirmed.

  Table 4 shows development processing conditions. For example, in the case of a color development processing step, the processing time in Table 4 is from when the color developing solution is supplied to the photosensitive material emulsion surface until the processing solution of the next processing step (for example, bleach-fixing step) is supplied. Or the time from when the tip of the photosensitive material is immersed in the first processing solution tank until it is immersed in the processing solution of the next step.

The following processing solutions were used.
(Color developer formulation: per liter)
30 g of diethylene glycol
Bishydroxylamine disodium 15g
CD-4 25g
40g potassium carbonate
Potassium hydroxide 6g
Chinovar SFP 3g
Polyvinyl pyrrolidone 10g
The pH was adjusted to 11.0 using potassium hydroxide or sulfuric acid.
(Prescription of oxidant-containing liquid: per liter)
Hydrogen peroxide solution 30ml
C ₇ F ₁₅ CONHC ₂ H ₄ NC ₅ H ₄ Cl 0.5 g
_{Here, C 7 F 15 CONHC 2 H} 4 NC 5 H 4 Cl was formulated as an additive to the oxidizing agent-containing solution, which is an example of a compound represented by the general formula (1).

The negative color film (Centuria 400 (manufactured by Konica Minolta)) that has been subjected to wedge exposure is developed, the processed film wedge is read using a film scanner, and the resulting digital information is processed by an inkjet printer after image processing. When output, the test pattern was almost reproduced. On the other hand, when a similar experiment was performed without performing the oxidant treatment as a comparative example, image unevenness occurred. That is, it was confirmed that the scanner reading characteristics were improved by injecting the treatment liquid containing the oxidizing agent. In addition to the compound represented by the general formula [1] such as the C ₇ F ₁₅ CONHC ₂ H ₄ NC ₅ H ₄ Cl as an additive to be added to the oxidant-containing liquid, the general formula [S1] It was confirmed that the effects of the present invention can be achieved more satisfactorily by adding a compound represented by [S2] or a water-soluble siloxane compound.

From the above experimental results, image information is optically read by a film scanner or the like after being photographed and subjected to development processing, converted into an electrical signal, digitized, and the obtained image information is converted into another image information. In the image forming method for forming an image on a recording material, it was confirmed that the scanner reading characteristics of the film are improved by injecting a processing liquid containing an oxidizing agent onto the film after the color development processing.
Example 3
A similar experiment was conducted with the configuration shown in FIG.

  In the experiment, a color negative film (Centuria 400 (manufactured by Konica Minolta)) subjected to wedge exposure was subjected to the following development processing, and the processed film wedge was read using a film scanner (film scanner DS1000 manufactured by Konica). The digital information thus obtained was subjected to image processing and then output by an ink jet printer (ink jet printer PM-3300C manufactured by Seiko Epson Corporation), and the image was visually confirmed.

  Table 5 shows the development processing conditions. The processing time in Table 5 is the same as that described in the second embodiment.

The following processing solutions were used.
(Color developer formulation: per liter)
30 g of diethylene glycol
Bishydroxylamine disodium 15g
CD-4 25g
40g potassium carbonate
Potassium hydroxide 6g
Chinovar SFP 3g
Polyvinyl pyrrolidone 10g
The pH was adjusted to 11.0 using potassium hydroxide or sulfuric acid.
(Bleaching solution formula: per liter)
1.3 150 g of ferric ammonium salt of propylenediaminetetraacetic acid
1.3 5 g of propylenediaminetetraacetic acid
Ammonium bromide 50g
(Fixing liquid formulation: per liter)
260g ammonium thiosulfate
30g ammonium sulfite
The pH was adjusted to 6.0 using aqueous ammonia or acetic acid.
(Prescription of oxidant-containing liquid: per liter)
Hydrogen peroxide solution 30ml
C ₇ F ₁₅ CONHC ₂ H ₄ NC ₅ H ₄ Cl 0.5 g
The above-mentioned development processing is performed on the color negative film that has been subjected to wedge exposure, the processed film wedge is read using a film scanner, and the obtained digital information is output by an inkjet printer after image processing. Was almost reproduced, and it was confirmed that there was little noise. On the other hand, when a similar experiment was performed without performing the oxidizing agent treatment as a comparative example, noise was generated in the obtained image.

  According to the above experimental results, in an image forming method in which image information is optically read by a film scanner or the like after image development and image processing is performed, and the obtained image information is formed on another recording material. It was confirmed that the scanner reading characteristics of the film were improved by injecting a treatment liquid containing an oxidizing agent onto the film treated with the treatment liquid having the ability.

It is a schematic block diagram of the color paper automatic processor which is an Example of this invention. It is a perspective view of the process liquid supply part which is an Example of this invention. It is a block diagram of the process liquid supply means which is an Example of this invention. It is a block diagram of the supply apparatus which is an Example of this invention. It is sectional drawing of the nozzle which is an Example of this invention. It is a conceptual diagram explaining an example of the image forming method in this invention. It is a conceptual diagram explaining the other example of the image forming method in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Automatic developing machine for silver halide photographic materials 20 Processing solution supply means 130 Paper feed part 140 Cutter part 150 Exposure part 160 Development processing part 170 Fixing process part 173 Oxidant injection part 175 Stabilization part 182 Opening / closing valve 183 Supply apparatus 183a Branch flow path 183b Nozzle 190 Drying section 272 Supply tank 273 Compressor 275 Liquid supply piping

Claims (10)

In an automatic developing machine for silver halide photographic light-sensitive materials, in which multiple types of processing solutions are sequentially jetted onto the exposed silver halide photographic light-sensitive material for development processing,
An automatic developing machine for a silver halide photographic light-sensitive material, comprising a step of spraying a processing solution containing an oxidizing agent after a step of spraying a processing solution having fixing ability. 2. The halogen according to claim 1, further comprising squeeze means for squeezing the silver halide photographic light-sensitive material immediately before the step of spraying the processing solution containing the oxidizing agent onto the silver halide photographic light-sensitive material. Automatic developing machine for silver halide photographic materials. The automatic developing machine for silver halide photographic light-sensitive materials according to claim 1 or 2, wherein the oxidizing agent is a peroxide. The treatment liquid containing the oxidizing agent contains at least one selected from a compound represented by the following general formula [1], [S1] or [S2], or a water-soluble organosiloxane compound. The automatic developing machine for silver halide photographic light-sensitive materials according to any one of claims 1 to 3.

In the formula, Rf represents a saturated or unsaturated alkyl group containing at least one fluorine atom.
X is sulfonamide,

Represents one of the following. Y represents an alkylene oxide group. Rf ′ represents a saturated or unsaturated hydrocarbon group containing at least one fluorine atom. A represents any hydrophilic group such as —SO ₃ M, —OSO ₃ M, —COOM, —OPO ₃ (M ₁ ) (M ₂ ), —PO ₃ (M ₁ ) (M ₂ ). M, M ₁ and M ₂ represent H, Li, K, Na or NH ₄ . m represents 0 or 1, and n represents 0 or an integer of 1 to 10.

In the formula, R ¹ represents a hydrogen atom, an aliphatic group or an acyl group, and R ² represents a hydrogen atom or an aliphatic group. E ¹ represents ethylene oxide, E ² represents propylene oxide, E ³ represents ethylene oxide, X represents an oxygen molecule or —R ³ N— group, and R ³ represents an aliphatic group, hydrogen molecule or

R ⁴ represents a hydrogen atom or an aliphatic group. _{l 1, l 2, m 1} , m 2, n 1, n 2 represents an integer of respective 0-300.

In the formula, A ₂ is a monovalent organic group. B or C is ethylene oxide or propylene oxide or

Represents. (However, n _1, m ₁ and l ₁ .X ₁ .m and n represents an integer of 0 to 100 each represent 0, 1, 2 or 3 is a hydrogen atom or an alkyl group, an aralkyl group, an aryl group Represents.) 5. The automatic developing machine for silver halide photographic light-sensitive materials according to claim 1, further comprising heating means for heating the silver halide photographic light-sensitive material to a temperature of 45 [deg.] C. or higher. 6. The method according to claim 1, further comprising control means for controlling a supply amount of the processing liquid sprayed to the silver halide photographic light-sensitive material to 5 ml to 100 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material. 2. An automatic developing machine for silver halide photographic light-sensitive materials according to item 1. After performing color development processing by sequentially jetting multiple types of processing solutions to the exposed silver halide photographic material,
In the image forming method of converting image information on the silver halide photographic light-sensitive material into optical information or electrical information and forming a color image on the recording material based on the information,
An image forming method comprising a step of spraying a processing solution containing an oxidizing agent to a silver halide photographic light-sensitive material after color development processing. 8. The image forming method according to claim 7, wherein the silver halide photographic light-sensitive material is squeezed before the step of spraying the processing solution containing the oxidizing agent. The treatment liquid containing the oxidizing agent contains at least one selected from the compound represented by the general formula [1], [S1] or [S2], or a water-soluble organosiloxane compound. The image forming method according to claim 7 or 8. After carrying out development processing by sequentially jetting multiple types of processing solutions onto the exposed silver halide photographic light-sensitive material,
In the image forming method for converting the dye image information of the silver halide photographic light-sensitive material into optical information or electrical information and forming a color image on the recording material based on the information,
A method of forming an image, comprising the step of jetting a processing solution containing an oxidizing agent onto a silver halide photographic material processed with a processing solution having fixing ability.

Images