JPS6172247A - Processing method of silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To eliminate the generation of edge stains even after long-term storage in the case of subjecting a photosensitive material to a non-washing process by exposing, developing and fixing the photosensitive material to a substrate coated with a resin cured by the irradiation of electron rays then subjecting the material to a stabilizing process without a washing stage. CONSTITUTION:The resin cured by the irradiation of electron rays contains both of the resin cured by initiating polymn. reaction in the presence of a polymn. initiator under the irradiation of the electron rays and the resin cured by initiating the polymn. reaction without the polymn. initiator. The compd. for initiating the polymn. reaction by the irradiation of the electron rays in the case of using the polymn. initiator includes the compd. having at least two epoxy groups in, for example, one molecule. The resin polymerizable by the electron ray irradiation in the case of not using the polymn. initiator is exemplified by, for example, the compd. having double bonds in the molecule, more preferably the compd. having plural double bonds in the molecule and more particularly preferably the compd. contg. an acryloyl group, etc. and unsatd. polyester, etc.

Description

[Detailed description of the invention]

[& Field of Application] Unreleased 1gj is used in the processing of silver halide color 'glue' true light-sensitive materials.
. Concerning methods. For more details, see Color Paper Leek/
The present invention relates to a method for processing silver halide color photographic materials that does not cause staining and improves the stability of images after processing. [Prior Art] Generally, after exposure, silver halide photographic materials are processed through a process of developing, fixing, washing with water, or developing, bleaching, fixing, and washing. Water resource issues are receiving increasing attention. For this reason, methods have been provided for carpenters to reduce the amount of washing water used. For example, West German Patent No.
．． No. 920.222 Ming Liao and S, R as technical documents
. Goldwasser, “Water Flow
rate in im＋＊version-washin
g or motion picture files+
" Jour, SMPTE. 64.248-253.May (IE15.5) is known. Furthermore, a method of omitting the water washing step and performing stabilization treatment without substantially washing with water is disclosed in JP-A No. 57-8543. , same 5
It is described in No. 8-14834, No. 5B-134636, etc. On the other hand, polyethylene coated paper is mainly used as conventional color paper, but these polyethylene coated papers are penetrated by the benzyl alcohol and color developing agent contained in the color developing solution, and are mixed with the thickening agent and the color developing agent contained in the color developing solution. It was found that the total ion concentration of ion was easily adsorbed and that it was easily contaminated during storage. In particular, when waterless washing is performed, the adsorbed treated material is not removed, so even if it is colorless immediately after treatment, it has been found that storage over time causes significant stone staining and causes the problem of edge contamination. Furthermore, it has been found that when images are stored, yellow staining and cyan dye fading are likely to occur. These phenomena are also significantly accelerated under high lb 1 degree r4
Yes. [Problems to be Solved by the Invention] The present invention has a technical object to provide a processing method for silver halide color photographic light-sensitive materials that does not cause edge staining even when subjected to waterless washing treatment and when stored over time. Let it be X1B. [Structure of the Invention] As a result of intensive research, the undiscovered silver halide color has a light-sensitive silver halide emulsion layer of at least le on a support coated with a resin cured by irradiation with an electron beam. By subjecting the photographic light-sensitive material to one-color development treatment after imagewise fogging, and stabilizing it with a processing solution having fixing ability without substantially undergoing a water washing step, the above technical section 2Ill.
(objective) was found to be solved. Conventionally, as a support for color paper, a support having a polyolefin resin liquid rye on the paper has generally been used. Color paper using these supports has been found to have the disadvantages of significant staining on the cut surface when the brit is stored for a long period of time, yellow staining on the emulsion surface, and significant fading of the dye. Ta. It has been revealed that these phenomena appear significantly when color paper is washed with water. Therefore, as a result of intensive research, the present inventor has completed the present invention. In other words, it was discovered that the problem described above was contamination at the interface between the polyethylene coating and the emulsion, resulting in deterioration of images, colors, etc. It has been found that this can be achieved by stably processing a color print material having at least one layer of silver halide photographic material on a support without washing with water. A method of coating a paper with a coating layer that can be cured by electron beam irradiation and curing it by irradiating it with an electron beam is disclosed in JP-A-57-27257 and JP-A-57-30.
No. 830, No. 57-49946 once, 59-12433
No. 6, Japanese Patent Application No. 59-32237, No. 59-10596
The method of 2nd residence can be adopted for No. 9 etc. When produced by the above-mentioned method, lJ! The photographic image forming layer (hereinafter simply referred to as the photographic layer), which is a woody colloid layer that forms a uniform layer, is
It is necessary to take some kind of contacting means to firmly attach the layer to the support. 11 of the support having such a photographic layer and the coating layer.
As a general method for producing an attractive force on 11, 1 is known, for example, a surface activation treatment method represented by corona discharge treatment, gluco emission treatment, or ultraviolet irradiation treatment on the surface of the support. After this surface activation treatment, a photographic layer can be directly coated, or a subbing liquid having an affinity for the photographic layer can be applied on the surface of the support to form a subbing layer, and then A known compound having an ethylenically unyielding Nito bond is coated on a support substrate, and a cured layer is formed by irradiation with an electron beam, and a cured layer is formed on the cured layer. In this case, the means for attaching the photographic layer to the support that removes the cured layer include surface activation treatment such as corona discharge treatment such as +III discharge. It is difficult to expect sufficient contact strength using only the epoxy method, but epoxy opening Q"
This can be improved by forming a cured resin coating layer by Q-coating. A resin that is cured by irradiating an unexploded 1 pl with an electron beam is a resin that is cured by irradiating an electron beam and starting a polymerization reaction in the presence of a polymerization initiator, or a resin that is cured by irradiating an electron beam and starting a polymerization reaction without a polymerization initiator. This includes both resins that have been cured. When using as an initiator, for example, a compound having at least two epoxy groups in one molecule can be used as a compound that initiates the initiator reaction by electron beam irradiation. That is,
A compound having at least two epoxy groups in one molecule (hereinafter referred to as an epoxy compound according to the present invention) is a compound in which ring-opening polymerization does not occur in China or Germany even when irradiated with an electron beam. A singing reaction occurs when a substance that initiates cationic polymerization is coexisting. Examples of the epoxy compound according to the present invention include epoxy resins such as those shown in 1 and 1 below.2 However, the epoxy compound according to the present invention is not limited to these. (Exemplary compound) [0 Glycidyl ether type of bisphenol A (n: 0
~10) (2) Bisphenol A side chain diglycidyl ether type C3J Di-(or tri-)glycidyl ether type of glycated phosphorus (n = 2) (n = 2) [4J Diglycidyl ether type glycidyl ester or lipid Cyclic di-β-methylglycidyl ester type (diglycidyl or di-
Compound having one structure of β-methylglycidyl ester type) (, t − t ) (n = 0 to 1) C

[13 〇(n=0~l) β” Cyclohexane oxide? -2 (Eboxy/compound containing one or two Schiff 0 hexane oxide or cyclopentene oxide groups in the molecule) (6J Novolac type Eboki 7 four shields (n = θ ~ 2) exemplified above The epoxy/compound according to the present invention such as
It can be obtained as a commercial product as shown below. J. Grindyl ether type of bisphenols, such as Shell Chemical Co., Ltd. 73 product names Epicote 82F, Epiquat 8
28. 834. 836. Same 1001, Same 1004
, 1007: Chipa Geigy ζ1 product name Araldite cY252, CY250. Same (]Y260. Same GY280, Same 6071. Same 6084, Same 6097:
Product name of Dow Chemical 2η DER330゜Giant 13
31. 337. 661. 664 Trade name of Nippon Ink Chemical Industry 1 Ebikuron 800. Same +010. Same 1000. 3010h> Bisphenol +'M
55 type zigly, sidyl ether; 1clI, Asahi Denka F η's trade name Adeka Resin E)' -4000 C) Glycerin G (also tri) sidyl ether type +? 1. For example, shell chemistry is the name of a mountain product.
Diglycidyl ester type 9 or di-β-methylglycidyl ester type, product name of Chipa Geigi 12℃ Araldai
0Y-183,4 0Y-182Ciel Chemical ■Product name 2pico-)E-190゜4F knee 871Showa Denko Sho)product name N1 Udain S-500゜S
-508, jgo1s-509, same S-601X. 4th S-603X, 4th S-607X, 4th S-609X,
Same S-729. Same S-540, Same S-550 Dainippon Ink Chemical Industry Koji product name Ebicuron 200, Same 400 e) Cyclohexene oxide type For example, UCC product name gRL-4221゜ Same 428
9. 4206. 4234゜4205 Chipa Geigy chew product name 0Y-179, 40Y-17
8. Same 0Y-180. Giant 1CY-175? y71N
Jf) Direct product name C,X-221,1PiJcX-2
89, ○X-206. Same CX-301, 40X-31
3 f) Novolac-type Epoquine resin, for example, Shell Chemical [11S brand name: Ebihut 15
2. 154: Dow Chemical (2) trade name DFN-431. 438. 439: Tepa Geigy@ product name J? PN-1] 38. FJCN-123s: Dainippon I/Ki Chemical's product name Ebicuron N-740
, same N-680, 4N-695, 4N-565, Fil
N-577 The EBOKI 7 compound according to the present invention preferably has a molecular weight of 10,000 or less, and more preferably has a molecular weight of 100,000 or less.
~3000 I7d range. Although there are no particular restrictions on the initiator, it is preferable to use onium salts that release Lewis α, which can initiate polymerization upon irradiation with electron beams. The onium tQ is expressed by the following general formula [! ” can be shown. General formula CIJ ShiBA Rc R5Z ) L NI
X m "n)""rn type drying, 几1, R2,
Bi and R4 may be the same or different.
Jti, II, b, e and d are each 0
Indicates an integer of ~3, a+1)+e+dD total Fiz f
Equal to i number. Zket NE"N, S, Se, TI-, P, ru, Sb. 1] 1. Halogen atoms (e.g., iodine, salt
atoms such as), and % (halogenated 1: 'it
sb.
, Sc, V. Represents Or, Mn, Co, etc. X represents a halogen atom, m represents a net charge in the halide complex ion, and represents the pattern of the halogen atom in the nh halide ion. The above general formula [4Xm・l-n in IC1]
An example of a complex anion represented by l-! , BF4
−, PF6−. ksF6- + 5bF6-, F'eC1,418
Examples include nC46,5bC44+B:OL5. Among the compounds represented by the above general formula [O], diazonium compounds do not necessarily have a good shelf life and have a short pot life, so they must be mixed at a two-component pressure, and they are coated with nitrogen = t gas generated by decomposition. Bubbles and pinholes may form in the film, and coloring may occur when cured. Therefore, in the present invention, it has excellent storage stability and -71
Compounds other than azonium compounds are preferred because they are compatible with the kC content and there is no concern about the generation of nitrogen gas. The onium-based 111-initiator represented by the general formula [IJ] is a diazonium compound in which Z is an N group (US/I permission pz3).
．． No. 708.296, 1. tj hand 3.7
94.5 76 (), same No. 3.949゜14
It is written 1'2 in No. 3 etc. Other onium series i [
- combination ij: l f combination 111, Belgium q? =”!-
No. 828.841. Vinegar 1 ring B28.669-ru. 7 lance r pregnant Z'l',
) 2.270, 269 No. 7 (°C). Above:, 1 diazonium compounds are listed in the above U.S. patent r:r
No.:, 708.29 F1 No. 3.949.143
10,000, l~, L, 5rayoo listed in the issue
ck Tokuno J, Organic Chemistry
, :1 5 1:5 , Nwa, 8 +
2532 pages (1970), I.
Goerdeler: Meth＊
dcr Organisehen Chemical
, 11/12, 59 1-6 4011 (
1958), K. 5asse: Ibid. 12/1,
79-112 (1963), MDrcxler et al.
It can be synthesized by the method described in 2010). The amount of the polymerization initiator according to the present invention to be used may be determined depending on the curing rate and the applied curing method, and is 0.05 to 1 liter per 100 parts by weight of the resin component of the m-composition layer according to the present invention.
It is preferable to use within the range of 0li parts. When a polymerization initiator is not used, examples of resins that can be polymerized by electron beams include compounds having a double bond in one molecule, preferably compounds having a plurality of double bonds in one molecule, and more. Preferably acryloyl group, methacrylic group,
Examples include compounds containing a loyl group, an acrylamide group, an allyl group, a vinyl ether group, a vinyl thousandthyl group, and unsaturated polyesters. Particularly preferred are A,
VrankerrFaLip@c Congress
1119 (1972), and have a molecular weight of about 1.000 to 20.000. The photosensitive material according to the present invention can contain an inorganic white pigment. As the inorganic white frJmine 1, those commonly used in the field of photographic paper may be used, such as titanium oxide (anatase type, rutile type), barium sulfate, aluminum carbonate, aluminum oxide, magnesium oxide. Any of these can be used, but titanium oxide, barium sulfate, and calcium carbonate are particularly preferred. Further, the surface of titanium oxide may be partially coated with a hydrous metal oxide compound, for example, a metal oxide such as hydrous alumina oxide or hydrous oxide ferrite, but the coating is not limited to these as long as it is an inorganic white pigment. The inorganic white pigment is a compound 1 that is hardened by rotational electron beam.
00 parts by weight, it is preferably in the range of 20 to 200 parts by weight. In addition, the average particle diameter of the pigment is preferably 0.1 to 10 particles. 1fii. Electron beam polymerizable resin according to the present invention,
The composition containing a polymerization initiator and an inorganic white pigment (hereinafter referred to as the composition according to the present invention) used as necessary may be coated on a support as a single constituent layer. II8 may be provided as a plurality of constituent layers. Examples of the paper support and body used for uncharging include paper made of natural pulp, synthetic pulp, or a mixture thereof. If desired, known paper strength enhancers, sizing agents, inorganic pigments, colorants, optical brighteners, etc. may be added to these papers. In addition to the above, synthetic papers such as polypropylene and polyester, and film bases such as polyethylene terephthalate can also be used as the support according to the present invention.Furthermore, a composite material can be formed by laminating the paper surface. Supports can also be used. The coating layer formed by hardening the scraps of the composition according to the present invention on these supports by irradiation with core beams (hereinafter referred to as the coated layer according to the present invention) is smoothed to a mirror surface. It depends on how you finish it, and you can also add molding if necessary. To achieve a mirror finish, the treated surface is brought into contact with a mirror roll, and the treated surface is irradiated with an electron beam to harden the surface, resulting in a mirror finish. In addition, after preliminary irradiation is performed to partially harden the surface, it is peeled off after contacting with a mirror roll.
A method of performing secondary irradiation and completely curing may be used. Examples of mirror-finished rolls include chrome-plated rolls and stainless steel rolls. In addition, when applying a pattern, surface polishing rolls such as stainless steel rolls and chrome-plated rolls can be used instead of mirror-finished rolls. One set [1
, a roll with a pattern such as a fine grain surface can be used. Mirror finishing and molding can be done by applying a 1M1 liquid and then removing some or all of the organic solvent, or by removing the organic solvent after molding.
In the present invention, the electron beam accelerator used for hair irradiation may be any of an electrocurtain system, a van de Graaf type scanning system, a double scanning system, and the like. In addition, the electron beam characteristics are 100 to 7 in terms of penetrating power.
It is preferable to use an electron beam accelerator at 50KV, preferably 150 to 100V, so that the absorbed dose is 0.5 to 20 Mrad. In addition, when irradiating with an electron beam, NZ, )Ie
The irradiation may be performed in an atmosphere of an inert gas such as , CCh or the like. The Wi layer according to the present invention exhibits good adhesion to the leather accessory layer as it is, but by subjecting the Rl1 layer to surface activation treatment such as corona centering treatment or glow discharge treatment F1. It exhibits even more excellent 76τ properties, and the same attractive effect as described above can also be obtained by fPIfli subbing processing using gelatin or the like. In the present invention, at least one of the coating layers according to the present invention is present on the surface of the support having a layer on which a photographic image is formed (for example, a silver halide emulsion layer, an image-receiving layer in a dye diffusion method, etc.). In addition, it is preferable that the RII calendar according to the present invention be provided on both sides of the support from the viewpoint of waterproofing, and if there is no layer on which a photographic image is formed on one side of the support, this type of calendar on this side is preferable. Covered f! ! The layer can also be a Tr layer having a structure in which the inorganic white pigment is removed from the rrI layer according to 1 of the present invention. The supports according to the invention preferably have at least one barrier layer between the base paper and the resin cured by electron beams;
It is described in detail in No. 9-124336. Each silver halide emulsion layer according to the invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye. In the present invention, conventionally known yellow couplers, magenta couplers, and cyan couplers can be used as the couplers. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and it is also possible to use diffusible dye-releasing type couplers etc. in combination with these couplers. Yellow couplers include active point -0-aryl substituted couplers, which are conventionally known as Kawa I/% open-chain ketomethylene compounds, called 2-equivalent type couplers;
Active point -〇-acyl 11-substituted couplers, active point hydantoin compound substituted couplers, active point urazole compound substituted couplers, active point Co-I/reconstituted imide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, Specific examples of yellow couplers that can be used include active site -0-sulfonyl substituted couplers, which can be used as effective yellow couplers, and U.S. Pat.
No. 3,408,194, No. 3,551,155, No. 3,582.322, No. 3,725,072, No. 3
, No. 891,445, West German Patent No. 1,547,888,
West German Application No. 2,219,917, No. 2,281,3
No. 81, No. 2,414.00B, British Patent No. 1.425
．． No. 020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 1977-
No. 26133, No. 4B-73147. No. 51-102636, No. 50-6341. No. 50-123342, No. 50-130442, No. 51-21827, No. 50-87650, No. 52-
No. 82424, No. 52-115219, No. 58-95
Examples of the magenta coupler used in the present invention include compounds of the pyrazolone type, pyrazolotriazole type, virazolinobenzimidazole type, and indashilon type. These magenta couplers are similar to the yellow couplers 4
A specific example of a magenta coupler is US Pat.
, No. 800,788, No. 2,983,808, No. 3,
No. 062,853, No. 127,289, No. 3,3
No. 11.476, No. 3,419,391, No. 3,51
No. 9,429, No. 3.558,319, No. 3,582
, No. 322, same: I, No. 815,508. 3.834.908, 3,891.445, West German Patent No. t, S10.464, West German Patent No. 11 (OLS
) No. 2,408,685, No. 2,417,945, No. 2,418,959, No. 2,424.467,
Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 51-20826,
No. 52-58922, No. 49-129538, No. 4
9-74027 1st issue 50-159336, 52-
No. 42121, No. 49-74028, No. 50-602
Examples include those described in No. 33, No. 51-26541, No. 53-55122, and Japanese Patent Application No. 110943/1983. Furthermore, useful cyan couplers used in the present invention include, for example, phenolic couplers, naphthol couplers, and the like. And these cyan couplers are not only 4-equivalent type couplers like yellow couplers, but also 2-equivalent couplers, J! ! Specific examples of cyan couplers which may be couplers include US Pat. No. 2,369,929 and US Pat. No. 2,434,272. 2,474:293, 2,521,908, 2,895. B2Ei No. 3.034.892, No. 3,311,478, No. 3,458.315, No. 3
, No. 478,583, No. 3,583,971, No. 3.
No. 591,383, No. 3.7B7.411, No. 4.0
No. 04,929, West German Patent Issue a (OLS) 2,41
No. 4,830, No. 2,454.329, Japanese Unexamined Patent Publication No. 1973-
No. 59838, No. 51-26034, No. 48-505
5, No. 51-146827, No. 52-69624, No. 52-90932, No. 5B-95:146, and the like. In order to incorporate these couplers into the silver halide emulsion according to the invention, they may be added as an alkaline solution if they are soluble in alkali [I], or in the form of an alkaline solution if they are oil-soluble. For example, US patent: fS 2,
No. 322,027, same: s 2. sar, No. 2,801,171, No. 2,272,191 and No. 2:] No. 04,940. It is preferable to dissolve it using a low-boiling point melt in combination, disperse it in the form of fine particles, and add it to the silver halide holes 5II.At this time, if necessary, other hydroquinone derivatives and ultraviolet absorbing parts 1. It is okay to use anti-fading agents etc. It is also possible to use a mixture of two or more types of couplers.Moreover, to explain in detail the preferred method of coupler addition in the present invention, one type or two or more types of couplers may be used in combination with other couplers as necessary. Kabuchi hydroquinone derivative,
In addition to anti-fading agents and ultraviolet absorbers, organic acid amides, calhemates, esters, ketones, urea derivatives, ethers, hydrocarbons X, etc., especially di-n-butyl phthalate, triresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-butyl sehecate, tri-n-hexyl phosphate, N,
N-di-ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate. n-7-nylphenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-5ec-7 milphenyl butyl ether, monophenyl-di-0-chlorophenyl phosphate, or a high-temperature point melt such as 7-paraffin, and /or Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, j-tetrachloride, chloroform, nclohexane tetrahydrofurano, methyl alcohol, acetonitrile, dimethylformamide, nooxane , methyl ethyl keto 7N dissolved in the low boiling point Gl
] Anionic surfactant and/or sorbita/-
1: Mix with an aqueous solution containing a nonionic surfactant such as schioleic acid ester and nrubitanmo/theuric acid ester and/or a hydrophilic binder such as gelatin, and use a high-speed rotary mixer, Colloid mill, ultra-A wave dispersion device, etc. It is emulsified and dispersed and added to a silver halide emulsion.The above coupler may be dispersed using a latex dispersion method.The latex dispersion method and its effects are described in JP-A-49-74538, 5t-59943 No. 1 54
-32552 publications and research disclosures
August 137S, No. +4850, pages 77-79. +1! Latexes such as 1, styrene, 7-acrylate, n-butyl acrylate, n-butyl methacrylate, 2-7cetoacetoxyethyl methacrylate, 2-
(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy/)propane-1-sulfonic acid sodium salt, N-inpropylacrylamide, tho(2-(2-methyl-4-oxinepentyl))acrylamide, 2- Acrylamide-2
- Homopolymers, copolymers and terpolymers of monomers such as methylpropane sulfone. The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives. For example, antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure Magazine 1764:1. agent, anti-staining agent, optical brightener. Color image fading prevention agent, antistatic agent, hardening agent, surfactant,
Plasticizers, wetting agents, etc. can be used. In the silver halide color photographic A light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, Hydroxyeth! Cellulose conductors such as cellulose conductors, carboxymethyl cellulose, S powder derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidasol, polyacryl amyl', etc. Included. The above-mentioned silver halide color photographic light-sensitive material has 1
After being subjected to a color development process and treated with a processing solution that improves the fixing ability according to the invention, it is then subjected to a stabilization process. Typical processing liquids having fixing ability include fixing liquids and bleach-fixing liquids. Fixed 2! ? When a solution is used, processing with a bleaching solution is performed between the one-color development process and the fixing solution process. In the present invention, the stabilization treatment refers to a treatment for stabilization that is performed immediately after treatment with a treatment liquid having fixing ability and does not substantially require washing with water, and the treatment liquid used for the stabilization treatment. is called a stabilizing liquid, and the processing tank is called a stabilizing bath or stabilizing tank. In the present invention, the stabilization treatment is carried out in 1 #fj or more, preferably 1 to 3 tanks, and preferably 9 tanks or less at most. That is, if the amount of replenisher is the same, the number of tanks is more than 1 #fj. The higher the amount, the lower the concentration of dirt components in the FI final stabilizing bath. However, if there are many tanks, the ml of tank liquid increases, so the renewal rate of the tank liquid by the replenisher decreases, and the residence time of the stabilizing liquid increases. Such an extension of the residence time of the bath liquid is not desirable because it impairs the storage performance of the liquid and promotes the occurrence of precipitation. The next step after the processing step which has a fixing ability is called a stabilization processing step. In the present invention, performing the stabilization treatment without substantially undergoing a water washing step means that the volume of the fixer or bleach-fixer brought into the first tank of the stabilization treatment is 1/20% of that of the stabilizer.
00 or more, preferably 11,500 or more, particularly preferably 1/250 or more, and the C degree of the fixer or bleach-fixer in the stabilization treatment front tank is I/200 (+1 or less) If necessary. Treatments such as very short rinsing treatment using a medium tank or multi-tank countercurrent method, auxiliary water washing, and washing promotion bath may be performed, especially if the C degree of the bleaching solution in the stabilizing solution or the bleaching stone solution is 500
It is preferable that it is PPl' or more. In the present invention, the pH of the stabilizer is preferably in the range of 2.0 to IO, and it is particularly preferable to adjust the pH to 3.0 to 3.0 from the viewpoint of stability in image storage. The stabilizing solution used in the present invention contains, for example, a chelating agent (polyphosphate, amino acid,
polycarboxylate, phosphonocarboxylate, aminophosphonate, etc.), organic acid salts (citric acid, acetic acid, succinic acid,
Oxalic acid, 2. (Kaugou, etc.), pHJ! I additives (1 M sulfite, phosphate, boric acid in, 7N, sulfuric acid, etc.), antifungal agents (phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, thiabendazole visiting conductors. 41 halogen compounds, Other additives such as antifungal agents known as slime control agents in the paper-pulp industry), optical brighteners, surfactants, preservatives, organic sulfur compounds, onium salts, formalin, and the like can be contained. A preferred chelating agent is polyphosphorus salt tolerant. Aminopolycarboxylate, oxycarboxylate. Although polyhydroxy compounds, organic phosphates, etc. are used, particularly good results can be obtained when aminopolycarbo/acid salts and organic phosphates are used in the present invention. Specific examples of chelating agents include, but are not limited to, those listed below. (1) CH Ko! HzOcop-c-pocoH2H (3) CHco)+00C-C-POcoH2H CHz C0OHC82C0OH The amount of chelating agent added is 0.05 g to 4 per stabilizer.
It can be used in the range of 0g, preferably 0.1~
It is in the range of 20g. Next, it is preferable that the stabilizing solution used in the present invention contains a metal salt, such as Ba, C
a, Ce, Go, In, La, Mn, Ni, P
b, Sn. Zn, Ti, Zr, Mg, A1. Examples include metal salts such as Sr. These are halides, hydroxides, sulfates, and carbonates! ! 4
．． It can be supplied as an inorganic salt such as phosphoric acid, acetate, or a water-soluble chelating agent. #The metal salt can be added in the range of lX+o to lXl0-'7 moles per 12 of the stabilizing solution, preferably in the range of 4X+o- to 2X+o-2 moles, more preferably in the range of 8Xzo- to lX+o-2 moles. Addition is a monkey. Things added to the stabilizer of the present invention include optical brighteners other than the above-mentioned compounds, softener iM compounds, onium salts, and hardeners, and furthermore, polyvinyl vinyl 01.1 door (PV
P K-15, Ruhi 7. -17*) can be given to Cole. It is particularly desirable that the stabilizer of the present invention contains the following compounds. [A] Phenol compound [B] Thiazoline compound [C] Triazine compound [D] Morpholine compound [E] Imidazole compound rF] Guanidine compound [A] - [F] are specific compounds. Examples include, but are not limited to, the following: [Exemplary compounds] (1): Sodium octophenylphenol (2):
2-octyl-4-isothiazolin (3) dibenzene 7zolin-3-one (4): 2-methyl-4-isothiazolin-3-one (5): 5-chloro-2-methyl-
4-isothiazolin-3-one (6): 2-thiomethyl-4-ethylamino-3-(1
,2-methylpropylamino)-S-triazine (7
): Hexahyto o-1,3,5-)lis(2-hydroxyethyl)-s-)lyazine (8): 4-(2-nitrobutyl)morpholine (9):
4-(3-nitrobutyl)morpholine. (IQ): 2-(4-thiazolyl)benzimidazole (+ 1): Written as dodecylguanidine hydrochloride [
The compound of A1-[F] was prepared using a stabilizing solution [0.001 to 1
Can be used in the range of 50g, preferably 0.0
Adding 1 to 20 g gives good results. For the stabilization of the present invention, at least t4 of the above compounds [A] to [F] can be contained, but it is preferable to contain other soluble iron complex ions. As a compound, ferric chloride, Via
: inorganic m2 iron salts such as fs2 iron, ferric nitrate, ferrous chloride, ferrous sulfate, ferrous nitrate, etc., ferrous 4!4, ferric acetate, citric iron #: jS 2 iron, etc. There are carboxylic acid iron salts and various iron & 1 salts, and compounds that form 'i51u with these iron ions have the following general formulas [II] to [X[
Examples include compounds represented by []. - General formula [II] MmPsO ■;
Hydrogen, alkali metals, ammonium. ts; An integer from 3 to 6. General formula [[11] Mn+z PnO3n +rn
; An integer from 2 to 20. General formula [rV] B -A+ -Z -A2-0 formula [
rV], [V], At to A6 are each substituted or unsubstituted alkyl group, Z is an alkyl group, -R-0-
R-1-ROROR- (R is an alkyl group) or >N
-Ay (A? is hydrogen,) hydrogen hydride, lower aliphatic carboxylic acid, lower alcohol), B, C:, D, E, F,
C is -OH1-(:00M, -POko A2(M
represents hydrogen, alkali metal, ammonium). General formula [71] % formula %) R2; hydrogen, Cs-C4 furkyl group, -(CH2
) At 00, phenyl group. R conihydrogen, -cooM. In: hydrogen, alkali metals, ammonium. Brother 9; O or l. n; an integer from 1 to 4. General formula [vI[] R4N(CH2PO:l M
2) 2R4; lower alkyl group, aryl group, aralkyl group, nitrogen-containing 6-membered ring group, [-OH as a substituent,
-0Rs (Rs: CI=C4(7)alkyl3), -PO3M2, -C)I2PO3M
2. -N(CHzPOkoMz)2,
-000A2. −N(CHz COOM) z ]. B: Hydrogen, alkali metals, ammonium. General formula [■] Rs, Rte, RI: hydrogen, 7'alkyl group. OH, -NJz (J is) I, OH, lower furkyl group, -(:2 Ha OH),
”X, Y, Z ;-OH,-COOM,
-POko A2゜H. F4: Hydrogen, alkali metal, ammonium. Synonymous with sentence, n general formula [VI]. General formula [IX] 0M Rto 0-P -0RLII Rs, Rto; hydrogen, alkali, ammonium, C
s -Crz alkyl group, alkenyl group, cyclic alkyl group. General formula [XcoRu; Ct NCa alkyl group, CI~C
12 flukoxy 71q, C+'' CI2 monoalkyl 7mi7 group, C2C+z dialkylamino group, amino 7, Cr-C24 7 lyloxy group, C
i = 7 arylami 7 groups and amyloxy group of C2t. Q1 to Q3; -OH, Cr to c24 noal) t
-C group, aralkyloxy group, aryloxy group, -0
M3 (A3 is a cation), amino group, monophorinone group,
It shows a cyclic 7-mino group, an alkylamino group, a dialkyl 7-group, an arylamino group, and a furkyloxy group. General formula [X+] R12, R1 conihydrogen, lower alkyl group. and hydrogen, alkali metals, and ammonium. General formula [X[[] RI4~R+s; hydrogen, alkyl group C substituent -
OH, -0CnHz n++ (nlIl ~4) -
poko M z, -CHz POko M
z, -NR2 (R is an alkyl group), -N(CH2P
OcoM2) 2゜M: Hydrogen, alkali metal, ammonium. In addition to the compounds represented by these general formulas [11] to [2], citric acid, glycine, etc. may also be mentioned. However, +ii
The compound represented by the general formula i exhibits even more excellent effects. Specific examples of the compounds represented by the general formulas [II] to [■] include those described in JP-A-58-14834. Especially preferably iron aminopolycarboxylate ion or iron(III) phosphonate! ! can be given. The soluble iron salt iron ion used in the invention can be added in an amount of Ihg-8 g per 12 of the stabilizing solution, preferably in a range of 50 mg to 2 g. In addition, in a continuous treatment method in which the treatment process consists of multiple stabilization tanks (baths), the treatment is carried out in a countercurrent manner, and the final tank is replenished, the desired amount of the above-mentioned soluble iron salt added is based on the number of stabilization tanks (baths). This is the concentration in the final tank. The silver complex ion that exists in the stabilizing solution may be any soluble silver ion, such as silver bromide complex ion, silver iodide complex ion, silver chloride complex ion, silver thiosulfate complex ion. , F & acid silver complex ion/, acetic acid complex ion, thiocyanate acid ion, etc. may be used. If necessary amounts of these are present, they are preferably brought in from a processing solution having fixing ability, and the necessary degree is determined by the amount of replenishment of the stabilizing solution. That is, when the amount of replenishment of the stabilizing solution is small, the concentration of silver ions increases by E, which is more preferable. The concentration of silver complex ions in the terminal stabilization tank is 2 X + o-5 mol to 2 X + o-' mol, preferably 6 X
to-5 moles-1X1O-3 moles. (Particularly desirable compounds to add to the stabilizer used in the invention include ammonium compounds. These can be supplied by various inorganic compounds, such as ammonium 1!x, but specifically ammonium hydroxide, lb ammonium, Ammonium carbonate Ammonium chloride Primary sodium chloride I
v7 ammonium, ammonium phosphate, ammonium phosphite, ammonium fluoride, resistant ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium bifluoride. M-hydrogen ammonium, M-ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium alarin triphosphate, ammonium, ff1.8 ~ ammonium, cal/< ammonium mate, citric acid Ammonium acid, ammonium dinityldithiocarpamate,
Ammonium formate. Ammonium hydrogen linodiate, ammonium hydrogen oxalate, ammonium hydrogen phthalate, ammonium hydrogen tartrate, ammonium lactate, ammonium malate, ammonium maleic acid, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate ,
Ammonium succinate, ammonium sulfanilate,
Ammonium tartrate, ammonium thousand oglycolate,
2,4.6-dolinitrophenolammonium and the like. Addition of these ammonium compounds +, H is stabilizer 12
It can be used in the range of 0.05 to 100g per unit,
Preferably it is in the range of 0.1 to 20 g. The treatment temperature during the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 40°C, and the shorter the treatment time is, the more preferable it is from the viewpoint of rapid processing.
Q seconds to 10 minutes, the most tT is 20 seconds to 5 minutes, and in the case of multi-tank stabilization treatment, it is preferable that the 111th stage treetops be treated in a short time, and the subsequent stage tank treatment time be long. In particular, it is desirable to carry out the IF primary treatment with a treatment time of 20% to 50% of the previous tank.Also, the stabilization treatment process should be performed in multi-stage tanks, with the replenisher being replenished from the last stage tank, and the replenishment liquid sequentially overflowing into the previous stage tank. Although the method may be used, it is most preferable to use an rri tank. In the uninvention, the fixing process is carried out in a processing bath containing a soluble complexing agent (fixing agent) that solubilizes silver halide as a silver halide complex salt. Not only general fixing solutions, but also bleach-fixing solutions, -bath development footstone solutions,
- Bath developer door white fixer is also included. As a fixing agent, thio&t1'W salt and thiocyanine diluted salt are used. There are iodides, bromides, 1,000-onythyl, and thioureas,
Preferred fixing agents in the present invention are thiosulfates, particularly preferred fixing agents are thiof! ammonium acid. These fixatives are 5g/! ;L or more, preferably 50g/i
It can be used in an amount that can be dissolved more preferably at least 70g/1. r used in bleach or bleach-fix solutions. As the whitening agent, the organic acid Metallic Rust 1N is used, and the assay pressure complex salt has the effect of oxidizing the metallic silver produced by development and converting it into silver halide, and at the same time coloring the uncolored parts of the coloring agent. The structure of No. 7 is one in which a total ion of iron, cobalt, copper, etc. is coordinated with an organic acid such as aminopolycarboxylic acid or citric acid. This kind of organic acid is the best metal rust! The most preferred organic acids used to form (diethylenediaminetetraacetic acid (2) diethylenetriaminepentaacetic acid (3) diethylenetriaminepentamethylphosphonic acid (4)
) cyclohexanediaminetetrabutyric acid (5) cyclohexanediaminetetrabutyric acid (6) triethylenetetraminehexaacetic acid (7) triethylenetetraminetetrabutyric acid (8) glycol ether diamine tetraacetic acid (9) glycol ether diamino tetraacetic acid Methylenephosphonic acid (10) 1,2-diaminopropanetetraacetic acid (+1) 1
．． 2-diaminopropane tetramethylenephosphonic acid (12)
Methyliminodiacetic acid (13) Methyliminodimethylenephosphonic acid (14) 1
．． 3-diaminopropan-2-ol tetraM acid (+5)
1.3-Diaminopropan-2-ol Tetramethylenephosphonic acid (1B) Ethylenediaminediorthohydroxyphenyl M acid (IT) Ethylenediaminediorthohydroquine Phenylmethylenephosphonic acid (18) Ethylenediaminetetramethylenephosphonic acid (19
) Ethylenediaminet (β-oxyethyl)-N,N
',N'-Triacetic acid (20) Nitrilotriacetic acid (21) Iminoniacetic acid (22) Dihydroxyethylglycinephenoic acid (or tartaric acid) (23) Ethyl ether diamine tetraacetic acid (24) Enale/diamine tetrapropionic acid (25) Phenyldi7minetetraacetic acid disodium salt (26) Ethylenedi7minetetraacetic acid disodium salt (27
) Ethylenediaminetetraacetic acid tetra(methylammonium) (28) Ethylene/diaminetetraacetic acid tetranate (29) Diethylenetriaminepentaacetic acid pentanate (30) Ethylenediamine-N-(β-ammonium) diethyl)
-N, N-n-Three-resistant sodium salt (31) Propylene diamine four-resistant sodium salt (3
2) Nitrilotriacetic acid sodium salt (33) Cyclohexanediaminetetraacetic acid sodium 9um salt In the invention, among the above organic acids, those of (1) to (+8) are preferably used, and these organic acids No. 29 Miscomplexation 11!
is preferred. A particularly preferred organic acid ferric chain salt is (I). Examples include compounds (2), (4), and (8). The organic acid ferric acid 1h '14 is a free acid (alkali gold 111n such as hydrogen 1!, sodium !mu, potassium 1!!, lithium 1!1, or ammonia L.j!1). or water-soluble amine f43, such as triethylamine, sodium 1!! and 7 ammonium salts. They may be used, but two or more types may be used in combination. The equipment to be used can be selected arbitrarily, and must be selected depending on the fFi amount and silver halide composition of the photosensitive material to be processed.However, since it generally has a high oxidizing power, other 7/polycarboxylic acids are used. 0 which can be used at lower concentrations than 1 e.g.
It can be used in an amount of 0.01 mol or more, preferably 0.05 to 0.6 mol, per 11 working liquids. In addition, it is desirable to use the replenisher in a state where the dissolved M degree is as high as possible in order to achieve high concentration and low replenishment. The bleaching solution and bleach-fixing solution can be used at a pH of 0.2 to 9.5, preferably 4 to 9.5. More preferably 5.5 to 8.
Used in 5. The treatment temperature is 80°C or lower, preferably 55°C or lower, most preferably 45°C or lower to prevent evaporation. The 75c white liquor used before the processing solution with fixing ability is 11
Various additives can be included along with the organic #:JS2 iron rust salt as a bleaching agent such as those described in 1. As an additive,
Particularly alkali/% rides or ammonium L1 halides, such as potassium bromide, sodium bromide, I! It is desirable to contain sodium sodium chloride, ammonium iodide, potassium iodide, sodium iodide, ammonium iodide, etc., as well as borates, oxalates, acetates, carbonates, phosphates, etc.
H-slow paper 1 agent, solubilizing agent such as triethanolamine, acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid. Those known to be commonly added to bleaching solutions, such as alkylamines and polyethylene oxides, can be added as appropriate. The bleach-fix solution mentioned above includes a bleach-fix solution containing a small amount of a halogen compound such as potassium bromide, or conversely, a bleach-fix solution containing a halogen compound such as potassium bromide or ammonium bromide. It is also possible to use a special bleach-fix solution having a composition consisting of a combination of the bleaching agent described in E and a halogen compound such as potassium bromide. In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. can also be used. In addition, as in the case of the above bleaching solution, the above bleach-fixing solution contains
pH buffers consisting of various substances such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, butyric acid, sodium acetate, ammonium hydroxide, etc. A combination of two or more types can be contained. Furthermore,
Various types of A can also contain optical brighteners, antifoaming agents, surfactants, and antifoaming agents. Also, droxyamine, hydrazine, sulfite, isomeric sesulfite. Preservatives such as bisulfite adducts of aldehydes and ketone compounds, organic compounds such as acetyl 7-setone, phosphonocarboxylic acid, polyphosphoric acid, ##organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid, and ami/polycarboxylic acid. Contain appropriate chelating agents or stabilizers such as nitro alcohols and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, and organic solvents such as methanol, dimethylformamide, and dimethyl sulfoxide. I can do it. In the processing method of the present invention, the most preferable processing method is to perform bleaching or bleach-fixing immediately after the first color development.
Bleaching or bleach-fixing treatment 1- may be used, or a pre-bath containing a bleaching accelerator may be used for bleaching or bleach-fixing. ! In addition to the 0 or more steps that may be used as a processing solution prior to white determination, known auxiliary J steps may be added as necessary, such as hardening, neutralization, black and white development, reversal, and washing with a small amount of water. good. Here are some typical examples of desirable processing methods. The following steps are included. (1) Color development - bleach-fixing - stability (2) color development - bleach-fixing - first stability - second stability (3)
Color development - Stable - Bleach-fixing - Stable (4) Color development -> Fixing - Bleach-fixing - Stable (5) Color development - Gate white - Stable - Stable - 1st stable - 2nd stable (8) Color development - Just before bleaching One stable (7) Color development → bleaching + fixing 1st stable - 2nd stable (8
) Black and white development → washing with water (or stabilization) - reversal → color development - bleaching constant fixation - stabilization (9) pre-hardening film - neutralization - black and white development one stop heating color development - bleaching constant fixation - stabilization and fixing solution in i , various inorganic golds) i! It is preferable to add salts, and it is also preferable to add these inorganic metal salts after forming them into metal complex salts together with various chelating agents. Aromatic compounds used in color developing solutions used in processing with bleaching solutions or bleach-fixing solutions: jS Primary amine color developing agents include 1 well-known ones that are widely used in various color photographic processes. be done. These developers include amine phenol and ρ-phenylenediamine derivatives. These compounds are in free form! 5 Generally pigeon form 1 eg hydrochloride or sulfuric acid 4 because it is more stable!
It is used in the form of 4. Additionally, these compounds generally have a concentration of about 0.1 g to about 30 g for the color developer 12;
More preferably, a concentration of about 1 g to about 15 g per serving is used. 7 As a minophenol developer, 5 is used, for example, 0-7 mm/
Phenol, P-amino/phenol, 5-amino-2-
Oquintoluene, 2-7 minnow 3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like. Particularly useful aromatic: i4 primary amine color developers are N, N
-difurkyl-p-phenyle/diamine type compound, in which the alkyl group and 7-yonyl group may be substituted or unsubstituted, among which a particularly useful compound is N,N-diethyl-p- -Phenyrange 7
571g acid 1g, N-methyl-p-phenyl diamine)! [Salt, N,N-dimethyl-p-2enylenediamine salt, 2-ami/-3-(N-ethyl-H-'r'F
cylamino)-toluene, N-ethylate β-methanesulfonamidoethyl-minoaniline i S th, toethylate β-hydroxyethylamino 7-niline, 4-amino-3-methyl-N
, N-dinitylaniline, 4-7minor N-(2-methquinethyl)-N-ethyl-3-methylaniline-p
- Mention may be made of toluenesulfonate a. In addition to the aromatic primary amine color developer mentioned above, the alkaline color developer preferably used in the present invention includes:
Furthermore, various components commonly added to color developing solutions, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkaline total sulfites, and alkali metal bisulfites. For alkali + dithiocyanic acid, alkali metal halide. Hensyl alcohol, diethylene trianine 5 I'l! acid, l-hydroxyethylidene-1.1
-Water softeners such as diphosphonic acid and eJI additives may optionally be included. The pH of this color developer is usually 7 or higher, most commonly about 10 to about 13. The uninvented door solution or bleach-fix solution has a surface tension of 55 dyn.
It is preferably less than e/cm, more preferably 5
0 dlne/cra or less, preferably 40 d7ne
/Cm or less. The surface tension of a treatment solution with bleaching ability used in an uninvented treatment can be found in "Analysis and Testing Methods for Surfactants" (co-authored by Fumio Kitahara, Shigeo Hayano, and Betsu Hara, published March 1, 1982. ■Kodansha) In the present invention, the value of surface tension is measured by a general measuring method at 20°C. In the case of the present invention, any method can be used to lower the surface tension to 55 dyne/c+a or less, and any method may be used, but surfactants are preferably used. These surface tensions are 55d! The surfactant whose concentration is less than ne/e+w is J
It may be added to the liquid solution rather than the li solution. Alternatively, it may be added by being attached to the photosensitive material from a Tij bath. Alternatively, the surfactant may be contained in the light-sensitive material and added to the bleaching solution or the bleaching solution. Among the above surfactants, 6. Especially the general formula CX0I
Compounds represented by I to [X] are frequently used. General formula [to] R17-CH-COA+R+TSLm -(:)I-GOOR? a In the formula, one of Rrr and Rag represents a hydrogen atom, the other represents a group represented by the formula -SO:1M (M represents a hydrogen atom or a -valent cation), A+ is an oxygen atom or a group represented by the formula - a represents a group represented by NR21- (Rn represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) Rrs and R211 each represent an alkyl group having 4 to 16 carbon atoms, (Ll , L, Ra
The alkaline crystal represented by g, Rx or R21 may be substituted with a fluorine atom. General formula [XIV] Az -0-(B)m -X+ In the formula, A2 is a monovalent alkyl group (for example, an alkyl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms),': C) or alkyl having 3 to 20 carbon atoms J, I! arylph substituted with (, and the substituent is preferably a carbon atom: f number is 3
~12 alkyl groups (e.g., propyl, butylpentyl, hexyl, hepnal, octyl, nonyl, tesyl,
Examples include phenyl, tolyl, quinyl, biphenyl or naphthyl groups, preferably phenyl, (or tolyl). , the bonding position 2 may be any of the ortho, meta, and para positions, B represents ethylene oxotho or propylene/oxide, and K represents an integer from 4 to 50. Llf hydrogen atom, SD coY Matata PO+ Y z'
e, Y is a hydrogen atom, an alkali metal atom (Na, K
or Li, etc.) or ammonium ion. In the general formula [XV] pη, R22, Rn, R24 and R2S each represent a hydrogen atom, an alkyl group, or a phenyl group. The total number of carbon atoms of Rn, R2:l, R24 and R3 is 3 to 50. X2 is a halogen atom, hydroxyl, sulfuric acid, nitric acid, acetic acid, p-
Toluenesulfonic acid/! 7 ions are shown. General formula [XVT] In the formula, Rn, Ryy, Rn and Rn are each water a
; h; <represents a child or a furkyl group, and has the same meaning as the general formula [k]. n and P each represent 0 or an integer from 1 to 4, and ! This value satisfies ≦H+p≦8. [Example] Hereinafter, the present invention will be explained in detail with reference to Pi9 (l), but the present invention is not limited thereto. Anionic starch and NaCt with a surface size of 51 were obtained.
o 11/m' high-quality paper on one side. The following composition liquid was mixed and dispersed in a Gale mill to a thickness of 20 μm.
A cloth was applied, and then a+ line thermal irradiation was carried out at ZtlOkV and 5 to Irad irradiation l in a nitrogen gas daytime atmosphere using a Kuji line accelerator. (Composition liquid) Apply the above composition to a thickness of 20 μm on the opposite side of the cured coating layer.
After applying it to a thick layer and curing it by electron beam irradiation in the same manner as above, a coupler-containing salt-beautified steel gelatin milk ~1 and a protective layer were applied to the surface of the first ω layer and dried to form an I- A silver halide color photographic material was prepared. The coating sample thus obtained is referred to as sample (ll).Next, the following composition liquid was mixed and dispersed in a ball mill on one side of a high-quality paper with a basis weight of loo&/m' that had been sized as described above, and then a 20 μm thick sheet was prepared. Then, using an electron beam accelerator, it was irradiated with an electron beam at a dose of 2 tJOkV and 5 Mrad.
After applying the coating to a thick layer and curing it with KTL irradiation as described above, the first coating IV coated with a silver chlorobromide gelatin emulsion containing a surface coupler and a preservative RI was applied and dried to form a silver halide color. A photosensitive material was created. The zero fabric sample obtained here is designated as sample (2). Furthermore, the size was processed as described above, tsubo j & + uo, 9/m1
After mixing and dispersing the following composition liquid on high-quality paper using a ball mill, it was rolled to a thickness of 30 μm, and then heated at 200 kV, S under a nitrogen gas atmosphere using an electron accelerator.
Electron beam irradiation was performed at a dose of &Irad. (Composition liquid) Apply the above composition liquid to a thickness of 30 μm on the opposite side of the cured coating layer.
After applying the coating to a thick layer and curing it by electronic eyelid irradiation in the same manner as above, a coupler-containing trW was applied to the surface of the first memory layer.
A silver halide color light-sensitive material was prepared by coating and drying a bromide gelatin emulsion and a bromide gelatin emulsion. l obtained here
Let the cloth sample be Sample (3). Furthermore, as a comparison sample, polyethylene mixture
/m- on both sides of the polyethylene mixture with dashed lines contains 1 part of titanium dioxide (Hl: 9 parts). This sample was used as a sample for comparison. After cooling the exposure using the method described above, The following treatments were performed. As a comparative treatment, a water washing treatment was performed instead of the stabilization treatment. The water washing treatment was performed at a flow rate of 52 per minute. Treatment process Processing temperature °C Processing time 1 Color development
37.8 3 minutes 15 seconds 2 Bleach fixing 3
7.8 1 minute 30 seconds 3 Stable 3
0 to 34 2 minutes 10 seconds 4 Dry The following color developing solution, bleach-fixing solution, and stabilizing solution were used. Color development 1 [liquid] Potassium carbonate 30. SI Ashichisha Sodium 2. Oy Hidokoki/Amine sulfate salt 2.2g diniterene triamine 5! ! I
Lower 1'ff 2. OJF sodium hydroxide
3.4g N-ethylene-N-β-hydroquinethyl-3-methyl-4-aminoaniline salt A? salt
4.6.9 Add water and finish with pi (adjust to 10.05 with sodium hydroxide). 10.f7chif
Ammonium sulfate (70% solution ¥L) 200m Ammonium sulfite (40% solution) 10mM Water was added to bring the total volume to 11, and the volume was adjusted to 16.8tc with aqueous ammonia. [Stabilizer] 2-methyl-4-indeacyly/-3-one 0.004
,9 2-Methyl-5-chloro-4-isothiazolin-3-one 0.02,9'1-hydroxy/ethylide/-1,1'-diphosphophone QO, (115' 2-octyl-4-inthiacyly/- 3-on U, 03
．． 9 agglomerated magnetum 0.17,? Bismuth chloride 0.14 & polyvinylpyrrolid 10.1. Sl Ditricotrinic acid 3.9 Ammonium hydroxide (28% water bath solution) 3I Water was added to make the total amount In, and the mixture was adjusted to -7.1K with acetic acid and potassium hydroxide. Add the above color developer, 1st grade white fixer and stabilizer to the automatic development L1 machine, and while processing the cypress printing of the upper epsilon color paper, perform the above color development and bleaching every 3 minutes. A running test was conducted with the fixer and stabilizer supplemented with the prescribed light. Suri 1 Koai is color paper tooada
2.0mj as punishment for each color developing tank.
! , fi bleach-fixer 15 as the replenishment amount to the white fixer tank.
-2.8 ml of stabilizing solution as a replenishment amount for 1 times stability?
i! i glowed. In addition, there are 1st to 3rd stabilizing tanks in the direction of the stable flow of photosensitive material in the automatic processor, and the final tank is replenished, and the overflow from @P:N is sent to the previous stage. The total replenishment of the 2 stable liquids is the total replenishment of the 1st to 3rd desired stable liquids. After storing for 2 weeks, roll and cut, step 4 of the edge part below.
73 animals were measured. For comparison, the unexposed part and the white base of the Usa Kulii image part (the most
i'lX ) t l'l a K 80 X RH,
60°C'k Injection T: Stored at 21 inils. c/) after storage, the change in 1i animals was compared with W8 degrees. Table-1K shows t6 rice at 11 Kunji/gu harvest ω time! −−−, , ・! -・2
'l'CL1゜・ , 2□ '(Llolo, 1□ 2
67 Z393 2 α09' 0.2
1 '0.10 Q, 12 165 240 Table-1
It is clear from the results that 1c, when the inventive material 1c is treated without water washing, has better edge contamination, image εl, stain 3, and color %σ degree Kfi than the comparative sample. In addition to this Example, the stabilizing liquid treatment was replaced with the water washing treatment, but no significant difference was obtained between the present invention and the conventional treatment as shown in Table 1, and it was confirmed that the effect was small. Example 2 The whitening agent in the bleach-fix solution was replaced with the one below, and the other conditions were as in Example 1.
The experiment was conducted in a similar manner. (Bleach Studio J) (1) Ethylenetriamine 5ttPf & 2nd V
A/Monilim Roll/fl (2) Cyclohexanediaminepentavinegar a'A 2 M
ammonium
8 (1/f(3) triethylenetetramine6aTtferric ammonium
As a result of 9 ag/l7, the same results as in Example 1 were obtained, and the effect of the present invention was confirmed.
I got it. Example 3 A sample according to the present invention was treated in the same manner as in Example 1, except that the degraded titanium used in the support was replaced with palitum sulfate, but with substantially no I.
Results similar to those in Example 1 were obtained. Example j4 Instead of Example 1, bleach-fixing i11 was divided into bleaching and constant aging processing, each time was 1 minute and 30 seconds, the processing temperature was 33°C, and the number of processing was Sakura Color NK-4. A processing agent was used. The other procedures were the same as in Example 1. The results obtained were substantially the same as in Example 1. Nobuaki Sakaguchi (and 1 other person) Representative of Konishiroku Photo Industry Co., Ltd. Patent attorney

Claims (1)

[Claims] After imagewise exposure of a silver halide color photographic material having at least one photosensitive silver halide emulsion layer on a support coated with a resin cured by irradiation with an electron beam, color development processing is performed and fixation is performed. 1. A method for processing a silver halide color photographic light-sensitive material, which comprises stabilizing a silver halide color photographic light-sensitive material after processing with a processing solution having the above-mentioned properties without substantially undergoing a water washing step.