JPH0257A - Direct positive color image forming method - Google Patents

Abstract

PURPOSE:To improve the light and the fading resistances of the photosensitive material, and to obtain the high max. image density of the material by incorporating a compd. shown by a prescribed formula in the photosensitive material, and by developing the obtd. material with a developer contg. N-hydroxyalkyl substd. p-phenylene diamine derivative. CONSTITUTION:At least one kind of the compds. shown by formula I is incorporated in the photosensitive material. In formula I Z is a group capable of being released at the time of carrying out a coupling reaction with the oxidant of a developing main agent, G1 is halogen atom or alkoxy group, G2 is hydrogen or halogen atom or alkoxy group which may be substd., R is alkyl group which may be substd. And the photosensitive material image-wisely exposed is developed with the developer contg. N-hydroxyalkyl substd. p-phenylene diamine derivative after a fogging processing and/or during the fogging processing. Thus, the light and the fading resistances of the photosensitive material are improved, and the picture having the high max. coloring density of the sensitive material is formed by a rapid development processing.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for forming a photographic image, and more particularly to a method for forming a direct positive image with excellent photobleaching properties.

[Conventional technology]

A method is known in which a positive image is directly obtained by using an internal latent image type silver halide emulsion that has not been coupled in advance and carrying out surface development after image exposure and then subjecting it to fogging treatment or while carrying out fogging treatment.

The above-mentioned internal latent image type silver halide photographic emulsion refers to a type of silver halide photographic emulsion that has photosensitive nuclei mainly inside the silver halide grains, and a latent image is mainly formed inside the grains upon exposure. .

Various techniques are known to date in this technical field. For example, U.S. Pat. No. 2,392°, 230;
Same λ, 1I-6 Otsu, ri 57, same, ≠97.173, same, zr♂, ri♂λ, same 3゜3/7, 32λ,
3,71. /, 21, 1. No. 3.76/, 271
．． No. 7, No. 677 and British Patent No. 1.
/j/, No. 363, direction l.

The most important ones are those described in the specifications of No./30,363, No. 0//, No. 01s2, etc.

These people are known! By using i-wo, it is possible to produce a relatively high-sensitivity photographic material as a direct positive type.

For the detailed structure of the direct positive image formation mechanism, for example,
T,)1. The Theory on the Photographic Process by James
of the PhotographicProc
ess), 4th edition, Chapter 7, pages /12 to /3, US Patent No. 3.7t/, 27A, etc.

In other words, capri nuclei are selectively generated only on the surface of silver halide grains in unexposed areas by a surface desensitization effect based on a so-called internal latent image generated inside silver halide by the initial imagewise exposure. Next, a normal so-called surface development process is performed to form a photograph gI (direct positive image) in the unexposed area.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called "photofogging method" (for example, British Patent No. 1./j/,
31. ．． No. 3) and a method using a nucleating agent called "chemical fogging method" are known. For this latter method, for example, [
Research Disclosure J
Disclosure) magazine, Volume 1-7, Fu/j/Otsu 2 (published January 2015), pages 71-7.

To directly form a full positive color image, the internal latent image type silver halide photosensitive material is subjected to full capri processing, or surface color development processing is performed while capri processing is applied, and then bleaching,
This can be achieved by fixing (or meeting fixing) processing. After the bleaching and fixing treatments, washing and/or stabilizing treatments are usually performed.

[Problem to be solved by the invention]

In direct positive image formation using the ex-Capri method or chemical Capri method, the development speed is slower and processing time is longer than in the case of normal negative type, so conventionally, the developer solution (p) is used.
Methods have been used to shorten the processing time by changing the temperature and/or the liquid temperature. However, there is a problem that the minimum image density of the direct positive image obtained generally increases when the pH is high.

Furthermore, under high pH conditions, the developing agent is likely to deteriorate due to air oxidation, and carbon dioxide gas in the air is likely to be absorbed, resulting in a decrease in pH. There is a problem that the imaging activity thereof is significantly reduced.

Another method for increasing the development speed for direct positive image formation is the use of hydroquinone derivative gold (U.S. Pat. Nos. 3 and 2).
27.3! No. 2), those using a friend mercapto compound having a carboxylic acid group or a sulfonic acid group (Japanese Unexamined Patent Publication No. 1986-1970)
♂≠3), etc., but the effect of using these compounds is small, and no technique has been found to effectively directly increase the maximum density of positive images. In particular, there has been a desire for a technique that can provide sufficient maximum image density even when processed with a low pH developer.

In order to maintain high development activity, it is preferable to use a benzoyl type coupler as the ie a-coupler; however, when the benzoyl type coupler is used, it has the disadvantage of poor photobleaching properties.

On the other hand, if all pivaloyl type yellow couplers are used to maintain good photobleaching properties, it is difficult to obtain a sufficient maximum image density due to low development activity, and it is difficult to obtain a high maximum image density. Therefore, when long-term development is attempted, the minimum image density also increases, and a solution to this problem has been desired.

Therefore, the first objective of the present invention is to provide good light fading resistance! The object of the present invention is to provide a direct positive image forming method that provides high maximum image density and high maximum image density.

A second object of the present invention is to provide a method for forming a direct positive image having excellent light fading resistance and sufficient maximum density by rapid development.

[Means to solve the problem]

The object of the present invention is to provide a photographic material containing at least one unfogged internal silver halide emulsion layer and a color image-forming coupler on a support after imagewise exposure. In a direct positive color image forming method in which development is performed after processing and/or while performing fogging, the photographic light-sensitive material contains at least -a of the compound represented by the following general formula (I), and all This is achieved by a direct positive color image forming method characterized in that it is carried out using a developer containing a xyalkyl-substituted p-7 22-diamine derivative.

In the formula, Z represents a group that can be separated during a coupling reaction with an oxidized form of a developing agent, G1 represents a halogen atom or an alkoxy group, and G2 represents a hydrogen atom, a halogen atom, or a substituent '? ! May represent an alkoxy fund. R
represents an alkyl group which may have a substituent.

The yellow coupler used in the present invention has the above-mentioned maximum % formula % (1) where Z represents a group that can be separated during the coupling reaction with the oxidized form of the developing agent, G represents a halogen atom or an alkoxy group, G2 represents a hydrogen atom, a halogen atom, or an alkoxy radical which may have a substituent.

几represents an alkyl group which may have a substituent.

More specifically, when Z represents a coupling-off group (hereinafter referred to as a leaving group), the leaving group is oxygen, nitrogen, sulfur, or all carbon atoms connected to the coupling active carbon, an aliphatic group, an aromatic group. , heterocyclic groups, aliphatic/aromatic or heterocyclic sulfonyl groups, groups that bond with aliphatic/aromatic or heterocyclic carbonyl groups, halogen atoms, aromatic azo groups, etc. Contains aliphatic,
The aromatic or heterocyclic group may be substituted with a substituent, and when two or more of these substituents are present, they may be the same or different, and these substituents may further have a substituent. Good too.

Specific examples of coupling-off groups include halogen atoms (e.g. fluorine, chlorine, bromine), alkoxy groups (e.g. ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), aryloxy groups (e.g. ≠-chlorophenoxy, ≠-methoxyphenoxy, ≠-carboxyphenoxy), acyloxy (e.g. acetoxy, tetrazocatyloxy, benzoyloxy), aliphatic or aromatic sulfonyloxy groups (e.g. methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (e.g. dichloroacetylamino, heptafluorobutyrylamino), aliphatic or aromatic sulfonamide groups (e.g. methanesulfonamino, p-)luenesulfonylamino), alkoxycarbonyloxy groups (e.g. ethoxycarbonyloxy, benzyloxy), carbonyloxy), aryloxycarbonyloxy groups (e.g. phenoxycarbonyloxy), aliphatic, aromatic or heterocyclic thio groups (e.g. ethylthio, phenylthio, tetrazolylthio), carbamoylamino groups (e.g. N-
Methylcarbamoylamino, N-phenylcarbamoylamino),! Negative or t-membered nitrogen-containing heterocyclic group (e.g. imidazolyl, pyrazolyl, triazolyl, tetrazolyl, /, 2-dihydro-2-oxo-/-pyridyl)
, imide groups (e.g. succinimide, hydantoinyl)
, aromatic azo groups (e.g. phenylazo), etc.
i. There are bis-type couplers obtained by condensing a four-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain photographically useful groups such as development inhibitors and development accelerators.

Preferably, a group that forms a coupling active carbon bond via an oxygen or nitrogen atom is desirable.

Particularly preferred leaving groups Z are the following (IA) to (1-
It includes a group represented by the general formula D).

(J)t2o(1-A) Approximately 2° represents an optionally substituted aryl group or a multicyclic group.

(1-B) (1-C) Approximately 21% R
22 is a hydrogen atom, a /10gen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, unsubstituted or substituted, A phenyl group represents a heterocycle, and these groups may be the same or different.

NO decision / \〆1-D) "wl" represents a nonmetallic atom required to form a complete membered ring or a membered ring.

Among general formulas (1-D), preferred CI-E) to (1
-G).

In the formula, R23 and R24 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group. or represents an acyl group, and W2 represents an oxygen or sulfur atom.

All specific compounds represented by the general formula (I) are shown below, but are not limited thereto.

(Y-/) (Y-,2) (Y-J-) H3 (Y-A) (Y-J) (y-1/L) I (Y-7) (y-, r) (Y- ta) SO□CH3 (Y-/Q) (JH (Y-/j) oon (Y-/Hiroshi) (Y-//) (Y-/ 2 ) (Y-/j) (Y-/[) oon (Y-/7) 1”/ (Y-/♂) C1-1cOOk+ l2H25 (Y-co/) (Y-,2,2) (Y-/ri) (Y-,20) (Y-23 ) (Y-,lt) The developing agent used in the present invention is a μ-class ammonium salt of an N-hydroxyalkyl-substituted-p-fuynylenediamine compound, and has the following general formula (D) 几2 In the formula, R is a hydrogen atom, an alkyl group having ~3 carbon atoms, or an alkoxy group having l-H carbon atoms, R is a hydrogen atom, and R is a hydrogen atom, and R is a hydrogen atom; is an alkyl group having carbon atoms, R is an alkyl group having /~≠ carbon atoms which may have a hydroxyl group, A is an alkyl group having at least 7 hydroxyl groups' (rNL, and a branched t- R4, R5, and R6 each represent a hydrogen atom, a hydroxyl group, or an alkyl group having 7 to 3 carbon atoms which may have a hydroxyl group; At least one is a hydroxyl group or an alkyl group having a hydroxyl group.n1%
R2 and R3 are respectively O1/, λ or 3 and represent hxFi hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, nitric acid or phosphoric acid.

The free amine of such a p-phenylenediamine color developing agent is unstable and is generally used as a salt. Typical examples include ≠-amino-3-methyl-monoethyl-N-(β-hydroxyethyl)-aniline salt and ≠-amino-N-ethyl-N-(β-hydroxyethyl)-aniline salt. .

Preferred N-hydroxyalkyl-substituted-p-7 unilene diamine derivatives used in the present invention include the following, but are not limited to these exemplified compounds.

2H5 \ /C2H4OH H2 D-≠ )10) I C 4 momme / C2H4OH C2Hs C2H4on \ / H2 D-♂ C3) 17, 2h4oh / He-A D-ta) 10H, 02, /C2) i4U) + H2 Above Particularly preferred are hydrochloric acid, sulfuric acid, and p-)luenesulfonic acid salts of D/-D compounds. Among these exemplified compounds, D-/, 2.3, Otsu, 7 and r are preferably used, and D-/, Ko, 3 and Otsu are more preferably used.

Since the color developing agent of the present invention has high solubility in water, the amount used is preferably within the range of 12/y-100, more preferably from 31 to 309 per y-100 of the processing solution.

These hemolytic axyalkyl-substituted -p-phenylenediamine derivatives of the present invention are described in the Journal of American Society, Vol. 73, p. 3100 (/
It can be easily synthesized by the method described in 2010.

Two or more of these N-hydroxyalkyl-substituted p-phenylenediamine derivatives may be used in combination, and if necessary, they may be used in combination with other p-phenylenediamine color developing agents. Representative examples of p-phenylenediamine compounds that can be used in combination include 3-methyl-≠-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline, 3-methyl-Hiro-amino- Examples include N-ethylhemethoxyethylaniline and their sulfates and hydrochlorides. Color development processing is at 30°C or higher, 1
The processing time is 30 seconds or less, preferably 33° C. or more and 1λO seconds or less, most preferably 3j° C. or more and 100 seconds or less. If the processing is carried out at 30° C. or more and 750 seconds or more, development fog worsens. In particular, processing time is more important than temperature; if it exceeds /J-0 seconds, development fog will increase significantly, which is undesirable. In addition, in the present invention, the processing time of color development processing refers to the time from the start of fogging processing until the start of the next processing, and the pre-immersion time before performing the original fogging processing is not included in the processing time. do not have.

If the processing temperature is too high, development fog will increase, so it is preferably 30°C or higher and J″θ°C or lower, more preferably 33°C or higher and ≠t°C or lower, and most preferably Jt
Processing should be carried out at a temperature of i3j°C or higher and ≠3°C or lower.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion in which the surfaces of the silver halide grains are not fogged in advance and furthermore, the latent image gold mainly contains at halide formed inside the grains. , more specifically,
A silver halide emulsion is deposited on a transparent support at a constant t(0,j~3
1/rr? ) and apply 0. When exposed for a fixed time of 0/- to 70 seconds and developed in the following developer A (internal type developer) at 7rC for 5 minutes, the maximum density measured by the usual photographic density measurement method is the same as above. All silver halide emulsions coated in the same amount and exposed in the same manner.Developer B shown below.
Preferred are those having a density of gold that is at least j times greater, more preferably at least 70 times greater, than the maximum density obtained when developed for 6 minutes at 20° C. in a surface developer.

Internal developer A Metol 2y Sodium sulfite (anhydrous) TaO Tahydroquinone
ry carbonated soda (-water salt)
j2. jri KBr
39K l
O, 39 Add water
/2 Internal developer B Metol 2. ! L-ascorbic acid 109NaBO2-Hiroshi)
120 36yKBr
/y add water
/i.

Specific examples of inner layer type emulsions include those described in US Patent No. 2. j
No. 2,230, the conversion silver halide emulsion described in U.S. Patent No. 3.71. /, 271
．． No. 3,160, 1.37, No. 3. ri23.31
No. 3, same amount, 03, No. lIr, same amount, 3rij, ≠7r
No., same μ, SO≠,! No. 70, Tokukai Sho J Co/jl, Otsu l≠ issue, same sr-/, 27j≠ri issue, same j3-Otsu 022
λ No., J"A-, 2-Ot/No., J" No., 201#
lAO issue, 60-107 Otsu≠/ issue, t/-3/37
No., Special Application No. 62, Research Disclosure Magazine/16λ3yo10 (/R♂3/July issue) P
Examples include core/shell type halogenated image emulsions described in the patent disclosed in No. 23 O.

The shapes of the silver halide grains used in the present invention include regular crystal shapes such as cubes, octahedrons, dodecahedrons, and tetradecahedrons, irregular crystal shapes such as spherical shapes, and length/ Tabular particles having a thickness ratio of 5 or more may be used. Further, an emulsion having a composite form of these various crystal forms or a mixture thereof may be used.

The composition of the silver halide includes silver chloride and silver bromide mixed silver halide, and the silver halide preferably used in the present invention is salt (iodine) bromide steel with less than 10 mol of silver iodide, (iodine)
Silver chloride or (iod) silver bromide.

The average grain size of silver halide grains is 2 μm or less.
Ifi/μ is preferably 61 μm or more, and particularly preferred.
m or less o, ij μm or more. The particle size distribution can be narrow or wide, but in order to improve granularity and sharpness, so-called "monodisperse" particles with a narrow particle size distribution are used.
Preferably, silver halide emulsions are used in the present invention.

Monodisperse silver halide grains in the present invention have a grain size distribution defined by the following formula! It is something to do. That is, when the standard deviation of the particle size distribution is divided by the Si average particle size T, the value is 0.20 or less.

In the case of spherical silver halide grains, the average grain size referred to here refers to the average diameter of the grains, and in the case of grains with shapes other than cubic or spherical, the projected image is converted to a circular image of the same area. 7 is defined by the following formula, where the individual particle diameter is ri and the number is ni.

Σn1ri ni The above particle size can be measured for the above purpose by various methods commonly used in the technical field. A typical method is Loveland's "Particle Size Analysis Method JA, S,
T, M, Symposium on Ride Microscopy, /9! , 3-year, ri≠~/2 pages Mayu, [The Theory of Four True Processes] co-authored by Meag and James, 3rd edition,
It is described in Chapter 2 of Macmillan Publishing Co., Ltd. (1966).

The particle size can be measured using the projected area of the particle or an approximate diameter value. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodispersed silver halide emulsions with different grain sizes or multiple types of monodisperse silver halide emulsions with the same size but different sensitivities are used in an emulsion layer containing substantially the same color sensitivity. The particles can be mixed in the same layer or coated in separate layers. Furthermore, a polydisperse silver halide emulsion of 2s or more or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. For detailed examples, see Research Disclosure magazine/16/7 All! -■(15'7!r years/2
(Published in May) P. 23 It is in the patent described in Nat.

The photographic emulsions used in the present invention are spectrally sensitized with photographic sensitizing dyes in a conventional manner. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. For detailed examples, see Research Disclosure Magazine/16/71. ≠3-■ (Iri7 published in 1 month of the year) Patents described in pages 23-2≠, etc.

The photographic emulsion used in the present invention may contain an anti-capri agent or a stabilizer for the purpose of preventing capri during the manufacturing process, storage or photographic processing of the light-sensitive material, or for stabilizing the photographic performance. For detailed specific examples, see Research Disc o-Jar, 46/7t4tj.
-ViC/? Published February 1971) and E, J, Bi
``5 tabilization of Ph'' by rr
otographicSilver Halide
Emulsion” (FocalPress),
177≠ Written in annual publications, etc.

Various color couplers can be used in the red-sensitive layer and green-sensitive layer of the photographic material of the present invention.

A color coupler is a compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized form of an aromatic primary amine color developer, and is itself a substantially non-diffusible dye. Preferably, it is a compound. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds. Specific examples of these cyan and magenta couplers that can be used in the present invention are given in "Research Disclosure" magazine A6/76≠3 (Published in February 2007) P.
, 2j, ■-ri term, same/16/♂7/7 (/ri7ri/
/ month issue) and patent application Sho 1. /-3,2 The compounds described in No. 2 and the patents cited therein.

A pyrazolone-based magenta coupler that can be preferably used in the present invention is one in which the 3-position is substituted with a fluoramino group or an acylamino group! - A pyrazolone coupler (especially a two-equivalent coupler that eliminates a sulfur atom).

More preferred are pyrazoloazole couplers, and among them, pyrazolo(3,/-c)[/,-2m≠]triazoles described in U.S. Pat. No. 3.72J, 067 are preferred; In terms of low yellow sub-absorption and light fastness, it ranks first in the US! '00
,／＞Imitazo described in No. 30 [/.

2-b] Pyrazoles are even more preferred, as described in US Pat. ≠O1 Otsuyo≠ Pyrazolo (/, j-b) listed in issue
[/, 2. μ]triazole is particularly preferred.

Cyan couplers that can be preferably used in the present invention include:
US 1 Patent No. 2,4'7≠, 223, same≠.

! Naphthol-based and phenol-based couplers described in Oλ, No. 2/2, etc., and phenolic cyan couplers having an alkyl group higher than ethyl group at the meta-position of the phenol nucleus, described in U.S. Patent No. 3,77λ, 002. and
Others! -Diacylamino-substituted phenolic couplers are also preferred because they have good color image fastness.

Colored couplers for completely correcting unnecessary absorption in the short wavelength range of the generated dyes, couplers whose coloring dyes have appropriate diffusivity, non-coloring couplers, DIR couplers that release a development inhibitor along with the coupling reaction, etc. Polymerized couplers can also be used.

The standard amount of color coupler used is photosensitive halogenated f! It ranges from 0.00/mole to 0.00/mole, preferably o, oi to 0.00/mole for yellow couplers.
J-mol, Fi for magenta couplers from 0.03 mol to 0.015 mol, and for cyan couplers from 0.002 to 0.03 mol.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. A typical example of a compound is JP-A No. 6
．． 2-2/! Examples include those described in No. 272, pages 37μ to 3, pages 7.

The coupler of the present invention and the magenta and cyan couplers are dissolved in an organic solvent with a high boiling point and/or a low boiling point, and are added to an aqueous solution of gelatin or other hydrophilic colloid by stirring at a diurnal speed using a homogenizer or the like, and then mechanically micronized using a colloid mill or the like. Emulsification and dispersion is carried out by chemical reaction or by a technique that makes full use of ultrasonic waves, and the emulsion is separated into all emulsion layers. in this case,
Although it is not always necessary to use a high boiling point organic solvent, it is preferable to use the compounds described in JP-A No. 2/272, Hiro≠O to Hiro, pages 67.

The coupler used in the present invention is JP-A-1.2-2/! 2
It can be dispersed in a hydrophilic colloid by the method described in No. 7λ≠6r to ≠7j.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamides as color anticaprilants or color mixing inhibitors. Phenol derivatives and the like may also be used. Typical examples of color antifogging agents and color mixing prevention agents are JP-A No. 1
s2-2/! 27.2, page t00-43.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
6-Hydroxychroman field! -Hindered phenols, mainly human O-xycoumarans, spirochroman M, p-alkoxyphenols, and bisphenols,
Typical examples include gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl groups of these compounds are completely silylated or alkylated. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

A typical example of these anti-fading agents is JP-A-62-Co/J-2.
It is described in No. 7λ, page O/~≠page 〇.

These compounds are usually for their corresponding color couplers! This can be achieved by co-emulsifying with 100 to 100 weight TST couplers and adding them to the photosensitive layer.

In order to completely prevent deterioration of the cyan dye image due to heat and especially sources, it is effective to completely introduce an ultraviolet absorber into the layers on both sides adjacent to the cyan coloring layer.

The ultraviolet absorber tJ5ii can also be added to a hydrophilic colloid layer such as a protective layer. A representative example of the compound is JP-A-62-. 2/yo, No. 272, pages 32/~≠00.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

The photosensitive material of the present invention includes a cross-agent for preventing irradiation and halation, an ultraviolet absorber, a plasticizer, an optical brightener, a matting agent, an air anti-capri agent, a coating aid, a hardening agent, and an antistatic agent. It is possible to add km such as a slippery improver. Representative examples of these swimming agents are listed in Research Disclosure Magazine 16/761A3 - X111 (/271/
February issue) 92j-17, and the same/za7/A (/
Published in 7 years//month) p ≠ 7 ~ t! It is described in l.

The invention is also applicable to multilayer, multicolor photographic materials having at least λ different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
At least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer are provided. The order of these layers can be arbitrarily selected as necessary. The preferable order of layer arrangement is from the support side to red sensitivity, green sensitivity, and blue sensitivity; from the support side, green sensitivity, red sensitivity, and blue sensitivity. Further, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist between λ or more emulsion layers having the same color sensitivity t. . 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 following compounds can be added for the purpose of increasing the maximum image density, decreasing the minimum image density, improving the storage stability of the light-sensitive material, or increasing the overall development speed.

Hydroquinones (e.g. U.S. Pat. No. 3,227.11)
Compounds described in No. 2, No. 2, No. 27, No. 7): Chromans (e.g., US Registration No. ≠, λ6♂, No. 62, JP-A-10303/No., Research Disclosure Magazine) , A6/121.≠(/ri 7 years to month issue) 333
～33≠Chemical@product described on page: Quinone wA (fC, Tobari Search Disclosure Magazine, /I6.21ko06(
/riJr1 year 7 year February 33-≠3≠ Compound described on page *)
; Ami 7 (for example, compounds described in US %F!lft1.izo, Tata No. 3, and JP-A-Sho! 1-/7≠7!7)
: Oxidizing agents (fc toeha JP-A-60-1s003 issue, Research Disclosure Magazine, 4/, 4-36 (
Compounds described on pages 10-//): Catechols (e.g., JP-A-5R-2IOI-3 and JP-A No. 1983-1999)
z-tz tag ≠ compound described in issue): Compound that releases a nucleating agent during development (e.g., compound described in JP-A-60-07022); Thioureas (fc, e.g., JP-A-60-07022);
-compounds described in JP-A No. 3333); spirobisindanes (7'C, for example, compounds described in JP-A No. 2003-111013);

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation agent,
It is preferable to appropriately provide auxiliary layers such as a back layer and a white reflective layer.

In the photosensitive material of the present invention, the photographic emulsion layer and other layers are described in Research Disclosure Magazine, 46/7t'A3X.
Item V// (issued in 1971/72) p.
7-276! It is coated on the support described in item j. The coating method described in Mayu Research Disclosure Magazine/I6/7 O≠3XV, page 21-λ can be used.

The color photosensitive material of the present invention can be applied to a variety of uses.

For example, typical examples include color reversal film for slides or television, color reversal paper, and instant color film. The present invention can also be applied to full-color copying machines and color hard copies for holding images of CI (, T).
The present invention can also be applied to black and white photosensitive materials using a three-color coupler mixed metal, such as those described in 2003/23 (published in July 2007, 7J').

After imagewise exposure, the photosensitive material of the present invention is subjected to fogging treatment with a base or nucleating agent, and then developed with a surface developer containing an aromatic primary amine color developer, bleached, and A complete positive color image can be directly formed by the viewing process.

As mentioned above, the fogging treatment in the present invention is carried out by applying a second layer to the entire surface of the photosensitive layer, which is called the so-called one-component fogging method, and by developing it in the presence of a nucleating agent, which is called the "chemical fogging method." Either method may be used.

Development may be carried out in the presence of a nucleating agent and a fogging agent.

Further, a photosensitive material containing a nucleating agent may be fog-exposed.

The entire surface exposure, that is, the fogging exposure in the one-element fogging method of the present invention is carried out after the imagewise exposure and/or during the development process. Exposure ftS is carried out by immersing the imagewise exposed light-sensitive material in a developer or a pre-bath of the developer, or taking it out from the developer before it dries, but it is most preferable to expose it in the developer.

As a light source for fogging exposure, is it a light source within the sensitive wavelength of the photosensitive material? ! - Any light source can be used, such as fluorescent lamps, tungsten lamps, xenon lamps, sunlight, etc. These specific methods are described, for example, in British patents /, /j
/, No. 3113, Tokusho≠3-/2710, II-
! -/270ri issue, same jr-693 issue, JP-A Show 1LL
f-5'7u7, s1, -137330, 37
-/, 29'A3? No. 31-A2A 7.2
No. 1,0732, same! Zaichi No. 70223 (
Corresponding U.S. patent μ, μ≠0゜13/), same 3! -/20
No. 2'l-r (corresponding European Patent No. 10/2).

For photosensitive materials that are sensitive to all wavelengths, such as color photosensitive materials, Japanese Patent Application Laid-Open No. 31/1989. -137330 and 31-70
．． A light source with high color rendering properties (as close to white as possible) as described in No. 223 is preferable. The illuminance of the party is 0.0/-2
000 lux, preferably O,O,t~30 lux, more preferably O0O! ~! Looks are the majority.

For sensitive materials that use emulsions with higher sensitivity, exposure at lower illuminance is preferred. The illuminance may be adjusted by changing the light source by 9 degrees, by reducing the light by using various filters, by changing the distance between the photosensitive material and the light source, or by changing the angle between the photosensitive material and the light source. Exposure time can also be shortened by using a weak light sound at the beginning of exposure and then using a stronger source.

It is preferable to immerse the light-sensitive material in a developer solution or a pre-bath solution, and to irradiate the light-sensitive material after the solution has sufficiently penetrated into the emulsion layer of the light-sensitive material. The time from penetration into the liquid to the original fog exposure is generally λ seconds to λ minutes, preferably j seconds to /minute, and more preferably Viio seconds to 30 seconds.

The exposure time for fogging is generally 0.0/sec to λ minutes,
Preferably dO is 1 second to 7 minutes, more preferably 1 second to 10 seconds.

Regarding the nucleating agent that can be used in the present invention, Japanese Patent Application No. 62-7≠
Those described in No. 232 specification, pages 7/10 to 107 can be used. In particular, it is preferable to use compounds represented by the general formulas (N-1) and [N-■] in the same specification.

Specific examples of the compound represented by general formula (N-1) are listed below.

(N-1-/) j-ethoxy-λ-methyl-/-probargylquinolinium bromide (N-1-,2) 2. Hiro-dimethyl-/-propargylquinolinium bromide (N-1-3) λ-methyl-/-(J-(J-(≠
-methylphenyl)hydrazo/]butyl)quinolinium iosito(N-1-13,1IL-dimethyl-dihydropyrido(
,2,/-b) Benzothiazolium bromide (N-1-J-) A-ethoxythiocarbonylami/-2-methyl-/-propargylquinolinium trifluoromethanesulfonate (N-1-A) 2 -Methyl-4-(J-'72-2-methyl-thioalido)-/-propargylquinolinium bromide (N-1-7) l, -<3--Benzotrianylcarboxamide)-2-methyl-7 -Propargylquinolinium trifluoromethanesulfonate (N-1-za) A-(j-(,2-mercaptoethyl)ureido]-λ-methyl-/ -Propargylquinolinium trifluoromethanesulfonate (N-1-ta) ) &-(J-(J-(J--mercapto-1,3,≠-thiadiazol-2-ylthio)propyl]waleido)-2-methyl-/-propargylquinolinium trifluoromethanesulfonate (N-1 -10) A-(j-Mercaptotetrazo-lunoyl)-2-methyl-/-Flopargylquinolinium iosito All specific examples of the compound represented by the general formula (N-I[) are shown below.

(N-If-/) /-formyl-2-(Hiro-[3-
(2-methoxyphenyl)waleido]phenyl)hydrazine (N-11-,2) /-formyl-λ-(≠-[3
-(3-(J-(,2,≠-di-tert-pentylphenoxy)propylquarido)phenylsulfonylamino]phenyl)hydrazine(N-n-J)/-formyl-2-(Hiro-[3-( j-
Mercaptotetrazol-/-yl)benzamido]phenyl) hydrazine (N-n-≠) l-formyl-λ-[≠-(3-(J
-(j-Mercaptotetrazol-/-yl)phenylquarido)phenyl]hydrazine (N-n-J-) /-Honoperuko [Hiroshi-(3-
[H-(j-mercapto-≠-methyl-1.2.≠-triazol-3-yl)carbamoyl)propanamido)phenyl]hydrazine (N-u-A) /-formyl-λ-(≠-[3- (
N-(≠-(3-mercapto-/, 2.≠-triazol-≠-yl)phenylcarbamoyl)propanamide]phenyl)hydrazine (N-■-7) /-formyl-2-[Hiroshi-13-( N
-(J--mercapto-7,3゜≠-thiadiazol-λ-yl)carbamoyl]buOpanamido)phenyl]-hydrazine(N-[[-J') 2-Chiro-benzotriazole-ocarboxamide)phenyl ] -/-Formylhydrazine (N-[-ta) 2-[≠-(J-(N-(benzotriazole-!-rupoxamide)carbamoyl]propanamide) Phenyl]-/-Formylhydrazine (N-■ -10)/-formyl-2-(Hiro-[1-(N
-phenylcarbamoyl)thiosemicarbamide]phenyl]hydrazine A nucleation accelerator may be added to the non-inventive direct positive photographic light-sensitive material for the purpose of promoting the above-mentioned fogging action. The same effect can be obtained even when the above-mentioned nucleation accelerator is added to the developer or its pre-bath.

Regarding the nucleation promoter that can be used in the present invention, please refer to the following patent application.
/≠j232/jN! It is written on page 0. A specific example is shown below.

(A-/) j-mercapto-1,2,gutriazo゛0[≠, j-a) pyridine (A-2) 3-mercapto-/, 2.44-)riazolo[≠,! -a) Pyrimidine (A-j) j-mercapto-/, 2. Hiro-Toarizo' (/*s-a)pyrimidine (A-≠)7
-(2-dimethylaminoethyl)-! -Mercapto-7
,2,≠-driazolo(/,J--aJ pyrimidine (A-1) j-mercapto-7-methyl-7゜λ,
≠-triazolo [≠, j-a]pyrimidine (A-A) 3. A-Shimelkafto/, 2. IA-
Triazo mouth [Hiroshi, j-bJ pyridazine (A-7) 2
-Mercapto-! -Methylthio-7,3,≠-thiadiazole (A-♂) 3-Mercapto-Hiro-Methyl/.

2, ≠-triazole (A-ta) J-(j-dimethylaminoprobylthio)-! -Mercapto 7,3. Hiro-thiadiazole hydrochloride (A-#)) λ-(2-morpholinoethylthio)-
Yo-Mercapto-/, 3. l/L-Thiadiazole Hydrochloride The color developing solution containing the N-hydroxyalkyl-substituted p-phenylenediamine derivative of the present invention may be a p)l-thiadiazole hydrochloride such as an alkali metal carbonate, borate or phosphate.
Buffers, bromide salts, iodide salts, benzimidazoles,
It is common to include development inhibitors or anti-capri agents such as benzothiazoles or mercapto compounds.

The pH range of these color developing solutions is ~/co, preferably, j
〜／／、! It is common that

The amount of replenishment of these primary developing solutions depends on the color photographic light-sensitive material being processed, but is generally less than the light-sensitive material/per square meter/L, and by reducing the total bromide ion concentration in the replenishing acid. It can also be made less than 300d. When reducing the replenishment to i', it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (III), copal) (
1), compounds of polyvalent metals such as chromium (Vl) and copper (II), peracids, quinones, nido-O compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromium salt; organic complex salts of iron 1) or cobal (Ill), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, /, 3-diaminoacetic acid, etc. Aminopolycarboxylic acids such as propanetetraacetic acid, glycol ether diamine tetraacetic acid, and complex salts of citric acid, tartaric acid, and malic acid; persulfates, bromates, permanganates, and nitrobenzenes can be used. Among these, aminopolycarboxylic acid iron (I[[) complex salts and persulfates, including iron(III) ethylenediaminetetraacetate complex salts, are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(11) complexes are particularly useful in both bleach and bleach-fix solutions.

Using these aminopolycarboxylic acid iron (n[) complex salts, p) 1 of the next bleaching solution or bleach-fixing solution is usually! ,! ~t, but it is also possible to process at an even lower pH for speeding up the process.

A bleach accelerator may be used in the bleaching solution, the whitening solution, and their pre-baths, if necessary.

Examples of fixing agents include thiosulfates, thiocyanine M salts, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, and ammonium thiosulfate is the most widely used. Can be used for Preservatives for the bleach-fix solution are preferably sulfite rIR salts, bisulfites, or carbonyl bisulfite adducts.

It is preferable to use softened water for the washing bath or stable bathing. Examples of the water softening treatment include using an ion exchange resin or a reverse osmosis device R'.

The main purpose of the washing bath is to wash out all of the processing solution components that have adhered to or occluded in the color photosensitive material, as well as all the constituent components of the color photosensitive material that should be removed to ensure photographic performance and image stability after processing. This is the next bath.

In addition, a stable bath refers to a bath that, in addition to the above-mentioned function as a washing bath, is also provided with an image stabilizing function that cannot be obtained with a washing bath. For example, a bath containing formalin corresponds to this bath. .

The amount brought in from the prebath in the enclosure means the volume of the prebath that adheres to and occludes the photosensitive material and mixes into the washing bath. It can be calculated by extracting the bath components and measuring the pre-bath component t' in the extract.

In the present invention, the amount of replenishment to the washing bath or a stable bath instead of the washing bath is determined by the amount of color light-sensitive material to be processed/rr? Hit 3jO
dl or less, preferably 0 to 3jO, more preferably d/20 to 2Od. In addition, the pH of water washing or stable bathing is Hiroshi ~ 10, preferably! ~ri, more preferably 6. ! ~♂,! It is.

In the washing step, it is common to carry out multistage countercurrent washing (for example, 2 tanks) of λ or more to save washing water. Furthermore,
Instead of the water washing step, a multistage countercurrent stabilization treatment step as described in JP-A-77-Ij'A3 may be performed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 3 minutes. More preferably 3θ seconds ~
It is 2 minutes and 30 seconds.

The temperature of each of the above treatment solutions is 10°C~! Used at Q°C.

A temperature of 30°C or a"c is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or conversely, lower temperatures can improve image quality and stability of processing solutions. be able to.

〔Example〕

EXAMPLES The present invention will be explained below using examples, but the present invention is not limited to the following examples.

Example / Paper support laminated on both sides with polyethylene (thickness 10
A color photographic light-sensitive material was prepared by coating the next four layers starting from the next layer (0 micron) on the front side, and applying the entire stack of the next five layers to the sixth layer on the back side. The polyethylene coating side of the first layer contains titanium white as a white pigment and a trace amount of group F as a bluish dye.

(Photosensitive I-composition) The components and coating amounts expressed in P/l are shown below.

Regarding silver halide, the coating amount is shown in terms of steel. The emulsion used for layer separation was prepared according to the manufacturing method of emulsion EM/.

However, as the emulsion for the 11th layer, a Lippmann emulsion without surface chemical sensitization was used.

witm (anti-halation layer) Black colloidal silver... o, i.

Gelatin... /, 30 @ 2 layers (
(middle layer) Gelatin...0.70 3rd layer (
Silver bromide spectrally sensitized with a red sensitizing dye (ExS-/, 2.3) (average grain size 0.3 μ, size distribution [coefficient of variation] r%, octahedral).・0.06 Spectrally sensitized with red sensitizing dye (ExS-/, 2.3) and subbrominated* (average particle size O0≠jμ, size distribution 10cm, octahedral) θ, / θ Gelatin... i, o.

Cyan coupler (ExC-/) Cyan coupler (ExC-2) ・ ・ ・ 0, I O Antifading agent (cpct-2, 3, 4t, /3 etc.)
・ O, /2 Coupler dispersion medium (cpd-3) ・ ・ ・ 0.03 Coupler solvent (S01 v 7 * -2+ 3 equivalents) o, ot 0.1/ ≠th layer (high sensitivity red sensitive layer) Red Silver bromide spectrally sensitized with a sensitizing dye (h x b −/ + 2* j ) (average grain size o, toμ, size distribution/!chi, octahedral) Gelatin cyan coupler (ExC −/) o, 1y-i, o.

Silver bromide spectrally sensitized with a green sensitizing dye (ExS-J)
Average particle size 0.2! μ, particle size distribution ♂chi, octahedral) 0, /j Cyan coupler (ExC-2) ・ ・ ・ O, / ! Antifading agent (cpa-2, 3, ≠, /3 etc. i1)・・
・ O, / from puller dispersion medium (cpct-t) ・ ・ ・ 0.03 coupler solvent (Solv-7+2m3 etc.-i ・ ・
・o,i.

5th layer (intermediate layer) Gelatin... /, 00 color mixing inhibitor (cpct-7)... o, or color mixing inhibitor solvent (
Solv-μ,! Equal amount)... 0. /l.

Polymer latex (Cpd-1r) ・　・　・　o,i.

・ ・ ・ O, O is spectrally sensitized with a green sensitizing dye (h x S j *≠) and becomes a framobrominated complex (average particle size O8≠jμ, particle size distribution //CH, octahedron)... 0 .06 Gelatin... o, t.

Magenta coupler (ExM-/, 2nd grade...
O, / / Anti-fading agent (cpa-ta)... 0.10 Anti-staining agent (Cpd-10,22 equivalent)... o, o
i ≠ stain inhibitor (Cpd-, 2j) e ・ ・ 0. 00/ Stain inhibitor (Cpd-12) ・ ・ ・ 0.0/ Coupler dispersion medium (Cpd-3) 6th layer (low sensitivity green sensitive layer) ・ 0.02 Coupler solvent (Solv-Hiroshi, 6 etc.)・ ・ 0./! 7th layer (high sensitivity green sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-3, ≠) (average grain size o, rμ, grain size distribution/j% ,
Octahedron) ・ ・ ・ o, i.

Gelatin o, t.

Magenta coupler (ExM-/,,2)...
O, / / Anti-fading agent (cpa-ta)...0.10 Anti-staining agent (Cpd-10,2,2 equivalent)...0.
0/, 3 Stin inhibitor (cpd-23) o, ooi stin inhibitor (Cpd-/2) 0.0/ Coupler dispersion medium (Cpd-1) ・0. ．． 02 Coupler solvent (8o1v-μ, 6 equivalents)・・・
o, iz Rth layer (intermediate layer) 7th layer (yellow filter layer) same as 5th layer Yellow Coro (Do silver --- 0,20 gelatin
---i-o.

Color mixing inhibitor (Cpd-7)... o, ot Color mixing inhibitor solvent (8o1v-≠, j, etc.)... o, iz Polymer latex (Cpd-J') ・ ・ ・ o, i.

1st O layer (intermediate layer) 11th layer (low sensitivity blue sensitive layer) same as 5th layer Silver bromide (average grain size o, ttzμ, Particle size distribution r, octahedral) ・ ・ ・ 0.07 Silver bromide spectrally sensitized with blue sensitizing dye (ExS-7% 6) (average grain size o, to μ, grain size distribution/≠
0.10 Gelatin 0.20 Yellow coupler (listed in Table 2) Anti-stinting agent (Cpd-//) 0.00/ Anti-fading agent (cpa-+) ... o, i.

Coupler dispersion medium (Cpd-J″) ・ ・ ・ O, OS Coupler solvent (Solv-, 2) ・ ・ ・ 0.0 12th layer (high sensitivity blue sensitive layer) Blue sensitizing dye (ExS-j, lI ) spectrally sensitized silver bromide (average particle size/, 2μ, particle size distribution/!chi, octahedron) ・0.23- Gelatin ... i, o.

Yellow coupler (listed in Table-λ) Anti-stinting agent (Cpd-//) 0.002 Anti-fading agent (cpci-g)... 0. lO coupler dispersion medium (Cpd-, t) Hao3- coupler solvent (Solv-2) ・ ・ ・ o, i.

13th layer (ultraviolet absorption layer) Gelatin...i, t.

Ultraviolet absorber (Cpd-/, 3./3 etc. it)...
i, o.

Color mixing prevention agent (cpa-g, /≠equal amount)・・・・
θ, 02 Dispersion medium (cpa-t)... O, OS ultraviolet absorber solvent (8o1v-/, 2 equivalents)... o,
is anti-irradiation dye (Cpd-/j.

76 equivalent) ... 0.02 anti-irradiation dye (cpa-/7゜/♂ equivalent)
... 0.0.2 11th A layer (protective layer) Fine grain silver chlorobromide (silver chloride 27 molti, average size θ0.
2μ) Acrylic modified copolymer of 0.02 polyvinyl alcohol (degree of modification 77%)
0.02 polymethyl methacrylate particles (average particle size 2. Hiromicron), silicon oxide (average particle size! Micron) equivalent amount...O,OS gelatin
... Ha! O gelatin hardening agent ()i-/)・
... O0/7 131st layer (JA layer) Gelatin ... Co, jO 1st layer (back film-protecting layer) Polymethyl methacrylate particles (average particle size, μ
micron), silicon oxide (average particle size 5 microns) equivalent amount...O,OS gelatin...
・K, OO gelatin hardening agent (H-/)... 0. /
/Emulsion EM/ How to make an aqueous solution of potassium bromide and silver nitrate are simultaneously added to an aqueous gelatin solution with vigorous stirring over a period of 75 minutes at 7J'C to form an octahedral bromide with an average particle size of o, I/Lo microns. Obtain silver particles. This emulsion contains 0.3y of 3
．． All chemical sensitization treatments were carried out by sequentially adding IIL-dimethyl-7,3-thiazoline-corchion, 6 ~ sodium thiosulfate, and 7 ■ chloroauric acid (≠ hydrate) and heating at 75°C for rO min. .

The grains thus obtained were used as cores and further grown in the same precipitation environment as in the first time, to finally obtain a core/shell silver bromide emulsion with an octahedral monodisperse having an average grain size of 0.7 microns. The coefficient of variation in particle size was approximately 10 inches. This emulsion contains one and a half moles of silver/, j■ sodium thiosulfate/,! ■
A chemical sensitization treatment was carried out by adding chloroauric acid (≠ hydrate) and heating at to° C. for 60 minutes to obtain an internal latent image type silver halide emulsion.

Each photosensitive layer contains E x Z K −/f as a nucleating agent.
Based on the amount of silver halide coated, 10% by weight of cpct-, 2≠>1o-2% by weight was used as a nucleation accelerator. Furthermore,
Each layer contains alkanol XC (Dup) as an emulsification dispersion aid.
ont) and alkylbenzenesulfonic acid sl-IJ
Umuwo, succinate ester and Mage as coating aids
fac F-/20 (manufactured by Dainippon Ink)? ! -Used. In the silver halide and colloidal silver containing layer, (Cpd-/20°2/) was used as a stabilizer. 1st/
The yellow coupler of the present invention shown in Table 2 was applied to the layer (low-sensitivity blue-sensing layer) and the 7.2nd layer (tube-sensitivity blue-sensing layer),
Sample number 10/~10IIt was prepared. In addition, comparative yellow couplers Bi 1st/layer (low sensitivity blue sensitive layer) and 72nd
Samples 1O7 to 10 except those coated on the layer (cylindrical sensitivity sensitizing layer)
All comparison samples were prepared in the same manner as 1/L, and this sample was designated as sample number 103. The compounds used in the examples are shown below.

Ext-/ ExS-2 x 5 ExS-≠ Cpd-/ ExS-3 S()3H ExS-6 cpa-≠ 04H9(t) cpct-t cpa-6 Cpd-zaCpd-/, 2 Cpd-/j Cpd -/≠ Polyethyl acrylate H cpa-ta Cpd-10 Cpd-// cpct-/I Cpd-/Otsu H Cpd-/7 Cpd-# pal Cpd-24L EXC-/ (J EXC-2 ・Cpd-, 20 Cpd-, 2/ EXM-/ EXM-J H 5olv-/ 5olv-2 olv-3 O O O ■-≠ -j v-1゜h-/ Ex ZK-/ Di(2 -ethylhexyl) phthalate trinonyl phosphate di(3-methylhexyl) phthalate tricresyl phosphate dibutyl phthalate trioctyl phosphate di(2-ethylhexyl) separate/, 2-bis(vinylsulfonylacetamide) ethane 7-(j- (j-mercaptotitrazol-/-yl)benzamidocou 1o-propargyl 1/,2,3,1I--tetrahuman CI7 clidinium is wedged directly into the positive color light-sensitive material prepared in this way. Exposure (17 io seconds, 10 CMS) was applied, followed by development according to the following processing step A to obtain a color image.

The treatment steps and treatment liquid used here are shown below. In addition, the color developing agents in the color developing solution are A-G shown in Table 1.
A composition with the following composition was used.

Processing step A Time Temperature Replenishment amount Color development 7 minutes 30 seconds 3r℃ 300al/r
r? Bleach fixing UO seconds 3J'''C300n
l/rrt'Wash ■ ≠O seconds 30~36℃Wash■ ≠θ seconds 30~36℃Wash■ 75 seconds 320w1/d Dry 30 seconds 75~♂O0C The method of replenishing the wash water is to replenish the wash bath ■. A so-called same-current supplementary light system was used, in which the overflow liquid from the washing bath (■) is led to the washing bath (■), and the overflow liquid from the washing bath (■) is led to the washing bath (■).

At this time, the carry-in of photosensitive material from the prebath is 31d/rr?
Therefore, the replenishment magnification is 7 times.

[Color developer]

Mother Solution Replenisher Ethylene Diamine Tetrakis Methylene Phosphonate Diethylene Glycol Benzyl Alcohol Sodium Bromide Sodium Chloride Sodium Sulfite O, Syza, 09/2. OP o, t, y o, sy λ, Ori! ri/3. Of/r, 3y 5noN,N-diethylhuman axylamine 3.3ta≠,rP Color developing agent (listed in Table 7) Potassium carbonate 30. Of 30.01 Fluorescent brightener (add Stilbe pure water 1000rxt 1000a
tp) i io, to io, ri OpH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach liquid]

ammonium thiosulfate sodium bisulfite Iron ethylenediaminetetraacetate (1) Ammonium・λ water salt Ethylenediaminetetraacetic acid λ Sodium/λ water salt Separate pure water sound p)1 Mother liquid = replenisher 2/, 0y so, oy s, oy oooow 6.3 The pH was adjusted with aqueous ammonia or hydrochloric acid.

[Washing water]

Pure water was used (mother solution = replenisher) Here, pure water means that the concentration of all cations other than hydrogen ions and all anions other than hydroxide ions in tap water is reduced by ion exchange treatment / I) I) m The following is a friend removed.

The maximum image density (Dmax) of the yellow image obtained through the development process was measured. In addition, a photobleaching test was conducted on the same developed sample under the following conditions, and the maximum image density of the yellow image was again measured in total.

(Photobleaching test conditions) In an environment of 30° C., 704 R)i, a xenon light source of 100,000 flux was irradiated for 72 hours and stopped for 12 hours, for a total of 20 hours.

The results obtained are shown in Table-2.

From Table 2, Sample 10/~IO≠ in which the yellow coupler of the present invention was used in the blue-sensitive layer is Comparative Sample 10! It can be seen that the photofading of the yellow image is less than that of the yellow image, and that a high Dmax can be obtained by processing with the color developing solution containing the developing drug of the present invention (processing A to F).

Example 2 Nucleating agent ExZK-/ and nucleating accelerator cpct-2≠ were removed from each photosensitive layer, except for Samples 10/-1 of Example 1.
Samples 207 to λQ B were created in the same manner as 0j.

These samples were given the same nz'i as in Example/, and then color images were obtained by the following processing steps.

The treatment steps and treatment liquid used here are shown below. The color developing agent in the color developing solution had the composition HL shown in Table 3.

Processing step B Bleach fixing aO seconds 36℃ 320ct/rr
? Stable■ Stable■ ≠Q seconds 31. ℃ l/LO seconds 3P℃ 320d/rr? *1) After immersing in the color developer for /J'' seconds,
! Color development processing was carried out with 7 lines of original fogging per second.

[Color developer]

Mother liquor Replenisher o, jyo o, sy Hydroxyethyliminodiacetic acid β-cyclodextrin Monoethylene glycol Benzyl alcohol Monoethanolamine Sodium bromide Sodium chloride N,N-diethyl hydroxylamine Color developing crude drug (listed in Table 3 Potassium carbonate 30 ha!1 ri, Oy ri, Ori2,!ri2.3y!, j)! 62ノ, Oy hajy 10.0P io, oy λ,! ri/, J'nohiro, Oy t, ry 3j, Ofl Optical brightener i, op/, 2F (
Stilbene type) pH 10, 3010, 70 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor = replenisher ammonium thiosulfate / 10P sodium bisulfite /, 2P diethylenetriaminepentaacetic acid ♂Oy iron (In) ammonium diethylenetriamine five nodes r1! sy λ-Mercapto-! -Ami7 0.3 no/, 3.
≠-Add thiadiazole pure water 10004p)i
B, ♂ OpH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

/-Hydroxyethylidene-/,/-diphosphonic acid 0-phenylphenol Potassium chloride Bismuth chloride Zinc sulfite Sodium ammonium sulfate 2.7y 0.2y Co,! 1 HaOy θ,, 2JP 0.31 ≠, jy Add pure water 1000vtp) 1
7. ．． 2 pH was adjusted with potassium hydroxide or hydrochloric acid.

Regarding the sample developed in this manner, density measurement and photobleaching test were conducted in the same manner as in Example.

I will show the obtained results to Tatsuhiro.

From Table ≠, Samples 20/~20≠ used in the yellow coupler of the present invention in the all-blue sensitive layer showed less photobleaching of the yellow image than Comparative Sample 20j, and also contained the developing agent of the present invention. It can be seen that a high Dmax can be obtained by processing (processing) 1-K) with a color developing solution.

Example 3 The 1st/layer (low sensitivity blue sensitive layer) and the 1st λ layer (
All silver bromide emulsions used in the high-sensitivity iv-sensitive layer) Emulsion EM described below
Samples 20/~20 of Example 2 were prepared according to the method of Example 2, except that the silver chlorobromide emulsion was changed to the one shown below. 'ff
Sample 30/~30 was prepared using the same method as the one used. It was created.

1st/r (low sensitivity blue sensitive layer) Silver chlorobromide (average grain size o, I/Lsμ, grain size distribution r%, odor silver oxide content 70 mol%) blue sensitizing dye (ExS-
j, silver chlorobromide spectrally sensitized with A) (average grain size o
, toμ, particle size distribution/4t, silver bromide content to mol) 72nd layer (high sensitivity blue-sensitive layer) Silver chlorobromide ( Average particle size/, 2μ, particle size distribution/j
%, silver bromide content≠! Molch) Preparation of emulsion EM, 2 Mixed aqueous solution of potassium bromide and sodium chloride and nitrate #I
The water solubility g of scissors is 3.4t-0.071 per mole of Ag.
Dimethyl-/13-teacyly/-coch-off klls were added simultaneously to an aqueous gelatin solution at 62°C with vigorous stirring over a period of about ≠ minutes, and the average particle size was about 0.2/min.
A monodisperse silver chlorobromide emulsion was obtained. 6/l per mole of silver in this emulsion! Add 9 of sodium thiosulfate and 1A2t9 of chloroauric acid (≠ hydrate) 6/
Next, perform chemical sensitization treatment by heating at ℃ for 60 min. The entire core of the silver chlorobromide grains obtained in this way was further grown in the same precipitation environment as the first time, and finally monodisperse particles with an average particle size of about o, t, o μm (silver bromide content 60 mol%) were formed. A core/shell chlorobromide emulsion was obtained. The coefficient of variation in particle size was approximately /≠chi. per mole of silver in this emulsion /, j■
Sodium thiosulfate and chloroauric acid (≠water salt)
- Chemical sensitization treatment is performed by adding and heating at to °C for to minutes,
An internal latent image type silver halide agent EM2 was obtained.

These samples were subjected to the same development process as in Example λ to obtain color images. Next, density measurements and photobleaching tests were performed on these samples in the same manner as in Example.

The results obtained are shown in Table-j above.

Table-! Therefore, Samples 30/~30≠ in which the yellow coupler of the present invention was used in the blue-sensitive layer exhibited less photobleaching of the yellow image than Comparative Sample 30; It can be seen that a high Dmax can be obtained by processing (processing) 1-K) with a developer.

Example In place of the nucleating agent ExZK-/, the following nucleating agent BxZK-
2 to the silver halide coating amount of each g-light layer.
Sample 1oi-/(1;
) Sample sample 〇/~1Aozy (created in the same manner as J').

These samples were subjected to the same exposure as in Example/, and then a color image was obtained by the same processing step A as in Example/. In addition,
The color developing crude drugs in the color developing solution had the compositions A1 and DG shown in Table 1 of Example 1.

ExZK-2/-formyl-,2-(Hiro-(3-[3-
<r-Mercaptotetrazol-7-yl)phenyl]waleito)phenyl]hydrazine The density measurement and photobleaching test similar to those in Example 1 were carried out on the sample developed in this manner.

The results obtained are shown in Table-6.

From Table t, it can be seen that the sample≠O/~aO≠ used in the all-blue sensitive layer of the yellow coupler of the present invention has less photobleaching of the yellow image than the comparative sample≠Oj. It can be seen that a high Dmax can be obtained by processing with a color developing solution (processing A, DF).

Example! No. 1111- Poly(polymerization degree IO) oxyethylene poly(polymerization degree 3) glycidyl p-nonylphenyl nityl 3
-! Sample 1 of Example/except that it was added to “f/rI?”
Sample 30/ was created in the same manner as 0/f was created.

When the surface resistance value of Sample 10/Toyo 0/ was measured, it was 3.
Does it mean that 0/ is more markedly reduced? confirmed.

Furthermore, when the above-mentioned material was subjected to the treatment step A described in Example 1, it was confirmed that the "wetness" of sample 60/ was improved.

〔Effect of the invention〕

According to the direct positive image forming method of the present invention, an image having excellent photobleaching properties and a high maximum color density can be obtained.

Moreover, the above-mentioned image can be obtained through quick and simple processing, and its usefulness is extremely large.

Claims (1)

[Scope of Claims] A photographic light-sensitive material containing at least one unfogged internal latent image type silver halide emulsion layer and a color image-forming coupler on a support is subjected to imagewise exposure and after fogging treatment. and/or a direct positive color image forming method in which a development process is performed while performing a fogging process, wherein the photographic light-sensitive material contains at least one compound represented by the following general formula (I), and the development process is performed with N-hydroxyalkyl substitution. A direct positive color image forming method characterized in that it is carried out using a developer containing a p-phenylenediamine derivative. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z represents a group that can be separated during the coupling reaction with the oxidized form of the developing agent, G_1 represents a halogen atom or an alkoxy group, and G_2 represents a halogen atom or an alkoxy group. Represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent. R
represents an alkyl group which may have a substituent.