JPS58137837A - Formation of color image - Google Patents

Abstract

PURPOSE:To inhibit color staining in a color image forming system, by color- developing an imagewise exposed color photosensitive silver halide material with a combined developing and intensifying bath in the presence of a heterocyclic compound contg. nitrogen and by processing the material with a soln. contg. an intensifying activity restrainer. CONSTITUTION:About 1X10<-7>-1X10<-2>/l heterocyclic compound contg. nitrogen such as benzotriazole is added to a combined developing and intensifying bath contg. hydrogen peroxide or a compound releasing hydrogen peroxide and a color developing agent but contg. practically no bromine and iodine ions. A color photosensitive material is color-developed with said combined developing and intensifying bath and processed with a soln. contg. about 1X10<-5>-2X 10<-1>mol/l intensifying activity restrainer such as KI or compound represented by the formula.

Description

[Detailed description of the invention]

Conventionally, many methods are known for reinforcing the IT-forming tube by subjecting silver halide photosensitive materials to reinforcing treatment. Oxidation of the paraphenylenediamine color developer agent by decomposition of hydrogen peroxide on the catalyst surface in the presence of a color former and subsequent formation of a dye by coupling with the color former (this phenomenon is referred to as color intensification). ) For K, for example, Fr
iedmanlj, bHistoryofeol
or Photography Jnd Ed. (1916), listed in 4406 members. In addition, there are descriptions of various other photographic methods that utilize the decomposition of peroxide on the surface of precious metals, including the West German patent publication WIACOL8).
/, 113,9 θ No., (b)/, 9! o, io- issue,
Same/, 96/, 0ko9, Same 2゜0410-. No. 131, 1WJ2,00141,993, same, 0ri'*3
No. 60, same, 0s6. j Su No. 9 and the same, /λ0,0
It is in issue 9/ etc. - For example, in the description of the color enhancement method using cobalt complex salts on handsome metal surfaces,
No. 972r, same ar-qy2, llJ reference r-441
No. 130, same≠? -ra--9, same tie-tait
Same as the tto issue? -974/41, same ll9-102
There are K such as 3rd issue, at-io 3/3rd issue, etc. In addition, the color intensification method using halous acid @ff of chlorite solution r:i JP-A-Sho r/-j Jr. Coro issue and tJ-/JJ
It is listed in J. , lAlso, the color intensification method using iodoso compounds such as iotonobenzoic acid 1-r% development! -17j7J/. These peroxides, halous acids, iodoso compounds, and compounds that have a reinforcing effect, such as Kobal (Tri)81j, are called reinforcing agents. The processing bath in which this process is carried out is called an intensification bath.Of these, representative technologies include tcolor II fJII II @ technology that utilizes the catalytic action of a peroxy compound or a co/2-rut(III) complex. Hydrogen peroxide reinforcement is considered to be the most efficient in terms of the expansion efficiency. Method 6: A silver photosensitive material is exposed to light for cleaning, and the resulting developed silver is used as a catalyst to efficiently form an intensifying agent and a color developing agent on the catalytic silver nucleus. This method is known as a method in which an oxidized product of the immersion agent is produced through a retox reaction of immersion, forming a high-density dye image (Ill'fr), and reinforcing the image III'fr. After on-site intensification bath, even red immersion is carried out. It is common to call this a processing method in which a coloring agent is retained in the film of a photosensitive material, and the coloring agent is brought in from the photosensitive material and applied to the surface of the color in an intensifying bath. In order to efficiently perform this technique, a large amount of the dipping agent is retained in the photosensitive material film.
It is necessary to bring the immersion agent into the intensification bath and to quickly oxidize the immersion agent in the membrane on the catalytic silver nucleus in a short period of time before the immersion agent in the membrane diffuses into the intensification bath. As a specific method from this point of view, a U.S. patent has been published that uses a highly oily herbal medicine in the present 9 solution! ,r/l,. No. 1, Tokukai Akita! -, 30J! J No. r is listed. !几The technology to suppress the reinforcement force fluctuation without lowering the activity of the catalyst nucleus is the % open-open tacho/JJJj issue, turn it! -/9F2
Small listed in No. 9 etc. In this way, the mixing of the present 9 liquid components into the intensification bath is an essential change in the Gakishinriki method, and the incorporation of intensification inhibitors reduces the intensification activity, and the incorporation of modern herbal medicines.
It is an unavoidable problem that fluctuations in the performance of the intensifying bath due to fj occur. On the other hand, iiiIgI! Compared to the conventional treatment process r in the reinforcement treatment, one or more treatment steps are added at the 6th time after the reinforcement bath 8,
The West German patents I, TI3. Qco No. 0, % Kaisho tJ
-/No. 3331, % opening 31-/, 27j j evening etc. wo
The possibility of performing e and reinforcement at the same time is presented. However, 1 kf of hydrogen peroxide in the normal coloring liquid from fl! f
Just by adding S, you can develop color like the skin as mentioned above.
Potassium bromide (usually added in the amount of 1,001,111/l) hardly achieves a one-bath in-situ intensifying effect in low-silver photosensitive materials. A method of forming a color intensifying image with a high gain ratio (less fogging) and a small number of processing baths using a color photosensitive material was invented, and this invention r1 patent application Sho Taro/
It has been filed as /7?7J. That is, in this invention, cleaning rj! Silver halide photosensitive material contains a compound that releases hydrogen peroxide or σ hydrogen peroxide and a color-forming immersion agent in the presence of a compound that reacts with silver halide and adsorbs bromine. One-bath on-site reinforcement g that does not substantially contain ions and iodine ions.
This is an image forming method that uses t% characteristics to process the color development by using . This method is innovative, but it tends to cause unnecessary generation in non-6 blue areas, and it is necessary to improve this point. . However, the above-mentioned MS formation method can greatly reduce chain reaction and reduce the number of processing baths, such as omitting bleaching baths, fixing baths, and omitting rinsing, but the above methods have disadvantages. ing. However, we have discovered that color staining does not occur even when using a post-treatment bath with a specific composition and omitting washing with water. The level is low enough even without it. Therefore, even though it is a simple process that does not require desilvering or water washing, it can eliminate staining of either the silver or dye, and has a sufficiently low stain level for many uses as a transmitting material. 2 but high quality image quality! The required technology is a color tree with a white reflective support.
There is a need for even greater suppression of sugain, which is highly evaluated by the industry. The object of the present invention is color stain suppression in color image scarring systems. For the purpose of the present invention, a silver halide color light-sensitive material which has been exposed to vertical VCn light is treated in the presence of a nine element-containing hetero-A compound, which releases hydrogen peroxide, and a compound which releases hydrogen peroxide. A one-bath intensifying liquid that contains a coloring active agent and is substantially free of bromide ions and iodine ions. 7'2: Afterwards, it is treated with a solution containing a liquid that suppresses the intensification activity of the silver halide fog nucleus.
i! IJgl! The nitrogen-containing heterocyclic compound used in the present invention may be used in combination with the nitrogen-containing heterocyclic compound used in the present invention. used. Preferably, the present invention uses tL and element-containing compounds (
7 potato σ) contains nitrogen atoms! Eclipse 6-membered hezoro]Wf compound, their condensed rings and the following general formula (I)
and (1) is a nitrogen-containing hetero field 1 [attached to general formula (I) general formula (II) general formula (I)
, In (II), A represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aralkyl group, and an aliphatic carbonyl group, and a substituted or unsubstituted aryl group; Refers to substituted or unsubstituted hydrocarbon divalent groups. For example, the following monovalent groups are preferred. -feH2n. -, -CH,U-(C)I2). −
(1-CH2-, n represents an integer from 1 to /2
This is a nonmetal group in which Z and N atoms form a heterocycle. More preferable examples of the above-mentioned nitrogen atom-containing heterocyclic compounds and their condensation methods can be shown by the following general formulas. General formula (■n) General formula (W) General formula (V) General formula (W) General formula (■)
General formula (■) 3 General formula t■) General formula (Xn General formula OiI
General formula T)1) General formula I
General ceremony! XPi') Kame819 In the general formula (■n~(ff), Lu, 几1, R3
and R4F:I each hydrogen atom, alkyl, aralkyl,
alkenyl, alkoxy, aryl, -N)LR'. −CU(JR, −8υ, M, RJLI to −CU, −
NH8 (J, R15 (J NRR', -NO,, halogen atom, -CN i or -OH group. (representing a hydrogen atom or an alkali metal atom), in the case of an alkyl group with R□ and R8, they may be combined with each other to form an aliphatic F2 element. alkyl, -8-1(
' / Hail the base. (However, the RI group represents a hydrogen atom, an alkyl, an aralkyl, or an aralkyl group.), R6 is a hydrogen atom, or an alkyl group. R7 is a small hydrogen atom, alkyl group, or aryl group. Includes alkyl, aryl, benzyl, and pyridyl groups. R, t-J alkyl,
Hail alkenyl and aryl groups. 1 (R1-J alkyl, alkenyl 10% 11, aralkyl group, and when RlG and R1□ are alkyl groups, they may bond to each other to form an aromatic mt shadow. Chapter 9 hetero IH containing a mercapto group) As a compound, a compound represented by the following general formula is preferable, and the compound represented by the general formula (X
V) In the general formula
Indicates an unsubstituted aryl group or aralkyl group. )Y
and 2 digits, each a carbon atom or a nitrogen atom, R1□ and R.13 each a hydrogen atom, an alkyl, an unsaturated alkyl group, a substituted aryl group or an unsubstituted aralkyl group + an unsubstituted aralkyl group , + S RIII , +
NH2 group (remember, FLI/// group n is a hydrogen atom, alkyl, aryl, aralkyl, alkyl carbon e, or an alkali metal salt thereof, alkyl sulfonic acid or an alkali metal salt of niso) Y When and 2 are both carbon atoms, R1 and ts may be substituted or unsubstituted aromatic compounds. Representative examples of the compounds of the present invention are listed below. (13 (2) (31 (41 (51 (61 HH) (71 (8) (9) 舖αυ Q3 ) 1 to 1 (13Q4) 0!9 as67)
Ql (JHOH H■ Qυ (2 Ka (ha)
(Foundation) @ (
To) @ (To) (A) (7)-■ @ (branch)■
- Ill - 關
(Foundation) 4 □ 啼 啜”F Fn6υ
1520
- 551 ωgo
ω The amount of the nitrogen-containing heterosakai compound with the above-mentioned fog suppressing effect added to the current reinforcement, the amount of lead (& the amount of halogen in the photographic element) and the type of silver supported There are different types of agglomerates that have the fog suppressing effect and are not particularly limited, but it is more effective than ordinary liquids and reinforcing liquids.
It is preferable to add it in an amount that is low in order of magnitude. Current Confucian intensification liquid/l×10mole/X101FnO1e
used in the range, but preferably <$7/X10m
Preferably fljx from ole to /x10mole%%
When used in the range of lo mole to /X/θmole, when halogenated scissors are added to a light-sensitive material, K is added to the light-sensitive material η! It is used in the range of 110 mole to 10 m01e, preferably in the range of 110 mole to 10 mole, and nitrogen-containing hetero-metallic metals described in the following known literature etc. are also used in the present invention. Can be used. U.S. Patent Co., ≠94. ? No. 0, British Patent Reference OJ, 71
No. 9, U.S. Patent Co., 4#7, No. 9/7, 2.6 Ta6.
277, etc., penttriazoles described in "Journal of the Photographic Society of Japan" (1994 Ir. ff.), U.S. Patent No. 2. /3/, 031
Peter, such as the benzthiazolium salt described in No. 2.69, No. 7/4, No. J, Jλ6, No. 41/etc.]llN
Dan, U.S. Patent Co., Ape, No. 6oz, Same, 1st, 6O
Tetrazaindenes described in No. 4, same, No. 607, etc., U.S. Patent No. 73,621, same, 3≠
, No. 723, same, 1st, toy, etc., and other heterocyclic compounds described in "Science Photo Handbook" Vol. 779
Page (Maruen 19! Published in 1999) listed in K. Compounds that can be used in the present invention to suppress the intensification activity of small silver halides include halide ion salts such as benzothiazolium salts, nitroindazoles, triazoles, and benzotriazoles. , benzimidazoles (% nitro or halogen substituted); heterosilicon mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (%/-phenyl-! - mercaptotetrazole), mercaptopyrimidines; the above-mentioned heteromercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; other mercapto compounds, such as mercaptocarbo/WIs, mercapto Alkanols; thioether compounds; thiourea compounds; sulfur-containing amino acid compounds such as cystine and cysteine; thioketo compounds such as oxasolinthion; There are a few small examples. Among these, iodide and sulfur-containing compounds are effective in %. All typical examples of the intensification activity-inhibiting compound used in this foaming are listed below. (4) (5) ti H
(6) (71 (6) f9) α[αD H side (131N f141 (19oQaη CH 0 type 03 HH ■ Punishment @ (goods) (goods) 6 CH τ -punishment (support) ■■ H (J (JC- CH-CI-12SH ■ N) (□ HU-CH2CH2-S-CH2CH, -only IH21t
, - to square ((foundation) HO-(,"H2(,'H2-h-(,:l-12CH
2-8-Cshima C) Chi-8-CH2 ('H2-U H(t) HOOC-C) deception-8-CH2Cl-1,,-To C1
12(:UUH porridge 1 112N-CH2CH2-8-CH2CH2-8-CI
-12CI-(2-to H2■ (9) (to) ta
f411 One-bar bath current intensification liquid (rc in the first bath λ) of the compound with f of the present invention.

[Although this book describes compounds that are effective when added, it does not necessarily mean that the same compound is highly effective. Nine, three odor ions, and one elementary ion are only for the first bath. When the above-mentioned intensification activity-inhibiting compound is added to the processing solution, the intensification activity can be completely suppressed by coating silver with I, halogenated N, and Hλ in the silver halide photographic light-sensitive material. Depending on the type r, %r is not limited, but is applied as patent application Sho Taro //79'7J. It is desirable to do so. If the adhesive of the present invention is added with the same amount of intensification activity-inhibiting compound as used in the processing solution, it will have a large poisoning effect and a very small color increase rate. I can't get what my colleagues want. On the other hand, in the present invention, a large amount can be used as a treatment after forming the color reinforcement #6. As a specific instruction, per light and processing liquid tl/X/Q'mole or λ
It is used within the range of ×lo moIe, but preferably /
×/ Omole/×/. It is preferably used in the range f2/X10 mole & jX10 mo16. Based on the discovery that staining can be prevented without lowering the intensification activity only when the present invention includes a one-bath sodium hydroxide treatment step and the intensification activity-inhibiting compound is applied at the end of this step. The combination with the intensification activation suppression f, which is significant.
Solution V' to add tff5: I, a treatment solution consisting of a buffer with a pH of 2 to 9 may be used, and sulfite, biN sulfate, metabisulfite, formaldehyde bisulfite adduct, thiosulfate, thiocyanate 2. The treatment solution containing the intensification activity suppressing compound of the present invention is used in a pH range of 0 to 9, so it is preferably 171 pHJ.
Known buffering agents can be used, preferably in the range of pH 4< to 7. For example, phosphoric acid-potassium-dipotassium phosphate, sodium citrate-hydrochloric acid, sodium citrate-sodium hydroxide, succinic acid-borax, acetic acid-sodium acetate, tartaric acid-sodium tartrate, borax-boric acid, diekylbarbic acid. Sodium turate-tJ [Flf, Glyci/
- Sodium chloride - Hydrochloric acid, lactic acid - Sodium lactate, Br
1tton-Robinson's wide range loose @ solution can be used. The concentration r of the buffer agent is small, which also depends on the type, but the processing solution t
A range of 1/X10 mole to 1/mole is preferred. For small cases where the water washing process after special f is omitted, VCF″3v
To suppress the salt adhering to the C material and contaminating the image as much as possible, the concentration of the buffering agent should be as low as possible, for example /7
! V/x10 mole Vsl. A range of /X10mole is desirable. In the case of using VC bent sulfuric acid salt and bisulfite lW salt in the treatment solution containing intensification activity suppression compound, and also 1 metabenzened sulfuric acid field, the trap Wl impacting ability is 6 months. ν], may not be used in combination with other buffers. These additions are added to t per t of treatment liquid.
A range of xlθ-2mole to 1xio'tno+e is desirable. In addition, thiosulfur is added to the treatment cylinder containing the inertia activity suppressing compound! I
! When 157I, thiocyanate, or formaldehyde bisulfite addition is used, the addition angle is preferably in the range of /x10 mole to /x10 m01e per liter of processing solution. It is also possible to add a water softener (chelating agent) or a suitable hydrating agent that dissolves the tonicity activity-inhibiting compound that is soluble in water to the liquid containing the tonicity activity-inhibiting compound of the present invention. As a water softener, aminopolycarboxylic acids such as ethylenediamine/tetraacetic acid or salts thereof, /-
Organic phosphonic acids such as hydroxyethane-l,l-diphosphonic acid and their salts can be used in organic solvents such as methanol, ethanol, acetonitrile, acetone, dimethylformamide, N-dimethylformamide, etc. It is desirable that the composition be easily miscible6.Additionally, a surfactant, an antifoaming agent, a hardening agent, etc. may be included as necessary. Intensification activity suppression of the present invention (the temperature of the treatment solution containing compound E is usually selected between ir"c and zoc'c, but ir@c
xr) Lower temperatures are also possible at tOoCklliL,b temperatures. A color developing agent containing a p-phenylenediamine derivative as a reducing agent for use in the present invention, US Pat. p-aminophenol derivative color developing agent in onium salt form as described in No. 79/, No. 127, etc., US Pat.
IJ, No. 401a, et al.
it-J! , No. 124, the diffusive color chart emitting type (DD
R) Redox compound, Special Publication Fgiur-39. /At
Reactions with amitracine compounds described in No. 1, etc., and reducing agents of the type that oxidize themselves to form pigments or form lakes (e.g., tetrazonium salts, 2.4
cm diaminophenol, α-nitrone-β-su7tolyco dyes), and others, JP-A-4<7-6, JJt
4+ A reducing agent capable of forming a colored et tube after oxidation, which is described on pages 2 to 73 of the specification,
etc. can be mentioned. These include those in which the reducing agent is the active agent and K tar that forms the pigment, which itself undergoes oxidation and must be coupled with the color forming agent, and the one which itself undergoes oxidation to form the pigment tube. Some are pre-colored and become non-diffusible dyes through oxidation. p-Finidine diamine rust conductor Cachichi
co-amino-t-(h-ethyl-urilaminophtoluene, ``'-C-h-ethyl-N-(β-hydroxyethyl)amine coaniline sulfate, -methyl-F-[
N-Ethyl-h-(β-hydroxyethyl)aminocoaniline sulfate, N described in U.S. Patent λ,/93.0Ij
-ethyl-N-(β-methanesulfamidoethyl)-3
-Methyl-3-aminoaniline sesquisal 7ate monohydrate, US% FFJtj121J6μM
-Phenylenediamine hydrochloride, U.S. Patent J, bZ&, 9
! No. 0, No. 3゜tqr, No. Z Kona, etc.-amino-3-methyl-he-ethyl-hemethoxyethylaniline, ≠-amino-3-methyl-N-ethylhehehe-1,000-N-β-ethoxyethylaniline Preferred representative examples include amino-3-methyl-ethyl-β-butoxyethylaniline and salts thereof (eg, sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.). Others L, F, A, Mason@Photogr
aphicProcessing Chemistry
y (published by Focal Press //?44) -16~. Those listed in No. 229 can also be used. As a reducing agent, there are types that form a color g1 association by themselves when oxidized, and types that form complexes with metal salts, and a small one belonging to this type is described in British Patent 1, Co 10,
ll No. 7 published by current tenant Mulberry, U.S. Patent J, l, j! , J.
Tetrazonium salts described in sub-paragraphs, guadiaminophenols, α-nitrone-β-7tols, etc.; b.
Although it is di-distilled, the oxidation reaction is only oxidized at a very slow rate in the absence of a catalyst. reacts with the coloring agent and ii! It has the movement of forming an iIgII chamber. For general photographic materials, silver equivalent 3 to / □ i / mt
Contains silver salts of up to 1g7t even in printing materials.
In the photographic material of the present invention, the amount of coated copper is less than b/11/fI%2, and (
It may be less than vcO, ri/in. The amount of silver coated on the platform of multilayer photographic light-sensitive material is / ll / per one light-sensitive layer.
tn2 or less, especially 0. ! I! /m2 or less/Misaki/Inada2
Small used above. The coloring agent used in the present invention is a coupler that reacts with the oxidized tl and the active ingredient to form a dye.The small couplers used in the present invention are as follows. Color-forming couplers such as tN, t, magenta couplers, which form color by oxidative coupling with aromatic primary amine developers (e.g., phenylenediamine derivatives, aminophenol derivatives, etc.) in color development processing. - There are pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include a list of acylacetamide couplers, such as benzoylacetanilides, pi/(roylacetanilides), and cyan. Couplers include naphthol couplers, phenol couplers, etc. It is desirable that these couplers have a hydrophobic group called a pallast group in the molecule and are non-diffusive or polymerized π. The coupler has a reference quantity v*iX with respect to silver ion.
Either J-symmetry is fine. It may also be a colored coupler having an effect tube for color correction, or a coupler that releases a development inhibitor upon development (so-called DIR coupler). In addition to 7tDIR couplers, there are also colorless DIRs in which the coupling reaction product is colorless and releases all of the development inhibitor.
It may also include one coupling Wt. The above-mentioned couplers and the like can be used in combination in the same layer in order to satisfy the characteristics required of a photosensitive material, and the same compound can of course be added to nine or more different layers. In order to introduce the coupler into the emulsion layer, a known method such as the method described in U.S. Pat. dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl 7-phosphate, tri-cresyl phosphate, dioctyl butyl 7-phosphate), citric acid esters (such as acetyl tributyl citrate),
Benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), to-11 mesinate esters (e.g. dibutoxyethyl succinate, diethyl azelate),
For example, trimesic acid), 11 butyl), etc., before the boiling point JO"
After melting in grade butyl alcohol, methyl isobutyl ketone, .beta.-ethoxyethyl acetate, methyl heptanolupacetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Also, Tokuko Sho 1 No. 3S No. 111, Tokuko Sho J/-JF de $
The dispersion method using polymers described in No. J can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. The color pigments used are conveniently selected to give intermediate scale images. The maximum absorption band of the cyan dye formed from the cyan coloring agent is approximately Oo to 7J0 nm.
The maximum absorption band of the magenta dye formed from the magenta color former is approximately! From 00! rOnrn, and the maximum absorption band of the yellow dye formed from the yellow color former is approximately UOO to 4! Preferably, it is between . A halogen hydride emulsion usually consists of a water-soluble halogen salt (e.g., nitric acid) and a water-soluble halogen salt (e.g., potassium bromide).
solution in the presence of a water-soluble polymer solution such as gelatin. As the halogenated trowel, silver dandelion, silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiobromide, etc. can be used. The average particle size of one halogen particle (expressed as an average based on the projected area, with the particle size being the particle diameter for particles close to spherical and the edge length for cubic particles) is preferably less than or equal to 1. However, the preferable percentage is 00 reference μ or less. The particle size distribution may be narrow or wide. The shape of these halogen t'-particles may be cubic, octahedral, or a mixed crystal thereof. First, separately formed halogenated photographic emulsions of 21% or more may be mixed. Furthermore, even if the crystal structure of the halogenated particles is uniform in the internal salt, it is also known that the inside and outside have a layered structure that is different from each other.
No., U.S. Patent J, 4 here. It could be a John-type book. Further, either a type in which latent molecules are formed mainly on the surface or an internal latent layer type in which latent molecules are formed inside the particles may be used. These E-emulsions are Mees (
i-S), “The Theory of Photog”
rapic Process' (The Theo II-・
Op Photographic Process), MacMHJa
Published by P. Qrafkides, “Chimie Photography”
, 'que' (shimmy photographic), Pau1
P, Glatlidesllc, which is also described in publications such as Monte 1 (1957) and is generally celebrated.
himieet Physique Photograp
hique (published by Pau1Monte1, 1947)
,G,F. Duffin@Photographic Emuls
ionChemistry (The Focal P
ress, 4 years ago), V, L, Zel
Makingand Coa by ikman et al
tingPhotographicEmulsion
(The Focalpre@s, 15F4). 1. I can do that. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble eulytic salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. . In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium%1. The emulsion is subjected to precipitation or physical ripening to remove S-soluble salts, and the long-known tardel water washing method, which involves gelling gelatin, may be used as a method for this purpose. Inorganic salts consisting of polyvalent compounds such as sodium ila, anionic surfactants, anionic polymers (e.g. polystyrene sulfone al),
Alternatively, use 1 ft of gelatin haze conductor (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carboxylated gelatin, etc.) and use flocculation sound. The process of removing soluble type 1 may be omitted. Although the silver halide emulsion can be used in so-called primitive milk 41 which is not chemically sensitized, it is usually chemically sensitized. Chemical sensitization (7')ff
laf>Kd, said Qlafkides f7t- is Z
eHkman et al.'s book or H, Fr1eser @
Die Qrundlagen ber Pho
tographi@chenProwesse mlt
8i1berhalogeniden (Akade
mische Verlagsgesellscha
ft. How to write Ar)K? Can be used. In order to obtain the desired properties of the photographic light-sensitive material Pσ (#custom-made, #i physical properties, film properties, etc.), it may be preferable to further include various additives. Organic compounds with 1 compound or mercapto free radical 1, e.g.
Phenylmercaptotetrazole, alkali metal iodide salts, etc. However, these ζ・j, poly 101! It is desirable to avoid using it. Photographic materials include increased sensitivity, increased contrast, and
For example, polyalkylene oxide or its derivatives such as ethers, esters, and amines,
Contains thioether compounds, thiomorpholite 7, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, etc. For example, US patent λ, ≠00. jJJ issue, same λ, 3.
! μri issue, same co, 714,042, same! , 4/7
．． No. 210, No. 3,77, No. 0, No. 1, No. 3,101゜030, No. 114? Allow/, ull,? Those described in No. 9/ etc. can be used. Generally, in the light-sensitive silver halide emulsion layer L and the non-light-sensitive auxiliary layer of a photographic light-sensitive material, antifoggants such as [71n] antifoggants, such as tetrazole, azaindene, triazole aminopurine, etc., are generally used. There are many organic compounds. Other additives include % hardening agent,
lubricants, surface abrasives, gloss additives and other additives known in the photographic art? It's okay to include it. As the binder for photographic emulsions, it is advantageous to use gelatin as a film-retaining colloid, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein, etc.+2) Cellulose derivatives such as hydroxyethyl cellulose on white matter carboxymethyl cellulose, cellulose gL acid ester, etc., sugars such as alginate, starch derivative 14, etc. Derivatives Polyvinyl alcohol, polyhinyl alcohol partial acetal, polyJ-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various synthetic hydrophilic polymeric substances such as polyvinylimidazole, polyvinylpyrazole, etc., either singly or as copolymers, can be used. Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, 8oc, 9ci, and Phot. % using the fermented gelatin described in Japall, A/4, J Oiij (/ri66).
In addition, gelatin hydrolysates and fermentation products can also be used. Examples of gelatin derivatives include gelatin, acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinylsulfonate derivatives,
T obtained by reacting various synthetic materials such as maleimide compounds, polyalkylene oxides, and epoxy compounds is used. A specific example is the US patent λ, ≦lda, ? a
T issue, same J13, 2≠! No., pyJJ, /rA, r4
(A, 3.3/co, 113, British patent xi, i,
si4! No., same/, 033. /r issue, same/, 001,
No. 71, Tokuko Sho-λ-2≦tμ! It is written in the number etc. The above-mentioned iratin and graft polymers include gelatin, acrylic sIS methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc., mono (homo) or copolymer of vinyl 7th polymer. A T-grafted one can be used. In particular,
Examples of polymers that are compatible with gelatin to some extent are preferably graft polymers with polymers such as diacrylic acid, methacrylic acid, acrylamide, methacrylic acid, hydroxyalkyl methacrylate, and the like. Examples of these are U.S. Patent Co., 7! J, 4th No. J, same. It is described in Ill, No. 747, λ, RT, reμ, etc. Typical synthetic hydrophilic polymer substances include, for example, West German Patent Application (ULS) Co., J/Co., No. 701, U.S. Patent No. 3,420.
, No. 711, 3. t7ri, Jll) No. 5, special public showμJ
-714/ issue. For photographic emulsions, if necessary, cyanine color 114M such as cyanine, merocyanin, carbocyanine, etc. can be used alone or in combination with styryl dye, etc., and spectral sensitization can be performed. can. The photographic light-sensitive material used in the present invention has at least one silver halide emulsion layer on a support, and usually
On the support, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide hole 11111. It has a blue-sensitive silver halide emulsion. Also, on a support. Cyan-1 forming coupler? A red-sensitive silver halide emulsion layer containing a red-sensitive silver halide emulsion layer, a magenta color-forming coupler layer, and a green-sensitive silver halide emulsion layer containing a yellow color-forming coupler layer. A blue-sensitive silver halide emulsion containing -11rit. Photographic light-sensitive materials contain water-soluble dyes for various purposes such as preventing irradiation, as well as hydrophilic colloid flK filter dyes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, and merocyanine dyes. Included are cyanine dyes and azo dyes. Among them, oxonol dyes; hexioxonol dyes and merocyanine dyes are useful. The photographic light-sensitive material contains an ultraviolet absorber in the hydrophilic colloid layer, such as a benzotriazole compound substituted with an aryl group, a thiacylidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, What about UV-absorbing polymers? Can be used. These ultraviolet absorbers can also be fixed in the hydrophilic colloid layer, and in photographic light-sensitive materials, stilbene-based, triazine-based, oxazole-based, or coumarin-based additives are added to the photographic emulsion layer and other hydrophilic colloid layers. Whitening agents may be included; these may be water-soluble, or water-insoluble whitening agents may be used in the form of a dispersion. In photographic light-sensitive materials, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they cannot be used even if they are mordanted with a cationic polymer.
Patent art, No. 7I, U.S. Pat. No. 7J, 316
No., same, 13ri, poi No., same co, teJ, tzt No., same J, 0 尰l, 3 t7 No., same J, /I4A, JOf No., same J, 41171゜131, Nishi'I! Ii patent application (UL8)/, Delhiro. No. 3j, Japanese Patent Publication No. 30-1977≦No. 20-7/J
Polymers described in No. 32 and the like can be used. Photosensitive materials are used as color capri-preventing agents, such as hydroquinone derivatives, mininophenol kasumi conductors, gallic acid derivatives, ascorbic acid tsuba conductors, etc.? May be contained. In the photographic material used in the present invention, the following known antifading agents may be used, and one or more types of color stabilizers may also be used in combination. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenol derivatives, p-oxyphenol derivatives, and bisphenol derivatives. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention is used for coating aid, antistatic, slippery, emulsifying dispersion, prevention of II adhesion, and improvement of photographic properties (for example, enhancement of appearance, high contrast, etc.). Various surfactants 11iIl'fr may be included for various purposes such as oxidation, sensitization, etc. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, /lyethylene glycol sorbitan esters) lli, hol alkylene glycol alkylamine or amide fist, polyethylene oxide adduct of silicone ml), glycidol [1 conductor (
Tomoe is a nonionic surfactant such as alkenylsuccinic acid polyglyceride, purkylphenol polyglyceride), polyhydric alkyl esters, etc. 1 alkyl carbon llftm, alkyl sulfone fII 11! , dilukylbenzene sulfone [
i, alkylnaphthalene sulfone #1. An-kyl sulfate esters, alkyl phosphates, N-acyl-N-thylkyltaurines, sulfosuccinates, sulfoalkylpolyonishetylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. , carboxyl group, and sulfo group. Phospho group, 4J! /ra Anionic surfactant containing acidic groups such as ester groups and cationic ester groups; aminosI! kind,
Ampholytic surfactants such as aminoalkyl sulfones, aminoalkyl sulfates or cationic esters, alkyl betaines, amine oxides; alkyl amine salts, aliphatic or aromatic secondary ammonium salts, pyridinium, imidazolium, etc. The heterocyclic tertiary ammonium salt, the aliphatic ring, the compound cationic surfactant, including the phosphonium and sulfonium salts? You can learn by using it. In the photographic light-sensitive material, the photographic emulsion 1 and other hydrophilic colloid layers may contain an inorganic or organic hardening agent. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) to)
. Active vinyl compound (/, J, !-triacryloyl-hexahydro-8-triazine, /, 3-vinylsulfonyl-coprobanol), active/11: 6-hydroxy-S-)riazine, etc.), mucohalogen acids (such as mucochloric acid, mucophenoxychloric acid, etc.). These can be used alone or in combination. The photographic light-sensitive material used in the present invention may contain a dispersion of a poorly water-insoluble synthetic polymer for the purpose of improving the qualitative properties of the photographic emulsion layer and other hydrophilic colloid layers. Tomoe is alkyl (meth)acrylate, alkoxyalkyl (1)'Y1 acrylate, glycidyl (
meth)acrylate, (meth)acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile,
Olefins, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. A combination of t and polymer as a monomer component? Can be used. The present invention can be applied to multilayer natural color photographic materials having at least one different spectral sensitivity on the support. Multilayer natural color photographic materials usually have a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a green-sensitive emulsion layer on the support. Each has at least four blue-sensitive emulsion layers. The order of these layers can be selected arbitrarily as needed. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The photographic elements used in the present invention are US%l? ! F.J.
. No. 724.411, British Patent III, 417%, British Patent Octopus J, No. 041-j, US Patent J,! /4゜II/
No. % - No. 10-4, 172, same! 0-1, III/
When one emulsion layer is composed of a fixed number of unit emulsions, as described in No. 1, etc., it may contain layers in the case of various layer configurations. As photographic supports, cellulose nitrate film, ryululose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, boron 17 styrene film, polyethylene terephthalate film, and boron There are 11 carbonate films, other laminates of these, thin glass, paper, and other products. Baryta or a
- Olefin polymer, carbon atom copolymer such as polyethylene, polypropylene/, ethylene butene copolymer, etc.
9 is laminated paper coated with 11-mer of α-olefin No. 10, and the surface is roughened as shown in Tokko Shosan 7-/l, No. 041 to improve adhesion with other polymers. Supports such as snack films also provide good cohesion. These supports are selected to be transparent or transparent depending on the purpose of the photosensitive material. In addition, when the stone is transparent, it can be made not only colorless and transparent, but also colored and transparent by adding dyes and pigments. This is Fix Ray Film 8
This has been done for a long time, such as f9J, 8MPTg
, j 7 , kokuj (/ri!l), etc. Opaque supports include those that are inherently opaque such as paper, as well as transparent films coated with pigments such as dyes and titanium oxides, or those that are prepared by the method shown in Japanese Patent Publication No. 7-IPal No. 1. Completely KI with surface-treated plastic film, carbon black, dye, etc. It also includes photosensitive materials, plastic films, etc. A layer having adhesive properties between the support and the emulsion layer is provided as a lower layer. Also, in order to improve the adhesion even better, use a support! ! Corona discharge, ultraviolet irradiation, flame treatment,
Preliminary processing such as The photographic light-sensitive material used in the present invention comprises a support and a dye image-providing unit layer thereon. The multilateral photosensitive material has at least two of the dye image-providing unit layers,
Here each first describes the vector light in a separate position. The dislocation layer includes a photosensitive layer, which is generally sensitive to spectral light at specific locations, and is combined with a color former. The color supply layers are mechanically separated from each other by spacing layers, spacing layers, layers containing current oxidant removers, etc. to prevent any color contamination between the dye-applied layers. Efficient separation of unit layers is well known in the art and is utilized in many commercial color products to prevent contamination. Upon request, US patent 2.7≦/, 7f/ issue, 1 cut J
, 101, ri4t7honor, same13? , 0de! According to the method described in the above issue, layers of Js and above may be modeled at the same time. US time permit! , 017. t/7, Mukai J, /II,
! No. 47, the same one? No. 13,401, Mukai J, Cozz, P
Ij No. J, --7,110, ke 13. Cocoa,
No. 111, same J, Ko J7112, 4 J, / da j, 4
No. 13, same J, reference lz, tda! No. Tomobi Dou 3. Reference/j,
For color-image transfer zero methods as described in No. 484,
and U.S. patents, 2. ! λ1. /! It may be designed for absorption transfer methods such as those described in No. 1. When pre-dye-forming color formers or redox-dissociation type G#3 colorants are used in the light-sensitive material, at least one color supplying unit layer contains these color formers based on - in the color layer. The 31J image intensifying liquid used in the present invention, which contains at least a % excess of the stoichiometric amount, contains one or more of the 116 active ingredients (reducing agents) as described above, and the intensifying agent. In addition to containing one or more active agents, it may also be impregnated with known liquid component compounds. /' 7/ / /' For example, it may contain a pH buffering agent, an antifogging agent or an antifogging agent. In addition, depending on the FK, water softeners, preservatives, organic solvents, present accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary coloring agents, viscosity additives, etc.
It may also contain a polycarbonate chelating agent, an antioxidant, an alkali agent, a solubilizer, a surfactant, an antifoaming agent, and the like. Specific examples of these additives include Research Disclosure (RD-/7444 J), US IE No. 149, No. 011.7λ3, and West German Publication (OL8). It is described in 6-co, RijO issue, etc. In one of the typical processes belonging to the present invention, after exposing an AgX color sensitive material, it is intensified by -bath development, treated with a processing solution containing an intensification activity-inhibiting compound, washed with water, and dried to obtain color II!
Give iIgN. - It is sufficient to simply carry out the above-mentioned treatment after bathing and adding strength. In another process, the coupler may be treated in an intensification solution to form an intensification image 9, and then treated with a treatment solution containing an intensification activity-inhibiting compound. In addition to the so-called diffusible external type couplers that are added to the honey intensification liquid, cyan couplers do not bind, for example, US Pat. ! For example, as a magenta coupler in books described in 4t4, 11λ, etc., Tokko Sho'l
1l-/J, /// etc., as a yellow coupler, US Patent 3゜! Examples include those described in No. 10, No. 304, and the like. In this case, the coupler is not O6j! l/l, especially in the range from / to λ111/l. In a separate process, the photosensitive layer and the photosensitive layer are superimposed, and the liquid is interposed between them, so that the liquid and the reinforcement are performed simultaneously, and it can be transferred by oxidation by the repellent agent. The resulting dye diffuses into the receiving layer. It is also possible to cause the mobile dye to be absorbed from the part that did not undergo the reverse ff@ conversion. The process of the present invention can be performed as a process after forming a color image in this manner. In either process, water washing may be carried out after the treatment of the present invention. Even if the water washing tube is omitted, there will be no practical problem. For detailed exposure to obtain photographs, ordinary methods may be used. i.e. natural light (sunlight), tungsten electric light,
Any of a wide variety of known light sources can be used, such as warning lights, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, and cathode ray tube flying spots. 1 from the 171,000 seconds normally used in cameras for exposure time.
Of course, the exposure time of 17 iooo seconds is shorter than 1/10 seconds using a xenon flash lamp or cathode ray tube.
An exposure of '~i7'io seconds can also be used,
Exposures of better than 1 second can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. It may also be exposed to light emitted from a phosphor excited by an electron beam, an X-ray, an r@s alpha ray, or the like. Example 2 First layer (lowest layer) to arth
A low-tone color photosensitive material is prepared by coating m<top layer>. (wsy/m in the table below represents the coating amount. 4th layer Gelatin (1000wg/m") 1st layer Silver chlorobromide emulsion (AfBrC/) (30% silver bromide (red sensitive layer)
Silver jug 7m", average particle size O, 2μ) Gelatin (/ 000q/m 1 Cyan coupler (*/) (II 00wg/mJ coupler solvent (*-) (Koo Misaki/m2) 3rd layer Gelatin (
l coowq7m town ultraviolet absorber (*J) (1000
wq/m”) Dioctylhydroquinone CjOQ/n)
No. 18 #1 Silver bromide emulsion (AfBrC/) (Silver bromide JOmo(m), tszwq/m', average grain size O, -μ) Gelatin (100Mf/l'n) Magenta coupler ( Ren 4') (J 00wv/q2
) Coupler solution*<rice z) (sooq7m”) 1st layer Gelatin (1000 cape/m town collection 1 layer Bromide-resistant silver emulsion (AfBr(j) (smell-resistant silver 1
0 mo (-) le regret, silver cape/m2. Average particle size O, reference μ) Gelatin (/coowy/m)
Cyan coupler: Ko [α-(Ko, Guji-t-
Amylfenoximibutanamide 1-4I, +-dichloro-! -Methylphenol Co coupler solvent: Phthalic acid-1-butyl ester *3 Ultraviolet absorber: Co (Co-hydroxy-3-se
c-Butyl-j-1-butylphenyl] benzotriazole magenta coupler〒: / -, (co, 1-trichlorophenyl)-J-(cochloro!-tetradecanamide]anilinocopyrazoline!- On rice! Coupler solvent; Phosphoric acid-〇-cresyl ester rice 4 Yellow coupler; α-piparoyl-α-[co,
dioxo z, r' -dimethyloxazolidine-
3-yl-,2-chloro-! -[α-(co,l-di-t-amylphenoxy]butanamide] Acetanilide This sample 1 was exposed to light with a photosensitive needle and the following treatment was carried out.Processing process Temperature Time - Bath current compensation power
Jl IC1 minute later Process Jj llCx seconds (x=!,
10.20.301 -Bath reinforcement liquid Potassium sulfite Tripotassium glycophosphate pop Dipotassium phosphate 6II/-Hydroxyethane/, /-Diphosphone@-2J
'Benzotriazole 411F Hiro-amino-J-methyl-he-ethyl-N-β-(methanesulfonando) Ethylaniline J/cosulfate Yume l Hydrogen peroxide (30 tatami) Jo- Add water /l ( 1) H//, 0) Treatment liquid used for post-treatment Potassium phosphate i, zg Dipotassium phosphate g, ip Add water / t (Compound (1) to pH 4,77A/f6/ /, 477 added 7%
J A/K (A compound with IfA added S da A/ff compound (sub) hydrochloride t-211 added! 5 trc compound @ added with cog 7%6 Sodium sulfite λ , zti Sodium bisulfite j , 077 Add water /l (pH 1,7) 7 Add ARrC compound (1) to i # force σ〕4t
9 Added -Ii of the hydrochloride of compound (to) to 44. 10 Added -I of ARK compound C11I and dried it after σJ treatment to obtain the lowest concentration ( pmin) with fi11 and compared with 6 No, /, No, λ ~ No, !, No, A compared with No
, 7 to No., /0 all show low Dmin with 4 short post-processing times. Note that no change in gradation or maximum S degree (Dmax) was observed due to the post-processing of the present invention. Patent Applicant Fuji Shagu Film Co., Ltd. Procedural Amendment March 1982 72) 1 Commissioner of the Japan Patent Office Shima 1) Haruki Tono 1, Indication of Case Patent Patent No. 200 f of 1982
4 71-2, Title of the invention Color-Image detection method 3,
Relationship with the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact information
106 26-30 Nishi-Azabu 2F, Minato-ku, Tokyo Telephone: (406) 2537, Fuji Photo Film Co., Ltd., Tokyo Head Office The description in the "Detailed Explanation" section has been amended as follows. 1) Correct the information on page 2. 2) On page 10, [General formula (translation) "Correct with general formula (■). S) 70th true "General formula 0Qv) r Correct with general formula (ff ). 4) 1st/IJ line Eye "802NRR' Jfr-80
Correct it as 1NRR'J. S) of the 14th c purchase.'' 6) Amend the information on page 11. 7) Correct with the 11th member. 8) Page 17 / Br CHrCH=CHs " 11) IP, / 7:RnorJ t-Delete. 1o) Correct with page 17. 11) 17th true 13) ko OJj 13) Amend the information on page 21. 14) The th core Jj " □□□ is corrected. 14) The th core Jj is corrected. 17) Correct as 1st/page. 18) 3rd λ member / 3rd line r After the present invention, process liquid” is corrected to ``Apprentice of the present invention!ll[J. ” is corrected to “published/ri4≦)”. to) Page 14, line 17, “Gelatin (10011
9/m”) Jt r gelatin: y (1000119/m”
) Correct as J. 21) 71st member Table 1 Stabilization treatment 1f! L42 X=
j Dmln (B) "Correct O0f/J to "0, / reference J.

Claims (1)

[Claims] In the presence of a nitrogen-containing heterocyclic compound, a silver halide color light-sensitive material that has been exposed to light is exposed to peroxide, arsenic, a compound that releases hydrogen peroxide, and a color-forming agent, and bromide ions and iodine ions. An image characterized in that a color development process is carried out using a single-bath intensification solution that does not contain any of the above-mentioned substances, and then treated with a solution containing a compound that suppresses the intensification activity of silver halide fog nuclei. Salary formation method.